(Journal) Chemistry and Technology of Fuels and Oils. 2007. No 1 (2007)

Chemistry and Technology of Fuels and Oils, Vol. 43, No.
1, 2007
CURRENT PROBLEMS
RUSSIAN ENVIRONMENTALLY CLEAN DIESEL FUELS OF EUROPEAN

QUALITY
V. G. Rassadin, O. V. Durov, G. G. Vasil’ev, N. G. Gavrilov, UDC 665.753

O. Yu. Shlygin, and N. M. Likhterova
The results of screening tests of foreign catalysts from Criterion, Haldor Topsoe, and Akzo Nobel for
production of EN–590 (Euro–2, Euro–3) diesel fuels are examined. The effectiveness of revamping the
LCh–24/2000 unit for processing these fuels using the Akzo Nobel catalyst package was demonstrated.
The physicochemical characteristics of the diesel fuel with additives that satisfies the requirements of
GOST R 52368-2005 for fuel with a residual sulfur content of less than 50 ppm are reported.
The high price of crude oil all over the world allowed diversifying the processing schemes for domestic oil
refineries (OR) at the beginning of 2000 to increase the competitiveness of their products on world markets. The
tendency to produce petroleum products of European quality at Russian OR became irreversible after the advent
of the law on “Technical Regulation” (June 26, 2003).
Revamping and retooling of motor fuel production units are now being conducted at almost all Russian
OR [1–10].
The leading oil companies have perfected technologies for production of high–quality motor fuels in two
directions. TNC and Angara Oil Company have primarily attempted to fully utilize domestic developments in the
area of technology, catalysts, and equipment in developing a strategy for retooling and revamping existing fuel
production plants.
LUKOIL has taken into account world experience, including purchase of licenses for the most promising
technologies, equipment, and catalysts from the leading firms in the USA and Western Europe. Guarantees of the
reliability of operation and high quality of the equipment and catalysts allowed organizing production of export
products of European quality at OR in record times, which expanded the amount of investments for further
development of their refineries combined with the high crude oil prices.
____________________________________________________________________________________________________
LUKOIL OJSC-Nizhegorodnefteorgsintez. Translated from Khimiya i Tekhnologiya Topliv i Masel,
No. 1, pp. 3 – 9, January – February, 2007.
0009-3092/07/4301–0001 © 2007 Springer Science+Business Media, Inc. 1

Table 1
Hydrogenation product obtained on catalyst
Feedstock for 448 T@ with
certification beads
of catalysts with diameter of,
mm
GM-85 Co
GKD-300
424 T@
TK-554
448 T@, GM-85 Co
Indexes
TK-554, 424 T@,
GKD-300
1.3 2.5
Density at 20°C, kg/m3 839 837 828 829 828 829 830 832
Content
total sulfur, ppm 10200 9700 100 600 170 500 1300 540
nitrogen, ppm 83 97 70,1 74,2 76 79,4 77,4 74
hydrocarbons, wt. %
unsaturated 0,26 0,93 1,06 1,4 1,23 1,08 0,8 1,02
aromatic (including thiophene derivatives) 32,5 22,9 22 21,6 21,1 23,2 27,5 32,5
Cetane number 51 53 55 50 54 54 54 52
The strategy for developing production of high–quality diesel fuels created at LUKOIL includes four
stages:
• hydrorefining of straight–run diesel cuts on high–efficiency foreign catalysts that allow obtaining
products with a residual sulfur content of less than 350 (version I) and less than 50 (version II) ppm in existing
hydrorefining units;
• combining hydrorefining and hydroisomerization of straight–run diesel cuts with a residual total sulfur
content of less than 10 ppm and less than 11% polycyclic aromatic hydrocarbons in newly constructed hydrotreating
units based on licenses from the leading foreign firms in this sector;
• combining desulfurizing, denitration, and hydrodearomatization of catalytic gasoils, coking, visbreaking
in complexes for exhaustive refining of crude oil using catalysts and technologies from the leading foreign
companies;
• hydrocracking of vacuum straight–run and secondary gasoils with a mandatory system for removal of
high–molecular–weight polycyclic aromatic hydrocarbons [11].
Within the framework of this strategy, LUKOIL is the developer of national standards for production
of EN–228 automotive gasolines (GOST R 51866–2002), domestic Jet A–1 fuel (GOST R 52050–2003),
and EN–590 diesel fuel (GOST R 52368–2005).
Development of national standards for motor fuels of European quality corresponds to the requirements
of the law on “Technical Regulation” and is totally harmonized with the text of the draft special technical regulation
“Requirements for Gasolines, Diesel Fuel, and Individual Fuel–Lubricant Materials.” The latter has been approved
and will become a Federal law in 12 months after the date of official publication.
LUKOIL is thus successively implementing diversification of oil refinery technology in view of world
trends.
According to the strategy developed, the first stage of diversification of diesel fuel production technology
is being implemented at LUKOIL–Nizhnegorodnefteorgsintez Co. User demand in internal and external markets for
2
Table 2
Hydrogenation product on KF–757
Indexes Feedstock for testing KF–757 catalyst
catalyst
Distillation, °C
IBP 111 164
10 % 183 242
50 % 277 313
90 % 358 368
EP 404 412
Content*, ppm
total sulfur 15289 10**
methylthiophenes 49 Not detected
C2–C4 thiophenes 2524 same
benzothiophenes 340 same
C1–C5 benzothiophenes 8088 same
C1–C5 dibenzothiophenes 4287
nitrogen 972 217
Cetane index 43.5 44.5
Notes. * Determined by atomic–emission analysis
** Determined by XFA
the products manufactured by the company is being evaluated to determine the niche in sales markets to 2014. In
conducting the market analysis, the following hypotheses were advanced concerning the development of internal
and external markets:
• the increase in the real earnings of the population will be up to 6% a year;
• the passenger car fleet will increase by 40% by 2010;
• production of passenger cars will increase to 2–2.5 million units by 2010 and imports will crease
to 400,000 units;
• the increase in demand for motor fuels in Russia will be determined by the growth rate of
the Russian GDP, slightly exceeding it;
• exports of gasoline to Europe will be limited except perhaps for a small amount of high–octane gasoline
to Baltic countries;
• the demand for diesel fuel for internal and external markets will increase.
According to market studies, potential annual sales volumes for the basic petroleum products
for LUKOIL–Nizhegorodnefteorgsintez by 2014 are projected at, in millions of tons: 2.8–2.9 for gasoline; 1–1.5 for
jet fuel; 4–5 for diesel fuel; 2.5–3 for boiler fuel.
Based on an analysis of sales markets and the status of the available production capacities for hydrorefining
of middle–distillate fuel cuts at the company, the LCh–24/2000 unit with output of 2 million tons/year in feedstock
started up in 1993 was selected for revamping. The unit includes the following blocks: reactor, hydrogen product
stabilization; treatment of circulating hydrogen–containing gas (CHCG) and hydrocarbon gas to remove hydrogen
sulfide, ammonia, and water with a solution of monoethanolamine (MEA); regeneration of MEA.
Before beginning revamping, a bid for selecting the catalyst for hydrotreating of diesel cuts to
obtain EN–590 fuel was conducted between the licensing companies Criterion, Haldor Topsoe, Axens, and Akzo
Nobel.
3
Sulfur content, ppm
Sulfur content, ppm
Temperature,°C
Temperature,°C
Fig. 1. Sulfur content in hydrogenation product as a function of the temperature in the

reactor for catalysts: a) TK–554; b) 424T@; c) 448 T@ with granules 1.3 mm (curve 1)
and 2.5 mm in diameter (curve 2); d) GKD–300 (curve 1) and GM–85 Co (curve 2);
e) STARS series KF–757.
The foreign catalysts TK–554 (Haldor To p s o e ) , 424T@, 448 T@ (Criterion),

and STARS series KF–757 (Akzo Nobel) in comparison to the domestic catalysts GM–85 Co (VNIIOS NK
[All–Russian Scientific–Research Institute of Organic Synthesis Oil Co.]) and GKD–300 (VNII NP
[ All–Russian Scientific–Research Institute of the Petroleum Industry]).
The tests were conducted at pressure of 3 MPa, feedstock space velocity of 4 h –1 , CHCG to sulfur ratio
of 250 nm 3/m 3. The domestic catalyst GKD–300 was tested in more severe conditions: pressure of 4 MPa, feedstock
space velocity of 3 h –1 . To obtain hydrogenation products with a residual sulfur content of less than 50 ppm, the
feedstock space velocity did not exceed 2–2.5 h –1 . The physicochemical properties of the feedstock used in
certification of the catalysts are reported in Tables 1 and 2.
In testing KF–757 catalyst on a wide middle–distillate cut that included heavy naphtha cuts (IBP–10%),
kerosene and diesel cuts with a high (404°C) end point by atomic emission analysis, we were able to follow the
degree of removal of thiophene derivatives of different molecular weight.
4
Content, wt. %
TK–554 424T@ 448 T@ 448 T@ GM–85 Co GKD–300

1.3 2.5
Fig. 2. Coke (1) and sulfur (2) content on catalysts after testing at 380°C.
The dependences of the total sulfur content in the hydrogenation products on the temperature in the
reactor were established during the experiments (Fig. 1). The residual sulfur content in the hydrogenates was
determined by x–ray fluorescence analysis (XFA). The data obtained show that KF–757 catalyst exhibits the
highest activity in reactions of hydrogenolysis of sulfur compounds.
The physicochemical properties of the hydrogenation products with a minimum content of sulfur
compounds obtained in testing the catalysts are reported in Tables 1 and 2.
The coke and sulfur content was determined after completion of the experiments at a temperature of 380 on
the domestic catalysts and Criterion and Haldor Topsoe catalysts. As the data show (Fig. 2), the domestic
catalysts have a high tendency to form coke deposits while GM–85 Co catalyst is also characterized by a low
degree of sulfiding.
As a result of testing the catalysts and generalizing the licensing company data, preference was given to
Akzo Nobel. This company’s catalyst package was purchased and loaded in 2003: KG–55, KF–542, KF–841,
KF–757. The characteristics of these catalysts are reported in Table 3. The total volume loaded was 77 m 3. The
loading diagram is shown in Fig. 3.
Before loading the catalyst system, partial revamping of reactor R–201 and individual units in the installation
was conducted to increase its efficiency:
• a new DUPLEX distribution tray from Akzo Nobel was installed in the reactor;
• the heat–exchange conditions were improved in the lower part of tower K–205 in the MEA regeneration
block to reduce the concentration of hydrogen sulfide in CHCG;
• defects in feeding MEA to tower K–205 were identified and eliminated;
• discharge of treated diesel fuel into the PLC system;
• the vapor cooling conditions in stabilization tower K–201 were improved and the possibility of fuel
entering the circulating water supply system was eliminated;
• the efficiency of operation of furnace P–201 was increased;
• a separate line was installed for taking environmentally clean diesel fuel (less than 350 and less
than 50 ppm sulfur) off the unit.
Installation of new lines for taking stable hydrogenation product off the unit was caused by the high
dissolving power of the hydrogenation product with respect to deposits in the pipelines that previously transported
hydrogenation products with a higher content of sulfur compounds and resins. These data were obtained as a
result of many years of domestic experience in production of thermostable RT and T–6 jet fuels.
KF–757 catalyst was delivered in oxide form and impregnated with a special composition that fixes the
position of the active sites on the support. In this respect, sulfiding was allowed only by the feedstock. Sulfiding
5
6
Table 3
Bulk density, kg/m3
Loading Granule
Catalyst Chemical composition Granule shape Application
method size, mm
real
loading
reactor, m3
content, %
Required sulfur
in laboratory
in leak-proof
determination
Volume loaded in
in hose loading
Protective layer to trap
KG-55 Segmented particulate contaminants
Hose 1.53 SiO2/Al2O3 880 — — 647 19.2 × 9.5 –
ring and pollution, slowing
increase in pressure drop
Hydrogenation of
unsaturated compounds,
trapping of particulate
KF-542-5R same 2.04 MoO3/NiO/CoO on Al2O3 670 596 — 637 6×3 Ring contaminants (has a high 5
volume of free space),
improving feedstock
stream distribution
Exhaustive denitration
and hydrogenation,
KF-841-2E same 8.16 Ni/Mo on Al2O3 780 686 803 686 2.1×4.5 Cylinder trapping of metals, 10
improving feedstock
stream distribution
Exhaustive
STARS series hydrotreating of middle
Leak-proof 64.13 CoO/MoO3 on Al2O3 780 694 803 795 1.4 × 3.5 same 15
KF-757-1.5E distillates to 50 ppm
sulfur content
STARS series
Hose 1.02 CoO/ MoO3 750 668 772 647 2.6 × 5.1 Quadrilobe same 15
KF-757-3Q
was conducted according to the company’s recommendations for straight–run diesel cut with a 0.9 wt. % sulfur
content.
After sulfiding of the catalyst and entry of the unit into normal operation, a fixed run in two regimes that
ensured production of diesel fuel with a residual sulfur content of less than 350 ppm (version I) and less
than 50 ppm (version II) was conducted.
The results of the two versions of runs (Table 4) correspond to Akzo Nobel recommendations primarily
with respect to the sulfur content. In charging feedstock at 310 m 3/h, the sulfur content in the product was on
Layer
Catalyst brand Layer height, mm Layer volume, m3
number
Beads with diameter of, mm
1 16 – 20 690 –
2 10 50 –
3 6 90 –
4 KF-757-3Q 100 1.02
5 KF-757-1.5E 6250 64.13
6 KF-841-2E 795 8.16
7 KF-542-5R 200 2.04
8 KG-55 150 1.53
Total 8325 76.88
Fig. 3. Diagram of loading Akzo Nobel catalyst in reactor 201 (internal diameter
of 3616 mm, height of 11.192 mm, volume of 114.9 m3).
7
average 310 ppm, and the mean weighted temperature in the catalyst bed was 334°C, which is 16°C lower than the
temperature predicted by the company.
At feedstock input of 230 m 3/hk (guaranteed input of 210 m3/h), the residual sulfur content was 31 ppm and
the weighted mean temperature in the catalyst bed was 10° lower than expected.
D u r i n g t h e r u n , i t was not possible to maintain the concentration of hydrogen in the CHCG
at 80 vol. % (contract data) due to the low hydrogen content (76 vol. % on average) in the fresh HCG entering the
unit. It was only 69 vol. %, which decreased the partial hydrogen pressure at the reactor inlet from 2.4 (initial data)
to 1.9 MPa. This negatively affected the work of the catalyst system and increased the rate of coke formation on
the catalyst.
D u r i n g t h e c o n t r o l r u n i n l o a d i n g f e e d s t o c k a t 3 1 0 m 3/ h , t h e p r e s s u r e d r o p i n t h e r e a c t o r
was 0.31 MPa, i.e., slightly higher than predicted (0.24 MPa), which was due to the following causes:
increasing the total volume of actually charged catalyst from 70 to 77 m 3 ;
a low hydrogen content (69–70 vol. %) in the circulating gas, which increased the viscosity of the gas and
the CHCT flow velocity to 86–96,000 nm 3/h (according to calculated data, 75,000 nm3/h at an 80 vol. % concentration
of hydrogen).
All of these factors caused a significant increase in the pressure loss in the catalyst bed and an increase
in the pressure differential. After completion of the fixed run, HCG began to be fed from the reforming unit
Recovery Place block to the LCh–24/2000 unit with continuous regeneration of the catalyst. The concentration of
hydrogen in the HCG from this unit was 90–91 vol. %, which allowed reducing consumption of hydrogen and
blowing off HCG.
Table 4
Data from fixed run according to version

Indexes I II
programmed real programmed real
Sulfur content
in feedstock, wt. % 1.6 (max) 0.95 1.6 (max) 1
in product, ppm <350 300 <50 31/8*
Flow rate, m3/h
feedstock 310 310 210 230
CHCG (in normal conditions) 75000 84000 7500 94000
Pressure at reactor inlet, MPa 3.25 3.28 3.25 3.28
Pressure drop in reactor, MPa 0.24 0.31 0.19 0.27
Concentration in HCG, vol. %
hydrogen 80 69.6 80 69.6
hydrogen sulfide <0.1 Abs. <0.1 Abs.
Partial hydrogen pressure, MPa 2.4 1.96 2.4 1.96
Temperature of catalyst layer, °C
at beginning of cycle
at reactor inlet 340 328 353 348
at reactor outlet 356 337 369 355
mean weighted 350 334 363 353
Note. *In the numerator – residual sulfur content in stable hydrogenation product, determined by energy–disperse
X–ray fluorescence spectrometry; in the numerator – determined by X–ray spectrometry.
8
Table 5
Fixed run producing hydrogenation product with a sulfur
Feedstock, products content of, wt. %
<0.035 <0.05
Taken, wt. %
Feedstock 100.0 100.0
HCG 2.3 2.3
Total 102.3 102.3
Obtained, wt. %
Stable hydrogenation product 98.0 97.5
Distillate 1.8 2.2
Hydrogen sulfide 0.7 0.7
Hydrocarbon gas 1.6 1.7
Losses 0.2 0.2
Total 102.3 102.3
Table 6
Diesel fuel,
Standards for mild climate
version II
Indexes
Sample Sample
A B C D E F
1 2
Cetane number 55 54
Cetane index min 46 52.6 52.2
Density at 15°C, kg/m 3 820—845 835.8 836.4
Content
polycyclic aromatics, wt. % max 11 – –
sulfur, ppm max 350 31 40
water, mg/kg max 200 Abs.
Flash point (closed cup), °C min 55 70 70
Carbon residue of 10% residue, wt. % max 0.30 0.012 0.011
Ash content, wt. % max 0.01 Abs.
Total contamination, mg/kg max 24 1 1
Corrosiveness (copper, 3 h, 50°C) class 1 class 1
Oxidative stability, g/m3 max 25 3.1 3.1
Lubricity: corrected wear scar diameter (WSD 1.4) at 60°C, μm max 460 533 534
2
Viscosity at 40°C, mm /sec 2.0 – 4.5 3.03 3.03
Distillation, vol. %
under 250°C max 65 33 33
under 350°C min 85 95 95
95 vol. % Distillation temperature, °C max 360 350 350
Limiting filterability temperature, °C, max +5 0 -5 -10 -15 -20 -7 -7
The nitrogen content and cetane number of the hydrogenation product were determined during the run
together with the sulfur content in the feedstock and products. In production of diesel fuel with a sulfur content
of less than 350 ppm, the nitrogen content decreased from 132 to 95 ppm and the cetane number was 55 points.
9
Table 7
Operation of LCh–24/2000 unit
Indexes on GKD–300, GKD–205
on KF–757 catalyst
catalyst system
Consumption
of 100% hydrogen to reaction, wt. % in feedstock 0.358 0.417
3
fresh HCG, nm /h 12000 – 13600 17200 – 22400
Concentration of hydrogen, vol. %
in fresh HCG 78 – 80 77 – 78
in CHCG, nm3/h 77 – 78 73
Emission of HCG, nm3/h 4000 9000
Table 8
Data from operation of LCh–
24/2000
Consumption indexes per 1 ton feedstock on GKD–300 on Akzo Nobel
catalyst catalyst package
real planned real planned
Electric power, kwh/month 12.5 12.5 11.6 11.6
Steam, thousands of kJ/month 77.93 94.28 67.46 67.46
Fuel, kg equiv. fuel/month 7.6 7.6 7.3 7.3
MEA (over 6 months), kg 0.006 0.013 0.01 0.01
Losses, g
catalyst over 6 months 7 7 – –
catalyst package over 1 month
KG-55 (protective layer) – – 0.15 0.15
KF-542-5R (hydrogenation of unsaturated compounds, improved distribution) – – 0.2 0.2
KF-841-2E (denitration, hydrogenation, improved distribution) – – 0.86 0.86
KF-757-1.5E (exhaustive hydrotreating) – – 7.84 7.84
KF-757-3Q (exhaustive hydrotreating) – – 0.1 0.1
In production of diesel with a sulfur content of less than 350 and less than 50 ppm, the decrease in the
density of the product in comparison to the density of the feedstock was 6–8 and 10–11 kg/m 3 , respectively.
Despite the very low partial hydrogen pressure, the catalyst system had high hydrogenating activity with
respect to polycyclic aromatic hydrocarbons. The increase in the partial hydrogen pressure in the system to the
calculated values additionally decreased the density and increased the cetane number of the product as a result of
hydrogenation of aromatic structures.
The material balances of the fixed runs of the LCh–24/2000 unit with the Akzo Nobel catalyst package are
reported in Table 5. It follows from these data that an increase in the degree of removal of sulfur compounds
decreases the yield of stable hydrogenation product and increases the yield of cuts that distill below the boiling
point of the feedstock, as well as an increase in the yield of hydrocarbon gases. This is due to intensified
degradation of the hydrocarbons in the feedstock as a result of the increase in the temperature in the reaction
zone (see Table 4). In refining fuel according to version II, the temperature in the reaction zone should be
increased by almost 20°C.
Revamping the unit and replacing the GKD–300 and GKD–205 domestic catalysts by the Akzo Nobel
catalyst package ensured obtaining diesel fuel with a residual sulfur content of less than 350 and less than 50 ppm.
10
Diesel fuel with a residual sulfur content of less than 2000 ppm was previously refined in
the LCh–24/2000 unit. At the minimum reactor temperature (320–322°C at the inlet and 330–333°C at the outlet),
the sulfur content in the stable hydrogenation product was 400–500 ppm. This allowed increasing the volume of
production of fuel with a sulfur content of less than 2000 ppm by 60 m 3/h by mixing the stable hydrogenation
product with the straight–run diesel cut.
In the course of the version II fixed run, pilot–industrial lots of diesel fuel of environmental
classes 3 and 4 were obtained. The physicochemical properties of the class 4 fuel are reported in Table 6. This fuel
totally satisfies the requirements of GOST R 52368-2005.
To increase the lubricity, Lubrisol 539 M antiwear additive in the concentration of 50 ppm was added to
the diesel fuel with a 50 ppm sulfur content.
After the fixed runs, the hydrogen consumption and specific standards for consumption of electric power,
heat carriers, reagents, and catalysts were compared with the same indexes for operation of the LCh–24/2000 on
the domestic catalyst GKD–300. The comparison showed that the total consumption of hydrogen increased and
the proportion of blown CHCG increased significantly in using highly active catalytic systems (Table 7).. On the
contrary, the specific standards for consumption of electric power, fuel, and steam decreased (Table 8). Due
to the decrease in fuel consumption, for example, the economic effectiveness of operating the P–201 furnace
was 770,051 rubles/year.
Since the draft specifications provide for introduction of environmental requirements for
classes 3 and 45 diesel fuels as a federal law from 01.01.2009 and 01.01.2010, the diversification of production of
diesel fuel allowed LUKOIL”Nizhegorodnefteorgsintez to assume a leading position among RF oil refineries and
to make additional profits for a long time from offering high–quality diesel fuels on internal and external markets.
REFERENCES
1. V. N. Chistyakov and D. A. Pidzhakov, Neftepererab. Neftekhim. No. 7, 7–11 (2004).
2. A. I. Emilin, G. P. Grishanov, V. A. Mikishev, et al., Ibid., No. 8, 23–31 (2003).
3. S. A. Logino, B. P. Lebedev, V. M. Kapustin, et al., Ibid., No. 11, 67–74 (2001).
4. S. A. Loginov, V. M. Kapustin, A. I. Lugovskoi, et al., Ibid., No. 8, 11–13.
5. S. A. Logino, V. M. Kapustin, A. I. Lugovskoi, et al., Ibid., No. 11, 57–61.
6. S. A. Loginov, V. M. Kapustin, A. I. Lugovskoi, et al., Ibid., No. 10, 8–11.
7. A. I. Lugovskoi, S. A. Loginov, K. B. Rudyak, et al., Khim. Tekhnol. Topliv Masel, No. 5, 35–37 (2000).
8. V. K. Smirnov, K. N. Irisova, E. L. Talisman, et al., Ibid., No. 4, 37–41 (2004).
9. L. N. Osipov, V. A. Khavkin, B. L. Lebedev, et al., in : Proceedings of the Annual Scientific and
Technical Conference “The Current State of Oil Refining Processes” [in Russian], GUP “INKhP”,
OAO Bashneftekhim, Ufa (2004), pp. 142–144.
10. V. P. Kostyuchenko, Ibid., pp. 145–155.
11. V. P. Bazhenov, InfoTEK: Statistika, Dokumenty, Fakty, No. 11, 83–90 (2002).
11
Chemistry and Technology of Fuels and Oils, Vol. 43, No. 1, 2007
TECHNOLOGY
EXPERIENCE IN OPERATING FUEL-CUT HYDROTREATING UNITS
G. G. Vasil’ev, O. V. Durov, V. G. Rassadin, N. G. Gavrilov, UDC 665.753

O. Yu. Shlygin, and N. M. Likhterova
The data on use of the GKD-205 and GKD-300 catalyst system in the L-24/7 unit are generalized. These
catalysts lose activity during each regeneration, which negatively affects the unit’s operating conditions.
In refining diesel fuel of environmental class 2 (Euro-2), the output in feedstock decreases sharply and
the temperature in the reactor increases. In addition, they are characterized by low mechanical strength:
losses from wear are greater than 10 wt. %. It is recommended that they be replaced by highly effective
catalysts with improved operating properties.
The development of a comprehensive systems program for retooling and developing the oil refinery
without fail includes an analysis of the current state of active plants. Revealing the cause-effect correlations in
unsatisfactory operation of units in production of higher quality products is the basis for developing substantiated
solutions in improving the technical and technological states of existing and newly constructed units.
A comprehensive inspection of fuel cut hydrorefining units to detect problems in their operation was
conducted in 2000-2002 at LUKOIL–Nizhegorodnefteorgsintez. The results of the inspection of the L-24/7
hydrotreating unit in operation on the system of GKD-205 and GKD-300 domestic catalysts are reported here.
Diesel fuels with a residual sulfur content of less than 0.2 wt. % have been produced according to GOST
305 in this unit since 1996. However, after converting the unit to production of diesel fuel with a residual sulfur
content of less than 0.05 wt. %, significant worsening of the activity of the catalyst system was noted, especially
after regeneration. This was manifested by a decrease in the output of the unit in feedstock, an increase in the
temperature at the reactor inlet, and a pressure drop in the reactors of both blocks (Tables 1 and 2).
For example, the temperature at the inlet to reactor R-1 increased significantly – to 355°C (345°C before
regeneration) and the pressure drop also increased to 1.2 MPa in unit I (see Table 1) 3 months after the first
regeneration of GKD-205 catalyst.
____________________________________________________________________________________________________
LUKOIL–Nizhegorodnefteorgsintez OJSC. Translated from Khimiya i Tekhnologiya Topliv i Masel,
12 0009-3092/07/4301–0012 © 2007 Springer Science+Business Media, Inc.

Table 1
Block I operating indexes
Duration of feedstock space temperature (°C) at reactor
pressure (MPa) in reactor sulfur content, wt. %
run, months consumption, velocity, inlet
m3/h h-1 R-1 R-2 overall in hydrogenation
R-1 R-2 in feedstock
(inlet/outlet) (inlet/outlet) differential product
On GKD-205 catalyst
fresh
27 120 3.8 340 340 3.6/3.1 3.1/3 0.6 0.63 0.09
135 4.3 345 348 3.8/3.3 3.3/3.2 0.6 1.13 0.18
after regeneration
8 40 1.3 230 232 3.1/3.1 3.1/3 0.1 Kerosene Kerosene
110 3.5 355 357 3.8/3.4 3.4/2.6 1.2 0.94 0.2
130 4.1 371 378 4.5/3.8 3.8/3 1.5 1.4 0.19
after recharging and screening
10 120 3.8 360 365 3.6/3.5 3.5/3.5 0.1 1.21 0.2
110 3.5 361 366 4.4/3.8 3.8/3.3 1.1 1.17 0.13
On fresh GKD-300 catalyst
1 40 1.3 235 237 3.6/3.5 3.5/3.4 0.2 Kerosene Kerosene
4 80 2.6 345 347 2.85/2.8 2.8/2.6 0.25 1 0.17
110 3.5 360 364 2.9/2.75 2.75/2.6 0.3 1.04 0.18
6 80 2.6 350 353 2.9/2.65 2.65/2.5 0.4 1.25 0.16
110 3.5 370 374 3.25/3 3/2.8 0.45 1.3 0.18
7 85 2.7 355 358 3.1/2.8 2.8/2.7 0.4 1.26 0.13
140 4.5 374 376 3.5/3.1 3.1/2.9 0.6 1.23 0.16
8 70 2.3 361 363 3.3/3 3/2.8 0.5 0.97 0.03
137 4.4 375 378 3.5/3 3/2.9 0.6 1.15 0.13
1.1
14 145 4.7 374 379 3.8/3.1 3.1/3 0.8 0.11
(tEP. – 350°С)
148 4.8 368 372 3.8/3 3/2.9 0.9 1 0.18
18 65 2.1 367 372 3.6/2.7 2.7/2.5 1.1 0.95 0.049
19 85 2.7 367 375 4.1/3.3 3.3/3 1.1 0.8 0.036
90 2.9 370 375 4.2/3.4 3.4/3 1.2 0.85 0.047
95 3.06 370 377 4.4/3.4 3.4/3.1 1.2 0.81 0.05
20 85 2.7 365 370 4.1/3.3 3.3/3.1 1 0.91 0.035
88 2.8 367 374 4.1/3.35 3.35/3.05 1.05 0.86 0.049
21 90 2.9 374 380 4.1/3.3 3.3/3.3 0.8 0.94 0.03
22 90 2.9 374 380 3.4/3.1 3.1/3 0.4 0.79 0.026
23 140 4.5 370 382 3.7/3.3 3.3/3.2 0.5 0.93 0.11
90 2.9 370 373 3.45/3.1 3.1/3 0.45 0.92 0.03
13
14
Table 2
Block I operating indexes

temperature (°C)
Duration of pressure (MPa) in reactor sulfur content, wt. %
feedstock at reactor inlet
run, months space velocity,
consumption, in
h -1 R-3 R-4 overall
m 3 /h R-3 R-4 in feedstock hydrogenation
(inlet/outlet) (inlet/outlet) differential
product
On GKD-300 catalyst
fresh
25 110 3.4 335 337 3.5/3.5 3.5/3.3 0.2 0.6 0.095
100 3.1 355 358 4/3.6 3.6/3.5 0.5 1.22 0.16
after first regeneration
17 105 3.2 355 357 4.1/3.8 3.8/3.7 0.4 1 0.2
120 3.5 365 370 4/3.7 3.7/3.5 0.5 0.9 0.15
110 3.2 380 385 3.6/3.3 3.3/3.1 0.5 1.17 0.1
after second regeneration
0 100 3.4 355 359 3.7/3.5 3.5/3.4 0.3 1.07 0.18
6 125 4.2 375 378 3.4/3.3 3.3/3.2 0.2 1.04 0.17
18 100 3.3 358 360 3.2/2.9 2.9/2.7 0.5 0.88 0.2
26 60 2 378 380 3.4/3.1 3.1/3 0.4 0.91 0.04
Important loss of activity after each regeneration was also noted for GKD-300 catalyst in
block II (see Table 2). After the first regeneration of the catalyst, the temperature at the reactor inlet
was 350-357°C (versus 335-337°C on fresh catalyst) in loading the block in feedstock at 105 m 3 /h (100 m 3/h after
regeneration).
After the second regeneration 17 months later, the temperature at the reactor inlet increased to 355-359°C,
and the block charge in feedstock decreased to 100 m 3/h. Refining fuel with a residual sulfur content of less
than 0.2 wt. % with an increase in the output of the block to 130 m 3/h (feedstock space velocity of 4.3 h -1 ) became
possible only when the reactor inlet temperature increased to 378-380°C.
Production of diesel fuel with a residual sulfur content of less than 0.05 wt . % on GKD-300 catalyst in
block I (see Table 1) was characterized by an increase in the pressure drop to 1.0-1.2 MPa and the reactor inlet
temperature to 370-380°C for a feedstock space velocity of 2.7-2.9 h -1.
In refining diesel fuel of environmental class 2 in block II (Euro-2) with a sulfur content of less
than 0.05 wt. %, the reactor inlet temperature was 378-380°C for a feedstock space velocity of 2.0-2.1 h -1 and a
pressure drop in the system of 0.4-0.5 MPa (see Table 2).
The data in Table 3 also confirm the decrease in the activity of GKD-300 catalyst as a result of regeneration.
After regeneration, the pore volume and specific surface area of the catalyst decreased by 42 and 38%, respectively.
Table 3
GKD-300 catalyst (block II)

after
passivation from after regeneration at catalyst plant (Ufa)
Indexes reactor
fresh
According to according to
R-3 R-4 LUKOIL–Nizhegorodnefteorgsintez catalyst plant
data data
Content, wt. %
dust and grit 0.03 0.19 0.15 0.21 –
coke — 3.54 2.56 0.07 0.12
sulfur 0.03 3.59 3.69 0.037 0.8
iron 0.01 0.054 0.045 0.014 –
Specific surface area, m2/g 240 131 124 140* 193.1
Pore volume, cm3/g 0.74 0.34 0.3 0.46 –
Note. *According to data from Nizhegorodskie Sorbenty, 160 m /g.2
Table 4
Content, wt. %
Catalyst
coke sulfur iron
Block I
GKD-205 from reactor
R-1 4.29 11.1 3.43
R-2 2.18 12.07 5.09
Block II
GKD -300 from reactor
R-3 3.5 6.75 2.25
R-4 1.54 6.54 1.72
15
The increase in the pressure differential in the reactor systems of blocks I and II during operation of the
unit is due to abrasion of the catalyst granules and clogging of its pore structure with products of corrosion. The
compositions of the catalyst dust and grit, determined in discharging the catalysts after passivation, are reported
in Table 4.
As follows from the data reported, GKD-205 catalyst has a high tendency to form coke deposits
and low hydrogenating power. The high concentration of sulfur in the grit of this catalyst indicates
participation of feedstock sulfur compounds in condensation of high-molecular-weight hydrocarbons and resinous
compounds. GKD-300 catalyst grit i8s characterized by a lower iron content, which is probably the case of the
high porosity of the bed of this catalyst, caused by the high mechanical strength of its granules.
It is thus necessary to replace the traditionally used catalysts by high-efficiency catalytic systems
characterized by improved performance properties in order to produce diesel fuels of European quality in existing
units.
16
REVAMPING THE EXTRACTION BLOCKS IN VACUUM RESID DEASPHALTING

UNITS
K. G. Ziganshin, A. A. Osintsev, G. K. Ziganshin, A. I. Elshin, I. V. Pavlov, UDC 665.637.6:665.662.3

L. A. Ponyaev, O. A. Chekenev, S. Yu. Tvorogov, A. A. Rytsev,
A. V. Pastukhov, S. V. Kuznetsov, S. P. Yanbaev,
Zh. Yu. Gusakova, and A. L. Samoshkin
Deasphalting of vacuum resid with liquefied propane is usually conducted in extraction towers of the
gravity type. Standard towers (Fig. 1a) have a small (~7 m) height of the propane and vacuum resid reaction zone
and are equipped with baffle trays that consist of metal trays 353 mm wide and 6 mm thick with a step of 68 mm
positioned at a 45° angle.
This design of the internals insignificantly increases the time the phases are held in the tower and causes
formation of “coke” deposits, which are high-melting asphaltite, on the trays. The extraction tower with baffle
trays is close to the spray tower in efficiency.
Table 1
Refractive index at 50°C for

Vacuum resid quality
Deasphalted product takeoff deasphalted product from
indexes
tower
Year nominal
flash point
in second in 36/2M [Engler]
in first block K-1 K-2 (closed
block unit viscosity at
cup), °C
80°C, sec
Before revamping 36/2M unit
2003 — — 37.0 Standard max of 1.5050 — —
After revamping of first extraction block
2004 41.0 37.3 39.3 1.5027 1.5035 19.2 195
2005* 41.2 36.5 38.9 1.5023 1.5030 19.7 200
After revamping of second extraction block
2005 41.8 41.2 41.5 1.5027 1.5034 22 210
Note. *For January–September, 2005.
____________________________________________________________________________________________________
IMPA Engineering Ltd.; Angara Petrochemical Company. Neftekhimmash Co. Prommet Ltd. Translated
from Khimiya i Tekhnologiya Topliv i Masel, No. 1, pp. 13 – 16, January – February, 2007.

a IV b IV
V V
V V
V I V
3
I
1
2
II II
III III
Fig. 1. Diagram of the vacuum resid deasphalting extraction tower: a) before revamping;
b) after revamping; 1) baffle trays; 2) IMPA Engineering packing; 3) mixer; I) vacuum
resid; II) propane; III) asphalt solution; IV) solution of deasphalted product; V) steam.
To increase the deasphalting efficiency, a combined technical solution is proposed: use of contact devices
from IMPA Engineering [1] combined with the vacuum resid preparation scheme in [2, 3]. The reaction of the
phases on the catalyst systems is potentiated inside the tower and additional reaction of the phases in a special
mixer in the feedstock preparation unit takes place outside the tower (Fig. 1b).
This solution was implemented in the 36/2M unit for deasphalting vacuum resid with liquid propane at the
Angara Petrochemical Co.’s Oil Refinery. The unit has two parallelly operating extraction blocks with separate
blocks for regenerating the deasphalted solution, which allows obtaining two deasphalting products.
The first extraction block was revamped in 2004, then the indexes of operation of the two extractors – the
first with IMPA Engineering contact devices and a vacuum resid preparation unit, and the second, with baffle
trays. The towers (3 m in diameter, 19.7 m high) operated on the same feedstock. In 2005, after revamping the
second block, the operating indexes obtained for the entire unit were generalized.
18
Table 2
Vacuum resid
Indexes after revamping of
before revamping*
first block** second block***
Density at 20°C, kg/m 967 – 993/977 993 –
Flash point, °C
closed-cup 180 – 206/194 175 – 210/206 180 – 210/207
open-cup – 250 250
Concentration of chlorides, mg/dm3, max – 5 – 9/7 9 – 12/11
Carbon residue, % – 14 – 15/14.4 13 – 15/13.7
Nominal [Engler] viscosity at 80°C, sec 13 – 28/19.3 16 – 28/21.6 15 – 23/19
Concentration of alkali, g/ton – 10 – 20/16 13 – 19/16
Note. In the numerator: limiting values; in the denominator: average value.
*For January–October, 2003. **For September–October, 2005. ***For November–December, 2005.
Table 3
Deasphalted product
Indexes after revamping of
before revamping
first block second block
Viscosity at 100°C, mm2/sec 18 – 24/21 18 – 24/21.5 19 – 24/21.7
Refractive index at 50°C 1.5000 – 1.5050/1.5028 1.4990 – 1.5050/1.5021 1.5000 – 1.5050/1.5026
Color, CST units 5.5 – 6.5/6 5 – 7.5/6 5.5 – 6/6
Carbon residue, % 0.82 – 1.1/0.93 0.72 – 1.1/0.93 0.8 – 1.1/0.95
Density at 20°C, kg/m3 914 – 923/920 908 – 922/917 913 – 922/918
Note. In the numerator: limiting values; in the denominator: average value.
* For January–October, 2003. ** For September–October, 2005. *** For November–December, 2005.
Both projects were executed in brief times due to the coordinated work of all participating organizations:
Angara Petrochemical Company, IMPA Engineering, Neftekhimmash Co., and Prommet Ltd.
IMPA Engineering, which specializes in improving extraction processes, won the bid for the projects. It
developed the revamping projects, procured the packages for internals and mixers, and supervised installation of
the equipment.
The advantages of the proposed conclusion include the effective phase reaction on contact devices.
This is done by increasing the active interface, varying the distribution of the contacting phases over the section
of the tower, and creating a film of solid phase with a two-sided working surface due to the hydrodynamically
permeable film-forming surfaces. Their assigned position forms a periodic phase collection and redistribution
system.
A number of factors that reduce “coking” of he packing is also characteristic of the IMPA contact devices:
optimum stream hydrodynamics and nonmagnetic packing material – stainless steel. Stainless steel is used because
high-melting asphaltite, which has polar properties, forms “coking” foci that subsequently enlarge on ordinary
carbon steel. The trays are also designed for simple and fast assembly/disassembly.
The feedstock preparation unit, where the vacuum resid is mixed with propane in its special mixer, allows:
• developing the phase contact surface before the feedstock enters the tower;
19
Table 4
Content, % Extraction coefficient
Components in vacuum in deasphalted product
DA-1 DA-2
resid DA-1 DA-2
Hydrocarbons
paraffins and naphthenes 9.4 27.5 23.8 2.93 2.54
aromatics 59.1 68 70.8 1.15 1.2
Resins 22.9 4.5 5.3 0.19 0.23
Asphaltenes 8.6 Abs. Abs. 0 0
Notations. DA-1, DA-2 – deasphalted products from first (with contact devices) and second (with baffle trays) blocks.
Table 5
Indexes Project 1 Project 2

Discount rate, % 10 10
Payback period, months 9.5 7
Discounted payback period, months 10.5 8
Accounting rate of return, % 231 313
Net present value, US$ 1,391,058 2,017,370
Investment profitability index 7.7 10.2
Internal profit rate, % 130 160
2.25
1.75
million US dollars
2
1.25
NPV,
1
0.75
0.25
−0.25
2004 2006 2008 2010 2012 2014 2016
Year
Fig. 2. Change in net present value NPV by years after revamping of 36/2M unit:
1) according to project 1; 2) according to project 2.
• bringing the feedstock and solvent entering the unit to a state of phase equilibrium and obtaining up to
one additional theoretical contact stage as a result;
• significantly improving phase distribution over the tower section and enhancing heat and mass exchange
in the extractor due to the decrease in the viscosity of the vacuum resid previously saturated with the solvent.
This technical solution allowed significantly improving the operating indexes of the 36/2M unit. The
results of monitoring operation of the two extraction blocks after revamping the first block are reported in Table 1.
The average monthly takeoff of deasphalted product in the first unit was 3-8% higher and the average annual
takeoff was 3.8-4.8% higher with stable product quality (Tables 2 and 3). The increase in the efficiency of the first
20
extraction unit allowed obtaining deasphalted product of better group composition (Table 4). After revamping the
second extraction block in October, 2005, takeoff of deasphalted product in the unit increased by 4% and more.
According to estimations of the economic efficiency of revamping the extraction blocks in the 36/2M unit,
the net present value of the investment projects is US$3.4 million for a discounted payback time of less than one
year (Table 5, Fig. 2). The calculated investment period (duration of designing, delivery of equipment, construction,
and startup) is 12 months, and the period for calculation of the efficiency was set at 10 years. The average sector
values of the cost of the base oil and profitability of production were used in the calculation. Mandatory payments
and taxes were calculated in accordance with active legislation.
The results of revamping demonstrate the possibilities of increasing the profitability of production of
deasphalted product s feedstock for manufacture of high-quality base oils or catalytic cracking feedstock and the
possibilities for reducing power consumption in existing units.
REFERENCES
1. K. G. Ziganshin, A. A. Osintsev, G. K. Zaganshin, et al., in: Catalog of Proceedings of the III
I n t e r n a t i o n a l C o n f e re n c e “ E x t r a c t i o n o f O rg a n i c C o m p o u n d s ” – E O S - 2 0 0 5 , Vo ro n e z h ,
October 17-21, 2005 [in Russian], Izd. VITA, Voronezh (2005).
2. RF Patent No. 1281586.
3. G. K. Ziganshin,. Doctoral Dissertation, Ufa State Petroleum Engineering University, Ufa (1999).
21
PULSED-MIXING CRYSTALLIZERS IN DEWAXING UNITS. BASIC RESULTS

OF INTRODUCTION
A. N. Polyakov, A. V. Tarasov, N. I. Suzdal’tsev, and S. P. Yakovlev UDC 665.772
The results of introducing pulsed-mixing crystallizers in dewaxing units at Novokuibyshevsk Lube Oil
and Additives Plant Ltd. are analyzed. Introduction of these units significantly increased the technical
and economic effectiveness of production of base oils and solid waxes.
A pulsed-mixing crystallizer (PMC) on the 39/4 dewaxing unit was started up at Novokuibyshevsk Lube
Oil and Additives Plant in January, 2006. The feedstock treated was raffinates of 340-430 and 370-500°C vacuum
distillates and residual. The basic physicochemical properties of the feedstock are reported in Table 1.
The manufacturing flow chart after inclusion of the PMC is shown in Fig. 1. In processing the residual
feedstock, the unit operates in a two-stage dewaxing mode and in a three-stage mode in processing distillate
feedstock.
Feedstock I enters pulsed-mixing crystallizer 2 and is mixed under the pulsing effect of a compressed inert
gas (created by pulser I) with wet solvent II fed into the lower collector of the crystallizer, cooled in block 9 for
utilization of the cold of filtrate III from the first stage. Dry solvent IV, fed for dilution and washing of sediments
in the filtration section, is cooled in the same block with the filtrate from the first stage.
Table 1
Raffinate
Indexes vacuum distillate
residual
340 – 430°С 370 – 500°С
Density at 20°C, kg/m3 845 – 850 863 – 874 880 – 884
Melting point, °C 27 – 30 40 – 42 49 – 52
Cut points, °C 330 – 440 370 – 520 360 – 540
Refractive index 1.4689 – 1.4695 1.4710 – 1.4740 1.4790 – 1.4840
2
Viscosity at 100 °C, mm /sec 4 – 4.6 6.63 – 8.2 15.91 – 16.91
____________________________________________________________________________________________________
Novokuibyshevsk Lube Oil and Additives Plant Ltd. VOKSTEK Ltd. Translated from Khimiya i
Tekhnologiya Topliv i Masel, No. 1, pp. 17 – 19, January – February, 2007.

2* VIII
IV
1* 6 7 8
3*
VII
5 IX
4*
V VI
III
9
II
II
IV IV
III
I
Fig. 1. Diagram of including a pulsed-mixing crystallizer in 39/4 and 39/8 units:

1) pulser; 2) pulsed crystallizer; 3) tank; 4) pump; 5) evaporative crystallizers;
6, 7, 8) filters for first, second, and third stages; 9) block for utilization of cold from first-
stage filtration; I) feedstock; II) wet solvent; III) first-stage filtrate; IV) dry solvent;
V, VI, VII) second- and third-stage filtrates and mixture of both; VIII) suspension from
pulsed-mixing crystallizer; IX) wax residue; the new equipment is indicated by the asterisk.
In processing distillate feedstock, a coolant – mixture VII of filtrates V and VI from the second and third
stages – is fed into the upper collector of the PMC. Filtrate V from the second stage is fed into the same collector
in processing residual raffinate.
Suspension VIII obtained in the PMC enters tank 3 by gravity feed and is pumped by pump 4 to ammonia
scraper crystallizers 5. Wax residue (petrolatum) IX enters the solvent regeneration block after three (two) filtration
stages.
It is not necessary to dry the wet solvent to obtain one of the coolants with the required low-temperature
potential in the unit operating in the dewaxing mode. This is because the temperature of the second-stage filtrate
or mixture of second- and third-stage filtrates used as one of the coolants allows obtaining a suspension at the
PMC outlet with a temperature of 2-5°C. This temperature totally satisfies the assigned conditions and corresponds
to the temperatures of suspensions obtained in regenerative crystallizers.
The basic results of a fixed run of the unit from January 1 to February 14, 2006, when raffinate of
the 370-500°C cut was primarily processed, are reported in Table 2. After introduction of the pulsed-mixing
crystallizer, the oil content in the slack wax decreased from 16-18 to 2-5 wt. % with a 4-5 wt. % increase in takeoff
of dewaxed oil.
One pulsed-mixing crystallizer in the unit replaced six previously used regenerative scraper crystallizers,
which eliminated the operating costs of maintaining and servicing them. Only ammonia scraper crystallizers,
where the suspension entering from the PMC is cooled to the filtration temperature, operate in the crystallization
mode. Some regenerative crystallizers with detached scraper shaft drives are used as heat exchangers for cooling
the wet solvent with the first-stage filtrate.
Introduction of the pulsed-mixing crystallizer in production of wax suspensions thus demonstrated the
high efficiency of this apparatus and confirmed the previously obtained results in [1-4]. However, the operating
life of the 39/4 unit with the PMC is still insufficient for fully assessing the technical and economic effect of
introducing the new equipment.
23
Table 2
Wax (slack wax) from
Indexes Dewaxed oil
deoiling stage
With pulsed-mixing crystallizer
Solid point, °C max -15 –
Oil content, wt. % – 2–5
Melting point, °C – 58 – 59
Yield of dewaxed oil, wt. % 81 – 82 –
With regenerative scraper crystallizers
Solid point, °C max -15 –
Oil content, wt. % – 16 – 18
Melting point, °C – 54 – 56
Yield of dewaxed oil, wt. % 77 – 78 –
Table 3
39/8 Unit
Indexes before installation of after installation of
PMC PMC
Yield of dewaxed oil, (wt. %) in vacuum distillate raffinate
II 77 – 78 83 – 84
III 74 – 75 82 – 83
Oil content (wt. %) in slack wax (wax) from vacuum distillate raffinate
II 12 – 14 under 2.3
III 16 – 19 under 5
This estimation was performed with the results of operating the 39/8 unit in 2004-2005, where the PMC was
installed in November, 2004. The unit operates in three dewaxing stages – the second- and third-stage filtrates are
fed for dilution of the feedstock suspension after mixing before the first filtration stage (see Fig. 1).
Some time was necessary for selecting the optimum operating conditions for the PMC, crystallization, and
filtration sections, since stable feedstock quality was not ensured [4]: raffinates of distillates from AVT-9 and
AVT-11 units (lube oil and fuel) entered almost haphazardly. As a result, it was possible to stably process slack
wax with an oil content of less than 5 wt. % – an analog of brand Ns wax – from vacuum distillate raffinate II and
slack wax with an oil content of less than 10 wt. % from vacuum distillate raffinate III [4].
After debugging the operating conditions for the PMC and filtration section on the 39/8 unit, delivery of
vacuum distillate raffinates II and III of stable quality was organized. As a result, it was possible to go from
processing wax with an oil content of less than 2.3 wt. % (brand T2 wax base) and slack wax with an oil content of
less than 5 wt. % (analog of brand Ns wax). Takeoff of dewaxed oil increased by 6 wt. %.
The basic indexes of operation of the 39/8 unit before and after installation of the PMC are reported in
Table 3.
The economic effect of introduction of the pulsed-mixing crystallizer in the 39/8 unit was calculated from
the condition of increasing processing of dewaxed lube oils and increasing the quality of the waxes and slack
waxes obtained. The cost of implementing the project, including the costs for manufacture and delivery of the
basic and additional equipment (crystallizer with pulser, tank, working and reserve pumps), and the costs for
24
assembling the pulsed-mixing crystallizer block (with consideration of the cost of the materials, cut-off and regulating
equipment, control and measuring instruments) were 16,240,600 rubles.
The following data were additionally used for the technical and economic calculations: 6 detached scraper
shaft drives in regenerative crystallizers; 7 kW scraper shaft drive power, 132 kW for additionally included N-101
(N-101A) pump; electric power cost of 1.05 ruble/kwh; annual costs for servicing one regenerative crystallizer: for
overhaul, 40,000 rubles; for one scraper shaft assembly, 510,000 rubles.
The results of the technical and economic calculations are reported below:*
Lifetime of project, years 10

Tax, %
on profit 24
on assets 2.2
VAT 18
Discount rate, % 10
Cost of project, thousands of rubles
with VAT 16,240.6
without VAT 13,763
Reduction in operating expenses, thousands of rubles
with VAT 2283.2
without VAT 1935.2
Increase in commercial products, thousands of rubles
with VAT 52,594.7
without VAT 44,572
Increase in profits, thousands of rubles 56,506.9
Depreciation deductions for year, thousands of rubles 1376
Net present value (NPV), thousands of rubles 205,952.4
Payback time, months 4
After adjusting the operating conditions of the 39/8 unit with a pulsed-mixing crystallizer and organization
of delivery of feedstock of the required quality, the increase in profits from introducing the PCM in comparison to
the basic version (use of regenerative crystallizers) was 46,506,900 rubles a year for a payback time of all outlays
of no more than 4 months.
The pulsed-mixing crystallizer was not washed even once for a year. No significant pressure differences
were observed in the lower part of the PCM and the temperature profile in the apparatus, which indicates the
absence of wax deposits in the sections of the crystallizer. The crystallizer, pulser, and coolant production and
feed system exhibited the required reliability in operation.
Due to the hermetic sealing of the pulsed-mixing crystallizer (absence of sealing of scraper mechanism
shafts), losses of selective solvents decreases and the environmental safety of production increases. The operating
expenses for repairs and servicing the regenerative scraper crystallizers are eliminated.
REFERENCES
1. S. P. Yakovlev, E. D. Radchenko, N. N. Khvostenko, et al., Nauka Tekhnol. Uglevodorodov, No. 2, 41-
45 (1999).
*These indexes can be corrected in consideration of the volume and cost of research and design-construction
work determined in each concrete case.
25
2. S. P. Yakovlev, E. D. Radchenko, V. F. Blokhina, et al., Khim. Tekhnol. Topl. Masel, No. 4, 12-15 (2000).
3. S. P. Yakovlev, E. D. Radchenko, V. F. Blokhinov, et al., Ibid., No. 2, 16-17 (2002).
4. S. P. Yakovlev, Ibid., No. 4, 12-15 (2005).
26
EQUIPMENT
MODERN COMPRESSOR EQUIPMENT
S. L. Utyushev, Yu. N. Bobrov, V. V. Yashin, and V. N. Kosogorov UDC 665.63.048:665.531
Penzkompressormash Co. is one of the leading domestic and compressor-building companies. With more
than half a century of history behind it, it has supplied approximately 23,000 air and gas compressors to different
sectors of industry in Russia and abroad. These are basically piston compressors on a 5G horizontal base and
M10 opposite base with output of 14-220 m 3 /min and final pressure of 0.22-40 MPa. In addition, 4400 special
compressors have been manufactured for the petrochemical, metallurgical, and air and space industries.
The equipment is distinguished by good quality and high reliability. Many compressors (5G-100/8,
5G-600/42-60, 5G-125/13-60, VN120) made more than 40 years ago continue to be used in oil refineries and other
plants.
At present, Penzkompressormash Co. is manufacturing piston compressors on a M10 base, both general
purpose and special purpose, equipped with a microprocessor automation system without lubrication of cylinders
and gaskets. Special compressors on this base for compression of hydrogen-containing gases are being
s u c c e s s f u l l y u s e d i n f u e l h y d r o t r e a t i n g u n i t s a t o i l r e f i n e r i e s i n P e r m ’ , U k h t a , Ya r o s l a v l ’ , a n d
Komsomol’sk-na-Amure.
Manufacture of MKZ-50U1 monoblock modules of the container type for compressor filling stations
where vehicles are filled with natural gas as motor fuel has been mastered. The demand for improved modules of
types MKZSA-50, MKZSA-100U1, MKZSA-100/20-250, and MKZSA-100/6-250 with automated filling control is
increasing. They are supplied with a heated operator module.
In 1992, due to a decrease in the demand for piston compressors, Penzkompressormash Co. began to
master mass production of screw air compressors (such compressors were previously manufactured in small
quantities and without noise-insulating housing). A decision was immediately made to create compressor units
with competitive advantages different from those manufactured by Kazan’ Compressor and Chita Machine-Building
Plants.
Screw compressors began to be supplied in the monoblock version in noise-insulating housing for the
first time in Russia. All of the mechanisms and units, including the oil trap, gas and oil cooler, and automation
____________________________________________________________________________________________________
Penkyhkompressormash OJSC. Prommashinvest TIC. Ob’edinenie “Kompressor” Ltd. Translated from
Khimiya i Tekhnologiya Topliv i Masel, No. 1, pp. 20 – 21, January – February, 2007.

system, which provides continuous regulation of output from 100 to 10% as a function of the demand for compressed
air.
The assortment began to expand with the increase in the demand for these compressors. In addition to
water-cooled units, air-cooled compressors, most in demand by the market, were rapidly mastered. The assortment
of air screw compressor units now includes 24 types and modifications with output of 4 to 40 m 3 /min.
The company takes a rigorous approach to ensuring the quality of the screw compressor units. A laboratory
with test benches was created in a short time. Each compressor manufactured is tested under the working load
and all technical characteristics are checked.
The company certified the compressors manufactured at the NASTKhOL Certification Center (Moscow)
and certified the testing laboratory.
By constantly keeping up with recent advances in compressor construction and considering the comments
and wishes of user sites, designers, and process engineers, the companies are continuously improving their
products. All design changes are usually only undertaken after tests on plant benches and in critical cases, on
compressors from the plant’s compressor facilities.
Penzkompressormash Co. was the first Russian compressor manufacturer to be certified in the Russian
marine navigation register by activating a quality system at the plant for satisfying international
standards ISO 9001:1994 and then also ISO 9001:2000.
The plant management conducted a reorganization directed toward optimizing the production areas and
plant management structure. Large investments were simultaneously made to acquire advanced imported equipment.
Plant specialists and management were trained in England.
Great attention is being focused on borrowing the leading advances in foreign screw compressor
construction. Several units of the latest constituents of screw compressor units, software for shaping the rotors,
and thermodynamic and geometric modeling of screw compressors have been acquired. Combined with the English
gear-milling machines and Holroyd precision milling cutter sharpening machines, this allowed designing and
manufacturing the most up-to-date compressor stages for screw compressor units with output of 1 to 100 m 3/min.
One such base stage which has no analogs in Russian compressor building has been designed, manufactured, and
is undergoing factory tests.
A great deal of work was done in 2004-2005 to increase the reliability and technical level of mass-produced
compressor units with output of 6, 20, 30, and 40 m 3 /min. Water-cooled screw compressors 1VV-20/9 and
air-cooled compressor 1VV-20/9M1 were improved significantly, so that their technical level and reliability were
much higher.
In 2005, air-cooled 1VV-30/9 and air-cooled 1VV-30/9M1 compressors were updated. A modification of the
1VV-30/9M1PCh air screw unit was created with a frequency converter and the most economical method of regulating
output: by changing the rotor rotation rate of the electric motor in the range from 100 to 30% and maintaining the
pressure established with accuracy of 0.02 MPa.
These compressors correspond to the foreign analogs on the technical level. They are equipped with
updated compressor stages with N progressive profile rotors, and an automation system based on a microprocessor
controller is used in them and provides for network connections with a complex compressor station automation
and control system based on a RS-485 interface.
The experience gained in creating screw compressor units, the modern production capacities, and the
competent personnel allowed the plant to set a new strategic goal in 2005 – to become the basic supplier of reliable
and efficient screw compressor aggregates for Russian Railways Co. (RR) traction-traveling brake systems. A
series of experimental samples of such aggregates was designed, manufactured and tested in the same year. In the
course of prolonged experimental design work and testing, compact compressor stages and many original units
28
were carefully worked out. In 2006, the plant began mass production of such compressor aggregates with output
of 2-4.5 m 3/min and delivered them to Transmashholding locomotive construction companies.
Production of general-purpose industrial screw compressor units with output of 2 to 9 m 3 /min, including
the most up-to-date unit using an aggregate compact compressor module which has no analog in domestic
compressor construction, was parallelly mastered based on these compressor aggregates.
Having mastered new kinds of compressor and associated equipment and satisfactorily reorganized in
complicated market conditions, Penzkompressormash Co. will continue to be one of the most reliable partners for
many Russian users by filling their orders in the optimum times and with the proper quality.
29
CHEMMOTOLOGY
CRITERIA FOR LIMITING CONTAMINATION OF MOTOR OIL BY FUEL
Yu. A. Gur’yanov UDC 621.836:681.518.54(04)
The change in the service properties of modern motor oils in contamination by fuel was examined. It was
experimentally shown that mineral and synthetic oils can totally lose their working capacity when
contaminated by fuel. The dependences of the properties of oils on the mechanical and thermal loads in
the friction unit and the degree of contamination of the oil by the fuel were obtained. The limiting and
damaging concentrations of fuel in oils of different quality were substantiated. Recommendations were
made for determining the limiting concentrations.
Increasing the efficiency of internal combustion engines (ICE) is associated with stiffening of the operating
conditions of their assemblies and units. Increasingly severe requirements are being imposed on lube oil for this
reason. A valuable and irreplaceable constructive element in the current stage of development of technology, lube
oil, together with other ICE elements, ensure their breakdown-free and long-term operation. Tribologists say that
any difference in the brand or quality of the lube oil will ineluctably be reflected in the reliability of the machine,
especially in its most complicated and highly loaded aggregate – the ICE [1].
An efficient lube oil ensures standard friction conditions in the joints of parts and rational use of the
lifetime of the unit. Lube oil which partially or totally loses its working capacity becomes the cause of high wear
of the friction surfaces of parts and this causes premature failure of the engine.
We know that lube oil can lose working capacity for a short time due to malfunctions of such ICE systems
as the cooling, air cleaning, oil, and fuel supply systems. Observation of the real state of motor oils
in ICE [2] suggests that contamination by fuel is the most probable cause of loss of working capacity by the oil.
In winter, lube oil is contaminated with fuel in an amount higher than the acceptable amount in 90% of
gasoline ICE on average.
Contamination of motor oil by fuel (diesel or gasoline) worsens its basic performance properties:
neutralizing (antioxidant and anticorrosion) and viscosity.
____________________________________________________________________________________________________
Chelyabinsk State Agroengineering University. Translated from Khimiya i Tekhnologiya Topliv i Masel,

P
1 Rb
N N
2
3
dr b
Fig. 1. Diagram of friction of parts of the “ball – ring” type: 1) ball; 2) ring sample;
3) antifriction layer; P – load on friction unit given by the machine’s weighting system;
b – working width of ring edge; R b – ball radius; d r – average ring edge diameter;
N – normal force acting in friction zone.
The neutralizing properties of lube oil contaminated with fuel are worsened by heavy fuel cuts. It has
been experimentally shown that cuts that distill at temperatures above 340°C are the most harmful [3]. Under the
effect of the operating temperature of ICE, light cuts evaporate, and heavy cuts accumulate in the lube oil.
As a result of worsening of the antioxidant and anticorrosion properties, the intensity of formation of oil-
soluble products increases by 1.5 times and by 2 times for insoluble products, and the induction period of formation
of sludge also decreases by 2 times [3]. These changes in the quality of the lube oil cause more intensive aging
of the oil, reduced oil filter lifetimes, increased contamination of parts with varnish and carbon deposits, and
coking of piston rings.
The decrease in the viscosity of oil contaminated with fuel makes the friction conditions much more
severe and causes a corresponding increase in the intensity of wear of working surfaces [4]. When the viscosity
of the oil decreases by one class, the wear intensity increases by 2-3 times. However, this was established in
studies of the previous generation of lube oils.
We evaluated the effect of fuel on the lubricating properties of modern motor oils and substantiated the
limiting values of fuel contamination of lube oils of different quality.
The effect of fuel on the service properties of modern motor oils was investigated with a MAST-1 machine
for assessing antifriction properties. LUKOIL motor oils were tested: Standart mineral (SAE 10W-40, API SF/CC),
semisynthetic Super and Lyuks (SAE 5W-40, API SJ/CF), synthetic Sintetik (SAE 5W-40, API SL/CJ). Each oil was
contaminated with winter diesel fuel in concentrations of 1, 3, 5, and 7 vol. % before testing.
The ring sample (Fig. 1) was made from the bearing liner of an ICE crankshaft with an aluminum antifriction
layer. A ball 12 mm in diameter from a standard bearing with surface hardness of the same order as the hardness of
the crankshaft neck was used as the top sample. The friction moments of clean and contaminated oil samples were
determined at oil temperatures of 24 to 120°C and mechanical loads from 50 to 184 N, which corresponds to the
conditions of operation of ICE sliding bearings.
• Results of Assessing the Antifriction Properties of Clean Lube Oils
The lube oils were comparatively evaluated with the friction coefficient and friction moment at an oil
temperature of 80°C. The friction coefficient for Sintetik synthetic oil was much lower than for Standart mineral
31
0.4
34 a
0.35
2
0.3
1
0.25
0.2
260
b
220
1
180
4
140
3
2
100
60
40 70 100 130 160 190
Fig. 2. Friction coefficient f (a) and moment M (b) vs. mechanical load P at 80°C in the
volume of fresh all-season motor oil: 1) Sintetik; 2) Lyuks; 3) Standart; 4) Super.
and Lyuks and Super semisynthetic oils, by 0.05-0.07 on average (Fig. 2a). The mineral and semisynthetic Super
oils gave approximately the same friction coefficient, while the Lyuks oil was in the middle. A decrease (by – 0.02)
in the friction coefficient with an increase in the load was observed for all of the oils.
The curves of the friction moment dependences are positioned in the same order (Fig. 2b) as the curves for
the friction coefficient.
Let us consider the dependences of the friction moment on the load at different bulk oil temperatures. For
the uncontaminated synthetic oil, the friction moment is almost independent of the temperature in the oil gap (Fig.
3a). This indicates that the given lube oil ensures stable lubrication and thus friction conditions. No breaks were
observed in the oil film in the mechanical load and temperatures ranges examined, except at the maximum mechanical
load of 184 N and low temperatures, 26 and 60°C.
The carrying capacity of an uncontaminated mineral oil film (Fig. 3b) was much lower than for the synthetic
oil. At oil temperatures from 60 to 120°C, the maximum load at which the integrity of the oil film was preserved did
not exceed 90 N. At 120°C, the oil lost the ability to ensure standard friction of the working surfaces. This caused
passage into a friction regime over the modified layers, indicated by the horizontal segment on the curve in the 90-
110 N load range.
% Results of Evaluating the Antifriction Properties of Lube Oils Contaminated with Fuel
When synthetic oil was contaminated with 1% diesel fuel, the minimum carrying capacity of the oil film
was 150 N at 60°C and the maximum carrying capacity was 184 N at 100 and 120°C (Fig. 4a). As a result of
contamination of the oil with this amount of fuel, the carrying capacity of the oil film decreased by 20 N (11%) at
60°C and by 14 N (8%) at 80°C. The oil retained temperature invariance in the entire range of mechanical loads.
The initial and final values of the friction moment did not change.
32
In contamination of the synthetic oil with 3% fuel, the dependences of the friction moment at 26 and 120°C
and 90 N mechanical load and higher changed significantly (Fig. 4b). The appearance on the curve of segments
with a smaller slope in the 90-110 N load range indicates the inability of oil in such a diluted state to ensure friction
of working surfaces by adsorption layers. This causes an adhesive reaction of the friction surfaces. The antiscuff
additive is activated as a result and ensures operation of the friction unit by modified layers and thus decreases
the friction coefficient.
The carrying capacity of the film at 80 and 100°C for this oil, in comparison to the oil contaminated with 1%
fuel, decreased from 170 to 150 N (by 18%) and from 184 to 170 N at 120°C (by 11%). This reduction was due to the
extremely important decrease in the film thickness caused by dilution of the oil by the fuel and as a result, onset
of the initial stage of adhesive reaction of the friction surfaces. The temperature in the contact zone is insufficient
to trigger activity of the antiscuff additive.
The signs of deterioration of the synthetic oil contaminated with 7% fuel were pronounced (Fig. 4c): at
low temperatures (60 and 80°C), the friction moment increased by 20 N×m, attaining the maximum value of 260 N×m
characteristic of overheated lube oils. At higher temperatures, friction took place over the modified layers beginning
with almost the minimum load, 50 N. The chemical modification mode was activated, confirmed by the decrease in
the friction moment by approximately 20 N×m in the region of high mechanical loads at 120°C.
In comparison to the oil contaminated with 3% fuel, the carrying capacity of the film of this oil did not
change, which was also due to an increase in the antiscuff additive’s activity in such severe friction conditions.
260
a
220
180
140
100
60
260
b
220
180
140
100
60
40 70 100 130 160 190
Fig. 3. Friction moment M vs. mechanical load P at different temperatures in the bulk of
Sintetik synthetic (a) and Standart mineral oils (b): – 26°C; – 60°C ; c – 80°C;
Δ – 100°C; × – 120°C.
33
At an oil temperature of 26°C and consequently low antiscuff activity, the carrying capacity of the film decreased
from 170 to 150 N.
In contamination with 1% fuel, the lubricating properties of the mineral oil worsened
significantly (Fig. 4d). In comparison to clean oil (Fig. 3b), the maximum increase in the friction moment
was 30 N×m at 60 and 80°C and 20 N×m at 26°C. Chemical modification of the oil strengthened significantly at
120°C, confirmed by the increase in the carrying capacity of the modified layers to 150 N at a relatively low friction
moment, 235 N×m.
260
a
220
180
140
100
60
260
b
220
180
140
100
60
260
220
180
140
100
60
40 70 100 130 160 190 40 70 100 130 160 190
Fig. 4. Friction moment M vs. load P at different levels of contamination with diesel fuel
and temperatures of synthetic Sintetik (a-c) and mineral Standart (d-f) oils; a, d – 1%;
b, e – 3%, c, f – 7%; – 26°C; – 60°C ; c – 80°C; Δ – 100°C; × – 120°C
34
In addition, the lube oil lost its ability to provide for friction over adsorption layers at 100°C. For this
reason, passage to a friction regime over modified layers began at mechanical loads of 90-110 N.
Contamination of mineral oil with 3% fuel (Fig. 4e) sharply worsened its lubricating properties. The
appearance of segments on the curves with a smaller slope in the 90-110 N load range at temperatures
of 80 to 120°C indicates activation of the antiscuff additive. In comparison to clean oil (see Fig. 3b), the maximum
increase in the friction moment at 60, 80, and 100°C was approximately 30 N×m (14%) and at 26°C, 20 N×m (10%).
This indicates a transitional state where standard friction conditions are lost and the antiscuff additive’s
activity is still inadequate. At 100 and 120°C, chemical modification of the lube oil is significantly activated: the
carrying capacity of the modified layers increased to 150 and 170 N for a friction moment equal to 265 N×m.
The initial friction moment at 50 N and high temperatures in comparison to clean lube oil (Fig. 3b) decreased
to 100 N×m, which indicates the effect of the antiscuff additive and loss of the ability to ensure standard friction
conditions by the oil.
In contamination of the mineral oil by 7% fuel, its basic service properties that ensure minimum wear of
working surfaces and friction by adsorption layers were totally lost (Fig. 4f). As a result, the character of the
dependences of the friction moment on the load and temperature of the lube oil changed to linear and the inflection
of the curves (see Fig. 3b and 4e) with the 90 N load disappeared.
This is due to attaining hazardous dilution of the oil by the fuel. Regardless of the mechanical load and
the temperature, with this dilution the oil cannot ensure friction of the working surfaces in standard conditions in
physical adsorption of surfactant molecules. In this case, friction is only ensured by chemical reaction of the
antiscuff additive with the working surfaces of the friction unit.
As indicated in [1, 5], the friction coefficient is almost the same in relative movement of working surfaces
over adsorption and modified layers. However, the intensity of wear in the last case is two to three orders of
magnitude higher than in friction over adsorption layers, i.e., than in standard functioning of friction units. As a
consequence, the level of fuel contamination of the oil that causes transition of friction from the standard conditions
to friction over modified layers to begin is the criterion of the limiting state of motor oil with respect to fuel
contamination.
In view of the above, we note:
standard lubricating conditions are characteristic of uncontaminated synthetic oil (see Fig. 3a) at all
mechanical and heat loads;
for oil contaminated with 1% fuel (see Fig. 4a), standard lubricating conditions are also realized at all
mechanical and heat loads; an exception is the regime at 120°C and a mechanical load in the range of 110-184 N,
where a clear decrease in the friction moment is observed relative to other conditions, which indicates activation
of the antiscuff additive; at this contamination, the oil can be considered totally efficient if its temperature in bulk
is no higher than 100°C.
In synthetic oil contaminated with 3% fuel (see Fig. 4b), the antiscuff additive starts working at a mechanical
load of 90 N and higher and temperatures of 26 and 120°C, which indicates loss of a significant part of the service
properties by the oil. As a consequence, contamination of synthetic oil with 3% winter diesel fuel can be considered
limiting.
Standard lubrication conditions are characteristic of uncontaminated mineral oil (see Fig. 3b) at all
mechanical and heat loads. However, at an oil temperature of 120°C and mechanical load of 90 N and higher, there
is a clear transition from standard friction conditions to friction conditions over modified layers. As a consequence,
when this oil is sued to ensure standard lubricating conditions, its temperature should not exceed 100°C.
The presence of 1% fuel in the mineral oil caused the friction moment to increase by 15% at temperatures
of 60 and 80°C, which indicates breakdown of adsorption layers, and at 100 and 120°C, manifest activation of the
35
antiscuff additive. As a consequence, contamination of the mineral oil with 1% winter diesel fuel can be considered
limiting.
In the case of mineral oil contaminated with 3% fuel, the standard lubrication conditions are lost and a
modified-layer friction regime is realized at a mechanical load of 90 N and higher and temperature in the 80-120°C
range (see Fig. 4e). This finding indicates degradation of the service properties of the oil at this level of
contamination, which causes wear of friction units two to three orders of magnitude higher in further operation of
the ICE in comparison to wear in the standard regime, and inefficient use of engine life as a result.
The mineral oil contaminated with 7% fuel on the contrary, like the synthetic oil but to a lesser degree,
reaches a hazardous state where all of its service properties (except for one) are lost and only the transport
function is fulfilled “ delivery of the antiscuff additive to the zone of actual contact of the friction surfaces. In this
period, the maximum consumption of this additive is attained, since the standard friction coefficient is ensured by
maximum activity of the corrosion-mechanical process. This explains the overlap of the two curves in Fig. 4f.
As soon as the additive reserve begins to be depleted, breakdown inevitably takes place, despite the fact
that the external conditions of ICE operation do not differ from the standard conditions.
Gasoline has approximately the same negative effect on the properties of motor oil, but its diluting power
is one order of magnitude higher than the power of winter diesel fuel.
Fuel in motor oil can thus cause total loss of its service properties and as a result, very rapid depletion of
the service life of the ICE. According to our observations, the real operating time of ICE between overhauls is
usually 15-100,000 km. To ensure rational use of the service life in designing and manufacturing ICE, it is useful
to not allow a concentration of diesel fuel greater than 2-3% in synthetic oil and greater than 1% in mineral oil.
Such fuel quantities cannot be detected in working lube oil by organoleptic methods. For this reason,
instrumental methods are used to monitor oil quality. In production conditions, portable instruments based on
fast methods of assessing the quality of fresh and working oils are preferred.
Instruments that do not use glass instruments and vessels and chemical reagents are most
convenient. One such instrument is the portable machine diagnostics kit based on the parameters of working
oils – KDMP-3 – which allows assessing the quality of working oil with ten and fresh oil with seven basic service
properties in field and stationary conditions [6, 7].
REFERENCES
1. A. V. Chichinadze (ed.), Friction, Wear, and Lubrication (Tribology and Triboengineering) [in Russian],
Mashinostroenie, Moscow (2003).
2. N. I. Skinder and Yu. a. Gur’yanov, Khim. Tekhnol. Topl. Masel, No. 5, 28-30 (2003).
3. V. B. Polyakova, Ibid., No. 3, 31-32 (1990).
4. V. I. Vorozhikhina, L. S. Ryaznov, E. P. Vol’skii, et al., Ibid., No. 2, 42-44 (1985).
5. R. Baltenas, S. A. Safonov, A. I. Ushakov, et al., Motor Oils [in Russian], Al’fa-Lab, Moscow”St. Petersburg
(2000).
6. N. I. Skinder and Yu. A. Gur’yanov, Khim. Tekhnol. Topl. Masel, No. 1, 38-40 (2001).
7. P. I. Tarasov and Yu. A. Gur’yanov, Gorn. Promyshl., No. 1, 57-61 (2005).
36
SEMILIQUID GREASES FOR REDUCING GEARS FOR GENERAL

MACHINE-BUILDING PURPOSES
A. A. Sirotenko, L. V. Pakina, and L. A. Savel’eva UDC 621.892.261
Plastic greases with a penetration index at 25°C above 380 according to GOST 5346–78, ultimate strength
according to GOST 7143–73 of less than 100 Pa, and whose viscosity in a wide temperature range is a function of
the strain rate gradient, are usually semiliquid. Because of these properties, these greases can be used together
with gear-case oils in the gears in gear boxes for general machine building.
However, in comparison to gear-case oils, semiliquid plastic greases require more power for moving the
gear at temperatures above 20°C, eliminate heat from the gear transmission worse, and restrict the speed of a
transmission wheel of larger diameter – maximum of 3 m/sec. When the grease is replaced by fresh grease, it is
usually necessary to disassemble the reducing gear.
However, the presence of a soap thickener in the structure of the semiliquid grease broadens the temperature
range of operation of the reducing gear and makes it possible to start up at 10-30°C below the solid point of the oil
that acts as the dispersion medium for the grease.
The use of semiliquid greases in industrial reducing gears is most frequently due to the desire to reduce
consumption of lubricant irreversibly lost through shaft collars, labyrinth seals, and slots in the reducing gear
body assembly.
In the USSR, the assortment of semiliquid greases was very limited. Transol-100, Transol-200, and
TsIATIM-208 greases were basically used in industrial reducing gears.
Transol-100 grease, developed for screw reducing gears at the end of the 1970s at MASMA SIA [1], was
manufactured at Berdyansk Experimental Petroleum and Oil Refinery according to TU 38.USSSR 201352–84 and
was widely used in different climatic zones in the country. This grease ensured prolonged operation of worm
reducing gears with an interaxial distance of less than 100 mm at ambient temperatures from –30 to +50C.
12-Hydroxystearic acid soap and a polymer were used as the thickener and a mixture of mineral and
synthetic oils was used as the dispersion medium. The synthetic oil prevented catastrophic wear of the material
of the worm wheel (basically bronze Br OF10).
____________________________________________________________________________________________________
Shaumyan Plant CJSC. Translated from Khimiya i Tekhnologiya Topliv i Masel, No. 1, pp.27 – 29,
January – February, 2007.

38
Table 1
Semiliquid grease
Indexes Standard AZMOL-Transol-100 Transol-100-PSh
before before
after testing after testing
testing testing
Drop point according to GOST 6793 – 74, °C >150 188 176 178 178
Colloidal stability according to GOST 7142 – 74, % pressed oil <35 38.2 37.4 33.4 28.3
Effective viscosity, Pa⋅ sec
according to GOST 26581 – 85*
at +50°C and 10 sec-1 3–5 3.1 2.6 4.1 6.7
Solidified
at –30°C and 10 sec-1 <100 – 58.5 –
at –20°C
according to GOST 7163 – 84 at –30°C and 10 sec-1 <1200 774.4 – 774 –
Volatility (100, 1 h) according to GOST 9566–74, % <1.5 4.2 – 1.24 –
Saponification number according to GOST21749 – 76*, mg KOH/g >100 45.3 45.2 145.4 148.8
Weakly Weakly
Free organic acid content according to GOST 6707 – 76, % in terms of oleic acid 0.1 0.57 0.43
basic basic
Note. Indexes added to TU 0254-015-56194358 – 2005.
Transol-100 grease is now manufactured by AZMOL Co. (Berdyansk, Ukraine) under the trade name
AZMOL-Transol-100 (TU U 23.2-00152365-181–2003). It virtually does not enter the RF due not only to the fall of
the USSR but also to a greater degree to halting of synthetic oil production in the territory of the former USSR.
The quality of the semiliquid grease of the Transol-100 type supplied to consumers through middlemen
does not always correspond to the standards for AZMOL-Transol-100 grease not only with respect to the individual
standards indexes but also with respect to the temperature range of utilization of the grease given in the standards.
There are data on the impossibility of running reducing gears serviced with a semiliquid grease of the Transol-100
type with no load at an ambient temperature below –20C.
Reduktor NTTs Co. (St. Petersburg) turned to Shaumyan Plant Co. (St. Petersburg) to solve the problem of
manufacturing their own semiliquid grease of the Transol-100 type of the required quality and in the required
amount.
The plant manufactures lubricating materials (motor and industrial oils, plastic greases, and LCPM) for
railroads, marine and river fleets, and for motor transport and industrial enterprises. In 1997-2002, it went through
three stages of bankruptcy, but retained its own capabilities and prospects. The plant is now manufacturing
marine oils, including oils for modern boosted ship diesels and diesel generators, and new brands of oils: helicopter
and motor for diesel engines.
Shaumyan Plant Co. has been manufacturing semiliquid greases for more than 20 years:
• in 1984 in collaboration with MASMA SIA, SKP-M grease (TU 0254-318-00148820–97) for medium- and
high-load gear (cylindrical and conical) reduction units and engine reduction units with a crankcase lubrication
system by dipping;
• in 1995, LZ-PZhL-00 grease (TU 0254-312-00148820–96) for joints of equal angular velocities of the
secondary shaft of the BAZ 212213 auto was developed at the request of AvtoVAZ Co.;
• in 1999, in collaboration with VNIITransmash, a new grease, Redusma (TU 0254-324-00148820–99), was
m a n u f a c t u r e d f o r t w o - s t a g e r e d u c i n g g e a r s i n s t a l l e d i n s e r i e s L M - 6 8 a n d LV S - 8 6 s t r e e t c a r s u s e d
by Go4elektrotrans GUP (St. Petersburg) and the new streetcars manufactured by Petersburg Streetcar-Mechanical
Plant.
Table 2
Temperature (°C) of grease in reducing gear
Duration of test,* h Load, %
AZMOL-Transol-100 Transol-100-PSh
5 72 68 50
8 101 102 100
10 104 103 100
15 91 103 100
20 91 98 100
25 95 92 100
30 90 96 100
35 93 84 100
40 91 86 100
45 90 86 100
50 80 86 100
55 83 82 100
56 89 86 100
Note. *The tests were performed at an ambient temperature of 20°C by N. V. Vasil’ev
39
A number of additional testing methods were used in developing the formula and technology for
manufacturing the semiliquid grease of the Transol-100 type, and they were then taken into consideration
in TU 0254-015-56194358–2005 for Transol-100-PSh grease. In comparison to AZMOL-Transol-100 grease, the
following indexes are additionally determined for this grease:
• e f f e c t i v e v i s c o s i t y a t + 5 0 a n d – 3 0 ° C a n d s t r a i n r a t e g r a d i e n t o f 1 0 s e c -1 a c c o r d i n g
to GOST 26581–85 – for controlling the structure and low-temperature properties;
• saponification number according to GOST 21749–76 – for controlling the amount and quality of synthetic
oil in the finished grease;
• open-cup flash point according to GOST 4333–87 – for controlling the quality of the dispersion medium.
These indexes were primarily incorporated in TU 0254-015-56194358–2005 for the following reasons. The
Rheotest 2 rotary viscometer and its modifications produce more stable results than instruments for determining
Table 3
Grease
(TU U 23.2-00152365-181–2003)
(TU 0254-018-56194358–2005)
(TU 0254-016-05766706–98)
AZMOL-Transol-200
Transol-200-PSh
Transol-200
Indexes Standard
Drop point, °C >150 169 161 168

Penetration at 25°C
without stirring – 420 385 410
with stirring 400 – 430 425 370 415
Effective viscosity, Pa⋅sec
according to GOST 7163 – 84 (–30°C, 10 sec-1) ≤1400 1629 1388 711
-1
according to GOST 26581 – 85 (+50°C, 10 sec ) 3–6 5.2 11,8 5
Lubricant properties
(Four-ball friction tester, according to GOST 9490–75
load, N
welding >2800 3286 2325 3090
critical >700 785 981 785
scoring index, N >390 500 441 491
Corrosive effect on copper M01 (100°C, 3 h) Passed
Flash point (open cup), °C 170 174 130 178
Volatility (100°C, 1 h), % ≤0.8 0.5 1 0.75
Content
free alkali ≤1 Abs.
free organic acids, % oleic acid max 1.0 0.54 0.28 0.8
Colloidal stability, % max 30 20.4 36.3 14.9
40
the penetration index for analyzing semiliquid greases at a temperature of +50°C. In our opinion, the penetration
index (over 380) in the subsequent revisions of the standard for semiliquid greases should be optional or it should
not be determined with a full-size cone according to GOST 1440–78 but with a micropenetrometer with a half- or
one-fourth-sized cone [2].
In studying the different semiliquid greases, we repeatedly encountered samples of greases from unknown
manufacturers. These greases contained some highly volatile fractions of petroleum oil components to improve
the low-temperature properties. Mechanisms cannot operate in such surrogate greases in nominal loading
conditions for a long time.
It was possible to detect the adulterant with the saponification number of the grease and the flash point
according to GOST 4333–87. However, for greases of the Transol type which contain lithium 12-hydroxystearate,
melting of the soap prevents correct determination of the flash point. For this reason, the rate of heating the
grease in determining the flash point in the given case should be no greater than 2°C/min.
Comparative tests of Transol-100-PSh experimental semiliquid grease and AZMOL-Transol-100 commercial
grease manufactured by AZMOL Co. (Berdyansk) were conducted on the bench at Reduktor NTTs Co. This bench
is a screw reducing gear with an electric motor installed in a rigid frame. A system for creating the necessary load
is placed on the shaft of the reducing gear. The power consumption, torque on the reducing gear shaft, and
temperature of the grease in the reducing gear were monitored in the tests.
The indexes for the properties of Transol-100-PSh and AZMOL-Transol-100 greases before and after
testing are reported in Table 1, and the experimental data on the dependence of the temperature of the grease in the
Table 4
Semiliquid plastic grease
Transol-100-PSh
Transol-200-PSh
LZ-PZhL-00
Redusma
SKP-M
Indexes
Type of thickener Li-soap Li-soap Na- soap Li-soap Li-soap

Oil base semisynthetic petroleum
Drop point, °C, min 150 150 120 140 160
Penetration at 400 – 430 400 – 430 380 – 430 380 – 450 400 – 440
Effective viscosity (GOST 26581–85, 10 sec-1), Pa⋅sec
100
at –30°C, max 100 250 70 –
(at 0°С)
at +50°C 3–6 3–7 4–8 – 5–8
Lubricant properties
(four-ball friction tester, GOST 9490–75)
load, N, min
welding 1780 2800 1648 1740 3200
critical 700 700 700 820 780
scoring index, N, min 350 400 380 380 490
Passed
Corrosive effect on metal (100°C, 3 h)
copper М01 copper М01 steel 20 steel 20 steel 20
Flash point (open cup), °C, min 170 170 160 245 150
Colloidal stability, % pressed oil, max 35 30 35 30 35
41
reducing gear on the duration of operation of the reducing gear on the bench are reported in Table 2. The results
of the tests confirmed the possibility of using Transol-100-PSh grease instead of AZMOL-Transol-100 grease in
single and multistage screw reducing gears.
Transol-200 grease, like Transol-100 grease, was developed at MASMA SIA [1]. It is intended for use in
cylindrical and planetary reducing gears. 12-hydroxystearic acid lithium soap and a polymer are used as the
thickener in it, and a mixture of mineral oils with addition of an additive package to improve the lubricant properties
is used as the dispersion medium.
This type of grease is supplied to the user under the brands AZMOL-Transol-200 (AZMOL Co., Berdyansk,
Ukraine); Transol-200 (RIKOS Co., Rostov-on-Don), and Transol-200-PSh (Shaumyan Plant Co., St. Petersburg).
The results of tests of commercial samples of these greases supplied to consumers in 2005 are reported
in Table 3. In comparison to ordinary plastic greases, it is not very easy to obtain stability of their “colloidal
stability” and “penetration” indexes. Not only the quality of manufacture and storage conditions of the product
by the manufacturer but also, to a greater degree, the conditions of storage and delivery of the goods to the
middleman, as well as the conditions of storage and use (i.e., conditions of delivery of the semiliquid grease to the
reducing gear and use) by the consumer can play the main role here.
The assortment and quality indexes of the semiliquid greases for reducing gears for different applications
manufactured by Shaumyan Plant Co. are reported in Table 4.
We would like to thank the General Director of Reduktor NTTs Co., V. I. Parubets, for collaborating in
testing Transol-100-PSh grease and for providing samples of AZMOL Co. and RIKOS Co. commercial greases,
and T. G. Malyshevaya for scientific and methodological assistance in developing the semiliquid grease
technology.
REFERENCES
1. V. M. Shkol’nikov (ed.), Fuels, Lubricants, and Industrial Fluids. Assortment and Use. A Handbook
[in Russian], 2 nd ed., Tekhinform, Moscow (1999).
2. V. V. Sinitsyn, Plastic Greases and Evaluation of Their Quality (Foreign Standards and Specifications)
[in Russian], Izd. Standartov, Moscow (1975), p. 192.
42
RESEARCH
EFFECT OF SHOCK-WAVE PROCESSES ON THE PHYSICOCHEMICAL

PROPERTIES OF CRUDE OIL
A. F. Maksimenko UDC 622.279.72+621.039
The effect of a shock wave on the physicochemical properties of crude oils was experimentally studied.
The complicated character of this effect on complex organic compounds was demonstrated. The
rheological properties and group composition of the crudes were changed by the shock wave.
The interest in the behavior of substances in unusual conditions has existed over entire historical epochs.
Until the beginning of the 20 th century, the temperature and active medium were the basic factors that acted on a
substance. Bridgeman’s classic studies stimulated the development of research on the effect of high static
pressure on different substances. In the mid-1950s, studies of the effect of dynamic loads and shock waves were
published.
Shock-wave loading of organic substances is complicated in nature. It is accompanied by heating of the
substance and an increase in its entropy. The heating temperature progressively increases with an increase in the
amplitude of the compression wave. Since unloading of the substance is isentropic, removing the pressure
decreases the temperature of the substance, significantly in some cases. As a result of these factors and
rearrangement of molecules in the phase transition, the properties of organic substances can be varied within wide
limits.
Polymerization of organic monomers on passage of shock waves was discovered* in 1964 at the Institute
of Chemical Physics, Russian Academy of Sciences. This discovery launched a new area of organic
chemistry – the shock-wave area. In conducting the first experiments, it was found that different reactions can
take place in organic compounds on passage of a shock wave: degradation, substitution, isomerization, etc. As
a result of studies of two large groups of organic compounds – aromatics and olefins, it was shown that
shock-wave degradation of aromatic compounds differs from their degradation at a constant temperature. According
____________________________________________________________________________________________________
I. M. Gubkin Russian State University of Oil and Gas. Translated from Khimiya i Tekhnologiya Topliv i
Masel, No. 1, pp. 34 – 35, January – February, 2007.

Table 1
Content (%) in Vasyugan crude
Structures before shock-wave after shock-wave
compression compression
Aromatics 35.24 35.40
benzenes 5.82 6.91
monocyclics 6.49 8.99
substituted polycyclics 22.93 19.50
Paraffins 29.27 38.95
Naphthenes 19.22 13.37
Unsaturateds 16.27 12.28
to the data of Block and Weir,* benzene does not undergo chemical changes at static pressure of 4000 MPa and
temperature of 600°C. However, in shock-wave loading, such changes take place for a pressure jump
to 1100-1500 MPa on the shock wave front, and the yield of reaction products is 0.4-1%.
Due to the development of effective new methods of processing hydrocarbon feedstock, the urgency of
investigating the changes in the physicochemical properties after shock compression increased. The results of an
IR-spectroscopic study of the group composition of different crude oils before and after shock-wave compression
are reported here.
The analysis of the IR absorption spectra of crude from the Yarega field showed that its group composition
before and after shock compression was qualitatively identical. However, some changes were observed in the
quantitative ratio of hydrocarbon structures. After shock compression, the paraffin content decreased by 2%, but
the naphthene and aromatic hydrocarbon content increased by the same amount. These at first glance insignificant
changes led to a 11% decrease in the kinematic viscosity of the crude at 22°C: from 2970 to 2643.3 mm 2/sec. The
character of the changes in crudes from Tuimazy and Grachev fields was similar.
The group composition of crude from the Vasugyan field was almost unchanged after shock
compression (Table 1). The total content of aromatic structures remained unchanged, but the ratio of short and
long alkyl radicals in them and their branching changed. The content of paraffin structures increased by
almost 10% due to a decrease in the content of naphthenes and unsaturated hydrocarbons. The content of
benzene and monocyclic substituted structures increased in aromatic structures due to a decrease in the content
of polycyclics. The viscosity of the crude at 22°C decreased by 17.3%, from 153 to 126.6 mm 2/sec.
The content of hydrocarbon structures in crude from the Zolotukhino field is reported in Table 2. New
structural groups did not form in this crude as a result of shock-wave compression, but the ratio of existing
hydrocarbon structures changed.
Zolotukhino crude is aromatic with a high content of polycyclic structures which gives it relatively high
viscosity. After shock compression, the content of paraffinic and naphthenic structures decreased, but the
content of aromatics increased. The amount of benzene structures in the latter almost did not change, but the
amount of monocyclic substituted structures increased due to a decrease in the amount of polycyclics. The
kinematic viscosity of the crude at 22°C decreased by 12.5%.
Crude from the Borovichi field is very inhomogeneous in consistency: the more fluid phase contains very
viscous amorphous inclusions. This crude is paraffinic-aromatic. It also contains up to 16% naphthenic and
approximately 7% unsaturated hydrocarbons. Its viscosity at 72°C is 336 mm 2 /sec.
*A. N. Dremin and L. V. Babar, Shock-Wave Chemistry of Organic Substances [in Russian], Nauka, Moscow
(1984).
44
Table 2
Content (%) in Zolotukhino crude

Structures before shock-wave after shock-wave
compression compression
Paraffins 34.78 26.48
Naphthenes 22.02 16.52
Aromatics 43.20 57.00
After shock-wave loading, the same structural groups are present in the crude. However, the sharp decrease
in the absorption band characteristic of intermolecular hydrogen bonds in its IR spectrum indicates rupture of
these bonds. A slight decrease in the amount of aromatic structures is observed due to an increase in the amount
of paraffinic structures with reduced branching of these structures. The content of monocyclic substituted
structures increased in the aromatic structures due to a decrease in the content of polycyclic structures. The
component composition of the crude changed: the proportion of asphaltenes and alcohol–benzene resins increased
due to a decrease in the proportion of benzene resins. As a result, the kinematic viscosity of the crude
at 72°C decreased by 17%.
It should be noted that in studying the changes in the component composition of gas condensate caused
by shock compression, formation of a naphtha cut – up to 12 wt. % per sample, a 9-12 wt. % increase in low-boiling
cuts, and a 2.5-3 wt. % decrease in heavy resids were observed.
All of these changes in shock-wave loading cannot be explained by the effect of pressure and temperature
alone. Macromolecular chain breaking under the effect of the mechanical energy of the shock wave is the basic
event in mechanochemical degradation, and critical local overloads that exceed the strength of chemical bonds
arise as a result of uneven distribution of energy in the molecular chain. The effect of pulsed loads on a substance
can differ as a function of their source, and it is only effective when it corresponds to the physical properties of
the substance and creates the maximum concentration of energy per unit of volume.
As we know, degradation, accompanied by breaking of chemical bonds, develops under the effect of
instantaneous force concentrated on small surfaces of macromolecular compounds in regions of intensive loads,
together with the appearance of fluidity due to the appearance of very large stresses. These processes do not
develop in the entire area of the intensive loads simultaneously, but are successively propagated at a very high
rate.
As a consequence, the initial stages of phase transitions – the appearance and growth of supramolecular
structures – are of important theoretical and practical significance. Due to the complexity of their composition
caused by the content of organic and inorganic compounds of different molecular weight and natural surfactants
(carboxylic acids, gums, asphaltenes, etc.), complex structural units consisting of a nucleus and an adsorption-
solvate layer arise in crude oil, gas condensate, and petroleum residues in ordinary conditions under the effect of
intermolecular interactions. Effects of redistribution of hydrocarbons between phases arise under the effect of a
shock pulse as a result of a directed change in the geometric dimensions of disperse formations and the interfacial
layer. In the final analysis, this affects the physicochemical properties of natural organic compounds and the
yield and quality of the products of refining hydrocarbon feedstock. For this reason, shock-wave technologies
can be used to enhance refining of this feedstock.
45
STRUCTURAL FEATURES OF INDUSTRIAL WATER-CRUDE OIL EMULSIONS.

MICROWAVE STUDIES
I. N. Evdokimov and M. A. Novikov UDC 665.7.033.28
The thermal properties and structural features of industrial water-oil emulsions were investigated with
microwave treatment. The critical concentrations of water at which abrupt structural changes take
place were determined. The effect of the mass fraction of water in the emulsion on its heating rate and
the efficiency of demulsification was studied. A 15-20 or 60-65% water content is recommended for
breaking down emulsions. Demulsification takes place with minimum power consumption and with the
highest efficiency.
The performance and user properties of crude oils and many petroleum products – fuel, viscous oils, and
greases – are to a great degree determined by the presence of water in them [1, 2]. The formation of emulsions of
water with fuel can cause engines to break down, and formation of emulsions with lube oil in the crankcase
ventilation system can diminish the protective properties of the lube oil. One negative factor in crude production
is its flooding, which causes problems related to formation of stable water–crude oil emulsions. Water also enters
crude oil when steam is pumped into the stratum and during desalting in electric desalting units (EDU).
Petroleum emulsions are easily formed in turbulent streams of a water-crude mixture when the pressure in
the pore channels changes and during movement through throttle plugs and different valves in pipeline systems.
An increase in the viscosity of the crude can increase the pumping costs due to higher power consumption. The
presence of emulsions intensifies corrosive wear of the equipment.
Typical natural emulsions are water in crude oil [3]. Crude oil contains surfactants (SF) such as asphaltenes,
naphthenic acids, and solid organic and inorganic particles. According to the Bancroft rule, a liquid
containing SF becomes a continuous phase [4]. In migrating to the phase boundary, SF form elastic protective
films around drops of water [1].
Modern methods of breaking down water–crude emulsions are based on using contact heating methods
or chemical additives (demulsifiers). Excessively high power consumption is characteristic of the first, and
____________________________________________________________________________________________________
I. M. Gubkin Russian State University of Oil and Gas. Translated from Khimiya i Tekhnologiya Topliv i
Masel, No. 1, pp. 36 – 38, January – February, 2007.

45
1
40
3
35
2
30
25
20
Fig. 1. Sample temperature T vs. microwave exposure time t : 1) pure water; 2) pure
crude ; 3) water–crude emulsion with 30% water.
contamination of wastewaters and oil refining products is characteristic of the second method. Contactless
microwave demulsification, patented more than two decades ago, is an alternative to these methods [5].
Microwaves have high penetrating power and act selectively on water, crude, and interfacial films, ensuring
separate energy input. As a result, the phase separation rate increases significantly in comparison to ordinary
heating methods and power consumption decreases [6-9].
Detailed information on the structural properties of the emulsions are necessary for controlling and
increasing the efficiency of demulsification [10]. Our studies provided new information on the character of the
structural changes in natural water–crude emulsions and revealed the features of their breakdown by microwave
treatment.
Emulsions based on crude oil taken from well No. 624 (Bobrikov stratum) in the Kuroki field
in Volgograd oblast were investigated. The degassed crude had a density of 832 kg/m 3 at 20°C and a solid point
below –18°C, and1% asphaltene, 8% resin, and 2% paraffin content. The aqueous phase was a double
distillate (pH=5.5) obtained according to GOST 6709–92 and stored in air.
All preliminary procedures were conducted in a thermally controlled cabinet at a temperature of 20°C.
Water in proportions of 0 to 100 wt. % (with a 5% step) was mixed with the crude oil with a mixer (~2000 ppm) for
8-10 min. Samples of the emulsions weighing 70±0.5 g were placed in 100-ml glass vessels for microwave treatment.
The type of emulsion (water in crude or crude in water) was determined by the drop test method [9]. All emulsions
with a water content of up to 80% (inclusively) were of the water in crude type.
An Elenberg Microwave Oven MS-1700M (2.45 GHz, 700 W) operating in the minimum (17%) output power
range was used as the microwave source in the experiments. In each experiment, the vessel with the emulsion
(initial temperature of 20±0.1°C) was placed in the center of the microwave oven and exposed to microwave
treatment for the assigned time (accuracy of determination of ±0.5 sec).
The temperature of the emulsion was measured with a calibrated thermocouple placed on the axis of the
sample at a depth of 10 mm from the surface of the emulsion. In addition, the heating time t d at which the beginning
of demulsification was visually observed was recorded: appearance of the first drops of water on the bottom/walls
of the vessel containing the emulsion or formation of a layer of pure crude on the surface. The effectiveness of
demulsification was defined as 1/t d.
47
2.0
1.6
dT/dt
1.2
0.8
0.4
0 0,2 0.4 0.6 0.8 1.0

c, mass portion
Fig. 2. Water–crude emulsion heating rate dT/dt vs. water content c.
Typical curves of heating the samples with pure water, pure crude, and a water–crude emulsion
with a 30% water content are shown in Fig. 1. As expected, they were almost linear for water, and heating took
place at a constant rate dT/dt which corresponded to absorbed energy of 5.8 W/cm 3 . For the crude oil sample,
linearity persisted at the beginning of heating to the temperature of 28°C with absorbed energy of 1.2 W/cm 3 .
Slowing of the heating rate on the 29-30°C segment indicates the appearance of endothermic processes
perhaps related to decomposition of colloidal aggregates of SF or melting of wax microcrystals. At higher
temperatures, the heating curve again became linear, and the absorbed energy was 1 W/cm 3. The insignificant
decrease in the heating level could be due to an increase in heat losses at high temperatures.
The water–crude emulsion heating curve has an even more complex shape. Its most distinctive feature is
the sharp increase in the heating rate at 35°C. The cause of this increase is the onset of demulsification, visually
detected by the appearance of layers of free pure crude and/or pure water. The constancy of the absorbed energy
in the first stage (0-6 sec) of microwave heating indicates preservation of the initial internal structure of the
emulsion, of which quantity dT/dt could be a characteristic.
The essentially nonmonotonic dependence of the initial heating rate dT/dt on the content of water in the
emulsion, which indicates sharp changes in the structure of the emulsion, is shown in Fig. 2. Such an effect of the
water content on the properties of an emulsion undergoing microwave treatment have not been published previously.
Our previous experiments [10] demonstrated the nonmonotonic effect of the water content on the viscosity and
density of natural water–crude emulsions. These effects were attributed to the characteristic formations of the
emulsion structure only observed in model microemulsions [11].
By analogy with the results in [10], the specific dependence in Fig. 2 can be identified with the appearance
of the same structural effects. Freshly prepared emulsions with a low water content can be regarded as suspensions
of individual, noninteracting drops of water [10, 11].
The initial heating rates of such emulsions are lower than for pure crude due to the well-known predominant
absorption of microwave energy by water. As a result, the energy absorbed by the basic (by mass) crude phase
decreases, and the low thermal conductivity of the crude prevents rapid heat transfer from the water drops.
We attribute the sharp increase in the initial heating rate in mass fractions of water close to 0.2 (volume
fraction of ~0.17) to the appearance of percolation. This event has been well investigated in model microemulsions,
but rarely discussed with respect to the behavior of natural water–crude emulsions. As a result of percolation, the
48
0.09
0.08
1/td, sec −1
0.06
0.04
0.02
0,05 0.20 0.35 0.50 0.65 0.80
c, mass portion
Fig. 3. Effectiveness 1/t d of demulsification vs. water content c in emulsion.
water drops form extensive “chains” that facilitate energy transfer over great distances and increase the
conductivity of the sample [3, 11, 12].
The experimental percolation thresholds in model emulsions with different SF were observed in the range
of 0.16-0.28 volume fractions of water [12, 13], which is close to the value of 0.17 in our experiments (see Fig. 2).
Consolidation of the protective layers of SF around the water drops caused by percolation can cause
formation of a new (bicontinuous) structure in natural water–crude emulsions [10]. Actually, it was hypothesized
more than four decades ago that the presence of an elastic protective layer which acts as a barrier to coalescence
of the drops could be the cause of the stability of water–crude emulsions.
It was recently shown in [13, 14] that this layer can have a very complex composition. For example, it can
include liquid-crystalline naphthenic acid structures, molecular aggregates of asphaltenes, and solid particles.
Such boundary layers are essentially a special “third phase” of water–crude emulsions. In the case of the
approximate equality of the proportions of water and crude, a “third phase” of thermodynamically unstable natural
emulsions can form transitional bicontinuous structures that externally resemble the stable bicontinuous structures
in model microemulsions [11, 12].
We previously [10] discovered the appearance of special bicontinuous structures in industrial
water–crude emulsions with a 0.4-0.6 (wt.) fraction of water by density and viscosity measurements. In view of the
results obtained, we correlated the appearance of the local heating rate minimum in Fig. 2 for a mass fraction of
water close to 0.4 (volume fraction of 0.37) with the onset of formation of such transitional structures.
The probable mechanism of the appearance of the minimum is a decrease in interfacial heat exchange in
the bicontinuous structure in comparison to the drop structure for the same water content in the case of contraction
of the total water–crude contact area.
The rapid increase in the initial heating rate observed in Fig. 2 for a water content greater than 0.4 could
be attributed to the appearance of important polydispersion of the aqueous phase after decomposition of the
bicontinuous structures. Actually, previous studies [10] showed that at this water content in water–crude emulsions,
the distribution of water drops by size becomes bimodal.
Large water drops constitute an “ordinary” aqueous phase, and closely packed drops less than 7-8 mm in
size constitute a “third phase.” Such closely packed disperse structures stabilized by small drops of water are
49
characterized by extremely high dielectric losses in comparison to a continuous aqueous phase. As a consequence,
the specific properties of the “third phase” can be responsible for the increase in the heating rate observed
in Fig. 2 for 0.55-0.7 mass fractions of water (0.5-0.66 volume fractions).
Finally, it follows from Fig. 2 that for a mass fraction of water greater than 0.65, the heating rate will
decrease to values close to those observed for pure water. In consideration of the absence of phase inversion in
the investigated samples up to a mass fraction of water of 0.8, such behavior can be assigned to the onset of
formation of “close packing” of the water drops. The value of 0.65 is close to the known mass fraction of disperse
phase in “arbitrary close packing” of identical drops (volume fraction of 0.637, mass fraction of 0.66).
The change in the heating rate can be attributed to the fact that additional pressure on the “third
phase” arises in “close packing” of large drops of water when they touch each other, and enlargement of the
smallest drops of water begins in this phase. For this reason, the “third phase” loses its high energy-absorbing
properties and the overall heating rate decreases.
The dependence of the effectiveness of demulsification on the fraction of water in the emulsion is
shown in Fig. 3. It is clear that the highest efficiency is attained for mass fractions of water close
to 0.2 and 0.6, corresponding to the formation of the special states of the structure of water–crude emulsions
described above.
The concentrations of water in an emulsion at which the structure of the disperse phase changes markedly,
causing a sharp change in the thermal properties of the emulsions, were thus found as a result of studying
industrial mixtures of crude oil and water. The heating rate and demulsification efficiency are maximum in emulsions
with approximately 20 and 60% concentrations of water. Maintaining the fraction of water near these values can
minimize power consumption and accelerate microwave demulsification processes.
REFERENCES
1. G. N. Poznyshev, Stabilization and Breaking of Emulsions [in Russian], Nedra, Moscow (1982).
2. N. M. Likhterova, V. P. Kovalenko, and V. V. Lebedev, Khim. Tekhnol. Topl. Masel, No. 4, 24-28 (2003).
3. W. Clayton, Theory of Emulsions and Technical Applications [Russian translation], Izdatinlit, Moscow
(1950).
4. W. D. Bancroft, J. Phys. Chem., 17, 501 (1913).
5. US Patent No. 4 582 629.
6. J.-H. Hong, B.-S. Kim, and D.-C. Kim, Korean Chem. Eng. Res., 42, No. 6, 662-668 (2004).
7. C. S. Fang, B. K. L. Chang, P. M. C. Lai, et al., Chem. Eng. Commun., 73, No. 1, 227-239 (1988).
8. L.-X. Xia, S.-W. Lu, and G. Cao, Ibid., 191, No. 8, 1053-1063 (2004).
9. C.-C. Chan and Y.-C. Chen, Separation Sci. Technol., 37, No. 15, 3407-3420 (2002).
10. I. N. Evdokimov, N. Yu. Eliseev, and V. A. Iktisanov, Khim. Tekhnol. Topl. Masel, No. 4, 37-39 (2005).
11. P. Sherman, Emulsion Science, Academic Press, New York (1968).
12. G. C. Bye et. al., in: Microemulsions: Structure and Dynamics, S. E. Friberg and P. Bothorel (eds.),
CRC Press, Boca Raton, Florida (1987).
13. S. I. Borisov, M. V. Kateev, E. S. Kalinin, et al., Neft. Khozyaistvo, No. 4, 74-77 (2004).
14. T. F. Kosmacheva and F. R. Bugaidulin, Ibid., No. 12, 114-118 (2005).
50
REFORMING OF n-HEXADECANE ON MODIFIED ALUMINOSILICATES
Ali Busenna, O. Zamumi, I. M. Kolesnikov, and Le Tu An’ UDC 66.023.66.007
Catalysts containing amorphous aluminosilicate and crystalline zeolite phases are widely used for industrial
cracking of petroleum cuts. These catalysts also exhibit high activity in cracking of individual hydrocarbons.
The activity and selectivity of the amorphous aluminosilicate phase can be increased by modifying it with
metal oxides, creating additional ensembles of tetrahedrons of the type (AlO 4⋅SiO 4⋅MeO 4) or ensembles of
polyhedrons of another composition: (AlO 6 ⋅SiO 4⋅MeO4 ) or (AlO 4⋅SiO4 ⋅MeO 6) in the lattice. These ensembles are
randomly positioned in the lattice, which also reflects the amorphous structure of metal silicates.
In special conditions – in liquid medium (water) at high pressure, metal silicates crystallize with formation
of zeolites. When incorporated in the amorphous phase, zeolites serve as active catalytic components.
Cobalt or zirconium compounds which also attack the aluminosilicate structure, changing the activity and
selectivity of the catalysts, can also be added to the amorphous phase. New data on the activity of metal
aluminosilicate catalysts containing these compounds in a fixed amount are reported here. The catalysts were
Table 1
Catalyst Chemical composition,* wt. %
pH of sol in
(arbitrary
synthesis Sio2 Al2O3 CaO ZrO2
designation)
К1 10.5 92 – 7.84 –
К2 4.5 92.2 – 7.74 –
К3 4.5 89.75 8.5 1.22 –
К4 10.5 90.8 6.97 1.38 –
К5 10.5 87.7 9.06 – 2.18
К6 4.5 86.9 11 – 1.38
Note. * Remainder – sodium oxide
____________________________________________________________________________________________________
M. Bucher University of Hydrocarbons and Chemistry, Algiers. I. M. Gubkin Russian State University of
Oil and Gas. Translated from Khimiya i Tekhnologiya Topliv i Masel, No. 1, pp. 39 – 41, January – February, 2007.

Table 2
Unit cell size, nm

Compound
a b c
Co2SiO4 0.4781 1.0296 0.5998
CoSiO2 1.8296 0.8923 0.5204
Table 3
Catalyst (see Pore volume (cm3/g) after heating at, °C Average pore radius (nm) after heating at, °C
Table 1) 500 700 900 500 700 900
К1 0.63 0.51 0.46 0.832 0.904 1.312
К2 0.64 0.55 0.23 0.447 0.954 1.162
К3 0.24 0.14 0.05 0.910 0.900 1.020
К4 0.65 0.47 0.19 0.388 0.821 1.594
К5 0.29 0.16 0.13 1.450 2.250 4.090
К6 0.24 0.17 0.16 1.970 2.430 4.300
used for conversion of n-hexadecane to reveal the basic types of reactions (cracking, reforming, isomerization,
etc.) that determine the composition of the catalyzate and hydrocarbon gases.
Aluminosilicate catalysts modified with cobalt and zirconium compounds were synthesized in a continuous
unit by feeding aqueous solutions of Al 2(SO 4)⋅18H2 O, Co(NO 3) 2 ⋅8H 2 O, and ZrOCl⋅8H 2 O salts and an aqueous
solution of liquid glass, Na 2SiO 3, in the corresponding ratios, in the mixing unit. In mixing the solutions
at 10°C and pH 4.5 or 10.5 (to establish the effect of the pH on the properties and activity of the catalyst), a metal
aluminosilicate sol was obtained.
The sol stream in the form of microdrops was passed through a grooved divider into a lower container
filled with transformer oil. In passing from the surface of the oil to the bottom of the vessel, the sol droplets
solidified into gel beads. The beads formed were placed in a separate container, washed with distilled water, and
underwent syneresis for 8 h at 40°C in the mother liquor separated from them. The mother liquor was displaced
from the container with an activating aqueous solution of (NH 4) 2 SO 4 and the gel was activated at 50°C for 24 h.
Substitution of Na + ions by NH +4 ions took place in bulk and on the surface of the hydrogel particles in activation.
Activation continued until the Na + ions were totally substituted, determined by the absence of these ions in the
hydrogel particles.
The activated hydrogel was washed with distilled water until the SO2-4 ions in the washing water totally
disappeared. The gel was separated from the moisture on a filter, placed in an oven, and dried at 110°C to a
constant weight, then calcined in an air stream at 500, 700, and 900°C for 6 h.
After calcination, the catalysts were stored in a desiccator to prevent sorption of moisture and organic
compounds from the environment. The chemical composition was determined, the IR and x-ray structural spectra
were recorded, and the acidity, external appearance, specific surface area, volume, and average pore radius were
determined for the catalysts calcined at 500°C.
The chemical composition and acidity of the external surface of the modified catalysts are reported in
Table 1. The basic components are SiO 2 and Al 2O 3 , CoO, and ZrO2 , which play the role of modifiers.
The x-ray structural analysis showed that the modified and initial aluminosilicates are x-ray amorphous
structures, while the cobalt silicate has a crystal lattice with an orthorhombic unit cell whose size is shown in
Table 2 for the two compounds identified.
52
Table 4
Specific surface area (m2/g) after heating at, °C

Catalyst (see Table 1)
500 700 900
К1 151 113 56
К2 271 260 151
К3 228 113 99
К4 335 295 67
К5 253 194 166
К6 246 168 161
Table 5
Acidity (meq H+/g) after heating at, °C
Catalyst (see Table 1)
500 700 900
К1 2.45 2.35 2.3
К2 3.76 2.7 2.35
К3 4.8 2.85 2.75
К4 2.8 2.4 2.2
К5 3.45 2.3 2.15
К6 3.8 2.8 2.4
The absorption bands at 730-780 cm -1 in the IR spectra of the modified aluminosilicates were assigned to
vibrations of the bonds in island ensembles of {AlO 4Table 3⋅SiO 4} tetrahedrons, those at 500-600 cm -1 were
a s s i g n e d t o p o l y m e r i z a t i o n e n s e m b l e s o f { M e O 6⋅ S i O 4} t e t r a h e d r o n s , t h o s e a t 1 6 0 0 - 1 7 0 0 c m -1 t o
h y d r o x y l a t e d > A l O 6H ⋅ S i O 4} p o l y h e d r o n s , a n d t h o s e a t 3 4 5 2 c m -1 t o h y d r a t e d s i l i c o n o x i d e
tetrahedrons {SiO 4⋅SiO 4}H 2O.
The texture of the catalysts was determined by adsorption of nitrogen. The average radius and pore
volume characterizing it are reported in Table 3. The pore volume decreased and the average radius increased
when the sample heating temperature increased from 500 to 900°C. The increase in the average radius is due to
destruction of blind pores joined by narrow pores into wider pores due to the effect of water vapor and a decrease
in the number of winding pores. These three causes of the change in texture reflect an overall change in the
physical properties of the catalysts. The wider-pore catalysts were synthesized in basic medium.
T h e c a l c u l a t e d s p e c i f i c s u r f a c e a r e a s o f t h e i n v e s t i g a t e d c a t a l y s t s a r e r e p o r t e d i n Ta b l e 4 .
Catalyst K 4 , synthesized at pH 10.5, has a higher specific surface area than the other catalysts. The specific
surface area of the catalysts decreased with an increase in the calcination temperature as a result of an increase in
the average pore radius.
The acidity was investigated by titration of suspensions of the samples in benzene with a solution
of n-butylamine to determine the nature of the activity of the modified catalysts in reforming and cracking
of n-hexadecane. The acidity of the accessible active ensembles of tetrahedrons containing or not containing
hydroxyl groups was determined in titration. The results of the experiments are reported in Table 5.
Catalysts K 2, K 3, and K 6 , synthesized from sol at pH 4.5, had higher acidity. Moreover, their specific
surface was lower than for catalysts K 1, K 4, and K 5, synthesized at pH 10.5. As a consequence, the activity of the
catalysts is not directly correlated with the acidity of their surface. It can be explained by the premises of the
theory of catalysis by polyhedrons in [1, 2].
53
80
K6
60
K3
K4
x, wt. %
40
K5
20
0
200 250 300 350 400
t, °C
Fig. 1. Degree of conversion x of n-hexadecane vs. temperature t on catalysts modified

with zirconium oxide (solid curves) and cobalt oxide (dashed curves).
According to this theory, amorphous lattices with a higher content of ensembles of tetrahedrons of
the {AlO 4⋅SiO 4}, {SiO4⋅ZrO4⋅AlO 4}, {SiO4⋅AlO 4⋅SiO 4}, and {CoO43⋅SiO 4⋅AlO 4} type are obtained from the sol in acid
medium. This is confirmed by the IR spectra of the catalysts synthesized from sols at pH 4.5 and 10.5.
After the physicochemical properties, composition, structure, and acidity of catalysts K 1-K 6, their activity
in cracking and reforming of liquid n-hexadecane was investigated. The reactions were conducted in a continuous
unit in the gas phase in conditions of ideal displacement of the vapor phase over the catalyst bed. The reactor
was charged with 40 cm 3 of bead or grain catalyst, and it was heated in a stream of dried air with impurities removed
at 500°C for 3 h.
Conversion of n-hexadecane took place in the 350-400°C temperature range at a feed rate of 1 cm 3/(cm 3⋅h)
for 1 h. At the end of the process, the degree of conversion of the feedstock and content of four classes of
hydrocarbons in the catalyzate: paraffins, olefins, naphthenes, and aromatics, were determined.
The increase in the degree of conversion with an increase in the temperature in the catalyst bed (Fig. 1) is
due to both activation of the hydrocarbon molecules in the feedstock and to electron promotion (or electron
respiration) of tetrahedron ensembles. Catalysts K 3 and K 5 synthesized at pH 4.5 and modified with cobalt and
zirconium compounds exhibited high acidity and consequently higher activity.
Catalyzate was obtained on catalyst K 6 that distills within 30-165°C and has the following hydrocarbon
composition, wt. %: 10.05 n-paraffins; 9.21 olefins; 18.50 naphthenes; 38.12 isoparaffins; and 23.49 aromatics.
The octane number (motor) of the catalyzate was 79.3.
Based on these data, we note that the n-hexadecane molecules undergo cracking and reforming reactions
in the presence of the zirconium aluminosilicate catalyst. The yield of gaseous hydrocarbons increased
from 0.9 to 4.5 wt. % with an increase in the temperature. The presence of C 1-C 15 hydrocarbons in the products of
conversion indicate catalytic cracking processes.
Hexadecane is present in the catalyzate both in the initial and in isomeric forms. Unsaturated hydrocarbons
and aromatics – benzene and alkylbenzenes with a shorter alkyl radical – are formed in cracking reactions.
The presence of isoparaffins, naphthenes, and aromatic hydrocarbons in the catalyzate indicates reforming
of n-hexadecane. Isoparaffins are formed by isomerization of n-paraffins on ensembles of tetrahedrons.
Reactions of dehydrocyclization of molecules of unsaturated hydrocarbons take place on the same
ensembles with formation of aromatics. Naphthenes can be synthesized in several reactions: Diels–Adler,
54
100
80
V, vol. %
40
0
40 80 120 160
tdis, °C
Fig. 2. Curve of distillation of liquid reformate into narrow cuts (V, t dis – distillation
volume and temperature).
cyclization of olefins with formation of cyclohexane and decalin, whose dehydrogenation yields benzene and
naphthalene, respectively.
This approach to explaining the chemistry of conversion of n-hexadecane on modified aluminosilicate
catalysts, i.e., with separation of cracking and reforming processes, will allow more clearly elucidating the quality
of the catalyzate obtained.
The liquid catalyzate was distilled from an Engler flask into narrow cuts to determine its motor properties.
The distillation curve obtained (Fig. 2) is characteristic of the commercial naphtha cut, 50 vol. % of which distills
at a temperature no higher than 120°C. As a consequence, a high-octane component as an additional additive for
commercial gasoline can be obtained in conversion of n-paraffins in low-octane naphtha cuts on cobalt- and
zirconium-modified aluminosilicate catalysts.
REFERENCES
1. I. M. Kolesnikov, G. I. Vyakhirev, M. Yu. Kil’yanov, et all, Solid Catalysts, Their Structure, Composition,
and Catalytic Activity [in Russian], Neft’ i Gaz, Moscow (2000).
2. I. M. Kolesnikov, Catalysis and Catalyst Production [in Russian], Tekhnika, Moscow (2004).
55
EFFECT OF A COPOLYMER MODIFIER ON DEWAXING OF LUBE DISTILLATES
I. K. Veliev UDC 665.547.391
Dewaxing with selective solvents in production of lube oils from paraffin-base crudes requires large
investments and operating expenses. Up to 40% of all expenses are for this process. For this reason, searching
for ways to enhance it is a pressing problem [1].
Use of modifiers is the most effective and simplest method of increasing the efficiency of dewaxing of lube
distillates with selective solvents. The efficiency of Paragel, Hightech E-603, Viscoplex, and N-500 pour-point
depressants, which are products of condensation of chloroparaffin with naphthalene and methacrylic acid ester
and aliphatic alcohol polymers in three-stage dewaxing of raffinates obtained from mixing crudes at Pleven Oil
Refinery (Bulgaria), was demonstrated in [2].
On addition of 0.2 wt. % of these additives, the yield of dewaxed oil increased by 2-3 wt. % and the
filtration rate of the suspension in all stages increased by 2-4 times.
Table 1
Raffinate from selective treatment wit phenol

Indexes from Ufa OR distillate from Novo-Gor’kovsky OR
I-20 oil I-40 oil I-40 distillate oil MS-20 residual
(distillate III) (distillate IV) (distillate IV) oil
Density at 20°C, kg/m3 866.7 881.3 884.3 893.8
Viscosity at 100°C, mm2/sec 4.43 7 7.02 17.6
Flash point, °C 210 230 226 282
Melting point, °C +21 +36 +36 +40
Color, CNT units 2.5 4 3 5
Solid paraffin content, wt. % 12.86 13.49 16.36 13.06
____________________________________________________________________________________________________
Yu. G. Mamedaliev Institute of Petrochemical Processes, National Academy of Sciences of Azerbaidzhan.
Translated from Khimiya i Tekhnologiya Topliv i Masel, No. 1, pp. 42 – 43, January – February, 2007.

Table 2
Dewaxing
of distillate raffinates at Novo-Gor’kovsky OR
Indexes of I-20 (distillate III)
and I-40 (distillate IV) I-40 oil distillate MS-20 oil residual
lube oils at Ufa OR raffinate raffinate
Solvent composition, wt. %
methyl ethyl ketone 60 60 50
toluene 40 40 50
Amount of solvent, wt. %
for feedstock dilution 280 300 420
for washing residue 100 100 100
Filtration temperature, °C -25 -25 -25
Solution cooling rate, deg/h 180 120 120
Approximately 40 pilot industrial products were tested as modifiers to enhance dewaxing at the Institute
of Petrochemical Processes (IPCP), Azerbaidzhan National Academy of Sciences [3-5]. DN-MA additive, an alkyl
methacrylate copolymer, was the most effective.
It is stable during storage and in solutions of slack wax and petrolatum in dewaxing. We found that the
optimum amount is 0.15 wt. % in raffinate in dewaxing of distillate and residual raffinates from furfural treatment
of Baku paraffin-base crudes.
We investigated the mechanism of action of this additive in distillate and residual raffinates. The increase
in the effectiveness of the process was due to a decrease in the viscosity of the cooled solution as a result of
formation of a primary coagulation structure. This improved diffusion of wax crystals to the crystallization center
and prevented formation of an extensive wax lattice during crystallization.
A correlation was established between the effectiveness of the additive and its dielectric constant, which
can be used as a criterion of the suitability of the modifier. It was 2.9600 for DN-MA versus 2.6933 for
AzNII and 2.5314 for PMA “D”, for example [3]
The use of DN-MA modifier additive has advantages over MAX-Dewax technology [6].
Due to the increase in production of high wax crudes, increasing the efficiency of dewaxing with selective
solvents has become very urgent. We investigated the effect of DN-MA additive on the effectiveness of dewaxing
raffinates from selective treatment of medium-sulfur crudes.
Distillate raffinates of I-20 and I-40 lube oils from Ufa OR and I-40 oil distillate raffinate and MS-20 oil
residual raffinate from Novo-Gor’kovsky OR were dewaxed. The quality indexes of these raffinates are reported in
Table 1, the dewaxing conditions used at these OR are shown in Table 2, and the results of dewaxing with no
additives and with DN-MA additive are reported in Table 3.
As Table 3 shows, when the amount of DN-MA is increased from 0.1 to 0.2 wt. %, the yield of dewaxed oil
and the suspension filtration rate increase in dewaxing of distillate and residual raffinates, while the solid point of
the oil remains unchanged, the viscosity index increases, and the oil content in slack wax and petrolatum decreases.
The greatest effect is obtained with 0.15 wt. % additive. Increasing the amount from 0.15 to 0.2 wt. %
insignificantly affected the results.
As a result of using DN-MA additive in the optimum amount (0.15 wt. %), it was possible to obtain
dewaxed lube oil with a high yield and improved physicochemical properties, reduce the oil content in slack wax by
2.5 times, and increase the filtration rate of the cooled solution by 2-4.8 times.
57
58
Table 3
Yield, wt. % Physicochemical properties

Amount of
DN-MA Filtration dewaxed lube oil slack wax (petrolatum)
additive, wt. slack wax rate, % viscosity at
lube oil density at viscosity solid point, melting oil content,
% (petrolatum) 10°C,
3
20°C, kg/m index °C point, °C wt. %
mm2/sec
DEWAXING
at Ufa OR
I-20 oil medium-viscosity distillate raffinate (distillate III)
0 81.2 18.8 100 878.2 4.43 100 -19 52 20
0.1 81.8 18.2 200 877.8 4.81 101 -19 54 11.5
0.15 82.6 17.4 300 869.6 4.75 104 -19 54 8.5
0.2 82.8 17.2 312 868.9 4.69 104 -19 54 8.2
I-40 oil viscous distillate raffinate (distillate IV)
0 79.7 20.3 100 887.8 7 90 -20 53 20.8
0.1 80.9 19.1 150 886.5 7.63 92 -20 54 13.5
0.15 82.3 17.7 200 886.4 7.5 94 -20 54 8.4
0.2 82.6 17.4 250 886.1 7.45 94 -20 54 8.2
at Novo-Gor’kovsky OR
raffinate (distilalte IV)
0 79 21 100 885.6 7.02 91 -15 52 21
0.1 82.2 17.8 200 884.6 7.65 91 -15 54 14.2
0.15 85.2 14.8 310 884 7.49 92 -15 55 9.1
0.2 85.6 14.4 312 883.8 7.45 92 -15 55 8.9
MS-20 oil residual raffinate [5]
0 68.5 (31.5) 100 897.9 20.5 90 -15 (62) (32.8)
0.1 79 21 266 897.1 20.3 91 -15 63 10
0.15 80.5 19.5 480 896.9 20.2 92 -15 64 5.6
0.2 81.2 18.8 480 895.7 20.2 92 -15 64 5.2
This additive is a universal modifier: it is equally effective in dewaxing of both distillate and residual
raffinates from phenol and furfural treatment obtained from both medium-sulfur and from low-sulfur crudes.
REFERENCES
1. L. P. Kazakova and S. E. Krein, Physicochemical Principles of Petroleum Oil Production [in Russian],
Khimiya, Moscow (1978).
2. P. G. Furnadzhieva, G. P. Abrashov, A. Atanosov, et al., Neft’ Khimiya (Sofiya), No. 11, 191-198 (1973).
3. I. K. Veliev, Candidate Dissertation, Institute of Petroleum Chemistry, AzerbSSR Academy of Sciences,
Baku (1982).
4. R. Sh. Kuliev, F. R. Shirinov, and I. K. Veliev, Azerbaidzh. Neft. Khozyaistvo, No. 3, 25-27 (1997).
5. R. Sh. Kuliev, F. R. Shirinov, and I. K. Veliev, Khim. Tekhnol. Topl. Masel, No. 3, 13-14 (1998).
6. R. Sh. Kuliev, I. K. Veliev, and S. R. Kulieva, Ibid., No. 6, 11-13 (2003).
59
METHODS OF ANALYSIS
A PIEZORESONANCE SENSOR SYSTEM FOR RAPID EVALUATION

OF THE QUALITY OF GASOLINES
A. V. Kalach and V. F. Selemenev UDC 543.662.6
The urgency of the problem of supplying the country’s growing auto fleet with high–quality motor fuel
with improved environmental characteristics is primarily due to entry of important amounts of harmful substances
contained in adulterated liquid fuel into the environment. Of all aspects of the overall environmental picture, the
problem of atmospheric pollution by harmful products of oil refining, primarily those released in use of gasolines
and diesel fuels in motor vehicles, has received the most attention [1].
Motor vehicles are responsible for more than 60% of the total volume of pollutants in most large cities.
Since adulteration of automotive fuel in Russia has become massive, it is urgent and necessary to develop and use
modern methods of quality control.
One of the most intensively developing branches of science “ sensors “ allows quickly obtaining reliable
information on product quality. We developed a new method for fast evaluation of the quality of commercial
gasolines using piezoresonance sensor systems.
Commercial A–76 and AI–92 gasolines purchased at service stations in Voronezh were selected for the
study. The studies were conducted with AL–cut quartz resonators (nominal oscillation frequency: 8–10 MHz)
manufactured at P’ezo Co. (Moscow). Polymethylphenyl silicone (PMPS) and squalane (Sq) were used as the
sorbent modifiers for the piezoresonance sensors (PrS). These sorbents were selected because of the stability of
the PrS analytical signal obtained.
The sorbent (25 mg) for modification of the PrS was placed in a 25–cm 3 graduated flask and the volume was
brought to the mark with the corresponding solvent (in our case, chloroform for PMPS and hexane for Sq). The
sorbent solution was applied to both electrodes of the quartz crystal with a microsyringe. The modified crystal
was held in the temperature range whose upper limit corresponded to the boiling point of the solvent. The shift of
the PrS oscillation frequency was only established after this.
____________________________________________________________________________________________________
Institute of RF Ministry of Internal Affairs. Voronezh State University. Translated from Khimiya i

The decrease in the working oscillation frequency of the PrS was calculated with the Sauerbrei
equation [2, 3]:
Δf = -2.3 ⋅ 10 -6 f 02 Δm / A
w h e r e Δ f i s t h e c h a n g e i n t h e r e s o n a t o r f r e q u e n c y, H z ; f 0 i s t h e r e s o n a n c e f r e q u e n c y o f t h e
piezosensor, MHz; Δm is the mass of the modifier, g; A is the surface area of the modifier (set equal to the area of
the electrodes), cm 2.
The original piezoresonance sensor system described in detail in [4] was used for analyzing the gasoline
samples.
The analysis of the published data showed that the principle of fabrication of adulterated gasoline
frequently consists of bringing the octane number of the blend to the required value [1]. As practice shows, this
can be conveniently done by adding an adulterant to the gasoline “ gas condensate or ethanol. However, such
additives increase the octane number of the gasoline only for a short time, after which the auto continues to
operate on gasoline of lower quality which unconditionally leads to early wear of the internal parts of the engine.
The complex implementation, use of a large number of chemical reagents, duration of the analysis, for
example with the PIANO method [5], are serious drawbacks of existing methods of assessing the quality of gasolines
in our opinion.
Taking into account the overall tendency of both researchers and consumers to assess the quality of a
product with rapid, simple, and economically expedient methods and instruments, attention should be focused on
developing portable instruments, test methods, and operative screening methods [6, 7].
We took into consideration the wide distribution of methods that allow assessing the integral (generalized)
indexes of the sample analyzed in developing a new method of assessing the real quality of commercial
gasolines [7]. It totally does not follow from the octane number of gasoline determined by some method, which,
for example, would be equal to 76, that the investigated gasoline will correspond to brand A–76. The results of the
analysis only show its octane number and this frequently means the version of assessing the quality of commercial
gasoline is not acceptable.
To establish the correspondence of a product to a real commercial brand and concrete standard, not to
speak of the manufacturer, it is necessary to determine so many indexes that the cost and time for solving this
problem in a large stream of samples would end at an impasse for both manufacturer and researcher.
Multisensor systems formed from nonselective sensors have been widely used in
practice [8–10]. Identifying the odor of the material and establishing the concentration of substances contained
in the sample if possible is the main problem that can be solved with such systems. This is due to processing the
data and identifying the multidimensional picture of the sensor signals: “odor pattern,” “visual impression.”
Sensors are usually characterized by cross sensitivity so that an important number of them complicates
processing of the results of the measurement in most cases. For this reason, reducing the size of the measurement
space by isolating the most informative sensor elements is justified.
The proposed method is based on use of a multisensor system formed of six piezoresonance sensors
modified with squalane and polymethylphenyl silicone, which allows rapidly evaluating the quality of commercial
gasolines in a maximum of 3 min [11].
Profile analysis was used for constructing the overall signal of the system, the so–called “visual
imprint.” This method is based on unifying the individual olfactory and other parameters of gasoline to obtain a
qualitatively new characteristic of the product. After statistical processing, the results can be represented
graphically in the form of the complete circumference profile (see Fig. 1).
61
400 1 200 1
2 2
200 100
0 3 0 3
200 1 500 1
2 2
100
0 3 0 3
Fig. 1. “Visual imprints” of samples of gasoline acquired at two Tyumen Petroleum

Company filling stations: A, C) A–76; B, D) AI–92.
The most informative piezoresonance sensors and an algorithm for identifying their signals in pairs of
analyzed gasolines that ensure obtaining different “visual imprints” of the products were distinguished. A
multisensor system for analysis of the investigated gasolines was formulated based on the PrS signals selected
for maximum recognition of analytes that differ significantly with respect to the overall response (“visual imprint”).
Optimizing the algorithm for forming matrix responses of six and more sensors allows obtaining the “visual
imprints” of analytes that differ significantly from each other. By comparing these imprints, it is possible to:
distinguish the characteristic geometric samples “ the “visual imprints” for all commercial gasolines studied;
rapidly order the sensors by maximum and minimum sensitivity to vapors of the investigated gasolines.
Using piezoresonance sensors with close affinity to the components of the gasolines increases the degree
of difference of the “visual imprints”.
As Fig. 1 shows, A–76 and AI–92 commercial gasolines at two different filling stations (samples A, B and
C, D) unfortunately differ significantly with respect to the “visual imprints.” This probably cannot be due to
different manufacturing technology alone.
This finding once more confirms the necessity of developing portable fast methods of quality control for
petroleum products (on the example of gasolines) and the applicability of our method for evaluating the quality of
purchased commercial gasolines. The method is characterized by simplicity and availability to users. It will allow
gasoline manufacturers to monitor the manufacturing process and filling station owners to monitor shipments.
The results obtained allow recommending the method for fast evaluation of commercial gasolines. In our
opinion, this method can be used for evaluating the quality of any petroleum products. As a consequence,
manufacturers of liquid fuel can operatively control the manufacturing process and act on it by attaining the
required indexes at minimal cost. However, it should be remembered that no fast analysis replaces the umpire
laboratory method of assessing product quality.
62
REFERENCES
1. A. S. Safonov, A. I. Ushakov, and I. V. Chechkenev, Automotive Fuels: Chemmotology. Performance
Properties. Assortment [in Russian], NPIKTs, St. Petersburg (2002).
2. V. V. Malov, Piezoresonance Sensors [in Russian], Energoatomizdat, Moscow (1989).
3. L. M. Dorozhkin, V. S. Doroshenko, Yu. I. Krasilov, et al., Zh. Anal. Khim., 50, No. 9, 979–982 (1995).
4. A. V. Kalach, Izv. Vyssh. Uchebn. Zaved., Khim. Khim. Tekhnol., 47, No. 9, 146–148 (2004).
5. V. I. Vershinin, B. G. Derendyaev, and K. S. Lebedev, Computer Identification of Organic Compounds
[in Russian], Akademkniga, Moscow (2002).
6. Yu. A. Zolotov, Zavod. Lab. Diagnost. Mater., 68, No. 1, 14–21 (2002).
7. Yu. A. Zolotov, Zh. Anal. Khim., 59, No. 7, 677 (2004).
8. I. V. Kruglenko, B. A. Snopok, Yu. M. Shirshov, et al., in: Proceedings of the Conference “Sensor”2000.
Sensors and Microsystems,” St. Petersburg, June 21–23, 2000 [in Russian], St. Petersburg (2000), p.
110.
9. A. V. Kalach, Ya. I. Korenman, and S. I. Niftaliev, Man–made Neuronal Networks “ Yesterday, Today,
Tomorrow [in Russian], Voronezh State Technol. Acad., Voronezh (2002).
10. A. V. Kalach, in: Proceedings of the All–Russian Conference “Russian Analysts”, Moscow, September
27–October 1, 2004 [in Russian], Moscow (2004), p. 104.
11. RF Patent No. 2248571.
63
QUALITY CONTROL OF PETROLEUM OILS WITH ADDITIVES
K. V. Kovalenko, S. V. Krivokhizha, and G. V. Rakaeva UDC 665.765.03
The performance properties of the initial components and finished product were evaluated during
fabrication of models of commercial lube oils by scattered light correlation spectroscopy. This method
allows determining the size and average radius of colloidal formations and the stability of colloidal
solutions against separation. Using the data obtained, changes can be made in the manufacturing
technology and formula of the oils by changing the mixing temperature and parameters of the initial
components: the indexes of the base, the sequence of incorporating the additives, and the concentration
and composition of the additives.
Many petroleum oils contain surfactants (SF) – additives that improve their performance properties:
colloidal stability against separation, chemical stability against oxidation, lubricity, detergent, anticorrosion,
demulsifying, and antifoaming properties [1, 2].
In high enough concentrations, these additives form micellar solutions. The formation and properties of
these solutions, the reaction of additives of different types in them and consequently, the effectiveness of the
additives are described by the laws of colloid chemistry, physical chemistry, and physics [3, 4]. These laws are
frequently used in selecting and increasing the effectiveness of additives to lube oils and fuels, which in turn
allows reducing consumption of power and the most important petroleum products in modern industry [5, 6].
Selection of the base oil – the bases in production of commercial lube oil – is determined by both the
required functional properties of the oil and the economic indexes of its production and use. Petroleum base oils
are the most high-volume. Additives are incorporated in them to enhance certain performance properties [7, 8].
One method of selecting additives for lube oils is to apply the principles of nanotechnology, to wit, to
create a stable structure (dispersion) of colloidal formations (CF) of nano dimensions in commercial oils.
Nanosystems, according to the classification used in colloid chemistry, are ultradisperse colloidal systems with a
particle size falling in the range of 1 to 100 nm [9-11].
____________________________________________________________________________________________________
P. N. Lebedev Physics Institute. Translated from Khimiya i Tekhnologiya Topliv i Masel, No. 1,
pp. 46 – 49, January – February, 2007.

This size range corresponds to the limiting degree of dispersion at which a colloidal system still retains
one of its most important properties – heterogeneity. According to the estimations in [12], the minimum size of
phase disperse particles is approximately 1 nm (3-5 molecular diameters).
The goal of our study* was to develop principles for energy-saving, environmentally clean technology
for manufacturing petroleum oils with additives that have assigned performance properties.
The method of correlation spectroscopy was used here for the first time to study intermolecular interactions
of additives in lube oils under the effect of UHF radiation. The possibility of optimizing the manufacturing
processes for production of industrial oils was demonstrated by the new method of UHF-radiation treatment.
Theoretical substantiation of the principles of the mechanism of the reaction of additives and their selection
to ensure the assigned performance properties of commercial petroleum products was proposed previously
in [13].
Correlation spectroscopy was used in [13, 14] to study the intermolecular interaction of additives and
their models and compositions to determine the colloidal stability of commercial oils. A hypothetical mechanism
of the intermolecular interactions of SF in low-polarity media was given in these studies. A correlation was
established between the average effective radius of colloidal formations, heating temperature, and time elapsing
since the oil composition was made up.
The possibility of developing a new, highly sensitive, economical, and effective method of evaluating the
performance properties of petroleum products was demonstrated. A method for objectively substantiating the
stability and performance characteristics of commercial oils based on the size of the CF in the additives and the
purposeful alteration of the size was substantiated.
It was found in [13, 14] that on one hand, CF form and enlarge on prolonged heating of a solution of
additives in a base oil, i.e., during the final stage of fabrication of commercial oils. On the other hand, according
to the data in [15, 16], the absorption spectrum of this solution in the infrared region changes in the same way both
on heating and in treatment of the solution with UHF radiation, i.e., microwave radiation with a frequency
of 2.45 GHz and tunable power of up to 750 W.
It is logical to hypothesize that in exposure of a solution of additives in base oil to UHF radiation, like
heating it, CF will form and enlarge.
I-20A base oil (SAE 10) manufactured by Tektron Ltd. (Moscow oblast) was used as the base for the model
compositions. Fenom from Tribotechnology Co. (Zelenograd), added in concentrations of 3.54 and 5 wt. %, was
used as the additive in the model compositions.
The viscosity of the base was measured with a Höppler viscometer. It was equal to 52.7 mPa⋅sec at 25°C
and 6.91 mPa⋅sec at 80°C. The refractive index was 1.4833 for I-20A oil and 1.4997 for the additive.
The samples were carefully dedusted before the measurements since light scattering on dust is much
stronger than on the CF in the additive.
Immediately after mixing, the same composition was filtered simultaneously into a cuvette with a metal
collar – for measurement of the size of CF on heating in a thermostat – and into a cuvette with a caprolon
collar – for treatment in the UHF-radiation chamber. The cylindrical cuvettes were fixed with these collars in the
center of a cylindrical immersion vessel during the measurements, which facilitated adjustment, eliminated the
problem of flashing, and improved the accuracy of the measurements.
Treatment with UHF radiation was conducted in a 20-liter chamber, and the frequency of the radiation
was 2.45 GHz with emitter power of 600 W. The temperature of the oil varied by no more than 1.5°.
The size of the CF in the additives in the oils was measured by light-scattering correlation
spectroscopy [17]. The width and shape of the central polarized Rayleigh line of light scattered by the solution of
*Conducted with the participation of L. L. Chaikov.
65
the additive in the oil were experimentally determined with this method. The average radius of the CF and if
necessary, the degree of their polydispersion as a function of the time the sample was heated or the exposure to
the UHF radiation was found with the width of this line.
The signal from the PEM (photoelectron multiplier) operating in the one-electron mode passed through an
amplifier-discriminator and entered a digital correlator. In [14], this was a correlator from Malvern Instruments,
Ltd. (England). We used a modern Fotokor correlator from Anteks-97 Ltd. (Moscow). The setup is described in
detail in [18].
For monodisperse suspensions of CF particles, the central polarized Rayleigh line of scattered light had
the shape of a Lorentzian with half-width G at half-height equal to:
G = Dq 2 = kTq 2 / 6πηr (1)
where D is the particle diffusion coefficient; q = q S − ql = (4π sin θ / 2 / λ ) ; q S, q L are the wave vectors of
scattered and laser light; n is the refractive index of the oil; è is the scattering angle; l is the wavelength of the
light; k is the Boltzmann constant; T is the absolute temperature; h is the viscosity of the base; r is the radius of
the CF.
For polydisperse systems containing CF with different radii, the spectrum consists of several superimposed
Lorentzians with a common center at zero frequency (based on the number of particles with different sizes). In this
case, the correlation function obtained is the sum of the same number of exponentials where each one has a
characteristic fall time equal to 1/G 1, 1/G 2, …. The amplitudes of these exponentials are proportional to the
intensity I of light scattering on CF with a radius corresponding to G 1 , G 2, …. We used three methods to process
the correlation function.
The results of earlier measurements, some of which are reported in [14], were processed as follows. A
complex function having the form of the sum of several exponentials was approximated by one exponential and
based on the value of G 1 obtained, the average effective radius of CF, by which we will subsequently mean radius
r measured by the method, was determined.
Due to improved processing of the intensity in plotting the correlation function, the modern Fotokor
correlator can be used to obtain a complex function in undistorted form, and its software can be used to perform
an initial analysis of the function obtained for polydispersion by two methods: the method of moments and the
Tikhonov regularization method.
The regularization method is very complicated and is beyond the scope of the study. We only note that
it makes it possible to plot a histogram of the distribution of the scattering particles by size.
The method of moments consists of the following. The dependence of the logarithm of the correlation
function on time t, which is linear in the case of a monodisperse sample and is curved in the presence of
polydispersion, and is distributed in series by degrees of time:
[ ]
ln G (τ ) / I 2 − 1 = G2τ + C 2τ 2 + C 3τ 3 (2)
where coefficient G2 for the first degree of time gives an average particle radius r determined from Eq. (1), coefficient
C 2 gives information on the width of the particle distribution by size, and coefficient C 3 gives information on the
asymmetry of this distribution.
The function processing program is available in the software for the Fotokor correlator. The particle
radius obtained in this way is basically used in discussing the results of a study. We will call it the average radius
of colloidal formations (ARCF).
66
60
I II
50
2
40
R, nm
30
1
20
10
0.2 0.4 0.6 1 2 4 6 10 20 40 60100
lnτ (τ, minutes)
Fig. 1. Average radius r of CF vs. logarithm of UHF radiation exposure time ln τ for a
composition of I-20A base oil with Fenom additive in the concentration: 1) 3.54 wt. %;
2) 5 wt. %; I) region of an increase in the size of CF; II) region of stability of the size
of CF.
The dependences of the size of CF on the duration of exposure to UHF radiation (Fig. 1) and the sample
heating time (Fig. 2) were obtained with the data from the measurements. As Fig. 1 shows, ARCF is also a function
of the concentration of SF.
We can draw the following conclusions from the data obtained.
• Formation and enlargement of CF in additives in lube oils under the effect of UHF radiation were found
for the first time by correlation spectroscopy.
• Formation and probably further enlargement of associates take place both in holding the solution at
high temperature (see Fig. 2) and in treating the solution with UHF radiation (see Fig. 1).
The results obtained confirm the hypothesis that when a solution of additives in base oil is treated with
UHF radiation, as in heating this solution, the CF in the additives form and enlarge [14, 16], mixing of the additives
in the base oil in exposure to a UHF field is almost independent of the initial and final temperatures of the mixed
components.
• We see from a comparison of the dependences of ARCF on the time of exposure to the UHF radiation for
composites with a different concentration of additives (see Fig. 1) that when the concentration increases, the
exposure time necessary for formation and growth of CF decreases sharply.
For obtaining stable colloidal solutions at a 3.54% concentration of additive, 15 min of exposure to UHF
radiation is required, and for a 5% concentration, 5 min is sufficient. Interruption of the time scale means that the
sample was held for 12 h at room temperature without exposure to UHF radiation..
The exposure time for each composition with a different concentration of additive should be experimentally
evaluated separately. The results obtained show that ARCF is a function of the concentration of additive and
stability of the colloidal solutions is attained with the duration of heating and/or exposure to the UHF radiation
(segment II in Figs. 1 and 2). In addition, exposure to UHF radiation is preferable, since 15 min is required for
obtaining the required CF size in this case, while 20 h is required for heating.
Important fluctuations in the scattering intensity with characteristic times of the order of several and even
tens of minutes were observed during the measurements. This effect could be due to either the rapid formation of
very large (of the order of 200 nm) individual particles which then decomposed into smaller particles, or to
nonuniformity of the rate of formation and enlargement of CF over the cuvette volume. The last hypothesis is in
agreement with the dependence of the duration of UHF radiation on the sample volume obtained in [16].
67
220
80
60
r, nm
40
20
I II
0
4 8.25 14 19 28.538.5
lnτ (τ, h)
Fig. 2. Average radius r of CF vs. logarithm of heating time at 80°C ln τ for composition
of I-20A base oil with 3.54 wt. % Fenom additive. See Fig. 1 for designations.
This effect can be used in low-tonnage production of commercial petroleum products. Commercial lube oil
differs from the initial solution by the presence of stable CF formed [7, 13, 14]. The structure and concentration of
these formations are a function of the concentration and composition of the additives, as well as of the oil
base [8, 14].
We can hypothesize that an external electromagnetic UHF field will alter the state of the solvation shells
of CF and accelerate their coagulation, bringing the commercial product to a stable colloidal state.
Formation (structuring) of disperse phase CF in the dispersion medium takes place in uniform distribution
of the mixed components in the total volume as a result of heating or exposure to UHF radiation, and this allows
obtaining a final product in a stable colloidal state with the necessary properties.
• Strong polydispersion of the solutions containing CF was found in the measurements. In addition to
particles whose size was close to or larger than the ARCF, the histogram analysis of the measured correlation
functions showed (after prolonged accumulation) the presence of 3-15-nm particles characteristic of micelles.
This confirms the hypothesis concerning the possible mechanism of formation and enlargement of CF, initially
related to formation and then aggregation of micelles of the additive [1].
The impossibility of reliably determining the amount of additive concentrated in the CF also indicates the
inhomogeneity of the process. This question is important from the point of view of both manufacture and ensuring
the colloidal stability of the oils.
The selected improved method of determining ARCF in colloidal solutions with the data from scattered-
light correlation spectroscopy demonstrates the possibility of using additives and their compositions in commercial
oils. It also allows assessing the effect of the reaction of the additives on the size of their CF (in the 0.01-100 mm
range) and the performance properties of commercial products.
This can be used in developing scientific principles for selecting additive compositions for commercial
oils to increase their colloidal stability based on optimization of process and formula factors in regulation of
intermolecular interactions of SF in low-polarity media.
This method can be used in technology for production and use of petroleum products: fuels, lubricants,
and industrial fluids. It can also be used in ecology for analysis of disperse pollutants and quality control of
manufactured commercial products.
68
REFERENCES
1. G. I. Fuks, Colloid Chemistry of Crude Oil and Petroleum Products [in Russian], Znanie, Moscow (1984).
2. I. G. Fuks, G. I. Fuks, and G. V. Rakaeva, in: Tribomechanics – Machine Building [in Russian],
Mashinostroenie, Moscow (1983), p. 26.
3. G. I. Fuks, G. V. Rakaeva, V. P. Tikhonov, et al., Koll. Zh., 45, No. 3, 515-519 (1983).
4. G. V. Rakaeva, E. K. Kozlova, S. B. Shibryaev, et al., in: Increasing the Reliability of Lubricated Friction
Units in Aviation Engineering Based on Improving the Technology for Using and Unifying Lubricating
Materials [in Russian], TsNIITEneftekhim, Moscow (1983), pp. 35-36.
5. A. A. Chesnokov, O. N. Nikol’skaya, I. G. Fuks, et al., in: Industrial Purity of Working Fluids in Hydraulic
Systems and Filtration [in Russian], NATI, Chelyabinsk (1983), pp. 71-72.
6. G. V. Rakaeva, G. I. Fuks, I. G. Fuks, et al., Khim. Tekhnol. Topl. Masel, No. 7, 35-37 (1984).
7. USSR Inventor’s Certificate No. 1453887.
8. G. N. Bakakin, G. V. Rakaeva, S. V. Kharitonov, et al., Khim. Tekhnol. Topl. Masel, No. 5, 15-16 (1991).
9. P. A. Rebinder and G. I. Fuks, Advances in Colloid Chemistry [in Russian], Nauka, Moscow (1973), pp. 5-
8.
10. D. H. Everett, Basic Principles of Colloid Science, Royal Society of Chemistry, London (1988).
11. J. Israelashvili, Intermolecular and Surface Forces, Academic Press, London (1994).
12. P. A. Rebinder, Selected Works. Surface Phenomena in Disperse Systems. Colloid Chemistry [in Russian],
Nauka, Moscow (1979).
13. G. V. Rakaeva, Candidate Dissertation, I. M. Gubkin Moscow Institute of Petrochemistry and Gas Processing,
Moscow (1984).
14. A. M. Kapustin, S. V. Krivokhizha, G. V. Rakaeva, et al., Khim. Tekhnol. Topliv Masel, No. 1, 26-28 (1995).
15. RF Patent No. 2158175.
16. A. A. Rukhadze, U. Yusupaliev, Yu. M. Egorov, et al., Kratk. Soobshch. Fiz. FIAN, No. 8, 23-26 (2001).
17. E. Jackman, in: Photon Correlation and Light Beating Spectroscopy, H. Z. Cummins and E. R. Pike (eds.),
Plenum, New York and London (1974).
18. L. L. Chaikov, Trudy Fiz. Inst. Akad. Nauk SSSR, 207, 84-152 (1991).
69
ECOLOGY
KINETICS OF CORROSION OF STEEL St3 IN WATER UNSATURATED

WITH CALCIUM CARBONATE. EFFECT OF EQUILIBRIUM
SOLUBILITY OF IRON HYDROXIDE
V. F. Sorochenko UDC 543.3.32:620.193.3
The possibility of decreasing the rate of deep penetration of corrosion in St3 steel in Dnepr water
unsaturated with calcium carbonate with pH 6.63 was theoretically substantiated and experimentally
confirmed.
As indicated in [1, 2], in natural and circulating water with pH 8.2-8.4, carbonic acid is in the form of HCO-3
ions. Water is considered aggressive or corrosive if its pH, measured with a pH-meter, is equal to the calculated
value of pH s of water saturated with calcium carbonate, or less than this value [3-5]:
pH ≤ pH S (1)
In such water, the concentration of carbon dioxide is higher than or equal to its equilibrium concentration
with calcium carbonate at pH s.
The tendency of natural water toward a deposit-free process when used in continuous systems or reuse
without intermediate cooling is determined by the difference between pH and pH s , called the stability index I:
I = pH − pH s (2)
____________________________________________________________________________________________________
National Technical University of Ukraine. Kiev Polytechnic Institute. Translated from Khimiya i

According to [1], this index can only serve as a qualitative index of the properties of water, which are a
function of the presence of carbonic acid. The reliability of determination of these properties by the given method
decreases if the circulating water contains alkaline substances.
According to other concepts [6, 7] concerning the corrosiveness of water, the corrosion resistance of iron
in it almost does not change at pH 4-9. In comparing these views, we can draw a conclusion concerning the
“indeterminacy” of the value of the pH in inequality (1). From our point of view, the value of the pH in this
inequality can be found by considering the thermodynamic features of formation of solid compounds of iron with
oxygen.
According to the potential–pH diagram of the iron–water system at 25°C [8], the thermodynamic conditions
of formation of a protective layer of iron hydroxide on the surface of iron are found from the solubility product of
the latter:
SPFe (OH )2 = aOH

2
−a
Fe 2 +
= 1.8 ⋅10 −15 mole 3 / dm 9 (3)
sat
where aOH − , a Fe sat -

2 + are the equilibrium activity of OH and Fe
2+
ions, mole/dm 3.
Since
(
a Fe 2 + = SPFe (OH )2 / K H2 2O a H2 +
sat
)
(where K H 2O is the dissociation constant of water at 25°C, equal to 1⋅10 -14 mole 2 /dm6 ; a H + is the equilibrium
activity of H + ions, mole/dm 3), we find from Eq. (3) at a Fe (OH )2 sat = a Fe sat 3
2 + = 1 mole/dm :
lg a H + = pH 6.63
Substituting this pH in inequality (1), we obtain:
6.63 ≤ pH ≤ pH S
For I £ 0, we find from Eq. (2) and Fig. 1 the boundaries of the high thermodynamic stability of Fe(OH) 2:
6.63 ≤ pH ≤ 8.4 (4)
According to our hypothesis, inequality (4) can be extended to the class of hydrocarbonate feed water
(the object investigated) of water cycles (WC) in the presence of free carbonic acid in return water.
At pH 7, from Eq. (3) a Fe 2+ =1.8 ⋅ 10 -1 mole/dm 3. As a consequence, the relation r of Fe 2+ ion activities
at pH 6.63 and pH 7 (for example) is equal to:
r = a Fe 2+ / a Fe 2 + = 1 / 0.18 = 5.5 (5)

sat ( pH6.63 ) sat ( pH7 )
71
100 0.25
1
80 0.2
4
CP, mm/year
60 0.15
N, %
40 0.1
20 0.05
2 3
.
0 0
4 5 6 6.63 7 8 8.4 9
pH
Fig. 1. Molar concentrations N for CO2 (1), HCO3 - (2), CO 32- (3), and rate CP of deep
penetration of corrosion in steel St3 (4) as a function of the pH of the water.
Iron(II)-hydroxide equilibrium at a Fe (OH )2 sat = a Fe 2+ = 1 mole/dm 3 corresponds

sat
to pH 6.63; the boundary of the equilibrium existence of carbon dioxide in the water
corresponds to pH 8.4.
Such a thermodynamically substantiated sharp decrease in the equilibrium activity of iron(II) hydroxide
ca determine the novelty of the view on the zero-waste environmental increase in the chemical resistance of
carbon steel to corrosive processes (object of investigation) in natural water of the hydrocarbonate type in the pH
range of 6.63-8.4.
The goal of this study was to reveal the high corrosion resistance of carbon steel in water unsaturated
with calcium carbonate in the region of the thermodynamic existence of the solid phase of iron hydroxide
at pH ≥ 6.63 .
The corrosion studies were conducted in Dnepr water with pH 8.05 from Kremenchusk Reservoir, which
had the following composition (mg/dm 3): 36.4 Ca 2+; 5.8 Mg2+; 75.2 HCO 3-; 5 Na + + K +; 8.6 SO 42-; 3.1 Cl -.
The quality of the water was evaluated with the methods in [9]. The rate of deep penetration of corrosion
in samples of steel St3 in aerated unmixed medium at 55±2°C for 20 days (GOST 9.502–82) was determined by mass
spectrometry. The hydrogen index was measured with a pH-meter. The given pH values were ensured by
adding 0.1 N cp hydrochloric acid to the river water.
The effect of the pH of Dnepr water on the rate CP of deep penetration of corrosion in samples of
steel St3 is shown in Fig. 2. The maximum values of CP were observed on the first-second and tenth days of the
corrosion tests, and the minimum values were observed on the fifth-seventh and twentieth days.
When the pH of the river water decreased from 7 to 6.5, 5.5, and 4.5, CP increased
from 0.089 to 0.220, 0.186 and 0.197 mm/year, i.e., by 2-2.5 times [7]. This confirms the validity of
inequality (4) (see Fig. 1) and the theoretical relation r = 5.5 (5). The same tendency toward a decrease
in CP (by 2 and 1.74 times) in going from pH 6.5 to 7 in the presence of 1 mg/dm 3 of natural LST complexone was
demonstrated in [10].
Based on the traditional concepts in [8] concerning the solubility of iron hydroxide from the
potential–pH diagrams of the iron–water system at 25°C, the well-known concepts in [6, 7] concerning the
stabilization of the corrosion resistance of iron in return water at pH 4-9 and simultaneously the concepts concerning
72
0.35
0.30
4.5
0.25
CP, mm/year
0.20
5.5
6.5
0.15
7.0
8.2
0.10
0 5 10 15 20
τ, days
Fig. 2. Rate CP of deep penetration of corrosion in steel St3 in Dnepr water with different
pH (see figures on curves) as a function of duration t of test.
the high corrosiveness of return water unsaturated with calcium carbonate at pH ≤ pH S (8.2 − 8.4) were thus
refined [1-5].
The physicochemical principles of the effect of the equilibrium solubility of iron hydroxide on slowing
corrosion of steel St3 in water from the Dnepr River unsaturated with CaCO 3 were elaborated and their extension
to WC used at return water pH within the following limits was recommended:
6.63 ≤ pH ≤ pH S (8.2 − 8.4)
Use of WC at return water pH of ≤ 6.63 is undesirable due to the increase in the rate of deep penetration of
corrosion in St3 steel by 2-2.5 times.
REFERENCES
1. A. F. Shabalin, Return Water Supply of Industrial Enterprises [in Russian], Stroiizdat, Moscow (1972).
2. A. P. Shut’ko, V. F. Sorochenko, Ya. B. Kozlikovskii, et al., Treatment of Water with Basic Aluminum
Chlorides [in Russian], Tekhnika, Kiev (1984).
3. I. L. Rozenfel’d, Corrosion Inhibitors [in Russian], Khimiya, Moscow (1977).
4. A. P. Askol’zin and A. P. Zhukov, Oxygen Corrosion of Equipment in Chemical Plants [in Russian],
5. SNiP 2.04.02–84, Water Supply. External Mains and Equipment [in Russian], Stroiizdat, Moscow
(1985).
6. L. P. Lyublinskii, What Do We Have to Know about Corrosion? [in Russian], Lenizdat, Leningrad
(1980).
7. M. A. Sukhotin, A. V. Shreider, and Yu. I. Archakov (eds.), Corrosion and Protection of Chemical
Equipment [in Russian], Vol. 9, Khimiya, Leningrad (1974).
73
8. Helmut Kaesche, Korrosion der Metalle—Physikalisch-chemische Prinzipien und aktuelle Probleme,
Springer-Verlag, Berlin-Heidelberg-New York (1966).
9. Methodological Handbook on Analysis of Wastewaters in Oil Refineries and Petrochemical Plants
[in Russian], MNKhP SSSR, Moscow (1977).
10. V. F. Sorochenko, Khim. Tekhnol. Topl. Masel, No. 1, 14-16 (1995).
74
REVIEWS
PHYSICOCHEMICAL ASPECTS OF MANUFACTURE OF THREE-PHASE

COLLOIDAL FUELS
S. L. Khil’ko and E. V. Titov UDC 622.75.552.57
The basic physicochemical characteristics of fabrication of three-phase colloidal fuels were analyzed.
The effect of the nature and content of solid and liquid phases, type of chemical additives (plasticizers,
emulsifiers, and stabilizers), and the basic methods of obtaining three-phase systems from bituminous
coals and brown coals were examined.
The search for an alternative to traditional liquid fuels is one of the most pressing problems in energetics.
In countries experiencing a shortage of fuel and energy resources, the problem of the rational use of energy
carriers has become especially acute.
Beginning in the 1970s, great attention has been focused on creation of new technologies for man-made
liquid fuels based on colloidal systems – suspensions and emulsions – in all developed countries. In 1975, The
European Economic Community created a program based on production of synthetic liquid fuels for development
of research and industrial studies, proposing replacement of more than 30% of petroleum fuels by man-made
fuels [1].
Three-phase colloidal fuels based on finely ground coal, petroleum hydrocarbons, water, and chemical
additives can be one alternative type of liquid energy carrier for heat and power plants. The basic physicochemical
properties of such fuels are determined by: the nature and concentration of the solid phase; the nature and
content of the liquid phase; the type of chemical additives (plasticizers, emulsifiers, and stabilizers); the method
of obtaining the three-phase systems.
Preparation of colloidal fuels involves solving a wide range of problems in physical chemistry and
physicochemical mechanics of disperse systems. As indicated in [2, 3], disperse systems of the solid–liquid type
____________________________________________________________________________________________________
I. M. Litvinenko Institute of Physical Organic Chemistry and Carbon Chemistry. National Academy of
Sciences of Ukraine. Translated from Khimiya i Tekhnologiya Topliv i Masel, No. 1, pp. 52 – 56,
January – February, 2007.

are three-dimensional structures of particles of the solid (disperse) phase. Such structures are characterized by
certain mechanical properties, and the most important ones are viscosity, plasticity, elasticity, and strength.
These properties are due to reaction of particles of the disperse phase with the liquid dispersion medium and with
each other.
In contrast to molecular systems, the concept of stability, meaning the constancy of the properties of
these systems in time, exists for disperse systems. According to Deryagin, the three kinds of stability of disperse
systems differ [4]:
• phase – resistance to separation, where a new system with a different concentration of particles capable
of coexisting with the initial concentration arises;
• aggregate – stability caused by the fact that the forces of interaction between disperse particles are
much greater than the intermolecular interactions and are differently dependent on the radius of their effect; in the
interaction of disperse particles, aggregates of two, three, and more particles can form (coagulation);
• resistance to a change in dispersion, i.e., invariability of the particle distribution by size.
Spontaneous adhesion of particles and formation of three-dimensional structures (structure
formation) from them through very thin layers of liquid phase is the manifestation of a combination of forces of
attraction and repulsion of the particles. Structure formation is primarily determined by the nature of the surface,
shape, and size distribution of particles of the solid phase, (granulometric composition), and the nature of the
liquid phase, type of chemical additives, etc.
The colloidal fuels obtained in the form of disperse systems should satisfy the following
requirements [5]:
• have a high heat value – the concentration of combustible components in them should be 65-75%;
• h a v e a l o w v i s c o s i t y l e v e l ; t h e e f f e c t i v e v i s c o s i t y η ef a t a s h e a r r a t e o f ε ≈ 1 0 s e c - 1 are
the most important rheological characteristics – the pumps for pumping fuel in fuel preparation systems and the
initial shear stress or dynamic yield point s 0 are usually calculated for this shear rate, and its value
determines the yield point of the structural network; these parameters should be within the following
limits: ηef = 1-2.5 Pa⋅sec, σ0 = 5-15 Pa;
• be sedimentation- and aggregate-stable.
Let us consider the basic factors that affect the physicochemical properties of three-phase colloidal fuels.
Nature of the solid phase. Solid fuel of different types, primarily energy-producing bituminous coals, is
used as the disperse phase in colloidal fuels. Brown coals and peat can also be used. Use of solid residues from
processing coal and crude oil, coke, coal tar, shale and coke tars is also known [6].
The surface properties of dispersions of bituminous coals are primarily determined by the degree of
metamorphism of the latter. Bituminous coals of different degrees of metamorphism are characterized by a
mosaic surface with a defined hydrophilic-hydrophobic balance, i.e., ratio of hydrophilic groups, for
example, COOH, CO, OH, NH 2, etc., and hydrophobic fragments [7].
Highly metamorphized coals (grades T, A, TA bituminous coals) are characterized by a low oxygen content
in the surface layer. For this reason, on the whole they have a hydrophobic surface, are poorly wet by water, do
not form a developed hydrated layer around particles, and the colloidal fuels containing them as the solid phase
do not have a pronounced capacity for formation of structural skeletons in the system, i.e., they have some
aggregate stability. However, systems with such a solid phase have weak sedimentation stability [8].
The coal particles in low stages of metamorphism (subbituminous coals, grades D, G, DG) are characterized
by high surface hydrophilicity‘. For this reason, they have a pronounced ability to form developed hydrate layers
around themselves and thus strong structural skeletons in colloidal fuel systems. Such systems are characterized
by pronounced sedimentation stability [8, 9].
76
The manifest hydrophilicity of the surface of brown coal and peat particles is due to the high content of
oxygen-containing functional groups. In addition, high porosity and the presence of water are characteristic of
the surface of these particles, and this creates difficulties in using brown coals and peat as fuel.
Nature of the liquid phase. The maximum concentration of combustible components in colloidal fuels can
b e a t t a i n e d b y i n c o r p o r a t i n g a t h i r d p h a s e b a s e d o n l i q u i d c o m b u s t i b l e h y d r o c a r b o n s . Wa t e r a n d
hydrocarbons are usually the liquid phase. Light and middle distillate crude oil cuts can be used as the
hydrocarbons [10, 11]. However, heavy crude cuts – different grades of atmospheric resids [6, 12, 13] or crude
oil [6, 14] – are most frequently used.
Three versions of the simultaneous existence of a water and oil phase in the system are possible. First, in
the form of an emulsion. As a function of the nature of the oil phase, the oil–water phase ratio, the type of
chemical additives, and the consumer properties of the fuel, both oil-in-water (drops of oil uniformly distributed in
water – O/W) and water-in-oil (drops of water in oil – W/O) emulsions can be obtained.
The other two versions of coexistence of the oil phase and water can be obtained by mixing one kind of
liquid with a solid phase and formation of a dispersion medium by addition of a second liquid.
Nature of chemical additives. Chemical additives in three-phase colloidal fuel systems perform different
functions. To obtain systems with sedimentation and aggregate stability and a low viscosity level, they must
have pronounced plasticizing, stabilizing, and emulsifying properties.
Surfactants (SF) of different types: ionogenic [15], nonionogenic [16], and polymers [17] and inorganic
substances [18] can be used to stabilize water-containing coal-oil systems.
Using mixtures of different additives, each with its own function, is the most acceptable version for giving
three-phase colloidal fuel systems the required properties. Different combinations of chemical additives that give
such systems the necessary properties are described in the literature [19]. Ionogenic SF, usually sulfonates, play
the role of plasticizing (dispersing, diluting) additives. Nonionogenic SF (polyalkylene oxides, for example) and
polymers (polysaccharides, dextrins, gelatin, casein, etc.) fulfill the functions of stabilizers and emulsifiers.
Combinations of high- and low-molecular-weight SF are most frequently used in chemical additives.
High-molecular-weight SF and polymers can ensure elevated stability for disperse systems by
creating a mechanically strong adsorption layer (“colloidal shield”) on the surface of particles [2, 3].
Low-molecular-weight SF can significantly decrease the surface tension between phases and exhibit plasticizing
(diluting) properties in disperse systems.
U)sing SF with a wide molecular-weight distribution as additives that improve the structural and
mechanical properties is a promising direction in solving the problem of fabricating colloidal fuels.
High- and low-molecular-weight fractions of SF of the same kind can fulfill different functions in disperse systems.
Such substances include some natural SF and products of their modification, for example, lignosulfonates and
humates.
Industrial lignosulfonates are products of complex transformations for which the initial raw material is
wood lignin. They are obtained by dissolving the noncellulose components of wood in production of paper with
sulfite technology. Industrial lignosulfonates as products based on natural raw material are distinguished by
wide polydispersity, and their molecular weight varies from several hundred to several tens of thousands of
units [20]. For this reason, they can perform different functions in disperse systems. The high-molecular-weight
fractions of these compounds in coal-based disperse systems exhibit pronounced stabilizing properties, while the
low-molecular-weight fractions are effective diluents [21, 22].
Humic acids obtained from brown coals and peat are another type of multifunctional SF. These
compounds are also distinguished by wide molecular-weight distribution, which can vary
from 4000-8000 to 30,000-40,000 units [23]. Humate additive fractions of different molecular weight can be used in
disperse systems for fulfilling different functions. The high-molecular-weight fractions of these compounds can
77
exhibit stabilizing and emulsifying properties, while the low-molecular weight fractions can act as effective
plasticizers and dispersants.
We have accumulated extensive data on use of native (natural) and modified (sulfonated) humic acid salts
as plasticizers for fuel suspensions [24-28], emulsifiers, and stabilizers of fuel emulsions [29, 30], etc.
Due to the above, it is evident that use of additives of one kind with a broad spectrum of action is
promising in production of three-phase colloidal fuel systems both from process and from economic points of
view.
Method of fabricating three-phase fuel systems. The physicochemical properties of three-phase colloidal
fuels are a function of the method of fabrication (i.e., method of combining three phases) to a significant degree.
Different methods are described in the literature. The type of solid fuel is the determining factor for selecting the
method, since the surface properties of bituminous and brown coals differ significantly.
Bituminous coals. An oil phase based on petroleum refining products is added to bituminous coal
suspension fuels to increase the heat value. Adding it to a water–coal suspension (WCS) is most acceptable from
a process point of view [31-34].
Water–oil–coal suspensions (WOCS) are obtained in two stages. WCS with plasticizers, emulsifiers, and
stabilizers are prepared in the first stage, usually by “wet grinding.” The coal is ground into particles of the
required size in aqueous medium together with the chemical additives. With this grinding method, power
consumption is much less than in “dry” grinding (Rebinder effect [3]). The concentration of coal in the suspension
must be lower than the maximum possible concentration, which allows regulating its rheological parameters on
addition of the oil phase. In the second stage, a petroleum component, atmospheric resid, for example, is added to
the WCS and stirred intensively until a homogeneous suspension is obtained.
Let us consider some drawbacks of this method of obtaining WOCS. Addition of the petroleum component
to WCS implies obtaining an emulsion containing some portion of the water from the WCS. Chemical additives
previously incorporated in the WCS should regulate the properties of the emulsion. It is impossible to obtain an
emulsion of the desired composition with the assigned optimum properties without changing the granulometric
composition of the solid phase and properties of the WCS. This is due to the comparability of the energy
expended for obtaining the emulsion with the energy required for dispersing the solid phase.
Repeated dispersion of the entire system for obtaining the emulsion together with coal previously ground
to particles of the required size can lead to overgrinding of the coal and perturbation of the granulometric composition
of the solid phase. In addition, the chemical additives previously incorporated in the WCS adsorbed on the
surface of the solid phase cannot have the required regulating effect on the properties of the emulsion obtained.
As a result, the physicochemical properties of the final product (colloidal fuel based on WOCS) can be
inconstant or can vary in time. WOCS without the required stability, i.e., not suitable for storage, can be considered
as an alternative fuel if they are used immediately after preparation.
Another method of preparing WOCS consists of fabricating an emulsion of the petroleum product, water,
and chemical additive followed by incorporation of finely ground coal powder in it [16, 17]. In this case, WOCS are
also prepared in two stages.
The emulsion is prepared in the first stage. The optimum physicochemical properties, primarily the particle
size and stability, are ensured by selecting an appropriate disperser and the type and concentration of the chemical
additives (emulsifiers and stabilizers).
Finely ground coal powder together with plasticizers are added to the emulsion and mixed until a
homogeneous system is obtained in the second stage. In mixing, the size of the particles in the emulsion will not
change, since the energy of preparing the emulsion will be much greater than the energy of mixing for blending the
mixtures [2, 3].
78
With this method, it is possible to obtain sufficiently stable WOCS with constant physicochemical
properties. The colloidal fuel based on such systems can be used in boiler units both immediately after preparation
and after storage for some time.
We developed this method of fabricating three-phase colloidal systems and investigated their rheological
properties. Subbituminous coal from the Donbas with particles with an average size of less than 20 mm was used
as the solid phase. The liquid phase was an O/W emulsion of diesel fuel in water with stabilizer additives (sodium
sulfohumate) made in an UZDN-A ultrasound disintegrator with treatment with ultrasound with a frequency
of 22 kHz for 3 min [30, 35].
These three-component systems remain fluid only at a rigorously determined content c o of oil phase in
the emulsion and a given concentration c so of solid phase. Addition of oil phase above the acceptable limit will
cause it to aggregate and sharply increase the rheological parameters. As follows from Table 1, when the ratios
between solid and oil phases are respected, stable suspensions with industrially acceptable values of the effective
viscosity h ef and dynamic yield point σ 0 .
It was shown in [30, 35] that production of WOCS from bituminous coals and emulsion liquid phase with
optimum physicochemical properties is only possible as a result of compromising on the combination of
concentrations of all components of the system. Such a combination can be attained by studying the rheological
properties of these systems.
The third method of preparation of WOCS consists of combined dispersion of all three phases – coal,
petroleum product, and water, with addition of chemical additives [17, 36]. This method is technically the simplest.
However, it is impossible to obtain a dispersion with the required solid-phase and emulsion particle size and with
the optimum physicochemical properties with this method: the probability of the appearance of different
uncontrollable processes, which can cause irreversible coagulation and aggregation, for example, is high, and
this negatively affects the properties of the final product.
Brown coals and peat. The use of these kinds of raw material involves certain difficulties, primarily
caused by their high natural moisture content, which attains 40-60%. Moisture is stably retained in the structure
of the coal due to its developed surface and the high content of oxygen-containing groups in its structure that
form hydrogen bonds with molecules of water. In addition, brown coals tend to spontaneously ignite, which
makes them difficult to store and ship.
However, the comparatively low cost (approximately $10 per ton) and large natural reserves of brown coal
make the problem of rationally using this kind of hydrocarbon feedstock as fuel very pressing.
One possible way of utilizing brown coals in energetics in which these drawbacks are eliminated to a
significant degree can be to make a liquid energy carrier from them – WOCS. Several methods of fabricating a
suspension fuel based on brown coals and peat are described in the literature.
One of them consists of grinding brown coal (or peat) with a high natural moisture content with addition
of a small amount of water to obtain WCS followed by addition of the petroleum product and homogenization of
the entire mixture [37-39]. This method differs little from the method of obtaining WOCS from bituminous coals
examined above.
Table 1
ηef at ε = 9 sec-1,
cso, wt. % co, vol. % σ0, Pa Stability, days
Pa⋅sec
50 30 0.84 7.98 >30
55 20 1.02 10.96 >30
60 10 1.32 15.56 >30
79
Table 2
cso, wt. % ηef at ε = 9 sec-1, Pa⋅sec σ0, Pa r
43.5 0.24 1.87 0.991
46 0.43 3.51 0.997
48 0.86 5.14 0.998
49 1.42 10.91 0.997
50 2.19 15.79 0.996
According to another method, brown coal or peat is first dried and then a suspension fuel is made from it.
Different methods are used to reduce the natural moisture content of brown coals. One of several methods widely
used in heat and power engineering is to dry the coal at a low temperature (100-160°C) in an atmosphere of waste
stack gases with simultaneous grinding to obtain a dispersion for powder combustion. The residual moisture
content of the product obtained is 10-20% (“cake”) [40, 41].
There are technologies for more exhaustive treatment of brown coal, for example, Hot Water
Drying (HWD) [42] and its analogs [43-46]. Exhaustive drying is conducted in closed vessels in conditions of
high temperatures (240-400°C) and pressures of the liberated gases. In addition to elimination of water, carboxyl
groups decompose with liberation of carbon dioxide from the structure of the coal and resinous substances and
oils. These components are strongly retained on the surface of the coal in micropores and make it hydrophobic.
After such treatment, brown coal becomes similar to bituminous coals in the character of the surface and heat
value and suitable for manufacturing suspension fuel.
The essence of our method of obtaining WOCS from brown coal [28, 47, 48] consists of increasing the
degree of surface hydrophoby by blocking some of the oxygen-containing surface groups in application of liquid
hydrocarbons (diesel fuel, GOST 1667–68) to the surface of the solid hydrocarbons and subsequent addition of an
aqueous solution of a chemical additive – sodium sulfohumate. The mixture is mixed with a mechanical stirrer in
the intensively turbulent mode (rotation rate of 1500 min -1). Brown coal (“cake”) from the Aleksandriisk
deposit (Ukraine) prepared for powder combustion at Aleksandriisk TEPP-3 was used for fabricating the suspensions.
Addition of petroleum hydrocarbons to the fuel composition increases its heat value. This method also
allows increasing the degree of hydrophoby of brown coal powder as a result of addition of oil phase and attaining
the surface hydrophilic-hydrophobic balance required for formation of coagulation structures in the suspensions.
Optimizing their composition, i.e., searching for the ratios of components at which the physicochemical
ratios of components best satisfy the process requirements, is an important stage in preparation of industrial
suspensions. Production of WOCS includes determination of the region of optimum concentrations of the chemical
additive, oil, and solid phases. In addition, a search is conducted for the granulometric composition of the
disperse phase at which the best rheological parameters of the suspensions are attained.
The regions of optimum concentrations of each component were determined as a result of studying the
rheological properties of WOCS in subsequent variation of the concentration of each of the three
components [28].
The rheological characteristics of brown-coal WOCS as a function of the concentration c so of solid phase
at the optimum concentrations of the suspension found (9% oil phase, 0.275% sodium sulfohumate) and the
optimum granulometric composition of the solid phase: maximum average particle size of 80 mm, are reported
in Table 2.
The effectiveness of the plasticizing effect of chemical additives in suspension fuels was evaluated based
on the ability of the SF to ensure viscoplastic flow of the suspension [26]. The values of correlation coefficient
80
r in the equation of viscoplastic flow: σ = σ 0 + η efε, are reported in Table 2. The high values indicate the
correspondence of the chemical additive used – sodium sulfohumate – to the effectiveness criterion.
There are published examples of preparation of suspensions from soft brown coals previously treated by
HWD or similar technologies that attain an approximately 60% concentration of combustible components in the
system. The suspensions contain SF that improve their stability and fluidity [42-46].
Using the proposed method of obtaining a suspension and sodium sulfohumate as chemical additive,
concentrations of solid phase (in terms of dry combustible mass) equal to 50 wt. % and rheological parameters that
satisfy the requirements of the technology can be attained: η ef = 2.19 Pa⋅sec; σ = 15.8 Pa; sedimentation stability
for more than 30 days; resistance to formation of aggregates. The total combustible hydrocarbon content – coal
and oil phase – reaches 59%.
One possible method of preparing three-phase colloidal fuels from brown coals can thus be to modify
their hydrophilic and highly porous surface by incorporating an oil phase with addition of sodium
sulfohumate (SF) as a regulator of the rheological properties of the suspension. A fuel system can be obtained
with industrially acceptable physicochemical parameters and a concentration of combustible components of the
same order as in using HWD and analogous technologies, but with much lower power consumption for exhaustive
drying of wet brown coals.
In conclusion, we note that the problem of preparing colloidal types of fuel is solved individually and
often empirically in each concrete case. The properties of such fuels can be predicted and regulated only by
knowing the mechanisms of physicochemical processes in heterogeneous systems.
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82

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

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