ing work, as well as in exported machinery and aggregates with hydraulic drives. The production and widespread use of the VMGZ hydraulic oil will have a positive effect on the national economy. LITERATURE CITED i~
2. 3. 4.
o
6. 7.
USSR Inventor's Certificate, No. 325,867. M. A. Drozdova, G. L. Gul'din, and V. S. Edigarova, Khim. Tekhnol. Topl. Masel, No. 9, 7-9 (1982). N. I. Alekhina, S. Z. Levinson, N. I. Kuritsina, et al., Khim. Tekhnol. Topl. Masel, No. 2, 20-23 (1984). B~ B. Krol', E. A. Ostroumova, and L. G. Zherdeva, in: Composition and Properties of High-Molecular Petroleum Fractions, R. S. Sergienko (ed.) [in Russian], Izd. Akad. Nauk SSSR, Moscow (1958), pp. 81-89. A. A. Polyakova, Molecular Mass-Spectrometric Analysis of Organic Compounds [in Russian], Khimiya, Moscow (1983). N. I. Alekhina, S. Z. Levinson, N. I. Kuritsina, et al., Khim. Tekhnol. Topl. Masel, No. 8, 29-31 (1984). V. A. Vasil'chenko, Hydraulic Equipment of Mobile Machinery [in Russian], Mashinostroenie, Moscow (1983).
PRODUCTION OF WHITE OIL FROM BAKU PETROLEUM F. I. Samedova, A. M. Kasumova, V. M. Alieva, and S. Yu. Rashidova
UDC 665.761.6
With increasingly strict requirements with respect to protecting the environment it has become impossible to produce white oils by the multistage oleum refining of oil fractions. The use of neutral oil (a difficult-to-utilize residue from the production of sulfonate additives) as the raw material for producing white oil made it possible to reduce the consumption of oleum for refining the initial raw material and to reduce the quantity of residues [I]. As a result of the growth in the demand for white oils, the limited nature of the raw material resources, and the need for improving the technology for producing these oils, investigations have been carried out in the Institute of Petrochemical Processes [INKhP], Academy of Sciences of the Azerbaidzhan SSR, directed to the development of high-efficiency technology for producing white oils from Baku petroleum, which had not been used earlier for this purpose [2, 3]. The possibility has been established of producing white oil from the vacuum distillate of Balakhansk heavy oil by a combination of the processes of selective purification with oleumusing technology existing in the Yaroslavsk oil refinery [2]. It was shown that the preliminary treatment of the distillate with a selective solvent (400%) m a d e i t possible to reduce the consumption of oleum by 25% and to considerably reduce the quantities of reagents needed and of difficult-to-utilize residues produced. The purpose of the present work is to investigate the possibility of producing medicinal liquid paraffin oil from the raffinate of this distillate by using a hydrogenation process. White oils were produced from the raffinate from the intensified purification (using 400% furfurol) under conditions described in [2] according to three schemes: hydrogenation in two stages + oleum after-treatment; hydrogenation in three stages + oleum after-treatment; or hydrocraeking + hydrogenation in two stages + oleum after-treatment. According to the first scheme, the hydrogenation of the raffinate was carried out in succession on the industrial catalysts AKM (stage I) and GR-3 (stage II) at temperatures of 340 and 350~ respecYu. G. Mamedaliev Institute of Petrochemical Processes [INKhP], Academy of Sciences of the Azerbaidzhan SSR. Translated from Khimiya i Tekhnologiya Topliv i Masel, No. 2, pp. 11-13, February, 1990; 72
0009-3092/90/0102-0072512.50 9 1990 Plenum Publishing Corporation
TABLE i Hydrogenate of stage
Vacuum Raffindistil- ate late
Parameter
Hydrogenation product in stage
]Hydrocracking IProduct hydro- fraction genate I> 350~
!
II
III
894 36,5 1,4878
891,8 32.98 1,4870
890,5 32,07 t,4844
886,4 20,42 1,4840 123
1
Density at 20~ kg/m3 Viscosity at 50~ Refractive index n~ 0
924,2
I II III IV
resins
889,3 29,57 t,4836
883,7 29,34 t,4815
1,5100 186 --31
185
185
184
I84
192
186
185
--30
--29
--29
--29
--
--24
--24
--25
>8
7
2
1,5
1
2
2,5
1,5
1
98
98
98
98
87
98
98*
--
89,31
90,4
94,43
40
Flash point, ~ pour point, ~ Color, TsNT units Yield, % based on raw material to process, Hydrocarbon group composition naphthenic-paraffinic aromatic groups
895,1 31.47 1,4858
895,8 36,82 1,4890
--
61
53,2
81,34
85,61
88,3
92,17
21,15 11,87 3,7 7,82 2,26
13,22 4,18 --1.26
12,04 2.05
8,6 2,4
7,43
--
--
8,93 1,46
8,41 0,96
5,19
--
0,3
0.7
0,4
--
0.3
0,23
0.38
*In distillate 49.9% (mass). TABLE 2 Medicinal liquid paraffin oil produced by scheme commer-from West I foreign I two 1 three Icial ISiberian one [i] ~ r o l e u m 1 [4]
Parameter
Requirements of GOST 3164-78 (for high-quality grades )
Density at 20~ kg/ms VSscosity at 50~ mmi/s
884,2 31,99
884,5 31,92
882,6 28,76
882.8 30.4
Flash point, ~ pour point, ~ Color, KNS-I units Ash content, % Content, % of sulfur compounds ~. reducing material low-boiling fractions up to 360~ Sample in the presence of organic impurities 20 Refractive index nD Yield, % with respect to raw material to process with respect to distillate Content (%)of ,aromatic hydrocarbons: from uv adsorption spectra at r_ne wavelengths (nm):
185 --29
182 --31
185 --25
192
195
--I0
--I0
4 0,003
0,002
-Not above --8 -- Not more than6 -- Not more than0,0()5
0,03
0,04
--
275 295 300
Colorless* Absent Absent
Absent Absent Passes test 1,4818
1,4800
1,4800
70
78.5 36,32
83,5 39,3
35,25
0,35 0~ 0 0,05
860 29,5
-
-
862--893 47--545**
870--890 28--38,5
176--262
Not b e l o w 185
---
Absent >> >>
Passes test
1,4817
1,4730
~
0,42 0,08 0,004
0,43 0,07 0,003
0,3 t --0,69 0,09--0,24 0.06--0.15
--
*By TsNT. **At 20~ tively, a pressure of 5 MPa, a volumetric rate of 0.5 h -I, and a quantity of hydrogen of 1000-1200 L/L raw material. The two-stage hydrogenation of the raffinate ensured a reduction of the contents of aromatic hydrocarbons and resins in the oil from 18.66 to 11.7% (see Table i). In the second scheme was carried out as in the at a temperature of 300~ of hydrogen equal to I000 it was possible to reduce Table i).
the hydrogenation of the raffinate in the first and second stages first scheme, while in stage III it was carried out on GR-3 catalyst pressure 5 MPa, volumetric rate of 0.5 h -~, and with a quantity L/L raw material. As a result of the three-stage hydrogenation, the content of aromatic hydrocarbons and resins to 7.83% (see
In the third scheme, hydrocracking of the raffinate was carried out on sulfide catalyst 8376 at a pressure of I0 MPa, volumetric rate of 0.5 h -l, temperature of 400~ and a quantity of hydrogen equal to i000 L/L raw material, and then the product was hydrogenated in 73
two stages. For producing the white oil the fraction >350~ of the hydrogenate was subjected to hydrogenation in stage I on catalyst AMK at 350~ and in stage II on industrial catalyst GR-3 at 300-310~ In stages I and II of the hydrogenation the pressure, volumetric rate, and quantity of hydrogen were, respectively, 5 MPa, 0.5 h -l, and i000 L/L raw material. The hydrocracking and the subsequent two-stage hydrogenation ensured a reduction in the content of aromatic hydrocarbons and resins in the oil to 5.57% (see Table i). Thus, the treatment of the raffinate by the schemes which have been considered make it possible to produce a raw material for the production of white oils with a content of aromatic hydrocarbons and resins from 5.57 to 11.7%. The further purification of the hydrogenates produced by the three schemes was carried out by the technology existing in the Yaroslavsk oil refinery, using oleum with 19-20% free S03: a feed of 5% oleum to each stage at 45~ subsequent neutralization with alcohol-water solution, and after-treatment with an adsorbent (gumbrin or an aluminosilicate) at 1200C with an inert gas feed. The white oils which are produced comply with GOST [State Standard] 3164-78 and are not inferior in physicochemical properties to commercial medicinal liquid paraffin oils and also to oil from West Siberian and foreign petroleum oils (see Table 2). The quantities of oleum for the after-treatment of the products obtained by the first, second, and third schemes amounted to 12, 7, and 5% (mass), respectively, and the quantities of the bleaching earth were 80, 70, and 50%. However, it is more convenient to produce the white oil by the second scheme, since it is simpler than the third. Thus, a three-stage hydrogenation of the raffinate of the vacuum distillate from the low-paraffin Balakhansk heavy petroleum oil makes it possible to produce white oils while reducing (to 7%) the quantity of oleum used in the treatment, and to obtain economies (compared to the existing scheme) in the amount of 702,400 rubles for a production of white oils of 20.,000 metric tons per year. LITERATURE CITED i.
2. 3. 4.
74
V. A. Potanina, T. I. Dremova, and T. P. Ponomareva, Khim. Tekhnol. Topl. Masel, No. 2, 11-12 (1987). F. I. Samedova, S. Yu. Rashidova, and A. M. Kasumova, Azerbaidzhanskoe Neftyanoe Khozyaistvo, No. 2, 47-50 (1986). L. A. Shabalinskaya, A. P. Mamedov, F. I. Samedova, et al., Khim. Tekhnol. Topl. Masel, No. 10, 32-35 (1986). W. Himmel et al., Erdol Kohle, 39, No. 9, 408-414 (1986).
