DK143071B - PROCEDURE FOR PREPARING SYNTHETIC LUBRICATION OIL WITH HIGH VISCOSITY INDEX - Google Patents

Description

(11) SUBMISSION 143071 DENMARK «o int ci.1 c 10« 3/12 f (21) Application No. 1322/74 (22) Filed on the 11th tnSX1 · 1 974 (24) Running Day 1 1. March 1 974 (44) The application presented and the petition published on 23 · ®βΓ · 1 9® ^

DIRECTORATE OF

PATENT AND TRADE MARKET (30) Priontet requested from death

Mar 12 1973 * 21459/73 * IT

(71) SNAM PROGETTI S.P.A., Corso Venezia, 16, Milan, IT.

(72) Inventor: Pierleone Girotti, San Donato Milanese, Via Ramiro Pabiani, 1, IT: Renato Tesei, San Donato Milanese, Via Piadena, 6, IT: Tele = maco Floris, San Donato Milanese, Via Piadena, 1, IT.

(74) Plenipotentiary in the proceedings:

International Patent Office.

(54) Process for producing synthetic lubricating oil with high viscosity® site index.

The present invention relates to a process for producing synthetic lubricating oil with a high viscosity index, very low flow point, low viscosity at -18 ° C, high thermal stability, high resistance to depolymerization, high flash point and very low carbon residue.

US Patent No. 3,113,167 discloses the production of synthetic lubricating oils from α-olefins which are first polymerized in the presence of a catalyst consisting of a titanium halide combined with an organoaluminum compound and having a titanium to aluminum ratio of 1: 1 to 1:20, after which more titanium halide is added, so that the atomic ratio of titanium to aluminum changes from 2: 1 to 20: 1 and the reaction is continued for some time.

German Publication No. 2,064,206 discloses a process for the production of synthetic lubricating oils by polymerizing α-olefins either in mixtures or in a single olefin having the general formula R-CH = CH 2, where R is a alkyl group having 2-16 carbon atoms, in the presence of a catalyst system consisting of a compound of a transition metal from groups IV to VIII of the periodic system and an aluminum compound which is a linear polyimine polymer having the formula: - -Al - N-- '1

SIR

n where n is an integer not exceeding 50 and R * is a hydrocarbon group. For the polymerization, a hydrogen pressure of 2 kg / cm or higher is used.

According to the invention, the present process for producing synthetic lubricating oil is characterized in that polymers with very high kinematic viscosity and boiling point higher than 175 ° C, obtained by polymerization at a pressure gauge of 2 up to 1 kg / cm and in an atmosphere of inert gas and / or hydrogen of normal α-olefins of the general formula R-CH = CH 2, where R is an alkyl group of from 2 to 16 carbon atoms, in the presence of the catalyst TiCl 2 / polyiminoalan, is subjected to catalytic cracking at atmospheric pressure at temperature within the range of 250 to 300 ° C, with the liquid volume per volume of catalyst per hour being between 0.1 and 5, preferably between 0.5 and 2, after which the obtained product is distilled in vacuo to a top temperature, calculated to atmospheric pressure, at 400 ° C and the residue having a boiling point higher than 400 ° C is subjected to catalytic hydrogenation.

Thus, for the preparation of the synthetic lubricating oils, two successive phases are used, the first of which is the preparation of polymers with very high kinematic viscosity and boiling point higher than 175 ° C is described in Danish Patent Application No. 1324/74. The aforementioned German publication specification 2.o64.2o6 also relates, as it appears, to a polymerization corresponding only to this first phase of the preparation, and further uses higher hydrogen pressures, giving polymers with substantially lower and less constant viscosity.

The use of the very high viscosity polymers obtained in the above-mentioned phase for the present process, consisting in a catalytic cracking under specified conditions, results in lubricating oil products having the initially mentioned good properties, in particular considerably improved thermal stability, and having a constant in them. properties not attainable in the two-step process known from the aforementioned U.S. Patent No. 3,113,167, the first stage of polymerization not utilizing the conditions for obtaining very high and constant viscosity polymers with respect to atmosphere and pressure prescribed in the abovementioned no. 1324/74, the second stage of which is quite different from the catalytic cracking of the present process.

3 143071

By appropriately changing the type of catalyst and the operating conditions' temperature and volume rate of the present process, oils of all desired viscosities can be obtained from 4 cSt up to 20-30-50 cSt at 99 ° C.

In the catalytic cracking treatment of the high molecular weight polymers, according to the invention, as the cracking catalyst, oxides or sulfides of the metals of groups VI to VIII of the periodic system deposited on a carrier which is a weak Lewis acid are preferably used for the purpose of high as low as possible to obtain the formation of low-boiling products.

In the treatment of the present invention, the variable factors, using a particular catalyst, are the temperature and volume rate. The applicable temperatures are between 250 ° C and 300 ° C. The volume rate expressed at v / v / hour, namely the volume of liquid per hour. catalyst volume per per hour, may range from 0.1 to 5 and preferably is between 0.5 and 2.

The catalytic cracking treatment is accomplished by bringing the very high viscosity polymer to flow at atmospheric pressure through a tubular electrically heated reactor containing the catalyst. The product thus obtained is fractionated at reduced pressure up to a top temperature, calculated at atmospheric pressure, of 400 ° C. The residue having a boiling point higher than 400 ° C constitutes an unsaturated synthetic lubricating oil, the yield of which is calculated in weight percent based on the polymer having a boiling point higher than 175 ° C used as the starting material.

Depending on the viscosity of the polymer used as the starting material, in the range of 660 cSt up to 1150 cSt at 99 ° C, the treatment yields range from 61% to 57% if oils with a viscosity at 99 ° C of approx.

18 cSt, and from 72% to 67% when viscosities of approx. 3o cSt.

The oil having a boiling point higher than 400 ° C is then subjected to hydrogenation to eliminate the unsaturation present therein.

The hydrogenation can be carried out by conventional and known methods. In the present case, it was carried out in the presence of a catalyst containing 0.3% Pd on alumina, at a temperature of 200 ° C at an initial hydrogen pressure of 100 kg / cm and over a total period of 5 hours.

The hydrogenated oil with a boiling point higher than 400 ° C is the high quality synthetic lubricating oil.

A hydrogenated oil representative of the process of the invention having a viscosity of approx. 19 cSt at 99 ° C, a viscosity index of 130 if calculated according to the ASTM D 2270 / A method and 154 if calculated according to the ASTM D 2270 / B method, a boiling point of -50 ° C, exhibits significant depolymerization. resistance, high thermal stability, very low carbon residue and flash point of 245 ° C,

The process of the invention is further described by the following Examples wherein Examples 1-2 show the cracking while Example 3 shows the subsequent hydrogenation.

In the examples, the kinematic viscosities are determined according to the method ASTM D 445. However, in view of the viscosity index two values are stated, one of which is calculated according to the method ASTM D 2270 / A and the other according to the method ASTM D 2270 / B, which is more correct for viscosity indices higher than 100. The point of flow was determined according to method D 97. the vertical is determined according to method IP 84.

Example 1

A polymer having a boiling point higher than 175 ° C, obtained by polymerization of cC-olefins (Cg-C4) from wax cracking, and having a viscosity at 99 ° C of 660 cSt, was subjected to catalytic cracking tests to reduce its viscosity and gain lubricating oils. The treatment was carried out by bringing said polymer to flow at atmospheric pressure and at controlled speed through an electrically heated tubular steel reactor having a diameter of 40 mm 3 and containing a catalyst layer of 200 cm activated alumina with a content of 99¾ A ^ O ^ (tablets about 3 mm).

The products obtained in the various samples were distilled in vacuo up to a top temperature, calculated at atmospheric pressure, of 400 ° C. The residue with a boiling point higher than 400 ° C was the synthetic unsaturated lubricating oil.

The results obtained are listed in Table I.

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These experiments showed that by catalytic cracking of a polymer with a viscosity of 660 cSt at 99 ° C, lubricating oils could be obtained by operating at relatively low temperatures.

The results show that an oil with a viscosity of approx. 18 cSt at 99 ° C could be obtained in a yield of approx. 61% by operating at a temperature of approx. 268 ° C and at a volume rate of 1.

Example 2

The catalytic treatment was carried out by using as a starting material a polymer having a boiling point higher than 175 ° C, obtained by polymerization of (Cg-C.Q) olefins from wax cracking and having a viscosity at 99 ° C of 1160 cSt. The catalyst was the same as used in Example 1, namely 200 cm activated alumina containing 99% A 2 And (tablets about 3 mm).

The apparatus was the same as in Example 1.

The results of the experiments performed are listed in Table II.

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From these results it was found that by using as a starting material a polymer having a viscosity of 1160 cSt at 99 ° C, lubricating oils could be obtained by operating at a relatively low temperature.

From the results it could be deduced that an oil with a viscosity of approx. 18 cSt at 99 ° C could be obtained in a yield of approx. 57% by working at a volume rate of 1 and at a temperature of approx. 270 ° C,

Example 3

The synthetic oil having a boiling point higher than 400 ° C obtained in Sample 2 of Example 2 (see Table II) was hydrogenated to completely saturate the olefinic double bonds. The operation was performed in autoclave in the presence of a catalyst containing 0.3% Pd on alumina at a temperature of 200 ° C and at 2 a hydrogen pressure of 100 kg / cm over a total time period of 5 hours.

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

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These results show that the hydrogenation did not substantially modify the properties of the oil which remained excellent.

From the value of the viscosities at 99 ° C and at -18 ° C, as well as from the flow point, it could be deduced that the oil worked well in both the heat and the cold.

Furthermore, the very low value for the carbon residue and the high flow point must be noted.

Examples 4-5 relate to stability tests on the hydrogenated oil.

Example 4

The hydrogenated oil of Example 3 was subjected to the shear stability test with Raytheon sound oscillator over a period of 15 minutes at a temperature of 38 ° C (ASTM D 2603-70).

The results are listed in Table IV.

TABLE IV

Hydrogenated oil from Example 3.

Before Trial After Trial

Kinematic viscosity at 99 ° C, cSt 19.2 19.1

Kinematic viscosity at 38 ° C, cSt 152 151

From these results, it was found that the hydrogenated oil obtained by the process of the invention was resistant to the sound depolymerization test.

Example 5

The hydrogenated oil of Example 3 was subjected to the thermal stability test by the method of the Federal Std. No. 2508 "Thermal Stability of Lubricating and Hydraulic Fluids" consisting of holding, at a temperature of 260 ° C and for 24 hours, 20 cm of the oil under examination in a flame-sealed glass tube, the oil being is degassed.

The results of the sample are given in Table V,

TABLE V

Hydrogenated oil from Example 3.

Before Sample After Sample

Kinematic viscosity at 99 ° C, cSt 19.2 19.1

Kinematic viscosity at 38 ° C, cSt 152 149