Current Speed

Chemistry and Technology of Fuels and Oils, Vol. 43, No.
5, 2007
CURRENT PROBLEMS
ETHANOL AS A HIGH-OCTANE, ENVIRONMENTALLY CLEAN COMPONENT

OF AUTOMOTIVE FUELS. Current Aspects of Use
S. A. Karpov UDC 665.7.038.3
The principle of the action of antiknocks consists of preventing explosive decomposition of the products
of pre-ignition oxidation of the fuel before normal combustion of the fuel blend begins. There are
several theories that explain the essence of knock combustion. The most widely accepted one is the so-
called peroxide theory.
At high temperatures where the ratio of the rates of formation of hydroperoxides and decomposition of
peroxide radicals attains ~10 -4 , products of decomposition of peroxide radicals and in the case of decomposition of
the secondary radicals formed from n-paraffins, highly reactive aldehydes enter the flame front.
When ethanol and/or other oxygenates are incorporated, the antiknock value of automotive gasolines
increases, since the heat of combustion of the fuel-air mixture decreases with an increase in the concentration of
oxygen in the fuel, heat is removed from the combustion chamber more rapidly, and the maximum temperature of
combustion decreases as a result. This makes it possible to increase the degree of compression of the fuel-air
mixture and thus increase engine efficiency.
In the USA, the leading automobile companies – Ford, General Motors, and Daimler-Chrysler – recommend
using oxygen-containing fuels, ethanol, for example. It does not pollute the atmosphere, has good performance
characteristics, and is an excellent cleaning agent. In new cars, ethanol keeps the engine clean and in older cars,
it strips pollutants deposited in the fuel feed system. The substances separated sometimes accumulate in the fuel
filter and are removed by replacing the filter.
All alcohols adsorb water. The water condensate formed in the fuel feed system is absorbed by ethanol as
it cannot scale off and freeze. For this reason, it is not necessary to add antifreeze to the fuel line in winter.
____________________________________________________________________________________________________
I. M. Gubkin Russian State University of Oil and Gas. Translated from Khimiya i Tekhnologiya Topliv i
Masel, No. 5, pp. 3 – 7, September – October, 2007.
0009-3092/07/4305–0355 © 2007 Springer Science+Business Media, Inc. 355

Ethanol is a fuel for automobiles with engines of both old and new design. In internal combustion engines
manufactured before 1969, the valve seats are unhardened, so that it can be necessary to replace the lead-containing
antiknock in the fuel to prevent premature wear. Ethanol blends do not cause charring of the valve, since ethanol
burns at a lower temperature than unleaded gasoline. This is also responsible for the use of pure alcohol as fuel
in many high-performance racing engines.
Modern computerized autos have higher performance characteristics than those not equipped with
computer systems when correctly used. Improved performance is attained by automatic correction of fuel feed
when the operating conditions change or a new fuel is used.
Dehydrated ethanol containing a minimum of 99.5% basic substance has been most widely used as fuel.
The positive properties of alcohol fuels are totally manifested when used in pure form. In converting a car to
operating with pure alcohols, it is necessary to:
• increase the fuel tank capacity (to preserve the usual fueling run, since specific consumption of alcohol
is much higher than for gasoline);
• increase the degree of engine compression e to 12-14 for complete utilization of the high antiknock value
of the fuel;
• readjust the carburetor for higher flow rates and a higher degree of leaning of the blend.
The advantages of alcohols are the high efficiency of operation and high antiknock value. The efficiency
of the alcohol engine is higher than for the gasoline engine in the entire range of compositions of working blends.
For this reason, the specific energy consumption per unit of power decreases. The amount of harmful emissions
simultaneously decreases significantly.
The high antiknock qualities of alcohols are due to their predominant use in internal combustion engines
with positive (spark) combustion. The low saturated vapor pressure and high evaporation heat of alcohols make
it almost impossible to start carburetor engines at temperatures below 10°C.
To improve the starting qualities, 4-6% isopentane or 6-8% dimethyl ether are added to the alcohols,
which ensures normal starting of the engine at an ambient temperature of – 20 to – 25°C. The engines are
equipped with starting heaters for the same purpose. Additional heating of the fuel blend, with the exhaust gases,
for example, is necessary in unstable operation of the engine at high loads due to the poor evaporation of alcohols.
Due to the difficulties listed above, use of pure alcohols is undesirable and it is better to add them to
ordinary petroleum fuels in amounts of up to 30%.
Brazil, where ethanol has been used since 1939, has the greatest experience in use of fuel ethanol. Due to
the high oil prices in the 1970s, the Brazilian government made a decision to manufacture autos that operate on
pure ethanol to reduce the dependence on imported oil and create added value for sugar cane growers. Today
more than 4.2 million vehicles in Brazil utilize ethanol as fuel. Approximately 40% of the autos operate on pure
(100%) ethanol and the rest run on a blend of 24% ethanol and 76% gasoline.
Research on ethanol-containing fuel compositions has been conducted in Russia for more than 20 years.
Formulas for ethanol-based additives are the result.
For example, a composition is proposed in [1] that includes low-octane gasoline and an oxygen-containing
component in the form of the distillation product of a 1:0.8-1:1.3 blend of the head fraction of ethanol distilling at
78-79°C and fusel oil (95-102°C). The composition is inexpensive and has high physicochemical and performance
characteristics. This additive is recommended for addition to gasoline in the amount of 10-14%.
A gasoline-based composition has been patented [2]. It is proposed for expanding the line of
high-octane unleaded gasolines with improved environmental properties that reduce the amount of carbon
monoxide and hydrocarbons in exhaust gases. The composition contains 5-15 wt. % ethanol additive which
356
includes, wt. %: 6-20% aromatic amine; 0.1-1.5% crotonaldehyde; 0.2-2% acetaldehyde; 0.5-1.5% water; 0.1-4%
organometallic additive. N-methyl aniline or a mixture of toluidines is used as the aromatic amine.
Ethanol-based octane-boosting additives were created at VNII NP: VOKE with a stabilizer – fusel
oils – and multifunctional LAZURIN. The specifications for these additives and for ethanol-containing unleaded
automotive gasolines (TU 38.401-58-2444 – 99) [4], and technology for manufacturing gasoline – ethanol fuels and
the instructions on using, storing, and shipping them were developed there.
An additive that includes high-performance antiknocks – an aromatic amine and organic derivative of
manganese, and a mixture of oxygenates: ethanol, methanol, and methyl tert-butyl ether – is proposed in a
patent [5]. In addition, a detergent whose presence is mandatory in automotive gasolines under European Union
standards is contained in the additive.
A method for obtaining stable high-performance antiknock additives that allow reducing consumption of
octane boosters in production of commercial gasolines has been patented [6]. The additive contains ethanol
stabilized with C 3-C 5 aliphatic alcohols or ethers or the aldehyde-ether-alcohol fraction obtained from wood ethanol
production wastes. It has a specific odor uncharacteristic of ethanol, which prevents mistakenly using it as
drinking alcohol.
Experience in using ethanol fuels has revealed some of their drawbacks related to the difference in the
physicochemical properties of gasoline and alcohol:
• high corrosiveness with respect to many construction materials;
• low heat value;
• negative effect on rubber and plastics (penetrates hoses and tight seals, which increases fuel losses to
evaporation);
• separation in the presence of water;
• high saturated vapor pressure and consequently high probability of formation of vapor locks in the fuel
system.
Most of these drawbacks can be easily eliminated. The corrosion rate incases with an increase in the
water content, but up to a certain limit: maximally up to 0.6 g/(m 2×h) at a 60 wt. % water content. The corrosion
rate of copper M1 in ethanol is 0.4 g/(m 2 ×h) at 85 wt. % water content. To improve the antiwear properties and
reduce corrosiveness, it is recommended that a package of modifiers, including additives to improve self-ignition,
a lubricant, and a corrosion inhibitor, be added to alcohol fuel.
AI95E gasoline containing 5-10% industrial ethanol (TU 38.302-15-02 – 94) was tested at AvtoVAZ. It was
found that gasoline with a 5% ethanol content does not negatively affect industrial rubber items. In accordance
with GOST R 51176, it is approved for production and use.
The ignition limits of the gasoline-ethanol blend are wider than for pure gasoline. Operation on lean
blends is possible because of this. Despite the lower heat value, ethanol-containing fuel consumption increases
insignificantly: by 5% on average. By selecting alcohol-resistant polymeric materials, fuel losses from evaporation
can be eliminated.
Phase instability caused by the presence of small amounts of water and consequently the restricted
reciprocal solubility of the components is the basic drawback of gasoline-alcohol fuels. This drawback can be
overcome by adding the corresponding modifiers and stabilizers to alcohol fuels. The water content affects
separation of alcohol gasolines to the greatest degree.
For ensuring the stability of these gasolines in production, storage, and use, it is necessary to: prevent
water from entering them; use stabilizing additives, in other words, cosolvents that homogenize the
357
gasoline – water – alcohol system. It is also recommended that the alcohol be added to the gasoline immediately
before delivery of the automobile.
The following have been proposed as stabilizers for gasoline – alcohol blends: C 3-C 12 aliphatic alcohols
of normal and branched structure, phenols, alkyl acetates, ethers and esters, their organometallic derivatives,
ketones, amines, surfactants, and glycols and their ethers, aldehydes, ketals, acetals, alkyl carbonates, carboxylic
acids, and blends of these compounds.
Stabilizers prevent separation of alcohol-containing gasoline at temperatures from – 40 to – 23°C. Fusel oils that
ensure homogeneity of the fuel at temperatures above – 25°C are good and inexpensive stabilizers.
The ability of gasoline – ethanol blends to separate is a function of the composition of the gasoline and the alcohol
and water content in the composition. The cloud point decreases with an increase in the content of aromatic compounds and
alcohol in the gasoline. However, the water content is a much more important factor for these fuel blends.
At the beginning of the 1970s, the possible ethanol content in gasoline was investigated with a number of methods
aimed at obtaining products. The possibilities of a suitable blend of gasoline and ethanol in the pipeline terminal are currently
being carefully investigated.
ETHANOL DEHYDRATION TECHNOLOGIES

Ethanol itself, which initially contains some water, is the basic source of water in alcohol fuel. For this reason,
dehydration of ethanol is the most effective method of reducing the water content in fuel. The main problem in dehydration
consists of forming an azeotrope of ethanol with 4 vol. % water which cannot be removed by simple distillation.
The dehydration problem is solved by distillation methods (azeotropic, extraction, salt, and vacuum) and hybrid
methods that combine distillation with separation, adsorption, and membrane separation. Pervaporation (evaporation through
a membrane) – a process based on the difference in the rates of penetration of components through a polymeric material – is
becoming increasingly important.
All methods of producing absolute alcohol can be divided into several types based on the use:
• low-temperature solid water-binding materials;
• liquid water-binding substances;
• azeotropism phenomena;
• solutions of salts that shift the azeotropic point (salt dehydration);
• phenomena of diffusion of vapors through porous membranes;
• vacuum.
The alcohol dehydration method with solid dehydrating substances has been used on industrial scales. Calcium
oxide is the best known of the solid absorbents [7]. There are two opinions on the possibility of using it in the literature: for
removal of large quantities of water and for post-dehydration for a water content of hundredths of a percent. However, this
method is not widely used.
Glycerin is primarily used as a liquid water absorbent [8]. In using pure glycerin, alcohol of 99.2 vol. % strength is
obtained, and with glycerin solutions of dehydrating salts (CaCl2, K2CO3), alcohol with 99.9-100 vol. % strength is obtained.
However, this method, too, like the dehydration methods based on the different rate of diffusion of alcohol and water vapors
through membranes and vacuum distillation, have not become widespread [9].
The azeotropic method of dehydration is of the greatest industrial importance. The dehydration method using salt
distillation developed by L. L. Dobroserdov is also promising [10].
However, no optimum dehydration method that is simultaneously effective, cheap, environmentally save, and suitable
for a wide range of moisture contents has yet been proposed. For this reason, the problem consists of selecting and improving
an existing or creating a new optimum method.
358
Dehydration with zeolites in steady-state conditions. The essence of the method consists of adsorption of water by
type NaX zeolites (pore size of 0.3 nm). These zeolites are used for dehydration as molecular sieves. The moisture removal
mechanism consists of not only adsorption of water molecules on the active site of the zeolite but also filtration of the
molecules through pores whose size permits passage of water molecules alone, separating them from the alcohol molecules.
The capacity of the zeolites for water is 18 wt. %. The problem consisted of obtaining alcohol with a different residual
water content: 3.3, 3, 2.7, 2.5, and 2 vol. %. The amount of zeolites necessary for obtaining alcohol with a given water content
was determined by calculation for each sample (50 ml). The samples were prepared as follows; the zeolites were added in the
calculated amount to 50 ml of ethanol, and the samples were tightly sealed and left for 24 h. The alcohol was then separated
from the water-saturated zeolites and the residual moisture content was determined. The losses of alcohol were 2-4 vol. %.
When zeolites were added to ethanol in the amount of 11.68, 10.29, 8.90, 7.51, and 6.12 g, the residual water content in
it was 2, 2.34, 2.74, 3.22, and 3.25 wt. %. It follows from these results that dehydration of alcohol with zeolites in steady-state
conditions is acceptable for obtaining alcohol of a given “purity” in a wide range of moisture contents. Subsequent regeneration
of the zeolites by calcination saves on consumption of additional reagents.
This method can be considered a combined method, since it uses two processes: adsorption of water molecules on
the active sites of zeolites and physical filtration through 0.3-nm micropores (the water molecule is 0.3 nm in size and the
ethanol molecule is 0.4 nm). However, use of this method on the industrial scale is not expedient since dehydration is a periodic
and very lengthy process (the cycle lasts for the order of one day).
This is due to the low diffusion rates of water to the outside of zeolites. In steady-state conditions, only the thermal
motion of water molecules uniformly distributed in the entire volume of the alcohol, which is not large at room temperature, is
the driving force of external diffusion.
We can say that continuous adsorption in the liquid phase is characterized by high rates. The kinetics of the process
is limited by the internal diffusion rate, which is low due to the small pore size, comparable to the size of the molecules of the
substances. For this reason, this method is not very efficient in small units. In addition, the lifetime of the zeolites in the
continuous liquid-phase process is not completely utilized, since “breakthrough” begins before the water molecules reach the
deep active sites in the zeolite.
Dehydration with zeolites in the vapor phase. The method consists of distilling the alcohol through a column packed
with zeolites NaX with 0.4 nm pores. In contrast to the mechanism of dehydration in steady-state conditions, the mechanism
of this method is based on adsorption alone. Selection of the type of zeolites is based on the ratio of their adsorption activity
and selectivity.
Zeolites of the NaY type adsorb water most actively, but they also relatively actively adsorb polar ethanol, which
increases losses of the target component. Zeolites NaX, which have a lower affinity for polar compounds, allow reducing
competitive adsorption and increasing the selectivity of dehydration.
Dehydration is more efficiently conducted in the vapor phase. For a hydrophilic zeolite such as NaX, the active site
– water bond is stronger than the active site – alcohol bond. The high vapor temperature weakens these bonds, so that
primarily water is adsorbed.
The large pore size allows passing both water and alcohol molecules in them, which could cause competitive
adsorption and thus reduce the life of the zeolite during dehydration and increase losses of the target alcohol.
However, at the boiling point, the thermal motion of the molecules is significantly intensified, and since
type NaX zeolites have a higher affinity for the polar water than for the less polar alcohol, desorption will predominate
for ethanol in these conditions and only water will be adsorbed.
Several similar experiments which differed in the rate of passage of ethanol vapors through a column
packed with zeolites were conducted. Each time the column was packed with new (regenerated) zeolite. The
experiment was conducted with the following method: 50 ml of alcohol was placed in a flask and distilled through
359
4.5
cw, wt. %
3.5
2.5
1.5
0 0.02 0.04 0.06 0.08 0.10 0.12
w, litre/(m2·sec)
Fig. 1. Residual water content c w as a function of the rate w of distillation of ethanol

through zeolites NaX with 0.4 nm pores.
a column 3 cm in diameter at different rates (0.012-0.11 liter/sec×m 2). The distillate obtained was analyzed for the
residual water content. The zeolites were regenerated by calcining at 350°C for 4 h.
The results of the experiments are shown in Fig. 1. The dependence of the residual water content on the
rate of distillation of ethanol through the zeolites is almost linear. In practice, it is necessary to consider another
factor – the capacity of the zeolites, which determines the size of the equipment – the adsorbers and time
between regenerations.
As a consequence, after selecting the distillation rate and volume of the zeolites (adsorber size), an
efficient and flexible process for dehydration of ethanol by zeolites in the vapor phase, which can easily be
implemented in industry can be obtained.
Dependence of phase stability on the concentration of ethanol in gasoline. Despite the fact that the
proposed process for dehydration of ethanol is efficient, environmentally clean, and comparatively inexpensive,
using it complicates production of ethanol-containing fuels. In world practice, dehydrated ethanol containing a
minimum of 99.5% basic substance is the most common octane booster. However, dehydration of ethanol to this
degree is not always required.
For this reason, it is important to determine the optimum residual moisture content in ethanol at which the
phase stability of the composition, corresponding to the requirements of GOST R 52201 – 2004, is not perturbed.
It will be different as a function of the quantitative ratio of alcohol and gasoline.
The cloud point with different volume contents of ethanol was determined to assess the mutual solubility
of the components of the alcohol – gasoline composition [7]. A winter gasohol cloud point, equal to – 30°C at the
production site, was accepted as satisfying the GOST.
The results of the evaluation are shown in Fig. 2. The stability of the compositions increase with an
increase in the alcohol content, which is in agreement with the published data.
Ethanol actually does not require such a deep degree of dehydration even in the traditionally low
concentrations. At a 10 vol. % ethanol content, the maximum acceptable with the active GOST, the residual water
content can attain 2.5 vol. %, while dehydration is totally unnecessary for a composition containing 50 vol. % (and
hardly greater than 40 vol. %) alcohol.
The level of ethanol consumption and production has increased significantly over the past 20 years due
to the high performance characteristics and competitive price of this fuel. When ethanol obtained from renewable
biomass is used, the global warming effect is partially compensated for as a result of gasoline consumption. Many
countries are either engaged in large-scale production and consumption of ethanol or are instituting measures to
stimulate expansion of its production and areas of application.
360
0
5%
−10
tcl,, °C
10
20
−20
30
−30
40
50
−40
1.5 2 2.5 3 3.5 4 4.5
cw, vol. %
Fig. 2. Cloud point t c of alcohol – gasoline blend as a function of water content c w in

alcohol for compositions with different alcohol contents (see figures on curves).
The introduction of new technologies will assist in reducing the environmental and monetary costs of
ethanol production. Harmful emissions with auto exhaust gases decrease when it is used. Ethanol is a renewable
type of fuel and for this reason has advantages that gasoline does not.
In many countries, the petroleum industry has had tax breaks and subsidies for many years. We can
hypothesize that the costs related to pollution of the air and water can be totally applied to the total cost of
gasoline in the very near future.
REFERENCES
1. RF Patent No. 2106391.
4. S. N. Onoichenko, Candidate Dissertation, VNII NP, Moscow (2000).
7. T. V. Danilenko, Candidate Dissertation, I. M. Gubkin Russian State University of Oil and Gas, Moscow
(2005).
8. Mariie, Distillation and Fractionation in the Alcohol Industry [in Russian], Snabtekhizdat, Moscow
(1934).
9. V. B. Fremel’, Spirt. Prom-st’, No. 7 (1936).
10. V. N. Stabnikov, Distillation and Fractionation of Alcohol [in Russian], Pishchepromizdat, Moscow
(1962).
361
Chemistry and Technology of Fuels and Oils, Vol. 43, No. 5, 2007
TECHNOLOGY
CHARACTERISTICS OF CATALYTIC REFORMING WITH CONTINUOUS

REGENERATION OF THE CATALYST
V. G. Rassadin, O. V. Durov, V. N. Slavin, O. Yu. Shlygin, N. V. Gavrilov, UDC 665.64.097.3

G. G. Vasil’ev, and N. M. Likhterova
The results of a pilot run of the LF-35/21-1000 reforming unit with continuous regeneration of the
catalyst at LUKOIL – Nizhegorodnefteorgsintez Co. are reported. It was found that all of the blocks and
units operate in accordance with the project requirements. Dependences that correlate the quality of
reforming naphtha with its yield and the yield of hydrogen-containing gas and power consumption with
the output of the unit were obtained.
Catalytic reforming naphtha occupies a leading position (52.8 vol. %) in Russia’s gasoline stock (more
than 30 million tons/year) [1]. This is due to catalytic reforming units with periodic catalyst regeneration, the base
for production of high-octane components of unleaded automotive gasolines, as well as catalytic cracking naphthas,
in all large oil refineries [2, 3]. The proportion of catalytic reforming and cracking naphthas is decreasing
significantly in high-quality gasolines due to stiffening of the requirements for the content of benzene (less than
1 vol. %), aromatics (less than 35 vol. %), and olefins (less than 5 vol. %) [4].
The universal introduction of catalytic reforming in oil refinery (OR) manufacturing schemes is also due to
the fact that hydrogen-containing gas (HCG) is the second target product of this process. The concentration of
hydrogen in HCG is 75-93% as a function of modification of the process. Production of environmentally clean jet
and diesel fuels is directly correlated with the presence of industrial hydrogen in the refineries, i.e., catalytic
reforming units [5].
The basic trends in improving catalytic reforming are:
• increasing the efficiency of the catalysts;
____________________________________________________________________________________________________
LUKOIL – Nizhegorodnefteorgsintez Co. Translated from Khimiya i Tekhnologiya Topliv i Masel, No. 5,
pp. 8 – 12, September – October, 2007.
362 0009-3092/07/4305–0362 © 2007 Springer Science+Business Media, Inc.

Table 1
By regime
Hydrotreating block operating indexes By design
1–3 4–6
Output in feedstock, m3/day – 2819–2900 3104–3709
Feedstock space velocity, h -1
4.8–8.1 5.3–5.42 4.24–7.03
HCG circulation ratio, nm /m
3 3
60–150 87.6–113.75 80.33–146.3
Excess pressure, MPa
at compressor outlet – 3–3.16 3–3.16
circulating HCG (CHCG) in product separator 2.3–2.4 2.44–2.45 2.44–2.45
Temperature at reactor inlet, °C 285–343 320 320
Temperature drop over reactors, deg – From 0 to +1 From 0 to +11
Concentration of hydrogen in CHCG, vol. % ≥75 98–99.3 98–99.6
Content in feedstock, ppm
sulfur ≤500 150–440 190–460
nitrogen ≤1 0.6–0.8 0.6–0.8
• revamping and retooling the units with a stationary bed of catalyst with a step with continuous
regeneration of the catalyst;
• introducing units with continuous regeneration of the catalyst;
• improving process and heat- and mass-exchange equipment [6].
In 2004, LUKOIL – Nizhegorodnefteorgsintez Co. completed construction of the LF-35/21-1000 unit based
on Platforming CCR UOP technology at a pressure of 0.35 MPa under a medium-term program for re-equipping and
developing production.
After completion of construction and starting the unit up, studies were conducted to determine the optimum
composition of the feedstock and target product, power consumption and real consumption of material and technical
resources, to establish the correspondence of the real operating parameters with the rated parameters, to optimize
operation of control systems, and to determine the cycle between repairs based on the results of operating
compressor equipment in the different operating conditions of the unit.
The studies of the feedstock hydrotreating block were conducted for 138 days, the reforming block was
investigated for 132 days, and the catalyst regeneration block was studied for 95 days. The feedstock load varied
from 67 to 120 tons/h, and the catalyst circulation rate varied from 400 to 715 kg/h. The unit operated in six
regimes.
The basic indexes of operation of the hydrotreating block are reported in Table 1. In all regimes, the
operating conditions for the block corresponded to the rated conditions. The quality of the hydrogenation
product satisfied the established requirements: maximum of 0.2 ppm residual sulfur content in hydrogenation
product, 0.4 ppm nitrogen content. These data were obtained at a feedstock space velocity of 5.5-6 h -1 , hydrogen
to feedstock circulation ratio of 120-140 nm 3/m 3, pressure at the compressor outlet of 3.1 MPa, and pressure in the
200 V 4 separator of 2.45 MPa.
The temperature at the bottom of the 200 V 6 stripping tower was 221-223°C, the pressure at the top of this
tower was 0.92 MPa, and the reflux ratio was 30-40% (40-50 m 3 /h). The moisture content in the hydrogenation
product was 7-8 ppm. Hydrogen sulfide was totally absent.
363
Table 2
By regime
Reforming block operating indexes By design
1–3 4–6
Output in hydrogenation product, tons/day – 2077–2200 2269–2700
Feedstock space velocity, h -1
0.97–1.95 1.29–1.47 1.33–1.64
HCG circulation ratio, nm3/m3 1.95–7.65 1.84–5.4 1.84–5.4
Excess pressure, MPa
at outlet from CHCG compressor – 0.394–0.457 0.394–0.457
in 300 R4 reactor – 0.312–0.35 0.312–0.35
in product separator – 0.249–0.25 0.249–0.25
Temperature at reactor inlet, °C ≤548 494–518 494–526
Temperature drop over reactors, deg – 224–282 224–282
Concentration of hydrogen, vol. %
in CHCG ≥75 88.4–93.2 88.4–93.2
in HCG from unit ≥90 91.3–96.7 91.3–96.7
Content in feedstock, ppm
sulfur ≤0.5 0.2–0.4 0.2–0.4
nitrogen 0.30–0.45 – 0.3–0.45
Weighted mean temperature in catalyst bed, °C – 468–491 468–493
Coke content, wt. %
on catalyst 3–7 3.47–5.72 3.47–5.72
same going from air consumption for regeneration – 2.28–6.97 2.28–6.97
Coke formation rate, kg/h
going from air consumption for regeneration – 10–50 10–40
going from feedstock quality and process parameters – 19–133 19–110
Amount of dust from catalyst, kg/day – 2–15.5 2.2–12
Catalyst consumption, kg/day 21.768 0.2–13.34 1.59–12
Total amount of catalyst dust after startup, kg – 2251.1 2323.8
Amount of added catalyst, kg – 2200 2200
Octane number (research) of target product 90–103 94.7–101.1 96.1–100.8
The concentration of hydrogen in CHCG varied in a narrow range – from 98 to 99 vol. %, and the
concentration of hydrogen sulfide varied from 500 to 600 ppm. Fresh HCG entered the hydrotreating block in the
amount of 0.1 wt. % in feedstock. The dry gas (0.2 wt. %) was sent to the fuel system. The naphtha cuts distilling
below the initial boiling point of the feedstock were removed from the unit in the amount of 14-20 tons/day at the
beginning of the studies and 3 tons/day at the end.
The basic operating parameters of the reforming block over the entire duration of the studies are reported
in Table 2. Feedstock was fed into the block in the amount of 85-120 tons/h and the ratio of hydrogen to feedstock
was 3.1-6.9 mole/mole. In production of gasoline with an octane number of 96 and 101 by the research method
(RON), the temperature in the catalyst bed was maintained at 503 and 523°C, and the total temperature difference
between reactors was 243 and 270°C.
364
Table 3
Content in HCG, vol. %

Component at beginning of cycle at end of cycle
in 300V1 in 300V5 in 300V1 in 300V5
Hydrogen 92.6 92.6 92.8 94.6
Hydrogen sulphide Absent
Methane 1.6 2.72 0.87 1.92
Ethane 1.87 2.31 1.07 1.92
Propane 1.67 2.06 1.02 1.4
Isobutane 0.64 0.42 0.41 0.13
n-Butan 0.53 0.12 0.4 0.03
1-Butene Traces – 0.01 0.01
1-Isobutene 0.01 – Traces –
2-trans-butene Traces – – –
Isopentane 0.47 0.05 0.38 –
n-Pentane 0.21 0.02 0.19 –
∑С5 0.4 – 2.85 –
0.93
Selection, wt. %
0.92
0.90
0.88
93 95 97 99 101 102
RON
Fig. 1. Effect of the octane number (RON) of reforming naphtha on selection of

catalyst.
0.10
Yield, wt. %
0.07
0.04
93 97 95 99 101 102
ON
Fig. 2. Effect of the octane number (RON) of reforming naphtha on yield of HCG.
The real temperature at the reactor inlet was 3.5-8° lower than the calculated temperature. The moisture
content of the CHCG entering the reactors varied within the limits of 10-15 ppm. The moisture content in the CHCG
365
7
Content, wt. %
4
1
80 84 88 92 96 100
IBP, °C
Fig. 3. Effect of the initial boiling point of the feedstock on the benzene content in the
target product.
Table 4
Consumption during a run for 1 ton of feedstock
Energy resources
maximum minimum
Electric power, kw⋅h 196 108
Steam, Mcal 188 104
Reference fuel, tons of reference fuel 147.9 63.5
Return water, m3/ton 24.38 14.9
decreased to 4.4-6 ppm when the catalyst regeneration block stopped. A decrease in the concentration of chlorine
from 4 ppm at the beginning of the cycle to 2 ppm at the end was found during the studies.
Ethyl mercaptan was fed into the reforming block in the amount of 0.1-0.18 ppm in feedstock
at a CHCG hydrogen sulfide content equal to 2.5-4 ppm. During the studies, the concentration of hydrogen in
the CHCG varied within the limits of 88.2-91.2 vol. %. The concentration of hydrogen in the HCG taken off the unit
was 92-95 vol. %. The excess HCG was removed from the unit in the amount of 32-39,000 nm 3 /h.
The composition of HCG before and after removal of C 5-C6 hydrocarbons is reported in Table 3. The total
amount of these hydrocarbons was approximately 47 wt. %. Equations that correlate the octane number of the
target product with its yield and the yield of HCG were obtained by correlation analysis as a result of the studies:
y1 = −0.0037 x + 1.2656
y2 = 0.0035x − 0.2737
where y 1 is the yield of naphtha, fractions of one; x is the octane number (RON); y 2 is the yield of HCT, wt. %.
The real values of the octane number (RON) and yield of catalyzate are shown in Fig. 1 and the data on the
yield of HCG as a function of the research octane number of the reforming naphtha are shown in Fig. 2.
Naphtha from the LF-35/21-1000 unit differs from naphthas obtained in units with periodic regeneration of
the catalyst. It is characterized by high density (up to 820 kg/m 3) and end point (up to 225°C). The density of the
naphtha obtained is correlated with its octane number and distillation of the feedstock. The latter does not
significantly affect distillation of the target product. The concentration of benzene in the target product
is 6.8-3 wt. %. Its correlation with the initial boiling point of the hydrotreated naphtha entering the reforming
block was established (Fig. 3):
366
return water, m3/h
400 2000
Consumption of naphtha, tons/h

4
Consumption of
electric power, Mwatt h
3 1800
1600
300
2 1400
steam, Gcal/h
1200
200
1
100
50
0 8 16 24 32 40 48 56
Time, days
Fig. 4. Change in consumption of energy resources for reforming in time: 1) naphtha;
2) electric power; 3) steam; 4) return water.
y 3 = −0.000076 x 3 + 0.010619 x 2 − 0.338037 x + 3.990720
where y 3 is the concentration of benzene in the target product; x is the initial boiling point of the reforming
feedstock.
The consumption of energy resources and production of steam in the unit as a whole were constantly
monitored during the studies (Table 4, Fig. 4). During the entire time, 0.09-0.27 Gcal/h of steam was taken from
the LF-35/21-1000 for the needs of the enterprise.
Mathematical processing of the statistical data allowed establishing the dependences of the specific
power consumption on the consumption of feedstock over the unit as a whole:
y4 = 0.0003 x 3 − 0.835 x 2 + 6.37972 x + 0.0053

y5 = 0.0019 x − 0.0023
y6 = 0.001022 x − 0.00023
y7 = −0.0001x 3 + 0.0091x 2 + 1.0054 x − 0.0056
y8 = 0.1558 x + 2.2055
where y 4 is the electric power consumption, kwh/ton; y 5 , y 6 are the production and consumption of
s t e a m , G c a l / ( h ⋅ t o n ) ; y 7 i s t h e r e f e r e n c e f u e l c o n s u m p t i o n , t o n s r. f . / t o n ; y 8 i s t h e r e t u r n w a t e r
consumption, m 3 /ton; x is the feedstock consumption, tons/h.
In addition, the real consumption of reagents and catalysts in comparison to the design data and
licenser’s recommendations were determined during the research. The requirements of the design plans and
specifications and the real data on consumption for agents and catalysts, as well as the consumption standards
established with generalized data on the real consumption of reagents and catalysts in consideration of the
licenser’s requirements are reported in Table 5.
The design indexes of operation of the waste-heat boiler, steam turbine, heat circuit, and heat-supply
systems were confirmed during the run. To improve operation of the waste-heat boiler, a filter was installed in
front of the deaerator for chemically treated water.
367
Comprehensive testing of the working capacity and safety of the electrical equipment was conducted. All
systems and protective devices, automatics, alarms and controls, and control-measuring instruments for electrical
units operating at voltage up to 1000 V and higher were tested. The operation of all equipment corresponded to
the design parameters.
The dynamic equipment operated normally. The loads on the electric motors and the vibration indexes of
the dynamic equipment did not exceed the values in the standards.
During the fixed run, 68 valve rings were replaced in the 300S2A-300S2S compressors. The analysis of the
operation of these compressors showed that most of the breakdowns of the discharge valves took place in severe
conditions of operation of the unit: at high loads (up to 155 m 3/h) for feedstock and a high concentration of
hydrogen in the HCG.
Prolonged operation of the compressors without shutting down for valve repairs was observed
at a 91 vol. % and lower concentration of hydrogen in the HCG. This suggested that the discharge valves were not
Table 5
Consumption
Reagent, catalyst real
based on developed
by design in
in October standard
November
Dichloroethane, kg/ton 0.0195 0.031743 0.023510 0.0254
Mixed natural mercaptans, kg/ton 0.0012 0.000363 0.000380 0.0005
Caustic soda (100%), kg/ton 0.0685 0.026021 0.020891 0.04
Dodigen 481 corrosion inhibitor, kg/ton 0.0011 – – 0.0011
Grade A propane fraction, kg/ton 0.00297 0.034959* 0.0297* 0.00594
Hydrazine hydrate, g/ton of steam 0.0993 0.0920 0.0134113 0.0993
S-120 catalyst, kg/ton 0.002748 0.002748 0.002748 0.002748
Active aluminum oxide, kg/ton 0.02816 – 0.028160 0.02816
R-274 catalyst
from dust collectors (dust + crumb), kg/day 21.7 2.7 3.385 10
support, g/ton – – – Standards reviewed
platinum + irrйversible losses, g/ton – – – Same
Trisodium phosphate, g/ton steam 0.0462 0.00881 0.00762 0.0231
Molecular sieves, ton/day 0.0244 0.0244 0.0244 0.0244
Takeoff (wt. %) of catalyzate with RON of
95 – – – 91.8
101 – – – 89
Energy resources for unit
fuel, kg ref. Fuel/ton feedstock – – – 90
electrical power, kwh/ton feedstock – – – 135
steam, Mcal/ton – – – 180
return water, m3/ton – – – 24
Notes. *Based on real feed time.
** After each load of catalyst
368
designed for use in conditions of a high concentration of hydrogen: 91 vol. % and higher versus 76 vol. %
according to the design.
The temperature at the compressor stage outlet increased significantly with an increase in the concentration
of hydrogen, which caused rapid ring wear. Rings designed for severe operating conditions were selected to
increase the operating time between repairs.
It was found during the tests that the technical state of the towers, capacitor equipment, pipelines and
fittings, relief valves, dynamic equipment, and ventilation equipment was satisfactory and satisfied the design
parameters of the manufacturing process.
The high working capacity of the breakdown protection system (BPS), pressure, flow, temperature, and
level sensors in the process equipment was noted during the run.
All parts of the LF-35/21-1000 unit thus operate efficiently according to the design requirements. The
mathematical dependences obtained allow predicting the quality and yield of the target product and determining
power consumption for production of 1 ton of target product of a given quality. The standards for
consumption of reagents and catalysts were refined and operation of CS, control-measuring devices and
automatics, SS, and BPS was corrected as a result of the studies.
REFERENCES
1. A. S. Safonov, A. I. Ushakov, and I. V. Chechkenov, Automotive Fuels [in Russian], NPIKTs, St. Petersburg
(2002).
2. P. G. Bannov, Oil Refining Processes [in Russian], Part 1, TsNIITEneftekhim, Moscow (2000).
3. S. A. Akhmetov, Technology for Exhaustive Refining of Oil and Gas [in Russian], Gilem, Ufa (2002).
4. M. I. Levinbuk, E. F. Kaminskii, and O. F. Glagoleva, Khim. Tekhnol. Topl. Masel, No. 2, 6 (2000).
5. M. K. Pis’men, Hydrogen Production in the Oil Refining Industry [in Russian], Khimiya, Moscow (1976).
6. V. M. Kapustin and S. A. Chernysheva, Basic Catalytic Processes in Oil Refining. Industrial Catalysis in
Lectures [in Russian], No. 5, Kalvis, Moscow (2006).
369
PETROLEUM COKE CALCINING UNIT. STARTUP AT

LUKOIL—VOLGOGRADNEFTEPERERABOTKA LLC
M. M. Akhmetov, E. G. Telyashev, N. N. Karpinskaya, UDC 665.777.4.002

and M. E. Maslennikov.
In 2003, LUKOIL Oil Co. made a decision to complete a two-furnace calcining unit on which construction
had stopped in 1990 at LUKOIL – Volgogradneftepererabotka Ltd. (LUKOIL – VNP Ltd.). Until 1990, the unit was
being constructed with Kennedy Van Saun technology (US) using imported equipment. Then two calcining
furnaces (77.7×3.2 m), two afterburner furnaces (23×5 m), two coke coolers (12.5´2.3 m), and one waste-heat boiler
were installed.
The unit was designed for calcining petroleum coke of isotropic structure and had a total output
of 100,000 tons/year in raw coke for two furnaces when appropriately equipped with basic and auxiliary equipment.
In consideration of the change in LUKOIL Oil Co. priorities, it was decided to finish building and
revamp the unit to increase the output to 280,000 tons/year in raw coke. The feedstock was changed: instead of
coke of isotropic structure, it was decided to calcine “ordinary” coke from the operating delayed coking units
at LUKOIL – VNP Ltd to obtain calcined coke for production of anode products in the aluminum sector.
The bid for developing the technology and equipment for implementing the project for completion
of construction and revamping was won by the State Unitary Company RB Petrochemical Processing
Institute (RB PPI SUC) and the general project engineer was LUKOIL – Rostovneftekhmproekt Co.
The project was to be executed in three stages. The first stage consisted of completing construction and
revamping one line to attain output of 100,000 tons/year with respect to raw coke in accordance with the output of
the waste-heat boiler constructed according to the initial project. The second stage would include completion of
construction and revamping of the second line and construction of a new waste-heat boiler to attain output
of 140,000 tons/year with respect to raw coke. In the third stage, the output of the first line would be brought
to 140,000 tons/year in raw coke and the output of the active waste-heat boiler would be increased or another one
would be built.
____________________________________________________________________________________________________
RB Institute of Petrochemical Processing State Unitary Enterprise. Translated from Khimiya i
Tekhnologiya Topliv i Masel, No. 5, pp. 13 – 16, September – October, 2007.

To ensure the assigned (by 2.8 times) increase in output, RB PPI SUC developed the corresponding
calcining technology and detail designs for a series of basic and auxiliary equipment.
The experience from many years of successful operation of the petroleum coke calcining unit
at Sibneft’ – Omsk OR Co., , designed with RB PPI SUC technology, was taken into account in developing the
process technology [1]. The experience of foreign firms and experience in operating calcining units
with Kennedy Van Saun Co. technology at Fergansk, Krasnovodsk, and Gur’evsk OR were also taken into
consideration. RB PPI SUC accumulated great experience on updating the individual parts and equipment in
startup and operation of these units [2-6].
The basic aspects of the petroleum coke calcining technology at LUKOIL – VNP Ltd. satisfy the basic
requirements and in comparison to the technologies used in the RF, CIS, and at many foreign companies, is
sufficiently complete. A diagram of the process is shown in Fig. 1.
The following problems remained unsolved in the first stage of revamping the first line due to the undefined
possibilities of efficiently utilizing the individual types of equipment:
• transporting the raw coke to the calcining furnace; the initial design solutions do not ensure feeding
coke of uniform quality due to segregation in “bunkers;”
• adapting the calcining furnace parameters to the conditions for calcining regular coke;
• treating stack gases to remove dust and sulfur dioxide.
The design of the calcining furnace was left unchanged in the first stage.
The length of the afterburner furnace was increased to increase the residence time of the coke dust for
more complete combustion. The units for feeding in air for burning coke dust and combustible volatiles were
updated. New technical solutions were aimed at intensifying mass exchange between stack gases and air. Feed of
2
I 3 4 17
III
1 15 16 22
5 22
IV
XI 3 6 21
7 20
XII 12 VII 18 23
13 14
X V
VI II
8 9 10
11 VII VIII
IX VI 22
V 19 IV
IX
Fig. 1. Diagram of the first line of the petroleum coke calcining unit: 1) crusher; 2) sieve;
3) raw coke conveyer; 4) crushed coke storage bunker; 5) loading bunker; 6) weighing
batcher; 7) smoke stack; 8) exhaust-gas fan; 9) damper; 10) waste-heat boiler; 11) guillotine
gate; 12) afterburner furnace; 13) drive; 14) calcining furnace; 15) cooling water tank;
16) cooling water circulation pumps; 17) air cooler; 18) burner; 19) calcined coke cooler;
20) cyclone; 21) filter; 22) calcined coke conveyor; 23) calcined coke storage bunker;
I) raw coke; II) calcined coke; III) chemically treated water; IV) circulating chemically
treated water; V) fuel; VI) primary air; VII) secondary air; VIII) aspirated air; IX) diluted
air; X) stack gases; XI) steam; XII) boiler water.
371
aspirated air from the calcined coke cooler to the afterburner furnace through the air inlet was organized. This
solution eliminates discharge of coke dust that “gets through” the dust removal system with the aspirated air.
The coke cooler was replaced by a new cooler made at Uralkhimmash Co. Its design was developed by RB
PPI SUC and is protected by RF patents. In many characteristics, the new cooler has advantages over the
domestic and foreign analogs. The main advantage is the longer warranty – a minimum of ten years, versus a
minimum of two years for the analogs. In addition, the cooler is distinguished by high efficiency of heat removal,
compactness, low water consumption, and accessibility for repairs of the basic design elements.
The unit was equipped with a new part for oiling the calcined coke to eliminate dust. The oiling technology
and mixer with helical contact devices were developed by RB PPI SUC and have been patented. The mixer eliminates
grinding of the calcined coke, in contrast to the screw mixers usually used in world practice. The dust suppression
efficiency attains 95-98%.
RB PPI SUC developed dual valves – air locks for the raw coke input devices and calcined coke discharge
devices. They ensure operation of the unit at high output with minimal inflow of air.
All parts and equipment not ensuring high output were replaced by new Russian equipment.
The unit was equipped with modern process monitoring and control equipment. The working design and
design of the control system for automation and monitoring of the operation of the calcining unit were developed
by Kvantor Engineering Co. This system included two automatic control blocks.
One of them controls operation of the calcining and afterburner furnaces, calcined coke cooler, stack gas
utilization system, auxiliary fuel preparation and intraplatform communications systems, and the other controls
operation of the conveyer lines, raw and calcined coke bunkers, systems for loading raw coke into the calcining
furnace and loading calcined coke into railway cars.
Each block is separated as a subsystem which allows synchronizing control and regulating processes of
different intensity such as: loading coke into silos, loading coke into the calcining furnace, utilization of stack gas
heat in the waste-heat boiler, control of the furnace burners, etc.
The original design solutions were used for monitoring operation of the calcining furnace, calcined coke
cooler, oiling device mixer, and conveyor speed. Contactless inductive proximity sensors eliminated use of
complicated mechanical devices. Due to the high degree of protection of their jackets, the system was sufficiently
reliable, especially in conditions of dust on the conveyors.
To measure the coke level in the bunkers, radar level gauges with special high-strength cable wave
guides were used and radio-isotope devices were used as level alarms.
High-temperature optical pyrometers are installed where the calcined coke comes out of the furnace to
monitor the temperature of the furnace lining and the temperature in the fuel combustion zone by a contactless
method. To prevent formation of a coke dust coating on the lenses of the optical pyrometers and optical flame
alarms, a system for blowing compressed air through is provided.
The temperature, vacuum, content of oxygen and carbon monoxide in the stack gases are monitored along
the entire process line (calcining furnace, afterburner furnace, including the pipe for taking off stack gases). This
allows regulating coke calcining, and utilization of the heat liberated with the stack gases by increasing-decreasing
feed of fuel to the burners, feed of air to the furnaces, the rotation rate of the body of the calcining furnace, feed
of raw coke into the calcining furnace, and other parameters. The quality of the calcined coke and the savings of
fuel and electricity, respect of environmental standards, etc., are ensured as a result.
The number of instruments and cable lines was reduced and processing of the results of measurements
was simplified as a result of using multiparameter devices in the liquid fuel, gas, steam, air, nitrogen, and water
lines.
372
A weighing batcher with a separate control block installed in the operator’s premises was used for feeding
the raw coke into the calcining furnace. The process of loading the coke into railway cars and then weighing them
was automated.
With respect to the degree of automation, the LUKOIL – VNP Ltd. calcining unit is one of the most
up-to-date. The operator of the unit controls all of the basic operations and process parameters. Video
observation of the movement and granulometric composition of the raw coke on the weighing batcher belt is
provided.
Protections and blocking for emergency situations are implemented in the design: presence of gas, failure
of the basic calcining furnace and calcined coke cooler drives, pumps, sudden shutdown of one or more
conveyors, etc.
The automated control system for manufacturing processes (ACSMP) and accident prevention (AP) are
implemented with Invensys equipment. Algorithms for controlling and locking the unit were developed
with RB PPI SUC specifications. Screen molds, FID-regulation blocks, etc., were executed in
special SCADA editor routines – the I/A Series system.
The unit went on line in August 2005 – two months after work to put it into operation
began. The output attained: 12.5-13.5 tons/h in raw coke, corresponds to the annual output of the first line
of 94-101,000 tons/year, i.e., the rated output planned for the first stage of revamping.
Despite the long time (more than 15 years) the assembled basic and auxiliary equipment had stayed on
open platforms and the unassembled equipment had been stored in warehouses, there were no serious
problems with startup and operation. The inspections performed by the plant’s technical service, reconditioning,
and screening of broken auxiliary equipment allowed avoiding serious problems with
equipment “failures.” The problems that arose were quickly solved by plant management, specialists
from RB PPI SUC, LUKOIL – Rostovneftekhimproekt Co., unit personnel, and the plant’s technical service.
In April 2007, after 20 months of operating the unit, concrete results were obtained. On the whole, it
operated satisfactorily.
The typical coke calcining regime satisfied the standards of RB PPI SUC specifications:
Output in raw coke, tons/h 12.5-13.5
Calcining furnace body rotation rate, min -1 1.045-1.25
Temperature, °C
calcining furnace lining in combustion zone 1222-1237
stack gases
coming out of calcining furnace 781-839
coming out of afterburner furnace 1021-1085
entering waste-heat boiler 813-897
coming out of waste-heat boiler 271-278
cooling water in circulation cooling system
entering calcined coke cooler 38-46
coming out of calcined coke cooler 56-74
Oxygen content in stack gases coming out of afterburner furnace, vol. % 5.5-6.5
Output of steam in unit (flow from unit), tons/h 12-13.4
Parameters of steam
temperature, °C 257-262
excess pressure, MPa 0.085-0.093
373
The quality of the calcined coke (see Table 1) satisfies the requirements of the aluminum sector for coke
used n production of calcined anodes. The slightly high content of dust particles in the calcined coke is due to
the high content of fine and powder (less than 1 mm) particles in the raw coke.
The problems that arose in getting the unit up and running were basically due to adapting the individual
kinds of equipment to the conditions of operating at the new output, 100,000 tons/year, and in some cases, to use
of equipment designed for the high output of 140,000 tons/year (after the third stage of revamping): the fans for
feeding air into the afterburner and calcining furnaces, exhaust-gas fan, etc.
Let us analyze the efficiency of operation of the individual types of equipment in the unit operating period
examined.
Calcining furnace. At output of 9-12 tons/h in raw coke through the compacting unit gap on the butt
joint between the calcining furnace and the afterburner furnace, it operates satisfactorily, while at higher
output (12.5-13.5 tons/h) the coke pours out through the compacting box. The cause is formation of a “hill” of
coke in the loading zone into the furnace by the hopper feeder.
The hill is converted into a ”springboard” for the coke to slide down, especially large particles to the side
of the compacting gap. Narrowing of the furnace’s smoke-flue space above the “hill” increases the velocity of the
stack gases and entrainment of coke dust particles. The small slope (1°11′) of the furnace and low rotation
rate (0.522-1.045 min -1 ) of its body cause the coke to be “held” in the loading zone and move slowly to unloading.
These furnace characteristics are defined by the initial design, based on the conditions of calcining coke
of isotropic structure – low heating rate and long residence time (5 h) of the coke in the furnace. The existing
calcining furnace is not adapted to the conditions of calcining ordinary coke for the aluminum sector at an optimal
furnace residence time of 1.5-2 h. This problem must be solved. Due to spilling of the coke through the gap in the
butt joint between the calcining furnace and the afterburner furnace, the losses are increased as a result of
entrainment of coke dust and even large particles of coke into the afterburner furnace and problems are created
with transport of the spilled coke.
RB PPI SUC and Uralkhimmash Co. performed calculations and issued recommendations on increasing the
maximum rotation rate of the furnace body from 1.045 to 1.25 min-1. As a result of implementing this recommendation,
spilling of coke at output of 12.5-13.5 tons/h decreased significantly. Nevertheless, the problem persisted. To
accelerate removal of coke from the loading zone, RB PPI SUC proposed a technical solution with screw
thresholds which will be tested in the very near future. A more efficient technical solution is possible in the
future – increasing the slope of the calcining furnace’s body, which will ensure output of 140,000 tons/year in raw
coke.
Table 1
Coke
Indexes
raw calcined
Content, wt. %
total moisture 7–10.5 –
volatiles 8–10.9 –
total sulfur 1.4–1.6 1.4–1.6
Ash content, wt. % 0.05–0.44 0.3–0.6
Real density, g/cm3 – 2.06–2.09
374
Afterburner furnace. It operates efficiently enough. Some problems with overloading are created in
loading 12.5-13.5 tons/h and more in the calcining furnace in raw coke. The consequences of “overloads” are
manifested by large coke-ash deposits on the surfaces of the waste-heat boiler pipes.
Calcined coke cooler. Prolonged operation confirmed the high efficiency of heat removal and the good
working capacity of the new type of cooler. All design elements operate normally and cool the calcined coke to the
required standards. The insignificant flaws detected during operation are related to assembly of support pipes.
These flaws were eliminated in one day by the plant’s technical service.
There are all grounds for assuming that the cooler will operate without being replaced for 10 years according
to the developer’s warranty. It should be noted that all calcined coke coolers used by foreign forms have a two-
year warranty and usually begin to break down after 2-2.5 years of use.
Waste-heat boiler (delivered based on the initial design). There have been some problems in its operation.
The interpipe space clogs up with coke and ash deposits in relatively short times. This requires partial washing
of the surface with water (every 30-40 days) and switching the calcining unit to bypass operation along the flue
tract. Measures are being instituted to solve this problem.
In the future, the output of the first-line calcining furnace should be restricted in accordance with the
output of the existing waste-heat boiler or it should be replaced with a new one that ensures utilization of stack
gas heat at output of the calcining furnace of 140,000 tons/year in raw coke.
The efficiency of coke production increased due to an increase in the price of the final product and
production of steam when the calcining process was introduced at the plant.
Work has begun on implementing the second stage of revamping and completion of construction with
consideration of the experience of the first stage of starting up the unit’s first line.
REFERENCES
1. M. M. Akhmetov, E. G. Telyashev, and N. N. Karpinskaya, Mir Nefteproduktov. Vestn. Neft. Kompanii,
No. 2, 9-12 (2006).
2. M. M. Akhmetov, Trydi IP NKhPi, 33, 22-34 (2001).
3. M. M. Akhmetov, E. G. Telyashev, N. N. Karpinskaya, et al., Neftepererab. Neftekhim., No. 9, 47-54 (1998).
4. M. M. Akhmetov, in: Research on Current Problems in Production and Use of Carbon Products [in
Russian], Elektrodin Co. and NIIGrafit, Chelyabinsk (2000), pp. 50-51.
5. M. M. Akhmetov, Khim. Tekhnol. Topl. Masel, No. 7, 6-14 (1986).
6. M. M. Akhmetov et al., Ibid., No. 10, 19-22 (1980).
375
EQUIPMENT
AIR COOLING EQUIPMENT WITH HIGH PERFORMANCE AND RELIABILITY
E. V. Chitrov, V. Z. Kanter, S. B. Pokhodyaev, and Yu. I. Anoshkin UDC 621.565.3:665.6
Air cooling equipment (ACE) of traditional design – AVG and AVZ with a ribbed pipe heat exchange
surface, have a number of important drawbacks due to the horizontal position of the 12-m tubes, as extensive
experience in using them has shown:
• sagging of the tubes and formation of a “dead” zone for heat-carrier overflow during operation and
thawing of the tubes on shutting down, which subsequently results in important breakdowns;
• the need for large areas for installing them and the use of fans with lower-speed electric motors and
large rotors;
• the decrease in cooling efficiency in the condensation mode; installation of heat-exchange sections in
the shape of a “cabin” (zigzag) causes uneven distribution of cooling air flow and parasitic leaks;
• uneven expansion of the tubes rigidly fixed to the collectors due to uneven distribution of media in the
intra- and intertube spaces so that the tubes buckle or crack in the region of connection; the same effect is
observed in the starting and transitional modes.
The analysis of these drawbacks demonstrated the necessity of using ACE of more up-to-date designs for
the newly constructed catalytic cracking plants (customer – TAIF – NK Co., general designer – VNIPIneft’).
Anod – Teploobmennyi Tsentr (TTs) Ltd. (Nizhnii Novgorod) is designing and manufacturing heat-exchange
equipment for the energy, petrochemical, transport, and other branches of industry.
This equipment is designed to operate with different media – any liquids and gases at pressures
up to 20 MPa, temperatures up to 600C, and cyclic loading. The material of the heat-exchange surface are selected
in consideration of the operating conditions, assigned life, and cost indexes.
The new design of the heat-exchange surface – made of coils with a small bend radius (Fig. 1) – is based
on the developments. This design has much better specifications than the straight-tube, plate, and ordinary coil
designs. Let us consider its advantages.
____________________________________________________________________________________________________
TAIF – NK Co.; VNIPIneft’ Co.; Anod – TTs Ltd. Translated from Khimiya i Tekhnologiya Topliv i Masel,
No. 5, pp. 17 – 20, September – October, 2007.

HIGH EFFICIENCY OF HEAT-EXCHANGE IN INTRA- AND INTERTUBE SPACES
The cooling medium is exposed to mass forces from the walls of the coil in moving in the coils. These
forces cause secondary currents and increase the intensity of heat exchange. At the same time, the air, in moving
along the intertube space, is divided into a multitude of individual streams which are partially swirled and constantly
mix with each other. This causes intensive heat and mass exchange between the boundary layer and the stream.
It is possible to select the optimum ratio of the flow areas and correspondingly the heat carrier flow rates
which allow attaining the optimum (assigned) thermohydraulic parameters for different media and conditions of
operation.
Tubes of small type-size (∅ 10-18 mm) can be used in the module due to intermediate connection
of the heat-exchange elements and consequently design of more compact heat exchangers in comparison to
straight-tube heat exchangers.
The maximum efficiency of using the heat-exchange surface in the circulation circuit is attained as a result
of counterflow movement of the media. The cooled medium moves from top to bottom inside the coils, and the air,
heated, moves from bottom to top over the intertube space.
RELIABILITY OF OPERATION
The thermoplastic heat-exchange surface in the form of a coil guarantees self-compensation of expansion
of its elements in rapid heating and compression in cooling.
Only the tube bank and round-section collectors, which withstand pressure well, are exposed to pressure.
All of their joints are welded with a continuous transition over the thickness of the wall.
The reparability of the coolers is ensured by sectioning the heat-exchange surface and the accessibility of
the coils for looking for and plugging a defective coil or module.
The use of heat-exchange elements of one type-size and effective mass exchange of air over the section of
the tube system levels the temperature fields.
MANUFACTURABILITY
The heat-exchange surface consists of individual elements and modules, which allows using aggregate
technology with organization of parallel production lines for manufacturing the ACE.
The large number of parts of the same type in the tube system and the minimum number of assembly
type-sizes allow maximum automation of the manufacturing process and increase the quality of assembly.
Fig. 1. Heat-exchange surface module.
377
The manufacturability of the design allows reducing the labor intensity and cost of the article while
ensuring its high efficiency and reliability.
At Anod – TTs Ltd., a number of ACE designs with a coil heat-exchange surface (ACE-12, ACE-16,
ACE-21, ACE-25, ACE-28) joined in flat modules has been developed for cooling and condensation of liquid media.
Let us examine their design features and advantages in comparison to traditional AVG and AVZ.
An experimental sample of the ACE-28 was made to confirm the estimated performance, and tests were
performed in the vapor-condensation and aqueous modes. The conditions of switching sections and operation of
the cooler in the natural circulation mode were tested during the tests and the estimated thermohydraulic
performances were also confirmed. Based on the results of the tests, the device for attaching the electric motor
was completed to increase its rigidity and eliminate vibration in the horizontal plane. The angle of attack on the
blades of the fan rotor was selected in testing two head items in the ACE-25 and ACE-28.
For convenience of assembly and shipment, the design of the ACE was divided into two blocks a maximum
of 3.2 m wide and 3.5 or 6.5 m long as a function of the design. The first block – the heat exchanger – consists
of a tube system with nipples for feeding and taking off the cooled medium. The second block includes the
supporting structure with a diffuser and fan, consisting of an electric motor and a rotor. The blocks are manufactured
with maximum factory readiness and they are installed on top of each other in assembly (Fig. 2).
Fig. 2. Air cooler in stock form: 1) heat exchanger; 2) supporting structure.
378
The heat-exchanger is made of flat modules (see Fig. 1) divided into independent sections over the tube
space and joined by common housing over the intertube space. The number of sections and nipple position is
determined by the customer. The number of independent sections allows rapidly disconnecting a defective section
or decreasing the heat-exchange surface in the winter. The independent sections can be used for different products.
Alternate switching on one modular section ensures more efficient operation of the other when one is
switched off. The experiments showed that when 50% of the heat-exchange surface is switched off, the thermal
capacity of the unit is 70-75% of the rated capacity. This is due to the high turbulization of flow and good mass
exchange over the intertube space.
The medium is fed in and removed from the module primarily according to a Z-scheme, which ensures
uniform distribution of the medium over the coils. The medium feed and removal collectors can be positioned on
one side at the customer’s request.
Uncondensed fractions can accumulate in the upper collector, through which products are fed into the
module. To eliminate this effect, the last coil, counted from the inlet, is removed from the upper “dead” zone of the
collector and joined to the lower collector near the outlet, where the velocity of the medium is maximal. As a result,
the uncondensed fractions are constantly taken out of the upper collector with the products coming out of the
heat exchanger.
The air is moistened to remove peak loads in hot weather. Nozzles for spraying water are installed in the
diffuser after the fan for this purpose. When it enters the air stream, the water evaporates, reducing the temperature
by 10-15°. Water consumption, when it is totally evaporated, is minimal.
Table 1
Power, kW Number
Processing
Weight, kg
position
Execution
Tube system
electrical
sections
thermal
Name of ACE
ACE
material
KhV-101 Light gasoil cooler ACE-25 633 30 1 4 11500 Steel 20

KhV-102 Heavy gasoil cooler ACE-25 473 30 1 4 11500 10Kh17N13М2Т
KhV-201 Naphtha vapor condenser ACE-25 10182 30 8 8 14500 10Kh17N13М2Т
KhV-202 Air cooler ACE-25 579 30 1 2 6500 Steel 20
KhV-203 Same ACE-25 730 30 1 2 6500 Steel 20
KhV-301 Liquid gas cooler ACE-25 2696 30 6 4 11500 Steel 20
KhV-302 Light gasoil cooler ACE-25 378 30 1 3 6500 Steel 20
KhV-306 C4 fraction cooler ACE-25 219 30 1 7 6500 Steel 20
KhV-303 C3-C4 fraction condenser ACE-28 3552 37 4 4 14 500 Steel 20
KhV-304 Stable naphtha cooler ACE-25 1669 30 1 4 11500 Steel 20
KhV-305 C3 fraction condenser ACE-28 1314 37 2 4 14500 Steel 20
KhV-401 Acid vapor condenser ACE-25 665 30 1 4 6500 08Kh17N15М3Т
KhV-402 Monoethanolamine solution cooler ACE-28 3457 37 2 4 11500 Steel 20
KhV-501 Naphtha and H2-containing gas
ACE-28 7680 37 6 4 14500 Steel 20
cooler
KhV-502 Cooler for vapors at top of stabilization
ACE-25 3280 30 1 4 6500 08Kh18N10Т
tower
KhV-503 Stable naphtha cooler ACE-28 1990 37 1 4 14500 Steel 20
379
Table 2
Product temperature, °C Product flow rate in tube

Processing Fan rotation
position real rated rate (real),* space, m3/h
(see Table 1) min
at inlet at outlet at inlet at outlet at inlet at outlet
KhV – 101 160 70 133 60 300 23 18.1
KhV – 102 130 85 178 90 385 7.5 9.3
KhV – 201 135 54 139.5 53.9 424 65 99.3
KhV – 202/203 160 73 152 80 428 75 119.8
KhV – 301 127 37 190 40 111 – 35
KhV – 302/306 – – 110 55 – – 34.27
KhV – 303 57 46 57.9 50.1 265 – 73.6
KhV – 304 125 42 185 50 244 25 27.35
KhV – 305 45 42 46.4 44.8 – – 34
KhV – 401 102 35 106.7 40 291 1.7 0.89
KhV – 402 – 40 96 55 364 45 60.2
KhV – 501 163.7 45 – 70 199.9 50 385 91 71.2
KhV – 502 110 50 – 55 109.6 50 428 8 4.57
KhV – 503 82.4 50 – 60 103 50 410 72 69
-1
Note. * According to specifications: 428 min .
An asynchronous electric motor in an explosion-proof execution with frequency regulation, is used to

rotate the rotor. The calculations show that at an ambient temperature of 15°C, the required motor power decreases
to ~30% of the rated power. This is due to the efficiency of heat exchange and the high level of natural circulation.
Coils made of tubes Æ18´2 mm and 12 m long are connected with the collectors from tubes Æ89´4 mm into
flat modules which in turn are joined with the input and output collectors in the section. All joints are welded with
smooth transition over the thickness of the parts. The design features of the tube system and the absence of
massive tube panels guarantee the reliability of the design at high pressures and cyclic loads.
The high reliability of the design is combined with good reparability. When leaks are found, the current
section must be cut off with locking fittings and the product must be examined and poured out. Repairs are
conducted during scheduled preventive maintenance of the entire system. Access is provided to each coil in the
region of welding to the collectors, which allows cutting it out of the tube system if necessary. A plug is welded
to the collector, leaving the coil as a spacer.
The electric motor of the fan is one of the possible objects of repairs. Its weight and size are important.
For dismantling it, clamps for attaching the beams and lifters are welded to the top of the diffuser.
The method of repairing the tube system and dismantling the electric motor was worked out on previously
manufactured ACE, including for TAIF – NK Co. (Nizhnekamsk).
The naphtha production units in Nizhnekamsk were equipped with such ACE by order of VNIIPIneft’ Co.
The ACE were designed for all process stages of the cracking process in consideration of the observations and
wishes of the designer. The results of the work are reported in Table 1.
380
After one year of operation of the ACE in the production cycle, they were inspected by specialists
from Anod-TTs Ltd. The results are reported in Table 2.
All equipment was completed with rotation rate regulators for the electric motors. They operated from
February to October 2006 in conditions of subzero temperatures in winter and high temperatures (up to 35°C) in
summer.
The results confirmed the design characteristics of the ACE and their reliable and stable operation both in
the manufacturing mode and in cyclic loads. The power of the electric motors and fan rotation rates decreased
during operation, caused by the high efficiency of heat-exchange and the contribution of natural circulation.
At the customer’s request, the basic models of ACE can be completed by different auxiliary equipment for
regulating parameters with baffles installed on the top of the heat exchanger, heaters, and different frequency
regulation schemes.
Only a few of the developments by Anod – TTs Ltd. are mentioned in this article.
381
CHEMMOTOLOGY
MECHANISMS OF THE CHANGE IN THE PROPERTIES OF DIESEL

FUELS DURING STORAGE
A. Marvan and I. M. Kolesnikov UDC 665.753.4.004.4
In countries with a developed vehicle fleet, above-ground, half-buried, and underground tanks for storing
motor fuels, diesel fuels in particular, of important capacity have been created to prevent breakdowns in the fuel
supply [1]. The fuels remain in these tanks for a long time: up to four years and more.
In selecting diesel fuels (DF) for long-term storage, the industrial production processes are taken into
consideration: primary – straight-run distillation of crude oils, liquid gas condensates, or mixtures of them, and
secondary – catalytic cracking of vacuum gasoils, atmospheric resids, and mixtures of them [2], coking, pyrolysis,
visbreaking, hydrocracking, etc.
Three classes of hydrocarbons are contained in DF from primary processes: aromatics, paraffins, and
naphthenes. These hydrocarbons are relatively resistant to oxidation and condensation during storage of the
fuels.
DF from secondary processes contain up to 25 wt. % unsaturated hydrocarbons, which are easily subject
to oxidation with formation of hydroxides and condensation with formation of gums and solid sediments. In
addition, they contain up to 0.3 wt. % sulfur compounds and a small amount of nitrogen compounds. It is
necessary to add antioxidants and anticorrosion additives to such fuel for prolonged storage in tanks.
In storage and shipment of DF, the gums and solid sediments formed in them, distributed in the form of a
disperse phase, are deposited on the walls of pipes and tanks in the form of thick deposits and on the bottom of
the tanks in the form of bottom sediments. In diesel engines, macromolecular or condensed hydrocarbon compounds
____________________________________________________________________________________________________

can form solid deposits on the walls of fuel lines and different engine parts, which worsens engine performance.
All of this must be taken into consideration in using DF from tanks after prolonged storage.
We determined the mechanisms of the change in the physicochemical properties of DF in storage in tanks.
The quality of DF was investigated during prolonged (1080 days) storage in underground tanks locate
din the southern, northern, and western regions of the Republic of Syria. The climate in this country is characterized
by high average annual temperatures, which can have some effect on the quality of DF stored in underground
tanks. Such tanks are buried 50 m deep and more. Their top covers are insulated by a layer of soil and sand for
more reliable thermostating.
The samples (1 dm 3 ) of DF with different storage times taken from the tanks were analyzed by
standard methods. The results of the analyses reported in Table 1 suggest that the physicochemical characteristics
change in prolonged storage of DF in the thermostated conditions of underground tanks in the southern
region: the 50% distillation temperature of the cut increases to 360°C and the viscosity goes
from 2.7 to 2.9 mm 2 /sec; the yield of cuts under 360°C and the cetane number decreased (by 2.4 points).
In prolonged storage in the north, the cetane number of the DF decreased by three points, due to partial
oxidation of n-paraffins by atmospheric oxygen into peroxides, which then participate in other chemical processes.
The increase in the density of the fuel indicates an increase in the content of aromatics. The decrease in
the 90% distillation temperature of the cut below 354°C is due to an increase in the content of volatiles. The gum
content increased significantly: from 0.03 to 0.57 wt. %.As a consequence, the mechanisms of the change in the
physicochemical properties of DF in storage in underground tanks are also similar for the northern region.
In storage in the western region, the mechanisms of the change in the physicochemical properties of DF were also
preserved: the cetane number decreased by 2.8 points, the density increased, and the gum content and flash point
increased.
For convenience of determining the change in the cetane number of the DF during storage in the different
regions, we plotted a graph (see Fig. 1). The smallest decrease in the cetane number occurred in the northern
region of the country, and the highest occurred in the western region.
Based on the results of analysis of the published data, we were the first to find the mechanisms of the
change in the physicochemical properties of DF in prolonged thermostated storage in regions with different
climatic conditions and their identity was established.
53
2
1
CN
52
3
51
50
0 400 800
τ, days
Fig. 1. Cetane number CN of diesel fuels as a function of duration of storage τ in

underground tanks in different regions of Syria: 1) southern; 2) northern; 3) western.
383
Table 1
Diesel fuel
Indexes before after storage for, days
storage 180 360 720 1080
In the south
Cetane number 53 – – – –
Distillation temperature, °С
50% 256 – 259 260 264
90% 350 – 348 346 342
Yield of cut under 360°С, vol. % 90 – 89 86 85
Viscosity at 15°С, mm2/sec 2.7 – 2.75 2.81 2.9
Gum content, wt. % 0.03 – 0.39 0.48 0.56
Carbon residue, wt. % 0.03 – 0.035 0.041 0.052
Flash point (closed cup), °С 73 – 73.5 74 75
In the north
Cetane number 53 52.8 52.4 51.2 50
Distillation, °С
50% 263 264 262 261 260
90% 354 340 345 343 341
Yield of cut under 360°С, vol. % 90 89 88 87 86
Viscosity at 15°С, mm2/sec 2.6 2.7 2.75 2.8 2.83
Gum content, wt. % 0.05 0.15 0.22 0.31 0.41
Carbon residue, wt. % 0.03 0.04 0.042 0.044 0.05
Density at 15°С,.kg/m3 828 832 833 835 838
Flash point (closed cup), °С 64 68 71 72 75
In the west
Cetane number 53 52.4 52.1 50.8 50.2
Distillation, °С
50% 266 267 269 270 271
90% 350 348 346 341 339
Yield of cut under 360°С, vol. % 98 90 89 87 86
Viscosity at 15°С, mm2/sec 2.5 2.55 2.65 2.71 2.77
Gum content, wt. % 0.03 0.12 0.26 0.41 0.57
Density at 15°С,.kg/m3 820 824 825 827 828
Flash point (closed cup), °С 62 63.5 65.2 69.1 72.5
Subsequent research will be directed toward establishing the causes of the change in these properties
using spectral, physical, and chromatographic methods.
384
REFERENCES
1. V. S. Azev, Preservation of the Quality of Motor Fuels in Underground Storage [in Russian], Khimiya,
Moscow (1984).
2. A. Abugri, Candidate Dissertation, I. M. Gubkin Moscow Institute of Oil and Gas and Gas Processing
(1986).
385
ALKYL METHACRYLATE AND STYRENE TERPOLYMERS AS LUBRICATING

OIL VISCOSITY INDEX IMPROVERS
Ante Jukic, Elvira Vidovic, and Zvonimir Janovic UDC 662.75:629.7
The properties of styrene/dodecyl methacrylate/octadecyl methacrylate terpolymers as viscosity index

improvers of lubricating mineral oils were investigated. Terpolymers of different composition and molar
mass were prepared by peroxide–initiated polymerization of the monomer mixture in a mineral base oil
solution. All the terpolymer solutions in base oil exhibited high kinematic viscosity and viscosity index
values (> 130), proving their high thickening efficiency. The ratio of viscosity values at 100°C and 40°C
of styrene/alkyl methacrylate additive solutions was between 0.95 and 1.0, showing the coherent
thickening effect in a wide temperature range, comparable with pure alkyl methacrylate additives.
Increasing content of styrene in the additive and decreasing molar mass of the terpolymer resulted in a
decrease in viscosity and viscosity index while the shear stability increased. The obtained results give
guidelines for optimization of the terpolymers composition and structure in order to assure the best
lubricant application properties.
INTRODUCTION
Polymers based ased on alkyl methacrylates are widely used as additives in modifying the rheology of
lubricanting oils, where they serve as viscosity thickeners, viscosity index improvers, and pour point depressants.
Most frequently, they are long-chained, linear terpolymers consisting of monomers with a changeable share of
lateral alkyl groups, mostly C 1 -C 18 . It was established that the methacrylate with medium-size lateral alkyl
groups (C 10 -C 14 ) enhances the viscosity index; the long-chained groups (C 16-18) mostly contribute to the lowering
of the pour point of solutions, while the methyl group contributes to the stiffness of the polymer chain. The
____________________________________________________________________________________________________
Faculty of Chemical Engineering and Technology, University of Zagreb. Published in Khimiya i

corresponding monomer unit ratio is optimized to assure the best properties for a given application. Besides
composition, the properties of an additive also depend on copolymer structural parameters such as molar mass
and molar mass distribution. Such polymers, apart from exhibiting high solution viscosities and viscosity index
values, should also be stable against the high shear stress that arises in lubricating conditions, over a broad
temperature range and heavy mechanical loads. Recently, the development of methacrylic additives has been
directed towards multifunctional activity and improvement of its thermal and oxidative stability as well as resistance
against mechanical breakdown. These were achieved by thebuilding, in small amounts, of a functional or stabilizing
comonomer into polymeric chains during the course of synthesis. Commonly used comonomers of such type are
maleic anhydride, maleic acid esters, maleimides, N-vinyl pyrrolidone, N-vinyl imidazole, and styrene and its
derivatives. [1-4] From the earlier studies on styrene–based methacrylate additives (mostly copolymers of butyl or
decyl methacrylate), particularly those conducted by Akhmedov et al., [4,5], it was shown that these additives
possess higher thermal stability and improved shear stability in comparison with poly(alkyl methacrylates). These
improvements are facilitated by increasing the styrene content, but application of copolymers containing a high
styrene content is limited by their relatively low solubility in mineral oils. Also, only the copolymers of low molar
mass, ranging up to 17000 g mol -1 , were considered.
The present paper describes some rheological properties of viscosity index improvers of lubricating mineral
oils based on terpolymers of styrene, dodecyl methacrylate, and octadecyl methacrylate. These additives were
prepared through a polymerization process in a mineral base oil solution with a peroxide initiator up to high
conversion and high molar masses. The influence of the terpolymer composition and molar mass on the solution’s
kinematic viscosity, viscosity index, and shear stability were studied. The obtained results were compared with
those of conventional methyl methacrylate and long-chained alkyl methacrylate terpolymers.
EXPERIMENTAL
Chemicals
Polymerization grade monomers, styrene (DIOKI Zagreb, Croatia), and dodecyl methacrylate and octadecyl
methacrylate (RohMax Chem. Co.) were used as purchased. The initiator used was tert-butylperoxy-2-ethylhexanoate
(Trigonox 21, Akzo Nobel). The chain transfer agent was n-dodecyl mercaptan (Atochem). Solvents were two
different grades of mineral base oil (INA - Refinery Rijeka, Croatia), i.e., SN-150 with a kinematic viscosity
of v = 25.7 and 4.68 mm 2 s -1 at 40 and 100°C, respectively, a viscosity index of 97 and a pour point of -12°C,
and SN-200 with a kinematic viscosity of v = 40.6 and 6.31 mm 2 s -1 at 40 and 100°C, respectively, a viscosity index
of 104, and a pour point of -9°C.
Polymerizations
Terpolymerizations of styrene and methacrylate monomer mixtures were performed isothermally at 100 °C
in SN-150 mineral base oil solution, under nitrogen atmosphere. Reactions were carried out in an oil jacketed glass
reactor of 1 dm 3 volume, equipped with a stirrer and reflux condenser. The total monomer concentration was 50 wt.
%. The concentration of the initiator was 1.0 wt. % relative to the monomers. The complete conversion of monomers
in the overall reaction cycle time of five hours was achieved by introduction of multiple initiator chaser shots
during the course of a batch reaction. The terpolymer composition was varied from 5 to 25 wt. % (10 to 50 mol. %)
of styrene content by changing the monomer mixture ratio. A set of terpolymers of different molar masses, ranging
from 150 to 300 kg mol -1 , was obtained by changing the concentration of the chain transfer agent (Table 1).
387
Table 1. Rheological and structural properties of styrene (STY), dodecyl methacrylate (DDMA) and octadecyl methacrylate (ODMA)
388
terpolymers in mineral base oil (5 wt. % solutions): kinematic viscosity, (i - initial, f - sheared), viscosity index, VI, shear stability
index, SSI, weight average molar mass, M w , number average molar mass, M n, polydispersity index, PI, and average degree of
polymerization, DP.a
Experiment 0b 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Content, wt.%
STY 8 5 10 15 20 25 15 15 15 15 15 15 15 15 15 15
DDMA 69 71.25 67.5 63.75 60 56.25 85 63.75 42.5 21.25 0 42.5 42.5 42.5 42.5 42.5
ODMA 23 23.75 22.5 21.25 20 18.75 0 21.25 42.5 63.75 85 42.5 42.5 42.5 42.5 42.5
Molar mass, kg/mole
Mw 173.7 306 244.3 186.4 171.1 159.7 232.1 267 291.3 288.5 299.2 238.8 252.3 19.14 174.9 156.1
Mn 59.1 72.8 58.6 54.9 56.2 48.8 89.95 91.74 92.65 95.92 97.19 94 90.4 79.1 73.5 66.8
IP = Mw / Mn 2.94 4.2 4.17 3.4 3.04 3.27 2.58 2.91 3.14 3.01 3.08 2.54 2.79 2.42 2.38 2.34
DP = Mn / Мо 229 285 245 245 267 260 430 420 405 399 384 411 395 345 321 292
Viscosity at 40°C 90.7 115.8 109.5 103.3 100.5 91.8 115.3 124.7 126.5 129.9 132.5 125.5 131.9 112.3 104.5 101.8
vi 76.6 84.9 86.5 87.4 85.8 82.3 90 92.7 92.6 95.4 96.1 94.69 95.86 90.24 85.5 86.92
vf
SSI at 40°C 15.5 26.7 21 15.4 14.6 10.4 21.9 25.7 26.8 26.6 27.5 24.6 27.3 19.6 18.2 14.6
Viscosity at 100°C
vi 14.3 18.2 17 15.7 15.2 13.9 17.7 18.7 19.2 19.6 20 17.04 17.89 15.23 14.18 13.77
vf 12 13.2 13.3 13.2 13 12.4 13.7 14 14 14.5 14.5 12.64 13.15 12.19 11.56 11.75
SSI at 100°C 16.1 27.5 21.8 15.9 14.5 10.8 22.6 25.1 27.1 26 27.5 25.8 26.5 20 18.5 14.7
Viscosity index
IVi 172 176 170 162 159 154 170 169 173 172 173 148 151 142 138 136
IVf 152 157 154 151 151 147 154 155 154 155 156 129 136 129 126 127
a
Terpolymerization conditions: concentration of monomer mixture in mineral base oil, c?M = 50 wt. %; concentration of initiator,
Notes.
tert-butylperoxy-2-ethylhexanoate, cI = 1 wt. % relative to monomers; overall reaction time, τ = 5 hours; reaction temperature, t = 100°C.
Experiments 13, 14, and 15 were performed by addition of chain transfer agent, dodecyl mercaptane, of 0.025, 0.05 and 0.10 wt. % with the
respect to the sum of monomers, respectively.
b
This experiment was performed using MMA as a third monomer, instead of styrene.
CH 3 CH 3 mineral CH 3 CH 3
base oil
CH 2 CH + CH 2 C + CH 2 C [ CH 2 CH ][ CH 2 C ][ CH 2 C]
Δ
C O C O initiator C O C O
chain transfer agent
O O O O
(CH 2 ) 11 (CH 2 ) 17 (CH 2 )11 (CH 2 )17
CH 3 CH 3 CH 3 CH 3
Methods
The polymer molar masses were determined using the size exclusion chromatography method (SEC) on a
Polymer Laboratories GPC 20 instrument. The polystyrene standards were used for calibration. Tetrahydrofuran
was used as a solvent/eluent at a flow rate of 1.0 cm 3 min-1 . The content of residual, unreacted monomers as well
as terpolymer compositions [6] were examined by 1H NMR spectroscopy using a Bruker Avance 300 MHz instrument.
The rheological properties of polymeric additive solutions in the SN-200 mineral base oil were determined using
standardized methods: kinematic viscosity by ASTM D-445, viscosity index by ASTM D-2270, and shear stability
by DIN-51382.
The most important properties of polymeric viscosity index improvers of mineral oils could be
quantitatively expressed by the values of the solution kinematic viscosity, the viscosity index, and the shear
stability index. All of them are directly related to the polymer additive composition, structure, and molecular
characteristics.
120
40 oC
-1
Kinematic viscosity, v / mm s
100 oC
2
105
90
20
10
0 5 10 15 20 25 30
w (STY) / wt. %
Fig, 1. Kinematic viscosity of 5 wt. % solutions of styrene/dodecyl methacrylate/octadecyl

methacrylate terpolymers in mineral base oil as a function of styrene content (mass ratio
DDMA/ODMA = 3).
389
EFFECT OF TERPOLYMER COMPOSITION
In order to investigate the effect of styrene content on the thickening efficiency of styrene (STY)/dodecyl
methacrylate (DDMA)/octadecyl methacrylate (ODMA) terpolymer, five terpolymers with different compositions
were synthesized. The mass ratio of long-chain methacrylates was kept constant, DDMA/ODMA = 3 (molar ratio,
DDMA/ODMA = 4), and the proportion of STY monomer was varied in the range from 5 to 25 wt. %. The styrene
160
before shear stability test

after shear stability test
150
Viscosity index, VI
140
130
120
150 175 200 225 250
-1
Mw / kg mol
Fig. 2. Viscosity index of 5 wt. % solutions of styrene/dodecyl methacrylate/octadecyl

methacrylate terpolymers in mineral base oil as a function of styrene content (mass ratio
DDMA/ODMA = 3).
28
24
Shear stability index, SSI
20
16
12
8
0 5 10 15 20 25 30
w (STY) / wt. %
Figure 3. Shear stability index of 5 wt. % solutions of styrene/dodecyl

methacrylate/octadecyl methacrylate terpolymers in mineral base oil as a function of
styrene content (mass ratio DDMA/ODMA = 3).
390
content in the terpolymer was limited by its solubility in the mineral base oil. The main lubricating
p r o p e r t i e s o f t e r p o l y m e r s o l u t i o n s i n m i n e r a l b a s e o i l w e r e e s t a b l i s h e d a n d a r e l i s t e d i n Ta b l e 1
(experiments 1 to 5) together with the composition and some structural characteristics of the synthesized
terpolymers.
The kinematic viscosities of 5 wt. % terpolymer solutions as a function of styrene content are
presented in Fig. 1. All the solutions show high viscosity values at both measured temperatures, indicating their
w (DDMA) / wt. %
0 20 40 60 80 100
1.10
w (STY) = 15 wt. %
Q = vred (100 C) / vred (40 C)
o
1.05
1.00
o
0.95
DDMA / ODMA = 3 in wt. %

0.90
0 5 10 15 20 25 30
w (STY) / wt. %
Fig, 4. Kinematic viscosity of 5 wt. % solutions of styrene/dodecyl methacrylate/octadecyl
methacrylate (15/42.5/42.5 wt. %) terpolymer in mineral base oil as a function of weight
average molar mass.
135 o
40 C
-1
100 oC
Kinematic viscosity, v / mm s
2
120
105
20
10
150 175 200 225 250
-1
Mw / kg mol
Fig, 5. Viscosity index of 5 wt. % solutions of styrene/dodecyl methacrylate/octadecyl

methacrylate (15/42.5/42.5 wt. %) terpolymer in mineral base oil as a function of weight
average molar mass.
391
high thickening efficiency. For example, the terpolymer with 20 wt. % of styrene has v ≥ 14 mm 2 s -1 at 100°C
and v ≥ 90 mm 2 s -1 at 40°C. Also, the measurements showed that increasing the styrene content will cause a
decrease in the viscosity. Furthermore, all the terpolymer/mineral base oil systems exhibited high viscosity index
values, VI > 150 (Fig. 2), comparable with conventional methacrylic viscosity index improvers (Table 1, exp. 0).
The loss of viscosity caused by the shear forces is expressed as the magnitude of the shear stability
index, calculated as:
SSI / % = (v i – v f) ⋅ 100 / v i
where v i is the initial formulated oil viscosity before its exposure to the shear forces (the shear stability test
implementation) and v f is the sheared oil viscosity. Lower values of SSI means lower viscosity loss and better
shear stability of polymeric additive. The obtained SSI values presented in Fig. 3 show that the shear stability of
additives increases with increased styrene content in the terpolymer and the lowering of its average molar mass
(see data in Table 1). For solutions of terpolymers with a styrene content higher than 10 wt. %, despite the high
solution viscosities and molar masses (polymerization degree) of terpolymers, low values of shear stability index
are obtained. Thus, conventional, pure methacrylate additive has the SSI value of 15.5 at 40°C and 16.1 at 100°C,
whereas the comparable styrene/methacrylate terpolymers have SSI values between 10.4 and 15.4 at 40 oC, and
between 10.8 and 15.9 at 100 oC.
The measured lubricating parameters for styrene/methacrylate terpolymer additives with varying dodecyl
methacrylate to octadecyl methacrylate ratio and a constant STY content equal to 15 wt. %, are given in Table 1
(experiments 6 to 10). Obviously the long-chain alkyl methacrylate ratio, DDMA/ODMA, does not significantly
affect either the viscosity values or the shear stability index. The viscosity and VI values remain high and vary
only slightly due to the terpolymer molar mass changes. The high values of SSI are the consequence of high
terpolymer M w values, which is the adjustable parameter in a polymerization process. However, an adequate
190
180
Viscosity index, VI
170
160
150
140
0 5 10 15 20 25 30
w (STY) / wt. %
Fig. 6. Shear stability index of 5 wt. % solutions of styrene/dodecyl

methacrylate/octadecyl methacrylate (15/42.5/42.5 wt. %) terpolymer in mineral base oil
as a function of weight average molar mass.
392
composition and ratio of long-chained alkyl groups, consistent with the composition of the base oil paraffinic
hydrocarbons, assures the optimal low-temperature properties of lubricating oil [7],
Besides these parameters, the lubricating properties may also be characterized by the Q factor [8], which
is the ratio of the normalized viscosity values at two different temperatures, usually 40 and 100ºC:
[vABO (100 o C) − vBO (100 o C)] / vBO (100 o C)

Q=
[v ABO (40 o C) − vBO (40 o C)] / vBO (40 o C)
where indexes BO and ABO denote base oil and polymer additive base oil solution, respectively. This Q factor, or
viscosity ratio, reveals the thickening effect of the additive and indicates the degree of interaction between the
polymer (additive) and the solvent (base oil) in the temperature range considered. When Q > 1, it indicates that the
additive improves the VI since the thickening effect is greater at 100ºC than at 40ºC. The ideal case is when Q = 1,
meaning that the thickening effect is the same at both temperatures. Although both values, the VI and Q, depend
on viscosity, there is no direct relation between them. The values of the Q factor in dependence on the composition
of terpolymer additives are shown in Fig. 7. It is evident that the thickening decreases at higher temperatures with
increasing styrene content in the terpolymer, while it increases at lower temperatures. However, it is important to
notice that these values do not differ significantly from ideal ones, which points to a coherent lubrication efficiency
with temperature change for the styrene / alkyl methacrylate polymeric additives with a styrene content up to 25
wt. % or 50 mol. %. The variation of Q with the DDMA/ODMA ratio is insignificant.
EFFECT OF TERPOLYMER MOLAR MASS

The effect of additive molar mass on lubrication properties was investigated for terpolymer of constant
composition, where STY/DDMA/ODMA was 15 / 42.5 / 42.5 (wt. %), respectively. In Figs. 4, 5, and 6 the kinematic
30
o
40 C
27 o
100 C
Shear stability index, SSI
24
21
18
15
12
150 175 200 225 250
Mw / kg mol-1
Fig. 7. The ratio of the normalized viscosity values at 100 and 40ºC, Q factor, of 5 wt. %
solutions of styrene/dodecyl methacrylate/octadecyl methacrylate terpolymers in mineral
base oil as a function of composition.
393
viscosity, viscosity index and shear stability index of 5 wt. % terpolymer solutions in mineral base oil are shown as
functions of terpolymer molar mass (Table 1, experiments 11 to 15). Obviously, the polymer molar mass strongly
influences all this properties. The shear stability index increases with increase in the molar mass, i.e., larger
molecules are more susceptible to cleavage under high shear stresses. The decreased molar mass of the polymeric
additive after stability testing is evident in the lowered viscosity of the solution. The decrease in the viscosity is
less than 20 % in comparison to the original pre-test value for solutions with terpolymer M w up to 200 kg mol -1,
which is quite similar to alkyl methacrylate terpolymer solutions. On the other hand, higher molar masses of
polymers contribute to higher viscosity index values as well as kinematic viscosities of oil solutions. The best
lubricating properties of mineral oils are obtained with additives having high VI values and low SSI values. Since
one of these key properties increases and the other decreases with an increase in the polymer molar mass,
optimization of the polymer structure is required in order to obtain the best application properties [9].
CONCLUSIONS
The results presented and discussed in this paper show that terpolymers of styrene, dodecyl methacrylate,
and octadecyl methacrylate could serve as advanced viscosity index improvers of lubricating mineral base oils. .
Their properties are fully comparable to conventional methacrylate additives; besides, they show better thermal
and shear stability. The content of styrene in the terpolymer was limited up to 25 wt. % by their solubility. It was
shown that an increase in the terpolymer molar mass causes an increase in the solution viscosity and viscosity
index; the opposite effect was obtained with increasing styrene content. The shear stability of terpolymer solutions
increases with an increase in the styrene content and decreases with an increase in the molar mass.
REFERENCES
1. E. Bielmeier, F. Camera, C. D. Neveu, A new breed of viscosity index improvers, Croatian Society for Fuels
and Lubricants Symposium Proceedings, Croatian Engineers Association, XXXVI Symposium Lubricants,
353, 13 (2003).
2. A. I. Akhmedov, Chem. Tech. Fuels Oils, 23, 147 (1987).
3. A. I. Akhmedov, A. M. Levshina, Chem. Tech. Fuels Oils, 20, 41 (1984).
4. A. I. Akhmedov, R. I. Ibragimova, Chem. Tech. Fuels Oils, 27, 160 (1991).
5. A. I. Akhmedov, T. K. Akchurina, A. M. Levshina, S. M. Gusein-zade, E. U. Isakov, Chem. Tech. Fuels Oils,
20, 211 (1984).
6. A. Jukiæ, M. Rogošiæ, E. Vidoviæ, Z. Janoviæ, Polym. Int. 56, 112 (2007).
7. Z. Janoviæ, A. Jukiæ, E. Vidoviæ, J. Romano, A. Barišiæ, M. Picek, Goriva i maziva/Fuels and Lubricants,
45, 143 (2006).
8. A. Jukiæ, LJ. Tomašek, Z. Janoviæ, Lubr. Sci. 17, 431 (2005).
9. P. Salaün, J.-L. Houzelot, J. Villermaux, S. Marchal, Chem. Eng. J. Biochem. Eng. J. 63, 19 (1996).
394
AFIBROUS SULFONIC ACID MATERIALS FOR REGENERATION

OF USED OILS
E. E. Sirotkina and L. Yu. Novoselova UDC 665.663/677.494
Filters which are a combination of fibrous polypropylene and sulfonate sorbents with disperse
ferromagnetic materials are proposed for regeneration of transformer and industrial oils to the level of
commercial oils. When such filters are used, traditional sulfuric acid treatment is eliminated from the
production cycle.
The composition of oils and consequently their performance and environmental properties worsen in the
conditions of use. The following fundamental processes take place:
• physical: contamination by particulate contaminants, absorption of moisture, evaporation of light
fractions, crystallization of solid hydrocarbons, etc.;
• chemical: oxidation of hydrocarbons and heteroatomic compounds, polymerization, polycondensation,
decomposition of unstable contaminants, corrosion of metals, etc.;
• physicochemical: coagulation of particulate contaminants and oxidation products, solvation, adsorption
and desorption on the metal surfaces of friction units, etc.
Distillation of oils is weighted as a result of these processes, and oxidation products (resins, solid residues),
particulate contaminants, water (flooding), and products from corrosion and wear of metals are formed and
accumulate, and the viscosity and acidity of the oils increase [1, 2].
In oxidation of oils, soluble and insoluble products are formed. The primary process of liquid – phase
oxidation takes place according to a radical – chain mechanism with formation of alcohols, aldehydes, ketones,
acids, phenols, and other products in the oils. These products usually trigger secondary condensation processes
____________________________________________________________________________________________________
Institute of Petroleum Chemistry, Siberian Branch, Russian Academy of Sciences. Translated from Khimiya
i Tekhnologiya Topliv i Masel, No. 5, pp. 28 – 30, September – October, 2007.

Fig. 1. AS 42 – 5 and VS 42 – 5 sieve filters.
Fig. 2. PEGOTMAS filter elements.
Fig. 3. FMM magnetic separators.
in the system (polycondensation, coagulation) with formation of resins, asphaltenes, carbenes and carboids. The
final products of oxidation of the oils are resins, sediments, varnishes, and carbon deposits.
Particulate contaminants in oils cause high wear of the friction surfaces of parts and mechanisms and clog
filters. Resinous substances clog filters, increase the viscosity and worsen the properties of the oils, and increase
396
the conductivity of transformer oil. Water worsens the pumpability, filterability, antiwear, dielectric, and
anticorrosion properties of oils, decreases their biostability, and intensifies electrochemical corrosion of parts.
Both physical (filtration, settling, centrifugation, separation, mixing of unconditioned product with fresh
product (quality margin for variable indexes, etc.) and chemical (hydrogenation, use of reagents, etc.) methods are
used for restoring the quality of oils.
Coarse (from 30 – 40 to 100 mm and more) and fine (from 2 – 16 to 40 mm) filters are very widely used for
treating oils. The design of the filters (Figs. 1 – 3) and the filter materials are very varied. Frequently used filter
materials are: paper impregnated with Bakelite, fiber materials, clay, powdered perlites and askanites [3], metal
sieves, metal ceramics, etc.
Paper filters are characterized by 1.5 – 2 mm fineness of filtration. Hydrophobic materials for separating
water are made of fibers (viscose treated with phenol”formaldehyde resin; basalt modified with clay or
carbamide [4, 5], etc.). Filter packages with bronze (nickel, brass) gauze with a filtration fineness
of 60 – 70 mm [1, 2] are used in oil filters.
We have developed effective materials with a set of properties (filtering, chemisorbing, water – repellent,
complexing) that allow regenerating used oils, including for recycling in the production cycle.
Sulfonic acid (SA) materials and disperse ferromagnets (FM) were developed as a result of the studies.
The former were made by sulfonation of the products of graft – polymerization of styrene to polypropylene
fiber (PPF) [6 – 8]. The effectiveness of the ferromagnetic materials in oil treatment processes has been investigated
in many studies, including in [9].
Treatment was conducted in two stages: fibrous SA materials were used in the first and PPF
combined with disperse FM were used in the second. The fibrous SA material was very effective and allowed
eliminating the sulfuric acid traditionally used in these processes which causes formation of a large amount of
sulfuric – acid – containing wastewaters.
The proposed combined filters proved effective in exhaustive treatment of oils to remove different
contaminants, including particulate contaminants, water, and oxidation products. This is because PPF is a bundle
of randomly oriented fibres (Fig. 4) that form a bulky elastic skeleton containing an open labyrinthine system of
Fig. 4. Photomicrograph of PPF (interfiber space).
397
Table 1
Breakdown number Breakdown voltage, kV
1 43
2 49
3 39
4 50
5 49
6 50
Note. Before treatment, breakdown voltage was 20 kV.
Table 2
Working voltage of electrical Breakdown voltage of oil, kV

equipment, kV boundary region of normal state maximum acceptable
≤15 – 20
≤35 – 25
60—150 40 35
220—500 50 45
750 60 55
cavities of different sizes (both large and capillary) in the interfiber spaces. Different contaminants – from suspended
particles and particulate contaminants to solid products of secondary oxidation of the oils – can be trapped in
these cavities during filtration by physical sorption.
In addition, chemical modification of the initial PPF results in formation of functional sulfo groups on its
surface, which causes the fiber material to retain a number of oxygen – containing compounds – products of
oxidation of the oils due to chemical sorption and complexation.
Coagulating and water – repellent membranes are used to separate water from oils [1]. Because of the
hydrophoby of polypropylene, the materials made from it are not wet with water but instead repel it. On contact
of drops of water with the surface of PPF, they coalesce, followed by separation of water and displacement of oil.
Testing of the filters confirmed their suitability for regenerating spent transformer and industrial oils.
Treatment of transformer oil. Insulating oils, including transformer oils, as liquid dielectrics insulate the
current – carrying parts of electrical equipment, executing the function of a heat – removing medium. Since
transformer oils must have high resistivity, particulate contaminants and water must not be present in them.
Special attention must be focused on ensuring the antioxidant properties [1, 2].
For this reason, in treating transformer oils with filters made of fibrous SF materials and disperse FM, the
acid number (according to GOST 5985–79) and breakdown voltage (GOST 6581–75) were determined first. After
treatment of used oil with an acid number of 0.2 mg KOH/g on filters 1, 2, and 3, the acid number was 0.0012, 0.003,
and 0.0015 mg KOH/g.
The results of determining the breakthrough voltage of used oil after treatment are reported in Table 1.
The arithmetic mean value of the breakdown voltage U bd was calculated with the equation:
398
U bd = 1/n∑ U bdi
where n is the number of breakdowns; U bdi is the voltage attained in successive breakdowns, kV.
It was 46.7 kV, which satisfies the requirements (Table 2) for oils used in electrical equipment with a
working voltage up to 500 kV [2].
Treatment of industrial oil. The purpose of industrial oil is to reduce friction and wear of parts of industrial
equipment, remove heat from friction units, protect parts from corrosion, clean contaminants off of friction
surfaces, etc.
The degree of treatment of petroleum oils (with no additives) and their stability in use and storage are
characterized by a number of indexes, and the most important one is the acid number. The acid number decreased
from 0.4 to 0.015, 0.02, and 0.023 mg KOH/g for combined filter samples 1, 2, and 3 after treatment of used
industrial oil.
The efficacy of the filters, a combination of polypropylene sulfonic acid fibrous sorbents with
disperse ferromagnetic materials was confirmed by the results of testing them at Tomsk GPZ – 5 laboratory in
treatment of two batches of oil. The acid number of one of them was 0.03 and the acid number of the other
was 0.019 mg KOH/g after treatment with a standard of 0.02 mg KOH/g.
The proposed filters thus ensure regeneration of transformer and industrial oils to the level of
commercial oils.
REFERENCES
1. I. G. Fuks, V. G. Spirkin, and T. N. Shabalina, Principles of Chemmotology. Chemmotology and Oil and
Gas Topics: A Study Aid [in Russian], Neft’ i Gaz, Moscow (2004).
2. V. M. Shkol’nikov (ed.), Fuels, Lubricants, Industrial Fluids. Assortment and Use. A Handbook [in
Russian], 2 nd ed., Tekhinform, Moscow (1999).
3. USSR Inventor’s Certificate No. 1011235.
6. L. Yu. Novoselova and E. E. Sirotkina, Plast. Massy, No. 1, 15 – 21 (2006).
7. E. E. Sirotkina and L. Yu. Novoselova, in: Proceedings of the Second International Scientific and Practical
Conference on Study, Development, and Use of Advanced Technologies in Industry, St. Peters burg,
February 7 – 9, 2006 [in Russian], Vol. 4, Izd. Politekhn. Universiteta, St. Petersburg (2006), pp. 138 – 141.
8. L. Yu. Novoselova, E. E. Sirotkina, and E. V. Sergeeva, Zh. Prikl. Khim., 79, No. 3, 378 – 382 (2006).
9. Ya. A. Kamenchuk, S. I. Pisareva, L. Andreeva, et al., Khim. Tekhnol. Topl. Masel, No. 1, 29 – 31 (2006).
399
RESEARCH
PRODUCTION OF FUEL GAS IN PYROLYSIS OF PLANT MASS
V. A. Glushkov UDC 620.952
The effect of design-process factors on the yield of products in pyrolysis of plant mass was investigated.
The yield of fuel gas in pyrolytic processing of pyrolytic resins was evaluated.
The search for factors that increase the yield of products in pyrolysis of plant mass is conducted to
determine a possible increase in the output and heat value of fuel gas in this process.
It was convincingly shown in the 1940s [1, 2] that the yield of basic liquid products of pyrolysis increases
when wood is ground (see Table 1). Processing of smaller wood chips increases the yield of the resin, methanol,
aldehydes, ethers, and unsaturated compounds which are fuel. In further grinding of the plant mass, there is a
tendency toward an increase in the yield of products of pyrolysis, an increase in the rate, and a decrease in
conversion power consumption.
As a consequence, the degree of grinding of processed plant mass is one factor that increases the yield of
products of pyrolysis, and that means the production volume and heat of combustion of the fuel gas.
In pyrolysis of wood in units with internal heating, the yield of products is higher than in units with
external heating [2]. This primarily concerns resin, whose yield is approximately doubled.
As a consequence, the placement of the heating source inside the chamber of the pyrolysis reactor is
another factor that increases the yield of products of pyrolysis, production volume, and heat of combustion of
fuel gas.
In pyrolysis of plant feedstock, dry wood, for example, the production volume of fuel gas
is 0.33-0.43 m 3 /kg and the heat value is 14-16 MJ/m 3 [3]. As a consequence, in burning fuel gas obtained in
pyrolysis of 1 kg of wood, 4.6-6.9 MJ of energy is produced. This is 10-15% of the energy from burning traditional
fossil fuels – crude oil and natural gas [4].
____________________________________________________________________________________________________
Izhevsk State Technical University. Translated from Khimiya i Tekhnologiya Topliv i Masel, No. 5,
pp. 31 – 32, September – October, 2007.

Table 1
Yield (%) in pyrolysis of absolutely dry wood with a chip volume of

Liquid products
11 cm3 77 cm3
Resin 15.46 13.15
Acids 4.43 3.05
formic 0.53 0.53
acetic 3.59 2.09
propionic 0.31 0.45
Methanol 0.89 0.87
Aldehydes 0.26 0.25
Ketones 0.33 0.62
Ethers 0.22 0.2
Unsaturated compounds 0.77 –
The yield in plant feedstock is approximately 25 wt. % for fuel gas, approximately 25% for carbon residue,
approximately 36% for water and carboxylic acids, and approximately 14% for resins [5]. Resins are also combustible
substances. But using them as fuel involves important technical difficulties, since modern energy-generating
devices cannot burn such fuel.
Resins must be transformed into fuel gas for use as energy carriers. As indicated in [6], complex
hydrocarbons decompose into simpler hydrocarbons at high temperatures. In exposure to heat, heavy resin
molecules decompose into lighter molecules of alkanes, alkenes, and other fuel gases, forming a mixture close in
physical properties to pyrolysis gas [4]: the density at 20°’C is 0.58-0.75 kg/m 3, and the heat value is 14-16 MJ/m 3.
As a consequence, additional processing of resins, which constitute 14% of the initial mass of
the plant feedstock, ensures a yield of 0.14 kg of fuel gas per 1 kg of plant mass. Expressed in volume, this
is 0.19-0.24 m 3 of gas which will yield 2.66-4.56 MJ of energy when burned.
These estimations were confirmed on a laboratory pyrolysis setup which can process the resins obtained.
The total energy from burning pyrolysis gas and gas formed in processing pyrolysis resins thus increases
to 7.26-11.46 MJ per 1 kg of feedstock or up to 16-25% of the heat value of traditional fossil fuels. The amount of
residual products of the process simultaneously decreases.
This analysis showed that the yield of fuel gas in pyrolysis of plant mass increases if the following design
and process conditions are fulfilled:
• grinding processed feedstock, which decreases the power consumed for processing and increases the
yield of fuel liquid products (primarily resins);
• using equipment with internal heating for pyrolysis, which also decreases power consumption and
increases the resin yield.
• thermal (pyrolytic) processing of pyrolysis resins.
REFERENCES
1. V. I. Koryakin, Thermal Processing of Wood: Fundamental Mechanisms of Processes in Equipment with
Internal Heating and Treatment with a Steam – Gas Mixture [in Russian], Gosudarstvennoe
Lesotekhnicheskoe Izd-vo, Moscow – Leningrad (1948).
401
2. B. M. Chernomordik, Theory and Calculation of Transport Gas Generators [in Russian], Mashgiz,
Moscow (1943).
3. V. I. Koryakin, Thermal Decomposition of Wood [in Russian], Goslesbumizdat, Moscow-Leningrad (1962).
4. O. N. Bryukhanov and V. A. Zhila, Natural and Artificial Gases [in Russian], Izdatel’skii Tsentr
“Akademiya”, Moscow (2004).
5. “Pyrolysis of wood,” in: Chemistry. Great Encyclopedic Dictionary [in Russian], 2 nd ed., Bol’shaya
Rossiiskaya Entsiklopediya, Moscow (1998), p. 442.
6. N. I. Sul’zhik and A. V. Stepanov, Conserving Resources in Petrochemical Plants [in Russian],
Nora-print, Kiev (2000).
402
VISCOSITY OF WATER – ATMOSPHERIC RESID EMULSION WITH DIFFERENT

CONCENTRATIONS OF WATER
Kh. M. A. Abdo, I. M. Kolesnikov, and S. I. Kolesnikov UDC 532.695+532.384
Emulsions of the water –atmospheric resid type, or water-in-oil emulsions, are burned in different heating
units. Addition of water decreases the viscosity, increases the completeness of combustion, and decreases
consumption of atmospheric resid and emissions of carbon and nitrogen oxides with stack gases. At up
to 10 wt. % water content in the emulsion, the heat of combustion of atmospheric resid (40,600 kJ/mole) decreases
insignificantly – by approximately 0.3-1%, but savings of atmospheric resid reaches 7% and higher.
One of the important properties of a fuel is the viscosity. It determines the pumpability in pipelines and
the dispersibility in coming out of nozzles. We investigated the characteristics of the change in the viscosity of
a water –atmospheric resid emulsion at temperatures of 20, 40, 60, and 80°C with a change in the concentration of
water in the emulsion and the mathematical description of these characteristics.
Atmospheric resid obtained from mixed West Siberian crudes with the following physicochemical properties
was used for the experiments: density at 20°C, 920-1000 kg/m 3; nominal [Engler] viscosity at 100°C, 61.4°E; resin
content, under 2.1 wt. %. Because they are surface-active or oleophilic compounds, the latter form kinetically and
aggregately stable emulsions.
Water –atmospheric resid emulsions with a 10, 20, 30, and 50 wt. % concentration of water were prepared
in a thermostat at 50 and 60°C with a Khotuntsev –Pushkin colloidal mill. The emulsions obtained were held at
room temperature for 24 h and separated from the bottom (aqueous) phase. Samples were taken from the emulsion
in the necessary volume and the dynamic viscosity was measured at temperatures of 20, 40, 60, and 80°C.
After holding for 24 h, the emulsion was again stirred in the colloidal mill and the viscosity was determined
at the indicated temperatures. The emulsion was then mixed a third time and the viscosity was determined again.
The dependences of the viscosity of the emulsion prepared at 50°C on the measurement temperature for
different concentrations of water in the emulsion and times mixed are shown in Fig. 1. The viscosity of emulsions
____________________________________________________________________________________________________

1.8
2 a
1
1.2
4
3
0.6
η , cPa⋅sec
0
1.6
0
3 4 b
2
1.2
1
0.6
0
20 40 60 80
t, °C
Fig. 1. Effect of temperature t on viscosity η of water–atmospheric resid emulsion

prepared at 50°C after mixing once (a) and twice (b) at different concentrations of water
in the emulsion: 1) 10%; 2) 20%; 3) 30%; 4) 50%.
mixed both once and twice decreased to the same value at 60°C when the measurement temperature increased
regardless of the concentration of water in the emulsion.
The viscosity of the emulsion mixed twice increased with an increase in the concentration of water
from 10 to 50 wt. %. The viscosity of the emulsion mixed once increased from 10 to 20 wt. % with an increase in the
concentration of water, and decreased with a subsequent increase in the water to 50 wt. %.
The data on the characteristics of the change in the viscosity of the emulsion prepared at a temperature
of 60°C are reported in Table 1 as a function of the composition of the emulsion and the measurement temperature.
The following features of the change in the viscosity can be observed with these data:
• when the temperature increases, the viscosity of the emulsion decreases sharply; this is because the
emulsion is in a structured state at low temperature, while it changes into a Newtonian fluid at high temperatures;
• when the concentration of water in the emulsion increases from 10 to 30 wt. %, the viscosity of the
emulsion decreases, and it increases when the water content increases from 30 to 50 wt. %;
• the viscosity of the emulsion at 20°C decreases with an increase in the times mixed due to breakdown of
the structure of the emulsion and passes through a minimum after the emulsions are mixed twice at other
temperatures.
404
Table 1
Water content in Viscosity (cPa⋅sec) of emulsion at temperature of, °C
Times
upper layer after
mixed 20 40 60 80
24 h, wt. %
For a water content in the initial mixture of
10%
1 10 14.7 1.2 0.25 0.106
2 10 11.6 1.1 0.3 0.105
3 10 10.7 1.3 0.36 0.106
20%
1 10 12.8 1.14 0.25 0.106
2 20 11.5 1.1 0.3 0.107
3 20 10.4 1.22 0.36 0.108
30%
1 20 7.35 1.04 0.26 0.106
2 20 3.54 0.65 0.3 0.106
3 20 1.72 1.09 0.37 0.108
50%
1 20 10.1 1.12 0.26 0.106
2 20 9.9 1.15 0.28 0.106
3 20 8.9 1.23 0.35 0.106
It follows from these data that at low temperatures, 20 and 30°C, the emulsions exhibit high viscosity,
which is due to the creation of a structured disperse phase in their volume. This finding can be correlated with
creation of a thick protective shell of oleophilic compounds around the particles of disperse phase.
The oleophilic compounds increase the elasticity of the particles in collisions and structuring of the
emulsion. The structure in the bulk of the emulsion is perturbed and turns into a Newtonian fluid only at high
temperatures due to a decrease in the surface tension of the solvation shells and an increase in the kinetic energy
of the particles of disperse phase.
Based on these theoretical conclusions and the experimental characteristics of the change in the dynamic
viscosity h of the emulsions with the temperature, we proposed an equation that describes these mechanisms:
η = η0 e E/RT + b (1)
where h 0 is the dynamic viscosity of the water –atmospheric resid emulsion at 20°C; E is the activation energy of
the reaction of the particles of disperse phase with the dispersion medium while mixing; R is the universal gas
constant; T is the absolute temperature; b is the energy expended on breaking down the structure of the emulsion.
The values of constants E and b in Eq. (1) are reported in Table 2.
405
Table 2
Concentration of water in
η0, cPa⋅sec E, J/mole b
emulsion, mass fraction
0.1 14.7 68195 -28.6915
0.2 12.8 65965 -27.7556
0.3 7.35 60269 -25.0988
0.5 10.1 63491 -26.5798
Actually, the activation energy decreased with an increase in the concentration of water in the emulsion
due to a decrease in adhesion of the particles of disperse phase with each other during mixing. However, coefficient
b increased with an increase in the concentration of water in the emulsion.
These theoretical parameters confirm the previously formulated assumptions concerning strengthening
of the structure of the water –atmospheric resid emulsion with an increase in the concentration of water. Activation
energy E and coefficient b can be correlated with in the emulsion by the following equations:
E = m1 + n1cH 2O (2)
b = m 2 + n2 cH 2O (3)
where m 1, m 2, n 1 , n 2 are empirical constants.

Substituting the data in Table 2 in Eqs. (2) and (3) and solving them, we obtain a mathematical model in the
following form:
E = 64234 + 396.1 cH 2O (4)
b = 307619 + 30.179 c H 2 O (5)
Equation (4) shows that the activation energy for adhesion and coalescence of droplets of water (disperse
phase) decreases with an increase in the concentration of water in the emulsion. Equation (5) determines the
increase in coefficient b due to strengthening of the structure in the highly structured emulsion.
Our mathematical model of the behavior of emulsions with a change in the concentration of water is in
complete agreement with the experimental findings, which reflects the validity of the theoretical assumptions with
respect to the experimental characteristics. It can be supplemented by the following temperature dependences:
68195
− 28.6915
η10 = 14.7e RT (6)
65965
− 27.7556
η20 = 12.8e RT (7)
60269
− 25 .0988
RT
η30 = 7.35e (8)
406
63491
− 26.5798
RT
η40 = 10.1e (9)
Equations (4)-(9) can be used for evaluating the viscosity of a water-in-oil emulsion stabilized by natural
emulsifiers in the given temperature intervals and concentrations of water in the emulsion. From a theoretical
point of view, they take into account energy E of viscous flow of the emulsion and the structural viscosity with
coefficient b.
Equations (4)-(9) adequately reflect the experimental dependences. Their reliability is confirmed by the
statistical accuracy of obtaining the data on the viscosity of water – atmospheric resid emulsions.
407
HYDROREFINING OF CATALYTIC NAPHTHA CUTS
G. D. Zakumbaeva, A. D. Gazizova, A. V. Danilov, R. I. Egizbaeva, UDC 541.128.13.665.65.2

and D. V. Sokol’skii
A polyfunctional catalyst for hydrorefining of the catalytic naphtha cut with a high olefin content is
proposed. This catalyst induces isomerization and hydrogenation of olefins on contact with the feedstock
with formation of isoparaffins, isomerization of n-paraffins, hydrotreating to remove sulfur, and other
processes. The naphtha obtained satisfies the Euro-4 standard (2005) with respect to quality.
The proportion of thermal and catalytic cracking processes is steadily increasing in world oil refining.
This is due to the increase in production of heavy crude and the necessity of conserving resources.
A high olefin content (40-50%) that reduces the stability and performance indexes is characteristic of
thermal and catalytic naphtha cuts. The quality of these cuts can be increased by catalytic hydrorefining, which
reduces the olefin and sulfur content.
Severe requirements are imposed on the quality of automotive gasolines in the USA, Japan,
and EU countries. In Russia and CIS countries, the requirements for the composition of automotive gasolines
Table 1
Catalyst
Indexes
KT–22 KT–23
Crushing strength of granules, 105 N/m2 413 412
Specific surface area, m2/g 150 79.6
Total pore volume, cm3/g 0.52 0.27
Total acidity (based on thermal desorption of NH3 molecules), mmole/g 1.96 1.93
Note. Both catalysts are pale green extrudates with 2-2.5 mm granules and a bulk density of 600 kg/m .
3
____________________________________________________________________________________________________
Institute of Organic Catalysis and Electrochemistry, Republic of Kazakhstan. Translated from Khimiya i
Tekhnologiya Topliv i Masel, No. 5, pp. 35 – 3 6, September – October, 2007.

have also been stiffened [1]. According to the Euro-4 standard (2005), the maximum contents in gasoline
are 1 vol. % for benzene, 50 mg/kg for sulfur, 35 vol. % for aromatic compounds, 18 vol. % for olefins,
and 2.7 wt. % for oxygen. The introduction of severe new standards for the composition of gasolines led to an
increase in the proportion of isomerization and alkylation processes in oil refining [2-5].
The results of hydrorefining of the catalytic naphtha cut on the polyfunctional c
atalysts KT-22 and KT-23, whose physicochemical characteristics are reported in Table 1, are reported here. These
catalysts allow parallelly and serially conducting several processes on contact with the feedstock: hydrogenation,
hydroisomerization, hydrocracking, hydrotreating to remove sulfur, etc. For this reason, the proposed technology
can be described as energy- and resource-conserving.
Hydrorefining was conducted on an enlarged laboratory entrained-flow unit at high pressure
of 2 MPa, optimum temperature of 380°C, H 2:feedstock ratio of 200, and variation of the feedstock space velocity
from 3 to 7 h -1.
The catalysts investigated were sulfonated with elemental sulfur with the method in [6, 7]. The hydrocarbon
composition of the naphtha cuts was determined chromatographically on a Chrom-4 chromatograph with a stainless
steel column packed with g-Al 2O 3 from Supelco and the sulfur content was determined according to GOST 19121.
The distillation and octane number of the cuts were investigated at the Center for Appraisal and Certification of
Crude Oil and Petroleum Products, TsESN ANALIT (Almaty).
Isomerization and hydrogenation of olefins, isomerization of n-paraffins into isoparaffins, hydrotreating
to remove sulfur, and hydrocracking take place during hydrorefining of the naphtha cut on KT-22 catalyst.
As Table 2 shows, the hydrocarbon composition of the target product “ the hydrogenate “ is a function of
the conditions of the process. When the feedstock space velocity is increased from 5 to 7 h -1 , the degree of
conversion of olefins changes extremally, attaining the minimum (18.4%) at a velocity of 6 h -1. This dependence is
also characteristic of the yield of n-paraffins. The aromatics content decreases from 5.1 to 0.3%.
Isoparaffins – environmentally clean components with a high octane number – are the basic product in the
hydrogenate. Their content is a function of the contact time of the feedstock with the catalyst and attains the
Table 2
Naphtha cut
after hydrorefining on KT-22 catalyst at feedstock
Indexes
initial space velocity, h-1
5 6 7
Hydrocarbon composition, wt. %
olefins 40.2 23.2 18.4 19.6
n-paraffins 6.3 5.3 2.5 3.6
isoparaffins 48.4 69.5 78.2 72.8
aromatics 5.1 1.6 0.3 1.3
C1-C4 paraffins – 0.4 0.6 2.7
Sulfur content, wt. % 0.1 0.013 0.01 0.018
Octane number
RON 88.9 87 89.2 86.7
MON 81.8 80.8 81.8 80.3
Yield, % in feedstock – 99.6 99.4 97.3
409
Table 3
Naphtha cut after hydrorefining on KT-23 catalyst at feedstock space
Indexes velocity, h-1
4 5 6
Sulfur content, wt. % 0.019 0.039 0.057
Octane number
RON 87.1 86.3 88.1
MON 80.8 80.1 81.3
maximum, 78.2%, at a feedstock space velocity of 6 h -1 ; it consists of 48.4% of the initial naphtha cut. The yield of
light C 1-C 4 paraffins within the limits of 0.4-2.7% is from exhaustive hydrocracking.
According to the data from an independent analysis of the initial naphtha cut and hydrogenates at the
TsESN PP (see Table 2) after hydrorefining on KT-22 catalyst in the optimum conditions, the research octane
number of the naphtha cut increases slightly, while it remains at the same level with the motor method. The sulfur
content decreases by one order of magnitude.
The loss of antiknock value as a result of the decrease in the concentration of olefins is compensated for
by an increase in it as a result of the increase in the isoparaffin content from 48.4 to 78.2%, i.e., the initial values
of the octane number are preserved. The yield of hydrogenate is 99.4 wt. %.
Changing the feedstock space velocity to 5 and 7 h -1 with all other conditions being equal decreases the
octane number by 1-2 points and the sulfur content to 0.013 and 0.018 wt. %.
The expanded tests showed that the proposed technology using KT-22 catalyst can be recommended for
production of high-quality varieties of motor fuel that satisfy the Euro-4 standard with respect to hydrocarbon
composition, sulfur content, and antiknock value.
KT-23 catalyst is less active than the KT-22 catalyst (Table 3). The maximum degree of hydrodesulfurizing
with KT-23 catalyst at a feedstock space velocity of 4 h -1 is no greater than 81%. The octane number of the
hydrogenate obtained in these conditions is 1-2 points lower than for the initial feedstock.
The polyfunctional KT-22 catalyst thus ensures hydrorefining of the catalytic naphtha cut in one
stage. It can also be used for refining the thermal cracking naphtha cut. The process on this catalyst
satisfies the resource- and energy-saving requirements. The yield of motor fuel with a maximum sulfur content
of 0.01% is 99.4% in feedstock. KT-22 catalyst contains no precious metals, is mechanically and thermally stable,
and does not become carbonized in prolonged use.
REFERENCES
1. S. N. Onoichenko, V. E. Emel’yanov, and I. F. Krylov, Khim. Tekhnol. Topl. Masel, No. 6, 3-6 (2003).
2. V. V. Kharlamov, Neftekhimiya, 38, No. 6, 439-457 (1998).
3. A. V. Lavrenov, G. A. Urzhuntsev, E. A. Paukshtis, et al., Zh. Prikl. Khim., 76, No. 4, 570-578 (2003).
4. E. I. Akhmetov, Neftekhimiya, 40, No. 1, 41-43 (2000).
5. R. R. Aliev, N. A. Batyrov, and A. K. Zamanov, Khim. Tekhnol. Topl. Masel, No. 1, 22-23 (1997).
6. E. D. Radchenko, B. K. Nefedov, and R. R. Aliev, Industrial Catalysts of Hydrogenation Processes in Oil
Refining [in Russian], Khimiya, Moscow (1987).
7. B. K. Nefedov, E. D. Radchenko, and R. R. Aliev, Catalysts for Exhaustive Refining of Crude Oil [in
Russian], Khimiya, Moscow (1992).
410
CHANGE IN DISPERSE PHASE PARTICLE SIZE IN PETROLEUM SYSTEMS

IN THERMAL TRANSFORMATIONS
B. P. Tumanyan and A. Yu. Ignonina UDC 665.65:[541[182+543.432]
The creation of new laboratory methods for evaluating transformations in crude oils and petroleum products
during production, shipment, refining, and storage has caused the wide introduction of colloid-chemical notions
concerning the structure of petroleum disperse systems (PDS) in oil refining theory and practice. According to
modern concepts of the physicochemical mechanics of PDS, changes take place in these processes, in particular,
in the size of structural formations [1-3]. The size can be used to estimate the degree of association of the
molecules [4] and level of intermolecular interactions in petroleum systems [5, 6].
Many methods have been proposed for measuring the disperse phase particle size. Most of them imply
investigation of transparent or dilute dark petroleum products. The previous research [7, 8] is interesting, and it
was used to develop methods of analysis of disperse systems based on light scattering, the formula, and nomograms
for calculating the particle size based on the optical density and intensity of the scattered light.
In subsequent studies in this direction, methods were proposed for determining the disperse phase particle
size directly in the PDS. The rheological and photocolorimetric methods are the most promising [9]. Dilution of
the sample investigated before conducting the determination and plotting of the calibration curves is a drawback
of many methods. The size of the structural formations in PDS is probably changed by the solvent, and this
reduces the reliability of the results of the measurements.
Samples of heavy petroleum resides, for example, are diluted with heptane–toluene solvent vapors in the
ratio of 1:3 or 1:4 before the measurements, while they are diluted with petroleum oils or similar products in the
ratio of 1:1 or 1:2 in other cases. Selection of the solvent is based on the necessity of ensuring the closeness of
the refractive index of the solvent and the dispersion medium.
The rheological method of measuring disperse phase particle size in dark PDS is of special
interest [10]. The complexity of this method makes it necessary to establish the dynamic viscosity of the disperse
____________________________________________________________________________________________________

9000 3000
a 1
7000 2500
2000
5000
1500
2
Paricle size, nm
3000 1000
Viscosity, mPa⋅sec
1000 500
3000 1400
b 1200
1000
2000
2 800
600
1000
400
1 200
0
0 1 2
Time, h
Fig. 1. Effect of the duration of thermal treatment on the disperse phase particle size
(curve 1) and viscosity (curve 2) at a shear rate of 100 sec -1 for vacuum distillate (a) and
base oil (b).
phase and the dispersion medium of the tested systems, which is not always possible in the conditions of real
measurements.
It was proposed in [11] that the disperse phase particle size of vacuum resid could be measured without
acting on it in any way by the photocolorimetric method. The measurements are conducted in two wavelength
regions, 540-670 and 670-750 nm, corresponding to the green and red spectra.
The results of our previous studies of vacuum distillate and base oil [12, 13] demonstrated the difference
in their viscosity-temperature characteristics, which can hypothetically be attributed to the change in the disperse
phase particle size. For this reason, it was interesting to investigate the change in the size of these particles in the
given petroleum products as a function of the duration of their heat treatment.
The experiments were conducted with our improved method of determining the disperse particle size for
dark petroleum products. The optical density was measured in a monochromatic light beam on a Spekol
photoelectrocolorimeter with blue and red light filters for wavelengths of 490 and 680 nm, respectively. The
sample investigated was placed between two slides installed in the instrument’s holder. The results of the
experiments are reported in Fig. 1a and b.
In heat treatment of the vacuum distillate, the asphaltene-containing structural elements in it must be
taken into consideration as they can actively react with each other at low intensity of the thermal effect. In the
initial stage of exposure, weakly cross-linked aggregate combinations are formed and part of the dispersion medium
can be immobilized in the interparticle space. This state of the disperse system is seen in the initial stage of
thermal treatment lasting for 1 h in Fig. 1a.
Further thermal treatment for 3 h can cause part of the immobilized dispersion medium to be discharged
from the interparticle space, and further growth of aggregate combinations takes place as a result of thermal
transformations in the medium. However, the layer of dispersion medium with a lower degree of thermal
transformations affects the viscosity of the system.
412
Viscosity, mPa⋅sec
Paricle size, nm
1000 1500
800
2 1000
400 500
1
0
0 1 3 4 5 6
Time, h
Fig. 2. Effect of the duration of heat treatment of vacuum distillate repeated 3 months
later on the disperse phase particle size (curve 1) and viscosity (curve 2) at a shear rate
of 100 sec -1 .
The layer begins to be intensively transformed when the thermal treatment lasts for more than 3 h. Marked
splitting of the large aggregate combinations formed in the system up to this time simultaneously takes place.
These assumptions are confirmed in Fig. 1a by the decrease in the size of the aggregate combinations as
a result of their partial thermal degradation and also by an increase in the viscosity of the system due to the onset
of thermal transformations of the immobilized phase separated into the reaction mass. Thermal treatment lasting
for more than 5 h causes the formation of a homogeneous reaction mass in the system, which is transformed with
enlargement of the disperse particles, strengthening of the structural skeleton formed, and a corresponding increase
in the viscosity of the system.
As Fig. 1a and b shows, the characters of the curves of the change in the viscosity of the system and
disperse phase particle size differ. When base oil was treated with heat for 5 h, its viscosity and the size of the
structures of products of thermolysis almost did not change. Continuing thermal treatment caused a comparatively
sharp increase in the size of the structural formations and viscosity.
The practical constancy of the viscosity and particle size in thermal treatment indicate the absence of
marked transformations of the structure, which should probably also be anticipated in the tests of the base oils. In
the temperature conditions of use of the oil, at 230-250°C, no important transformations should take place in the
system until the thermal effects are extremely severe.
Repeated thermal treatment of the vacuum distillate three months later showed (Fig. 2) a significant decrease
in its viscosity and disperse phase particle size, as well as the disappearance of extrema on the experimental
curves. These findings can be correlated with the ongoing interaction of the disperse phase particles in the
system investigated at a state of rest and formation of a more homogeneous structure.
REFERENCES
1. B. P. Tumanyan, Scientific and Applied Aspects of the Theory of Petroleum Disperse Systems [in Russian],
Tekhnika, Moscow (2000).
2. F. G. Unger and L. N. Andreeva, Fundamental Principles of Chemistry. The Nature of Resins and
Asphaltenes [in Russian], Nauka, Novosibirsk (1995).
3. Z. I. Syunyaev, R. Z. Syunyaev, and R. Z. Safieva, Petroleum Disperse Systems [in Russian], Khimiya,
Moscow (1990).
4. M. N. Seliverstov, A. P. Sidorenko, and G. N. Panova, Khim. Tekhnol. Topl. Masel, No. 10, 37-38 (1986).
5. V. I. Obraztsov and A. A. Khrustaleva, Zh. Fiz. Khim., No. 4, 812-814 (1973).
6. Ya. I. Frenkel’, Kinetic Theory of Liquids [in Russian], Nauka, Leningrad (1975).
7. I. Ya. Slonim, Opt. Spektrosk., 8, No. 1, 98-108 (1960).
413
8. I. Ya. Slonim, N. M. Fodiman, and Z. M. Ustinova, Ibid., No. 2, 243-246.
9. M. Al’ Dzhomaa, Candidate Dissertation, I. M. Gubkin Russian State University of Oil and Gas, Moscow
(1992).
10. L. P. Gilyazetdinov and M. Al’ Dzhomaa, Khim. Tekhnol. Topl. Masel, No. 3, 27 (1994).
11. N. A. Pivovarova, B. P. Tumanyan, and N. M. Beregovaya, Nauka Tekhnol. Uglevodorodov, No. 4, 168-169
(2001).
12. B. P. Tumanyan and A. Yu. Igonina, Khim. Tekhnol. Topl. Masel, No. 2, 52-53 (2005).
13. A. Yu. Igonina and B. P. Tumanyan, Tekhnol. Nefti Gaza, No. 6, 25-27 (2006).
414
TRANSFORMATIONS OF RESINS AND ASPHALTENES IN

PHOTOIRRADIATION
Ch. K. Salmanova, S. F. Akhmedbekova, A. P. Mamedov, UDC 665.61.62

S. M. Kyazimov, and Sh. N. Abdulova
The photooxidative transformations of resins and asphaltenes in petroleum residues were investigated
by IR spectroscopy. In photooxidation, these substances undergo both degradation and condensation.
Gaseous products are formed in degradation – hydrogen, low-molecular-weight alkanes, formaldehyde,
carbon monoxide and dioxide, and in condensation, highly condensed aromatic structures and oxidation
products insoluble in organic solvents are formed.
Problems involved in more exhaustive refining and rational utilization of crude oil have stimulated interest
in its high-molecular-weight compounds, particularly in resins and asphaltenes (RA). Such important products as
radical process inhibitors, thermal and light stabilizers for polymer materials, luminophores, and dyes for polymer
materials are also based on RA [1-7].
Thermo- and photooxidative transformations of resins and asphaltenes are of interest in both the chemistry
of RA of petroleum residues and in solving some practical problems. Thermooxidative transformations of RA have
been relatively widely discussed in the literature [8-11], but photooxidation has been investigated much less.
In studying RA in petroleum residues, attention was focused on the problem of separating and storing
them without exposure to light, temperature, and atmospheric oxygen. Attempts were made to study the oxidative
properties of resins and asphaltenes containing alkyl-substituted polyconjugated systems, heterorganic
compounds, etc. [2-7, 10-15]. The inhibiting properties of resins and asphaltenes in photochemical transformation
of petroleum luminophore were investigated [5].
We studied the photooxidative transformations of resins and asphaltenes obtained from heavy
catalytic gasoil (HCGO) and heavy pyrolysis resin (HPR) with distillation above 400°C by IR spectroscopy
and GLC – gas-liquid chromatography.
____________________________________________________________________________________________________
Yu. G. Mamedaliev Institute of New Chemical Problems, National Academy of Sciences of Azerbaidzhan.
Translated from Khimiya i Tekhnologiya Topliv i Masel, No. 5, pp. 39 – 42, September – October, 2007.

80
60
40
1
20
0
2
20
80
60
40
1
20
2
0
0
400 800 1200 1600 2000 2800 3600
Fig. 1. IR absorption spectra of resins (1) and asphaltenes (2) obtained from heavy
catalytic gas oil (a) and heavy pyrolysis resin (b) before photoirradiation.
High-boiling products refined at Azerneftyanadzhag Oil Refinery were used as feedstock, in particular,
mixed light and heavy gasoils distilling above 170°C obtained in catalytic cracking of crude oil vacuum distillate
and the cut above 200°C of HPR from straight-run naphtha from Sumgait Ethylene-Polyethylene plant. Cuts
above 400°C were obtained from HCGO and HPR by vacuum distillation.
The heavy gasoil contained, wt. %: 94.4% oils, 4.8% resins, 0.6% asphaltenes, and 0.2% carbenes and
carboids; the pyrolysis resin contained 21.1% oils, 23.8% resins, 53.6% asphaltenes, and 1.5% carbenes and
carboids.
The resins and asphaltenes were obtained by deasphalting and deresination of both kinds of feedstock
with the method in [16]. n-Heptane was used as the precipitant, benzene and alcohol – benzene mixture (1:4) was
416
used as the solvent. The adsorbent was γ-Al 2 O 3. The resins and asphaltenes obtained were stored at room
temperature in the dark.
The samples were prepared in the form of films 30 mm thick from alcohol – benzene solution of the resins
and benzene solution of the asphaltenes. The resin and asphaltene films underwent photoirradiation with a
standard illuminator with a PRK-2 mercury-quartz lamp (distance between lamp and sample: 0.2 m). Additional
heating of the sample was eliminated and the photoirradiation range was expanded by using quartz optics in a
water filter.
The composition of the gaseous products in photooxidation of resins and asphaltenes was
determined on an LKhM-8MD chromatograph: Polysorb-10 sorbent, thermal conductivity detector, helium carrier
gas, 240 cm×3 mm column, 40°C temperature, 25 ml/min flow rate.
The degree of oxidation of the resins and asphaltenes was determined by IR spectroscopy based on the
optical density of the carbonyl group with an absorption band at 1720 cm -1 . The IR spectra of the samples were
recorded before and after irradiation on an M-80 spectrophotometer.
The IR spectra of the resins and asphaltenes obtained from HCGO are shown in Fig. 1a. The observed
absorption bands at 700, 780, 840, and 880 cm -1 correspond to nonplanar deformation vibrations of a substituted
benzene ring, the absorption bands with maxima at 1510 and 1580 cm -1 correspond to deformation vibrations of a
benzene ring, and the band at 1610 cm -1 corresponds to the C=C bond of an aromatic ring.
The absorption bands at 1625 and 1650 cm -1 and the stretching vibrations of the C – H bond
at 3040 and 3060 cm -1 belong to condensed aromatic hydrocarbons. The rocking vibrations with maxima
at 725 and 760 cm -1 are characteristic of a CH2 group, the bands at 1380 cm -1 from deformation and at 2860 cm-1 from
stretching vibrations are characteristic of methyl groups, and the bands at 1450, 1480, 2920, and 2940 cm -1 are
characteristic of the methylene groups of the alkyl substituent in aromatic hydrocarbons and naphthenes.
In addition to the listed absorption bands, the spectrum contains bands at 1290 cm -1 corresponding to
stretching vibrations of an Ar – O – Ar group and bands at 1040, 1070, and 1175 cm-1 of deformation and
at 3440 cm -1 of stretching vibrations characteristic of an OH group. The absorption bands at 3440 cm -1 , however,
are also characteristic of nitrogen-containing groups.
The stretching vibrations at 1700 and 1720 cm -1 are from a C=O group, and the vibrations at 3112 cm -1 are
from an oxygen atom in a ring. The absorption bands at 530 cm -1 belong to S – S bonds, and those
at 660 and 680 cm -1 belong to C – S bonds.
Based on the above, we can hypothesize that alkyl-substituted condensed aromatic and alkyl-substituted
heterocyclic(N,S,O)-naphthenes and aromatics are present in the structure of the resins and asphaltenes obtained
from heavy gasoil before irradiation. However, the absorption bands corresponding to condensed
aromatic and nitrogen-and sulfur-containing cyclic structures are more intensive in the spectra of
asphaltenes than in the spectra of resins. In addition, in contrast to the resins, the asphaltenes contain cyclic
esters (1780, 1820, 1850 cm -1) and the resins contain aromatic ketones (1720 cm -1).
The IR spectra of the resins and asphaltenes obtained from heavy resin before photoirradiation are shown
in Fig. 1b. They are basically the same as the IR spectra of the resins and asphaltenes obtained
from HCOG. However, they contain no absorption bands assigned to nitrogen- and sulfur-containing groups.
Judging by the IR spectra, the resins and asphaltenes obtained from HPR before photoirradiation contain
alkyl-substituted condensed aromatic and alkyl-substituted naphthene – aromatic and oxygen-containing cyclic
hydrocarbons.
The absorption bands characteristic of functional groups are basically more intensive in the spectra of
resins than in the spectra of asphaltenes. However, in contrast to the resins, the asphaltenes contain more highly
417
condensed aromatic hydrocarbons and cyclic esters (1780, 1820 cm -1), and the resins contain more alkyl-substituted
aromatic structures and aromatic ketones (1720 cm -1).
In analyzing the IR spectra of RA obtained from HCOG and HPR, we can conclude that there
are more alkyl groups in the former and less highly condensed aromatic structures than in the latter.
Alkyl-substituted condensed cyclic structures are thus more important in the structure of RA: naphthene-aromatic
and heterocyclic-naphthene-aromatic structures.
Based on the GLC studies and IR spectra of the initial and photoirradiated resins and asphaltenes, we can
state that oxygen-containing compounds are formed from the hydrocarbon part of RA in photoirradiation: alcohols,
aldehydes, acids, phenols, and alkylaromatic ketones.
Dehydrogenation and dealkylation of alkylaromatic hydrocarbons take place during photooxidation and
such gaseous products as hydrogen, methane, ethane, propane, formaldehyde, and carbon monoxide and dioxide
are formed.
In photoirradiation, the molecules of the RA pass into the electron-excited state. They can decompose
at C – C and C – H bonds with formation of resin-asphaltene (•R RA ) and alkyl (•Ralk) radicals, atomic hydrogen,
carbon monoxide [10, 17]:
O
RRA — C — Ralk + H
hν
RRA — C — Ralk(T) Ralk + RRA + СО
O O O Ralk + RRA − С = О
where S, S*, and T are respectively the ground, excited singlet and triplet states of RA molecules.
Alkanes are formed as a result of recombination of both free radicals and radicals with a hydrogen atom,
while formaldehyde forms in the reaction of a •CH 3 radical with molecular oxygen. According to [18], carbon
monoxide and dioxide can form as a result of degradation of the intermediate and final products of photooxidation
of RA:
O O O
hν
Н Н Н
O O O
hν
Н ОН ОН
This is confirmed by the decrease in the intensity of the absorption bands at 1380 and 1480 cm -1 assigned
to CH 3 and CH 2 groups. We can thus hypothesize that photochemical degradation takes place.
The naphthene rings are compacted as a result of dehydrogenation and pass into more highly condensed
aromatic compounds. This is confirmed by the increase in the intensity of the absorption bands with maxima at
3040 and 3060 cm -1 characteristic of condensed aromatic structures.
418
O
ОН - Н 2O
O
In addition, condensation of alcohols and acids causes the formation of aromatic esters, while condensation
of phenols results in ethers:
Absorption bands appear at 1750 cm -1 in the IR spectra and the intensity of the absorption band
at 1290 cm -1 increases. These bands are respectively characteristic of esters and ethers. In addition, the
concentration of paramagnetic centers decreases under the effect of light [19] and the C=O p-bond breaks in the
molecules of the aromatic ketones with formation of OH groups:
hν
hν
RRA Н
OН
RRA — C
Ar2
This is indicated by the increase in the intensity of the absorption band at 3440 cm -1 corresponding to
an OH group:
Ar2 — C — OН
Ar2 — C — OН
2
1
D1720
0 1 2 3 4 5
τ, h
Fig. 2. Optical density D 1720 of carbonyl groups as a function of t of photoirradiation of

RA obtained from heavy gasoil (solid curves) and heavy resin (dashed curves):
1) resins; 2) asphaltenes.
419
Table 1
Resins Asphaltenes
Indexes
HCGO HPR HCGO HPR
Degree of aromaticity fa 0.3788/0.4265 0.61/0.63 1.026/1.326 1.28/1.32
Optical density
D1380(CH3) 0.9362/0.8239 0.7597/0.7397 0.3975/0.3253 0.3405/0.3185
D1480(CH2) 0.9119/0.8745 0.6628/0.6185 0.3988/0.381 0.4197/0.3944
D3440(OH) 0.2996/0.3543 0.2314/0.3195 0.0969/0.1264 0.0447/0.0625
D1720(C=O) 0.1823/1.5265 0.4867/1.2538 – /0.926 – /0.6145
Note. In the numerator: before photoirradiation; in the denominator: after photoirradiation.
We can thus hypothesize that photochemical condensation takes place.

The characteristics of these resins and asphaltenes before and after photoirradiation are reported
in Table 1. As a result of photoirradiation, the optical density D decreases for the CH3 and CH 2 groups increases
for the OH group. Moreover, the optical density of the C=O group increases sharply and the degree of aromaticity
increases.
T h e d e p e n d e n c e o f t h e o p t i c a l d e n s i t y D 1720 (C=O) o f c a r b o n y l - c o n t a i n i n g g r o u p s o n t h e
duration of photoirradiation was investigated to analyze the kinetics of photooxidative transformations
in HCGO and HPR resins and asphaltenes. As Fig. 2 shows, this value increases sharply in the first hour of
photooxidation, increases slowly when the photoirradiation time increases to 3 h, and begins to decrease
after 3 h.
The sharp increase in this parameter is due to oxidation of side alkyl substituents with formation of
aldehydes, ketones, and carboxylic acids. Photooxidation in alkyl groups has a radical-chain character. After
photooxidation for 1 h, an absorption band with a maximum at 1750 cm -1 appears in the spectrum, corresponding to
vibrations of ester bonds, as indicated by the slow increase in D 1720(C=O), This is due to the reaction of alcohols
and acids with formation of ester groups.
It should be noted that photochemical reactions in RA from heavy gasoil take place more efficiently than
in RA from pyrolysis resins. This is due to the larger proportion of the alkyl part in substances of the second type.
The oxidation products formed after 3 h of photoirradiation do not dissolve in such organic solvents as
alcohol – benzene mixture, benzene, carbon tetrachloride, and dichloroethane.
Photochemical reactions thus take place in photoirradiation of resins and asphaltenes from petroleum
residues: degradation with formation of gaseous products (hydrogen, methane, ethane, propane, formaldehyde,
carbon monoxide and dioxide) and condensation with formation of highly condensed aromatic structures and
oxidation products insoluble in organic solvents.
REFERENCES
1. V. F. Kam’yanov, V. S. Aksenov, and V. I. Titov, Heterogeneous Components of Crude Oils [in Russian],
Nauka, Novosibirsk (1983).
2. V. V. Uglev and V. F. Kam’yanov, Neftekhimiya, 42, No. 1, 55 (2000).
3. N. L. Edilashvili, Ibid., 22, No. 4, 525 (1982).
4. RF Inventor’s Certificate No. 1803412.
420
5. Ch. K. Salmanova, Protsessy Neftekhim. Neftepererab., No. 2(13), 27 (2003).
6. Ch. K. Salmanova, R. A. Czhafarova, S. F. Akhmedbekova, et al., Ibid., No. 1(20), 19 (2005).
7. Ch. K. Salmanova, Azer. Khim. Zh., No. 3, 76 (2001).
8. N. V. Pokonova, Chemistry of Macromolecular Compounds in Crude Oil [in Russian], Izd. LGU, Leningrad
(1980).
9. F. G. Unger and L. N. Andreeva, Fundamental Aspects of Crude Oil. Nature of Resins and Asphaltenes
[in Russian], Nauka, Novosibirsk (1995).
10. U. Utebaev, A. A. Kamenskii, G. A. Mashukova, et al., Neftepererab. Neftekhim., No. 11, 21 (1990).
11. A. A. Velikov and N. V. Sizova, Neftekhimiya, 42, No. 1, 55 (2002).
12. E. B. Zeinalov, F. I. Samedova, K. U. Velieva, et al., Azer. Khim. Zh., No. 2, 119 (1985).
13. E. B. Zeinalov and Kh. A. Mastalieva, Ibid., No. 2, 40 (1987).
14. A. K. Golovka, L. V. Gorbunova, V. F. Kam’yanov, et al., Neftekhimiya, 43, No. 2, 83 (2003).
15. L. D. Melikadze, B. G. Kutrashvili, Sh. Sh. Barabadze, et al., Ibid., 26, No. 3, 315 (1986).
16. L. I. Bogomolova, M. B. Temyanko, and L. I. Khotyntseva, Modern Methods of Investigating Crude Oils
[in Russian], Nedra, Leningrad (1984).
17. B. Renby and J. Rabek, Photodegradation, Photooxidation, and Photostabilization of Polymers, Wiley,
New York (1975).
18. B. K. Zeinalov, K. G. Gasanov, Ch. K. Salmanova, et al., Azer. Neft. Khozyaistvo, No. 11-12, 42 (1994).
19. M. A. Nadzhafova, Ch. K. Salmanova, and A. P. Mamedov, Neftekhimiya, 43, No. 4, 273 (2003).
421
CARBON ADSORBENTS MADE FROM PETROLEUM ASPHALTITE SEMICOKE
Yu. V. Pokonova UDC 661.183.123
Petroleum asphaltite semicoke added to the batch makes it possible to synthesize adsorbents with
important sorption capacity and selectivity in extraction of silver from multicomponent polymetallic
solutions with the existing industrial scheme.
A stable trend toward using active carbons as adsorbents for extracting precious metals is being observed
in our country and abroad [1]. A specific feature of silver-containing ores is an extremely low silver content and
the complexity of the component composition determines the necessity of using relatively voluminous and selective
Table 1
Indexes Asphaltite Semicoke* from asphaltite
Group composition, wt. %
12.6 –
oils
8 –
resins
79.4 –
asphaltenes
Heteroatom content, %
S 5.45 5.67
N 0.86 1.3
O (by difference) 2.04 5.03

1.02 2.18
С:Н (atomic)
Note. *60% yield of semicoke.
____________________________________________________________________________________________________
St. Petersburg State Institute of Technology – Technical University. Translated from Khimiya i
Tekhnologiya Topliv i Masel, No. 5, pp. 43 –45, September – October, 2007.

adsorbents for extracting silver from them. Readily available and economically suitable feedstock is necessary for
obtaining such adsorbents.
It was shown in [2-4] that adsorbents made from petroleum asphaltites and products of their chemical
transformations have higher adsorption characteristics than domestic and foreign industrial adsorbents. We
report the manufacture and investigation of adsorbents made with asphaltite semicoke.
A sample of asphaltite (Table 1) underwent semicoking in a ZK-1 industrial delayed coking unit. The
process was conducted for 10 h at 500-550°C with a temperature elevation rate of 50-60°/h. At the
end of the process, the asphaltite was held for 1 h at the same temperature. The yield of products
was, wt. %: 55-60% semicoke, 34-40% gas, and 3-5% condensate.
As a result of semicoking, the C:H ratio increased by two times. As indicated in [2-4], the asphaltenes
obtained in heat treatment of oils and resins contain fewer heteroatoms, are more aromatized, and have an ordered
structure in comparison to native asphaltenes.
The adsorbents were molded from a batch obtained by mixing previously ground asphaltite
semicoke with 10% total shale phenols – a mixture of alkylresorcinols, 37% wood resin, and the dust
fraction (0.1 mm particles ≤ 1%) of lean dug coal for 4-6 min in a two-paddle mixer at 60-70°C.
The ash content of the latter was 7.09%, the moisture content was 1.25%, and the volatiles content
was 13.2%. The batch obtained was granulated, then carbonized in carbon dioxide medium while heating
from 200 to 800°C and activated in steam at 800-900°C.
A significant amount of volatiles (4-7%) was liberated during carbonization, and the yield of carbon
residue was 70-74%. The mechanical strength and density of the adsorbents did not change up to high degrees of
combustion loss (Table 2).
Experimental isotherms of adsorption of benzene vapors at 20°C on a vacuum microbalance were made to
characterize the pore structure and they were used to calculate the pore parameters of the adsorbents [5]. The
isotherms were processed with the Kiselev method to calculate the specific micro- and mesopores
volumes [6]. The parameters of the microporous structure were calculated with Dubinin’s theory of volume
filling [7].
Table 2
Adsorbent with degree of combustion loss, %

Indexes
0 56 (Sample 1) 70 (Sample 2)
С:Н (atomic) 5.52 7.35 7.95
Content, wt. %
heteroatoms 8.7 12.56 12.9
ash 3.4 5.8 8.5
Density, g/cm3 0.77 0.5 0.41
Total pore volume, cm3/g 0.26 0.71 1.13
Volume, cm3/cm3
micropores 0.01 0.14 0.22
mesopores 0.04 0.14 0.2
macropores 0.21 0.29 0.32
Specific surface area of mesopores, m2/g – 105 167
423
Table 3
Sorption capacity, mg/g Ag
Sorption selectivity
time, h Au Ag Cu Zn Ni Co total coefficient,
%
Adsorbent
Sample 1 (see Table 2)
2 0.7 0.32 5.5 0 0 0.05 6.57 5.25
4 0.31 0.42 8.5 0 0 0.10 9.33 4.5
8 0.42 0.55 14.5 11.5 0 0.25 27.22 2.02
12 0.6 0.68 23 18 0 0.3 42.58 1.6
24 0.96 0.84 23 20 0 0.3 45.1 1.87
48 1.08 1.06 23 24 0.03 0.36 49.53 2.1
72 1.25 1.11 25.5 27 0.03 0.4 55.29 2.1
96 1.51 1.17 28.5 29.5 0.05 0.44 61.17 1.91
120 1.64 1.29 28.5 35.5 0.05 0.44 67.42 1.91
Sample 2 (see Table 2)
2 0.17 0.36 5.5 4 0 0 10.03 3.49
4 0.32 0.52 9.5 7.5 0 0.05 17.89 2.9
8 0.58 0.77 9.5 16 0.2 0.3 27.35 2.81
12 0.76 0.84 12.5 22.5 0.24 0.35 37.19 2.25
24 1.13 0.95 13 24.5 0.27 0.35 40.2 2.3
48 1.13 0.97 16 24.5 0.27 0.35 43.22 2.2
72 1.5 1.07 16.5 26 0.27 0.39 45.73 2.2
96 1.66 1.08 16.5 28.5 0.3 0.3 51.83 2.2
120 1.86 1.77 16.8 29 0.33 0.32 50.08 3.55
SKT*
120 1.58 0.83 24.5 17.5 0.06 0.45 44.92 1.85
Norit**
120 1.46 0.86 19 44 0.4 0.6 66.32 1.29
Futamura**
120 1.97 1.22 26.5 33.5 0.18 0.5 63.87 1.91
Note. *Domestic
**Foreign.
Using semicoke makes it possible to use an important amount of petroleum feedstock for making the
adsorbents. Addition of shale phenols causes development of a microporous structure [8]. An important advantage
of asphaltite semicoke adsorbents is the low ash content. A characteristic feature is the significant development
424
of a mesoporous structure, which is not observed when asphaltites themselves and feedstock of another type are
used.
The microporosity and sorption characteristics increase with an increase in the degree of activation
(combustion loss). The high heteroatom content in the adsorbents obtained ensured their high surface polarity.
Solutions of complex salt composition, mg/dm 3: 0.01 Au, 0.9 Ag, 63.2 Cu, 55.8 Zn, 0.48 Ni, 0.33 Co,
obtained from a gold mining plant were used to study* the sorption characteristics. The content of metals in the
solutions was determined by atomic-absorption spectrophotometry on a Perkin – Elmer Mod. 503 instrument.
The sorption characteristics of the adsorbents were evaluated by the method of constant concentrations
of the salt composition (changing the solution) [9]. The selectivity coefficient with respect to silver was determined
as the mass fraction of silver absorbed by the adsorbent to the sum of all metals sorbed in the form of cyanide
complexes (Table 3).
The experiments showed that in the presence of all metals listed, the adsorbents were more rapidly saturated
with dicyanoaurates, even at an extremely low content of them in the initial solution. The sorption rate of
dicyanoargentate was also very high. The kinetic activity of the silver complex is probably based on the smaller
size of the silver ion. According to the data in Table 3, adsorbents with the optimum ratio of pore volumes of
different types and the highest heteroatom content exhibited the highest selectivity for silver.
The high sorption capacity and selectivity of the semicoke adsorbents are due to a specific feature of the
initial feedstock. The unordered structure of semicokes, the important content of heterorganic compounds and
metals of variable valence (especially vanadium and nickel) cause the formation of functional groups during high-
temperature self-catalyzed oxidation of functional groups with no special oxidation stage.
Functional groups can be formed due to the stable radicals initially present in the feedstock; the radicals
formed during splitting of alkyl substituents; the reactive sites formed during dehydrogenation of alicyclic
fragments; the unsubstituted and spatially accessible positions in aromatic and heterocyclic rings. It is necessary
to consider the presence of easily oxidized sulfur-containing fragments capable of forming strongly and weakly
acid groups in oxidation.
As a result of oxidation of nitrogen-containing cyclic compounds in the overall highly condensed system,
the adsorbents acquire the properties of weak amphoteric ion exchangers. The static exchange capacity of the is
0.1-0.4 meq/g. The oxygen-containing acid and basic nitrogen-containing functional groups with unshared electron
pairs participate in the overall system of conjugation of the p-electron cloud of the graphite-like aromatic plates
by intensifying the micropore adsorption field.
The adsorbents obtained with asphaltite semicoke are thus characterized by better sorption capacity and
selectivity in extraction of silver from solutions of complex salt composition in comparison to the best industrial
adsorbents – domestic SKT and foreign Norit and Futamura.
REFERENCES
1. B. V. Polat, V. N. Zaitseva, and A. G. Romanchenko, Methods of Extracting Precious Metals from Solutions
and Wastewaters [in Russian], TsNIIEITsM, Moscow (1983).
2. Yu. V. Pokonova and Dzh. Speit, Use of Petroleum Residues [in Russian], IK Sintez, St. Petersburg (1992).
3. Yu. V. Pokonova, Petroleum Residues [in Russian], IK Sintez, St. Petersburg (2004).
4. Yu. V. Pokonova, Petroleum and Petroleum Products [in Russian], Professional, St. Petersburg (2003).
*A. I. Grabovskii participated in the studies.
425
5. S. J. Gregg and K. S. W. Sing, Adsorption, Surface Area and Porosity, 2 nd ed, Academic Press, London
(1982).
6. A. V. Kiselev, Usp. Khim., 44, No. 5, 367 (1975).
7. Yu. V. Pokonova and V. S. Fainberg, Shale Chemistry. Scientific and Technical Results. Organic Substances
Technology Series [in Russian], Vol. 10, Izd. AN SSSR, Moscow (1985).
8. M. M. Dubinin, Adsorption, Specific Surface Area, Porosity [in Russian], Khimiya, Moscow (1972).
9. Yu. V. Pokonova and A. I. Grabovskii, Tsvetn. Metally, No. 1, 33 (1998).
426
METHODS OF ANALYSIS
A DEVICE FOR FAST QUALITY CONTROL OF OILS
E. V. Shatokhina UDC 681.2:681.518.52:665.7
The results of fast quality control of oils by nonstandard methods are reported. The possibility of
developing methods of determining the basic indexes of oils – the dielectric loss tangent, the base
number based on the measured dielectric constant, and the resistivity – is examined. Motor oils from
different manufacturers have different dielectric constants, which allows identifying the manufacturing
company.
Dielcometric methods of analysis have traditionally been used for measuring the water content in fuels
and oils. The fundamental quality indexes can be determined with the dielectric constant and resistivity of motor,
industrial, and transformer oils: degree of purity, base number, dielectric loss tangent, and breakdown voltage.
Regular checking of the degree of purity of an oil is necessary to determine when the oil should be
changed. This is especially pressing in use of units equipped with expensive engines. This index can be estimated
with the results of measuring the dielectric constant of oils with different degrees of contamination.
Measuring the resistivity of petroleum products, especially contaminated fuels and oils, for quality control,
is also of practical interest.
The results of measuring the dielectric constant ε and resistivity ρ ν of clean and incompletely
treated I-20 industrial base oil in a SHATOX SX-300 instrument are reported in Table 1.
The higher the degree of treatment of the oil, the lower the values of its ε and the higher ρ ν are. These
dependences can be the basis for developing an instrument for monitoring the degree of cleanness of oil using the
dielectric constant and resistivity.
Let us consider similar data for some other oils (Table 2).
____________________________________________________________________________________________________
Institute of Monitoring of Climatic and Ecological Systems, Tomsk. Translated from Khimiya i

Table 1
I-20 oil with a degree of cleanness
ε ρν, МΩ·m
of, %
100 2.282 637 200
99.7 2.309 159 300
99.06 2.324 5310
98.8 2.336 4248
98.6 2.345 3839
98.36 2.356 3345
98.23 2.361 2867
97.06 2.418 797
Table 2
Oil ε ρν, МΩ·m
Synthetic Castrol 5W-40 2.244 1487
Industrial
dirty 2.361 1871
obtained in hydrocracking (Angara OR) 2.162 637 200
SАЕ-10 2.280 7222
М8G2 2.308 117
LUKOIL-Standard 2.292 945
M10G2 (Permnefteorgsintez Co.) 2.355 1009
Visco 3000 2.305 181
Residual oil component (Permnefteorgsintez Co.) 2.376 57 598
Dirty motor 2.4115 80
Transformer
tgd = 0.1% at 20°С, U = 60 kV 2.163 584 100
tgd = 17.14% at 20°С, U = 55 kV 2.270 31 860
Transformer oils are oxidized when used for a long time, and this worsens their performance properties. In
this case, the dielectric loss tangent tan δ , which increases when the oil becomes conducting with a simultaneous
decrease in breakdown voltage U to an unacceptable value, must be monitored.
As Table 2 shows, these changes affect the dielectric constant ε and resistivity ρ ν . With an increase
in tan δ , the value of ε increases, while the value of ρν decreases. It also follows from Table 2 that clean base motor
oil can be distinguished from dirty oil based onρ ν .
In comparing the results of measurement of the dielectric constant and resistivity of motor oils with the
manufacturers’ data (Table 3), the dependence of rn on the presence of detergents in the oil, established with the
base number (BN), and consequently the possibility of determining the BN of the motor oil and the manufacturer
was revealed.
The regression was calculated based on generalization of the results of measuring rn and BN of motor oils
and an equation was derived for calculating the BN:
428
BN = 14.59 − 0.04179 ρν (1)
The dependences of the BN measured with a pH-meter and calculated with Eq. (1) on ρ ν are shown
in Fig. 1. As we see, the calculated indexes differ slightly from the measured indexes, but the curves of the
dependences exhibit a common trend.
As a result of statistical processing of many measurements of the dielectric constant and resistivity of
motor, industrial, and transformer oils entered in a data base, the dependences of these characteristics on the
degree of cleanness for motor, industrial, and transformer oils, the dielectric loss tangent for transformer oils, and
the base number for motor oils were found.
Using these dependences, we built an instrument for fast analysis of the quality of petroleum products
and for conducting analytical measurements in chemmotology.
The instrument for monitoring the degree of cleanness of oils with the values of ε and ρ ν is equipped with
a pickup consisting of a capacitor in the form of two coaxial cylinders in which the oil sample is poured. The
capacitor is located in the circuit of a generator whose measured frequency is a function of the dielectric constant
of the sample.
The dependence of the dielectric constant ε on the frequency f of the pickup (Fig. 2) is described by the
equation:
ε = 4.575 − 3.641 ⋅10 −4 f − 3.3119 ⋅10 −8 f 2
Dielectric spectrometric methods, which consist of feeding an electric signal from an external source to
the sample at a frequency of up to several megahertz, are used for studying the frequency characteristics of liquid
dielectrics.
Table 3
ρν ,
Sample
Base
No.
Manufacturer Grade Type of oil ε number,

МΩ·m
mg KOH/g
1 ZIC SAE 10W40 Synthetic 181 2.207 10.5
2 Castrol SAE 0W40 Same 239 2.211 9.7
3 Hessоl SAE 5W40 Same 58 2.229 10.2
4 Neste Diesel Same 58 2.251 9.3
5 LUKOIL Lux Same 58 2.268 9.09
6 Same Standart Mineral 239 2.273 5.5
7 Same Standart 2 Same 239 2.270 5
8 Consol Standart SAE 10W30 Same 181 2.275 6.5
9 Havoline (Texaco) SAE 15W40 Synthetic 117 2.282 9
10 Visco Visco 3000 Same 58 2.292 10.5
11 Same Visco Diesel Mineral 181 2.305 8
12 LUKOIL M8G2 Same 297 2.308 5
13 Shell Diesel Super Synthetic 58 2.321 11.5
14 LUKOIL M10G2 Mineral 297 2.342 6
429
14
BN, mg KOH/g
10
2
50 100 150 200 250 300
ρν , ΜΩ m
Fig. 1. Base number BN as a function of resistivity ρν : _____: calculated; ——: measured.
2.4
2.2
ε
2.0
1.8
4300 4500 4700 4900 5100
f, Hz
Fig. 2. Dielectric constant ε as a function of natural frequency f of the pickup.
The dependences of the tan δ of the investigated substances on the frequency, caused by orientation
polarization of the polar components of these substances, are the physical basis for using these methods.
The dielectric loss tangent can be calculated with a KUMETR instrument with the equation:*
tan δ = [(Q1 − Q2 ) / Q1Q2 ] [C1 / (C1 − C 2 )]
where Q 1, Q 2 are the Q of the circuit before and after switching on the instrument capacitor; C 1, C2 are the capacitance
of the reference capacitor before and after switching on the instrument capacitor, F.
Direct measurement of tan δ can be conducted with the SHATOX SX-300, which measures rn of petroleum
products up to 200 GW and ε in the range from 2 to 3. The method of determination of tan δ at f = 50 Hz consists
of the following. Two parameters were measured for the same pickup in the form of a cylindrical
capacitor: ε and ρ ν . Then tan δ in the capacitor was calculated with the equation:
tan δ = K / ρν εω (2)
*F. L. Sayakhov et al., Neftepromysl. Delo, No. 4, 20-23 (2001).
430
Table 4
Sample No. ε ρν, MΩ·m tan δ, %*
1 2.18 1062 0.05
2 2.19 637 0.08
3 2.173 531 0.1
4 2.186 425 0.1
5 2.2 372 0.15
6 2.203 345 0.16
7 2.215 152 0.4
8 2.216 74 0.75
Table 2
9 2.276 69 0.8
10 2.285 37 1.4
11 2.293 18 3
12 2.303 17 3.2
13 2.3065 11 5
Note. *Measured at 20°C.
where K is a constant scaling factor; ω = 2πf (f = 50 Hz) is the angular frequency, sec -1 .
Equation (2) was obtained after expressing tan δ in terms of active P a and reactive P r power:
Pa = Pr tan δ = U 2 /R
Pr = U 2 ωC
where U is the voltage on the capacitor, V; R is the resistance of the capacity, Ω; ω is the angular
frequency, sec-1 (GOST 6581–75); C is the capacitance of the capacitor, F.
To determine R and C with the equations
R = ρν d/S
C = ε S/d
ρ ν and ε were measured with the same pickup in the form of a capacitor with plates with area S and
distance d between them.
Scaling factor K in Eq. (2) was tested by calibration with test transformer oils. At a pickup capacitance
of C = 47 πF and angular frequency ω = 314 (at f = 50 Hz), K = 7300 and Eq. (2) becomes:
tan δ = 7300 / R ⋅ 314ε = 23.25 / R ε
where tan δ is in % and R is in GΩ.
431
Table 5
Sample No. ε tan δ, % Sample No. ρν, MΩ·m tan δ, %

1 2.16 0.05 12 133 37
2 2.17 0.062 13 143 35
3 2.18 0.09 14 159 32
4 2.19 0.102 15 170 28
5 2.21 0.2 16 186 26
6 2.22 0.26 17 196 22
7 2.23 0.33 18 212 18
8 2.24 0.41 19 223 16
9 2.25 0.7 20 239 12
10 2.26 1.9 21 250 9
11 2.27 2.5 22 265 5
The loss tangent was determined at different temperatures: from 20 to 90°C. It increased by ~15 times
with an increase in the temperature in this range. Knowing this, the fast analysis can be performed at room
temperature and the loss tangent can be estimated at 90°C. Using Eq. (3), tan δ is calculated at room temperature.
The results of the measurements of tan δ as a function of ε and rn for transformer oils are reported
in Table 4.
The dependences of tan δ on the dielectric constant ε and resistivity rn were derived as a result of
processing a large number of results of measurements of tan ä and used in developing an instrument for quality
control of oils.
At low values of tan ä, a simplified version of calculating it with the dielectric constant is possible, and at
high values, it can be calculated with the resistivity (Table 5).
The conductivity of motor oils is much higher than for transformer and industrial oils. When an engine is
running, particles enter the oil and additionally increase its conductivity. In view of this, the fast method for
estimating the degree of contamination of the oil in the crankcase can be significantly simplified by making the
pickup a contact pickup. In this case, a small amount of oil removed from the motor with a dip stick must be
smeared on the plate, the pickup must be applied to it, and the conductivity must be rapidly measured.
The fast instrument that operates by measuring the dielectric constant and resistivity allows studying the
quality of petroleum products for quality control. It transforms these quantities with a data base into indexes
available to the users of the instruments – the dielectric loss tangent, breakdown voltage, degree of cleanness,
and base number.
432
α-PYRENE IN PETROLEUM WAXES

METHOD OF DETERMINATION OF BENZO-α
G. S. Serkovskaya UDC [543.544:547.814]:665.772
In the 1960s, the waxes used for different purposes in the food industry and medicine contained a large
amount of a carcinogenic hydrocarbon – benzo-α-pyrene (BP). Its content in such waxes was simply determined.
The wax investigated was briefly drenched with n-octane, which extracted the BP. The amount of BP was determined
with the quasilinear luminescence spectra on a DFS-12 spectrometer.
As a result of improved wax production technology, the BP content was reduced significantly, and it
became impossible to determine it by the simple method. For this reason, a method using chromatography conducted
with two columns and plates was developed.
The first column 1 m long and 1 cm in diameter was heated. Water circulated in its jacket at a temperature
of 100°C. The temperature and circulation of the water was maintained with a thermostat. The column was packed
w i t h f i n e - p o r e g r a n u l a t e d ( 0 . 2 - 1 m m g r a n u l e s i z e ) s i l i c a g e l p r e p a r e d a t 2 0 0 ° C a t Vo s k r e s e n s k i e
Minudobreniya Co. Then 10 g of the wax was applied on the sorbent and eluted with n-octane (25 ml) with a
boiling point of 129°C.
The wax came out of the column first, followed by the n-octane. If the wax contained resins, they came out
with the wax. After the wax and n-octane came out, the column was disconnected from the thermostat and cooled
to room temperature. The BP and contaminants remained in the column.
Then with the sorbent in the column at room temperature, elution was continued with ethyl
ether (50 ml) with a boiling point of 30°C. n-Octane (10 ml) was added to the ethyl ether eluate and the ethyl ether
was naturally evaporated under a hood. The n-octane eluate contained BP, contaminants, and an insignificant
amount of wax. This eluate (10 ml) was applied to the sorbent in the second column.
____________________________________________________________________________________________________
Scientific-Research Institute of Carcinogenesis. N. N. Blokhin Cancer Research Center, Russian Academy
of Medical Sciences. Translated from Khimiya i Tekhnologiya Topliv i Masel, No. 5, pp. 49 – 50,
September – October, 2007.

∅15
100
∅7
300
Fig. 1. Diagram of the second column for chromatographic analysis
The second column 40 cm long consisted of two parts (see Fig. 1): a narrow (30 cm long, mm in diameter)
and a widened part (10 cm long, 15 mm in diameter). The widened part turned into a small balloon at the top.
The narrow part and for a length of 1.5-2 cm the widened part were packed with activated large-pore
granulated (0.2-0.5 mm granule size) silica gel, also fabricated at 200°C at Voskresenskie Minudobreniya Co.
The n-octane eluate from the first column was placed on the sorbent and eluted with petroleum
ether (70-100°C). The first 20 ml of wax-containing eluate obtained was poured off and the next 50 ml of eluate was
evaporated naturally to 2-3 ml under a hood.
A glass plate (9´12 cm) with a loose thin (2 mm thick) layer of neutral aluminum
oxide (TU 6-09-426 – 75, St. Petersburg) was used for thin-layer chromatography. The concentrated eluate from
the second column was placed (0.2 ml) on the plate with a 2-ml pipette. The size of the drops from the pipette
allowed placing the solution in one line on the plate (7-9 drops). The chromatogram was developed
with a 6:1 mixture of petroleum (40-70°C) and ethyl ethers. Without preliminary drying, the plate was divided into
narrow zones 1 cm wide that fluoresced in the ultraviolet beams from a PRK-4 lamp.
434
Table 1
Product Supplier Color BP content, mg/kg
Wax
VN-2 Ufa OR Brown 150
EVP Same Same 67,5
match TU-38 Novo-Yaroslavskiii OR Yellow 30
solid P-2 Same White 20
soft VNII NP Same 15
food-grade Same Same Not detected
YaV-1 wax Novo-Yaroslavskiii OR Dark yellow 50
Medicinal Vaseline Pharmaceutical Administration
Tallin White 0,2
Khabarovsk Same 0,3
The wide fluorescing zone on the plate began from its top end, which the front of the fractionating mixture
of solvents approached, and ended in the middle. It did not separate into distinct bands and ended with lilac
luminescence. BP was usually detected in the lilac luminescence zones and the following band.
For qualitative analysis, the sorbent in each zone was removed into a separate test tube and extracted
once with ethyl ether (1.5-2 ml) by shaking. Then 3 ml of n-octane was added to the same test tubes and they were
shaken. After the aluminum oxide settled, the extract was frozen in liquid nitrogen.
The luminescence spectra were recorded on a DFS-12 spectrometer with a DRSh-500 lamp in
the 402-405 nm region. The sorbents for the zones exhibiting a BP line in the spectra (403 nm) underwent
repeated (8-10 times) extraction with ethyl ether (2 ml each time) until the 403 nm line disappeared in the spectra of
washoffs.
The eluates from the zones of the plate containing BP were poured into one beaker and evaporated
naturally to 4-5 ml under a hood. Quantitative analysis of the extract obtained was conducted on
a DFS-12 spectrometer with the Shpol’skii quasilinear luminescence spectra [1-3] with the addition method. The
instrument was set up against a background created by luminescing contaminants in the investigated
extract [4-6]. The error of spectral determination of the BP content was ±10%. The coefficient of variation in
parallel studies of the same sample did not exceed ±20%.
The results of the studies (see Table 1) indicate a low BP content in modern light waxes.
The background natural level of BP – an indicator of environmental pollution by polycyclic aromatic
hydrocarbons (PAH) – is not a function of anthropogenic sources of carcinogenic PAH and is 3-5 mg/kg. It does
not exceed 5-10 mg/kg of dry matter for soil and 1-5 mg/kg for plants. The synthetic activity of plants and
microorganisms, volcanic activity, and fossil fuels, primarily crude oil, as well as coal and shale, are the basic
natural sources of the background level of BP and other PAH [7].
Light waxes with a low BP content can be used in medicine, the food, match, and other sectors of industry.
REFERENCES
1. E. V. Shpol’skii, A. A. Il’ina, and L. A. Klimova, Dokl. Akad. Nauk SSSR, 87, 935 (1952).
2. E. V. Shpol’skii, Usp. Fiz. Nauk, 71, No. 2, 214 (1960).
435
3. T. A. Teplitskaya, T. A. Alekseeva, and M. M. Val’dman, Atlas of Quasilinear Luminescence Spectra [in
Russian], Izd. MGU, Moscow (1978).
4. R. I. Personov, Zh. Anal. Khim., 17, No. 4, 506 (1962).
5. R. I. Personov, Ibid., 20, No. 10, 1125 (1965).
6. B. Muel and G. Lacroix, Bull. Soc. Chim. France, No. 11-12, 2139-2147 (1960).
7. A. P. Il’nitskii, V. S. Mishchenko, and L. M. Shabad, in: Carcinogens in the Environment [in Russian],
Vol. 2, Gidrometeoizdat, Moscow(1979), pp. 5-10.
436
REVIEWS
PHYSICOCHEMICAL PRINCIPLES OF PREPARATION OF EMULSION FUELS
S. L. Khil’ko and E. V. Titov UDC 611.51.29.23.25
The basic physicochemical principles of preparation of emulsion fuel compositions based on heavy and
extra-heavy crude cuts were analyzed with consideration of the nature and content of the phases
constituting the emulsion, type of chemical additives – emulsifiers and stabilizers, and type of equipment
for production of emulsion fuels.
Heavy and extra-heavy crude oil cuts constitute an important part of oil-refining products [1, 2].
Straight-run atmospheric resids and heavy residues from cracking of petroleum products – cracking atmospheric
resids, are heavy cuts, and vacuum resids are primarily extra-heavy cuts.
The introduction of new technologies in oil refining is aimed at increasing the yield of light and middle
distillates, and this has altered the chemical composition and physicochemical properties of the heavy
cuts [3]. The latter are rich in high-molecular-weight and highly aromatic components, so that their viscosity and
density increase.
The change in the properties of the heavy cuts creates difficulties in using them as fuel. These products
are sprayed much worse by nozzles, since the nozzles are stopped up and coked. In the final analysis, this
decreases the efficiency of boiler units.
The amount of extra-heavy cuts in different crudes ranges from 10 to 35% [1, 2]. These cuts cannot be
directly used as boiler fuel due to the high density and viscosity. The viscosity of vacuum resids is more than ten
times higher than the viscosity of atmospheric resid M-100.
Emulsification with water and chemical additives is one method of utilizing extra-heavy cuts as boiler fuel
and improving the heating properties of heavy cuts.
____________________________________________________________________________________________________
Institute of Physical Organic Chemistry and Carbon Chemistry, National Academy of Sciences of Ukraine.
Translated from Khimiya i Tekhnologiya Topliv i Masel, No. 5, pp. 51 – 56, September – October, 2007.

It is necessary to not only solve industrial-process but also fundamental problems for preparation of
emulsion fuel compositions of optimum composition with given physicochemical properties. Production of
emulsion fuel includes two basic stages: emulsification of the hydrocarbon base with water and stabilization of
the emulsion.
The physicochemical properties are primarily determined by the type of equipment (disperser) used for
preparing it, the type of hydrocarbon base, the nature and ratio of the phases constituting the emulsion, the type
and concentration of chemical additives – emulsifiers and stabilizers, and some other factors, for example, the pH,
concentration of electrolytes, temperature, etc.
Let us examine the basic physicochemical factors that affect the characteristics of production of emulsion
fuel compositions in more detail.
TYPE OF EQUIPMENT
Dispersion is the basic method of making emulsions. The dispersion equipment is selected as a function
of the nature of the liquids being emulsified, the necessity of obtaining emulsion particles of a given size, and the
output. The designs of such equipment can be based on different principles of dispersion, but each one is
characterized by a certain value of the energy that can be expended per unit of initial material.
Colloid mills of different designs [4-8], where emulsification takes place when the liquid is extruded into
the narrow gap between the rotor rotating at a high rate (1000-20,000 rpm) and a stationary stator, are most
frequently used to obtain emulsion fuels. The high rotor rotation rate and small gap between the rotor and the
stator induce high tangential stresses and centrifugal forces which cause the liquid jet to almost instantaneously
break up into drops. Industry has mastered production of colloid mills with output of 1 to 20,000 m 3/h and higher.
The average drop diameter in the emulsions obtained is of the order of 2 mm.
Different kinds of mixers and homogenizers are also used for production of fuel emulsions [9, 10]. Emulsions
with drops with a minimum diameter of 5-10 mm can be obtained in the mixers (propeller, turbine, and others). The
liquid is dispersed in homogenizers by passing it through small holes under high pressure, and the drop size in the
emulsion can attain 1 mm.
Equipment of more complicated design that combines different dispersion principles can be used to obtain
emulsions with particles less than 1 mm in size. They include centrifugal elliptical mills and others (for example,
the AGO and APF designed by the Institute of Solid-State Chemistry and Mechanochemistry, Siberian Branch,
Russian Academy of Sciences), vibrocavitation homogenizers (FCH designed by St. Petersburg State Institute of
Technology), rotor-pulsation equipment (RPE designed by Ekologiya Planety MNVTs, Khar’kov), and others.
Ultrasound is sometimes used to make fuel emulsions [11, 12].
HYDROCARBON BASE
In the case of fuel emulsions, water is one of the phases so that their properties are primarily determined
by the type of hydrocarbon base [13]. Different crude oil refining cuts can be used as the hydrocarbon base,
primarily heavy cuts – atmospheric resids, and extra-heavy cuts – vacuum resids.
Mineral tar and asphalts are used as the hydrocarbon base of natural bitumens [14-16]. So-called
Orimulsions in Venezuela (state of Orinoco) are made on this base. These emulsions have long been successfully
used as boiler fuel in many other countries [17, 18].
The nature of the hydrocarbon base determines the surface tension between phases and the interfacial
viscosity, on which the ability of the base to disperse and form emulsion systems and consequently the
microstructure and properties of these systems are dependent [19-21].
438
The ability to form emulsions is more pronounced for those hydrocarbon bases whose molecules are
characterized by a low degree of condensation and high ratio of acid and basic groups [22].
Resins and asphaltenes are the basic constituents of the extra-heavy cuts [1, 2]. Asphaltenes are the
highest-molecular-weight constituents of crude oil and contain a large quantity of condensed arenes, basically
with nuclei consisting of 10-20 rings. The resins from these cuts are heteroatomic compounds with condensed
arene and cycloalkane rings. The extra-heavy petroleum residues (vacuum resids) have physicochemical properties
(viscosity, density, heat of combustion) similar to bitumens such as mineral tars and asphalts.
For heavy and middle cuts, the degree of condensation of the molecules of the hydrocarbon base is much
less pronounced. For this reason, with all other conditions being equal, these cuts have a greater ability to form
emulsion compositions than extra-heavy cuts.
PHASE RATIO
This factor is important in obtaining emulsions compositions [23]. As a function of the phase ratio,
emulsions of two types can form – oil-in-water and water-in-oil. In oil-in-water emulsions, the more polar liquid
serves as the dispersion medium; this is usually water for fuel emulsions. The oil drops in them are uniformly
distributed in water – the O/W type. In water-in-oil emulsions, the more polar liquid forms the disperse
phase, i.e., the water drops are distributed in the oil – the W/O type.
In certain conditions, so-called multiple (complex) emulsions can be obtained, where the dispersion medium
is partially dispersed in drops of the disperse phase. In this case, an oil-in-water or water-in-oil emulsion including
drops of the multiple emulsion usually exist together. In one case, there are the oil-in-water emulsion and drops of
water in the oil and in water (O/W + W/O/W), and in the other, the water-in-oil emulsion and drops of oil in water
and in oil (W/O + O/W/O) coexist.
The type of emulsion formed in dispersion of two liquids is a function of the ratio of the volumes of the
mixed liquids to a significant degree. The liquid present in a much larger amount usually becomes the dispersion
medium. If the volume content of two liquids is approximately the same, then according to Rebinder [24], emulsions
of both types (oil-in-water and water-in-oil) can simultaneously arise during dispersion, but the one with the
highest resistance to coalescence of the drops and subsequent separation “survives.”
In obtaining fuel emulsions, the water content c w (vol. %) in the system is one of the most important
indexes. In colloidal fuels, it should not exceed 45%, since the fuel will not be combustible with a higher water
content. Many studies [25-27] have shown that the heat of combustion decreases with an increase in the c w in the
colloidal fuel from 2 to 35%, and the volume of combustion products increases.
An increase in the water content in the fuel decreases the adiabatic combustion temperature and decreases
the efficiency (overall) of the boiler unit. It is necessary to increase consumption of the fuel burned in such cases
to maintain the given steam capacity, and this causes the load on the blower and exhaust fan and in many causes,
makes it necessary to change the burner design.
The amount of water in emulsion fuels is a function of the type of hydrocarbon base and problems related
to the consumer properties of the fuel obtained. If heavy petroleum residues (atmospheric resids, heavy atmospheric
resids) are used as the hydrocarbon base, emulsions with a low water content are more suitable, i.e., water-in-oil
emulsions. The amount of water in this case can vary within the limits of 2-25% as a function of the physicochemical
properties (viscosity, density) of the initial fuel [28, 29].
If extra-heavy cuts with high viscosity and density are used as the hydrocarbon base, oil-in-water
emulsions with a water content within the limits of 25-45% are better [30, 31]. In this case, the viscosity of the
extra-heavy cuts decreases significantly, which allows using them as liquid fuel.
439
On industrial scales, it is better to make complex emulsions, i.e., a mixture of different
emulsions: O/W + W/O/W or W/O + O/W/O [23]. This is due to the broader possibilities of regulating the
physicochemical properties of the finished product. However, there are comparatively few studies of the process
of obtaining complex emulsions in the literature on production and use of fuel emulsions. Such emulsions usually
contain 20-30% water [32-34].
In making stable multiple emulsions, the sequence of mixing the components of the system [32] and the
type of chemical additives used [33, 34] play an important role. An important advantage of these emulsions is the
possibility of significantly decreasing the viscosity of the composition in comparison to the viscosity of the
hydrocarbon base at a comparatively low water content.
We i n v e s t i g a t e d t h e p r o p e r t i e s o f e m u l s i o n s f o r m e d b y h e a v y a t m o s p h e r i c r e s i d s e l e c t e d
at Ukrtatneft’ (Kremenchug), water, and SF – a surfactant, as a function of the phase ratio. The physicochemical
properties of the atmospheric resid are reported below:
Density at 20°C, kg/m 3 985

Viscosity at 80°C
nominal [Engler], °E 20.7
2
kinematic, mm /sec 153
plastic, Pa⋅sec 0.21
Temperature, °C
flash point (open cup) 126
solid point 30
Heat of combustion, kJ/kg 9500
Sulfur content, wt. % 4
Ash content, % 0.14
The emulsions were made with a UZDN-A laboratory ultrasound disintegrator at a frequency
of 22 kHz with irradiation of the mixture with ultrasound for 3 min. An anionic surfactant made of sulfohumic acid
salts (sodium and calcium) was used as the chemical additive. The rheological characteristics of the emulsions
were obtained on a RHEOTEST-2 rotary viscometer (cone-plate measurement system) at a temperature of 80°C and
variation of shear rate Ýfrom 180 to 4850 sec -1.
The plastic viscosity was calculated with the dependences of shear stress σ (Pa) on shear
rate ε ′ . The type of emulsion obtained was determined by the microscopic method using water-soluble (methylene
blue) and oil-soluble (Sudan III) dyes [35].
The curves of σ = f( ε ′ ) for flow of the emulsions made from heavy atmospheric resid have a different
character as a function of the water content c w (vol. %) (Fig. 1). The Newtonian character of flow characteristic of
the initial heavy atmospheric resid is preserved for systems with c w of up to 15 vol. %. Increasing the water
content in the emulsion alters the character of flow of the disperse system: in the composition
with c w = 35 vol. %, it clearly becomes pseudoplastic.
The microscopic analysis of the emulsions made from heavy atmospheric resid with a water
content c w from 0 to 60 vol. % showed that the systems with c w of up to 15 vol. % are water-in-oil
emulsions (W/O), systems with c w > 55 vol. % are oil-in-water emulsions (O/W), and compositions
with c w from 15 to 55 vol. % are complex emulsions consisting of oil-in-water or water-in-oil emulsions with
inclusions of drops of multiple emulsions.
440
5000
4000
1
ε ′ , sec -1
3000
2
2000
1000
0 200 400 600

σ, Ра
Fig. 1. Flow curves of heavy atmospheric resid (dashed line) and emulsion compositions
made from it (solid lines) with a water content of: 1) 15 vol. %; 2) 35 vol. %
The dependence of the plastic viscosity of the emulsion compositions on their water content is shown
in Fig. 2. An increase in the water content from 5 to 15 vol. % causes the viscosity of the emulsion to increase
slightly. With a further increase in the water content, the viscosity of the emulsions decreases significantly. A
comparison of the flow curves and viscosity properties of the emulsion compositions with the data from the
microscopic analysis shows that the changes in the rheological properties are due to phase inversion.
This effect is observed at a certain water content in the system. It is due to the appearance of an unstable
state of the system when the emulsion type changes: in going from water-in-oil emulsions to oil-in water emulsions
through a series of intermediate multiple emulsions. The boundaries of these transitions are indicated by the
dotted lines in Fig. 2.
THE NATURE OF THE STABILIZER (EMULSIFIER)

An emulsion is a two-phase system whose disperse phase contains microscopic drops 0.1-100 mm in
diameter. Such systems are thermodynamically unstable because the phase interface has high free energy. When
the drops coalesce, the interface spontaneously decreases, while the emulsification process requires expenditure
of energy.
Three types of breaking of emulsions are distinguished; sedimentation, coalescence, and phase
inversion [23]. In sedimentation, the emulsion is not completely broken: two emulsions are formed, one is rich in
disperse phase (i.e., more concentrated) and the other is rich in dispersion medium. In coalescence, the emulsion
is totally broken and its individual components separate in pure form.
A stage of flocculation, where drops of disperse phase form aggregates that can easily decompose when
gently stirred, precedes complete breaking of an emulsion. During flocculation, the drops approach each other at
a distance corresponding to their potential energy minimum. The drops coalesce when the stable surface layer is
destroyed.
In phase inversion, the type of emulsion changes from W/O to O/W or vice versa. The transitions
between oil-in-water and water-in-oil emulsions take place with a change in the ratio of components (oil – water),
substitution of the SF, a change in the temperature, and other factors [23, 36, 37].
441
0.24
0.20
ηpl , Pa⋅sec 0.16
0.12
W/O W/O+O/W/O O/W+W/O/W O/W
0.08
0 20 40 60
cw, vol. %
Fig. 2. Plastic viscosity η pl and type of emulsions formed from heavy atmospheric resid
as a function of the water content c w in the composition.
Chemical additives – stabilizers and emulsifiers – are used to increase the stability of emulsions. The
relation of the stabilities of oil-in-water and water-in-oil emulsions and consequently also the type of emulsion
formed are determined by the nature of the stabilizer or emulsifier added. Without chemical additives, the stability
of an emulsion is minimal.
Selecting the chemical additives (emulsifiers, stabilizers) that would give emulsion compositions the required
physicochemical properties is an important problem in fuel emulsion production technology. The defined properties
are ensured by addition of SF.
The following basic requirements are imposed on chemical additives. Stabilizers and emulsifiers
must [23]: reduce the surface tension at the interface of two liquid phases; be sufficiently rapidly adsorbed on
drops, creating a thin adsorption layer on the phase boundary, preventing coagulation and coalescence; have a
molecular structure with polar and nonpolar groups; dissolve readily in the dispersion medium; give the emulsion
a defined electrokinetic potential; affect the viscosity of the emulsion; have emulsifying and stabilizing properties,
even at low concentrations; be inexpensive, safe to handle, and nontoxic.
Different types of SF and combinations of SF are used to stabilize fuel emulsions.
Ionogenic SF are used for making stable emulsions from heavy and extra-heavy cuts.
Of the anion-active SF (ASF), the following are most frequently used: Sulfonol, DB wetting
agent [38], alkylbenzene sulfonates [39-41], products of condensation of formaldehyde with sulfonic acids,
lignosulfonates [42, 43], or naphthalene sulfonates [44], products of polyalkylation and hydroxyalkylation of alkyl
and aryl sulfonates [45, 46], fatty acid salts [47], etc.
Of the cation-active SF (CSF), different lower amine salts, imidazoline, diamine [48], alkylbenzyl
alkylamines [49, 50], etc. are cited most frequently in the literature.
442
Nonionogenic SF (NSF). Products based on polyalkylene oxides of high molecular
weight [51-54, etc.] and carboxylic or dicarboxylic acid hydroxy esters [55, 56] are most frequently used.
Water-soluble high-molecular-weight compounds can be used: proteins, cellulose derivatives, starch,
dextrin [57-59], bioemulsifiers [60], and chemical industry wastes [61].
SF composites. Composites of SF of different classes, where a SF of one type plays the role of emulsifier
(disperser) and a SF of another type plays the role of stabilizer, are most effective. Ionogenic SF are most
frequently the dispersers in the composite and nonionogenic SF or polymers are the stabilizers.
As an example, we cite as an example several typical ASF + NSF composites. Some ASF can contain:
more than one component based on products of the reaction of aliphatic aldehydes with alkylnaphthalene
or alkylbenzene sulfonate compounds;
lignosulfonate derivatives;
copolymers of polystyrenesulfonic acids and their salts; copolymers of maleic and/or itaconic anhydrides
and other monomers (mol. wt. of up to 500,000);
salts of sulfuric acid esters and C 4-C 18 alcohols;
alkalyl-, alkenyl- and/or alkylarylsulfonates and their salts;
sulfonates, phosphates, and their salts with alkylene oxide adducts;
sulfosuccinate salts;
alkyldiphenyl resin acid disulfonates and their salts;
saturated and unsaturated C 4-C 18 fatty acids and their salts, and similar compounds;
alkylsalicylic acids and their salts.
The following are usually added to the composite as NSF:
alkylene oxide adducts and compounds with phenol OH groups;
monohydric aliphatic alcohols and/or C 2-C 50 aliphatic amines;
block or “cross-linked” polymers (C 2H 4O) n, (C 3H6O) n, (C 4H8O) n and styrene oxide;
adducts of alkylene oxides and polyhydric alcohols (glycerin, sorbitol, saccharose, polyethylene
glycol) [62-67, etc.].
Other combinations can also be used in making fuel emulsions: CSF + NSF [68, 69]; ASF + polymers
[70, 71]; ASF + NSF + bioemulsifier [72], etc.
To improve the performance properties, in addition to additives that regulate their colloid-chemical
properties, additives that inhibit soot formation and increase the efficiency of combustion, for example, are also
added to emulsion fuels. These additives contain an organic acid with OH and COOH groups, humid acids from
peat or lignite and their salts or derivatives, for example [73].
Emulsion fuel can also contain additives that decrease the corrosiveness and toxicity of the
emulsions [74, 75] and additives that neutralize SO x (desulfurizers) and NOx (denitrifiers) [76].
Combinations of different types of dispersing devices and emulsifier (stabilizer) can be used in preparation
of fuel emulsions with assigned physicochemical properties and other required parameters (average diameter,
degree of homogeneity, specific surface area, etc.) for the disperse phase particles. Each type of chemical additive
has optimum concentrations and durations of homogenization of the system in the concrete dispersing unit for
obtaining an emulsion of defined composition with defined properties.
Stabilized emulsions should be stable for hours, days, or months. The emulsifying agent adsorbed on the
interface forms a molecular barrier between liquids. The emulsifier on one hand reduces the surface tension
between the phases and on the other hand can oppose coalescence of drops. The ability of emulsifiers (stabilizers)
443
to reduce the surface tension and make emulsions stable is primarily determined by the structure of their molecules
and by the reaction energy of these compounds with polar and nonpolar media.
The relative saturation of the SF market makes it possible to select them for each manufacturing process.
This is important not only on the technical but also on the economic level, since both the effectiveness of the
concrete emulsifier and its market cost must be taken into consideration. For this reason, developing methods of
manufacturing new types of cheap SF that are just as effective as the existing industrial analogs is always a
pressing problem.
A method of manufacturing a new kind of anionic SF has been developed at the Institute of Physical
Organic Chemistry and Carbon Chemistry, National Academy of Sciences of Ukraine (Donetsk) – sulfohumic acid
salts. Cheap brown coal (price of approximately $10/ton), with very important reserves in nature, is the feedstock.
We investigated the features of solid-phase synthesis of sodium sulfohumates (incorporation of sulfo groups in
the structure of the humic acid molecules) in vibrating machines designed by VOTUM SIA (Odessa) as a function
of the vibration parameters – frequency, amplitude, vibration acceleration.
The optimum conditions of this mechanochemical process were found and sodium sulfohumates with a
high degree of sulfuration, high yield, and good surface-active properties were made [77-79]. Based on preliminary
estimations the price of this SF could be more than one order of magnitude lower than the price of industrial
synthetic SF from the anionic SF group based on sulfo products – Sulfonol, Dofen, etc. With respect to the
efficacy of the regulating effect, the sulfohumate additives are as good as and in some cases better than the
synthetic analogs in many disperse systems.
Sodium sulfohumates exhibit pronounced plasticizing properties in suspension fuels of different
types [77, 80-82] and the ability to stabilize muds based on bentonite and palygorskite clays [83, 84]. Sulfohumic
acid sodium and calcium salts can be effective emulsifiers and stabilizers for emulsion fuel compositions based on
oil-in-water and water-in-oil emulsions of heavy, extra-heavy, and middle petroleum cuts [85-88].
In addition, sulfohumate additives exhibit high resistance to strong electrolytes and temperature and for
this reason can be used as regulators of the structural and mechanical properties in disperse systems with a high
degree of mineralization and at high temperatures [89-91].
Selecting chemical additives for regulating the physicochemical properties of emulsions is a major problem
in colloidal fuel system production technology. Giving such systems defined properties requires solving a number
of physicochemical and technical problems and considering economic factors.
Three fundamental requirements must be fulfilled for preparing emulsion composites from heavy and
extra-heavy cuts suitable for use as boiler fuel.
• The concentration of the hydrocarbon (combustible) phase must be high – a minimum of 60-65 vol. %.
The physicochemical properties of the system must be close to standard atmospheric resids (for example, to
atmospheric resid M-100 for the viscosity: h pl is a maximum of 1 Pa⋅sec at 80°’C and the shear rate is ~10 sec -1).
• The emulsions obtained must be aggregately and sedimentationally stable, coalescence and separation
must not occur in them, and the particle size must remain constant.
• The emulsions obtained must be resistant to phase inversion.
The difficulty in fulfilling these requirements is that successful fulfillment of each one can lead to the
appearance of impediments to fulfilling the others. For example, increasing the content of the fuel base – extra-
heavy cuts – to 65 vol. % and higher in oil-in-water emulsions causes a sharp increase in the viscosity of the
system and loss of aggregate stability. Ensuring the constancy of the particle size in the emulsions and consequently
the aggregate and sedimentation stability of the system is only possible for a certain combination of the type of
dispersing equipment, type and concentration of SF, phase ratio and nature, etc.
444
As a consequence, the technology for production of emulsion composites based on heavy and
extra-heavy cuts must be developed with consideration of the physicochemical characteristics of production of
the emulsions and use of a comprehensive approach to regulation of their properties.
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