CS208698B2 - Method of making the syntetic lubricating oils - Google Patents

Abstract

Synthetic lubricating oils are obtained by subjecting a polymer having a viscosity in the range of 250 to 15,000 cSt at 210.degree.F and a boiling point higher than 175.degree.C, prepared by polymerizing normal alpha-olefines having t?? general formula R-CH = CH2 wherein R is an alkyl radical containing from 2 to 16 carbon atoms, in the presence of a TiCl4/polyiminoalane catalyst and in an atmosphere of an inert gas and/or hydrogen having a hydrogen pressure of less than 1 kg/cm2, to a catalytic cracking carried out at atmospheric pressure and at a temperature of from 250 to 300.degree.C, the volume of liquid per volume of catalyst per hour being comprised between 0.1 to 5, distilling the resulting product under vacuum up to a head temperature, referred to atmospheric pressure, of 400.degree.C and subjecting the residue having a boiling point higher than 400.degree.C to a catalytic hydrogenation. The oils produced by this process have a high viscosity index, very low pour point, low viscosity at 0.degree.F, high thermal stability, high resistance to depolymerization, high flash point and very low carbon residue.

Description

The invention relates to a process for the production of synthetic oil oils having a viscosity index of 129 to 136, measured according to the ASTM method 2 270 / A, the melting point of -50 ° C, the absolute viscosity

^5, 9 centipoise at -18 ° ^C kheematieké viscosity of 19.2 mm ² .s' ^{* 1 C} at 98.9 C and 152 mm ² .s ^{* 1} * ^* At 37.8 ° C the stability tepe3.né if you odpovíddjící-viscosity odcl ^ LCE ^{0. 1} mm ² .s ^-1 at 98.9 ° ^C and ^even with ozitní odehylce ^{to 3.0} mm ² .s ~ ^'p ^ s 37 ° C, resistance depolyneelzaci odppv ^Daiichi-vi-d skozitn deviation of ^0, 1 mm ² .s "p ^{s 1 9} 8 ⁹ ° C ^{and the} viscosity deviation I ⁰ mm ² .s ^{- p} ^ s 37 ° ^C, flash point of 246 ° C and the residue uhlíkaéém 0.008 hmoonootndho%.

The process according to the invention consists of two successive phases.

The first phase concerns the production of polymers having very high molecular hmoonnosi and wide Rozsa ^h at viscosities from ⁶⁶⁰ dr ¹ 15 ⁰ mm ² .s ^{- 'p} s ⁹ 8 ⁹ ° C. These polymers are in bulk. high yield by polymerizing the debris of normal alpha-olefins from the cracking of wax or individual normal alpha-olefins of the general formula

R-CH = CH 2 in which

R denotes an alkyl radical having 2 to 16 carbon atoms, in the presence of a catalyst consisting of a titanium tetrachloride complex on a polyminolane, in an inert atmosphere or in an atmosphere at least partially hydrogen-substituted to a hydrogen pressure not exceeding 0.1 MPa and subsequently distilling the polymerization product at 175 ° C column head.

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The second phase of the process according to the invention consists in subjecting the polymer to catalytic cracking on metal oxide catalysts or metal simulators VI. to VII. Lewis, on a slightly acidic support at atmospheric pressure, at a temperature of 250 to 300 ° C and a liquid volume per catalyst volume of 0.1 to 5, preferably 0.5 to 2, wherein the product obtained is distilled under vacuum to The column head temperature, based on atmospheric pressure, of 400 ° C and the residue obtained with a boiling point above 400 ° C is subjected to catalytic hydrogenation using a catalyst containing 0.3% by weight of palladium on alumina at 200 ° C, initial pressure hydrogen at 10 MPa and an autoclave residence time of 5 hours.

The catalytic cracking treatment was carried out in such a way that the very high viscosity polymer obtained in the first phase was allowed to flow at atmospheric pressure through an electrically heated cylindrical reactor containing the catalyst.

The product thus obtained was fractionated under reduced pressure to a column head temperature of 400 ° C based on atmospheric pressure. The residue having a boiling point above 400 ° C consists of a synthetic lubricating oil, the yield of which is given in percent by weight, based on the polymer at boiling point above 175 ° C, used as a filler.

^r 2—1

Depending on the viscosity of the polymers fed in the range from 660 to 1150 mm / s, the yield ranges from 61 to 57% by weight in the case of producing oils having a viscosity of 18 mm ² . with ¹ at 98.9 ° C and from 72 to 67% by weight in the case of oils having a viscosity of about 30 mm ² . .а ¹ .

The oil boiling above 400 DEG C. is then subjected to hydrogenation to saturate the unsaturated bonds present.

The hydrogenation can be carried out by methods known per se. In the particular case, it is carried out in the presence of a catalyst containing 0.3% by weight of palladium on alumina, at a temperature of 200 ° C, an initial hydrogen pressure of 10 MPa and a total reaction time of 5 hours.

The hydrogenated oil obtained, boiling above 400 ° C, is a synthetic lubricating oil of superior quality.

The hydrogenated oil according to the invention has a viscosity index of 129 to 136, measured according to ASTM 2 270 / A, a pour point of -50 ° C, an absolute viscosity of 5.9 Pa.s at -18 ° C, a kinematic viscosity of 19.2 mm ² .s ” ¹ at 98.9 ° C and 152 mm ² .s ^-1 at 37.8 ° C, a thermal stability corresponding to a viscosity deviation of 0.1 mm ² .s ^-1 at 98.9 ° C and a viscosity difference of 3.0 mm ² -s “ ¹ at

37.8 ° C, depolymerisation resistance corresponding to a viscosity deviation of 0.1 mm ² at

98.9 ° C and a viscosity deviation of 1.0 mm ² .s ~ ¹ at 37.8 ° C, a flash point of 246 ° C and a carbonaceous residue of 0.008 weight percent.

The following examples serve to illustrate the process of the invention in more detail without limiting its nature.

In the examples, the kinematic viscosity was determined according to ASTM D 445. Two values are given for kinematic viscosity; one calculated according to ASTM D 2 270 / A and for a viscosity index higher than 100, a more precise procedure according to ASTM 2 270 / B was used. The freezing point was determined according to D 97. The iodine number was determined by the IP 84 procedure.

Example 1

The polymer of a point more than 175 ° C obtained by polymerizing alpha-olefins from cracking wax having a viscosity at 98.9 ° C, 660 pl ^ .s ^"1, was subjected to tests of catalytic cracking in order to reduce its viscosity and to obtain lubricating oils.

The polymer was allowed to flow at atmospheric pressure and at a controlled rate through a cylindrical, 40 mm diameter, electrically heated steel reactor containing a catalyst bed consisting of 200 ml of activated alumina containing 99% AlgO 3, the size of the tablets

1/8.

The products obtained in the various tests were distilled under vacuum to a column head temperature, calculated at atmospheric pressure, of 400 ° C. The residue boiling above 400 ° C was a synthetic lubricating oil.

The results obtained are shown in Table I.

This example demonstrates that relatively low temperatures can be used in the manufacture of lubricating oils by catalytic cracking of a polymer having a viscosity of 660 mm · s ^-1 at 98.9 ° C. It can be deduced from the table that the yield of oil having a viscosity of 18 mm ² · s ^-1 at 98.9 ° C would be 61% by weight, at a temperature of 268 ° C and a space velocity of 1.

Table I

Oil boiling above 400 ° C Test no. space speed / h temperature ° C % wt. 2 -1 mm, 98.9 ° C nm ² s ^-1 37.8 ° C viscosity index ASTM D 227 0 / A ASTM D 2270 / B 1 1 250 78 37.4 324 129 173 2 1 270 60 16.9 125 132 157 3 1 290 51 8.04 47.9 136 151

Test Nr. freezing point iodine number 1 - - 2 -49 42 3 - - Example 2

For the catalytic treatment, a polymer having a boiling point greater than 175 ° C, obtained by polymerization of C 8 -C 16 olefins from wax cracking, with a viscosity of 1160 at 98.9 ° C was used as starting material.

The catalyst was similar to Example 1 (200 cm ^{3 of} activated alumina, containing 99% ΙΙΙ tablety tablets 1/8). The apparatus used is similar to Example 1.

The results obtained are shown in Table II. The results show that when processing a polymer having a viscosity of 1160 mm ² · s ^-1 at 98.9 ° C, lubricating oils are obtained at a relatively low cracking temperature.

From the table it can be deduced that the yield of oil having a viscosity of 18 mm ² s · s at 98.9 ° C would be 57% by weight, at a space velocity of 1 and a temperature of 270 ° C.

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Table

II

Oil boiling above 400 ° C

Test

C. spatial velocity tepjota yield mass. % mm ² e- ¹ mm. with 98.9 ° C mm ² .s @ -1 37.8 ° C viscosity index freezing point iodine. no. ASTM D 2270 / A ASTM D 2270 / B 1 1 250 81 50.1 443 129 184 2 1 270 57 18.2 139 131 156 -50 , 40 3 1 290 48 8.5 52.4 134 149

Example 3

Synthetic oil having a boiling point above 400 ° C obtained in Test 2 of Example 2 (see Table II) was hydrogenated to completely saturate the olefinic double bonds. The operation was carried out in an autoclave in the presence of a catalyst containing 0.3 wt% Pd on alumina, at a temperature of 200 ° C, under a hydrogen pressure of 10 MPa and a reaction time of 5 hours.

The properties of the oil before and after hydrogenation are given in Table III.

From the above results, it can be seen that the hydrogenation did not substantially change the oil performance, which remained very good.

From the viscosity values at 98.9 ° C and -18 ° C, as well as from the freezing point, it can be deduced that the oil showed good hot and cold operation properties. Furthermore, a small carbon residue and a high flash point are evident.

Table III

Oil Properties of Test 2 of Example 2, before and after hydrogenation Method non-hydrogenated oil hydrogenised oil specific gravity kinematic viscosity ASTM D 1481 0.840 0.839 at 98.9 ° C mm ² · a 'kinematic viscosity at 37.8 ° C ASTM D 445 18.2 19.2 2 —1 mm · p ASTM D 445 139 152 viscosity index ASTM D 2,270 / A 131 130 ASTM D 2270 / B 156 154 absolute viscosity (-18 ° C Pa.s) ASTM D 2602 5 700 5 900 pour point ° C ASTM D 97 -52 -50 carbon residue; % ASTM D 524 - 0.008 flash point ° C ASIM D 92 - 245 molecular weight osmom. - 650 iodine Number g / 100 g IP 84 40 2

Example 4

The hydrogenated oil of Example 3 was subjected to a shear stability test using a Raytheon sound oscillator for 15 minutes at 37.8 ° C (ASTM D 2603-70). The results obtained are shown in Table IV.

Table IV

Hydrogenated oil according to Example 3

before tese after the test cinematic and viscous rye ^at 98.9 ° C ^{mm 2} . ^s_1 19 ^ 2 19.1 cinematic viscosity ^p s ^ 37.8 ° C for ^{the second} ^ ¹ 152 151

Comparing the results, it can be seen that the hydrogenated oil of the invention was resistant to sonicity by depolymerization tests.

Example 5

The hydrogenated oil of Example 3 was subjected to a thermal stability test according to Federal Std. No. 2508, Tiermal Stability of Lubbicants and Fluorescence, by exposing 20 ml of oil in a glass tube which had been sealed after prior de-aeration of the oil at a temperature of 260 ° C for 24 hours. The results obtained are shown in Table V.

In Ulka Tib before TESE after test kinematic viscosity at ⁹³ ° C, 9 mo ² .s' 19.2 19.1 kinematic viscosity at ³⁷ ° C for 8 MRN ² .s''152149

The results obtained confirm that the oil according to the invention is thermally stable.

Claims (1)

SUBJECT OF THE INVENTION Process for producing synthetic lubricating oils having a viscosity index of 129 to 136, measured according to ASTM 2270 / A, a pour point of -50 ° C, an absolute viscosity of 5.9. Pa.s at -18. ° C, a kinematic viscosity of 19.2 mm ^{2 I} .s ^- 'at 98.9 ° ^C and ¹ 52 mm ² .s ^-' on. ^37, 8 ° C, thermally stabilized ^é-Lite deviation odpoovdající viscosity ^0.1 mm ² .s' s ^{1 P 9B,} 9 ° C and viscosity of 3.0 ^ deviation ^{second BC-1} and ^37, 8 ° C against odobnooti (^ tepol erizaci odpooídající ^d ocfchylce viscosity 0.1 mm ² .s' s ^{1 p} 98.9 ° C and the viscosity deviation ^{d 1} 0 mm ² .s ^-1 at ³⁷ ° C for 8 bo ^d u flare ² 4 ⁶ ° C and a carbon ZB ^{y in} tk 0.008% by weight, characterized in that the polymers prepared from the n-alpha-olefin of the general formula R-CH = CHg in which R 8 is an alkyl radical from 2 to 16 carbon atoms and a boiling point higher than 175 ° C and a viscosity of 660 to 150 mm ^{2 I-1} at 96.9 ° C is subjected to catalytic cracking catalysts comprising oxides or metals of Group VI Sims. to VIII. a Lewis weak acidic support group at atmospheric pressure, 250-300 ° C and a liquid volume per catalyst volume of 0.1-5 per hour, preferably 0.5-2, the product obtained being distilled under vacuum to a column head temperature of 400 ° C relative to atmospheric pressure and the residue obtained at boiling point above 400 ° C is subjected to catalytic hydrogenation using a catalyst containing 0.3% by weight of palladium on alumina, at a temperature of 200 ° C, a hydrogen pressure of 10 MPa and an autoclave residence time of 5 hours.