DE1470505C - Process for the production of lubricating oil base materials - Google Patents

Description

From British patent specification 846 634 it is known from petroleum fractions or deasphalted petroleum residues by treatment with hydrogen over catalysts at elevated temperatures and pressures Manufacture lubricants. In U.S. Pat. No. 2,904,505, for the production of lubricating oils Treated distillate fractions from paraffinic crude oils with hydrogen in the presence of catalysts. It has also been suggested to use paraffin wax or. Hydrocarbon mixtures that are at least Contains 20 percent by weight waxy hydrocarbons, at elevated temperatures and in the presence to isomerize from hydrogen. Among the products of such a process are High viscosity index lubricating oil fractions. In the manufacture of lubricating oil base oils that is suitable for use in motor oils that include multiple SAE grades or numbers however, not only a high viscosity index, but also a minimum viscosity required, and this . the two requirements often conflict with one another.

It has now been found that lubricating oils of the appropriate specification can be produced if Waxes containing no more than 40 percent by weight of oil are used as starting materials. After the procedure of the invention make lubricating oil base oils without the addition of polymeric viscosity index improvers formed the sufficient viscosity and viscosity index for use than in multi-grade engine oils that have a range of at least three normal SAE grades, e.g. B. K) W / 20, 20 W / 30 and 20 W / 40.

The invention relates to a process for the production of cutting oil base materials with a kinematic. Viscosity of at least 5 cSt at 99 ° C and a viscosity index of at least 110, which fall in the area above and to the right of the line ABCD of FIG. 1, wherein a petroleum feedstock at 343 to 454 ° C and elevated pressure with a metal having a hydrogenating effect is treated on an acidic carrier-containing catalyst in the presence of hydrogen, and lubricating oil fractions are obtained by fractionation and dewaxing in a known manner, which is characterized in that a wax with not more than 40 percent by weight of oil is used as the starting material, a platinum group metal as a catalyst a carrier, which consists for the most part of aluminum oxide and to a lesser extent of an acidic component, is used, and works at a pressure of 35 to 210 atmospheres, in particular 35 to 70 atmospheres. , ...-..- ..

The starting materials that are rich in wax are pure or impure waxes with an oil content of at most 40 weight percent (i.e. products containing at least 60 weight percent wax). A a particularly suitable starting material of this type is so-called gatsch. Gatsch becomes during dewaxing heavy petroleum fractions boiling above the gas oil range, e.g. B. waxy Distillates, waxy lubricating oil fractions and residues, are preserved and ceased in general By-product of limited utility. It is therefore for the purposes of the invention particularly suitable as a starting material. It is true that one could use the purified waxes that result from these Are available, use them to produce lubricating oil, but they are relatively expensive materials due to the cleaning process, and it is a particular feature of the invention that the use of these purified materials is not required because a highly active catalyst is used. It is possible to use brightstock waxes or to use distillate waxes.

The catalyst used in the process according to the invention contains 0.0 Γ to 5 percent by weight,

ίο preferably 0.1 to 2 percent by weight, of the platinum, group metal. Platinum is preferred as the platinum group metal.

The carrier contains a major proportion (i.e. more than 50 percent by weight, based on the total catalyst) aluminum oxide, a special one However, the hallmark of the catalyst is the presence of a minor amount (i.e. less than 50 percent by weight of the total catalyst) of an acidic component. It is believed that this acidic component imparts isomerization and cracking activity to the catalyst. This activity is valuable in that it forms hydrocarbons with a high viscosity index and has components with it low viscosity index. However, the acidic component is in a smaller proportion .existent, since too high an acidity tends to increase the cracking activity to a level at which the Product viscosity is too low. Oxides (with the exception of aluminum oxide) are suitable as acidic components of groups III to V of the periodic table, e.g. B. the oxides of boron, silicon, titanium or zirconia, or halogens, e.g. B. fluorine or chlorine. The Group III through V oxides are preferred present in an amount of 5 to 25 percent by weight. The oxides of silicon and are preferred Bors. The halogen is preferably in an amount of 1 to 15 percent by weight, in particular 5 to 15 percent by weight, present. Fluorine is preferred as the halogen. Optionally, two or more acidic components will be present. Particularly preferred are those made from a fluorinated platinum group metal and Aliuminiumoxyd existing catalysts, which are the subject of the German patent 1 198 951 are.

As already mentioned, the temperatures and pressures are in the following ranges:

temperature 343 to 454 ° C

Pressure 35 to 210 atm

For the other main process variables the following areas come into question:

Room flow rate 0.5 to 5 V / V / hour.

Gas volume (circuit or

straight passage) 180 to 1800 m ^s / m ³

These process conditions are determined according to the starting materials and those desired Products chosen. In general, the desired viscosity index of the product can be determined all the more easily achieve the higher the wax content of the starting material. In particular, it was found that high pressures are not required and that good results are obtained at pressures in the range of 35 to 70 atmospheres can be achieved.

These low pressures simplify the construction of the system and reduce operating costs,

However, the use of higher pressures can also be achieved for more than 500 hours.

borrowed. without the need for regeneration.

With an increase in temperature or one of the products from the hydrocatalytic

Reduction of the space flow velocity increases Conversion takes place after the separation of the water

the viscosity index lowering the viscosity 5 of the substance-rich gas that under the lubricating oil range

and increased breakdown to lower-boiling pros-boiling material separated by fractionation,

ducks An intersection point in the range from 350 to is suitable

With increasing molecular weight of the starting 450 ° C.

materials will also be the leeway with regard to the soil products of this fractionation

the choice of process variables is greater, since the stronger io is then processed into the desired lubricating oils,

Reduction in viscosity, which is accepted by dewaxing or dewaxing

the application of more stringent conditions and fractionation to the desired cuts,

gen allows that the advantage of an increase in the order in which the dewaxing and

Have viscosity index. It is also possible for fractionation to be carried out is indifferent.

the higher molecular weight in combination with 15 The dewaxing can be done in any way.

to use milder conditions, followed by products, preferably a temperature in the

with a higher viscosity and a sufficient viscosity range of -18 to -40 ° C is used,

quality index can be obtained. Preferred as. hochmole- The various lubricating oil fractions can,

Cellular starting materials will be bright stock - as is customary, to be mixed as needed

Waxes and deasphalted residues. For longer, 20 finished lubricating oils with the desired SAE numbers

Operating time can maintain the process conditions for mern. In cases where the viscosity

Compensation for falling catalyst activity in the known index is above the required minimum,

Way to be changed, e.g. B. by increasing the you can also use common oils of moderate

Temperature. Viscosity index can be mixed. - For example

After the activity of the catalyst is below a 25 can according to the method according to the invention

If the acceptable level has fallen, the light lube oil fraction produced by the catalyst becomes high

tor regenerated in a known manner. With fluorine-containing viscosity index, but moderate viscosity with usual

Catalysts are then, if necessary, bright stock oils with a moderate viscosity index.

the fluorine content can be remixed by a further fluorination to reduce the viscosity without excessive

set. 3 ° lowering of the viscosity index.

The entrances to the hydrocatalytic zone. ,,

Set materials can be fresh material as example 1 also the so-called "unreacted" material

include the product. This unconverted A catalyst 0.55 ⁰ Zo platinum and 6.0 GeMaterial may be either a residue containing 35 weight percent fluorine on alumina as the carrier of the separation of the desired Schmierölfraktio-, was prepared as follows: NEN by fractionation remains , or it can be 500 cm ^{3 of} a commercially available platinum-aluminum wax which has been separated from the products boiling in the lubricating oil sector with a platinum content of 0.58 ge or more. percent by weight were placed in an upright reactor. It was found that the circuit grows easily filled and can be converted by circulating dry nitrogen ter as fresh starting materials at 354 ° C and at an operating pressure of 6.9 atmospheres and that their use is not only the total flushing until the water content of the lubricating oil yield from the reactor increased, but also the emerging nitrogen was less than 10 ppm. Aiming at a certain quality level makes it easier. The reactor was then filled with carbon tetrafluoride

In particular, the fresh starting materials 45 brought a pressure of 8.3 atmospheres, whereupon the gases

considerable amounts of sulfur compounds can be circulated for 10 hours,

The catalyst was then used for hydrocatalytic

conditions at least partially in sulfur water- see treatment of a obtained from Middle Eastern crude oil-

substance can be converted. This, however, results in a bright stock mess with the following key figures

no poisoning of the catalytic converter, since operating 5 ° is used:

Solidification point 64 ° C _;

oil content 10.7 percent by weight

Average molecular weight. 698

Sulfur content .... 0.44 percent by weight

After the hydrocatalytic treatment, 60 was converted into a fraction 380 bis under reduced pressure

the hydrogen-rich gas for circulation from 430 ° C, one fraction from 430 to 490 ° C, one fraction

separated and the product fractionated in two stages, 490 to 550 ° C and one above 550 ° C sie-

being decomposed in one stage at normal pressure and in the residue. The factions were

other stage worked under reduced pressure mixed in such a way that one encompasses several SAE grades-

and a separation of the material into a base oil 10 W / 20 above 380 ° C 65 with a kinematic viscosity

and a product boiling below 380 ° C, 8.5 cSt at 99 ° C and a viscosity

was men. The. Higher boiling fraction was obtained when index greater than 120 was obtained.

-29 ° C and dewaxed by fractionation.

applied conditions and the results obtained
are listed in Table 1 below. While
of the experiment, which lasted more than 400 hours, the temperature was gradually increased to keep the conversion constant. hold while the other variables were not changed.

Table 1 Conversion of Brightstock Gatsch

Running time, hours 84 to 107! 300 to 323 I 484 to 501

Temperature, ° C ..

Pressure, atü:

Room flow velocity V / V / hour

Gas cycle, m ³ / m ³

Make-up gas ........

Product output.

Gaseous products, percent by weight

Liquid products, percent by weight

Liquid product boiling below 380 ° C, percent by weight

Reclaimed wax, weight percent

Dewaxed oil above 380 ° C, weight percent

Lubricating oils

380 to 430 ° C

Yield, percent by weight (based on input) "..

Kinetic toughness in cSt at 99 ° C

Kinetic toughness in cSt at 37.8 ° C

Viscosity index

SAE no

430 to 490 ° C

· .- Yield, percent by weight (based on input) ..

Kinetic toughness in cSt at 99 ° C

Kinetic toughness in cSt at 37.8 ° C

Viscosity index.:

SAE no

490 to 550 ° C

Yield, percent by weight (based on input) ..

Kinetic toughness in cSt at 99 ° C

Kinetic toughness in cSt at 37.8 ° C

Viscosity index

SAE no

Residue yield, weight percent above 550 ° C
(based on use)

6.7

416 427 438 49 49 49 1.0 1.0 1.0 270 270 270 H ₂ H ₂ H ₂ 4.4 ^:
95.6 4.0
95.0 3.5
96.5 50.0 35.0 39.6 18.8 28.3 31.7 26.8 31.7 25.2 6.9
6.8
41.5
127
lOW / 20 12.2
4.5
"22.9
124 7.2
5.4
30.3
126 6.6
9.6
68.3
124
20 W / 20 8.8.
9.6
70.6
121
20 W / 20 14.2
11.9
93.9
120
20 W / 30 6.6
12.9
105.9
119
20 W / 30 5.7
13.7.
116.0
118
20 W / 40 2.1
24.3
281.5
112

5.0

1.7

Example 2

The by dewaxing the product of
Example 1 recovered slack was again 6o with the same catalyst as in Example 1
and treated with the same product work-up
except that the intersection between
the third lube cut and the backlog
5O4 ' ^J C lay. The process conditions and the results obtained are shown in Table 2 below
specified.

Table 2

Conversion of the wax recovered from processing brightstock satchel

Running time, hours .... 52 to 63

Temperature, 399 ° C

Pressure, atü 49

Room air velocity, V / V / hr. 1.0

Gas circuit, nWm ³ 270

Make-up gas hydrogen

Product output

Gaseous product, weight percent 3.5 Liquid product, weight percent ...... 96.5

Product reconditioning

Liquid product boiling below 380 ° C, weight percent based on

on use.;

Recovered wax, weight percent dewaxed oil, weight percent

Lubricating oils
up to 430 ° C
Yield, percent by weight

(based on use)

Kinetic toughness in cSt

at 99 ° C

• Viscosity index

52.0 16.1 28.4

17.5

6.36 36.02 133

up to 490 ° C
Yield, percent by weight

(based on use) ..
Kinetic toughness in cSt

at 99 ° C

at 37.8 ° C

Viscosity index

SAE number ............

5.2

11.35 82.53

126

20 W / 30

up to 504 ° C \

Yield, percent by weight

(based on stake) '5.5

Kinetic toughness in cSt

at 99 ° C .... 16.74

at 37.8 ° C 139.7

Viscosity index 125

SAE number 20 W / 40

Residue boiling above 504 ° C,

Weight percent (based on the insert) 0.2

A comparison of the 'results in Table 1 (Example 1) and Table 2 (Example 2) shows that by treating the recovered wax Products were obtained which had a higher viscosity index than the products obtained from the original gate use obtained at a lower temperature of the hydrocatalytic treatment became. This is in FIG. 2 shown graphically. In this figure, the .visosity indices are according to the two examples, the products obtained are shown as a function of the viscosity. The special one The benefit that is achieved by recycling the "recovered" wax is derived from this Presentation clearly. ·.

Example 3

The catalyst prepared according to Example 1 was used to produce a distillate grease with the following characteristic numbers hydrocatalytically treated: * · ■

Freezing point, ⁰ C 53

oil content, weight percent 33

. Average molecular weight .. 502

as sulfur content, percent by weight .., 0.67

The hydrocatalytic treatment and the product work-up were carried out in the same manner as carried out in Examples 1 and 2 with the exception that the points of intersection for the fractionations were chosen differently. These values are shown in Table 3 below along with the key figures the fraction and the conditions of the hydrocatalytic treatment used.

Table 3 Conversion of distillate gossip

41 to 51

Running time, hours

I 195 to 210 I 250 to 262

Temperature, ° C

Pressure, atü ......:

Room air velocity, V / V / hr

Gas cycle, m ^s / m ³ ;

Make-up gas

Product output

Gaseous products, percent by weight

Liquid products, percent by weight

Liquid product boiling below 430 ° C, weight percent

Reclaimed wax, weight percent

Dewaxed oil, percent by weight

Lubricating oils

430 to 450 ⁰ C

Yield, percent by weight (based on input).

Kinetic viscosity in cSt at 99 ° C ..:

Kinetic toughness in cSt at 37.8 ° C

Viscosity index

SAE number

450 to 470 ° C

Yield, percent by weight (based on input).

Kinetic toughness in cSt at 99 ° C

Kinetic toughness in cSt at 37.8 ° C ...:

Viscosity index

SAE grade _

* 450-452 ° C and residue is chromatographed over 452 ⁰ C.

800
49

1.0
720

H ₂

0.7
99.3
73.5

9.2
16.6

- 7.2
5.95
33.29
132

8.9 *

8.06

51.93

127

10 W / 20

800
49

1.0
720

1.2
98.8
40.8
20.6
37.4

12.9

780
49

1.0
720
H ₂

1.3
9S, 7
19.6
36.4
42.7

3.9

14.6
5.23
28.41
128

23.3

66.4

37.7
121
10 W / 20

109 651Λ

Continuation table

10

Running time, hours 41 to 51 195 to 210 250 to 262

Lubricating oils.-.- :.
470 to 490 ° C

Yield, percent by weight (based on input)

. Kinetic toughness in cSt at 99 ° C

Kinetic toughness in cSt at 37.8 ° C.

: Viscosity index

: SAE number ... ...,. '.

Residue above 490 ° C

Yield, percent by weight (based on input)

Kinetic toughness in cSt at 99 ° C .......

Kinetic toughness in cSt at 37.8 ° C

Viscosity index

SAE number '.

'* 450 to 452 ° C and residue above 452 ° C

0.5 *

3.4 15.1 6.32 8.81 37.19 ... 63.05 127.; 120 - 20 W / 20 6.5. 0.4 7.62 - 49.34 ' ■ - ' 125 ; > 10 W / 20

The lubricating oil fractions and products obtained according to the examples all have viscosity indices and viscosities that are within the above range and on the right. Side of the line ABCD of FIG. It can be seen that the fractions without any polymeric additive can be used to improve the viscosity index and can be combined into motor oils which have three normal SAE numbers, e.g. E.g. 10 W / 20 and 20 W / 30. In two cases, oils comprising four normal grades, namely 20 W / 40, were obtained.

Claims (3)

Patent claims: 1. A method of making lubricating oil base stocks having a kinematic viscosity of at least 5 cSt at 99 ° C and a viscosity index of at least 110 falling within the range above and to the right of the line ABCD of FIG C and elevated pressure with a catalyst containing a hydrogenating metal on an acidic carrier in the presence of hydrogen, and lubricating oil fractions are obtained by fractionation and dewaxing in a known manner, characterized in that the starting material is a wax with not more than 40 percent by weight oil is used, as a catalyst a pfeting group metal on a support, which consists mainly of aluminum oxide and to a lesser extent of an acidic component, uses, and works at a pressure of 35 to 210 atmospheres. 2. The method according to claim 1, characterized in that the treatment with hydrogen is worked at a pressure of 35 to 70 atmospheres. ■ 3. The method according to claim 1, characterized in that separated from the product, unconverted material is returned to the hydrocatalytic zone. 1 sheet of drawings