DE1271292B - Process for the production of lubricating oils or lubricating oil components - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

Clog

German KL: 23 b-1/04

Number:
File number:
Registration date:
Display day:

1271292
P 12 71 292.4-44
December 6, 1965
June 27, 1968

The invention relates to a method for producing lubricating oils or lubricating oil components from petroleum waxes by isomerizing treatment.

Petroleum wax is of particular interest as a source of lubricating oil because it is about the same molecular weight like lubricating oil. It differs from lubricating oil in that it has fewer isoparaffins, d. H. contains fewer branches in the long paraffin chains. Because of this, the wax becomes treated under suitable conditions, whereby the hydrocarbon constituents of the wax are in isomers which have practically the same molecular weight but a more branched structure exhibit.

The production of lubricating oils by catalytic isomerization of petroleum waxes is from the U.S. Patent 2,668,790, Belgian Patent 537,743 and French Patent 65 963, which correspond to one another, as well as the German patent specification 931 826 known. ao

The processes described in these patents operate with an isomerization zone in which a sulfur-sensitive catalyst is used. In order to achieve acceptable lubricating oil yields, relatively strict process conditions have to be applied from the beginning, whereby on the one hand the starting material is cracked to a considerable extent into less valuable lubricating oils (boiling point ^{approx. 308 to 400 °} C.) and ^{hydrocarbons boiling below 300 ° C.} and, on the other hand, there is only little leeway available to compensate for the rapid decrease in catalyst activity due to the poisoning of the sulfur-sensitive catalyst due to an increase in temperature.

Furthermore, from the German Auslegeschrift 1033193 there is also a one-step process for Isomerization of petroleum wax known, which works with a catalyst that is insensitive to sulfur. This process is even with a fresh catalyst and is below that in terms of lubricating oil yield Under favorable conditions, only unsatisfactory yields of lubricating oil with an acceptable viscosity index can be obtained. These known methods for Production of lubricating oil by isomerizing (2) petroleum waxes can thus all with regard to the The lubricating oil yields, the achievable viscosity index and / or the catalyst life are unsatisfactory, so there is a need for a better method in this regard.

The object of the invention was to create a method which overcomes the disadvantages of the methods according to the prior art, ie a method, method for the production of lubricating oils
or lubricating oil components

Applicant:

Shell Internationale Research Maatschappij N.V., The Hague

Representative:

Dr. E. Jung and Dr. V. Vossius, patent attorneys,

8000 Munich 23, Siegesstr. 26th

Named as inventor:

Emil Oscar Kindschy, Pasadena, Tex .;

Charles Terrel Adams,

Houston, Tex. (V. St. A.)

Claimed priority:
V. St. v. America 8 December 1964
(416 894)

after which lubricating oils or lubricating oil components are formed by isomerizing treatment of petroleum waxes Can be produced in high yield and with a high viscosity index without the catalyst in short Needs to be regenerated or replaced at intervals.

This object is achieved by a method for producing lubricating oils or lubricating oil components dissolved from petroleum waxes by isomerizing treatment, which is characterized by

(1) that the wax is in a first zone in the presence of hydrogen and one opposite sulfur stable catalyst, which has a hydrogenation-dehydrogenation component and a solid, contains acidic, refractory supports, is isomerized;

that of the outflow obtained in the first zone at least the portion that is in the area of the Lubricating oil boils, if necessary after separating off those boiling below the lubricating oil boiling range Hydrocarbons, in a second zone in the presence of hydrogen and one opposite Sulfur sensitive catalyst that has a hydrogenation-dehydrogenation component and a solid, acidic, fireproof

809 567/507

3 4

Contains carrier is isomerized, the iso-platinum oxides and sulfides. There can be more than one merization present in both the first and the second zone at temperatures between 371 and 371. Very good results are achieved in the first zone 427 ° C, pressures between 35 and 140 ata, space with catalysts, which are made up of two or more speeds between 0.1 and 5 m ³ wax / 5 oxides of molybdenum, cobalt, chromium and zinc hour / m ^{3 of} catalyst and molar ratios.

Hydrogen to wax between 5 and 50 through- In the first (isomerization) zone a counter

to be led; Sulfur resistant catalyst used as itself

(3) that the boiling in the area of the lubricating oil separated by the relatively small amounts of sulfur and partly from the outlet of the second zone, ¹⁰ nitrogen, which sometimes interwoven as a feed with a practically wax-free lubricating oil or waxes, especially residue waxes , such a lubricating oil component are incorporated by unloading, sensitive to sulfur is recovered to grow, and that the decision-m when a catalysts. If the wax is poisoned to such an extent, it may grow little- ^ f '. ^d f * ^HRE activity and selectivity will soon influenced to TeM in the circuit in the second isomerization ¹ S ^ ed. Particularly active catalysts, sierungszone is recycled. ^ Resistant to sulfur are ^Gn ^ ^lt T f ⁿ

or more oxides and / or sulfides of the metals

As a feed for the Verunken side of the group VI and / or the iron group according to the invention a petroleum wax is suitable for driving. It can ent- the Periodic Table of the Elements. In the first neither distillate or residue waxes used ao zone, a catalyst is preferably used, However, residue waxes produce the best of the tungsten and nickel in the form of their oxides and / or Yields in the process according to the invention. Contains sulphides.

With the expression "distillate wax" a wax becomes The acidic, fireproof carrier of the in the

denotes the catalysis distillate used in refining a lubricating oil first and / or second zone accrues, while the expression »Rückassator consists expediently of a mixture of Stand wax "refers to a wax used in silicon dioxide and aluminum oxide; Aluminum oxide Refining a residual lubricating oil is removed. and boron trifluoride; Silica and Magnesium-One A particularly suitable charge is a soft oxide; Silicon dioxide, aluminum oxide and zirconium wax as a by-product of the de-oiling of the oxide or aluminum oxide and fluorine. Even with acid raw wax is obtained with the help of a solvent. 30 treated clays, montmorillonites, zeolites or The raw wax is made by dewaxing a lubricant- Molecular sieves are suitable for this purpose. Around oil distillate or a residual lubricating oil with hooves to increase the activity of the catalyst is the obtained from a solvent. Carrier expediently a halogen, preferably fluorine,

The process conditions in the two zones are added, reducing the acidic character of the carrier can be the same or different. The changeable 35 is reinforced.

borrowed process variables in the two (isomerization In the first zone of the inventive method

tion) zones are within the following ranges: driving is preferably a catalyst with a

Supports made of silicon dioxide and aluminum oxide at a temperature of 371 to 427 ° C. Preferably the carrier consists of about 50

Pressure 35 to 140 ata, ₄ "to 90 percent by weight, in particular about 70 to

preferably 70 to 126 ata 90 weight percent silica and 50 to 10

Space velocity 0.1 to 5 liters of wax / hour / percent by weight, in particular about 30 to 10 liters of wax Catalyst, weight percent alumina.

preferably 0.1 to 11 wax / hour / although in the outlet of the first zone, which is in the

Liter of catalyst 45 second zone is further isomerized, small amounts

Hydrogen wax- ^ on hydrocarbons below the lubricating oil ratio 5 to 50, boiling range, may be present, so

preferably 10 to 25 but preferably separated because they are

unnecessary diluent act and thereby the

The effectiveness of the subsequent process steps used in the (isomerization) zones Catalysts contain compounds with hydration lowering. Therefore there is the feed for the rendering and dehydrating activity in connection with the second zone, preferably only from the proportion of the with an acidic, refractory carrier with an outlet from the first zone, which is within the lubricating isomerization activity. The amount of the hydrogenation oil boiling range is boiling. The entire, normally dehydrating component can be contained within a further liquid fraction of the outlet of the first zone can be changed, expediently it is finally neopentane and higher-boiling coal 0.1 up to 50 percent by weight, based on the finished hydrogen, or a fraction selected from it, Catalyst. The amount of carrier is, however, can be used in the second zone, corresponding to 99.9 to 50 percent by weight. provided that it is within the lubricating oil boiling range

The hydrogenation-dehydrogenation component of the 60-boiling portion contains. Furthermore, the loading the second or first zone catalyst used for the second zone also contain wax from preferably consists of one or more metals removed from the outlet of the second isomerization zone group II, V, VI and / or VIII of the has been separated.

Periodic Table of the Elements or a or As »boiling within the lubricating oil boiling range

Several oxides and / or sulphides of one or more hydrocarbons become high-boiling coals these metals, e.g. B. from the oxides and hydrogens with such a viscosity, Sulphides of molybdenum, tungsten, vanadium or which make them suitable as lubricating oils or their components made of chrome and / or made of iron, nickel, cobalt and suitable.

Although some lubricating oils can be more volatile, most lubricating oils have one Initial boiling point at atmospheric pressure of at least 316 ° C.

The hydrocarbons boiling below the lubricating oil boiling range are expediently separated off by fractional distillation and / or tower distillation. However, others can do just as well Separation methods are used.

In the second isomerization zone of the process according to the invention, an opposite sulfur sensitive catalyst can be used, since the product from the first zone is only a very small amount Has sulfur content.

By using a sulfur sensitive catalyst in the second isomerization zone becomes a higher yield of lubricating oil and a better selectivity in terms of conversion from wax to lubricating oil. A suitable catalyst sensitive to sulfur contains platinum on an aluminum oxide carrier, the acidity of which is due to the incorporation of chlorine or preferably fluorine is reinforced.

Catalysts with a fluorine content of at least 1.5 weight percent deliver in the second zone better results than catalysts with lower fluorine content. To avoid excessive splitting and to maintain the selectivity, the catalyst preferably contains no more than 4.0 weight percent fluorine.

The portion boiling within the Schmieiölsiedbereiches, which is to be dewaxed, is appropriate separated from the outlet of the second zone by fractional distillation and / or tower distillation. If necessary, however, other separation methods are also used.

The portion boiling within the lubricating oil boiling range that is obtained from the outlet of the second zone is dewaxed in a manner known per se. A solvent is expedient for dewaxing used. In this process, a waxy feed is converted into an organic one Solvent dissolved and then cooled, whereby the wax crystallized and from the solvent-oil mixture can be filtered off. Suitable solvents for this process are liquid propane, Benzene, toluene, methyl ethyl ketone and mixtures of methyl ethyl ketone and toluene.

The wax obtained in the last stage is expediently recirculated to the second (isomerization) zone returned. If necessary, this wax is also circulated in the first (isomerization) Zone led; However, this is economically less favorable, since this wax is already up to a certain point Degree is isomerized.

The examples illustrate the invention.

Example 1 (comparative tests)

A wax with a sulfur content of 0.17 percent by weight and a nitrogen content of 0.0293 Weight percent obtained by dewaxing a residual raw material with a solvent is isomerized into two zones in a single pass; H. without it in the Cycle is conducted. Then, for comparison, wax of the same origin is applied in a single zone isomerized under conditions determined by a previous experiment in terms of yield and Quality of the lubricating oil obtained was determined to be optimal. The following Table I gives the Details and results of the comparative tests to:

Table I.
Comparison of the one-step and two-step isomerization of wax to make heavy lubricating oils

First
Isomerization Stage Second
Isomerization stage

One step isomerization

Procedural conditions

Catalyst ¹ )

Pressure, ata

Temperature, ⁰ C

Space velocity,

m ³ wax / hour / m ³ catalyst ..

H ₂ / oil molar ratio

Hjs consumption, Nm ³ / m ³ wax.

Yields and properties of the
Products

W-Ni / SiO _{2 -Al 2} O ₃ 105
382

0.5 15
32

W-

■ Ni / SiO ₂ -105
371

0.4
15th
61

Yield, percent by volume

Dewaxed oil ² ) above 316 ° C
boiling

Wax, ^{boiling above 316 0} C ..

50.4
18.8

■ ALO _a

W-Ni / SiO ₂ -Al ₂ O ₃ 105
403

0.4
16
102

46.0
11.8

1) 18% tungsten, 12% nickel on solid silica-alumina with a content of 75% SiO ₂ and 25

2) Dewaxed with a methyl ethyl ketone-toluene mixture.

The above results show that using the two-call isomerization process im A clear increase in the yield of lubricating oil compared to the isomerization in one step is achieved.

Example 2

In a further test, a series of three 3500 hour test methods according to the invention

search carried out, where in place of the sulfur-resistant tungsten-nickel catalyst in the second (isomerization) zone a sulfur-sensitive platinum catalyst (0.65 percent by weight) is used, which is applied to an alumina support and as an acidic component Contains 3.0 percent by weight fluorine. The results of this series of tests are given below and are used with the results of the two-stage

o Method according to Example 1 compared.

Table II

Comparison of the two-call isomerization process for wax using one resistant to sulfur and a sulfur sensitive catalyst in the second (isomerization) zone

D (example J)

Procedural conditions
First isomerization zone

catalyst

Pressure, ata

Temperature, ⁰ C

Space velocity, m ³ wax / hour / m ³ catalyst

H ₂ / O 1, molar ratio

Hsä consumption, m ³ / m ³ wax

Second isomerization zone

Pressure, ata

Temperature, ⁰ C

Space velocity, m ³ wax / hour / m ³ catalyst

H ₂ / O 1, molar ratio

H ₂ consumption, Nm ³ / m ³ wax

Yields and properties of the products

Yield, percent by volume

Dewaxed Oil ¹ ) boiling above 316 ° C

Wax boiling above 316 ° C

Viscosity of the dewaxed oil boiling above 316 ° C

SSU at 99 ° C

SSU at 38 ° C

Poise at -12 ° C

Viscosity index of the dewaxed, over 316 ° C

boiling oil

1) Dewaxed with a methyl ethyl ketone-toluene mixture.

The results of this second series of tests show that when a sulfur-sensitive catalyst is used in the second (isomerization) zone, the heavy lubricating oil yields achieved in the two-stage process according to Example 1 are further increased and the heavy lubricating oil obtained has the desired properties at lower levels Temperature. Of far more interest, however, is the fact that the use of the sulfur-sensitive platinum catalyst 6g in the second zone increases the selectivity with respect to the conversion of the wax to the desired lubricating oil. For example, in W — Ni / SiO _{2 —Al 2} O _3, 105
382

0.5

15th
32

catalyst
Pt / MA - F

105

382

0.5
16

55

58.1
21.7

52
239
15.9

105
385

0.5
16
64

57.3
20.5

52
231
13.5

126

105
393

0.5
16
80

54.1
6.8

44
131
5.2

137

W-Ni / SiO ₂ Al ₂ O ₃

105

371

0.4

15 61

50.8 18.9

52 252 8.6

122

Experiment A 15 ° / ₀ more lubricating oil appropriate quality as in Test D produced. This is all the more surprising since, despite the stricter isomerization conditions, 382 ° C. versus 371 ° C., a higher yield of products boiling above 316 ° C. is achieved in experiment A.

Claims (3)

Patent claims: 1. Process for the production of lubricating oils or lubricating oil components from petroleum waxes by isomerizing treatment, thereby marked, (1) that the wax is in a first zone in the presence of hydrogen and one opposite Sulfur resistant catalyst which is a hydrogenation-dehydrogenation component and contains a solid, acidic, refractory carrier, is isomerized; (2) that of the outflow obtained in the first zone at least the portion that boils in the area of the lubricating oil, optionally after the hydrocarbons boiling below the lubricating oil boiling range have been separated off, in a second zone in the presence of hydrogen and one sensitive to sulfur Catalyst, which contains a hydrogenation-dehydrogenation component and a solid, acidic reacting, refractory support, is isomerized, the isomerization in both the first and in the second zone at temperatures between 371 and 427 ⁰ C, pressures between 35 and 140 ata, space velocities between 0.1 and 5 m ³ wax / hour / m ³ catalyst and molar ratios of hydrogen to wax between 5 and 50; (3) that the as Part separated from the outlet of the second zone whereby a practically wax-free Lubricating oil or such a lubricating oil component is obtained by growth, and that the wax obtained during dewaxing, if appropriate, at least partially in the circuit is returned to the second isomerization zone. 2. The method according to claim 1, characterized in that a catalyst in the first zone is used, the one or more sulfides and / or oxides of the metals of the left side of the Group VI and / or the iron group of the Periodic Table of the Elements and as a carrier Mixture of aluminum oxide and silicon dioxide, aluminum oxide and boron trifluoride, silicon dioxide and magnesium oxide or of silicon dioxide, aluminum oxide and zirconium oxide or one with Contains acid treated clay, a montmorillonite, zeolite, or a molecular sieve. 3. The method according to claim 1 and 2, characterized in that a in the second zone Catalyst is used, the one or more metals from the platinum group and / or the palladium group of the Periodic Table of the Elements as well as fluorine and / or chlorine and aluminum oxide as a carrier. Considered publications:
German Patent No. 931 826;
German Auslegeschrift No. 1 033 193;
French Patent Nos. 659 631, 1,068,757; Belgian Patent No. 537,743;
U.S. Patent No. 2,668,796.