You are on page 1of 89

Chemistry and Technology of Fuels and Oils, Vol. 43, No.

2, 2007

CURRENT PROBLEMS

COMPUTER MODELING AND OPTIMUM INVESTMENT PLANNING


IN OIL REFINING AND PETROCHEMISTRY

N. V. Mostovoi and A. S. Khokhlov UDC 665.6.001.57

The possibility of using the special option of the RPMS 4.9.1 system for optimum investment planning
was demonstrated. This option allows optimizing not only a companys operation but also its structure,
as well as the value of added facilities and the size of investments. An example of preliminary selection
of the version for revamping a conventional oil refinery is given. The basic technical and economic
indexes of the selected design are calculated and its economic efficiency is demonstrated.

Selection of the most economically efficient direction in revamping (modernizing) or constructing oil
refineries or petrochemical plants is a complex problem. The required product assortment of a given quality can be
manufactured from a certain kind of feedstock by using manufacturing processes that differ in complexity, cost,
and economic and other characteristics. It is obviously impossible to find the optimum solution to this problem
based on the empirical experience of specialists in the companies in the sector or planning institutes alone.
Computer modeling methods based on linear programming are actively used in solving such problems.
Use of the Bonner & Moore RPMS 2000 computer system for solving investment planning problems was
communicated previously [1]. The principles of constructing a computer model of a company using this system to
create versions for revamping companies of different structure. By comparing the models of the revamping
versions, the version that allows obtaining the maximum gross profit in consideration of the given restrictions can
be selected: output with respect to crude oil, assortment and quality of commercial products, price of feedstock
and manufactured products, etc.
This method allows selecting the most acceptable version of revamping. However, it did not initially take
into account the amount of investments to revamp existing or construct new plants.

____________________________________________________________________________________________________
Institute of Management Problems, RF Academy of Sciences. Honeywell. Translated from Khimiya i
Tekhnologiya Topliv i Masel, No. 2, pp. 3 6, March April, 2007.

0009-3092/07/43010083 2007 Springer Science+Business Media, Inc. 83


Table 1

Unit Oil refinery (OR) structure according to version


1 2 3 4 5 6 7 8 9 10
AVT + + + + + + + + + +
Hydrotreating of summer-grade diesel + + + + + + + + + +
fuel
Same for winter-grade diesel + + + + + + + + + +
Asphalt + + + + + + + + + +
Hydrotreating of kerosene + + + + + + + + + +
Reforming + + + + - + + + + +
Hydrotreating of catalytic feedstock - + + - + - - + + -
Catalytic cracking of gasoils - + + + + - + + - -
Catalytic cracking of residues + - - - - - - - + +
Desulfurizing of atmospheric resid + - - - - - - - + +
Hydrogen production + + + + + - + - + +
Methyl tert-butyl ether production + + + + + + + + +
Alkylation + + + + + + + + +
Visbreaking - - - - + - + + - +
Hydrocracking + + - + - - + - - +
LS-fining - + + + + - - - + -
Partial oxidation of heavy residues - + - - + - - + - -
with production of hydrogen
Oxygen production - + - - + - - + - -
Gross profit, millions of dollars/year 104 193.7 177.9 258.5 72.7 335.5 235.4 105 321
Capital investments, millions of 420.5 827.2 588.5 681.5 633.7 376.2 444.8 741 603.5
dollars/year
Payback time, years 4.1 4.3 3.3 2.6 8.7 1.12 1.9 7 2

An updated version of the RPMS 4.9 computer system program has been issued in Russia and abroad
under the Honeywell trade name (its Honeywell Process Solution subdivision). This company obtained ownership
of this system by purchasing Bonner & Moore and Petrokom JV.
The RPMS 4.9 system can automatically select the most economically effective structure for a revamped
enterprise in which not only the technical and economic operating indexes but also the size of the investments in
constructing new and expanding existing manufacturing units as a result of optimizing their productivity and
calculating investments are optimized.
The methodology for calculating the size of investments, which varies nonlinearly with a change in the
productivity of the manufacturing unit, was examined in detail in [2]. RPMS has a special FACL table for defining
new processes and their basic parameters: the initial output of each unit, investments for construction with
consideration of general plant facilities (GPF) and tax rates on profits and discounting, property life, process
lifetime, and some others.
The effectiveness of revamping a company is assessed with the results of selecting a model based on the
calculated repayment of investments. Earnings from both introducing new capacities and from the activity of the

84
Table 2

Process Costs, millions of dollars


Optimum
code in
Process capacity, construction
RPMS catalyst total
tons/day
system refinery GPF
Version 7
FCC Catalytic cracking 2.702 63.145 18.651 0.378 82,174
RGH Reforming 534 43.065 12.944 0.083 56,092
ALK Alkylation 144 14.195 4.980 0.034 19,209
H2N Hydrogen production 652 34.920 12.439 0.621 47,980
HCR Hydrocracking (light) 5.919 90.903 33.014 3.423 127,340
VBK Visbreaking 4.414 10.334 3.100 13,434
MTB MTBE production 488 22.072 7.765 0.115 29,953
Total for refinery 278.634 92.894 4.655 376.183
Version 10
RCC Catalytic cracking of atmospheric resid 5.172 114.848 34.074 1.209 150,132
RGH Reforming 944 60.641 18.236 0.147 79,025
ALK Alkylation 194 17.225 6.045 0.046 23,315
H2N Hydrogen production 896 42.985 15.344 0.854 59,182
HCR Hydrocracking (light) 7.766 107.032 39.033 4.491 150,557
VBK Visbreaking 4.414 10.334 3.100 13,434
ARD Hydrotreating of atmospheric resid 3.599 72.511 22.293 1.799 96,604
MTB MTBE production 521 23.026 8.102 0.123 31,251
Total for refinery 448.603 146.228 8.669 603.499

existing enterprise are taken into account. The RPMS system can be used for optimum investment planning not
only in solving problems of revamping existing plants but also in determining the structure of new plants.
In [3], the investment planning capabilities of the RPMS system were utilized for selecting the structure of
a new oil refinery in India. Based on an analysis of the market situation in the region where construction of this
refinery was contemplated and in consideration of the projection for the long-term market prospects for petroleum
products, the structure of the refinery and the assortment and quality of the petroleum products manufactured
there were determined.
Using the RPMS system, twenty versions of the structure of the future refinery were first investigated and
the version that allowed obtaining the maximum gross profit with the minimum payback time was selected.
It should be noted that the RPMS system is especially effective for optimizing investment planning in
construction of new or revamping of existing plants in oil-refineries and petrochemical plants. This is due to the
necessity of simultaneously solving a series of process and economic problems caused, for example, by the market
situation in the region (product assortment), feedstock and product quality requirements determined by state
standards and environmental restrictions, necessity of attaining the highest financial effectiveness of investments,
and flexibility of the companys process scheme which allows varying production according to the changing
market situation.

85
Different crude oil refining schemes, manufacturing processes, and commercial product formulas that
ensure the required quality can be used to solve this problem. In these conditions, it is necessary to select the
most economically effective version from all possible versions that will allow operating in conditions of stiff
competition. The RPMS system and its investment planning module are designed for solving such problems.
As an example, let us consider revamping of an arbitrary oil refinery using this system.
Crude with 45 wt. % light cuts and 2.6% sulfur is processed at the refinery. It contains units for primary
refining of crude, hydrotreating of straight-run kerosene and diesel cuts, and an asphalt unit. The refinery only
makes straight-run naphtha as petrochemical feedstock. Automotive gasoline is not manufactured. The yield of
atmospheric resid is ~50% in crude.
Preliminary development of a strategy for the evolution of the company included an evaluation of its
current state, internal and external market analysis (in the very short term and in the longer term), as well as
manufactured and potential products and finally, based on this analysis, selecting, calculating, and justifying the
optimum structure of the revamped enterprise.
According to the RFP, the company should manufacture: high-quality automotive gasolines that satisfy
the requirements of the Euro-4 standard: A-95 in the maximum possible amount and A-98 a maximum
of 850,000 tons/year; diesel fuel satisfying the requirements of European standard EN 590 minimum
of 0.7 million tons/year; grade 40 atmospheric resid (as fuel for the local heat and electric power plant) maximum
of 1.7 million tons/year.
The physicochemical properties of the petroleum products used in the calculations are reported below.

Naphthas
Content (maximum), wt. %
sulfur 0.003
hydrocarbons
aromatics 30
benzene 1
olefins 14
Saturated vapor pressure (maximum), kPa 60
Diesel Fuels
Flash point (minimum), closed cup, C 55
Cetane number (minimum) 53
Content (maximum), wt. %
sulfur 0.035
aromatic hydrocarbons 11

A daily investment RPMS model of the refinery was constructed for conducting the study and solving the
problem posed. The process data for the manufacturing units yield of products, costs of energy and auxiliary
materials, investments, etc., were taken from the RPMS-system process library and were partially based on licensor
data.
The depreciable life and economic life were set equal to seven years, the discounting factor was set
at 8%, and the arbitrarily fixed outlays, including salaries, some operating expenses, and many indirect expenses
were set at $100,000 a day. The costs for feedstock, products, and utilities were set in USD at the time the model

86
was created. Selection of the manufacturing processes was determined by the performance specifications that
regulate the product assortment and quality.
Ten different refinery structures were examined (Table 1).
The program calculates the gross profit based on feedstock and product costs, energy and materials
costs, tax on profits, and fixed costs and the unit load and product stream movement are optimized so that the
requirements of the commercial product specifications are satisfied.
The effectiveness of the versions of oil refinery structure was compared with respect to the gross profit
and payback time. As Table 1 indicates, versions 7, 8, and 10 are distinguished by the shortest payback time.
Version 6, consisting of adding only a reforming unit to the basic structure, does not guarantee obtaining commercial
products of the given quality.
In this respect, note the models high sensitivity to the level of the requirements imposed on product
quality. For the other versions, the payback time was much longer, basically due to the high cost of the more
exhaustive processes LC-fining or synthesis gas production from petroleum residues. These versions were
subsequently not considered.
The solutions of the investment model for revamping versions 7 and 10 are reported in Table 2. Despite
important differences, both versions provide products that satisfy the revamping performance specifications.
The product yields with versions 7 and 10 and for comparison with version 4, which includes hydrocracking
of LC-fining vacuum resid, are reported in Table 3. The total output of naphthas and diesel fuels is higher in
version 10 than in versions 4 and 7, and the output of atmospheric resid and the sulfur content in the latter are
significantly lower.
It follows from a comparison of refinery revamping versions 7 and 10 (see Table 2) that desulfurizing and
atmospheric resid catalytic units are included in the refinery together with a light hydrocracking unit according to
version 10. The atmospheric resid hydrocracking and hydrotreating units provide additional feedstock resources
for the cat cracker, which in turn increases the yield of naphthas. In addition, the atmospheric resid hydrotreating
unit allows decreasing the sulfur content to 1%.
The RPMS system thus allows selecting the best revamping version from several possible versions based
on a comparative analysis. In the case examined, this concerns versions 7 and 10. The basic processes are
single-pass hydrocracking, catalytic cracking, and the related alkylation, MTBE production, and reforming
processes, i.e., processes that yield low-sulfur naphthas and high-quality middle distillates. The hydrocracking

Table 3

Yield (thousands of tons/year) with version (see Table 1)


Products
4* 7 10*
Liquefied gases 132 123 162
Naphtha petrochemical feedstock 730 834 739
Automotive gasolines 1097 1112 1579
Kerosene 255 235 255
Diesel fuel 2630 2409 2763
Atmospheric resid 1470 1629 699
Other 686 658 803
Total 7000 7000 7000
Note. *Atmospheric resid 40 manufactured according to this version contains 1 wt. % sulfur.

87
unit produces low-sulfur gasoil high-quality feedstock for catalytic cracking and the low-sulfur component of
diesel fuel; the cat cracker produces low-aromatic naphtha, the basic component of commercial gasolines.
In addition, both versions include the relatively inexpensive visbreaking process, which results in
commercial atmospheric resid that satisfies viscosity specifications.
Of the two versions examined, version 7 has the fastest payback time. In version 10, the product assortment
and yield of clear petroleum products are slightly better. This is due to the presence of two relatively expensive
exhaustive processes (hydrotreating and catalytic cracking of atmospheric resid) which is the cause of much
higher investments and payback times, however. As Table 1 shows, the investments in versions 7 and 10 are
respectively $376.2 and $603.5 million and the payback times are 1.1 and 2 years.
Version 7 was selected for a detailed technical and economic analysis. The analysis was conducted with
the investment feasibility study software (TEOINVEST). Some of the required initial data was automatically
imported from the RPMS solution results with the R-VRIV program specially developed by Honeywell. Another
part of the data, including information on liquid assets, investment structure, and some other information on the
company was manually incorporated in the TEOINVEST software.
The basic technical and economic indexes of the investment plan are reported below:

Date plan began May 2006


Projection step, months 12
Depth of projection: number of periods 15
Discount rate, %/year 15
Investment costs, millions of rubles
in fixed assets 10,157
in circulating assets 27.9
Sources of financing, millions of rubles
own funds 10,322
stock investments 0.0
reinvested profits 2165
reinvested depreciation 8157
budgetary stocks and shares 0.0
borrowed funds 775
commercial credits 775
state credits 0.0
Integral effectiveness characteristics
net present value (NPV), millions of rubles
invested capital 3754.7
share capital 4096.4
profitability index (PI) 1.72
payback time,* months 14
internal rate of return (IRR), %/year
invested capital 30.2
share capital 34.4
*With consideration of cash flow discounting.

88
120
100
a
60

20

IRR, %/year
20
80
70 b
50
30
10
10
85 90 95 100 105 110 115
Price, %

Fig. 1. Sensitivity of IRR project to product (a) and crude (b) prices.

The basic plan indexes demonstrate its economic feasibility. The internal rate of return (IRR) for invested
and share capitals are respectively equal to 30.2 and 34.4% and the payback time is slightly more than one year.
The plan is extremely sensitive to the OR product price (see Fig. 1a): an even 10% reduction in product
cost makes it unprofitable. The sensitivity of the plan to the feedstock cost is not as critical (see Fig. 1b).

REFERENCES
1. N. V. Mostovoi and L. V. Sheichenko, Khim. Tekhnol. Topl. Masel, No. 4, 10-11 (1997).
2. V. P. Antonchenkov, Yu. R. Shishorin, and A. P. Molchanov, Ibid., No. 6, 3-36 (2000).
3. S. N. Malti, D. J. Adams, et al., Hydrocarb. Processing, 43 (June, 2001).

89
Chemistry and Technology of Fuels and Oils, Vol. 43, No. 2, 2007

TECHNOLOGY

REVAMPING OF STABILIZED TOWERS ON DIESEL FUEL HYDROTREATING


UNITS

Yu. N. Lebedev, E. V. Karmanov, G. S. Vulisanova, A. Ya. Lozhkin, UDC 665.658.2


M. B. Vikhorev, and A. R. Proleskovskii

Hydrotreating of diesel fuel cuts is one of the largest tonnage processes in oil refining. Typical units for
this process the L-24/6 and L-24/7 were developed by Lengiprogaz at the beginning of the 1960s. The
requirements for the quality of diesel fuel and the equipment in the units have naturally changed significantly
since then, so that revamping these units is a very pressing problem.
One cause of unsatisfactory operation of stabilization towers is insufficiently distinct separation between
the hydrotreated diesel cut and the naphtha cut taken off at the top of the tower. The consequence is a high
naphtha cut end point (above 200C) and loss of part of the diesel cut. To improve the operation of stabilization
towers, it is necessary to increase the efficiency of separation, which is attained by a number of measures:
selection of the optimum process parameters: reflux ratio, hot stream flow, and feed tray number;
replacement of mass-exchange units by more efficient and productive units.
Kedr-89 NPK Co. recently revamped four diesel fuel hydrotreating units at different oil refineries. At two
refineries, in Ryazan and Samara, the clients wanted to keep the tower housing and maximally utilize the existing
equipment. Having a set of modern contact units, Kedr-89 NPK successfully solved the problem.
The process and design parameters of the revamped towers are reported in Table 1.
It was decided to change the feed tray number, increase the furnace power for heating the hot stream, and
replace the existing trays by Kedr-89 NPK centrifugal trays on the LCh-24/6 unit at Ryazan OR to ensure the
required target product quality.
The existing trays were replaced by trapezoidal-valve trays on the LCh-24/7 units at Ryazan OR and
Kuibyshev OR (Samara), where the stabilization towers were of larger diameter and the heating furnace was

____________________________________________________________________________________________________
Kedr-89 NPK OJSC. Translated from Khimiya i Tekhnologiya Topliv i Masel, No. 2, p. 7,
March April, 2007.

90 0009-3092/07/43010090 2007 Springer Science+Business Media, Inc.


Table 1

Unit
LCh 24/6
Indexes LCh 24/7 LCh 24/7 LCh 24/6
Ryazan Oil
Ryazan Oil Kuibyshev Salavat OR
Refinery
Refinery Co OR Co. Co.
(OR) Co
Output of one stabilization block in feedstock, tons/h 137.5 137.5 110 125
Specific output of tower, t/(m2h) 36.19 17.1 17.87 32.9
Excess pressure at top of tower, MPa 0.1 0.1 0.15 0.2
Temperature, C
at top 142 147 155 157
at bottom 280 283 257 283
Thermal load on furnace for heating hot stream, GJ/h 20.53 22.75 22.63 14.46
Tower diameter, mm 1200/2200 2000/3200 1800/2800 1600/2200
Number of trays in tower 20 22 22 20
Trapezoidal
Tray type Centrifugal Trapezoidal valve valve and
centrifugal
Quality of diesel fuel cut
3
Density at 20C, kg/m 831 828 836 830
Flash point (closed cup). C >80 >80 74 78 >62
Quality of naphtha cut
3
Density at 20C, kg/m 764 764 694 714 712
EP, C 170 170 160 170
Note. **Theoretical data.

designed for a thermal load of 16.76-22.63 GJ/h. The stabilization towers on the LCh-24/6 unit at Salavat OR were
totally replaced due to physical wear of their housings and the existing equipment and piping were maximally
preserved.
After revamping, a fixed run of the units was conducted to verify the correspondence of the real operating
indexes of the stabilization towers to the specifications. The results of the run are reported in Table 1. The
hydrotreated diesel fuel cut satisfied the requirements on all parameters and the end point of the naphtha cut did
not exceed 170C when the charge was varied in a wide range. The specific output of the towers with centrifugal
trays was two times higher than with trapezoidal-valve trays.

91
Chemistry and Technology of Fuels and Oils, Vol. 43, No. 2, 2007

ADVANCES IN DEWAXING AND DEOILING TECHNOLOGY

A. V. Vishnevskii, V. P. Kostyuchenko, A. G. Vikhman, UDC 666.637.73+665.637.76


M. E. Tsaplina, A. P. Bronshtein, and A. V. Kotov

Hydrocatalytic processes are playing an increasingly large role in production of petroleum base oils due
to the increase in demand for high-quality lube oils that satisfy API group II and III requirements and to stiffening
of the requirements for limiting atmospheric emissions of the harmful solvents used in traditional technologies.
Increasing the quality of lube oils while simultaneously improving the ecology inevitably involves higher
production costs. New highly efficient technologies and equipment are being developed to reduce product costs,
which determine the competitiveness on the consumer market. The Yutec Technologies Ltd. crystallizer and the
dewaxing technology based on it allow effectively solving this problem.

SITUATION IN THE TECHNOLOGIES MARKET


Selective treatment is either replaced by hydrocracking or is combined with hydrorefining or
hydroconversion of raffinate for organizing development of groups II and III lube oils at newly constructed and
revamped plants [1].
The traditional dewaxing unit using selective solvents (solvent dewaxing) usually remains in the oil block
scheme or is supplemented by the stage of catalytic dewaxing to decrease the solid point of the dewaxed oil after
separation of slack wax. Traditional dewaxing technology has been totally replaced by hydrocatalytic processes
in some refineries.
The active competition between traditional and hydrocatalytic dewaxing methods will undoubtedly continue
in the near future. However, traditional technologies will probably dominate over hydrocatalytic processes in the
foreseeable future. This prediction is based on the following factors:
traditional dewaxing combined with deoiling will allow obtaining petroleum waxes, which are increasingly
in demand;
the slack wax obtained in this process is excellent feedstock for production of ultrahigh-index group III
oils;

____________________________________________________________________________________________________
Yutec Technologies Ltd. Orsknefteorgsintez Co. Petrochem Engineering Co. TNK-VR Management Co.
Translated from Khimiya i Tekhnologiya Topliv i Masel, No. 2, pp. 8 11, March April, 2007.

92 0009-3092/07/43010092 2007 Springer Science+Business Media, Inc.


traditional dewaxing combined with preliminary hydroconversion of raffinate ensures processing of
group II oils;
some special-purpose oils processed by hydrocatalytic dewaxing are inferior to the oils manufactured by
the traditional method;
power consumption and consequently atmospheric emissions of combustion products in hydrocatalytic
dewaxing combined with hydrogen production are higher than for the traditional process;
in contrast to the hydrocatalytic process whose results are mainly a function of the catalyst, the traditional
technology has enormous and to a significant degree unrealized potential for improvement.

METHODS OF CRYSTALLIZATION OF WAX FEEDSTOCK


The effectiveness of traditional dewaxing is primarily a function of the crystallization method used and
the features of its implementation. Three wax crystallization methods are used in industrial conditions: isohydric,
evaporation, and mixing, which differ significantly from each other.
The isohydric method of supersaturating the feedstock mixture is conducted by cooling it through a blind
partition with a liquid or boiling coolant. This method is most popular for dewaxing oils and deoiling slack waxes,
since it allows varying the dilution ratio of the feedstock with the solvent in the optimum range without markedly
affecting the cooling rate and degree of supersaturation of the suspension. Scraping crystallizers of the pipe-in-
pipe type, sometimes called Armstrong Crystallizer or Double-pipe Scraped-surface Exchanger and Chiller in the
literature, are used in the isohydric method.
The evaporation method has very limited use [2]. It is only used in a few lube oil dewaxing units in
propane solution (Propane Autorefrigerant Dewaxing Process). In this method, the suspension is cooled in
propane crystallizers in the form of horizontal containers by evaporation of the solvent in adiabatic conditions in
discontinuous-continuous conditions.
The method of mixing feedstock with a supercooled solvent is used in 17 industrial units operating on
dewaxing and/or dewaxingdeoiling schemes. Mixing takes place in two types of units: with mechanical (Dilchill
Process) [3] and with pneumatic (pulsing crystallizer) [4] mixing of the suspension.
Mixing crystallizers have many advantages over double-pipe crystallizers: simplicity of design, greater
reliability in use, high yield of target products, and lower oil content in slack wax. However, the following
drawbacks prevent their wide use:
the necessity of exhaustively drying the solvent to ensure its supercooling in shell-tube condensers
without fear of ice formation;
relatively high investments and equipment assembly time: in addition to the crystallizer itself, an additional
tank, pumps for transporting the suspension, and a solvent drying and supercooling block are required;
impossibility of use in place of evaporative (ammonia or propane) crystallizers, as well as for propane
dewaxing and for production of waxes by the filter-press method;
insufficient process efficiency in dewaxing highly viscous residual raffinates and deoiling petrolatums;
high power consumption due to the necessity of cooling the superheated raffinate and compensating for
the heat of crystal formation with an excess amount of supercooled solvent.
In other words: the degree of dilution of the feedstock with the solvent in the mixer is higher than in the
double-pipe crystallizer, since this parameter is not selected based on the optimum crystal formation conditions
and filtration of the suspension, but based on the heat balance.

93
Based on the results of the analysis, Yutec Technologies Ltd. concentrated its efforts on perfecting the
most universal method of crystallization the isohydric method and developed a new unit that solves the
problem posed.

BASIC FACTORS AND PROCESS PARAMETERS


One of the main goals of developing a new crystallizer for any substance, including wax, consists of
creating conditions for minimizing the rate of formation of nuclei (nucleation) without markedly reducing the
crystal growth rate. Nucleation and growth of crystals are competing processes and their kinetics differs sharply.
Fractions of a second are required for nucleation, and hours, days, or even months are required for
growing a large and homogeneous crystal. The linear crystal growth rate is extremely low and in crystallization in
the volume of the suspension, is 10 -8 -10-7 m/sec and 10 -7-10 -5 m/sec on a cooling surface.
The nucleation rate is described by the equation [5]:

B0 = KM j A l S b (1)

where B 0 is the number of nuclei formed per unit of volume per unit of time; K is the rate constant,
which is a function of the crystallization temperature and nature of the substance; M is the density of the
suspension; j, l, b are exponents; A is the intensity of mixing (can be evaluated as the peripheral speed of the mixer
or as the ratio of the power P of the mixer to the volume V of the suspension); S = CC* is the degree of
supersaturation; C is the real concentration of the solution; C* is the solubility of the substance at the given
mixture temperature.
The crystal growth rate can be defined as:

G = kS g (2)

where G is the crystal growth rate along the length per unit of time; k is a parameter which is a function of the
temperature, degree of mixing, and nature and purity of the crystallized substance; g is a parameter that characterizes
the substance.
It follows from Eqs. (1) and (2) that any increase in the degree S of supersaturation of the solution or melt
will accelerate nucleation to a greater degree than crystal growth. For this reason, the problem consists of
decreasing this difference or increasing the crystal growth time.
The degree of supersaturation is the most important factor, especially in crystallization of solid wax from
multicomponent petroleum feedstock. For low degrees of supersaturation, the amount of occluded oil and
hydrocarbons with a melting point close to n-alkane decreases in the wax crystal. However, in this case, more time
is required for growing a large and homogeneous crystal.
Another important parameter that can be varied is the intensity A of mixing the suspension. The thickness
of the laminar layer near the surface of the formed crystal is a function of this parameter. Diffusion and incorporation
of the substance in the body of the crystal pass through this layer. The thickness of the laminar layer on an
immobile crystal is usually 20-150 mm, while it approaches zero near the crystal in an intensively mixed
low-viscosity solution.
Extremely intensive mixing of the suspension usually does not increase the growth rate, since it prevents
transport of the nucleus formed to the surface of the previously formed crystal. As a result, the sprayed nuclei

94
become the seeds of new small crystals. In addition, with extreme mixing intensity, the wax crystals can be
destroyed. The microwaxes separated from the residual feedstock are destroyed to a greater degree than macrowaxes
obtained from distillate cuts.
The mixing intensity should be limited by the rate of scraping the wax from the chilled surface. This factor
is frequently underestimated. In fast scraping of the wax layer, the suspension is enriched with an excess amount
of microcrystals which have surface energy and are additional undesirable crystallization centers. However, the
thermal conductivity of the unit decreases when the mixing intensity is insufficient, since the thermal resistance
from the suspension is dominant with respect to the overall thermal conductivity coefficient.
The effectiveness is a no less important characteristic of mixing in crystallization. It is evaluated by the
uniformity of distribution of the solid phase in the bulk of the suspension and is not only a function of the amount
of energy introduced in the system (P/V) but also the geometry of the crystallizer. The ideal geometry of the unit
will level the concentration and temperature gradients over the entire volume of the suspension, which results in
homogeneous crystals of the proper shape.
In developing a crystallizer design, it is necessary to take into account three types of mixing: macro,
micro, and meso. Macromixing concerns the overall circulation of the suspension, micromixing takes place on the
molecular level, and mesomixing occurs at the feedstock feed point. The last type of mixing has a large effect on
the results of crystallization, especially in the first stages of cooling the mixture. Ineffective mesomixing alters the
kinetics of the process toward an increase in the nucleation rate and causes formation of contaminated
heterogeneous nuclei consisting of a mixture of molecules of n-, iso-, and cycloalkanes.
The best results of dewaxing distillate feedstock are usually obtained with no solvent or with minimum
amounts of solvent (separate cooling of feedstock and solvent and mixing them before filtration). However, in
industrial conditions, scraper crystallizers of the double-pipe type do not allow implementing this technology due
to the sharp rise in pressure as the undiluted or weakly diluted suspension is chilled.
For this reason, the incremental dilution procedure is used in practice, where a gradually increasing
amount of solvent is added to the suspension as it cools and thickens. However, the heat transfer coefficient
decreases, which requires an additional cooling surface.

STATEMENT OF THE PROBLEM, STAGES OF DEVELOPMENT AND INTRODUCTION


The arguments presented above allow formulating the basic positions for developing a new high-efficiency
unit for crystallization of wax [6]. Its design should provide for the following crystallization conditions:
minimum degree of supersaturation of the mixture;
maximum crystal growth time;
effective macro-, micro-, and mesomixing;
high heat transfer coefficient;
minimum pressure difference over the chilled mixture.
For solving this problem, Yutec Technologies Ltd. conducted a set of studies on a specially constructed
continuous pilot unit equipped with a model of the new crystallizer in the first stage of development. Based on the
experimental results and subsequent scaling, data were obtained for designing an industrial unit.
The engineering design for the regenerative crystallizer was executed by Petrochem Engineering Co., the
leader in designing nonstandard high-tech equipment for the oil refining and petrochemical industry.
The first industrial unit was manufactured at the UTS-Tuimazykhimmash Co. chemical machine building
plant and was delivered to the platform of Orsk Oil Refinery. Due to the clear organization of the work of the
corresponding plant services, the crystallizer was assembled and connected to the acting unit in a very short time.

95
a b

Fig. 1. Regenerative crystallizers: a) disk; b) double-pipe type.

The crystallizer was started up in hours since principles and solutions that maximally facilitated starting, stopping,
and using the unit, going off line, and optimizing operation over several days after startup were used.
Industrial use of the first regenerative disk crystallizers, with no analog in world practice, began in the
dewaxing unit at Orsknefteorgsintez Co. in December 2005.

CRYSTALLIZER DESIGN AND PRINCIPLE OF OPERATION


The crystallizer (see Fig. 1a) is a horizontal cylindrical apparatus whose volume is divided into separate
sections with cooling disks. A coolant filtrate from the first stage formed in separation of wax crystals from the
liquid phase is fed inside the disks. The suspension moves along the body and passes through all sections of
the apparatus, successively flowing from one section to another along peripheral or central ring gaps. The wax
crystallizes on the surface of the cooling disks and in the volume of each section.
The distance between disks is established so that the required ratio of cooling surface and suspension
volume that allows controlling the degree of supersaturation of the suspension and prevents formation of a
superfluous number of nuclei is attained in each section.
The much larger volume of the housing of the new unit in comparison to the volume in the internal pipes
of the traditional double-pipe crystallizer (see Fig. 1b) ensures a longer residence time of the suspension and
lower crystallization rates: 15-20 deg/h.
Each disk is equipped with a scraper attached to the low-speed horizontal shaft which is driven by a
two-step reducing gear motor. The scrapers remove the wax crystals formed. Formation of the chilled suspension
stream and heat and mass exchange are conducted by movement of the scrapers and paddle mixers and by changing
the movement of the stream inside each section. The overall direction of the coolant stream is organized by
countercurrent movement of the chilled suspension.

96
The high peripheral rotation rate of the scraper (within the acceptable wax scraping frequency) ensures
the necessary degree of mixing and turbulization of the suspension, which causes an important increase in the
heat transfer coefficient in comparison to the value in the existing crystallizer.
The original design of overflows of the suspension from one section to another combined with the low
flow rates of the stream and the pumping effect of the mixers provides for an anomalously low (almost
zero) pressure drop over the housing, even without dilution of the feedstock with the solvent.
The new disk crystallizers with a 34 m2 cooling surface is equivalent to the double-pipe
regenerative crystallizer with a 100 m 2 cooling surface in thermal conductivity. The preliminary dimensions of the
unit are: 1800 mm in diameter, 2600 mm high (from the base of the supports to the upper connecting
pipes), 8200 mm housing length (without the reducing gear motor).

RESULTS OF INDUSTRIAL OPERATION


The important advantages of both the unit itself and the technology used were confirmed during industrial
operation of the new disk crystallizer on the 39-4 unit at Orsknefteorgsintez Co.:
the yield of dewaxed oil increased by 3-4%;
the oil content in slack wax decreased by one-third;
the suspension filtration rate increased by 15-20%;
the number of hot washings of the vacuum filters dropped to once a day;
the amount of solvent circulating in the unit and the load on the refrigerant section decreased;
it became possible to chill the feedstock with minimum dilution with the solvent or with absolutely no
solvent at all;
the pressure difference over the suspension was almost equal to zero;
one low-speed shaft ensured noiseless operation of the crystallizer and eliminated solvent leaks;
the unit does not require hot washing and dried solvent;
the unit operates reliable and is simple to service.
The new Yutec Technologies Ltd. crystallizer can also be successfully used for deoiling slack wax. In this
application, evaporative crystallizers are not required.

REFERENCES
1. A. Yu. Evdokimov, I. G. Fuks, T. N. Shabalina, et al., Lubricant Materials and Environmental Problems [in
Russian], Neft i Gaz, Moscow (2000).
2. Avilino Sequeira, Jr., Lubricant Base Oil and Wax Processing, Marcel Dekker, New York-Basel-Hong
Kong (1994).
3. V. A. Citarella, E. A. Ruibal, and S. Zaczepinski, Refining PTQ, 37-39 (Winter 1999/2000).
4. S. P. Yakovlev, V. A. Zakharov, V. A. Boldinov, et al., Khim. Tekhnol. Topl. Masel, No. 2, 13-15 (2006).
5. W. I. Genck, Chem. Eng., No. 10, 94-100 (1997).
6. A. Vishnevsky, I. Grinberg, and A. Pivovarov, Lubricant World, No. 2, 19-20 (2001).

97
Chemistry and Technology of Fuels and Oils, Vol. 43, No. 2, 2007

EQUIPMENT

PULSING FILTERS IN PRODUCTION OF LUBE OILS AND


WAXES. Prospects for Introduction

S. P. Yakovlev and V. A. Boldinov UDC 665.637.7:66.067.3

Studies on the development and introduction of a dynamic pulsing filter in production of base oils and
solid waxes are continuing. The results of pilot tests of the filter and subsequent calculations
demonstrated the high effectiveness of its addition in separation of wax suspensions.

The results of studies on the development and introduction of new filter equipment for dewaxing and
deoiling processes using selective solvents the dynamic pulsing filter are reported in [1].
The latest results of the study and the previously obtained results in [2-4] were generalized to investigate
operation of the dynamic pulsing filter in the continuous mode.
A diagram of control of the operation of the pulsing filter in the continuous mode is shown in Fig. 1. The
pressure in the filter housing is maintained by regulating the pressure of the compressed inert gas fed into the
buffer tank, which prevents the abrupt fluctuations characteristic of feeding the suspension into the housing
directly by pumping. The degree of thickening of the sediment is regulated with a flow viscometer, since the
dynamic viscosity of the sediment is a function of the concentration of solid phase in it.
The analysis of the previously obtained dependences in [1] showed that separation of a wax suspension
in the pulsing filter operating in the periodic mode can arbitrarily be divided into three stages. The features of
each stage are determined by the degree of thickening of the sediment.
In operation of the filter in the continuous mode, continuous feed of the separated suspension and
continuous takeoff of sediment and filtrate are accompanied by movement of the thickened suspension along the
filtering surface from the site of entry into the filter housing to the site of exit of the sediment (see Fig. 1). In

____________________________________________________________________________________________________
VOSTEK Ltd. Translated from Khimiya i Tekhnologiya Topliv i Masel, No. 2, pp. 12 15,
March April, 2007.

98 0009-3092/07/43010098 2007 Springer Science+Business Media, Inc.


moving along the filtering surface, the suspension is thickened as a result of constant takeoff of filtrate and
undergoes the same changes as in thickening in the periodic mode with no takeoff of sediment.
At certain ratios of the size of the filter cartridge and housing and mixer configuration and rotation rate,
the conditions of movement of the thickened stream in the space between housing and cartridge approach the
conditions of ideal displacement. In this case, thickening of the suspension divided into three stages in the
periodic filter can be represented as occurring in three zones positioned along the filtering surface of the cartridge.
Zone A. Thickening of the suspension from initial concentration of solid phase of 2-8% to 17-20%.
The suspension thickens in this zone at a high filtration rate. The filtering surface is basically regenerated by
pulsation. The mechanical effect of the mixer provides for mixing of the thickened mass between the wall of the
unit and the filtering surface, i.e., in the ring-shaped gap between filter cartridge and housing. The concentration
of solid phase in the cross section of the filter is averaged as a result.
Zone B. Thickening of the suspension from a concentration of solid phase of 17-20% to 30-35% at a
14-17% higher filtration rate. In this zone, the suspension acquires pronounced non-Newtonian properties. The
filtering surface is regenerated by pulsation with the increasing effect of the mechanical action of the mixer
paddles, which also increases the filtration rate.

2
1

4
II
I
3 5

IV

III 7

Fig. 1. Diagram of insertion of the pulsing filter: 1, 5) level regulators; 2) feed tank;
3) pressure regulator; 4) pulser; 6) flow regulator; 7) flow viscometer; I) suspension
from pump; II) compressed inert gas; III) solvent for washing; IV) filtrate; V) sediment.

99
Movement of the mixer paddles along the filtering surface at high viscosity of the thickened mass causes
shear stresses to appear in the space between paddles and filtering surface. The boundary layer of sediment is
removed and then mixed with the basic mass of the suspension as a result. The concentration of solid phase in the
cross section is leveled more effectively under the effect of the mixer.
Zone C. Thickening of the suspension from a concentration of solid phase of 30-35% to 40-45%. The
filtration rate decreases in this zone. The effect of the paddles on the sediment is similar to their effect in Zone B.
The high viscosity and pronounced pseudoplastic non-Newtonian properties of the suspension at such
solid phase concentrations cause three-dimensional crystal structures to break down and the included mother
liquor to separate from them under the effect of the shear stresses created by the blades in the bulk of the stream.
This keeps the filtration rate at a relatively high level despite the very low content of liquid phase in the thickened
sediment and the important increase in its viscosity.
It should be noted that in filtration of wax suspensions with no mechanical action on the sediment, the
three-dimensional crystal structures formed are not broken down and concentrations of solid phase in the sediment
greater than 20-25% usually cannot be attained. Separation of the mother liquor included in crystal aggregates
(solution of oil in solvent) additionally incorporated in a significant amount with the washing liquid (fresh solvent)
is ineffective.
In the pulsing filter, breakdown of the crystal structures of the thickened suspension is accompanied by
their compacting under the pressure created by the thickened stream along the filtering surface (similar to the
effect of a piston on the sediment) and simultaneous extrusion of the mother liquor from the intercrystalline space.
In addition, the constant stirring by the mixer prevents structuring of the sediment when the liquid phase is
removed.
In zone A, where the viscosity of the thickened stream is relatively low, intensification of filtration by
mixing basically amounts to removal of the layer of sediment from the region bounded by the filtering partition. In
zones B and C, the mixer paddle transports the highly viscous mass of the thickened stream to the filtering
surface, reducing the distance to the filtering partition surmounted by the liquid phase.
A separated suspension is formed in chilling of the mixture of wax-containing feedstock and solvent. This
process is accompanied by formation of wax crystals and the uncrystallizable part of the feedstock the oil
dissolved in the solvent (mother liquor).
In this case, the suspension a two-phase system consisting of wax crystals and oil solution can be
represented as three basic components: wax crystals (solid phase), oil (substance washed out), and solvent
(washing liquid). The initial separated system is a mixture of wax crystals and oil.

Gw11 Gw12 Gw21 Gw22

Gf xs11f xs12f xs21f xs22f


xs.c.

II
I

Fig. 2. Diagram of inclusion of dynamic pulsing filters in two-stage dewaxing with feed
of solvent for washing sediments: I, II) filtrates from first and second stages; see text
for other designations.

100
A mathematical description of filtration of suspensions in a dynamic pulsing filter was
elaborated previously. A method for calculating the filters and process parameters is proposed based on this
description [2-4].
Two-stage filtration of a wax suspension in continuous pulsing filters with feed of washing liquid (fresh
solvent) into the housings of the filters to a thickened stream of the suspension is examined
below (Fig. 2).
The mathematical description of the process and the computer software can be used to determine the
version of distribution of the washing liquid between filtration stages (G w11 and Gw21) and for washing the thickened
streams (G w12, G w22) to attain the assigned quality of separation of the suspension. The latter is determined in this
case by the yield of dewaxed oil for the minimum required filtering surface.
The following are used as initial data for the calculation (see Fig. 2):
G f consumption of wax-containing petroleum product (feedstock), kg/h;
x s.c concentration of solid phase (crystalline wax), wt. % in feedstock;
x s11f, x s12f, x s21f, x s22f assigned final concentrations of solid phase in sediments at washing liquid (solvent)
feed sites and on going out of filter of the corresponding stage, wt. %;
G w11 , G w12, G w21, G w22 consumption of solvent for washing and repulping sediments, kg/h.
The total consumption of washing liquid should not exceed some maximum value based on the process
parameters of the dewaxing process in using traditional equipment vacuum drum filters.
This method and the corresponding software allow calculating the individual filtration stage without feed
of washing solvent and two-stage separation of a suspension with and without feed of solvent for washing the

Table 1

Version of solvent distribution


Indexes
1 2 3 4
Solvent consumption for washing and repulping sediment,
tons/h
Gw11 29.1 20 29.1 35.9
Gw12 6.8 6.8 0 0
Gw21 7.5 7.5 7.5 7.5
Gw22 4.5 4.5 4.5 4.5
Taken final concentration of solid phase in sediments before
washing begins and on coming out of filter of corresponding
stage, wt. %
s11f 20 20 35 40
s12f 25 25 37 41
s21f 30 30 45 45
s22f 45 45 50 50
Calculated filtering surface, m2
first stage 25.1 22.8 33.1 48.3
second stage 15 15.8 9 7.8
Total filtering surface, m2 40.1 38.6 42.1 56.1
Yield of dewaxed oil, wt. % 77.1 76.5 77.5 77.9
Oil content in second-stage slack wax, wt. % 7.2 8.5 5.4 4.4

101
sediment. The required filtering surface and optimum distribution of the solvent for washing and repulping of
sediments are determined.
The results of calculating two-stage filtration of 420-490C cut raffinate of mixed Western Siberian crudes
with different versions of distribution of the solvent for dilution of the feedstock, washing, and repulping the
first-stage sediment are reported in Table 1 as an example. The output in crude used was G f = 17 tons/h.
The concentration of solid phase (crystalline wax) x s.c = 16 wt. % in feedstock was determined based on
the solubility of the waxes in the separated suspension feedstock solution at the corresponding temperature
and dilution ratio with the solvent, in the given case a mixture of methyl ethyl ketone and toluene in the ratio
of 60:40 vol. %, was determined.
In version 1, the distribution of the solvent for dilution of the feedstock, washing, and repulping of the
first-stage sediment was taken to correspond to the traditional process regime of two-stage dewaxing for the
indicated output with respect to the feedstock. At solvent dilution ratios and washing similar to the traditional
scheme, the calculated yield of dewaxed lube oil was 77 wt. % in feedstock for required filtering surface in the first
and second filtration stages of 25.1 and 15 m 2, respectively.
When the same suspensions of three (four) and two (three) vacuum drum filters with 75 (50) m 2 each,
i.e., with a total filtering surface in the first and second stages of 225 (200) and 150 (150) m 2 were used in the first
and second filtration stages, the yield of dewaxed oil was usually within the limits of 73-75 wt. %.
The increase in the yield of dewaxed oil to 4 wt. % is due to the high degree of thickening of the sediments
an increase in the concentration of solid phase in them, i.e., the parameter that determines the quality of
separation of the suspension (together with the fraction of solid phase entering the filtrate).
In version 2, the amount of solvent fed for dilution of the feedstock decreased by 31%,
i.e., G w11 = 20 tons/h, which insignificantly decreased (in comparison to version 1) the yield of dewaxed oil with all

100 20 10

80 16 9
1
60 12 8

40 8 7

20 4 6

0 0 5
5 10 15 20 25

Fig. 3. Takeoff O of filtrate (curves 1), calculated filtering surface F c (curves 2), and
logarithm of the filtration rate lnw in filtrate (curves 3) as a function of the concentration
x s.c of solid phase in the sediment for the first stage of separation of the suspension on
pulsing filters in dewaxing of 420-490C cut raffinate from mixed West Siberian crudes:
before feeding in washing solvent; after dilution of sediment in
filter.

102
other parameters being the same to 76.5 wt . % at the required filtering surface in the first and second stages
of 22.8 and 15.8 m 2.
In version 3, no solvent for washing the first-stage sediment was fed in with an increase in the degree of
thickening of the sediments: G w12 = 0. The insignificant increase in the yield of dewaxed oil to 77.5 wt. % was
accompanied by an important (to 33.1 m 2) increase in the required filtering surface in the first stage.
In version 4, the first-stage washing solvent (G w12 = 6.8 tons/h) was mixed with the solvent fed in for
diluting the feedstock in preparing the initial feedstock suspension: G w11 + G w12 = 29.1 + 6.8 = 35.9 tons/h. In
addition, the degree of concentration of the sediments increased. This caused an increase in the required filtering
surface in the first stage to 48.3 m 2 with an insignificant (to 77.9 wt. %) increase in the yield of dewaxed oil.
Of the versions examined, the second version, which allows increasing the yield of dewaxed oil
by 5 wt. % at a required filtering surface of 38.6 m 2 and decrease in the overall ratio of solvent to feedstock
by 19%, is thus best.
The dependences of the calculated takeoff of filtrate (determined as the ratio of filtered liquid phase to the
initial amount in the suspension), required surface, and filtration rate (with respect to the liquid phase) in the first
stage on the degree of thickening of the suspension, characterized by the concentration of solid phase in the
sediment, are shown in Fig. 3 for version 1.
In feeding the washing liquid into the filter, the filtration rate increased sharply due to a decrease in the
concentration of wax crystals and the viscosity of the liquid phase: most of the oil had already been taken off with
the filtrate.
After feeding the washing liquid, the relative amount of filtrate taken off did not
exceed 49% for a 25% concentration of solid phase in the sediment, versus 77% at a 20% concentration before
feeding.
These dependences illustrate the dynamics of the change in the filtration characteristics of the suspension
(in separation on dynamic pulsing filters) when the degree of thickening changes, and this can be used to optimize
the distribution of the washing solvent.
The filtration rate (with respect to filtrate) on vacuum drum filters, calculated for the immersed and total
surface area of the drum, is 1.8-2 and 5.4-6 times lower than the average filtration rate in pulsing filters with feed
of washing liquid.
The developed method of calculating filtration in dynamic pulsing filters and the corresponding software
allow operatively finding the process parameters that ensure a given yield of dewaxed lube oil at minimum ratios
of solvent to feedstock and required filtering surface. The generalized results of these studies and the examples
of calculations confirm the promise of introducing pulsing filters in production of waxes and lube oils.

REFERENCES
1. S. P. Yakovlev, V. A. Boldinov, N. M. Shakhova, et al., Khim. Tekhnol. Topl. Masel, No. 6, 17-21 (2005).
2. S. P. Yakovlev, V. A. Sukhov, and Yu. M. Fadeev, Neftepererab. Neftekhim., No. 12, 37-40 (1989).
3. S. P. Yakovlev, V. A. Sukhov, and Yu. A. Chebanov, Ibid., No. 8, 32-34 (1990).
4. S. P. Yakovlev and Yu. A. Chebanov, Ibid., No. 4, 18-21 (1992).

103
Chemistry and Technology of Fuels and Oils, Vol. 43, No. 2, 2007

NEW TECHNOLOGIES FOR MECHANICAL REMOVAL OF COKE DEPOSITS


FROM FURNACE COILS

I. E. Petrukhin UDC 66.041.66.042.947

The method of mechanical cleaning of furnace coils using a plastic scraper (pig element) is widely used by
oil refineries and petrochemical plants worldwide. The basis of the method was elaborated in Canada in 1991. A
pumping unit capable of forcing the plastic scraper inside the pipe with a water stream was constructed by order
of ESSO Oil Co. The unit consisted of high-pressure pumps and powerful electric motors, had very impressive
dimensions, and was installed directly in the ground. Despite the large number of malfunctions and unforeseen
circumstances, the results of the first cleaning were successful. This formed the basis for subsequent improvement
and practical use of the mechanical cleaning method for the inside of pipes to remove coke deposits with plastic
scrapers.
Modern pumping units utilize diesel motors and do not require connection to the oil refinery (OR) power
grid. They have a dual structure that allows doubling output and using the second unit for completing the
operation if the first goes out. Cleaning is under computer control and an official report on the work done is
issued as it is completed.

Fig. 1. Diagram of passage of a plastic scraper through the U-shaped turn of a pipe.

____________________________________________________________________________________________________
CTK-EURO Co. Translated from Khimiya i Tekhnologiya Topliv i Masel, No. 2, pp. 16 17,
March April, 2007.

104 0009-3092/07/43010104 2007 Springer Science+Business Media, Inc.


The official report includes the results of tests for a change in the flow rate inside the pipe before and after
cleaning, all conditions of conducting cleaning, and recommendations for conducting subsequent cleanings.
The principle of mechanical cleaning of furnace coils is very simple at first glance:
the heating sections of the furnace are opened at the OR and all temperature-sensitive elements and
other devices which could interfere in passing the plastic scrapers inside the pipes are removed;
devices for introducing and receiving the plastic scrapers (launchers) are connected to the pipe flanges;
the pumping unit, which creates the required pressure and flow reversal is connected to the launchers.
The entire cleaning process takes 14-18 h on average as a function of the length and degree of coking of
the coil (without counting the time for connecting and disconnecting the unit from the section).
As the work is completed, OR mechanics reassemble and reconnect the sections.
The simplicity of the method, however, is only apparent. When the scraper moves inside the pipe, there
is always the probability of blockage by coke or mechanical damage to the pipe (Fig. 1). There is still
no one opinion about which plastic scraper is more effective and reliable. There are two basic types of
scrapers (Fig. 2): with hard and soft cores.

a b c d

e
Fig. 2. Types of plastic scraper: a) break-through for beginning work; b) hard for
removing solid coke; c) soft for removing soft coke; d) hard for complex work; e) special
(covered by pins over entire surface at 360).

Fig. 3. Computer diagnosis of problem sections of a pipe.

105
Fig. 4. Diagram of passage of the smart pig.

a b
Fig. 5. Inside of a pipe: a) before cleaning; b) after cleaning.

The geometry of application of pins on the surface of the scraper significantly affects the efficacy of
cleaning. This has caused manufacturers to work on creating special plastic scrapers for the different cleaning
stages to use them safely and attain the maximum effect.
Cleaning is thus a complicated and critical process that requires great experience and knowledge.
Smart pig technology, which allows diagnosing the condition of the inside of pipes after cleaning, was
introduced in industry in developing the described technology (Fig. 3).
On completion of mechanical cleaning, a so-called smart pig, equipped with ultrasound sensors which
inspects the entire length of the pipe, is placed in the pipe through launchers. The smart pig is moved by a water
stream created by the same pumping unit used for mechanical cleaning (Fig. 4). The information obtained is
processed by a computer built into the first module and the results are stored in the memory of the smart pig.
After removing the smart pig from the pipe, it is connected to the operators computer and the stored
data are analyzed with special software and displayed on the screen and printed out. The information obtained
gives a detailed picture of the condition of the pipe that can be used to draw conclusions concerning its reliability.
The mechanical cleaning method can thus be supplemented by devices for diagnosing the condition of
the surface of pipes.
The basic advantages of the method for mechanical cleaning of pipes using this technology include:
high efficiency;
important reduction in time: by more than two times in comparison to the steam-burning method;
safety of conducting the operations;
important savings on power consumption;
safety of the cleaning technology for the pipes: no damage;
possibility of removing extraneous objects left in furnace sections by builders and assemblers which
cannot be removed by ordinary methods;
possibility of additionally diagnosing the surface of the pipe with the smart pig;

106
946

Flow rate, litre/minute


757

568
2

379
2
2
189

0
0.7 1.4 2.1

Fig. 6. Diagram of the flow rate inside a pipe at different fed water pressure: 1) before
cleaning, 2) after cleaning.

environmental cleanness.
In Russia, the only company of use in mechanical clean inning of furnace coils in oil refineries and
petrochemical plants using plastic scraper technology is CTK-EURO Co.
In August, 2006, furnace coils in the VA-801 visbreaking unit at TAIF-NK OR were mechanically cleaned
with this method for the first time in our country. The positive results of cleaning (Fig. 5) confirmed the high
efficiency of this method (Fig. 6); the flow rate (passability of the pipe) increased by 35%; the maximum temperature
of the furnace coils when the unit passed into the operating field decreased by 30C.

The details of the cleaning results can be obtained from CTK-EURO Co.:
Tel: (495) 797-6922, 797-6943
Fax: (495) 797-5641
Web site: www.ctkeuro.ru
E-mail: info@ctkeuro.ru
121099, Moscow, Smolenskaya Pl., d. 3, Smolenskii Passazh, 8th floor.

107
Chemistry and Technology of Fuels and Oils, Vol. 43, No. 2, 2007

CHEMMOTOLOGY

MULTIFUNCTIONAL ADDITIVES FOR AUTOMOTIVE GASOLINES

B. Kh. Borzaev, S. A. Karpov, and V. M. Kapustin UDC 665.733

One of the necessary requirements for manufacturers of motor fuels is regulation of the high antiknock
value of gasoline. This is done with modern manufacturing processes with the lowest losses of hydrocarbon
feedstock by converting it into less valuable by-products.
Domestic gasoline manufacturing technologies differ significantly from the foreign technologies. Catalytic
reforming and primary distillation naphtha cuts predominate in domestic gasolines. They have a low fraction of
catalytic naphtha cuts and insignificant alkylate, isomerizate, and oxygenate contents. Large capital investments
are required for converting to production of high-octane gasolines with a significant alkylate and isomerizate
content.
Modern commercial automotive gasolines are usually manufactured by blending components obtained by
primary distillation, thermal cracking, catalytic cracking and reforming, coking, hydrocracking, alkylation,
polymerization, isomerization, and other crude oil refining processes. One of the fundamental indexes that determines
the ratio of components in commercial gasolines is their antiknock value. For this reason, in the present stage of
development of domestic oil refining, antiknock additives antiknocks are currently most widely used to
increase production of high-octane gasolines.
Compositions based on tetraethyl lead (TEL) were previously widely used as antiknocks. However, many
countries have totally prohibited its use. They include Japan, the USA, Austria, Sweden, Belgium, Denmark,
Luxembourg, Finland, Norway, Switzerland, Argentina, Brazil, and others. Searches for additives to eliminate
engine knock have been conducted for more than 70 years. All of the antiknocks used now can be divided into
three basic groups: metal-containing; ashless; oxygenates.

____________________________________________________________________________________________________
I. M. Gubkin Russian State University of Oil and Gas. Translated from Khimiya i Tekhnologiya Topliv i
Masel, No. 2, pp. 18 20, March April, 2007.

108 0009-3092/07/43010108 2007 Springer Science+Business Media, Inc.


Table 1
Oxygenate

sec-butanol
isopropanol

tert-butanol
methanol

MTBE*
ethanol
Indexes

Density at 20, kg/m3 795 790 780 780 802 740


Heat, kJ/kg
heat value 22 707 26 945 33 300 35 590 35 690 38 220
evaporation heat 1104 839 666 536 562 337
Flash point (closed cup),C 6.5 12 13 11 24 28
Octane number
RON 122 121 117 106 108 115
MON 93 97 95 94 91 97
Saturated vapor pressure, kPa 35 17 13 14 9.7 61
Note. * Methyl tert-butyl ether.

The organic compounds of many metals exhibit antiknock properties: lead, potassium, lithium, nickel,
iron, manganese, etc. However, most of these compounds cannot be used as antiknocks due to high toxicity, poor
solubility, and negative effects on fuel or construction materials. Additives based on manganese and iron have
been used most widely. Lithium antiknocks are being investigated in Russia.
Based on concepts of the mechanism of the effect of antiknocks, which decompose hydroperoxides in the
combustion chamber, an antiknock effect was found in existing antioxidants amines and phenols. Aniline was
the first aromatic amine to be used as an antiknock. However, aniline is limitedly soluble in gasoline and in high
concentrations can precipitate into sediment. In view of its not very high antiknock effect, this is an important
drawback. Aniline itself is not used, but its derivatives are used in practice for this reason.
In many countries, including Russia, use of oxygenates is considered a promising direction for increasing
the antiknock value of gasolines. Oxygenates allow conserving crude oil resources for manufacture of commercial
gasoline, reducing the requirements for the octane characteristics of traditional gasoline components, and improving
the environmental characteristics of automobiles.
The physicochemical properties of some oxygenates are reported in Table 1 [1]. These additives have a
high blending octane number, low volatility, minimum carbon formation, and reduced photochemical activity.
When they are present, the completeness of fuel combustion increases, carbon monoxide emissions decrease
by 32.5%, and hydrocarbon emissions decrease by 14.5% as a result. Due to the use of oxygenates, especially
alcohols [2], the environmental and performance properties of gasoline improve and motor fuel reserves are expanded
due to use of nonpetroleum feedstock.
Ethanol is better than methanol as an octane-enhancing additive for gasolines since it is physically more
stable and less toxic and aggressive with respect to industrial rubber parts of the fuel system.
Ethanol-based octane-enhancing additives have been investigated for a long time. An enormous number
of compositions containing ethanol, stabilizers, and corrosion inhibitors together with other antiknocks (for example,

109
MTBE, higher alcohols, aromatic amines, organometallic compounds) as well a detergents, de-icers, and other
components that expand the area of application of octane-enhancing additives, has been patented.
The use of antiknocks based on N-methylaniline [3] and oxygenates such as low-molecular-weight alcohols,
ethers, and blends is well known [4].
Similar additives and fuel compositions based on them have also been patented in Russia [5, 6], although
they were processed a relatively short time ago. Oxygenates combined with amines have a synergistic
effect. For this reason, many of the patented ethanol additives contain N-methylaniline or its homologs or
derivatives [6, 7].
In addition to N-methylaniline and oxygenates, antiknocks also contain stabilizing components, for
example, crotonaldehyde and acetaldehyde and ethyl ether [7]. However, aldehydes and ethyl ether do not provide
for addition of the required stabilizers.
All domestic additives contain watery ethanol which tends to separate at low temperatures
(minus 15 minus 30C) when mixed with gasoline. For this reason, stabilizers are added to the gasoline ethanol
blend to improve its low-temperature properties.
We propose an additive which has higher stability in storage and at low temperatures and improved
antiknock properties while preserving elevated performance properties. It differs from the above additives due to
the higher content of ethanol and acetaldehyde, presence of a 60-200C hydrocarbon fraction, and ratio of
components. If necessary, up to 6 wt. % detergents can be added to it as well.
All components of the proposed additive are industrially manufactured, readily available products. The
additive is manufactured with zero-waste technology. The compositions of samples and results of testing them in
reference fuel a blend of 70 wt. % isooctane and 30 wt. % n-heptane with a set of qualification evaluation
methods are reported in Table 2.

Table 2

Additive sample
Indexes
1 2 3 4 5
Component composition, wt. %
N-methylaniline 6.5 9 12 30 45
tert-butanol 1 0.5 10 5 2
methanol 30 20 15 0.5 12
MTBE 20 20 45 10 10
acetaldehyde 0.7 0.5 0.3 0.5
60-200C hydrocarbon fraction 0.8 1.5 0.8 0.5
AMDOR detergent 5 4.5 6
ethanol Other (to 100)
Gasoline with additive
Concentration of additive, wt. % 7 7 7.5 7.5 8
3
Chemical stability: total content of oxidation products, mg/cm 31.2 33.6 33.8 31.8 32.8
2
Corrosiveness (steel 10), g/m 0.6 0.6 0.5 0.4 0.4
Detergent properties: wetting factor Kwe 84 83 87 76 74
Increase in octane number (MON) 11.8 11 11.2 11.7 10.9

110
Table 3

Alternative antiknock TEL Ferrocene MMCT Amines Oxygenates


TEL + +
Ferrocene +
MMCT + 0
Amines + + + +
Oxygenates + 0 +
Notation. MMCT manganese methylcyclopentadienylcarbonyl; +: synergism; : antagonism;
0: simple summation

The results of the tests confirmed that only a combined acetaldehyde and hydrocarbon fraction content in
the stated ratio (samples 1 and 4) ensure high antiknock properties, improved stability, and elevated performance
properties. Increasing the N-methylaniline content in the additive (sample 5) is not economically advantageous
due to its high cost. In addition, it causes a smaller increase in the octane number even with a high concentration
of the additive.
Many developments concern composite antiknocks containing oxygenates, iron and manganese
compounds, and amines in different combinations. This allows summing the antiknock effect of all components of
the additives and in some cases, obtaining a synergistic effect. The extensive experience with such additives in
Russia indicates the functional compatibility of the components of the additives [3] (Table 3).
The use of composite antiknocks is even advantageous in the case of antagonism of their components,
i.e., when the effect is lower than the overall effect. The number of possible composites is very large, but the same
approaches to them have been created.
Antiknocks, for example, MMCT and N-methylaniline [8] or ferrocene compounds and aromatic amines
and a detergent, Avtomag, for example, are another type of composite. Composites mixed with ethanol are also of
great practical interest.
There is an ashless high-octane additive [9] based on MTBE and containing methanol and N-methylaniline.
However, this additive does not provide gasolines of the required stability during storage and with elevated
anticorrosion properties. The high corrosiveness of gasolines with this additive is due to accumulation of acid
products as a result of oxidative processes initiated by oxygenates.
One way of improving the performance properties of antiknocks is to incorporate nitrogen- and
oxygen-containing compounds in them together with organometallic compounds: iron, manganese, molybdenum,
etc.
For example, there is the additive in [10] containing MTBE, N-methylaniline, a mixture of C 3-C 8 alcohols,
methanol, and an organometallic compound: iron or manganese naphthenate or ferrocene or a mixture of them.
However, this additive is characterized by low effectiveness and high consumption.
An additive composition based on ethanol and containing ferrocene and/or a-hydroxyisopropylferrocene
is reported in [11]. The additive is stabilized with an aldehyde ether alcohol fraction obtained from wastes from
production of ethanol from wood feedstock.
The additive in [12] based on ethanol and N-methylaniline and containing an organometallic compound
has been patented. The drawbacks of this additive are: low stability at low temperatures and during storage and
insufficiently high antiknock and performance properties of the gasolines containing it.

111
112
Table 4

Additive sample
1 2 3 4 5 6 7 8
Component composition, wt. %
N-methylaniline 20 20 25 25 70 20 20 20
acetaldehyde 5 3 4 3 5 3 5
60-200C hydrocarbon fraction 1 1 1.5 1 1 1 1
a-hydroxyisopropylferrocene 0.01 1 0.01 0.01
MMCT 0.5 0.5 0.5
hexacarbonylmolybdenum 0.5
diethyl phthalate 4 3
AMDOR detergent 3 3 5
2,6-di-tert-butyl-4-methylphenol (Ionol) 1.5 1.5
ethanol Other (to 100)
Gasoline with additive
Concentration of additive, wt. % 2 3.5 2 3.5 3 4 3 3
3
Chemical stability: total content of oxidation products, mg/cm 31.8 33.6 35.4 36.2 37.4 33.7 34.2 32.6
2
Corrosiveness (steel 10), g/m 0.5 0.5 2 1.5 0.8 0.4 0.5 0.4
Detergent properties: Kwe 84 86 78 75 73 86 85 88
Increase in octane number (MON)
reference fuel (70:30 9.7 10.8 8.9 10 9.6 11.8 9.8 9.5
straight-run naphtha 12 12.2 10.2 12.3 11.4 13.2 12.2 11.8
We developed an additive based on readily available industrially manufactured products with high antiknock
properties which ensures that the gasolines containing it have improved stability at low temperatures and during
storage.
The proposed additive additionally contains the 60-200C hydrocarbon fraction. The detailed ratio of
components in it ensures improved stabilizing properties. The antioxidant and detergent added to the composition
give the gasolines improved performance and environmental characteristics. This additive is manufactured with
zero-waste technology.
Eight samples of the additive were prepared (Table 4). They were tested in the 40-180C straight-run
naphtha cut and reference fuel, a mixture of 70 wt. % isooctane and 30 wt. % n-heptane.
The results of the tests (see Table 4) confirmed that only a combination of acetaldehyde and the
hydrocarbon fraction (samples 1, 2, 6, 7, 8) in the given ratio ensures high antiknock properties, improved stability
at low temperatures, and elevated performance characteristics.
By using multifunctional additives, the consumer properties of standard fuels can be improved. The
detergent components of the ethanol-based additives can improve their protective, environmental, detergent, and
other properties. In addition, the ethanol-based additives increase the octane number of commercial gasolines.
The proposed additives allow increasing manufacture of high-quality automotive gasolines which will
keep the engine fuel system clean with economical consumption.

REFERENCES
1. S. N. Onoichenko, Use of Oxygenates in Production of Future Automotive Gasolines [in Russian], Tekhnika,
Moscow (2003), p. 5.
2. T. V. Rasskazchikova, V. M. Kapustin, and S. A. Karpov, Khim. Tekhnol. Topl. Masel, No. 4, 3-7 (2004).
3. A. M. Danilov, Use of Additives in Automotive Fuels [in Russian], Khimiya, Moscow (2000), p. 232.
4. E. L. Zakharova, V. E. Emelyanov, F. V. Oktyabrskii, et al., Khim. Tekhnol. Topl. Masel, No. 2, 35-38 (1994).
5. RF Patent No. 2068871, 2186832.
6. RF Patent No. 2078118.
7. RF Patent No. 2148077.
8. RF Patent No. 2161639.
9. RF Patent No. 2139914.
10. Polish Patent No. 108252.
11. RF Patent No. 2129141.
12. RF Patent No. 2161639.

113
Chemistry and Technology of Fuels and Oils, Vol. 43, No. 2, 2007

CLEANING OF USED COMPRESSOR OILS FOR REFRIGERATING MACHINES

V. V. Ostrikov, N. V. Fokina, and N. N. Tupotilov UDC 621.892

Specific requirements caused by the direct contact of oil with the coolant and the constant change in
ambient temperature, pressure, and contamination* are imposed on compressor oils for refrigerating machines.
Mineral and synthetic oils with a low solid point and high chemical stability are usually used in the
compressors of refrigerating machines. The ability to dissolve in coolants and the temperature of deposition of
wax flakes from solutions are important performance properties of these oils. Ammonia is most frequently used as
the coolant. In the conditions of use, it is necessary to monitor the aggressiveness of mixtures of coolant and oil
with respect to metals and other materials.*
XA-30 oils have been the most common. An analysis of samples of these oils from different machines
shows that during use, particulate contaminants, water, and dissolved ammonia are the basic contaminants of the
oil. The oil can be restored to a state corresponding to fresh (commercial) by removing these contaminants.
There is a relatively large number of methods for regenerating compressor oils for refrigerating machines.
One consists of first removing ammonia (coolant) from the used oil, then mixing it and heating it to 855C. The
mixed oil is washed three times with water. The water is added at a temperature no lower than 50C in the amount
of 50% of the weight of the oil. The mixture is stirred and left to settle.
The water-contaminated sludge formed is drained and the treated oil is fed into a furnace where it is
heated to 150C and then goes to an evaporator to remove water vapors. After this, the oil is cooled in a condenser
to 80C, filtered, adsorbed with silica gel to reduce the acid number, filtered, and collected in a container for
storage.

*V. M. Shkolnikov (ed.), Fuels, Lubricants, and Industrial Fluids. A Handbook [in Russian], Tekhinform, Moscow
(1999).

____________________________________________________________________________________________________
All-Russian Scientific-Research and Process-Design Institute on Use of Engineering and Petroleum
Products in Agriculture (VIITiN). Translated from Khimiya i Tekhnologiya Topliv i Masel, No. 2, p. 21,
March April, 2007.

114 0009-3092/07/43010114 2007 Springer Science+Business Media, Inc.


The drawbacks of this method include: great complexity of implementing the manufacturing process;
additional oxidation of the oil on heating to 150C; impossibility of removing iron oxides dissolved in the oil.
The simplified version of this method of treating used oil is conducted at 90-100C with removal of
particulate contaminants, water, and ammonia vapors simultaneously during centrifugation. The quality of the
treated oil is increased.
Used oil contains di- and trivalent iron compounds with predominance of trivalent iron compounds, as the
brownish color of the oil indicates. Iron(II) oxide is not totally precipitated by ammonia. At high concentrations
of NH +4 ions, it even dissolves, which prevents it from precipitating during treatment of the oil to remove iron
compounds.
The iron(II) hydroxide not dissolved in the ammonia medium can form colloidal solutions which also
prevent it from precipitating during treatment of the oil to remove iron compounds.
The aqueous solution of sodium carbonate added to the oil causes formation of iron(II) carbonate, which
is rapidly hydrolyzed and oxidized into iron(III) hydroxide. Iron(III) carbonate is also formed in strong solutions
of sodium carbonate. Iron(III) carbonate and hydroxide rapidly precipitate into sediment which is separated from
the oil by centrifugation on a UOM-3M instrument.
Treatment with this method is conducted as follows. The used oil is heated in a special tank reactor. An
aqueous solution of sodium carbonate is then added. After stirring for 15-30 min, the mixture goes to a reactive
bowl centrifuge to remove both coagulated (enlarged) particles of contaminants and water. The duration of
operation of the centrifuge is 0.5-2 h as a function of the degree of contamination of the oil.
In another simplified method of treating used compressor oils, concentrated hydrochloric acid is used as
the coolant. This method is suitable for treating oil to remove not only products of its aging but also coolant,
ammonia in particular, which has entered it in a relatively high concentration.
As noted previously, the presence of ammonia prevents precipitation of iron hydroxides into the sediment.
By neutralizing the ammonia contaminant in the oil, the acid causes the most frequently encountered contaminants
to be removed by precipitation: iron(III) hydroxide and the iron(III) chloride formed.
The ammonia and iron(III) chlorides formed during the reactions are distinguished by very high adsorptive
power. They absorb other contaminants from the oil and these coagulate into larger particles capable of rapidly
precipitating.
Treatment with this method consists of the following stages:
heating the contaminated compressor oil in a tank reactor;
adding concentrated hydrochloric acid in the amount of 0.2-0.5% (as a function of the degree of
contamination of the oil) while stirring and continuing to stir until floc-like particles of coagulated products
visibly form over the entire volume of the oil;
cooling the mixture by settling and passing the upper settled layer of oil through the UOM-3M to remove
water and contaminant residues.
The treated used XA-30 compressor oil corresponds to fresh (commercial) oil with respect to the
physicochemical properties and is suitable for direct reuse.

115
Chemistry and Technology of Fuels and Oils, Vol. 43, No. 2, 2007

RESEARCH

MONGOLIAN CRUDE FROM TAMSAGBULAG FIELD

B. Davaatseren, A. K. Golovko, and M. Tuyaa UDC 665.7 (517.3)

The physicochemical properties of the crude, its naphtha and diesel cuts, and atmospheric-vacuum
distillation residues were investigated for manufacture of commercial products.

The industrial oil content of sedimentary rock in the territories of East and Southeast Mongolia was
established more than 50 years ago, but the crudes produced as feedstock for refining have almost not been
investigated.
We investigated crude from Tamsagbulag field (well XIX-3) to obtain data on the composition and properties
of its straight-run cuts and whether they satisfy the requirements of the technical conditions for commercial
products.
Tamsagbulag crude lies at a depth of 2300-2600 m (Upper Jurassic). It was investigated by
well-known [1, 2] or standard methods. According to the data obtained (Table 1), it is a heavy, high-solid-point,
high-wax crude. In distillation according to GOST 2177 99, 15% cuts under 200C and 51% cuts under 350C were
obtained.
With respect to the hydrocarbon composition, Tamsagbulag crude is of the methane type [3]. Its naphtha
cuts contain 68.6 wt. % paraffins, 13.9% naphthenes, and 17.5 wt. % aromatic hydrocarbons, and they
contain 26.8% n-paraffins in them and approximately 41.8% isoparaffins. We note that n-paraffins usually dominate
in the naphtha cuts of methane crudes from other oil-bearing regions [3-5].
Of the different hydrocarbons, aromatics have the highest density and paraffins have the lowest density.
Naphthenes occupy an intermediate position. For this reason, cuts with the same initial boiling and end points
obtained from paraffin-base crudes have the lowest density in comparison to similar cuts from naphthene-base
crudes or from crudes with an important aromatic hydrocarbon content [3].

____________________________________________________________________________________________________
Institute of Petroleum Chemistry, Siberian Branch, Russian Academy of Sciences. Translated from Khimiya
i Tekhnologiya Topliv i Masel, No. 2, pp. 24 28, March April, 2007.

116 0009-3092/07/43010116 2007 Springer Science+Business Media, Inc.


Table 1

Indexes Value
3
Density at 20C, kg/m 835.9
Viscosity, mm2/sec
at 20C
at 30C 17.06
at 40C 8.53
at 50C 5.48
Solid point, C
before heat treatment 20
after heat treatment 19
Flash point, C
open cup 22.5
closed cup 21.5
Elemental composition, wt. %
sulfur 0.06
nitrogen 0.14
carbon 86.46
hydrogen 13.28
oxygen 0.06
Molecular weight 295
Content
solid waxes, wt. % 16.87
n- paraffins, wt. % 31.17
particulate contaminants, wt. % 0.007
chlorides, mg/dm3 3.24
Saturation vapor pressure, kPa
at 38 8.8
at 50 12.7
Component content, wt. %
oils 95.07
Silica gel resins 4.67
asphaltenes 0.26
Distilation, vol. %
IBP, 77
under 120 1
under 150 6.5
under 200 15
under 250 24
under 300 36
under 350 51

117
Table 2
Number of carbon atoms in n-alkane molecule n-Alkane content in crude, wt. %
9 2.02
10 1.98
11 1.78
12 1.78
13 1.64
14 1.72
15 1.72
16 1.66
17 1.68
18 1.74
19 1.76
20 1.79
21 1.82
22 1.47
23 1.35
24 0.95
25 0.97
26 0.71
27 0.68
28 0.47
29 0.45
30 0.33
31 0.24
32 0.16
33 0.11
34 0.07
35 0.06
36 0.03
37 0.02
38 0.01
Total 31.17

The investigated crude is characterized by a low resin (4.67 wt. %) and asphaltene content (total
of 0.26 wt. %). The analysis of its elemental composition showed a low sulfur (0.06 wt. %) and
nitrogen (0.14 wt. %) content.
The crude was enriched with n-paraffins: 31.17 wt. % (see Table 1). The study of their molecular-weight
distribution showed (Table 2) that 16.87% are C 17-C 38 hydrocarbons, which are solid at room temperature. Due to
the high n-paraffin content, primarily of high molecular weight, the crude solidifies at 20C, which creates problems
in production, shipment, and refining.

118
Table 3
Refractive
Density at index Viscosity at Sulfur content,
Cut, C Yield, wt. % Solid point, C
20C, kg/m3 20 20C, mm2/sec wt. %
n D
35 40 0.4 655.8 1.3740
40 50 0.39 676.6 1.3902
50 60 0.32 690.6 1.3946
60 70 0.93 704.7 1.3990 0.6398
70 80 1.17 715.2 1.4007 0.6882
80 90 0.77 725.8 1.4048 0.7995
90 100 0.7 728.7 1.4064 0.8482
100 110 0.68 731.7 1.4080 0.9081
110 120 0.99 739.8 1.4107 0.9672
120 130 1.33 748 1.4143 1.0602
130 140 1.39 751.7 1.4172 1.1245 -92
140 150 1.12 755.5 1.4202 1.1772 -80
150 160 3.09 763.4 1.4267 1.3645 -67
160 170 1.97 771.4 1.4312 1.5703 -57.5
170 180 1.27 778.1 1.4345 1.7122 -51
180 190 1.75 784.9 1.4384 1.9217 -43
190 200 1.44 792.7 1.4422 2.1075 -36.5
200 210 1.98 800.6 1.4472 2.3855 -31
210 220 1.29 803.9 1.4491 2.6324 -26.5
220 230 1.38 807.2 1.4508 2.9144 -22.5
230 240 1.43 809.5 1.4521 3.1965 -18.5
240 250 1.84 811.9 1.4532 3.6662 -13
250 260 2.11 813.9 1.4542 4.2259 -7.5
260 270 1.83 816 1.4548 4.7506 -3
270 280 1.97 816.5 1.4552 5.3154 2
280 290 1.99 817 1.4556 6.0706 6
290 300 3.06 820.5 1.4572 7.3567 11
300 310 2.38 824 1.4590 8.4075 15
310 320 1.62 824.7 1.4604 9.4381 19
320 330 1.34 825.5 1.4618 21.5
330 340 3.48 830.1 24.5
340 350 2.74 833.3 27.5
350 360 2.32 836.5 30
360 370 2.78 839.5 32
370 380 2.53 843.3 0.04 34.5
380 390 2.32 847.6 0.05 36.5
390 400 2.64 853.8 0.05 38
400 410 2.62 860.7 0.06 39.5
410 420 2.59 869.4 0.06 41
420 430 2.36 875.2 0.06 42.5
430 440 1.75 879.5 0.06 44
440 450 2.52 886.2 0.06 45
450 460 2.81 892.9 0.06 46.5
>460 20.29 922.4 0.18 37
Losses 2.32

Tamsagbulag field crude, according to the processing classification in [5], belongs to class I (low-sulfur,
sulfur content in cuts, wt. %: IBP-180C naphtha, 0.04; 120-240C jet fuel, 0.07; 240-350C diesel fuel, 0.08),

119
type T2 (content of cuts under 350C, 51 wt. %) and type P 3 (16.87 wt. % content of paraffins with a melting
point of 54.4C).
Several aliquot portions of the crude with takeoff of 10-degree cuts required for compounding into
broader cuts underwent standard distillation on an ARN-2 unit (GOST 11011) to study their commercial properties
by VNII NP methods. In all cases, distillation was halted at a temperature of ~460C at the top of the tower due to
thermal decomposition of the components of the bottoms.
The results of distillation of the crude and the physicochemical properties of the 10-degree cuts are
reported in Table 3. The yield of IBP-200C naphtha cut was 19.71 wt. %, the yield of IBP-350C light cut
was 50.15 wt. %, the yield of >350C atmospheric resid was 47.53 wt. %, and the yield of >460C vacuum resid
was 20.3 wt. %. The density, viscosity at 20C, refractive index nD20 , and solid point of distillates increased with
their cutpoints.
The cuts below 370C contained no sulfur, the sulfur content in the 370-380C cut was 0.04%, it increased
to 0.06% in the 380-390C cut, and remained at the 0.05% level in subsequent distillations. Most of the sulfur
compounds were contained in the vacuum resid: 0.18 wt. %.
Figure 1 shows that their properties uniformly increase with an increase in the cut takeoff temperature.
The curves make it possible to determine the commercial properties of cuts distilling under 460C.
The required blends were prepared from the narrow cuts obtained in distillation and their physicochemical
characteristics were investigated with VNII NP methods [6].
The individual hydrocarbon composition of the IBP-180C naphtha cut is reported in Table 4. The content
of isooctanes, isodecanes, isononanes, n-decane, and n-nonane was greater than the content of other hydrocarbons.
As noted previously, the naphtha cuts of this crude are very rich in aliphatic hydrocarbons, especially
isoparaffins, whose content is almost 1.6 times higher than the n-paraffin content. The domination of hydrocarbons
of iso structure is due to the higher antiknock value of the naphtha cut of Tamsagbulag crude in comparison to

1.47
1.46
1.45 950 n20D
1.44 900 500
20, kg/m3

1.43 450 20
nD20

850
1.42
800
400
0.07
350
t, C

1.41 S 60
1.40 750 300 RBP 0.06
1.39 700 250 40 10 0.05
200 20
cS , %

1.38 9
650 150 0.04
8
20, mm 2/sec

t
t, C

100 0 7 0.03
50 -20 6
0.02
-40 5
20 -60 4 0.01
3
-80 0
2
-100 1
0
0 10 20 30 40 50 60 70 80
Yield, wt. % in crude

Fig. 1. Curve of real boiling points (RBP) and curves of the change in the physicochemical
properties of Tamsagbulag crude cuts distilling under 460C: t cut takeoff temperature;

D refractive index; t s solid point; 20 kinematic


20 density at 20C; n 20
viscosity at 20C; c S sulfur content.

120
these cuts of Jurassic West Siberian crudes. The higher the antiknock value, the higher the quality of the
gasoline [7].
The basic characteristics of the IBP-180C naphtha cut are reported below:

Yield, wt. %, in crude 16.53


Density at 20C, kg/m 3 744.7
Distillation (according to GOST 2177 99), C
IBP 71
10% 107
50% 137
90% 174
EP 195
Sulfur content Abs.
Group hydrocarbon composition, wt. %
n-paraffins 26.8
isoparaffins 41.8
naphthenes 13.9
aromatics 17.5
Octane number (according to data from GLC analysis) 52

The low octane number (52) of the naphtha cut is due to the high n-paraffin content. This cut does not
satisfy the requirements of GOST R 51105 97 for automotive gasolines based on the 10, 50 vol. % distillation
temperatures and initial boiling point, which is due to the content of light cuts. It is almost sulfur-free.
The overhead naphtha cuts are satisfactory as reforming feedstock for production of aromatic
hydrocarbons since they consist by half of isoparaffins and contain almost 27 wt. % n-paraffins. In addition,
the IBP-180C cut can be used as a component of jet fuel or a solvent for the paint and varnish industry.
It follows from these data that high-octane automotive gasoline can be obtained from Tamsagbulag crude
only after catalytic refining of the naphtha cut.
The 140-320 and 180-350C cuts were investigated to assess the possibility of manufacturing diesel fuels.
The physicochemical properties of these cuts are reported in Table 5.
The 140-320 and 180-350C cuts can be considered to satisfy the requirements of GOST 305 82 for
summer and winter diesel fuels with respect to the viscosity, density, closed-cup flash point, sulfur content,
carbon residue of 10% resid, and 50 and 96% distillation temperatures, despite the small differences with respect
to the standard values.
The low sulfur content also results in production of diesel fuels without hydrotreating and additional
refining because of the sulfur content. However, the solid and cloud points of these cuts do not satisfy the
specifications for feedstock for production of diesel fuel.
The cetane index of these cuts is higher than provided in the specifications. It is due to their hydrocarbon
composition. n-Paraffins have a high cetane index. The index increases with an increase in their molecular weight.
However, as the paraffins branch, it decreases. The high flash point of these cuts indicates a deficiency of light
cuts in their composition.
None of these diesel cuts thus satisfy the requirements for both winter and summer fuels with respect to
almost all of the basic parameters. The cuts must undergo partial dewaxing to obtain diesel fuels.

121
Table 4

Hydrocarbons Content in naphtha cut, wt. %


Butanes 0
Isopentanes 0.4
n-Pentane 0.7
Isohexanes 1.1
n-Hexane 2.6
Isoheptanes 3.4
n-Heptane 0.2
Isooctanes 9.3
n-Octane 5.7
Isononanes 8.8
n-Nonane 7.4
Isodecanes 18.8
n-Decane 10.2
Cyclopentane 0.2
Cyclohexane 6.6
Methylcyclohexane 4.8
C8+ Cycloalkanes 2.4
Benzene 0.8
Toluene 1.6
Ethylbenzene 2
p,m-Xylenes 3.8
o-Xylene 1.7
Isopropylbenzene 1.4
Propylbenzene 0.6
Ethyltoluene 2.2
Mesitylene 2
Pseudocumene 1.1
Durene 0.3

Vacuum resids from different takeoff depths above 350, 400, and 460C are characterized by medium
density, high solid point, low sulfur content, and low nominal [Engler] viscosity at 80 and 100C (Table 6). They
satisfy the requirements of GOST 22245 90 for grades BND 200/300, BN 200/300, and BN 130/200 paving asphalts
with respect to the softening and closed-cup flash points [8]. However, their penetration is much higher than the
value provided in the specifications for paving asphalts.
The low ductility and unsatisfactory low-temperature properties of these residues can be corrected by
oxidation during production of asphalts. However, the main impediment to obtaining paving asphalts from
Tamsagbulag crude is its high n-paraffin content. In addition, the content of asphaltenes and resins in these
resids is clearly insufficient for manufacturing quality paving asphalts.

122
Table 5
Diesel fuel cut
Indexes
140 320 180 350
Yield, wt. % 33.54 33.64
Cetane index 59.5 59.8
3
Density at 20, kg/m 800.8 813.4
2
Viscosity at 20, mm /sec 2.98 4.62
Distillation (according to GOST 2177 99),
50 vol. % 250 272
96 vol. % 312 339
Flash point, C 67 88
Solid point, C -1 -0.5
Cloud point, C -9 1.5
Sulfur content, wt. %
total 0.07 0.08
mercaptan abs. abs.
Carbon residue (10% residue), % 0.04 0.13

Table 6
Resid, C
Indexes
>350 >400 >460
Yield, wt. % in crude 47.52 34.94 20.29
3
Density at 20, kg/m 882.7 908.2 922.4
Nominal [Engler] viscosity, E
at 50 6.71 Does not flow
at 80 2.45 4.18 12.93
at 1000 1.75 2.72 6.03
Solid point, C 33 36 37
Flash point (open cup), C 232 280 337
Softening point, C 34 37 28
Penetration at 25C >220 >220 >220
Low heat value, kJ/kg 42 210 42 060 41 950
Ductility at 25C, cm 0 0 0
Content, wt. %
sulfur 0.17 0.18 0.18
resins 6.55 9.87 14.06
asphaltenes 0.5 1.21 2.27

Except for the flash point, these resids are also practically unsuitable for production of
construction (BN 50/50, BN 70/30, BN 90/10) and insulating (BNI-IV-3, BNI-IV, BNI-V) asphalts.

123
Resids above 400 and 460C can be used as boiler fuels (residual fuel oils), as their correspondence to
grades 40 and 100 residual fuel oils for the nominal [Engler] viscosity at 80C indicates [GOST 10585 75). The low
sulfur content in the residues satisfies the stiff requirements imposed on fuels of this type.
Tamsagbulag crude thus cannot be used for production of gasolines, winter and summer diesel fuels, and
construction and paving asphalts without secondary processing and refining of its straight-run cuts.

REFERENCES
1. B. M. Rybak, Analysis of Crude Oils and Petroleum Products [in Russian], Gostoptekhizdat, Moscow
(1962).
2. A. I. Bogomolov, M. B. Temyanko, and L. I. Khotyntsevaya (eds.), Modern Methods of Analysis of Crude
Oils [in Russian], Nedra, Leningrad (1984).
3. Al. A. Petrov, Petroleum Hydrocarbons [in Russian], Nauka, Moscow (1984).
4. Al. A. Petrov, Chemistry of Alkanes [in Russian], Nauka, Moscow (1974).
5. V. F. Kamyanov, Characteristics in the Composition of Naphtha Cuts of Crude Oils and Gas Condensates
[in Russian], Preprint No. 8, TF SO RAN, Tomsk (1985).
6. G. A. Lastovkin, E. D. Radchenko, and M. G. Rudin (eds.), Oil Refiners Handbook [in Russian], Khimiya,
Leningrad (1986).
7. V. M. Shkolnikov (ed.), Handbook of Commercial Petroleum Products, Properties and Use [in Russian],
Khimiya, Moscow (1978).
8. V. M. Shkolnikov (ed.), Handbook of Fuels, Lubricants, and Industrial Fluids: Assortment and Use [in
Russian], Tekhinform, Moscow (1999).

124
Chemistry and Technology of Fuels and Oils, Vol. 43, No. 2, 2007

CHARACTERISTICS OF CRACKING OF KEROSENE GASOIL CUT


AND ATMOSPHERIC RESID BLENDS

Ali Busenna, I. M. Kolesnikov, S. N. Ovcharov, and S. I. Kolesnikov UDC 665.637

Catalytic refining of heavy cuts is an important direction in increasing takeoff of light cuts with an
increase in the total volume of heavy crude produced. The most highly productive of these processes is catalytic
cracking in the continuous-flow or microsecond mode. Atmospheric resid or blends of atmospheric resid and
kerosene gasoil cut or vacuum gasoil in a given ratio can be used as feedstock for such processes.
Not only the process conditions but also the type and chemical composition of the catalyst must be
selected for optimizing catalytic cracking of this feedstock.
Experience in operating a cat cracker shows that zeolite-metallosilicate catalysts, of which
zeolite aluminosilicate catalysts are most widely used, are the most promising for this process. Their stable

Table 1

Chemical composition, wt.

area, m2/g
Density,

Specific
surface
kg/m3

Catalyst
Na2O Al2O3 CaO MgO ZrO2 NaY REEY SiO2

CaSi REEY 0.4 7 11.5 81.1 511 404


MgSi REEY 0.35 8.9 11.6 79.5 557 303
AlSi REEY 0.35 6 12 81.25 655 280
CaSiNaY 0.5 7.3 11.9 80.3 524 241
MgSiNaY 0.5 9.2 10 80.3 586 278
ZrSiNaY 0.4 6.3 11.9 81.4 927 326

____________________________________________________________________________________________________
National University of Hydrocarbons and Chemistry (Boumerds, Algeria). I. M. Gubkin Russian State
University of Oil and Gas. Translated from Khimiya i Tekhnologiya Topliv i Masel, No. 2, pp. 29 31,
March April, 2007.

0009-3092/07/43010125 2007 Springer Science+Business Media, Inc. 125


activity and selectivity are determined by the type, composition, and content of zeolite and the chemical
composition, i.e., the Al 2O 3 :SiO2 ratio, and the texture of the particles of the amorphous aluminosilicate catalyst.
The results of a study of cracking of atmospheric resid and blends with the kerosene gasoil cut on
calcium-, magnesium-, aluminum-, and zirconium-zeolite-silicate catalysts are presented. The kerosene-gasoil
cut distills within the limits of 203-336C; its density at 20C is 862 kg/m 3; the hydrocarbon composition

Table 2

Cracking Yield, wt. %


temperature, cut unsaturated
C HCG coke H2S H2+CH4 iso-C4H10
diesel fuel naphtha hydrocarbons

Catalyst
AlSi REEY
460 33.8 24.2 7.6 8 7.93 19.08 15.28 27.25
480 33.7 25.1 11.1 8.3 7.35 21.39 12.96 30.17
500 31.1 26.5 13.5 8.4 6.69 24.57 8.9 32.67
540 24.5 26.9 14.3 8.8 4.98 31.02 3.55 36.13
CaSi REEY
460 40.5 16.9 7.7 5.9 5.74 13.2 15.06 24.41
480 37.7 20.7 10.3 6.9 5.25 19.48 11.12 27.9
500 35 22.1 12.2 8.1 4.77 23.23 7.28 29.32
540 31.3 19.6 14.7 10.5 2.29 28.43 2.12 35.03
MgSi REEY
460 49.9 17.2 7.6 9.9 11.77 15.53 14.25 25.89
480 47.2 18 8.1 10.1 9.41 19.47 10.95 28.04
500 43 18.5 11.5 10.7 8.14 21.1 8.62 30.36
540 31 19.6 17.6 11.9 6.22 24.96 2.37 34.67
CaSiNaY
460 40.7 12.8 4.5 6.2 6.66 29.55 8.75 25.84
480 39.3 19.5 6.7 6.3 6.32 29.1 6.7 27.69
500 38.9 19.6 8 6.9 6.28 26.83 5.94 32.45
540 36.3 24.7 12.1 8.3 4.29 25.95 3.94 33.45
MgSiNaY
460 50.5 14.5 6.3 8.2 10.2 23.13 8.03 21.58
480 46.5 17.5 8.8 9.2 9.76 29.13 6.88 27.35
500 43.2 20.1 10.9 10.2 9.5 24.79 4.43 31.01
540 37.1 21.4 15.4 10.8 7.63 20.99 2.15 35.29
ZrSiNaY
460 36.2 19.8 7.2 7.4 11.23 15.94 11.95 29.8
480 37.7 21.9 11.7 9.5 10.03 20.02 9.58 30.73
500 37.6 23.5 12.8 11.2 8.96 26.42 6.34 30.92
540 34.2 23.1 15.1 12.5 7.85 32.73 3.49 31.86

126
is, wt. %: 36.6 paraffins, 38.1 naphthenes, 25.3 aromatics. Atmospheric resid from West Siberian crudes distills
within the limits of 93-500C, its density at 20C is 964 kg/m 3, and the sulfur compound content is 2.31 wt. %.
The catalysts were synthesized by the sol-gel method in a continuous-flow unit and was molded into
beads 3-6 mm in diameter. Type NaY and REEY zeolites were added to the metallosilicate hydrosol during its
synthesis. The hydrogel underwent washing, syneresis, activation, drying, and calcination by the standard
method. The atmospheric resid and blends of atmospheric resid and kerosene gasoil cut were cracked in a
continuous-flow unit.
The chemical composition and characterization of the texture of the catalysts are reported in Table 1. The
density of the Zr Si NaY catalyst was highest, which determined its high energy capacity. For this reason, in
going from the cat crackers generator to the reactor, it transfers a larger amount of energy in comparison to other
catalysts.
Before charging in the reactor, the catalyst (100 cm 3) was heated to 550C, and air treated to remove
contaminants and dried was passed through a bed of the catalyst for 3 h after charging. In these conditions, the
surface of the catalyst underwent oxidative treatment to remove sorbed organic contaminants and sorbed moisture
was separated from it. The temperature in the catalyst bed was then decreased to the assigned level.
Atmospheric resid was cracked on the investigated catalysts (see Table 1) at a temperature
of 460-540C and feedstock space velocity of 1 h -1 for 1 h. The results of cracking are reported in Table 2. The
liquid catalyzate was distilled into 200-350C diesel fuel and 200C C 5 naphtha cuts. The hydrocarbon
gases (HCG) obtained in cracking were analyzed chromatographically.
As Table 2 shows, coke was deposited on the catalyst in cracking of atmospheric resid. The yield of
diesel fuel cut and H 2S decreased, and the yield of naphtha cut, HCG, and coke increased with an increase in the
process temperature from 460 to 540C on all catalysts investigated. Of the catalysts containing zeolite REEY, the
highest yield of diesel fuel cut was obtained with the Mg Si REEY catalyst. These catalysts can be ranked in
the following order with respect to the yield of this cut:

Mg Si REEY > Ca Si REEY > Al Si REEY

With respect to the yield of naphtha cut, these catalysts are in the opposite order.
The catalysts containing zeolite NaY are in the following order with respect to the increase in the yield of
diesel fuel cut:

Mg Si NaY > Ca Si NaY > Zr Si NaY

and with respect to the increase in the yield of naphtha cut, in the order:

Zr Si NaY > Ca Si NaY > Mg Si NaY

These data indicate the high selectivity of the synthesized catalysts with respect to the yield of diesel
fuel cut. Their selectivity can be changed by diluting the atmospheric resid in a certain ratio of kerosene gasoil
cut (KGC).
A blend of atmospheric resid and KGC can be cracked in these conditions with a higher yield of
naphtha cut in comparison to the yield of diesel fuel cut. Experiments were conducted on blends

127
Table 3

Cracking Yield, wt. %


temperature, cut unsaturated
C HCG coke H2S H2+CH4 iso-C4H10
diesel fuel naphtha hydrocarbons

Kerosene gasoil cut


4610 30.5 45.6 10.5 1.2 0.09 0.63 39.77 33.75
480 28.8 51.8 12.9 1.3 0.11 2.2 37.96 36.96
500 27.6 48.5 16.6 1.4 0.21 2.96 33.68 40.66
540 27 43.1 18.1 1.9 0.4 5.91 27.88 47.86
Blend of 1 wt. % atmospheric resid with 99 wt . % KGC
460 30.6 46.6 13 1.4 0.56 2.47 32.56 33.56
480 30.3 52.8 15.6 1.5 0.42 2.53 38.19 38.4
500 27.2 50.6 17.6 1.6 0.34 3.97 41.2 42.15
540 24.2 46.7 20.1 2 0.27 6.2 47.57 48
Blend of 10 wt. % atmospheric resid with 90 wt. % KGC
460 30.9 43.9 13.9 1.9 0.74 2.26 36.36 32.35
480 31.9 48.5 15.8 1.9 0.63 3.73 33.2 35.59
500 28.5 48.5 17.7 2.1 0.5 6.43 28.2 40.59
540 25.4 38.6 19.3 2.2 0.33 9.59 21.44 45.73
Blend of 30 wt. % atmospheric resid with 70 wt. % KGC
460 31.9 38.8 14.7 3.9 1.42 4.99 31.7 32.71
480 33.9 42.8 16 4.1 1.41 6.11 29.58 34.85
500 32 41.8 17 4.3 1.38 8.84 24.38 38.9
540 27.1 35.9 18.8 4.7 1.32 13.84 14.81 44.81
Blend of 50 wt. % atmospheric resid with 50 wt. % KGC
460 33.5 36.5 11.5 5.5 3.51 8.65 26.72 30.5
480 36 35.5 13.9 5.6 3.23 10.98 23.82 33.8
500 34 33.6 14.7 5.8 3.03 12.93 19.04 38.52
540 27.9 31.8 17.7 6.1 2.72 19.54 12.01 41.7

containing 1, 10, 30, and 50 wt. % atmospheric resid to investigate the selectivity of the Al Si REEY catalyst.
The results of the experiments are reported in Table 3.
In cracking of KGC on Al Si REEY catalyst at all temperatures, the yield of naphtha cut was ~2 times
higher than the yield of diesel fuel cut. With an increase in the cracking temperature, the yield of naphtha cut
reached the maximum at 480C. This indicates that synthesis of naphtha at lower temperatures predominates over
its decomposition into hydrocarbon gas. At temperatures above 480C, on the contrary, decomposition of naphtha
into hydrocarbon gases predominates.
In cracking of KGC blended with 1 wt. % atmospheric resid, the yield of naphtha cut is higher than in
cracking of KGC alone. The KGC is promoted by the compounds in the atmospheric resid. However, the yield of
hydrocarbon gas, unsaturated hydrocarbons, and isobutane fraction increases.

128
The yield of naphtha cut decreases with an increase in the atmospheric resid content in the blend
with KGC, and the yield of diesel fuel cut, methane, and hydrogen sulfide increases.
The results obtained allow recommending addition of up to 10 wt. % atmospheric resid to cracking feedstock
to increase production of the high-octane component of commercial gasoline. This additive allows increasing the
yield of naphtha cut by 1-3 wt. % in the same process conditions. In switching operation of the unit to production,
atmospheric resid or a blend of atmospheric resid and KGC must be used as cracking feedstock in a larger volume
of diesel fuel cut.

129
Chemistry and Technology of Fuels and Oils, Vol. 43, No. 2, 2007

TRANSFORMATIONS OF OIL CUT HYDROCARBONS IN CATALYTIC


MODIFICATION WITH -OLEFINS

F. I. Samedova, B. M. Aliev, R. Z. Gasanova, S. B. Khanlarova, UDC 546.665.66.095


and N. Z. Kadymalieva

The change in the structural and group composition of paraffins and naphthenes and aromatics in the
oil cut before and after alkylation with a-olefins was investigated. Oligoalkylation of these hydrocarbons
and rupture of naphthene rings in hybrid structures and isomerization of alkyl fragments are reflected
in the quality of the products obtained.

Exhaustive treatment, hydrocracking, and compounding of mineral oils with synthetic oils ensure
production of high-index base oils that satisfy current and future requirements. The use of these oils is somewhat
restricted by their high cost [1-4].
The chemical composition of crude oils from different fields in Azerbaidzhan, as the studies showed, do
not allow producing oils with a viscosity index (VI) above 90 due to the nature of the hydrocarbons in the oil cuts.
Basic research has revealed the necessity of using catalytic processes for rearranging the structure of oil cut
hydrocarbons to obtain oils with a high VI from them.
The studies in [5] showed that hydrogenation processes can be used to obtain base oils with VI higher
than 90. It was simultaneously shown in [6] that the quality of the base oils from Azerbaidzhan crudes can be
improved by adding synthetic components obtained in oligomerization, alkylation, esterification, and other
processes, i.e., by creating semisynthetic oils [6].
The technology for production of high-index (100 and higher), low-pour, semisynthetic oil based on oil
cuts and ethylene oligomers (a-olefins) in the presence of acid catalysts developed at the Institute of New Chemical
Problems, National Academy of Sciences of the Azerbaidzhan Republic (INCP), is of great interest. This technology
allows transforming the structure of molecules of oil cuts and increasing the VI of the oil from 70 to 100 and
higher [7].

____________________________________________________________________________________________________
Institute of New Chemical Problems, National Academy of Sciences of Azerbaidzhan. Translated from
Khimiya i Tekhnologiya Topliv i Masel, No. 2, pp. 32 34, March April, 2007.

130 0009-3092/07/43010130 2007 Springer Science+Business Media, Inc.


Table 1

Viscosity, mm2/sec

in feedstock

Solid point,

Molecular
Viscosity

weight
Yield,
wt. %

index

C
Object investigated
at 100C at 40C

Initial oil cut 2.78 11.38 79.2 20


Hydrocarbons separated from initial oil cut
paraffins and naphthenes (fraction I) 76.37 2.78 11.02 90.6 25 309
aromatics (fraction II) 23.63 3.8 25.07 37.6 14 345
Hydrocarbons separated from alkylate >350C
paraffins and naphthenes (fraction I) 63.2 6.84 38.63 129.9 12 423.6
aromatics (fraction II) 61.3 10.14 124.85 39.5 14 517.6

In addition, it allows eliminating selective treatment and dewaxing with selective solvents and the stage
of compounding mineral oil with synthetic oil from the traditional oil production scheme. Environmental problems
related to the use of toxic and volatile solvents are eliminated in this way.
Several versions of this process which differ in the feedstock, conditions, catalysts, and process scheme
have been developed [8-10]. One version is processing the oil cut with a-olefins in the presence of aluminum
chloride. A semisynthetic oil is obtained as a result, and it basically differs from the synthetic, semisynthetic, and
mineral oils described in [11, 12] in chemical composition.
Transformations of oil-cut hydrocarbons in catalytic treatment with olefins were investigated in the present
study. The oil cut with a viscosity of 2.78 mm2/sec at 100C and VI of 79.2 and the C9-C 11 -olefin fraction obtained
in cracking paraffin was used for the studies.
The oil cut underwent liquid-adsorption separation on ASK silica gel and aluminum oxide to obtain paraffins
and naphthenes (saturated) and aromatic hydrocarbons. Elution was conducted with hexane, hexane benzene
mixture (1:1), benzene, and alcohol benzene (1:1). The fractions with a refractive index at 20C of nD 1.49 were
paraffins and naphthenes and the fractions with n D > 1.49 were aromatics.
The products of adsorption-chromatographic separation were analyzed by elemental composition, average
molecular weights, and the 1H NMR spectra. The molecular weight was determined cryoscopically in benzene and
the elemental composition was determined on a Perkin Elmer-240 analyzer (the oxygen content was found by
difference).
The PMR spectra of the investigated fractions were taken on a Bruker Fourier pulsed spectrometer at an
operating frequency of 300 MHz in solutions of deuterated chloroform (CDCl 3) at room temperature. The relative
proton content of different structural groups was determined by integration of the corresponding resonance
absorption bands.
The structural parameters of average molecules were calculated with the method described in [13]. The
following were determined with the selected method:
number and fraction (rel. %) of carbon atoms and aromatic (C a), naphthene (C n), and paraffin (C p) structures;
total number (Kt ) of rings in the molecule;
number of aromatic (K a ) and naphthene (K n ) rings;

131
Table 2

Elemental composition, wt. % Hydrogen


Hydrocarbon H:C
Empirical formula unsaturation
fraction C H N S O (atomic)
factor z
Before alkylation
I 85.02 12.9 0.14 0.04 1.9 1.81 C 21.9 H 39.5 N 0.03 S 0.01 0.037 4.3
II 87.65 10.25 0.17 0.15 1.78 1.39 C 25.2 H 35.0 N 0.04 S 0.02 0.38 15.4
After alkylation
III 85.78 13.95 0.11 0.06 0.1 1.94 C 30.3 H 58.5 N 0.03 S 0.01 0.03 2.1
IV 86.44 11.72 0.23 0.2 1.41 1.62 C 37.3 H 60.1 N 0.09 S 0.03 0.46 14.5

number of carbon atoms in side alkyl substituents: in methyl and methylene-methine groups directly
bound with the aromatic ring (C ); in CH 2 and CH groups distant from aromatic nuclei and CH 3 groups
in -positions to the latter (C ); in terminal methyl groups (C ).
number of carbon atoms in aliphatic chains ( C p )
The degree of substitution ( ) of aromatic nuclei and branching (X ) of aliphatic substituents were also
determined.
The basic physicochemical characteristics of the oil cut and paraffin and naphthene and aromatic
concentrates separated from it before and after alkylation with -olefins are reported in Tables 1 and 2. Alkylation
was conducted in the presence of aluminum chloride (4% in olefins) at 60C and feedstock:olefins mass ratio
of 1:1 for 3 h. The products were fractionated to separate the >350C fraction.
After treatment with the olefins, the VI of the paraffins and naphthenes and aromatics increased.
Hydrocarbon fractions I and II separated from the initial feedstock had average molecular weights of 309-345, and
their average molecules contained 22-25 carbon atoms and 35-40 hydrogen atoms.
The H:C atomic ratios are characteristic of paraffin and naphthene and aromatic concentrates, except for
fraction IV. The relatively high value of H:C in the latter can be attributed to the high (~19.9) proportion of C p
aliphatic hydrocarbons in the average molecule as a result of oligoalkylation.
After treatment of fractions III and IV with -olefins, the molecular weight and number of carbon and
hydrogen atoms in the average molecule increased.
The relative distribution of hydrogen atoms by structural groups in the paraffin and naphthene and
aromatic fractions (Table 3) shows that in the average molecules of these fractions, the hydrogen atoms are
basically concentrated in saturated fragments (H sat). The proton content (H a) in the aromatic ring varied within the
limits of 7.6-13.2% in fractions II and IV. Protons in positions H and then H and H predominate in the average
molecules of almost all products.
The analysis of the most important structural parameters of the average molecule of these fractions
shows that molecules of paraffin and naphthene fraction I consist of three naphthene rings containing short alkyl
units with 4-5 carbon atoms. There is 64.4% of molecules of this fraction in naphthene fragments and 35.6% of
carbon atoms or paraffin fragments out of the total number in the molecule (Table 4). Compounds with four
saturated rings in the molecule constitute no more than 15% in the indicated fraction.
After alkylation of paraffin-naphthene fraction I with -olefins, the number K s of saturated rings decrease
in the average molecule of fraction III and the paraffin part increases sharply: C p = 73.9%. In naphthene

132
Table 3

Hydrocarbon Hydrogen atom content in molecule, % Average number of hydrogen atoms in molecule
fraction Ha Hsat H H H Ha Hsat H H H
Before alkylation
I 100 68.8 31.2 39.5 27.2 12.3
II 13.2 86.8 21.1 44.1 21.6 4.6 30.4 7.4 15.4 7.6
After alkylation
III 100 73.4 26.6 58.5 42.9 15.6
IV 7.6 92.4 15.4 56.8 20.2 4.6 55.5 9.3 34.1 12.1

Table 4
Average structural parameters of molecules
number of carbon atoms
Hydrocarbon number of proportion of
fraction carbon atoms
number of rings
carbon atoms, %
in fragments of the X
molecule
Ca Cn Cp Kt Ka Kn Ca Cn Cp C C C C p

Before alkylation
I 14.1 7.8 3.15 3.15 64.4 35.6 17.8 4.1 3.7 1.53
II 9.6 7.7 7.9 3.78 1.84 1.94 38.1 30.6 31.3 3.8 9.3 2.5 5.4 1.66 0.45
After alkylation
III 7.9 22.4 2.05 2.05 26.1 73.9 25.1 5.2 17.2 1.71
IV 10.6 2.8 23.9 2.82 2.08 0.74 28.4 7.5 64.1 4.5 18.2 4 19.9 1.87 0.5

structures, the proportion of C n atoms decreases from 64.4 to 26.1%. These structures basically consist of bicyclic
saturated rings: K n = 2.05.
The length of the side substituents in the average molecule after alkylation with -olefins increases
from 3.7 to 17.2 carbon atoms: 57% of the total number of carbon atoms. Branching of aliphatic substituents also
increases: C = 5.2.
The structural parameters of aromatic fractions II and IV (before and after alkylation with -olefins,
respectively) differ significantly. In particular, after alkylation, the degree ( ) of substitution of aromatic rings
increases from 0.45 to 0.5.
The decrease in the degree of aromaticity in fraction IV (C a 28%) is basically due to an increase in the
carbon atom content in the paraffin chains of the average molecule from 21 to 54%. The value of C = 4 could
indicate the presence of terminal methyl groups in paraffin units in the presence of several constituents.
The sharp decrease in the proportion of carbon atoms in naphthene structures from 30.6 to 7.5% after
alkylation with a simultaneous synchronous increase in the hydrocarbon content in paraffin fragments
from 31.3 to 64.1% is partially due to opening of rings in saturated structures (see Table 4), which increases the
length of paraffin chains in the average molecule ( C p 19.9), which is in agreement with the data for the
individual hydrocarbons in [11, 12, 14, 15].
In alkylation of concentrates of paraffins and naphthenes and aromatic hydrocarbons with -olefins
separated from the initial oil cut, the structural parameters of their average molecules undergo important changes,
which is reflected in the properties of the products obtained.

133
REFERENCES

1. N. Stanko and V. Stepina, Ropa Uhlie, 30, No. 10, 598-604 (1988).
2. W. Wozniczko-Kadela and A. Bednarski, Nafta, 44, No. 4-5, 114-115 (1988).
3. A. Willschke, D. Humbert, and A. Rossi, J. Synth. Lubrication, 5, No. 1, 13-53 (1988).
4. D. E. Ripple and J. F. Fahrmann, Ibid., 6, No. 3, 209-232 (1989).
5. F. I. Samedova, Azerbaidzh. Neft. Khozyaistvo, No. 9-10, 17-21 (1991).
6. R. Sh. Kuliev, Khim. Tekhnol. Topl. Masel, No. 1, 28-29 (2000).
7. F. I. Samedova and R. Z. Gasanova, Nontraditional Methods of Manufacturing Petroleum Oils [in Russian],
Elm, Baku (1999).
8. RF Patent No. 1778148.
9. RF Patent No. 1810378.
10. Azerbaidzhan Patent No. 990071.
11. A. B. Aliev, G. A. Mamedaliev, A. G. Azizov, et al., Neftekhimiya, 28, No. 4, 484 (1988).
12. A. G. Azizov, G. A. Mamedaliev, A. B. Aliev, et al., Azerbaidzh. Khim. Zh., No. 2, 24 (2002).
13. V. F. Kamyanov and G. F. Bolshakov, Neftekhimiya, 24, No. 4, 4350 (1984).
14. L. F. Albright and A. R. Goldsby (eds.), Industrial Laboratory Alkylation, ACS Symposium Series 55,
Washington, D. C. (1977).
15. Yu. G. Mamedaliev, in: Selected Works [in Russian], Vol. 1, Baku (1964), p. 422.

134
Chemistry and Technology of Fuels and Oils, Vol. 43, No. 2, 2007

RESINS AND ASPHALTENES MODIFIERS FOR EPOXY RESIN

Yu. V. Pokonova UDC 665.45:66.095

I investigated the reactivity of concentrates of resins and asphaltenes obtained in deasphalting naphtha
residues and in redox reactions in processing of acid tars [1-3]. Condensation, sulfonation, chloromethylation,
radiation chemical oxidation, nitration reactions, etc., were investigated.
Practically important new products characterized by elevated thermal and radiation stability and low cost
were obtained from the products of chemical transformations. Synthesis of new products from petroleum asphaltites
epoxy-containing derivatives is described and the results of a study of their properties are reported.
Asphaltites (Table 1) obtained in naphtha deasphalting or residues from pyrolysis of gasoil and naphtha
and from straight-run tar were investigated. Their elemental composition after treatment [4] with chloromethyl
ether by the liquid-phase method in the presence of titanium tetrachloride is reported in Table 2. The
chloromethylated products (CMP) were epoxidized with glycidic alcohol (glycidol) at 802C in the presence of an
aqueous solution of caustic soda.
The experimental design method was used for fast determination of the optimum epoxidation
conditions [5] (Table 3). The amount of epoxy groups incorporated in the CMP sample 2 was optimized (see
Table 2). The experiments were reproducible.
The coefficients of the regression equations were found with the results of the experiments (Table 4) in
accordance with the design matrix. However, the equations themselves were inadequate, so that it was not
possible to obtain a mathematical model of the process.
No correlation was found between the excess of glycidol and the content of epoxy groups in the final
product. However, it was found that the concentration of alkali and the time basically affect the course of the
reaction. For this reason, primarily these two parameters were varied in the subsequent experiments. The results
of the experiments reported in Table 5 were used to determine the optimum reaction conditions at 802C: time

____________________________________________________________________________________________________
St. Petersburg State Institute of Technology Technical University. Translated from Khimiya i
Tekhnologiya Topliv i Masel, No. 2, pp. 35 37, March April, 2007.

0009-3092/07/43010135 2007 Springer Science+Business Media, Inc. 135


Table 1
Asphaltite
Indexes from pyrolysis residue from vacuum
gasoil naphtha resid
Density at 20C, kg/m 3
1026 1015 1160
Molecular weight 500 650 700
Carbon content (Conradson), % 41.6 31.4 39.5
Softening point (R&B), C 135 124 135
Group composition, %
oils 24.3 30.2 23.8
asphaltenes 65.3 63 67
resins 1.59 6.8 9.2
carboids 8.8
Elemental composition, %
carbon 92.3 92 89.5
hydrogen 6.5 7.22 6.3
sulfur 0.58 0.07 4.2
nitrogen 0.02 0.07
oxygen 0.6 0.64
Total vanadium and nickel content, % 0.0155 0.0034

Table 2
Sample Elemental composition, %
Chloromethylated asphaltite
No. Cl C H O S N
From pyrolysis residue
1 gasoil 16.95 70.01 5.02 6.79 1.18 0.05
2 naphtha 14.25 68.89 4.86 10.56 1.42 0.01
3 From vacuum resid 12 70.11 6.15 10.1 1.56 0.08

Table 3
Factor levels Variation
Factors
0 + step
Reaction time X1, h 6 7 8 1
Amount of glycidol X2 per 1 pt. by wt. CMP, pts. by wt. 2 3 4 1
Amount of water X3 per 1 p. by wt. of 25% NaOH solution, pts. by wt. 0 2 2 1

of 4 h, ten-fold excess of 30% alkali, two-fold excess of glycidol. In these conditions, the epoxy group content
was 2.57%.
In the optimum reaction conditions, the change in the nature of the initial CMP did not increase the epoxy
group content (Table 6). This can probably be attributed to steric hindrances in conducting the reaction in
cross-linked CMP and the important size of the substituents epoxy and chlorohydrin groups.

136
Table 4
Amount of reagent, pts. by
Characterization of epoxidized CMP
wt. per 1 pt. by wt. CMP
Reaction group content, % elemental composition, %
solution of
NaOH
time, h
25%

glycidol water
epoxy hydroxyl Cl S N C H O

2 1 6 2.55 3.2 5.3 1.21 0.02 71.03 5.84 16.6


2 1 2 6 2.08 3.34 5.2 1.19 0.03 71.96 5.72 15.6
4 1 2 6 2.3 3.38 5.19 1.52 0.02 71.13 5.94 16.2
4 1 6 2.26 3.49 5.01 0.88 0.01 69.95 5.65 18.5
4 1 2 8 1.92 3.62 5.1 1.22 0.03 71.56 5.77 16.32
4 1 8 2.3 3.55 4.85 1.2 0.05 71.31 5.8 16.79
2 1 2 8 2.27 3.05 5.89 1.35 0.03 71.4 5.66 15.67
2 1 8 2.22 3.11 5.81 1.29 0.01 71.6 5.77 15.52
3 1 1 7 2.31 3.05 5.85 1.06 0.04 70.92 5.81 16.32
Note. Content of chlorine in CMP: 14.25%

Table 5
A m oun t of
Concentration of

Reaction time, h

reagen t, pts. by
C haracterization of epoxidized C M P
w t. per 1 pt. by
NaOH

w t. C M P
group content, % elem en tal com position , %
glycidol N aO H
epox y h ydrox yl Cl S N C H O
4 4 12.5 6 1.76 3.16 8.88 1.15 0.08 70.29 6.06 13.54
12 20.8 6 1.8 3.18 8.14 0.84 0.6 70.51 5.88 14.57
2 3 8.3 6 1.29 3.73 5.5 1.18 0.05 70.17 5.69 17.41
10 25 4 1.3 3.69 5.8 1.2 0.03 70.01 5.5 17.46
2 10 30 4 2.57 3.95 3.78 0.67 0.05 69.02 5.93 20.55
2 1 30 4 2.57 3.92 3.81 0.73 0.05 69.13 5.89 20.39
2 1 30 2 2.28 2.48 7.02 1.02 0.02 71.84 5.76 14.34
2 10 30 1 1.8 3.2 8.15 0.83 0.05 70.52 5.89 14.56

Table 6
Number of Characterization of epoxidized CMP
chloromethylated
group content, % elemental composition, %
asphaltite sample
(see Table 2) epoxy hydroxyl Cl S N C H O
1 2.26 4.17 7.35 1.01 0.03 70.43 5.7 15.48
2 2.3 3.38 5.19 1.52 0.04 71.13 5.94 16.18
3 2.29 2.45 4.8 0.88 0.08 70.81 5.73 17.7

The nature of the groups was established by functional analysis and IR spectroscopy. The
spectra (see Fig. 1) were made on a G-15-225 instrument (Hitachi) in KBr pellets. Bands characteristic
of epoxymethylene groups in a ring (3040 c m -1) , symmetric (1270-1255 c m -1) , and

137
100

80
620
Absorption, %

680
739705
60
885
40
1681 1255
2340 1583
1498
20
11151080
3400 2930
4000 3000 2000 1800 1600 1400 1200 1000 800 600 400
Wave number, cm 1

Fig. 1. IR spectrum of epoxidized asphaltite

asymmetric (885 cm-1 ) stretching vibrations of the ring were present in the spectra [5]. The presence of absorption
bands in the 1050 cm -1 region indicates the presence of primary OH groups in the products, and those in
the 1100 cm-1 region indicate the presence of secondary OH groups.
Bands of hydroxyl groups with hydrogen bonds appear in the 3500-3300 cm -1 region. The bands in
the 1385 cm-1 region correspond to plane deformation vibrations of associated OH groups [6]. The bands in
the 1080-1115 cm -1 region indicate different C O C bond stretching vibrations. There are also bands
characteristic of the chloromethyl group.
Epoxy, chlorohydrin, residual chloromethyl, and benzyl groups are thus present in the product obtained.
The reaction for fabricating it takes place according to the scheme:

O
Hl
Asph 2 l + HOCH2CH CH2
-Hl
NOH O
AsphCH2OH

where Asp is the asphaltite molecule.


Sample 3 from Table 6 was used to modify ED-20 epoxy resin; curing was conducted with
polyethylenepolyamine. Incorporation of epoxidized asphaltite in epoxy resin accelerates curing and increases
the thermal stability of the cured product (Table 7). Curing is also accelerated when the initial asphaltite is
incorporated, probably due to the presence of catalytic organometallic complexes in the molecules of resin and
asphaltene compounds.
The catalytic effect found also persists in incorporation of epoxidized asphaltites. The epoxy resins
acquire a number of positive properties (Table 8): the dielectric characteristics improve by an order of magnitude;
the adhesive strength does not change.
The data obtained indicated that epoxidized asphaltite can increase the degree of cross-linking of epoxy
resin during curing, i.e., it is a co-oligomer. Fragments of resin and asphaltene compounds containing highly

138
Table 7
Vicat heat resistance (C) after
Epoxy resin modified with asphaltite (see Curing time, min
curing
Table 6, sample 1)
at 20C at 45C at 20C at 45C
Epoxidized, pts. by wt.
0 28 76
5 18 15 92 96
7 16 11 93 98
10 14 9 95 100
Initial, pts. by wt.
5 25 85
10 18 89

Table 8
Epoxy resin modified with epoxidized
Indexes asphaltite, pts. by wt.
5 10
Adhesion to steel St3, MPa 15 14
Water absorption, % 0.3 0.2
15
Specific resistance, cm 1.110 1.81014
Relative elongation, % 2.3 1.9
Rockwell hardness 117 120

condensed aromatic and heterocyclic fragments to the cured product increase its thermal stability and decrease
water absorption.

REFERENCES
1. Yu. V. Pokonova, Chemistry of Macromolecular Compounds in Crude Oil [in Russian], Izd. LGU, Leningrad
(1980).
2. Yu. V. Pokonova, Petroleum Resids [in Russian], IK Sintez, St. Petersburg (2004).
3. Yu. V. Pokonova, Petroleum and Petroleum Products [in Russian], Professional, St. Petersburg (2003).
4. Yu. V. Pokonova, Chemistry and Technology of Halogen Ethers [in Russian], Izd. LGU, Leningrad (1982).
5. S. N. Sautin, Experimental Design in Chemistry and Chemical Engineering [in Russian], Khimiya,
Leningrad (1975).
6. K. Nakanishi, Infrared Absorption Spectroscopy, Holden-Day, San Francisco (1962).

139
Chemistry and Technology of Fuels and Oils, Vol. 43, No. 2, 2007

METHODS OF ANALYSIS

FEATURES OF ANALYSIS OF ASSOCIATIVE HYDROCARBON


MEDIA. Applicability of Refractometric Methods

I. N. Evdokimov and A. P. Losev UDC 665.7.033.28

The refractive index and optical absorption of solutions of crude oil in toluene were investigated. It was
found that the optical properties of systems with an extremely low content of macromolecular substances
deviate significantly from Bouguer Lambert Beer and other laws. The sensitivity of the refractive
index to association of the macromolecular components of hydrocarbon systems was revealed. To increase
the accuracy of the analysis, the necessity of a detailed study of the optical properties of associative
hydrocarbon systems before plotting calibration curves was demonstrated.

Refractometric methods of assessing product quality and composition are widely used in petrochemistry,
and the refractive index of petroleum refining products is a quantity regulated by state standards. For this reason,
great importance is attributed to the reliability of determining the broad spectrum of properties based on the
refractive index.
In recent years, instrument-building companies have proposed flow analyzers for monitoring product
quality in oil refineries (OR). Many domestic OR Yaroslavl, Kirishsk, Omsk, etc. have already introduced
systems for monitoring product quality and production processes that include automated instruments flow
analyzers.
The analyzers (photometers and prismatic refractometers) are equipped with a built-in microprocessor or
external computer which allows obtaining information on the manufacturing process in real time. The principle of
action of most of these instruments the flow refractometer is based on measuring the refractive index of the
medium at a certain wavelength or taking the refractometric spectrum. The instruments are tuned for operation in
the visible or UV regions of the spectrum. Linear calibration curves are used to interpret the data.

____________________________________________________________________________________________________
I. M. Gubkin Russian State University of Oil and Gas. Translated from Khimiya i Tekhnologiya Topliv i
Masel, No. 2, pp. 38 40, March April, 2007.

140 0009-3092/07/43010140 2007 Springer Science+Business Media, Inc.


1
0.292
2

(n21)/(n2+2)
0.288

0.284

1 10 100 1000
c, mg/litre
Fig. 1. Dependence of the refractive index function (n2 1)/(n 2+2) for a solution of crude
in toluene on the concentration of asphaltenes c: 1) experimental; 2) calculated with the
additive rule for ideal solutions.

Stiff requirements are imposed on the accuracy of the calibration models since the course of the
manufacturing process and in the final analysis, the product (fuel) quality, are a function of the parameters
measured.
The reliability of any measurements can be limited by the accuracy of the instrument, which is a function
of the level of development of the engineering at the time. However, the error introduced by the method of
measurement is primarily a function of the depth of the investigators knowledge and the adequacy of the proposed
calibration model. It has long been known that the widely used linear dependences of the refraction on the
concentration of substance in solutions of hydrocarbons are not always valid, but the causes of the nonlinear
deviations are frequently not determined.
The results of studies of the effect of the aggregate state of macromolecular compounds in crude oil on
the refractive index of solutions of crude in toluene are reported here. Previously unknown features that affect the
results of optical measurements were found.
Dilute solutions of crude oil in toluene were investigated in the experiments. Toluene is used as the
standard solvent in optical studies of crudes and refining products. Crude from the Aznakaevo region of the
Romashkino field was taken from a well in 2001 and stored in a tightly sealed container in the dark at room
temperature. The concentration of asphaltenes in the crude was 3.6 wt. % and the density was 876 kg/m 3 at 20C
according to Tatneft Co. data.
The solutions were prepared by two methods. The first method consisted of dilution of relatively large
volumes of the crude in toluene. The reproducibility of the results of the measurements was unsatisfactory for
solutions prepared in this way. For this reason, the second method, similar to titration, was selected to increase
the reliability of the results: crude or a 5% solution in toluene was dropped into a fixed volume of toluene with a
micropipette, producing solutions of accurately defined concentration. The average mass of one drop of crude
coming out of the micropipette was 10.72 mg.
The optical characteristics of heavy fuels and gas condensates containing negligibly small amounts of
macromolecular, polyaromatic compounds [1] are determined in the visible and UV regions of the spectrum by the
presence of asphaltenes. For this reason, the composition of the solutions was subsequently characterized by the

141
3
2
0.2925

(n21)/(n2+2)
1

0.2920

0.2915

0 100 200 300 400


c, mg/litre

Fig. 2. Linear calibration curves for determining concentration of asphaltenes c:


1) obtained with the standard method for concentrated solutions; 2) calculated with the
additive rule; 3) experimental.

equivalent content of these compounds. In the experiments discussed, the concentration of asphaltenes in the
solutions was 0.4-150 mg/liter.
The degree of the effect of resins and other macromolecular components of crude, in addition to asphaltenes,
on the results of optical measurements was assessed in [2]. The determining contribution of asphaltenes to the
value of absorption in the visible and near-UV regions of the spectrum was demonstrated. Detailed information on
the spectra of crudes and gas condensates and the problems of their optical analysis are reported in [3, 4].
Since industrial flow analyzes are built to operate in the UV and visible regions and according to the data
in [5], absorption (intensity of characteristic bands) of fuels in these regions is a function of the production
technology to a significant degree, it becomes necessary to study the features of the optical properties of fuels
and intermediate products in these regions of the spectrum.
The fundamental studies were conducted with an IRF-454-B2M standard refractometer connected
to a U2 liquid thermostat or an ELMI 2.1 digital liquid thermostat. Additional experiments were conducted
on a KFK-2 photocolorimeter and on Specord UV-VIS and Shimadzu UV-4402 spectrophotometers.
Dependences of the refractive index of the solutions of crude in toluene on the concentration of asphaltenes
were obtained with the results of the refractometric measurements. Special attention was focused on the region of
high dilutions, since the concentration of macromolecular components in the intermediate products and fuels is
extremely low. Since the refractive index of the solutions is a nonadditive quantity [6], the theoretical calculation
of the characteristics of the solution was performed with the refractive index function proposed by Lorentz, which
has the property of additivity:

n 2 1 n12 1 n22 1
= + 2 (1 )
n 2 + 2 n12 + 2 2
n + 2

where n, n 1 , n 2 are the refractive indexes of the solution, pure dissolved substance, and pure solvent; j is the
volume fraction of dissolved substance.

142
0.8

1 2
0.6

0.4

0.2

0 20 40 60 80 100
c, mg/litre

Fig. 3. Optical density D of solutions of crude in toluene as a function of concentration


c of asphaltenes: 1) experimental; 2) calculated.

This dependence is used in engineering to plot linear calibration curves. The refractive indexes of the
pure substances are assumed to be constant.
The dependences of the experimental and calculated functions of the refractive index on the concentration
of asphaltenes in the solution are reported in Fig. 1. The abscissa is represented on the logarithmic scale so that
the linear theoretical dependence (curve 2) is distorted. Perturbation of the rule of additivity is observed at an
asphaltene concentration of ~5 mg/liter. The maximum positive deviation of the refractive index function is noted
at an asphaltene concentration greater than 100 mg/liter. The deviations which we found are not described in the
literature.
In estimating the concentration of macromolecular components in fuels or other parameters directly
correlated with the refractive index, there can thus be a relatively large error in the results. For example, two linear
calibration curves are shown in Fig. 2: calculated according to the additive rule and obtained by extrapolation of
the experimental values of the refractive index function at high concentrations of asphaltenes in the solution.
The results of calculating the concentration (or other parameter) based on the measured refractive index
of the sample are a function of the calibration curve selected. For constructing the linear calibration model, the
refractive index of model solutions is usually measured with a large concentration step. The equation for a
straight line was selected based on the results of the measurements.
We obtained dependence 1 in Fig. 2 for the traditionally used region of concentrations of asphaltenes (in
studies of crudes and gas condensates) in this way. The experimental values of the refractive index function
(curve 3 in Fig. 2) deviate significantly from this calibration curve. Line 2, plotted from the concepts concerning
the ideality of the solution, is even further from the experimental values.
As a consequence, the error of determination of the concentration of macromolecular components can be
greater than 100% according to Fig. 2, when the preliminary study of the optical properties (or in plotting the
model with a large concentration step) is insufficiently complete. In addition, at 50-150 mg/liter concentrations of
asphaltenes, it is totally impossible to use the proposed linear calibrations.
This example demonstrates the necessity of accurately plotting and analyzing the calibration curves. The
linear calibration curves can probably only be used in limited concentration ranges.
The Bouguer Lambert Beer law [7], which correlates the optical density of a solution with the
concentration of substance, can frequently be used to plot the linear calibration curves:

143
3.0 1.1

2.5 1.0

nc


1
2.0 0.9
2

1,5 0.8
0 50 100 150
c, mg/litre

Fig. 4. Effective refractive index n c of crude (curve 1) and extinction coefficient (curve
2) as a function of concentration c of asphaltenes in the solution.

D = lc

where D is the optical density of the solution; is the extinction coefficient; l is the thickness of the layer of
solution; c is the concentration of substance in the solution.
The extinction coefficient is assumed to be constant. It should be noted that for dilute solutions of crude
in toluene, this coefficient coincides with the absorption coefficient [4], i.e., there is almost no scattering of light.
The results of photometric studies of the solutions at the wavelength of 670 nm are shown in Fig. 3. Curve 1 of
the experimental values of the optical density fits relatively well on line 2, described by an equation of the
type y = 0.00775x (regression coefficient r 2 = 0.998). However, this does not mean that the observed small deviations
are not reflected in the results of the calculations of any parameters.
According to the data in [7], linear approximation in constructing the calibration model with the Bouguer
law can lead to an error of up to 30% in calculating the concentration. if follows from this that plotting the
dependences of the optical density on the concentration is not informative and is the cause of important errors.
It is much more convenient to study real solutions with the dependences of the extinction coefficient on
the concentration. In Bouguers law, this coefficient, as noted above, is assumed to be constant, so that any
deviations o this dependence from a horizontal line will indicate some intermolecular interactions that take place
in the solution.
The dependence of the extinction coefficient of the solutions on the concentration of asphaltenes is
shown in Fig. 4 (curve 2). It graphically demonstrates perturbation of Bouguers law, which assumes this coefficient
to be constant. At 4-8 mg/liter concentrations of asphaltenes, the maximum extinction coefficient is observed.
With an increase in the concentration, the curve of the dependence of the extinction coefficient becomes more
gently sloping, and at asphaltene concentrations greater than 100 mg/liter, it goes out onto a horizontal line. In
the 20-100 mg/liter concentration range, there are two stepwise rises in the dependence.
In our interpretation, the change in extinction at extremely low concentrations of asphaltenes in the
solutions indicates the intermolecular interaction that takes place in the solution association of asphaltene
molecules. We thus fixed the beginning of self-association of asphaltenes at concentrations of 5-7 mg/liter in a
photometric experiment.

144
The latest results of foreign studies [8, 9] confirm that asphaltenes begin to aggregate in toluene at
concentrations under 50 mg/liter. These results were obtained independently by absorption and fluorescence
spectroscopy [8] and by the ultrasound propagation velocity in the medium [9].
The extinction spike in Fig. 4 at a concentration of less than 7 mg/liter indicates the appearance of
asphaltene monomers (or unimers). The sharp drop in the dependence indicates formation of the simplest
aggregates dimers. The subsequent insignificant increase in extinction at a concentration of 100 mg/liter and
higher, accompanied by rises and gently sloping segments in the form of a step, can be interpreted as enlargement
of associates and formation of molecular nanostructures.
Other investigators have come to the same conclusions concerning the stepwise association of asphaltenes,
in osmometric experiments, for example [10]. We directly observed primary aggregation of asphaltenes for the first
time in studies of the viscosity, NMR relaxation, and optical absorption of solutions of crude and solid asphaltenes
in toluene [11-13]. These results were confirmed in studying solutions of asphaltenes by fluorescence
spectroscopy [14].
As a consequence, the identified deviations of the dependences from Bouguers law are due to the capacity
of asphaltenes for self-organization and formation of molecular aggregates.
The refractive index function discussed above undergoes uncharacteristic changes at concentrations
corresponding to self-association of asphaltenes. This probably indicates the same nature of the features of the
behavior of the Lorentz function and absorption coefficient.
The effective refractive index n c of the crude in solution was calculated with the additive rule to compare
the refractometric and photometric data for the refractive index function. This index was obtained based on the
hypothesis that the solution is ideal and the change in its optical properties is due to a change in the refractive
index of the crude alone.
The dependences of the extinction coefficient (curve 2) and effective refractive index of crude in solution
(curve 1) on the concentration of asphaltenes shown in Fig. 4 behave similarly. The similarity can be attributed,
for example, to the correlation of the real and imaginary parts of the refractive index [15]:

n = n i (n )

where n is the complex refractive index; n is the real part of the refractive index; (n ) = / 4 is the refractive
index; is the wavelength.
In reporting the conclusions, we note that the experimental finding of the sensitivity of the refractive
index to molecular aggregation of asphaltenes was one of the basic results of the study. No similar results were
previously published in either western or domestic publications.
The theoretical possibility of such sensitivity was hypothesized in 1936 by M. M. Kusakov. He observed
the greatest deviations of the refractive index function from the theoretical dependences when the character of the
chemical bonds between atoms changed. In his opinion, even greater deviations are characteristic of compounds
containing conjugated bonds [16]. In other words, the refractive index is only sensitive to primary molecular
aggregation, where the character of the bonds between molecules or parts of complex molecules of asphaltenes
changes.
In our laboratory studies, the most important deviations of the optical properties from the generally used
dependences according to Bouguer Lambert Beer and other laws are manifested for media with an extremely
low content of macromolecular substances. Such a composition is characteristic, for example, of a large number of
automotive fuels.

145
The sensitivity of the refractive index to the associative components of fuels is not taken into consideration
in processing data from optical analyses at present. As a consequence, it is necessary to change the approach to
processing these data and to plot calibration curves (for example, of the refractive index property type).
The new approach should consist of a more detailed study of the phase state of the associative complexes.
Linear calibration curves should probably only be used in limited concentration ranges.
We would like to thank N. Yu. Eliseev and N. K. Zaitsev for assistance in setting up the experiments.
REFERENCES
1. N. V. Busygina and I. G. Busygin, Natural Gas and Gas Condensate Processing Technology [in Russian],
IPK Gazprompechat Orenburggazpromservis OOO, Orenburg (2002).
2. I. N. Evdokimov, N. Yu. Eliseev, and B. R. Akhmetov, J. Petrol. Sci. Eng., No. 37, 135-143 (2003).
3. S. Betancourt, G. Fujisawa, O. C. Mullins, et al., Oilfield Rev., 54-61 (Autumn, 2003).
4. O. C. Mullins, Structures and Dynamics of Asphaltenes, Springer, New York (1999).
5. A. G. Siryuk, E. D. Radchenko, and M. M. Fernandes-Gomes, Khim. Tekhnol. Topl. Masel, No. 7, 48-51
(1979).
6. L. G. Gurvich, Scientific Principles of Oil Refining [in Russian], Gostoptekhizdat, Moscow-Leningrad
(1940).
7. K. L. Gawrys, Doct. Dissertation, Raleigh (2005).
8. S. Goncalves, J. Castilo, A. Fernandez, et al., Fuel, No. 83, 1823-1828 (2004).
9. G. Andreata, N. Bostrom, and O. C. Mullins, Langmuir, No. 21, 2728-2736 (2005).
10. H. W. Yarranton, J. Dispersion Sci. Technol., No. 26, 5-8 (2005).
11. I. N. Evdokimov, N. Yu. Eliseev, and B. R. Akhmetov, J. Petrol. Sci. Eng., 37, No. 3-4, 145-152 (2003).
12. I. N. Evdokimov, N. Yu. Eliseev, and B. R. Akhmetov, Fuel, 82, No. 7, 817-823 (2003).
13. I. N. Evdokimov, N. Yu. Eliseev, and B. R. Akhmetov, Ibid., 85, No. 10-11, 1465-1472 (2006).
14. F. Arteaga-Larios, A. Cosultchi, and E. Perez, Energy Fuels, 19, No. 2, 477-484 (2005).
15. R. V. Pol, Introduction to Optics [in Russian], OGIZ, Moscow Leningrad (1947).
16. M. M. Kusakov, Methods of Determination of the Physicochemical Properties of Petroleum Products [in
Russian], ONTI KNTP SSSR, Moscow Leningrad (1936).

146
Chemistry and Technology of Fuels and Oils, Vol. 43, No. 2, 2007

ECOLOGY

DULROMABSORB SORBENT FOR RECOVERY OF PETROLEUM PRODUCTS


FROM SITES OF ACCIDENTAL SPILLS

A. A.-da Konseisao, N. A. Samoilov, and R. N. Khlestkin UDC 665.61

The Mozambique sorbent of plant origin, DULROMABSORB, was investigated. Due to the high-tech
oleophilic and hydrophobic properties, it can be used as an absorbing substance in eliminating
accidental spills of crude oil and a broad spectrum of petroleum products on the surface of water and
soil in a wide temperature range. The sorbent can be used in both disperse form and as a filler for
oil-absorbing mats and blankets. The sorbent is highly competitive with respect to specialized sorbents
for recovery of petroleum products and many potential natural and industrial sorbents.

Large-tonnage spills of crude oil and petroleum products in mechanical or corrosive rupture of pipelines,
in accidents in ship, rail, and automotive transport, and in oil refineries are a powerful source of environmental
pollution and occasionally environmental catastrophes [1, 2]. For example, one spill of petroleum products on the
surface of waters from ocean-going tankers can involve tens of thousands of tons.
The greatest environmental hazard is presented by oil spills on the surface of oceans, reservoirs, and
rivers, since the thin film that moves with the current can cover several square kilometers of the surface in several
hours. These spills are relatively difficult to fully localize with oil booms. They can be localized much more simply
on the surface of soil: by damming them up.
Recovering crude and petroleum products from the surface of soil and especially water is technically a
very complicated problem. Crude is recovered from the surface of water as a function of the layer thickness of the
spill with cutoff and pumping systems, mechanized petroleum-gathering systems, and various sorbents. Both
specialized sorbents and industrial and agricultural wastes can be used as sorbents [1, 2].

____________________________________________________________________________________________________
Josina Machel School, Mozambique. Ufa State Petroleum Engineering University. Translated from Khimiya
i Tekhnologiya Topliv i Masel, No. 2, pp. 42 46, March April, 2007.

0009-3092/07/43010147 2007 Springer Science+Business Media, Inc. 147


Table 1

Density at 20C, Viscosity at 20C,


Petroleum product
kg/m3 mm2/sec
Automotive gasoline 730 1.9
Diesel fuel 820 3.2
NOVOIL motor oil 890 247
Siberian crude 835 21

Table 2
Amount (g/g sorbent) of
Layer petroleum product Degree of
Sorbed petroleum product
thickness, cm squeezing, %
absorbed squeezed out
Siberian crude 4.1 33 43 28.6 37.8 86.6 90.5
NOVOIL 1.7 50 60 43.9 52.6 87.8 91.3
Automotive gasoline 3 32.8 33 25.8 26.6 78.7 80.6
Diesel fuel 4 24.9 30.9 19.4 26.1 77.1 84.4

A large number of industrial and agricultural wastes have been investigated as absorbents for crude oil
and petroleum products at Ufa State Petroleum Engineering University (UGNTU). It was shown that regenerability
is the most important property of a sorbent, together with absorption of crude and moisture, that characterize its
performance efficacy and degree of universality (sorbents with high moisture absorption can be used for recovering
crude from the surface of soil alone) [3].
Partially squeezing the gathered crude from the sorbent is the simplest method of regeneration. An
important part of the crude can be used for refining, and the regenerated sorbent can be reused to recover crude,
which reduces the costs of eliminating accidental spills.
Of the reagents investigated, one of the most interesting and promising was the sorbent DULROMABSORB
(henceforth sorbent I). It is the fibrous part of the fruits of the sumauma tree, widely distributed in the
Republic of Mozambique. The fiber is pale yellow in color and consists of bundles of thread-like linear
structures 15-20 mm long and 0.005-0.006 mm in diameter. In structure, it resembles cotton boll fiber previously
used to develop the effective sorbent SINTAPEX (henceforth sorbent II) at UGNTU [2].
Some features of recovering Siberian crude and characteristic petroleum products automotive gasoline,
diesel fuel, and NOVOIL motor oil from the surface of water and soil were examined (Table 1).
Sorbent I, like sorbent II, is hydrophobic. When the fibres are placed on the surface of both fresh and salt
water, absorption almost does not take place. After 1-24 h of contact with the water, water absorption by the
sorbent is a total of 0.1-0.2 g/g for sorbent II). The hydrophoby of both types of sorbent is due to the presence of
a thin oil film on their surface which prevents wetting of the fibres with water.
A series of experiments on recovering a film of crude oil and different petroleum products from the surface
of water with sorbent I at 20C showed intensive absorption for several minutes (Fig. 1). The absorptive power of
the sorbent, generally called oil absorption, increases as the thickness of the film of crude or petroleum product
increases.
The maximum oil absorption is attained when the thickness of the layer of dispersed fibrous sorbent
distributed over the surface of the spill is commensurate with the layer thickness of the spill (Table 2). In cases

148
60

40

20

0 1 2

Fig. 1. Oil absorption G by DULROMABSORB sorbent as a function of petroleum product


layer thickness h on the surface of water: 1) automotive gasoline; 2) diesel fuel;
3) NOVOIL; 4) Siberian crude.

a b

c d e
Fig. 2. Structure of SINTAPEX (a, b) and DULROMABSORB (c-e): a, c) in initial state;
b, d, e) after absorption of an oil spill; d, e) in the initial and final stages of absorption.

where the spill layer thickness is less than the sorbent layer thickness, the petroleum product is also removed from
the surface of the water beyond the boundaries of the position of the sorbent.
The sorbent absorbs NOVOIL in the largest amount (see Table 2). This oil is probably closest in component
composition to the oil film on the surface of the fibres of the sorbent, which also determines the high affinity of the
sorbent for the sorbed oil.
The absorptive power of sorbent I is very high. It is 2-3 times higher than for sorbent II, and 5-7 times
higher than for such common specialized sorbents used to eliminate oil spills as Lessorb or Peat Sorb. This is
because sorbent I differs from other sorbents due to the very low bulk density, 910 -3 g/cm 3 (for comparison, it
is 410 -22 g/cm 3 for sorbent II) and corresponding higher porosity.

149
Formation of a three-dimensional structure of the sorbent absorbed substance system is a characteristic
feature of recovering petroleum products whose layer is commensurate in thickness with the layer of sorbent I
from the surface of water. This structure differs significantly from the structure formed when sorbent II is used,
for example (Fig. 2).
The fibres in sorbent II (see Fig. 2a) are in the shape of a relatively compact coil (textile nut) in which the
free space is filled with the petroleum product (see Fig. 2b) and the linear fibres of sorbent I (see Fig. 2c) are free
to move apart as the petroleum product is absorbed (see Fig. 2d, e), creating a sorbent petroleum product
quasigel structure.
This structure gradually begins to be compressed by gravity after it is removed from the site of the spill
and placed in a used sorbent collection container.
In picking up relatively low-viscosity products (gasoline, diesel fuel, crude), excesses of the products are
filtered off during transfer of the saturated sorbent from the surface of the spill to the container. The real absorption
properties of the sorbent are characterized by an oil absorption value at the level of 30-40 g/g. In recovery of
highly viscous NOVOIL motor oil, excesses are filtered, i.e., flow out of the swollen layer of sorbent slows sharply
and takes place in the container. For this reason, oil absorption increases to 50-60 g/g (see Table 2).
Sorbent I is easily regenerated by simply squeezing out the absorbed petroleum product (see Table 2).
The regenerated sorbent also absorbs petroleum products in important amounts (Table 3). The absorptive power
of the sorbent immediately after the gathered petroleum product is squeezed out is slightly lower than after
holding for one day in open air. This could be due to evaporation of some of the petroleum product remaining in
the sorbent after regeneration and thus an increase in the oil absorbing power of the used sorbent, which is most
pronounced in recovering gasoline.

Table 3

Amount (g/g of sorbent) of petroleum


Layer thickness, product Degree of
Sorbed petroleum product at 20C
cm squeezing, %
absorbed squeezed out
DULROMABSORB sorbent
fresh
Siberian crude 0.3 18.1 19.6 13.4 15.5 61 71
NOVOIL motor oil 0.4 0.5 18.6 19 10.5 11.8 55 63
Diesel fuel 0.2 13.5 14 8.8 9.7 63 72
Automotive gasoline 0.2 17.1 17.4 13.9 14.6 81 83
immediately after regeneration
Siberian crude 0.3 0.4 21.6 22.5 18.3 18.4 83 93
NOVOIL motor oil 0.4 0.5 18.5 18.8 15.3 16.4 81 87
Diesel fuel 0.3 13.2 17.2 11.2 12.4 70 78
Automotive gasoline 0.2 17.2 18.3 15.2 16.3 84 90
regenerated (after drying)
Siberian crude 0.3 0.4 20.7 21.5 19.3 89 93
NOVOIL motor oil 0.4 0.5 20.4 20.7 19.3 93 94
Diesel fuel 0.2 15.8 16.1 12.4 13.3 77 84
Automotive gasoline 0.2 14.5 16.8 13.1 16.1 90 98

150
Despite the high oil absorbing power, sorbent I is unsuitable for processing and is difficult to use: important
technical difficulties arise in spraying the sorbent over the surface of the spill and then recovering the used
sorbent. It is much more convenient to use it as a filler for oil-absorbing mats which can be more easily distributed
over the surface of an accidental spill, picked up after absorbing the petroleum product, and transported to the
site where the product recovered is squeezed out. It is necessary to assess the features of the kinetics of oil
absorption by the sorbent to develop a design for oil-absorbing mats.
The analysis of the kinetics of absorption of petroleum products by a layer of sorbent I showed that the
rise height of the petroleum product in the layer is no greater than 5 cm (Fig. 3a). The higher the density of the
petroleum product, the lower its rise height in the sorbent layer (Fig. 3b). We can hypothesize that the density of
the petroleum product as a gravitational characteristic in increasing partially compensates for the oppositely
directed capillary forces that ensure penetration of the petroleum product in the sorbent layer.
The observed phenomenon qualitatively obeys Jurans law, where the rise height of a liquid in capillary
tubes in a first approximation will be inversely proportional to the density of the liquid. The rates of rise of
different petroleum products in the sorbent layer are close and change in time according to a hyperbolic
dependence (Fig. 4).

8 1
2
, cm

4
4

3
b
0 50 100 700 750 800 850
, minute , kg/m 3

Fig. 3. Height H of penetration of a petroleum product in a layer of DULROMABSORB


sorbent as a function of its contact time t with the petroleum product (a) and the density
r of the petroleum product (b): 1) automotive gasoline; 2) diesel fuel; 3) NOVOIL motor
oil; 4) Siberian crude.
, cm/min

0 20 40 60 80 100
, min

Fig. 4. Rise rate n of a petroleum product in a layer of DULROMABSORB sorbent as a


function of its contact time with the petroleum product: automotive gasoline;
diesel fuel; NOVOIL motor oil; Siberian crude.

151
Table 4

Sorption time at 18C, Amount (g/g sorbent) of petroleum product


Degree of squeezing, %
min absorbed squeezed out
Automotive gasoline
10 45.5 38.7 84.9
20 37.2 31.2 83.8
40 37.2 31.2 83.8
60 37.2 31.2 83.8
Diesel fuel
10 36.9 28.7 77.8
20 32.2 31.8 98.8
40 32.2 31.8 98.8
60 32.5 31.9 98.2
NOVOIL motor oil
10 58.5 50.7 86.8
20 47.3 44.5 94.1
40 47.6 44.6 93.7
60 62 52.7 85
Siberian crude
10 2.6
20 2.9
40 5.4
60 5.4

Table 5
Oil absorption (g/g) at 20C from surface of soil
Petroleum product
sandy chernozem clay
Siberian crude 32.6 35 27.6
NOVOIL 48 40.4 47.5
Diesel fuel 22.2 32.7 30.7
Automotive gasoline 25.6 26.2 22.5

An intensive rise rate is observed in the first 10-15 min of contact of the sorbent with the petroleum
product. The dependence of the rise rate n of the petroleum product on the contact time t with the sorbent is
satisfactorily approximated by the equation:

= 3.5 exp( 0.75 )

Based on the experimental data obtained, it is recommended that oil-absorbing mats be made 3-5 cm thick.
Such mats are universal. Due to the unified design, they can be used to recover different petroleum products.

152
Table 6

Water absorption, Degree of squeezing


Sorbents Oil absorption, g/g
g/g out of crude, %
Organic of industrial origin
Polystyrene foam (granules) 9.26 4.45 0
Polypropylene (granules) 1.6 0.8 0
Ground up tires (crumb) 3.58 7.2 55
Rubber (vulcanized rubber) crumb 5.11 0.3 0
Carbamide formaldehyde resin
lump 23.3 0.1 0
powder 39.6 60
Phenol formaldehyde resin (powder) 4.42 14.54 0
Porolon
sheet thickness
3 mm 14.5 1.3 75
18 mm 35.2 25.92 85
granulated (5 8 mm) 39.89 30.71
Syntepon 46.31 42 52 94
Ground brown coal -1
Ground asphalt 4 4.5 0.2 1
SINTAPEX (spinning production waste) 24.45 0.2 83
Macroporous industrial carbon 4 4.5 01 10 81
Nonwoven material (Lavsan): sample
14.05 13.91 82
B 7.27 7.08 66
C 4.71 4.33 60
Agryl-A with surface
smooth 13.9 1.46 0
rough 13.6 1.8 0
Agryl-B (smooth surface) 8.2 1.48 0
Batting 24 27 0.5 87
Cotton roll cloth 3.2
Inorganic of industrial origin
Foamed nickel (5 mm thick) 2.91 3.03 0
Quilted fiberglass 5.42 1.72 60
Plant wastes
Wheat straw (chaff) 4.1 4.3 36
Reed chaff 8.2 2.66 4.68 18 30
Sawdust 1.72 4.31 10 20
Buckwheat hulls 3.05 3.5 2.2 44
Cotton production wastes 8.3 0.26 60
Dried moss
whole 3.5 3.1
ground 5.8 3.5
Peat 17.71 24.28 74
Specialized oil absorbents
Lessorb (treated peat dust) 9.1 2.5 66
Peat Sorb (FRG, Clon Inc.) 6.19 0.71 0
Developed
DULROMABSORB 33 43 0.2 86 90

153
The experiments on recovery of petroleum products at low temperatures (up to 18C) demonstrated the
possibility of using sorbent I for picking up petroleum products from the surface of ice or snow (Table 4). A
sorbent petroleum product system in the form of a gel-like mass, which simplifies recovery, is formed after more
than 40 min of contact of the petroleum product with the sorbent. The high oil absorption at low temperatures is
commensurate with the oil absorption at 20C.
For example, the amount of absorbed diesel fuel at 20 and 18C was 30 and 33 g/g, respectively.
Sorption of Siberian crude is an exception. The crude is absorbed as effectively as at 20C only when the temperature
is down to 4C. With a further decrease in the temperature, the viscosity of the crude increases sharply and its
absorbency in the sorbent layer on the surface of the spill decreases by 6-8 times (see Tables 2 and 4).
The absorbing properties of sorbent I in recovering petroleum products from the surface of soil at 20C
were assessed for sandy, clay, and chernozem soils. The experiments showed (Table 5) that the amounts of crude
and petroleum products recovered from the different soils are very close and are commensurate with the amounts
picked up from the surface of water (see Table 2).
The small differences in the fixed oil absorption values are due to the difference in the magnitude of
compacting of the investigated sorbent samples and consequently the difference in their porosity. On the whole,
sorbent I can be characterized as a universal sorbent for a wide variety of petroleum products recovered from the
surface of water and soil in different climatic conditions.
Sorbent I was compared with specialized sorbents for recovering petroleum products and with many
potential natural and industrial sorbents with respect to the oil-absorbing and water-absorbing properties and
also with respect to the possibility of squeezing the absorbed petroleum products out of them (Table 6).
This sorbent is only inferior to the expensive powdered carbamide formaldehyde resin, porolon, and
syntepon. The last ones are not universal due to the almost identical oil- and water-absorbing power and cannot
be used for recovering petroleum products from the surface of water without additional hydrophobization.
DULROMABSORB natural sorbent thus has unique sorption properties. It can be widely used for gathering
spilled petroleum products in port areas and from the surface of the sea and other bodies of water not only in the
Republic of Mozambique. Due to the very low cost (less than $0.1 US per kg), this sorbent can be exported to
other countries, to the Russian Federation in particular.

REFERENCES
1. A. Solovyanov, Neft Rossii, No. 2, 38-40 (1999).
2. N. A. Samoilov, R. N. Khlestkin, A. V. Shemetov, et al., The Sorption Method of Eliminating Accidental
Spills of Crude Oil and Petroleum Products [in Russian], Khimiya, Moscow (2001).
3. R. N. Khlestkin and N. A. Samoilov, in: Proceedings of the International Scientific and Technical
Conference on Environmental Problems of Ural Industrial Zones, Magnitogorsk, May 20-21, 1997 [in
Russian], Vol. 2, State Mining and Metallurgical Academy, Magnitogorsk (1998), pp. 9-15.

154
Chemistry and Technology of Fuels and Oils, Vol. 43, No. 2, 2007

REVIEWS

FUEL ADDITIVES. Development and Use in 2001-2005

A. M. Danilov UDC 665.7.038.5

The situation in development and use of fuel additives in 2001-2005 was examined based on published
and patent data. The basic types of additives that satisfy the increasing requirements for motor fuels
were characterized. The additives market in Russia was especially examined. Production of modern
fuels at Russian oil refineries is dependent on importing foreign additives to a great degree. However,
in the last five years, domestic development of additives corresponding to the current level and capable
of replacing imports has occurred. The most important promising directions in development of additives
in the near future were formulated.

In continuing the reviews in [1] covering the period from 1985 to 2000, we will examine the situation for
fuel additives in Russia and the world in the next five years. An intensive increase in the attention focused on this
product is characteristic, especially in our country. It is sufficient to recall that from 2000 to 2004, three specialized

Table 1

Requirement Standard Additive


Diesel fuels
Euro-3 CN 51 Ignition promoter
Euro-4 Sulfur content 50 ppm Antiwear
Automotive gasolines
100,000 km run of automobile with no
European Union Directive 97/70/EU Detergent
increase in exhaust gas toxicity

____________________________________________________________________________________________________
VNII NP Co. Translated from Khimiya i Tekhnologiya Topliv i Masel, No. 2, pp. 47 56,
March April, 2007.

0009-3092/07/43010155 2007 Springer Science+Business Media, Inc. 155


6

5
4

Part of oatents, %
3
50
2

0
1981 1986 1991 1996 2001 2006
Year

Fig. 1. Structure of world patenting of fuel additives in 1981-2005: 1) detergent;


2) depressant-dispersant; 3) ignition modifiers; 4) combustion modifiers; 5) antiwear;
6) other.

Fig. 2. Structure of patenting of detergent additives for automotive fuels in 2001-2005:


1, 2, 3) that wash carburetor, intake valves, and combustion chamber.

conferences on fuel additives were held in Russia [2], the Committee on Fuels and Lube Oils of the Association of
Petroleum Refiners and Petroleum Chemists met [3], many articles and reviews were published, and dissertations
were defended. I have two editions [4, 5] of a handbook which I hope reflected almost all of the practical experience
in using additives in our country.
The number and volumes of use of fuel additives at OR simultaneously increased. The number of additives
approved for use in the 25 years under review increased in geometric progression. Of the multitude of types, the
greatest attention has been focused on the additives required for developing fuels that satisfy world environmental
and performance standards. This directly or indirectly derives from legislatively established standards (Table 1).
For example, the use of ignition promoters the simplest and cheapest method of bringing the cetane number
(CN) of diesel fuels to 51 units is regulated by the standard established in Euro-3.
The interest in ignition promoters is also due to the attempts to use gaseous fuel characterized by an
extremely low CN in automotive transport [6]. Antiwear additives are required to compensate for the inadequate
lubricating properties of exhaustively hydrotreated diesel fuel. Finally, to implement European Union
directive 98/70/EU (although it is not an absolute law) concerning the 100,000 km run of an automobile with no

156
increase in the toxicity of its exhaust requires combining optimum design, competent technical servicing, and use
of detergents.
In addition to the above additives, the additives required for refining fuels with improved low-temperature
properties also play an important role in Russia. This is not only due to the climatic conditions of the northern
country. Depressants increase the end point of diesel fuels and thus increase their yield. In one study [7], it was
shown that for each US dollar spent on a depressant, diesel fuel at $4.4 can be additionally processed, i.e., a
greater than 300% economic effect is possible.
The data on patenting of fuel additives over the past quarter of a century graphically illustrate the
above (Fig. 1). We note that the protected documents do not always contain the really important inventions.
They are most probably part of the developers know-how. Such patents cover the area of technical solutions
claimed by their authors, who predict the prospects in the near future, to the maximum possible extent. The data
in Fig. 1 should be examined from this point of view.
The largest number of protected documents in the period examined traditionally concerned detergent,
more precisely, multifunctional, additives for automotive gasolines. This is due to the importance of these additives
and the large number of possible compositions.
Structural changes take place within the class of these additives. Although additives to prevent formation
of deposits in the choke valve were primarily developed in 1950-1970, additives that clean the intake valves of
injection engines were basically developed in the next 20 years. The number of developments concerning
additives that remove carbon from the engine combustion chamber with direct injection of gasoline is now
increasing (Fig. 2).
Russia has the most patents for additives that wash the carburetor, usually in composites with
amine-containing antiknocks. These developments are oriented toward obsolete carburetor automobiles that use
gasolines with a maximum research octane number (RON) of 92.
The additives that wash the intake valves of injection engines are represented by composites containing
well-known polybutene- and polyesteramines. These are probably the most effective compounds and no alternatives
to them are being sought. The searches are occurring in secondary areas: radicals are varied, individual functional
groups are incorporated, and oil carriers are being selected.*
The developers of additives that prevent formation of deposits in the combustion chamber are oriented
toward the advent of engines with direct fuel injection in the cylinders in the relatively near future [8]. Such
additives are necessary for keeping the injectors clean and for reducing the increase in the engines requirements
for the ON of gasoline due to fouling of the combustion chamber. They are created on different bases.
In the general case, they are composites of SF with carbon modifiers (alcohols, esters, hydroxyethylated
compounds) and combustion catalysts (iron, copper, manganese, rare-earth element compounds). Compounds
with high thermal stability from the group of Mannich bases [9], succinimides [10, 11], products of alkoxylation of
compounds with an active hydrogen atom [12, 13], etc., are used as SF. However, a SFs membership in these
classes of compounds is no guarantee of its effectiveness.
From this point of view, the results of tests of polyisobutenyl succinimides made with different amines are
characteristic (Table 2) [14]. The detergent properties of these compounds in gasoline were assessed with the

*Macromolecular surfactants (SF), the base of detergent additives, are deposited on valve stems so that they can
stick. To prevent this, the additives are diluted with a large amount of oil in a petroleum or synthetic base.
Synthetic oils are more expensive, but more thermostable and correspondingly more effective.

157
Table 2
Weight of deposits
Intake valve cleanness, Average molecular
Amine in succinimide (according to
points* weight of succinimide
ASTM D-3041), mg
Ethylenediamine 0 .1 70 .3 1832
Propylenediamine 3 +70 2140
Diethylenetriamine 2 +44 .5 1975
Tetraethylenepentamine 0 .2 61 .9 2308
Butylamine 1 25 .8 1390
Octylamine 0 .2 52 .4 1265
Gasoline
with no additives 2 .2 +100
with commercial additive 0 .1 86 .7 2087
Note. *+100: use of gasoline with no additives; 100: carbon absent

methods in ASTM D-6201 (intake valve cleanness), and the weight of the deposits was determined according to
the method in ASTM D-3041 (thermooxidative stability of jet fuels). As these data show, with amines very close
in structure (ethylenediamine and propylenediamine), the additives strongly differ in effectiveness.
The mechanism of the detergent action and principles for selecting additives are thus still not sufficiently
clear. Nevertheless, it has been empirically established that in the general case, a dispersant with high thermal
stability (succinimide, alkylphenol Mannich base, etc.), detergent agent (very frequently a hydroxyalkylated
product phenol, alcohol), and a solvent (turpentine, oxygen-containing compound), which can simultaneously
fulfill the function of carbon modifier, should be incorporated in the composite.
On the contrary, such separation of the functions of the components is relatively arbitrary. It is necessary
to assume that the effectiveness of the composites is ensured by the combined effect of the components. These
principles are also used in creating detergent additives for diesel fuels [15], although the operating conditions of
these additives differ. The number of such patents is still small, but these additives are already available on the
foreign market and have appeared in Russia.
Depressants are also represented by a large number of patents, although the number has been decreasing
from year to year. We can hypothesize that the basic principal technical solutions in this area have already been
found. They are based on two types of compounds: modified copolymers of olefins and vinyl acetate and
polyalkyl methacrylates or their copolymers with olefins and other monomers.
Such additives are now also manufactured in Russia. VES-410D additive for middle-distillate fuels and
VES-503 for boiler fuels are manufactured at Angarsk Catalyst and Organic Synthesis Plant. Depran Co. is
manufacturing the polyethylene vinyl acetate additive DMN-2005, designed for use in marine and boiler fuels,
and in crude oils.
Interest in low-molecular-weight polyolefins has also persisted; attempts have been made to obtain them
by decomposition of macromolecular polymers or copolymers, for example, ethylene propylene rubber [16] (in
direct polymerization, oligomers with a wide molecular-weight distribution are formed, which is undesirable).
Pilot-industrial production of one of these additives DEP-M at Aromasintez Co. (Kaluga) is reported
in [17]. Incorporation of this additive in diesel fuel in the concentration of 0.05% ensures a decrease in the solid
point and limiting filterability temperature by 16 and 11C (initial values: 15 and 5C).

158
The variety of the assortment of depressants is due to the features of their action. They are very sensitive
to the group composition of the fuels and characteristics of the waxes in them. Actually, the optimum additive
must be selected for each fuel. The problem is complicated by the fact that the depressants do not prevent cold
separation of diesel fuels and they are currently necessarily paired with so-called wax dispersants.
The compositions of the wax dispersants and principles of processing them are secret. These additives
should inhibit growth of wax crystals to a size where they settle on the bottom. From this point of view, compounds
with charged functional groups, for example, quaternary ammonium salts that ensure reciprocal repulsion of
nucleated crystals, can be used. In any case, the patents containing such technical solutions were published in
1970-1980.
Polymers with specially selected functional groups that modify the surface of the microcrystal and prevent
its further growth, for example, polyimide with C 20-C 40 and C 16 -C 18 carbon radicals [18, 19], added to the fuel in the
concentration of 0.0025-0.1% (better, 0.005-0.025%), are frequently proposed.
There are both wax depressants and dispersants individually and composites following the two in one
principle on the market. The last solution is convenient for both suppliers and process engineers, but the optimum
effect is not guaranteed. For each fuel, the ratio of depressant and dispersant is individual and varies within wide
limits from 1:1 to 5:1. It is necessary to consider that the wax dispersant is more expensive than the depressant.
Ignition modifiers are represented by two large groups: alternative antiknocks and ignition promoters for
diesel fuels. Alternative antiknocks are being especially intensively patented, but only in Russia, Ukraine, China,
and other countries where industry does not provide for developments of high-octane naphtha cuts in a sufficient
amount. Conversion of Russian refineries to production exclusively of unleaded automotive gasoline was completed
in 2002, earlier than in many foreign countries.
However, the production volume was not balanced with the oil refining possibilities with respect to
manufacture of high-octane cuts (alkylate, isomerizate, etc.). Supplying it only became possible by creating an
assortment of additives based on N-methylaniline and organometallic iron and magnesium compounds. This
caused a turbulent increase in research and commercial activity in this area.

Table 3
Increase* in ON (MON)
Additive Concentration, vol. %
of model blend
N-methylaniline
sample 1 1 12
sample 2 2 18
1:1 blend with
N,N-dimethyl-N-isobutylidene hydrazine 2 10,5
cyclohexylamine 2 10
N,N-dimethylaniline 2 10,6
industrial blend of xylidenes 2 16
N-(2-hydroxy-5-methylbenzyl)-dimethylamine 1 6
N-(2-hydroxy-5-tert-butylbenzyl)-dimethylamine 1 6
Note. *The improbably high values of the increase in ON are probably due to incorporation of additives in the
model blends but not in the commercial gasolines.

159
Most active patents protect different versions of composites of N-methylaniline with oxygenates that
sometimes contain organoiron or manganese compounds. All specialists agree that it is not desirable to incorporate
metal-containing antiknocks in gasolines. To prevent carbon buildup on spark plugs and wear, the additives must
be carefully dosed, but this can be perturbed on the way from fuel manufacturer to consumer.
In addition, the careless supplier can add more additive to commercial gasoline, which already contains
the permitted amount of antiknock, so that the concentration of metal increases to an unacceptable level.
Nevertheless, additives of this type will still be used in Russia (especially by small fuel manufacturers) for years
to come, although in only a few cases.
The attempts to find new antiknocks based on different metals are of some interest. The series of studies
by V. Yu. Mavrin et al. on developing antiknocks based on lithium compounds merit attention. The high antiknock
effectiveness of alkali metals has been known for a long time [20], but many circumstances prevent their use. All
alkali metal compounds are poorly soluble in hydrocarbons, so that important concentrations in the fuel cannot be
attained.
However, the lithium cation differs from potassium and sodium cations by its smaller size and higher
capacity for complexation. The nature of the counterion affects the antiknock capacity of lithium [21]. As for the
response of hydrocarbons of different groups to lithium, it is approximately the same. This means first
that the increase in the motor and research octane numbers (MON and RON) is the same and second, that the
lower ON higher increase rule observed for metals of variable valence does not hold in the case of lithium
compounds.

Table 2
Property Alkyl nitrates Alkyl peroxides
Based on statistical data, it is possible
At 0.3% concentration of additive, to hypothesize that the effectiveness
Ability to increase CN
CN increases by 2-6 units of peroxides is approximately 85% of
the effectiveness of alkyl nitrates
Working concentration 0.05 0.5 % 0.05 0.3 %
Basically stable on impact and
Explosion hazard Dangerously explosive
friction
Stable during storage in ordinary
Stability during storage Can decompose with explosion
conditions
Oxidation of fuel is accelerated, gum
Effect on oxidative stability of fuels Weakly affect oxidation of fuel
formation is increased
Effect on antiwear properties of fuels Worsen Do not affect
At a 0.1% concentration of
Effect on increasing the concentration 2-ethylhexyl nitrate, the concentration
Do not contain nitrogen
of nitrogen in fuel of nitrogen in the fuel increases by 80
mg/liter of fuel
Compatibility with antiwear additives Poor Good
Compatibility with construction Compatible with metals and poorly
Corrosive with respect to metals
materials compatible with sealants
Toxic (LD50 of cyclohexyl Low toxicity (LD50 of dicumyl
Toxicity
nitrate = 425 mg/kg) peroxide = 5000 mg/kg)
Relative cost (cost of alkyl nitrates set
1 1.5 2
at unity)

160
We also note the studies on metalloporphyrins [22, 23]. The metalloporphyrin fraction is separated from
crude by selective extraction and treated with manganese acetate. The mixture of manganese complexes of petroleum
porphyrins obtained dissolves in gasoline and can be used to increase its ON.
With respect to effectiveness, metalloporphyrin complexes are as good as ferrocene and MCTM
(methylcyclopentadienyltricarbonyl magnesium), and superior to the above with respect to the stability (duration
of storage before the appearance of sediment). In addition, they absorb atmospheric oxygen, forming dioxygen
adducts that catalyze combustion and decrease the toxicity of exhaust gases.
However, N-methylaniline is the most effective and convenient in practice. The searches for more acceptable
antiknocks have not been successful. As an illustration, we cite some data obtained in tests of a model mixture
(MON = 70) of 70% isooctane and 30% n-heptane with a number of nitrogen-containing compounds (Table 3) [24].
N-methylaniline is manufactured in Russia in the amount of several tens of thousands of tons a year by
alkylation of aniline, obtained by reduction of nitrobenzene. Alternative paths are also being examined. For
example, a method of obtaining N-methylaniline by the catalytic reaction of nitrobenzene with methanol in the
presence of hydrogen has been proposed [25]. The prospects for using N-methylaniline are a function of two
contradictory factors.

58

1
2
CN

53

48
0 0.2 0.2
Concentration, %

Fig. 3. Cetane number of diesel fuel as a function of the concentration of additive:


1) 2-ethylhexyl nitrate; 2) di-tert-butyl peroxide; 3) dicumyl peroxide.

Fig. 4. Structure of patenting of diesel fuel combustion modifiers in 2001-2005: 1) soot


suppressants; 2) combustion catalysts; 3) smoke suppressants.

161
On one hand, the demand for alternative antiknocks is decreasing with an increase in production of
high-octane naphtha cuts. On the other hand, the increase in the ON of gasolines in accordance with the Euro
standards have increased this demand. The need for N-methylaniline will probably persist in the future, but new
composites that include detergents, antioxidants, and other additives and will allow using it in gasolines of
European rating.
Ignition promoters have become some of the most demanded additives due to the introduction of stiff
requirements for the CN of diesel fuels, but the assortment is not especially large. This is because
they are basically alkyl nitrates in chemical nature substances that must be manufactured in special
conditions. 2-Ethylhexyl nitrate is almost exclusively manufactured abroad. 2-Ethylhexyl nitrate and cyclohexyl
nitrate are manufactured in Russia. Isopropyl nitrate was also developed and used previously.
All alkyl nitrates are obtained by nitration of the corresponding alcohols. To expand and lower the price
of the feedstock base, variants of nitration of alcohol-containing feedstock are being examined. For example, an
additive which is even slightly better than 2-ethylhexyl nitrate according to [26, 27] has been obtained by nitration
of the 160-190C bottoms fraction from production of butanols containing approximately 75% 2-ethylhexanol.
Alkyl nitrates with different hydrocarbon radicals have similar effectiveness, although it is believed that
cyclohexyl nitrate is slightly more effective than its analogs. For this reason, the most convenient technology for
manufacturing it is being sought in some countries [28].
Alkyl nitrates with sufficiently high effectiveness are characterized by a number of serious drawbacks.
They are toxic, corrosive, and worsen the color of fuels during storage. In addition, their effectiveness gradually
decreases during storage of the fuels [29]. For this reason, attempts to create ignition promoters based on other
compounds have not stopped.

Table 5

Fuel Average wear scar diameter, mm


With no additive 533
With 0.2% di-tert-butyl peroxide 672
With 0.005% Dodulube-4940 antiwear additive 322
With 0.005% Dodulube-940 and 0.2% di-tert-butyl peroxide 270
With 0.2% Dodulube-4940 and 0.3% 2-ethylhexyl nitrate 330

Table 6
Approximate
Estimated future Total for future
consumption
Total, millions of consumption, consumption,
Additives volume in 2005,
rubles/year thousands of millions of
thousands of
tons/year rubles/year
tons/year
Alternative antiknocks 46 2700 Decrease
Ignition promoters 12 45 70 25 30 900 1200
Antiwear 0.1 0.5 3.5 20 57 200 300
Depressants-dispersants 1 1.5 130 200 35 450 750
Detergents 5 10 350 800
Antioxidants 0.2 0.5 1.5 4 0.2 0.5 1.5 4

162
The greatest attention is being focused on organic peroxides. We note that due to restriction of the
nitrogen content in diesel fuel, the California Air Resources Board is providing for gradual conversion to
manufacture of diesel fuels with peroxides [30]. Based on an analysis of the publications on use of alkyl nitrates,
the properties of these promoters are compared in Table 4.
Of the organic peroxides, symmetric dialkyl and diaryl peroxides are of practical interest. They are the
most stable during storage and heating and do not decompose on contact with water, olefins, and other compounds
which can be present in commercial fuels. The comparatively inexpensive and easiest to transform di-tert-butyl
peroxide (DTBP) has been most intensively studied abroad.
Domestic industry manufactures it in the form of a liquid with a flash point of 80C and a minimum
content of basic substance of 95%. Dicumyl peroxide a crystalline substance with a melting point of
approximately 40C is also of interest. The promoting effectiveness of these compounds was investigated on
a UIT-1 unit with the method in ISO 5165:1998 in diesel fuel with an initial CN = 48 [31].
According to the results obtained (Fig. 3), the CN of the fuel linearly increases with an increase in the
concentration of DTBP from 0 to 0.5%. The increase in the CN is 2 units per 0.1% added DTBP, i.e., this
peroxide acts similarly to 2-ethylhexyl nitrate. The CN of the fuel did not decrease during storage of fuel
with 0.3 wt. % DTBP for 6 months.
Their good compatibility with antiwear additives is an important advantage of peroxides. Alkyl nitrates,
which are strong SF, displace the active principle of an antiknock additive from the surface, reducing its
effectiveness by 3-5 times (the concentration of additive must be increased by as many times). Peroxides remain
in the volume of the fuel and do not compete with antiwear additives for the surface (Table 5) [31].

150
Number of additives

100

3 1
50

2
0
1985 1990 1995 2000 2005
Year
Fig. 5. Dynamics of authorization of additives for use in Russia: 1) domestic; 2) imported;
3) total.
120
Number of additives

80
3 1
40
2
0
1985 1990 1995 2000 2005
Year

Fig. 6. Dynamics of authorization of additives for use in Russia (without consideration


of alternative antiknocks): 1) domestic; 2) imported; 3) total.

163
We assigned the combustion catalysts proposed for fuel of all types but primarily for boiler fuels and
smoke suppressants and scavenger additives to additives that improve fuel combustion. The patent structure
over the past five years is shown in Fig. 4.
Classic smoke suppressants based on barium compounds have drawn the attention of developers but no
one uses them. This is due to a number of reasons: the increase in the ash content and filterability coefficient of
diesel fuel on addition of additives, the toxicity of barium-containing compounds, and the increase in emissions of
solid particles metal oxides, carbonates, and sulfates. Especially since the effect exercised by these additives
decreasing exhaust gas smoke can be obtained another way, for example, by maintaining optimum engine
operating conditions as a result of timely servicing and use of detergent additives.
Some metal compounds, primarily metals of variable valence: iron, manganese, copper, cerium, zinc, and
nickel, have been proposed as combustion catalysts. Ferrocene, which reduces emissions of carbon black by
more than 90%, is frequently used [32]. This compound prevents formation of carbon black deposits on heat-
exchange surfaces and worsens the heat transfer coefficient. As a result, heat losses can be reduced by 6% [33].
There are also additives designed for middle-distillate fuels. Envirox additive (from Cerulean Int.),
consisting of nanoparticles of CeO, is discussed in [34, 35]. Added to fuel in the concentration of 5-10 ppm in
metal, it ensures 10% savings and does not affect the properties of the lube oil.
The combustion catalysts 0010 (for diesel fuel) and 0011 (for automotive gasoline) based on iron
compounds were developed and approved for use in Russia in 2000. In testing fuels with 0.01% of these additives
by Passazhiravtotrans ATP No. 1 (St. Petersburg) on 400 Ikarus-250 buses with RABAMAN engines for 2.5 months,
emissions decreased by 25-70% [36].

Table 7

Approved for use in Russia


Fuel additives
before 2001 2001-2005
Antioxidants 6 0
Diesel fuel stabilizer 1 0
Biocide 1 0
Antiknocks 19 1
Ignition promoters 4 6
Depressants for diesel fuels 15 4
Wax dispersants (in composite with depressants) 1 1
Two-in-one depressants-dispersants 3 6
Depressants for marine boiler oils and ship fuels 9 5
Smoke suppressants and combustion catalysts 7 0
Detergents 8 2
Antiwear for diesel fuels 3 5
Antiscuff 1 0
Antiturbulence 1 1
De-icers 2 0
Antistatic 1 0
Marker 1 0
Total 83 31

164
Combustion catalysts can also be used as soot suppressants. For example, finely disperse CeO particles
from Rhodia Electronics and Catalysis deposited on a soot filter decrease the soot combustion temperature
to 410C [37]. The concentration of additive in the fuel is 10 ppm in metal. The metals (cerium, iron, copper) which
are the base of the soot suppressants are most frequently added to the fuel in the form of carboxylic acid salts,
adding ashless detergents to increase the stability of the solutions [38].
Such an important effect of soot suppressants should only be expected in engine operating conditions
where the temperature of the exhaust gases is comparable to the soot combustion temperature. At low loads and
crankshaft rotation rates, there will be no effect [39]. However, emissions of harmful substances in these cases are
low.
Antiwear additives for low-sulfur diesel fuels are a very intensively developing research area. This is due
to the practical importance of the problem and to the fact that the number of potential technical solutions has not
yet been exhausted. The production volume of low-sulfur fuels is increasing rapidly. At the same time, of all
additives, antiwear additives have been most intensively patented by foreign firms in Russia.
Engine manufacturers were also included in solving this problem (for example, improving the antiwear
properties of the working surfaces of fuel pump pistons by applying a coating consisting of a composite of
chromium, molybdenum, zirconium, and titanium nitrides has been proposed [40]), but with a large lag at this time.
Antiwear composites traditionally contained carboxylic acids (for example, tall oil [41]), their derivatives, or different
composites [42-46]. Other compounds can also be used, and their important characteristics are high surface
activity and good adhesion to metal surfaces.
Including a polyoxyethylated fragment in the composite and grafting it to the acid molecule are relatively
widespread [47]. It was noted long ago that the effectiveness of antiknocks decreases in the presence of other
additives with high surface activity detergents and depressants due to their competition for the surface.
This caused the creation of bifunctional additives, for example, with antiwear and depressant properties [48] or
antiwear and detergent additives [49].
We assign additives used in a small volume and in a limited assortment to the category of other additives.
They include additives of undoubted practical importance (antistatic, antioxidant, demulsifying) and those which
only appeared due to the fantasies of their developments, foaming, for example [50].
No interesting solutions were proposed in this period for antioxidant, stabilizing, and antistatic additives.
This could be because these products have been relatively well studied and their low volumes of use and
consequently small market are not stimulating new developments. Industry is satisfied with the existing assortment.

Table 8

Actually used
Additives
domestic imported
Alternative antiknocks 5 1
Ignition promoters 2 5
Antiwear 0 6
Depressant-dispersant 1 19
Detergent 0 0
Antioxidants 2 0
Total 10 31

165
100
6

Part of patents, %
5

50 4
3
2

1
0
Europe USA Russia

Fig. 7. Patenting structure for fuel additives in 2001-2005: 1) detergent; 2) depressant;


3) ignition modifiers; 4) combustion modifiers; 5) antiwear; 6) other.

Interest in marking additives dyes and markers (i.e., additives that do not color fuel but are found with
a certain effect) is increasing. Fuel manufacturers distinguish their products from fakes with these products.
For example, addition of 10 -4% anthraquinone or diazo dye, which is invisible to the naked eye but absorbs light in
a certain range, has been proposed [51]. One such marker OLOA-2510x has been approved for use in
domestic gasolines and diesel fuels.
Many studies have been dedicated to additives that reduce evaporation of gasolines during storage and
consequently save on fuel and reduce atmospheric emissions. Compounds with high surface activity that form a
strong film on the surface of the fuel, for example, carboxylic acid salts, organosilicon liquids, and nonionogenic
and cation-active SF, are used as such additives [52, 53].
According to the calculation in [54], this type of additive is more suitable for use in small tanks (up
to 1000 m 3) in comparison to alternative methods (floating roofs, etc.), while the opposite is true for tanks of larger
capacity. The disadvantage of these additives is that they are only effective in static storage conditions. In
pumping, when the integrity f the SF film is perturbed, nothing prevents the gasoline from evaporating.
The attempts to find a replacement for the classic organosilicon liquids are interesting with respect to
antifoaming additives. Polyisobutylene in relatively high (over 2.5%) concentrations [55] and polyalkylbenzene
glycols and esters in concentrations of under 0.5% [56] have been proposed as additives to prevent foaming of
light cuts.
Of the other additives, we mention thickeners, proposed for addition to gas-condensate diesel fuel to
increase its viscosity [57], and antiscuff additives based on carboxylic acid chromium complexes [58].
We note the additives designed for residual fuels. These additives have unjustly drawn little interest
from developers, although furnace residual fuel oils are relatively widely used in all countries and especially in
Russia. Not too large, but successful companies are involved in their development. Application of additives of
this type derives from the concepts of ERC (Emissions Reduzierings Concepte) GmBH: decreasing soot
formation, emissions of metal oxides with ash, and formation of bottoms [59].
The assortment of additives for residual fuels in Russia will stop satisfying the new conditions. Addition
of residues from thermal decomposition processes (thermal cracking, visbreaking) in boiler fuels will perturb their

166
Table 9

Weight (mg) of carbon


Level of carburetor
Automotive gasoline in combustion
fouling, points in intake valves
chamber
With no additive 8.8 86 727
With detergent
Alkor-Avto (0.08%) 9.7 19 719
foreign analog (0.06%) 9.8 16 875

Table 10
Temperature, C
Diesel fuel
solid point limiting filterability
With no additive -28 -17
With 0.05% additive
VES-410D combined with
with Keroflux-3502* -36 -40
with Dodiflow-4500* -40 -43
Keroflux** -34 -54
Dodiflow** -40 <-45
Notes. * Wax dispersant
** Wax dispersant and depressant composite (two in one).

aggregate stability: separation, formation of deposits, clogging of fuel preparation systems. It was found that
domestic, as well as the well-known foreign, additives are ineffective in this case [60, 61].
The ADDITIVES MARKET in Russia amounts to less than 50,000 tons/year, and monetarily, to
approximately 3 billion rubles* (Table 6). At first glance, it is comparable in volume with the market in industrially
developed countries, but in Russia it is basically constituted by the alternative antiknocks mentioned (2.7 billion
rubles).
The volume of utilization of diesel fuel additives is slightly higher than 200 million rubles, while it
is 7.5 billion rubles in Europe, and is projected to reach 11 billion rubles in 2008. In the future, when the countrys
refineries will refine fuels of world level alone, the market volume could increase to 1.5-2 billion rubles (with
consideration of gradual turning to use of alternative antiknocks).
This market has both domestic and imported products, with predominance of the latter. The interest in
foreign additives is due to the significantly increasing level of fuel quality requirements, which is outstripping the
processing capabilities of our refineries. Unfortunately, the most important additives for contemporary fuels are
almost all imported.
The dynamics of authorizing fuel additives for use in Russia over the last 25 years is shown
in Figs. 5 and 6. The data in Table 7, which reports information on the most important domestic and imported
additives approved for use in our country, can also serve as an illustration.

*This figure is less than the previously published figure in [62] due to a reduction in production of N-methylaniline

167
Table 11
Average wear scar diameter (mm) in diesel fuel
Additive
1 2 3

With no additive 576 552 497


With 100 ppm of
Alta 377 415 402
Lubrizol-539M 372
Dodulube-4940 358 356

Table 12

Additive Application Proposed nature of active component


Decrease soot combustion Metal-containing combustion
Soot suppressant temperature on soot filter to exhaust catalysts (concentration of metal in
gas temperature fuel under 10 ppm)
Compounds with charged or strongly
Prevent separation of fuel containing
Wax dispersant polar groups that cause wax
a depressant in cold storage
microcrystals to repel each other
Prevent formation of carbon in
SF composites, combustion catalysts,
Detergent-scavenger combustion chamber in engines with
and carbon modifiers
direct fuel injection
Increase physical stability of blended
Dispersant SF composites
residual fuels

Note that not all domestic developments are used in practice (Table 8). The cause of this is either the lack
of feedstock resources or the important lag behind foreign analogs with respect to quality and price, or the poor
familiarity of fuel manufacturers with domestic additives, or mistrust of them.
The patent statistics over the last five years (Fig. 7) indicate the inadequate attention of domestic developers
for additives that ensure manufacture of fuel of European quality. Most of the patents concern the same alternative
antiknocks that ensure an enormous immediate profit. This means that in production of fuels of world level, the
country is almost totally dependent on foreign companies.
This is still not especially noticeable, since Russian OR use foreign fuel additives that satisfy the European
standards EN-228 (gasolines) and EN-590 (diesel fuels) in small quantities and exclusively for export. However,
sooner or later, high-quality fuels will also be used in our country, and then the dependence on imports will
become totally obvious.
Domestic developers understand this very well. A tendency to create additives capable of displacing
imports from the Russian market has been observed in recent years. We will briefly characterize the basic completed
developments.
Alkor-Avto (TU 0257-003-11475232 2003) is the first domestic detergent for automotive
gasolines which is not inferior to foreign analogs in the effectiveness of preventing carbon in intake
valves [63]. The results of tests of Euro-2 Regular gasoline with the additive in the VAZ-2101 engine according
to STO ANN 40488460-001 2004 are reported in Table 9. Like the foreign additives for this application, it does not
affect sooting in the combustion chamber.

168
VES-410D ((TU 38.401-58-332 2003) and VES-503M (TU 38.401887 91) are depressants for diesel and
residual fuels.
DMN-2005 (TU 0257-001-26666001 96) is a depressant for marine and residual fuels and for crude oils.
VES-410D additive is a solution of a copolymer of ethylene and vinyl acetate in a hydrocarbon solvent.
The production technology at a pressure of 10-15 MPa, i.e., 10 times lower than the usual technology, is original.
This expands the possibilities of manufacturing the additive, in particular, in small batches, in a periodic reactor.
However, due to the lack of domestic wax dispersants, VES-410D additive is still used with a foreign component.
Some data on its effectiveness are reported in Table 10 [64].
Alta, Kaskad-5, and BV-01 are antiwear additives obtained, like many foreign analogs, with tall oil acids.
The compositions of the composites that ensure their high effectiveness and compatibility of the fuels containing
them with water and lube oils are a trade secret.
Domestic antiwear additives are similar to foreign additives in effectiveness. The results of tests of three
samples of low-sulfur diesel fuels with Alta and imported additives are reported in Table 11: the average wear scar
diameter was assessed with the HFRR method (ISO 12156).
In conclusion, the promising trends in developing new domestic fuel additives are noted in Table 12 based
on an analysis of the trends in engine building and oil refining and world practice.

REFERENCES
1. A. M. Danilov, Khim. Tekhnol. Topl. Masel, No. 5, 34-40 (1992); No. 1, 35-38 (1998); No. 6, 43-50 (2001).
2. Proceedings of the Scientific and Practical Conference New Fuels with Additives September 14-15,
2000; June 18-21, 2002; June 1-3, 2004 [in Russian], Academy of Applied Research, St. Petersburg
(2000, 2002, 2004).
3. Tekhnol. Nefti Gaza, No. 2, 4-36 (2004).
4. A. M. Danilov, Use of Additives in Fuels for Automobiles. A Handbook [in Russian], Khimiya, Moscow
(2000).
5. A. M. Danilov, Use of Additives in Fuels. A Handbook [Russian translation] Mir, Moscow (2005).
6. M. Alam, S. Goto, K. Sugiyama, et al., SAE Tech. Papers, Series N 2001-01-3680 (2001).
7. J. S. Manka, E. A. Lindenfelser, and F. E. Heller, Ibid., No. 2001-01-1927 (2001).
8. H. Eichsleder, E. Baumann, P. Muller, et al., Motortechn. Zeitschr., 61, No. 3, 144 (2000).
9. US Patent No. 6179885, 6511519.
10. European Patent No. 1116779.
11. Russian Patent Application No. 99121863/04.
12. British Patent Application No. 2361932.
13. US Patent No. 6183524.
14. L. O. Aleman-Wasquez and J. R. Villagomez-Ibarra, Fuel, 80, No. 7, 965-968 (2001).
15. US Patent No. 6299655, 6458173.
16. V. N. Pronyaev, E. V. Dunyashkina, V. I. Blokhin, et al., Khim. Tekhnol. Topl. Masel, No. 6, 143-15 (2002).
17. E. K. Sarandi, A. G. Martirosyan, K. M. Musaev, et al., Neftegaz. Tekhnol., No. 4, 90-93 (2005).
18. US Patent No. 6206939.
19. German Patent Application No. 10012267.
20. M. O. Lerner, Chemical Regulators of Motor Fuel Combustion [in Russian], Khimiya, Moscow (1979).

169
21. V. Yu. Mavrin, O. N. Kadkin, A. P. Kovalenko, et al., in : Proceedings of the II International Conference
New Fuels with Additives, St. Petersburg, June 18-21, 2002 [in Russian], Academy of Applied
Research, St. Petersburg (2002), pp. 57-65.
22. G. F. Miralamov, Neftegaz. Tekhnol., No. 5, 77-78 (2005).
23. G. F. Miralamov, Khim. Tekhnol. Topl. Masel, No. 4, 25 (2005).
24. Yu. D. Batrin, M. K. Starovoitov, V. A. Yakunin, et al., See [21], pp. 362-366.
25. V. V. Belov, in : Proceedings of the International Scientific and Technical Conference on Progress in
Technologies for Fuels and Lube Oils and Greases, Dnipropetrovsk, September 12-15, 2005 [in
Ukrainian], UDKhTU, Dnepropetrovsk (2005), pp. 97-98.
26. A. I. Elshin, Nauka Tekhnol. v Promyshl., No. 3-4, 19-25 (2004).
27. Russian Patent Application No. 2002130555.
28. Hu Ying-Xi, Chen Chi-Yang, and Lin Xia, J. Petrochim. Univ., 15, No. 1, 18-20 (20020.
29. Z. A. Sablina and A. A. Gureev, Motor Fuel Additives [in Russian], Khimiya, Moscow (1977).
30. T. J. Russel, R. J. Batt, and S. M. Mulqueen, in: 3 rd Int. Colloquium Fuel 2000, Technische Akad.
Esslingen, Ostfildern (Jan. 17-18, 2001), pp. 333-340.
31. A. M. Danilov, T. N. Mitusova, V. A. Kovalev, et al., Khim. Tekhnol. Topliv Masel, No. 6, 22-24 (2003).
32. Mod. Gebaudetuhn, No. 5, 10 (2002).
33. Techn. Bau, No. 12, 67 (2001).
34. Eur. Chem. News, 79, No. 2072, 19 (2003).
35. Chem. Eng. (USA), 111, No. 8, 17 (2004).
36. D. V. Serdyuk, V. V. Serdyuk, and L. A. Ashkinazi, Neftepererab. Neftekhim., No. 1, 17-19 (2001).
37. Th. Seguelong, Motortechn. Zeitschr., 63, No. 11, 956-958 (2002).
38. European Patent No. 1344809.
39. B. Terry and P. Richards, SAE Techn. Paper, Series N 2000-01-1922 (2000).
40. US Patent No. 6802457.
41. Russian Patent Application No. 99107667/04.
42. European Patent No. 1088880.
43. British Patent Application No. 2358192.
44. FRG Patent Applications No. 199955354, 1995651, 10058357.
45. Germany Patent Application No. 10143021
46. US Patent No. 6719814.
47. FRG Patent Applications Nos. 10156024, 10155748.
48. German Patent Applications No. 10000649, 10048682, 10058359.
49. US Patents No. 6270539, 6458173.
50. Russian Patent Application No. 99118558.
51. US Patents No. 6274381, 6811575.
52. O . V. S h a l a m b e r i d z e a n d R . Z . M a g a r i l , i n : P ro c e e d i n g s o f t h e S c i e n t i f i c a n d Te c h n i c a l
Conference Oil and Gas: Problems of Utilization of Resources, Production, and Shipment, Tyumen,
September 24-26, 2002 [in Russian], Tyum. GNTU, Tyumen (2002), pp. 220-221.
53. Russian Patents No. 2208040, 2208041, 2246529.
54. S. N. Volgin and V. A. Sereda, See [21], pp. 210-212.
55. British Patent Application No. 2359094.
56. FRG Patent Applications No. 10006623, 10006624.

170
57. E. N. Kabanova, S. T. Bashkatova, S. D. Likhterov, et al., Khim. Tekhnol. Topliv Masel, No. 1, 35-36 (2005).
58. V. E. Revyuk, E. I. Tishkov, V. S. Perekalov, et al., See [21], pp. 186-190.
59. Sch. Dreifacher, Brennstoffspiegel, No. 4, 20-21 (2002).
60. T. N. Mitusova, I. A. Pugach, V. S. Zubovich, et al., NITU, No. 1, 43-46 (2003).
61. T. N. Mitusova, I. A. Pugach, M. V. Bobkova, et al., Neftepererab. Neftekhim., No. 6, 35-38 (2005).
62. A. M. Danilov, Mir Nefteproduktov, No. 2, 2-6 (2004).
63. E. A. Nikitina, V. E. Emelyanov, I. F. Krylov, et al., See [25], pp. 90-94.
64. A. M. Danilov, See [3], pp. 4-19.

171