CS208697B2 - Method of making the syntetic lubricating oils - Google Patents

Abstract

The process for producing synthetic lubricating oils of high viscosity index, high thermal stability and extremely low carbonaceous residue starts from polymers of extremely high viscosity, having a boiling point above 175 DEG C. These polymers are obtained by polymerisation of normal alpha-olefins of the general formula R-CH=CH2, where R is an alkyl radical having 2 to 16 carbon atoms. The polymerisation is carried out in the presence of the TiCl4/polyimine-alane catalyst in an atmosphere which is inert or at least partially replaced by hydrogen. These polymers are subjected to a catalytic hydrocracking treatment at temperatures varying from 300 to 400 DEG C. The hydrogen pressure is between 20 and 200 kg/cm<2>. The product is then distilled in vacuo up to a top temperature of 400 DEG C, relative to atmospheric pressure. Finally, the fraction of boiling point above 400 DEG C is separated off.

Description

(54) Production method of synthetic lubricating oils i

The invention relates to a process for the production of synthetic lubricating oils. More particularly, the invention relates to a process for producing synthetic lubricating oils having a viscosity index of 124 to 134, measured according to ASTM 2270 / A, a pour point of -50 ° G, a thermal stability corresponding to a viscosity deviation of 0.1 mm ² s ^-1 at 98.9 ° C and a viscosity deviation of 1.0 mm ² · s ^{* 1} at 37.8 ° C, a depolymerisation resistance corresponding to a viscosity deviation of 0.0 mm ² .s ~ ¹ at 98.9 ° C and a viscosity deviation of 1.00 mnAs " ¹ at 37.8 ° C, flash point 246 ° C and carbonaceous residue 0.01 wt%, absolute viscosity 5.8 Pa.s at -18 ° C, kinematic viscosity 19.2 mm ² .s "'at 98.9 ° C and 152 mm ² at 37.8 ° C, of polymers of boiling point above 175 ° C, obtained by polymerizing n-alpha-olefins of the general formula r-ch = ch ₂ in which

R denotes an alkyl radical having 2 to 16 carbon atoms, having viscosities of 660 to 5 330 mm ² · s ¹ at 98.9 ° C in the presence of a catalyst consisting of titanium tetrachloride and polyiminoalan, in an inert atmosphere or at least partially substituted with hydrogen to 0 1 MPa.

The process according to the invention is characterized in that said polymers are subjected to hydrogenation catalytic cracking at a temperature of 300 to 400 ° C using a catalyst consisting of catalysts containing oxides or metal sulfides VX. to VIII. and a carrier, preferably slightly acidic Lewis, with a liquid volume per catalyst volume per hour ranging from 0.1 to 5, preferably 0.25 to 1.5, an air pressure of 2.0 to 20. MPa, preferably 2.0-10 MPa, and the product obtained is distilled under vacuum at 400 ° C based on atmospheric pressure, and the fraction boiling above 400 ° C is separated.

20869 by catalytic cracking of very high viscosity polymers gives lubricating oils which delimit excellent properties and particularly greatly improved thermal stability. Vaatnoots of the oils obtained are determined by the choice of the catalyst and the hydrogenation cracking reaction conditions such as temperature, space velocity and hydrogen pressure.

In the process according to the invention, the temperature, the room velocity and the hydrogen pressure are varied with the catalyst used at a constant rate. The swollen temperature range is 300 to 400 ° C, the gas space velocity per hour is 0.1 to 5. The catalytic cracking is carried out in such a way that the ultra-high molecular weight polymer obtained in the first phase is fed through the reactor at a controlled hydrogen pressure. , electrically heated, which comprises a hydrotreating catalyst.

The product obtained is fractionated under reduced pressure to a maximum temperature, based on atmospheric pressure, of 400 ° C. The residue, boiling above 400 ° C, forms high quality synthetic lubricating oil.

Oil vychááející tydrogenačního of treatment may be sufficient saturation with further requires ^p · tydrogennaL ccording viscosity iv ^ i ^ eny ^ ^p ^ of the rates ^at rozmmsí from ⁶⁶⁰ m .s ⁿ "'and ⁵ ° 33 mm ² .s"' s ^p 9 ⁸ 9 ° C @ tytauje howl ^Ez ek oil, bo ^d at boiling point higher not ^of 4 ⁰⁰ ° ^C; from 66 to 61 tamtnnotní ^% ^p s viscosity ^P ro ^d uktu ¹ 8 Mn ^ s ^{"1 p} s 98 9 ° C of from 77 ^{d 74%} tomtanotní ^ s ^p vi & Ozitech ^p roducts οΛβ 30 * 98.9 ^{1 P} s · ° C

The oil according to the invention exhibits a viscosity of 18 mm ² · s ^-1 at 98.9 ° C, a viscosity index of 132 using the measurement method of ASTM 2270 / A of 158 using the method of ASTM 2270 / B, a freezing point of -48 ° C, very high. low carbon residue from high resistance to depolymeerzaal, high thermal stability from flash point 246 ° C ·

The invention will now be illustrated by way of examples of practice, which do not in any way limit the invention.

In the examples, the kinematic viscosity was determined according to ASTM D 445.

Two values were obtained for the viscoe index determination, one of which was determined according to ASTM D 22 * 70 / A and the other more accurately according to ASTM D 227 0 / B, for a viscosity index higher than 100.

The freezing point was determined according to ASTM D 97 ·

The iodine number was determined according to IP 84 ·

Example 1

Polymer'o a boiling point higher than 175 ° C, the obtained polymeerzací ^ Oq Oio alpha-olefins from cracking wax viscosity ^p ^ s of 98.9 ° C, ⁶⁶⁰ mm ≤ T ', tulle exposed hýrogenačnímu katalytco ^ he cracking zz tael viscosity reduction of production ^d for uktu vtotaéto jzko mmzací .olej ·

The tulle process was carried out by conducting a polymer stream at a controlled rate of hydrogen pressure of 5-10 M @ 2 and a cylindrical reactor of 40 mm diameter, electrically heated, containing a Co-based Tydrogenation Catalyst from a 1.6 mm orifice rod. · Gas recycling was carried out during the tulle test · Fractions up to 400 ° C, based on the atmospheric pressure, were distilled off from the products from the various tests ·

The remainder above 400 ° C consisted of synthetic oil,

The results obtained are shown in Table 1.

Table 1

Oil boiling above 400 ° C

Test spatial spacingH-OSt / h temperature ° C pressure H ₂ MPa hmoo yield. % mm ² · s' at 98.9 ° C _mm 2 o-1 mm. at 37.8 ° C viscosity index pour point ° C iodine number 1 0.25 365 5.0 79 35.8 318 129-168 3.4 2 0.25 375 5.0 65 17.6 135 131-154 -45 4.0 3 0.5 350 5.0 87 114 1 170 125-204 4 0.5 375 5.0 76 29.0 244 130-166 5 0.5 375 10.0 78 31 J 259 130-170 -45 2.3 6 0.5 400 5.0 51 3, 3 67.6 133-150 -51 7 0.5 400 10.0 48 9.3 58.9 134-150 -48 3.3 8 1.5 375 5.0 85 66.9 633 127-188 9 1.5 375 10.0 81 45.8 416 128-176 10 1.5 400 5.0 64 16.6 121 132-158 -48 11 1.5 400 10.0 66 17.6 131 132-158 -48 2.5

Comparing the results, it is evident that the most important variable was the temperature and spatial velocity of the gas, while the hydrogen pressure had a negligible effect. While keeping the other reaction conditions at constant values, a pressure change of 5.0 to 10.0 MPa did not substantially affect the results.

The table shows that the hydrogenated oil having a boiling point higher than 400 ° C and a viscosity of 18 mm ² .s ^- 'at 98.9 ° ^C are zl ^ slráváiny during application ^{of p} rostorově rychlooti and 0.25. 375 ° C or a room speed of 0.5 at 385 ° C, or a room speed of 1.5 at a temperature of about 400 ° C.

Oil yields of such viscosity values were approximately the same and were 65 to 66% by weight. Viscosity values were high and pour points were very low.

In determining the iodine value, the oils obtained were considered saturated.

Example 2

The polymer having a boiling point greater than 175 ° C used in Example 1 and exhibiting a viscosity at 98.9 ° ^{C of 660} mm @ ^-1 was sown by hydrogenation totality shortening using the same apparatus as in Example 1 and an oxide catalyst. of cobalt and molybdenum on a nooichi, consisting of 25% by weight of silica and 75% by weight of aluminum oxide having a particle size of 1.6 mm.

The test results are shown in Table 2,

5 ^

Table 2

Oil boiling above 400 ° C

Test space speed temperature ° C pressure Hg №> a yield% wt. viscosity _mm 2 _s ¹ mm · s 98.9 ° C viscosity visco- pour point ° C iodine number _mm 2 mm. with 37.8 ° C rye index 1 0.5 325 5.0 80 90 921 125-193 2 0.5 350 5.0 64 21.1 169 130-157 -5 ' 4.0 3 0.5 375 5.0 39 39 37.1 134-142 4 1.5 325 5.0 85 110 1 200 124-195 5 1.5 350 5.0 72 35.3 307 129-170 4> 5 6 ', 5 375 5.0 52 12.1 82 133-154 -50

By comparing these results with those of Example 1, it is evident that the equivalent viscosity yields oils with a boiling point higher than 400 ° C lower than when using a catalyst with a higher acidity, that the required temperatures were lower.

The table shows that when the catalyst pouužtí obtained oil having a viscosity of about 18 mm ² .s * '9 at ^8, 9 ° C at ua ^ CONTRARY TO space velocity per hour ^0, 5 at about 355 ° C or downtime at a temperature of about 365 ° C.

The yields in both cases were about 60%.

The viscosity values remained high and the freezing points very low.

Example 3

Hydrogenation catalytic cracking treatment was carried out using a starting material in the form of a polymer having a boiling point above 175 ° C, obtained. polymeedzací alpha-olefin ^of from Cg-CjQ toatování with ^a wax, it Vyka ^^ viscosity of 5 33 ^{0 2} .s TNM ^{e1 p} s ^98, 9 ° C.

^B Katolyzátor yl stance ^to I o ^p of ^IKL range of ¹ and 5 možžtví corresponding to ^{1 0} cm ³ based on oxides of cobalt and molybdenum on alumina. The equipment used was similar to Example 1.

The results obtained are shown in Table 3.

Ta b u 1 k and 3

Oil boiling above 400 ° C

Test space speed / h temperature Noc: 2 ° C pressure H ₂ MPa % wt. viscosity 2 1 mm · s 90.9 ° C viscosity visco- pour point ° C iodine number mm. with" 37.8 ° C rye index 1 0.5 350 5.0 88 139 1 845 122-186 2 0.5 375 5.0 78 38.5 347 128-169 3 0.5 400 5.0 50 11.5 76.9 133-153 -52 2.5

Comparing the results to those of Example 1, where the tests were carried out with an alumina catalyst, it was apparent that using a higher viscosity polymer feedstock required higher temperatures to obtain oils of the same viscosity. yields were lower.

The table shows that an oil having a boiling point of 400 ° C and a viscosity of 18 mm ² · s ^ ^ at 98.9 ° C was obtained by applying a space velocity of 0.5, at a temperature of about 390 ° C and yielding 61% by weight. · The viscosity of these oils was approximately the same and the freezing points remained very low ·

Example 4

The synthetic oil obtained in Test 11 of Example 1 (see Table 1) was selected as representative of the process of the invention. The other properties of this oil are listed in Table 4 ·

Table 4

Saturated oil properties from Test 11 according to Example 1

determination procedure saturated oil specific gravity at 20 ° C ASTM D 1481 0.839 kinematic viscosity at 9S, 9 ° C ASTM D 445 17.6 kinematic viscosity at 37.8 ° C, mm ² .s ¹ ' ASTM D 445 131 viscosity index ASTM D 2270 / A 132 ASTM D 2270 / B 158 absolute viscosity at -18 ° C; ASTM D 2602 5.8 pour point, ° C ASTM D 97 -48 % carbonaceous residue, wt. ASTM D 524 0.010 flash point, ° C ASTM D 92 246 molecular weight osmometričky 650 iodine value, g / 100 g IP 84 2.5 From viscosity values at 98.9 ° C and -18 ° C and from freezing point it follows that

It has good properties at high and low temperatures.

Also important is the very low carbon residue value and the high flash point.

Example 5

The oil boiling in the range of 400 ° C + (boiling above 400 ° C) obtained in Test 11 of Example 1 was subjected to a shear test using a Rayton sonic oscillator for 15 minutes at 37.8 ° C ( ASTM D 2603-70).

The results obtained are shown in Table 5.

Table 5

The oil according to Test 11 of Example 1, the original kinematic viscosity at

98.9 ° C, mm ² .s ^-1 17.6 17.6 kinematic viscosity at

37.8 nnn ² .s'

130

131

As a result, it can be seen that the oil obtained by the process of the invention was resistant to the sonic depolymerization test.

Example 6

The oil having a boiling point above 400 ° C obtained in Test 11 of Example 1 was tested for thermal stability by heating in a sealed glass tube in an amount of 20 ml to 260 ° C for 24 hours. The results obtained are shown in Table 6>

Oil from test 11 of Example 1 original after test kinematic viscosity at 98.9 ° C, am ² .s * ¹ kinematic viscosity at 37.8 ° C, mm ² .s ^-1

17.6 17.5

131 130

The above results show a steady.

The process according to claim 1, wherein the oil obtained by the process of the invention is thermally

Claims (1)

D δ E D M T T OF THE INVENTION Process for producing synthetic lubricating oils having a viscosity index of 124 to 134, measured according to ASTM 2270 / A, a pour point of -50 ° C, a thermal stability corresponding to a viscosity deviation of 0.1 mm ² .s ~ ¹ at 98.9 ° C and a viscosity deviation of 1 0 at 37.8 ° C, depolymerisation resistance corresponding to a viscosity deviation of 0.0 mm ² .s ¹ at 98.9 ° C and a viscosity deviation of 1.00 mm ² .s "^ at 37.8 ° C, flash point 246 ° C and 0.01 wt% carbon residue, absolute viscosity 5.8 Pa.s at -18 ° C, kinematic viscosity 19.2 mm ² .s ¹ at 98.9 ° C and 152 mm ² s · s at 37.8 ° C, of polymers of boiling point above 175 ° C, obtained by polymerizing n-alpha-olefins of the general formula r-ch = ch ₂ in which o 1 R denotes an alkyl moiety having 2 to 16 carbon atoms, with viscosities of 660 to 5.330 mm. s pri 98.9 ° C in the presence of a catalyst consisting of titanium tetrachloride and polyiminoalan, in an inert atmosphere or atmosphere ⁴ at least partially substituted by hydrogen to a pressure of 1 bar, characterized in that said polymers are subjected to hydrogenation catalytic cracking at 300 to 400 ° C use of a catalyst consisting of catalysts containing oxides or metal sulfides VI. to VIII. % of the periodic system of the elements and the carrier, preferably weakly acidic according to Lewis, wherein the liquid volume per catalyst volume per hour ranges from 0.1 to 5, preferably from 0.25 to 1.5, a hydrogen pressure of 2.0 to 20 MPa, preferably 2.0-10 MPa, and the product obtained is distilled under vacuum at 400 ° C based on atmospheric pressure, and the fraction boiling above 400 ° C is separated.