DE2361652A1 - PROCESS FOR PRODUCING 10W / 30, 10W / 40, 20W / 40 AND 20W / 50 LUBRICATING OILS - Google Patents

Description

SIiELL INTERNATIONAL RESEARCH MAATSCHAPPIJ B.V. The Hague, Netherlands. .

"Process for the production of 1QW / 3O-; iOW / 40-, 2ÖW / 4O- and: 20W / 50 ~ 3 lubricating oils "-

Priority: December 13th-1972 - Great Britain - No. -57 472/72

The invention relates to a method for the production of lOW / ^ O-,. 2OW / 4Q and 2QW / 50. lubricating oils. In particular concerns the invention a method for producing the aforementioned. Lubricating oils, either as such or after adding a Additive package, but without the addition of a polymeric viscosity index improver, meet the conditions for the aforementioned oils.

According to the SAE classification, lubricating oils for combustion ■■ '■ motors on the basis of their 'viscosity into two groups, viz divided into winter and normal oils. Any of these groups. is again divided into a number of classes. Lubricating oils that are classified as winter oils are identified by the letter

ben W and one

digit, e.g. as SAE-5W-, -10V / - or

-20W-OIe. These oils. must meet certain conditions

409825/1049

visibly their dynamic viscosity at -I ¹ J; Meet 8 ⁰ C. AIc

Lubricating oils classified as normal oils are only identified by a number, e.g. as SAE ~ 20, -30, -4θ or -50 oils. Djese oils must meet certain conditions in terms of kinematic "viscosity at 98.9 ⁰ C lubricating oils that only the conditions in terms of SAE class (either the conditions for ^'! Winters oils or the conditions for NoTmalöle) fulfiller / be. Commonly used single-grade lubricating oils are, for example, SAE-20 and SAE-30 oils.

Monograde lubricating oils are known lubricating oils that have the viscous

I-jormal oils both winter and /.

When used as motor oil, these multigrade lubricating oils have the advantage that they are sufficiently thin in winter so as not to cause any problems with a cold start and that they have a sufficient viscosity at the operating temperatures of the running engine to sufficiently lubricate the engine. Important classes of multigrade lubricating oils are the low / 30, lOW / 40, 2ÖW / 40 and 20W / 5Q oils -17.8 ⁰ C of at least 12 and at most 24 P) and the viscosity requirements for the SAE 30 oils (kinematic viscosity at 98.9 ⁰ C of at least 9.6 and not more than 12.9 cSt). the 10W / 40 -Oils meet both the viscosity requirements for SAE-LOW oils and the viscosity requirements for SAE-40 oils (kinematic viscosity at "98.9 ° C of at least 12.9 cSt and at most 16.8 cSt). The 20W / 40 oils satisfy both the viscosity requirements for SAE 20W-oils (dynamic viscosity at 17.8 ⁰ C of at least 24 and at most 96 P) and the Viskositätsanforde-

-. 40982.5 / 1Q49

stanchions for SAE 40 oils. The 20W / 50 oils. satisfy both the viscosity SANF or requirements for the SAE 20W-oils and the viscosity requirements' for SAE 50 oils (kinematic viscosity at 98.9 ⁰ C of at least 16, 8 and not more than 22.7 cSt). The in the present

♦ - - ■

the description mentioned dynamic and kinematic ^viscosity: activities are determined according to ASTM D-2002/71 bzw.gemäß ASTM D 445/71. "

The production of multigrade oils of the classes IOW / 30-, IOW / 40, 20W / 40- and 20.W / 50 -is in practice ¹ by adding a series of quality-improving additives to one of a lubricant-

oil or a blend of lubricating oils with high viscosity in (the)

dex made in a conventional manner or by hydrocracking

(are
has been / and as such the requirements for 10W / 50--, 10W / 40-,

20V // 40- or 2GW / 50-ö.le not fulfilled, carried out. '

The production of lubricating oils with a high viscosity index. conventional manner is carried out as follows. A paraffinic one Crude oil is made into a by distillation at atmospheric pressure Series of distillate fractions (generally sequentially into one or more gasoline, kerosene and light gas oil fractions) and separated a residue (top residue). The top residue will then by distillation at reduced pressure into a series of Distillate fractions (especially one after the other into one or more heavy gas oil, spindle oil, light machine oil and medium weight Machine oil fractions.), And a residue (vacuum residue) separated. From the distillation at low pressure The cutting oil fractions obtained are the corresponding lubricating oils made by refining. Refining the spindle oil

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fraction, the light machine oil fraction and the medium-heavy machine oil fraction is removed by removing the aromatics and dewaxing these fractions carried out. When refining the vacuum residue, it is first deasphalted. from the deasphalted oil obtained in this way are then separated the aromatics and paraffin. The residual lubricating oil produced in this way is called a drightstock designated. That while refining the various Schinierö.1 tractions obtained paraffin is, depending on the nature of the output ?; material The lubricating oil fraction used is referred to as distillate or residue preservative.

The production of lubricating oils with a high viscosity index by Hydro splitting is carried out as follows. A heavy faction of a paraff-containing Ron petroleum, such as a vacuum disti hat., a deasphalted oil, or a distillate or residue paraffin slack, is passed over a suitable catalyst under hydrocracking conditions. One or more fractions of lubricating oil are separated from the hydrocracking product by distillation. The corresponding lubricating oil is produced from the lubricating oil fraction obtained in this way by dewaxing this fraction.

The lubricating oils prepared in the foregoing manner may be either as such or after blending as Basisö'le for the production of 10W / 30, low / 40-, 2OWZ ² IO or 20W / 50 oils can be used. As mentioned earlier, these oils are made by adding a number of quality enhancing additives to the base oil

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SAD ORfGfNAt

2361852

manufactured. These accessories can be divided into two groups will. The first group "contains additives to prevent the Oxidation (anti-oxidation agents), additives to prevent corrosion (anti-corrosion agents), additives to prevent foam formation (means to prevent the Foam formation) and additives to prevent the formation of deposits in the engine (detergents), as well as additives to improve the lubricating effect at high pressures (extreme pressure additives). The additives belonging to this group show im generally one that does not exceed 10,000 and is customary Molecular weight far below this value on * Die Additive packages traded by a number of manufacturers generally contain additives of the aforementioned type. The addition of such a lubricating oil additive package to a base oil also changed when the additive package is added in proportionately high concentrations the viscosity index of this oil barely. The viscosity index of the oil changes depending on the composition of the additive package that is added to the base oil not, increases slightly, or may even decrease slightly. The term "additive package" in the present description is a mixture of • lubricating oil additives of the aforementioned first Group understood. A property of this admixture mixture is that when it is added to a base oil in a con- ' centration of 15 percent by weight the viscosity index of this approach (85 percent by weight base oil plus 15 percent by weight admixture mixture) increased by a maximum of 10 units compared to the viscosity index of the base oil. The second for the production of LOW / 30-, LOW / 40, 2ÖW / 40 and 20W / 50 oils used group of quality

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■ - 6.-

Improving additives also includes viscosity index improvers a. The additives in this group are generally - mean a molecular weight above 10,000 and often a lot molecular weight above this value.

The use of viscosity index improvers in manufacture the present multigrade lubricating oils have serious disadvantages. First, the assign used for this purpose Compounds (generally polyalkyl acrylates and polyalky! Methacrylates) insufficient resistance to the shear forces occurring in the engine and are beyond that susceptible to oxidation. This leads to the degradation of the polymer in the engine and also to the deposition of degradation products in the engine, which results in a continuous decrease in the viscosity of the oil »In addition, an orientation; dor polymers under the influence of P. the shear forces occurring in the engine lead to a temporary loss of viscosity when using "the lubricating oil due to the reduction in the" internal friction of the oil. With increasing Shear forces, the effective viscosity of the oil containing polymers approaches that of an oil that does not contain any polymers.

From the above description it is clear that an urgent There is a need for lubricating oils that meet the requirements for lOW / ^ O-, IOVJ / ^ O, 20W / 4Q or 2QW / 50 oils without the addition of polymeric viscosity index improvers fulfill. Attempts to obtain such oils in a "conventional manner, i.e. by distillation and refining

4098 2 5/1 (H 9 ^

making them have not proven successful.

It has now been found that lubricating oils which meet the requirements for 1OW / 3Q-, 1 OW ₇ Ao-T ,. 20W / 40 or '20W / 50 oils either as such or after adding an additive package, but without additives

correspond to a polymeric viscosity index improver i /, in high Yield from a peroxide treatment of a hydrocarbon mixture manufactured. can be achieved if the following requirements with regard to the starting material and the treatment conditions' are fulfilled.

A mineral oil fraction or a mixture of a mineral oil fraction and one or more mono-olefins with 6 to 20 carbon atoms in the molecule must be used as the starting material. The mineral oil fraction used as feed has an initial boiling point of at least 60 ^o C and a paraffin content of. less than 10% by weight, determined "under the standard conditions defined below, and" must have been obtained either in the distillation of a mineral crude oil or a hydrocracking product from the hydrocracking of a mineral oil fraction with a paraffin content of less than 40% by weight, determined under standard conditions .

The term "dewaxing, under standard conditions" a dewaxing process is understood in-the present specification, in which a mixture of a _r paraffinic ul and a Lösung3nittel-in a volume ratio of 1: 4 is heated to a temperature of 50 ⁰ C and then with a Geschvfin-

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A temperature of 1 to 2 ° C per minute is cooled to a temperature of -> 0 ° C will. The solvent consists of equal parts by volume of methy lathy lke clay and toluene. Under "under S t and £ w.-d conditions certain paraffin content of the oil "will serve the on." Way, amount of paraffin separated from 100 g of paraffin-containing oil Understood.

The hydroxide treatment must be carried out by contacting the feed at elevated temperatures with an organic peroxide, which has the general formula ROOP p., In eggs

the groups R and R are alkyl, aryl or acyl radicals.

The lubricating oils produced in this way that meet the requirements for LOW / 30, 10W / 40, 20W / 40 or 20V // 50 oils either air, such or after adding an additional package, but without Addition of a polymeric viscosity index improver J5 " can - as described below - marked will.

The "low / 30 oils" have, at 17.8 ⁰ C clynamisciic a viscosity of at most 24 P and at 98.9 ⁰ C, a kinematic viscosity of at least 7.0 cSt, preferably at least 8.4 cSt. The "low / 40-oils" have, at -17.8 ° C, a dynamic Virskoüität of at most 2k P and at 98.9 ⁰ C, a kinematic viscous:; i-

at least ■ act of at least 10.0 and preferably of / 11.0 cSt on »Di ^ "20W / 40 oils" have a dynamic viscosity of -17.8 ° C at most 96 P and a kinematic viscosity veη at 98.9 ° C at least 10.0 and preferably at least 11.0 cSt. on .

409825/1049 * äd ö & gi'nm.

The "20Y // 5p oils" have, at 17.8 ⁰ C, a dynamic viscosity of at most 96 P and at 9859 ° C has a kinematic viscosity of at least "13 * 0 and preferably at least l4,5 cSt. On."

The invention accordingly relates to a method for producing IOW / 30, IOW / 40, 20W / 40 and 2QW / 5O lubricating oils (as defined above), which is characterized in that a mineral oil fraction or a mixture of a mineral oil fraction and one or more monoolefins) having 6 to 20 carbon atoms in the molecule is contacted at elevated temperatures with an organic peroxide which has the general "formula ROOR", in which R and R are alkyl, aryl or acyl radicals, and that one mineral oil fraction is used as feeding in which an an, fangssledepukkt of at least 36O ⁰ C and a Paraffih'gehalt of less than 10 weight percent (determined under standard conditions), and the fraction in either the distillation of a mineral crude oil or a hydrocracking product from the hydrocracking a. mineral oil with a paraffin content of less than 40 percent by weight (determined under standard conditions).

As a feed for the production according to the invention of IOW / 30-, 10W / 40, 20W / 40 or 20W / 50 oils can either be a mineral oil fraction or a mixture of a mineral oil fraction and one or more monoolefins) with 6 to 20 carbon atoms in the. Molecule to be used. As a starting material for the invention In the preparation of the present lubricating oils, a lubricating oil fraction is preferably used which is used as a residue in the

_Ä4i 409825/1049

filiation of a hydrocracking product from hydrocracking of a deasphalted oil. Others preferably -Used starting materials for "production according to the invention of lubricating oils' are mixtures of one or more Konoolefin (s) with 6 to 20 carbon atoms in the molecule and a distillate oil fraction prepared either in a conventional manner or a residual lubricating oil fraction produced by hydrocracking. The monoolefins used together with the lubricating oil fraction as feed for the process according to the invention preferably contain at least 8 and at most 18 carbon atoms in the molecule. When the method according to the invention is a Mixture of a lubricating oil fraction and one or more C, - ~~ - Monoolefin (s) used as a feed, one achieves an er. Considerably higher yield of IOW / 30, 10W / 40, 20W / 40 or 20W / 50 oils than with the peroxide treatment of a feed which consists only of the lubricating oil fraction as such without added monoolefins. Obviously, the peroxide treatment becomes a considerable one Part of the monoolefins converted to lubricating oil.

The peroxide treatment according to the invention is carried out by contacting the feed over a certain period of time at elevated temperatures carried out with an organic peroxide, which has the general formula R-O-O-R, in which R and R are alkyl, aryl and are acyl radicals. Suitable organic peroxides are e.g. dimethyl peroxide, diethyl peroxide, dipropyl peroxide, di-n-butyl peroxide, Diacetyl peroxide and dibenzoyl peroxide. Di-tert-alkyl peroxides with 8 to 20 carbon atoms in the molecule are preferred such as di-tert-butyl peroxide, di-tert-amyl peroxide, tert-butyl

■.: - ■■ - 409825/1049

tert-amyl peroxide and di-tert-octyl peroxide and in particular, Di-tert.-butyl peroxide used. Since it was found that honoperoxides (peroxides in which only one egg has two hydrogen atoms of hydrogen peroxide by an alkyl, aryl or acyl group are replaced) practically do not react with the mineral oil action and therefore do not see .suitable for the present purpose it is essential that diperoxides in the process according to the invention (in which both hydrogen atoms of the hydrogen peroxide are replaced by an alkyl, aryl or acyl radical) will. The amount of peroxidation used in the method according to the invention can vary considerably '. Usually the peroxide is used in amounts of at least 2.5 percent by weight, based on the entire feed used. Will a peroxide amount of at most 30 percent by weight, based on the total feed, is used, a mineral oil fraction is preferably used as feed which, after dewaxing under standard conditions, a dewaxed oil with a dynamic viscosity at -17.8 ° C of at least 3 P and a kinematic Vinkosi-

'ο · ι

tat at 99 * 9 'C of at least 4 cSt. In the invention Process will preferably use an amount of 5 to 25 peroxide Percentage by weight, based on the total feed, used. The reaction times and reaction temperatures used can do this vary considerably, but response times are usually from 5 minutes to 10 hours and reaction temperatures applied from 100 to 225 ° C. Peroxide treatment is preferred with such a reaction time and at such reaction temperatures carried out that before the end of the treatment at least 90 and preferably at least 95 percent of the

...... 409 8 2 5/10 /, 9 BAD ORIGINAL

oxyds are broken down. The reaction time depends on the rate of degradation of the peroxide in question and can be selected to be shorter, the higher the reaction temperature used ^: .; St. The peroxide treatment can be carried out in one process stage in which the entire required amount of peroxide is added in one amount for feeding, or in several process stages, in which case

Process stage a part of the total required peroxide pressure is added to the reaction mixture.

It is essential that the paraffin content of the mineral oil fraction used as feed to the process according to the invention w-: η Ip: er as 10 percent by weight, determined under standard conditions ,,; amounts to. It has been found that with a paraffin content of this fraction above 10 percent by weight a considerable part of the oil is converted into paraffin, which is probably due to the binding of paraffin molecules to oil molecules. Since the 10'.// 30, 10W / 40, 20W / 40 and 20W / 50 oils should have a low pour point, the paraffin must be removed from the product of the Pcr ⁱ o ;. yi treatment which leads to a loss of yield.

In addition, the binding of paraffin molecules to oil molecules leads

the .

(and / or the binding of araffin molecules to paraffin molecules, which is very likely also taking place), leads to increased peroxy consumption. Since the mineral oil frolct S used as feed for the production of 10W / 30 »> 1OViX ¹ JO, 20W / 40 and 20W / 50 oils are usually derived from paraffin-containing crude oils, they usually have one above the aforementioned 10 Gey. 'icht-spro -, -: - nt lying paraffin content. They are therefore preferably dewaxed before Pcrovyu treatment. Preference is given to grounding

409 & 25/1049 »AD ORIGINAL

Wine oil fractions used as feed for the process according to the invention, which have a paraffin content (determined under standard conditions) of less than 5 percent by weight and in particular of less than 2.5 percent by weight.

For the production of 10V // 50--, 10W / 40 ~, 20W / 40- and 20W / 50 oils are preferably mineral oil fractions as feed used, which after dewaxing under standard conditions to a dewaxed oil with a dynamic " Viscosity at -17.8 ° C and a kinematic viscosity at -98.9 ° C of at least 5 P and 5 cSt, 5 P and β cSt, 10 P and 6 cSt or 10 P and 7 cSt lead.

The method according to the invention makes it possible to produce lubricating oils which, as such, ie without adding additives, meet the requirements of IOW / 30-. 10W / 40, 20W / 40 or 20W / 50 oils. In addition, the method according to the invention makes it possible to produce lubricating oils which as such do not meet the requirements of 10W / 30, 10W / 4Q, 20W / 40 or 20W / 50 oils, which, however, are easy to use without use convert polymeric viscosity index improvers into IOW / 30, IOW / 40, 20W / 4-0 or 20W / 50 oils by adding a certain amount of an additive package. The Zusa.tzmittelpakete 'commercially available, which are now used in practice for the production of multigrade lubricating oils which contain a number of compounds, each of which .to the addition of lubricating oil oil improves one or more properties of that lubricating. Examples of these additive packages

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Additional symbols held are, inter alia. Antioxidants, rust preventives, Anti-corrosive agents, preventive agents of wear and tear, means to prevent foam formation, Detergents, metal passivators and extreme pressure additives. In some cases there are several properties of the lubricating oil improved by a single additive. Should that according to the invention manufactured lubricating oil is used as engine oil, it is the same even if the lubricating oil is already used as such Requirements for a LöW / 30, LOW / 40, 20W / 40 or ■ 20W / 50 oil, it is advisable to use a certain amount of one of these lubricating oils Add additional packages. In the production of. 10V // 50, 10W / 4.0, 2OW / 4O or 20V // 50 oils are preferred such an amount of an additive package to the base oil (the possibly already as such the requirements for a LOW / jJO-LOW / 40-, 20W / 40- or 20W / 50-Ö1) added that one an oil genius receives the 87th, 5 to 95 percent by weight base oil and Contains 5 to 12.5 percent by weight of additives.

The following examples illustrate the invention. In the examples various feeds are treated with di-tert-butyl peroxide. Mach the peroxide treatment will be the. Degradation products of the peroxide (mainly tert-butyl alcohol) Removed plasma from the reaction product.

example 1

Feeding in: mineral oil fraction in the hydrocracking a deasphalted oil, and subsequently by means of the hydraulic topping cleavage product at 590 ⁰ C, and dewaxing the above

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390 ° C boiling fraction has been obtained under standard conditions is. · '

Properties of the "feed:

Initial boiling point: 390 C

dynamic viscosity 'at'-17.8 ⁰ CT 13 P

kinematic viscosity at 98.9 ⁰ C 7.2 cSt

Pour point -Ιο C

By treating this feed for 2 hours at 145 C "with 10 percent by weight peroxide is added practically quantitatively to a lubricating oil with the following properties

'converts:

Initial boiling point € 39O.

dynamic viscosity at -17.8 ⁰ C .22 P ''

kinematic viscosity at 98.9 ⁰ C 9.4 cSt - ■ 'viscosity index l40

. Pour point '--19 ° C

An oil with comparable. Viscosity properties is obtained without Peroxydbehaiidlung from above 390 ⁰ G-boiling feeding in by abtoppt The feed at 440 C. In this case, however, the yield is only 60 percent by weight.

Example

Feed: Mineral oil fraction that is deasphalted during hydro-splitting Oil and by subsequently topping off the hydrocracking products at 400 ° C and dewaxing the above

-; ..- <·: »^ 40982 5/10 4 9 ^;

■ - ιβ - ..

4qo ° C boiling fraction has been obtained under standard conditions is.

Properties of the feed:

Initial boiling point '400 ° C

dynamic viscosity at 17.8 ⁰ C '27 P kinematic viscosity at 98.9 ⁰ C 9, j5 cSt Pour Point -19 C

By treating the feed for 6 hours at 145 ° C. with 9 percent by weight Peroxide, the feed becomes practically quantitative converted into a lubricating oil with the following properties:

Initial boiling point 400 ° C

dynamic viscosity at 17.8 ⁰ C Bo P '■ ■ kinematic viscosity at 98.9 ⁰ C 15.5 cSt

Viscosity index 129

Pour point -20 ° C

Example 3

Feed: kineral oil fraction which is produced during the hydro-splitting of an "asphalted" Oil and by means of topping off the hydrocracking product - at 400 ° C and depai-affine those boiling above 400 ° C Fraction has been received under standard conditions,

Properties of the feed:

Initial boiling point 40O ⁰ C

dynamic viscosity at 17.8 ⁰ C 35 P

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,8th CSt 236 1 652 9 ° c 22nd

■ · -17 -

kinematic viscosity at 98.9 ⁰ C pour point

By treatment with peroxide, this feed is converted practically quantitatively into a lubricating oil with an initial boiling point of 4.0O ⁰ C and a pour point of -23 ° C. The peroxide treatment is carried out in three different ways.

The conditions for both peroxide treatment and the viscometric Properties of the obtained lubricating oil are summarized below.

Experiment No. 1 2 - 3

Peroxide treatment 9 wt .- ^ Feroxide 9 wt .- ^ Peroxide 9 wt .- ^

'- ■' Peroxide

Test conditions

6 hours at 145 ° C

1 hour. 165 ° C

6 hours. 165 ° C

dynamic viscosi
type of lubricating oil
at -17.8 ⁰ C, P 84 93 '· 95 kinematic viscosi
type of lubricating oil
98.9 ^O C, cSt. * - 15.9 i6.3 16.5 Viscosity index 128 127 127

'' From the comparison of the results from experiment 1 and 2 it can be seen that that the use of a higher reaction temperature. a shorter one. Response time allows. A comparison of the results from experiment 2 and 3 show that increasing the response time from 1 to 6 hours at 165 ° C practically no influence on the viscometric

40982 5/1049

"See properties of the obtained lubricating oils on v / eist. Obvious the reaction is practically complete after 1 hour at a temperature of 165 ° C.

Comparative example 1

Feed: Mineral oil fraction that is used in "the hydro-splitting of a deasphalted oil and by means of subsequent topping of the Hydrocleavage product at 400 ° C and dewaxing the above 400 ° C boiling fraction has been obtained.

Properties of the feed:

Initial boiling point 400 ° C

kinematic viscosity at 98.9 ⁰ C 10.1 cSt.

Paraffin content, determined below

Standard conditions' l4 Gevs .-% -

Pour point. +10 ⁰ C

By treating this feed for ⁶ hours at 145 0 CnUt 13.5 percent by weight peroxide, the feed is practically quantitatively converted into a reaction product with an initial boiling point of 400 C, from which, after dewaxing under standard conditions, 46 percent by weight of paraffin and only 5 percent by weight of lubricating oil with the has the following properties:

Initial boiling point 400 ° C dynamic viscosity at -17.8 ° C 52 P kinematic viscosity at 98.9 ° C 12.2 cSt

Pour point -18 ° C

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It can be seen from this comparative example that when treated. a feed with an initial boiling point of at least 560 ^° C. and a paraffin content, determined under standard conditions, of more than 10 percent by weight (in the present case of 14 percent by weight) with peroxide a considerable part of the oil (in the present case J> 2 . Weight percent) is umgeviandel.t in paraffin. '-...-.

B ice ρ ie 1 %

Feed: kineral oil fraction obtained by hydro-splitting a deasphalted Oil and by means of subsequent topping off of the hydro, cleavage product at 400 C and dewaxing the -above 400 ° C boiling fraction has been obtained. .

Properties of the feed:

Initial boiling point. 4o.Q ^J C '-

kinematic viscosity at 98.9 ⁰ C 10.1.cSt

Paraffin content, determined under · ■

Standard conditions 6 wt .- $

Pour point "■ -9 ° C

By treating the feed for an hour at 145 ° C. with 13.5 percent by weight peroxide, the feed is practically quantitatively converted into a reaction product with an initial boiling point of ^ Op ° C, which is obtained after dewaxing under standard conditions ? M percent by weight Paraffin and 76 percent by weight of a lubricating oil having the following properties.

4 0 9 8 2 5/1 0 k 9. ^mu ORiGfNAL

Initial boiling point

dynamic viscosity at -17.8 ° C 90 P \

kinematic viscosity at 98.9 ⁰ C l6.4 est

Viscosity index 130

Pour point -18 ° C

From a comparison of the results of Example 4 and from Vergleichε Example 1 / in which petroleum fractions with the ^ lr-ic ^ s kinematic viscosity at 98.9 ⁰ C (10.1 cSt), but with different paraffin contents (6 or 14 Weight percent) under the same

Conditions _o

/ treated with peroxide. (6 hours, 145 ° C., 13.5 percent by weight peroxide), it can be seen that the use of a feed with a lower paraffin content leads to a higher yield of lubricating oil and that the lubricating oil obtained from the feed with a lower paraffin content has a higher dynamic viscosity at -17.8 C and a higher kinematic viscosity at 98.9 ° C. In Example 4, a yield of 76 weight percent oil with a dynamic viscosity at.-17.0 ⁰ C obtained by 90 P and a kinematic viscosity at 98.9 ° ^ of l6, ^J l cSt, while in Comparative Example 1, a yield of only 5 ^ weight percent lubricating oil with a dynamic viscosity at -17.8 ° C of 52 P and a kinematic viscosity at 9% 9 ⁰ C of 12.2 cSt is obtained.

At. game 5

Infeed: mineral oil fraction, which occurs during the hydro-splitting of a deasphalted Ü3s and by means of subsequent topping off at ² 100 ¹ O and dewaxing of the fraction boiling above 400 ° C

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Standard conditions has been obtained. '.

Characteristics of the feed: '

Initial boiling point ² J-OO ⁰ C

kinematic viscosity at 98.9 ⁰ C 10.1 cSt " ^:

Pour point. "-18 C

By treating the feed for 6 hours at 145 ° C. with 9.5 percent by weight peroxide, the feed becomes practically quantitative . converted into a lubricating oil with the following properties:

Initial boiling point:. '400 ° C. ·

dynamic viscosity "at -17.8 ⁰ C. 9.0 ^P!

kinematic viscosity at 98.9 ° C l6.5 cSt -

Viscosity index - 130

Pour point · ■ -20 ⁰ C - ''

'From the results of Examples 4 and * in which petroleum fractions are treated with the same kinematic viscosity at 98.9 ⁰ C (10.1 cSt), but different paraffin contents (6 or Ό weight percent) with Peroxyü 5, it is apparent that the use of a feed with a lower paraffin content leads to a higher lubricating oil yield. In addition, when using a feed with a lower paraffin content, there is a lower amount of peroxide. necessary. In Example 5, the reaction with only 9.5 percent by weight of peroxide gives about 100 percent by weight of lubricating oil, while in Example 4, only 76 percent by weight of lubricating oil is obtained when reacting with 15.5 percent by weight of peroxide. . -

409825 / 1Q49

■ Comparative example · 2

400 ⁰ C 10 , 1 cSt 11 Weight +2 ° G

Feed: Mineral oil fraction that is deasphalted during hydro-splitting Obtain oil and by means of subsequent dipping at 400 ° C and dewaxing of the fraction boiling above 400 ° C has been.

Properties of the feed:

Initial boiling point

kinematic viscosity at 98.9

Paraffin content, determined under standard conditions

Pour point

By treating the feed for an hour at 1-45 ° C with IJ, 5 percent by weight Peroxide, the feed becomes practically quantitative.

'ο

into a reaction product with an initial boiling point of 400.degree converted from which one after dewaxing under standard conditions 37 percent by weight paraffin and only 63 percent by weight Lubricating oil with the following properties is given:

Anfängssiedepunkt 40ü ° C dynamic viscosity at 17.8 ⁰ C 68 P kinematic viscosity at 98.9 ⁰ C l4,2 cSt

Pour point -18 ° C

From the comparative example it can again be seen that when treating a feed with an initial boiling point of at least 360 ° C. and a paraffin content, determined under standard conditions, of more than 10 percent by weight (in the present case of .11 Ge

■ 409825/1049

weight percent) with Peroxyd.ein considerable ^m oi.] / of the oil (in the ναι · -, lying Pall 26 weight percent) is converted into paraffin.

A comparison of the results of Example 4 and Comparative Example 2, in which kineral oil fractions with the same kinematic viscosity at 98.9 ° C (10.1 cSt), but different paraffin contents (6 or 11 percent by weight) .under the same Conditions treated with peroxide (6 hours, r45 ^P C, 13 * 5 percent by weight peroxide) again shows that the use of a feed with a lower paraffin content leads to a higher yield of lubricating oil and that the lubricating oil obtained there is a has higher dynamic viscosity at -17.8 ^O C "and a higher kinematic viscosity at 98.9 C. In Example 4 " J6 percent by weight of oil with a. dynamic viscosity at -ΐγ, 8 ⁰ C of 90 P and a kinematic viscosity at 98/9 ⁰ C of 16.4 eSfe, while in Comparative Example 2 only 63 percent by weight of oil with a dynamic viscosity at -17.8 ⁰ C of. only 68 P and a kinematic viscosity at 98 * 9 C of only 14.2 cSt can be obtained.

Bei.spiel6 ',

Feed: A mixture of 100 parts by weight of those in Example 3 mineral oil fraction used and 40 parts by weight Ο, ν »^ - monoolefins. _. ·. ,,

By treating the feed for 6 hours at 145 ° C with 9 'weight parts Peroxide is the feed into a Realctionsprodul't uit; p; q-

raan "" - ' _o . -

converts, from / after topping up at i | 00 C 126 parts by weight

4098.2571049:

of a lubricating oil with the following properties:

Initial boiling point 400 C dynamic viscosity at -17.8 ⁰ C 66 P kinematic viscosity at 98.9 ⁰ C 16.4 cSt

Viscosity index 159

Pour point -16C

From a comparison of the results of Example 6 and Experiment 1
from example jj shows that when treating a mixture
from a lubricating oil fraction and monoolefins with peroxide gin 'loil of the olefins (in the present case 26 percent by weight of the 40 percent by weight in the starting material) are converted to lubricating oil, in comparison to Experiment 1 of Example J>, in which no olefins
are used, the addition of the monoolefins results in a
higher yield of lubricating oil bej a higher kinematic viscosity at 98.9 ⁰ C. and a lower dynamic viscosity has -17.8 ° C.

Example 7

Feed: A mixture of 100 parts by weight of the mineral oil fraction used in Example 1 and JO parts by weight of CL,. _O -I '·· «" - "- olefins.

By treating this addition for an hour at 1 ^ 5 ⁰ C with 9 parts by weight of rerpxyd, the addition in (? In Reaktiorujprodii! '' ..

man _o

converted, from deir / after topping at 400 C 125 Gev / j cn '. · .- · -

parts of a lubricating oil having the following characteristics: ¹ ['L

ORfQfNAL /.09825/1049

Initial boiling point. 400 ° C

toxicodynamic viscosity at -17.8 ⁰ C 90 P kinematic viscosity at 98.9 ° C 17.2 cSt

Viscosity index. 1; 51

Pour point. -26 ° C.

Example

Feed: A mixture of 100 parts by weight of a conventional one Wise prepared (Purfuralextraktion. And dewaxing under standard conditions) SpindolÖls and 50 parts by weight C.h ·, / - monoolefins.

Properties of the spindle oil used in the mixture:

.Initial boiling point 37O ⁰ C

dynamic viscosity at -1-7.8 ⁰ C 9 P "kinematic viscosity at 98.9 ⁰ C 4.8 cSt -

By treating this feed for 6 hours at 1 ^ 5. c with 17 parts by weight of peroxide the feed becomes a reaction product converted, from which, after topping off at 370.C I30 parts by weight of a lubricating oil with the following properties are obtained:

Initial boiling point 370 ° C

.Dynamic viscosity at -17.8 ⁰ C 76.P. kinematic viscosity at 98.9 ⁰ C 13.7 cSt

Viscosity dex '. 122 " /

Provide all lubricating oils prepared according to Examples 1 to 8 According to the invention produced lubricating oils. The according to the

409825/1049

Examples 2 to 6 and 8 produced lubricating oils meet the conditions for a 20W / 40-Ö1 (dynamic viscosity at -] 7.8 ° 0 • of at least 24 and at most 9 Q P and kinematic Vis kor; it Ut at 98 * 9 C of at least 12.9 and at most 16.8 eist) as such, i.e. without adding additives. The one prepared according to Example 7 Lubricating oil meets the requirements for a 20W / 50-Ö1 (dynamic viscosity at -17 * 8 C of at least 24 and at most 96 P and kinematic viscosity at 98.9 ° C of at least 16.8 and at most 22.7 cSt.) as solcfres * i.e. without adding Additives. ·

An additive package is added to the lubricating oil produced according to Example 1 which does not meet the requirements for a 10W / 30 lubricating oil and to the lubricating oil produced according to Example 6 which meets the requirements for a 20W / 40 lubricating oil .. Two additive packages are used, the additive packages. A and B are designated. These additional packages differ in terms of the. chemical composition of the additives contained in them, but both have practically the same effect, namely antioxidant effect, rust preventive effect, wear and tear prevention effect :, corrosion protection ¹ -

Metal passivation effect, prevention effect, anti-foaming effect / improved lubricating effect at high pressures and the effect of preventing the formation of deposits in the engine. Under Verv / cndung of ^Zusatzm:; .ttelpakets A, a lubricating oil mixture is produced that contains 92 * 5 weight percent base oil and 7.5 weight percent additive package. By adding the additive package B to the lubricating oil, a lubricating oil mixture is produced, the 89 * 9 percent by weight base oil

A 0 9 8 2 5/1049

and contains 10.1 weight percent additive package. The own

Shafts of the manufactured lubricating oil mixtures are in the next, in the table below. ·

A09825 / 10V9

Tabel

Properties of the base oil

Base oil, without additives package

herge viscosi- kinerna-

steeply activity- tical see visual

according to dex viscosity at at -17.8 ⁰ C,

spi3l 9S, 9 ° C, P

No. cSt

Properties of a lubricant Eigenschaften'eines lubricating oil mixture used of 92.5 wt .- ^ oil mixture used of 89.9 wt .- ^ base oil and 7.5 wt .- $ inflow base oil and 10.1 wt -.% To set medium package A εatzmitte ! Package B

Viscosi- kinematitätsinsehe Vis-

dynamic viscosity in at 98, STC; at -17.8 ° C, dex cSt. P.

Viscominematic dynamism tables see Vi s viscosity

did at

cS

-17.8 ⁰ C,

1 β

140

139

9, Λ 16.4

22nd

6β 10.0

139

18.0

78

A-

cn

CD

cn

N)

The results summarized in the table show that that lubricating oils produced according to the invention, the ^ as those the Requirements for an IOW / jO oil (see example I) '' do not meet simple way without the addition of the usual viscosity improvements High molecular weight agent by adding the additive package A can be converted into 10W / j50 oil. By clogging of the additive package B to one produced according to the invention Lubricating oil that "already meets the requirements for one as such 2OW / 4O-Ö1 is fulfilled, a 20W / 50-Ö1 is obtained (see example 6).

409825/1049

Claims (1)

Patent claims AJ A process for the production of IOW / ^ -, iOVJ / 40 -, * 20W / 40 and 20W / 50 lubricating oils (as defined above), characterized in that a mineral oil fraction or a mixture of a mineral oil fraction and one or more F.or: oolefin (s) with 6 to 20 carbon atoms in the molecule is contacted at elevated temperatures with an organic peroxide, dna has the general formula ROOR, in which R and R are alkyl, aryl or acyl radicals, and that one Mineral oil fraction used as "feed" wii-u, which has an initial boiling point of at least 150 ° C and a paraffin content of less than 10 percent by weight (determined under standard conditions), and which; either in the distillation of a mineral crude oil or a hydrocracking product from the hydrocracking of a mineral oil fraction with a paraffin content of less than ko Gev / icnt% (determined under standard conditions) has been obtained. 2. The method according to claim 1, characterized in that at most J> 0 percent by weight of peroxide, based on the total feed, are contacted with a mineral oil fraction as feed, which after dewaxing under standard conditions to a dewaxed oil with a dynamic viscosity of at least 3 P. leads at -17.8 ° C and a kinematic viscosity of at least 4 cSt at 98.9 ⁰ C. 3 »Method according to claim 1 or 2, characterized in that that as. Mineral oil fraction for feeding a lubricating oil fraction is used as the residue in the distillation 409825/1049 of a Hydrospaltungprodulctes from the Hydrospartüng a Entas-. paused oil has been obtained. '' k. Process according to claim 1 or 2, characterized in that a mixture of one or more cigons ^: F.onoolefin (s) and either a conventionally produced distillate lubricating oil fraction or a residue lubricating oil fraction produced by hydrocracking is used as feed will* 5. - The method according to claim 1 to 4, characterized in that '' that 'as feed component "monoolefins with at least 8 and a maximum of 18 carbon atoms per molecule can be used. 6. The method according to claim 1 to 5 » characterized, that a di-tert-alkyl peroxide with 8 to 20 carbon atoms in the molecule is used from peroxide. 7. The method according to claim 6, characterized in that as Peroxide di-tert'-butyl peroxide is used. 8. The method according to claim 1 to J _1, characterized in that. wit'c uses the peroxide in quantities of 5 to 25 percent by weight, based on the total feed. 9. The method according to claim 1 to 8, characterized gokennzej f..hne} ■ :, that the Peroxydbehandlung with a reaction time of 5 Kinut ··: a to 10 hours and at _{Reaktionstei:} Mf temperatures of 100 223 'C ⁰ "is carried out . 409825/1049 , 32 - ' 10. The method according to claim 9> characterized in that c3-ß the peroxide treatment is carried out with such a reaction time unu bo.i such a reaction temperature that cu u peroxide is degraded to at least 90 percent before the end of the treatment. 11. The method according to claim 10, characterized in that d.ii? the peroxide treatment with such a reaction time and with sol Chen reaction temperatures is carried out that the Perox ^ / a before to
Completion of the procedure / at least 95 percent is dismantled. 12. The method according to claim 1 to 11, characterized., that as a feed a mineral oil fraction with a paraffin content (determined under standard conditions) of less than 5 percent by weight is used. ■ ■ 13 · The method of claim 12, characterized in that <* -. / Is used as feeding in a mineral oil fraction having a paraffin content (determined under standard conditions) of less than 2.5 weight percent used i. lh. Process according to Claims 1 to 13, characterized in that a kineral oil fraction is used as feed which has been produced from _r , ur, a paraffinic crude oil and dewaxed before the peroxide treatment. 15. The method according to claim 1 to Ik / characterized in that for the production of IOW / 30-, IOW / 40-, 2OW / 4O- or 20V, ^T /50-ü'V3.n 40982S / 1049 ÄAD ORJGfNAL Mineral fraction no. as used Zuspelsungen 'are, from which one after the dewaxing under standard conditions entp-araffinierte oils with a dynamic viscosity at 17.8 ⁰ C and a kinematic viscosity at 98.9 ⁰ C of at least 5 cSt P and 5, 5 and P 6 cSt, 10 P and 6 cSt or 10 P and 7 cSt. 16. The method according to claim 1 to 15 / characterized in that IOW / 30-, IOW / 40-, 20W / 4-0 or 20W / 50 oils with a kinematic viscosity of at least 8.4, 11.0, . 11.0 ° or St i4,5 be prepared at 98.9 ⁰ C. ■ 17. The method according to claim 1 to l6, characterized in that that a lubricating oil is produced without the addition of additives the requirements for 1.OW / 30-, 10W / 40-, 20W / 40- or 20W / 50 oils. . · 18. The method according to claim 1 * to l6, characterized in that that a lubricating oil is produced that ..- without adding additives the requirements for a'lOVJ / 30-, 10W / 40-, 20W / 4Q- or 20W / 50-Ö1 not fulfilled; . from which, however, by adding one no additive packs containing lubricating oils containing polymeric viscosity index improvers are produced which meet the requirements for a LOW / 30-, LÖW / 40-, 2CW / 40- or 20W / 50-Ö1, 19. The method according to claim 17 or l8, characterized in that a LOW / 30-, LöW / 40-, 20W / 40- or 20W / 50-Ö1 is produced, which contains 87.5 to 95 weight percent base oil, which optionally the requirements of a 10W / 30 -, - LOW / 40-, 20W / 40- or ^ 09825/1049 5OV // 5O-ÖIS corresponds to ^ and the 5 bis. 12.5 GewLohtGprorT ^ r.t one no polymer viscosity index improvers Contains additive mixture,. 409825/5 049