DE2453773A1 - METHOD FOR MANUFACTURING OLEOPHILIC MATERIAL - Google Patents

Description

PATtNTA ^ WMTE 2 A 537 7

DR.-ING. BY KREJSLER DR.-lNG. SC ^ ONWAlD DR.-ING. TH. MEYER DR. FUES DIPL-CHEM. ALEK VON KREISLER DIPL-CHEM. CAROLA KELLER DR.-ING. KLÖPSCH DIPL-ING. SELTING

5 COLOGNE 1, DEICHMANNHAUS

Cologne, November 12th Fu / Ax

The British Petroleum Company Limited, Britannic House, Moor Lane, London EC2Y 9BU (England).

Process for the production of oleophilic material

The invention "relates to the preparation of oleophilic Graphite, mixtures of oleophilic graphite with metals and of oleophilic metal sulfides.

British patent specification 1,168,785 describes a method for the production of oleophilic graphite by grinding graphite in an organic liquid in a vibrating ball mill.

British Patent 1,527,375 describes a method for the production of oleophilic graphite, mixtures of oleophilic graphite with metals and of oleophilic metal sulfides by grinding graphite or metal sulfides in an organic liquid in an agitator mill.

Oleophilic graphite is suitable as a solid lubricant and as Thickening agents for lubricating greases. The British patents 1 168 764 and 1 327 375 describe the usage of oleophilic graphite as a thickener for lubricating greases. In the known processes for the production of oleophilic Graphite, mixtures of oleophilic graphite with metallon or metal sulfides had to be the graphite, the graphite with the metal. the metal sulfides about 8 hours

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be grind to a graphite, graphite metal Geniisehe
and to obtain metal sulfides with satisfactory properties.

The invention relates to a method for production
of oleophilic graphite, oleophilic graphite / metal mixtures and oleophilic metal sulfides using a
[Mill, with the good cleophile graphite, graphite-metal mixtures and metal sulfides in a much shorter time than with
the mills used so far can be obtained. j

° The method according to the invention for the production of oleophilic graphite, oleophilic graphite / metal mixtures or
of oleophilic metal sulfides is characterized by
that one can graphite or graphite with a metal or a
Metal sulfide in an organic milling liquid in a
^ Mill grinds, in whose grinding chamber a horizontally mounted one
Shaft is arranged with attached stirring elements
and are present in the grinding media, the peripheral speed of the stirring elements at least 10 m / sec. amounts to. j

In the mill used for the purposes of the invention, fin-. The grinding takes place by moving the grinding media through the rotary! hung of the axis with the agitator elements attached to it

. .to be stirred and moved. j

ί The mill is preferably with the organic grinding liquid so filled - that there is no air in the grinding chamber is, and the axle is preferably in airtight bearings

stored. . j

The grinding media preferably consist of balls of high ^; Density for example made of steel or zircon. The balls ί preferably have a diameter of less than 5 mm.

The grinding chamber is preferably made of steel. .j

The stirring elements may take the form of discs, _rods; Have paddles or propellers. A mill is preferred, - '

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whose stirring elements consist of disks, which are optional are perforated. Suitable mills are manufactured by Willy A. Bachofen Maschinenfabrik Basel and are sold under the name "Dyno Mill".

Any organic liquids that do not react with the millbase or the grinding media are suitable as organic grinding liquids. Preferably organic ¹ milling liquids are used which have a surface tension: less than 75 dynes / cm at 25 ° C, a viscosity of j less than 600 cSt at 38 ⁰ C and a boiling point of Weni-j ger than have 500 ⁰ C. Examples of suitable organic grinding liquids are hydrocarbons, for example through -!

Hydrocarbons obtained by distillation of crude oil and oxygenated hydrocarbons such as alcohols to name. The preferred organic grinding fluids are paraffinic coals.

If the oleophilic graphite, the mixture of oleophilic Graphite with metal or the metal sulfide to be used as a thickener for lubricating greases can do that Grease in situ by grinding the graphite, graphite with metal, or metal sulfide in a lubricating oil are formed. The lubricating oil can be used alone or in admixture with another liquid. If that Lubricating oil is mixed with another liquid, preferably becomes a hydrocarbon as the other liquid used, which is more volatile than the lubricating oil and through Distillation is separated from the product.

The process according to the invention can be carried out batchwise or continuously. In the batch process _; the mill is filled with the grinding media, the grinding stock and the organic grinding liquid, whereupon it is operated for a certain time. After grinding, the slurry formed from liquid and ground material is separated from the grinding media.

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In a preferred embodiment of the invention, the mill is operated in a cyclical process. In this embodiment, the mill forms part of a closed circuit , in which the organic grinding liquid and the grinding stock can be circulated. The circuit is filled with the organic grinding liquid, after which the solid material and the grinding media are placed in the mill. The circuit is closed and the mill is operated while the organic grinding liquid and the ground material are continuously circulated through the mill. Filters are provided to prevent the grinding media from leaking out of the mill. Furthermore, a storage container can be connected to the circuit, in which organic grinding liquid is stored during grinding to take account of changes in volume during grinding.

If a continuous or semi-continuous process is to be used, several mills can be used be connected in series, with the product from the first mill, the second mill, etc. to the last Mill fed, wq the product is drawn off. This eliminates the need for circulation avoided.

Normally, during the grinding of the graphite, the graphite-metal mixture or the metal sulfide, the Viscosity of the organic grinding liquid and grist slurry. To prevent the If the viscosity becomes too high for effective grinding, the mill can be heated or additional organic grinding liquid can be added during milling.

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In one embodiment of the invention, a lubricating \ fat is prepared as follows: graphite, a graphite-metal; Mixture or a metal sulfide is ground in a lubricating oil j. Which is heated to such a high temperature that it is prevented that the mixture of graphite or metal sulfide and oil is too viscous and the grinding efficiency is poor. The heat generated by the grinding can bring the oil temperature to a sufficiently high value. After grinding, the hot slurry of oil and oleophilic graphite or of oil and mixture of oleophilic graphite and metal or of oil with oleophilic. Metal sulfide separated from the grinding media. More oil is added as required and the mass is optionally passed through a homogenizer. Additional oil can be added during milling to keep the viscosity within the desired limits.

The heating of the oil can be done by the oil flowing through the circulatory system or the steel housing or both are heated.

Graphite and metal sulfides are used as regrind, e.g. molybdenum disulfide, antimony trisulfide, lead sulfide, Tungsten disulfide and tin sulfide. Mixtures these metal sulfides with graphite can also be ground.

Metals of groups IB, 2B, J5, H- and 5 of the periodic table according to Mendelejev and the transition metals are preferably used as metals in the graphite-metal mixtures. In particular, copper, zinc, aluminum, tin, antimony, iron, cobalt are used as metals

30. and any alloys of these metals are used.

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Lead is particularly preferred as the metal.

In a preferred embodiment, there is
Mixture of graphite and metal from 10 to 50% by weight "
Lead and from 90 to 70 wt -.% Graphite.

The grease formed contains the oleophilic one

Graphite, the mixture of oleophilic graphite and metal
or the oleophilic metal sulfide, preferably in one
Amount from 10 to 10% by weight .

The lubricating greases based on oleophilic graphite
Polymers can be added to increase their hardness
increase, ie lower their penetration values. the
Polymers can in the context of the invention during
after milling or after milling.
The addition is preferably carried out immediately before the end of the milling process.

Preferred polymers are polyethylenes from!

high density and atactic polypropylene. The poly- j

Merisate can be used in amounts of up to 5% by weight , based on j

on the weight of the fat, alone or in a mixture j

· Be added. These polymers can also be used for! Adjustment of the viscosity of the grinding liquid added

will. j

Various common fat additives, e.g. additives
to increase the load capacity or high-pressure ^additives: rust and corrosion prevention additives, can likewise j if added during milling or after milling
will. ι

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Oleophilic graphite adsorbs ή-Dotriaoontane from n-heptane preferentially compared to adsorption from n-butanol from n-heptane. The degree of affinity for the adsorbed liquid can be determined by the measurement the heat of adsorption can be determined.

The heat of adsorption of n-dotriacontane from n-heptane is a. Measure of the base area of the graphite existing area, i.e. the area which is formed by the areas designated as the base and by the splitting of the Graphite is formed parallel to the main surface of the graphite crystal resulting areas, and the Heat of adsorption of n-butanol from n-heptane is a measure of the area known as the polar area of the Graphite, which is formed by splitting the graphite crystals perpendicular to the main surface of the graphite crystals. The heat of adsorption can be measured with a flow microcalorimeter are measured as described in "Chemistry and Industry" from March 20, 1965, pages 482 to 489.

It has been found that the ability to thicken oils to fats with increasing ratio of Base surface to polar surface gets better. Preferably the ratio measured in this way is from base surface to polar surface 10: 1.

25th

The invention is further illustrated by the following examples.

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• f 8,

example 1

A mill with the trade name "Dyno-MiIl" (manufacturer Willy Bachofen Maschinenfabrik Basel). This "mill" consists of a cylinder with an inner diameter of 11.0. cm and a length of 3.0 cm (internal volume 0.3 l) and is provided with a corrugation on the inside. Of the ... The cylinder is arranged horizontally and a disk 9.6 cm in diameter is attached to the shaft.

The cylinder was charged with 150 ml of a solution of 60 g of fish oil lubrication of the type 110/95 (a solvent refined lubricating oil having a viscosity of 110 RediüDod no. 1 seconds at 37.8 ⁰ C and a viscosity index of 95) in heptane filled.-250 cm steel balls with a diameter γ, οη 1.0 mm and 10.5 g of powdered synthetic graphite were then placed in the mill.

The mill was 30 minutes at a speed of 3000 rpm (Peripheral speed 15 m / sec.) Operated. After grinding, the mixture of n-heptane, oil and graphite was taken out and the n-heptane is distilled off. The fat formed had the following properties:

Table 1

Rest penetration 1/4 scale 200

Walk penetration 1/4 scale 252

Bleeding, 100 ⁰ C, 30 hours,
Weight loss 0

Example 2

Which was ^v beseech with a similar mill as in the in

Example 1 described experiment carried out. The meal- '.

cylinder had an inner diameter of 7.5 cm and a '.

13 cm long and contained a centrally mounted shaft;

and three stirring discs. The panes had a through |

knife of 6.4 cm. The cylinder was made with 510 cm ³ steel '

balls of 1 mm diameter filled, and the agitators were at 6000 rpm (circumferential speed 20 m / sec.)

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turns. Through the cylinder was 1 1 of a base oil (same oil as in Example 1) 150 g of powdery _synthetic: containing see graphite, in an amount of 1.2 1 / h. ge ] pumped. The temperature of the slurry at the outlet of deni cylinder was allowed to rise to 118 ^0G. The agitation of the slurry was continued for -40 minutes. After a grinding time of 40 minutes, the product I was a soft fat i with a resting penetration of 436.

Example 3

The mill used in the experiment described in Example 2 was switched into a continuous circuit in such a way that the ground material could be continuously circulated through the milling cylinder j with the aid of a pump connected to the circuit j. A magnetic filter and a feed container provided with a stirrer were also inserted into the circuit. 850 g of a lubricating oil were circulated through the mill without water cooling the mill. While the
Mill was operated at 4500 rpm (peripheral speed 15 m / sec.), The temperature of the oil reached 80 ⁰ C im

Storage container and 100 ⁰ O in the grinding chamber; The oil were! 0.5 wt .- ^ of a high density polyethylene ("Rigidex
Type 9 ") was added. After 150 g of graphite had been added, the water-cooling of the mill was started and the speed was increased
increased to 6000 rpm (circumferential speed 20 m / sec.).

Milling was continued for 3.5 hours and the resulting fat was cooled.

The grinding conditions are given in Table 2 (in Example 4).

Example 4

The experiment described in Example 3 was repeated under different conditions. The results are shown below in Table 2 named.

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Act 2 Grinding time, hours Example 2 Example 3 Graphite weight, g 7th 3 Amount of graphite in wt .- ^ 160 150 Weight of the oil . 15th 15th Walk penetration, 60 strokes 850 g 937 g * Resting penetration 310 291 ' Bleeding, wt .- $ 248 - ■ 0 2.4

• "" The oil used was a synthetic ester with the following characteristics

^r "numbers used * ■. j

ι viscosity at 37.8 ⁰ C 28.0 cSt ■

Viscosity at 99 ^° C. 5.3 cSt

Viscosity index - 135

Pour point. -65 ° C ^!

Vapor pressure "at 20 ⁰ C 8x10 ~ 9 Torr"

I The ester was made by reacting 28 moles of caprylic acid,

10 moles of trimethylolpropane and 1 mole of sebacic acid were prepared. The ester contained common antioxidants, anti-wear additives and anti-foam additives.

Example 5 j

The experiment described in Example 3 was repeated,
However, instead of graphite, a graphite-lead mixture was used, which was filled in with a powdery
• 25 graphite-lead mixture produced in the feed tank
became. The experiment was repeated using a synthetic ester oil. The results are shown in Table 3 below. !

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10

20th

30th

! 35

- 11 -

Table 3

850 937 * 317 316 - 276 4.7 3.0

Grinding time, hours

Weight .- $ graphite / lead mixture (14.0 $ graphite) (14, OjS graphite)

17.6 % 17.696

Oil weight, g
Walk penetration
Resting penetration
Bleeding

^ Same synthetic ester oil as in example 4

Comparative experiment

A fat which had similar properties to the fat produced according to Example 3 was produced using an agitator mill which was provided with a vertically mounted shaft and horizontally attached perforated plates. The peripheral speed of the plates was 10 m / sec. This mill is marketed under the name '- "Sussmeyer Type RS-2". It was in a closed circuit. The same graphite content,
the same base oil by type and quantity and the same
Polymer as in Example 3 were used. The results are given in Table 4. In column A are the at; the result obtained in the experiment described in Example 3 and in column B the results obtained in the comparative experiment.

Table 4

Use per unit volume of the grinding chamber, kg / 1 .1.6

Grinding time, 3.5 hours

Walk penetration of the fat, 60 strokes, mm 345

Power consumption, MJ 4.0

Grinding capacity, kg / hour 0.27

Relative efficiency: amount of grease generated e / hour d..per MJ, kg. . 0.02

347

12.2 0.48

.1

0.002

These values show that the relative efficiency of the for
for the purposes of the invention used mill 10 times

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of the mills used so far

ι:: j

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Claims (13)

Claims 1) Process for the production of oleophilic graphite,
oleophilic graphite / metal mixtures or oleophilic metal sulfides, characterized in that
that you can graphite or graphite with a metal or
a metal sulfide in an organic milling liquid
grinds in a mill, in the grinding chamber of which a horizontally mounted shaft with attached stirring elements is arranged and in which the grinding media are present, the peripheral speed of the stirring elements at least 10 m / sec. amounts to. .. j 2) Method according to claim 1, characterized in that j a mill is used whose grinding chamber is connected to the j organic grinding liquid is filled, and in which the; Shaft is mounted in airtight bearings'. j 3) Method according to claim 1 or 2, characterized in that net that steel balls with a
Diameter · less than 5 mm used. ■ ■ 4) Method according to claim 1 to 3, characterized in that that perforated disks are used as stirring elements. 5) Method according to claims 1 to 4 »characterized; that one uses an organic grinding liquid that! a surface tension of less than 75 dynes / cm; 25 ° C, a viscosity of less than 6CO cSt
37.8 ⁰ G and a boiling point below 50O ⁰ O has. 6) Method according to claim 1 to 5, characterized in that 'that the metal sulfide used is molybdenum disulfide, antimony tri \ sulfide, lead sulfide, tungsten disulfide or a tin sulfide. | 7) Method according to claim 1 to 6, characterized in that that lead is used as the metal in the metal-graphite mixture. 509820/1049 - i.4 - ί 8) Method according to claim 7 »characterized in that a graphite-lead mixture is used, the 10 to Contains 30% by weight of lead and 90 to 70% by weight of graphite. 9) - Process according to claim 1 to 8, characterized in that one.als organic grinding liquid is a lubricating oil used. 10) Method according to claim 1 to 9, characterized in that that the lubricating oil is heated during milling. ί 11) Method according to claim 1 to 10, characterized in that the grist is used in such an amount that after grinding and cooling the shark oil the latter is thickened into a fat. j 12) The method of claim 1 to 11, characterized in that the ground material in a comparable amount of 10 to 30So, based on the weight of lubricating oil plus millbase] applies. 13) Method according to claim 9 to 12, characterized in that the lubricating oil with a more volatile Hydrocarbon mixes and the more volatile hydrocarbon is distilled off after grinding. .14) Method according to claim 1 to 13 »wherein the mill; as part of a closed circuit that includes a storage tank and recirculation of the organic grinding liquid and the grist and made with the organic grinding liquid | is filled, with the grist and the grinding media ί in the mill and the grinding media with the help of Filters are kept in the mill, characterized in that the organic grinding liquid during of grinding is continuously circulated through the mill. · J 509820/1049