DE1246146B - Process for the simultaneous production of lubricating oils with a high viscosity index and low-boiling distillates - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. CI .:

Clog

German class: 23 b - 1/04

Number: 1246 146

File number: C 34006IV d / 23 b

Filing date: October 2, 1964

Opened on August 3, 1967

There have been numerous methods of making improved lubricating oils from less suggested suitable oils by treatment with hydrogen in the presence of catalysts, whereby such procedures ranged from mild hydrotreatment to severe offsetting hydrogenation. It is known to use high viscosity index lubricating oils in the feedstock existing aromatics with low viscosity index by hydrogenation to more saturated compounds to convert into compounds with a higher viscosity index. Another procedure exists in breaking down condensed ring compounds to give branched chain compounds of the same molecular weight with fewer rings, thus creating compounds with a higher viscosity index are formed. Where the resistance of otherwise good lubricating oils is to be improved, there has been a mild one Hydrogen treatment to hydrogenate the hetero compounds, such as. B. sulfur and nitrogen compounds, used, which cause poor stability. A sharp hydration or hydrocracking often leads to the elimination of natural inhibitors, leaving a less persistent oil.

The method according to the invention leads in a new way to a stable lubricating oil with a high viscosity index. At the same time, the process leads to high-quality, low-boiling distillates. According to the invention, high-quality lubricating oils and lower-boiling distillates are obtained from heavy oils with a low viscosity index by selective hydrodealkification at or above the reforming strength. According to a preferred embodiment of the invention, the process consists in the selective conversion of aromatics and polycycloparaffins, which are present in a heavy oil feed material with a low viscosity range that is predominantly boiling in the lubricating oil range, to aromatics, cycloparaffins and paraffins boiling below the desired lubricating oil range, without the total number of moles of the aromatics is substantially reduced by catalytic hydrodealkylation of the feed at reaction conditions close to its reforming strength. A distillate is obtained from the reaction products which is richer in aromatics than the feedstock and consists of hydrocarbons boiling below the lubricating oil range and a lubricating oil which is characterized by a high viscosity index. The desired viscosity index of the product is above 100 and is preferably at least 110. The catalyzed Oxyda process for the simultaneous production of
High viscosity index lubricating oils and low boiling distillates

Applicant:

California Research Corporation, San Francisco, Calif. (V.StA.)

Representative:

Dr. W. Beil, A. Hoeppner- Dr. HJ Wolff
and Dr. H. Chr. Beil, lawyers,
Frankfurt / M.-Höchst, Adelonstr. 58

Named as inventor:

Robert James White, Pinole, Calif .;

Clark James Egan, Piedmont, Calif. (V. St. A.)

Claimed priority:

V. St. ν. America October 3, 1963 (313 521)

tion resistance of the lubricating oil is preferably at least 3 hours.

The process according to the invention works under reaction conditions at or above the reforming threshold of the feedstock at temperatures and pressures in the hydrodealkhenings range and Contact times that result in substantial conversion to lower boiling distillates. The above The "reforming swell" cited is the combination of conditions from a) an increased one Temperature which leads to the dehydrogenation of cycloparaffins, and b) an increased hydrogen partial pressure, which causes the hydrogenation of the aromatics, in which the dehydrogenation and hydrogenation conditions are in equilibrium so that the molar concentration of the aromatics in the overall product is not significant differs from their molar concentration in the total feed. The total concentration of Aromatics does not drop significantly when the process is carried out near the reforming threshold will. In particular, the total number of moles of aromatics in the products should not be less than

709 619/588

90% of the moles of aromatics in the feed. To work close to the reform threshold ensure the procedure is carried out so that there is at least a slight increase of aromatics when comparing the total reaction products with the total feed he follows.

The drawing is a graph that indicates the hydrogen pressure required to achieve a dehydration of the perhydrophenanthrene with the formation of more than 10% aromatics in one To prevent equilibrium as a function of temperature, reducing the reforming threshold of the Perhydrophenanthrene effectively delimited in the hydrodealkylation range of temperature and pressure conditions will.

In the drawing represent the combinations of pressure and temperature above and to the left of the curve the hydrogenation conditions under which the aromatics are hydrogenated to saturated compounds and the Prevents dehydration of the perhydrophenanthrene. With combinations of elevated temperatures and pressures below and to the right of the curve, the perhydrophenanthrene is dehydrated to different levels less saturated compounds, such as B. aromatics. Perhydrophenanthrene is the typical one Tricycloparafnkern of higher molecular weight alkylated tricycloparaffins, which occur in natural petroleum, that boils in the lubricating oil boiling range.

The reforming threshold of a heavy hydrocarbon oil depends on the boiling range of the same, its composition in the type of paraffins, cycloparaffins and aromatics and the distribution of various compounds within these groups in the boiling range. In the current state of the art, therefore, the determination of the reforming threshold of a particular feedstock requires experiments, but these can easily be carried out, to determine the temperature and pressure conditions at which the aromatics concentration in the product is not significantly less than in the feedstock. As a general rule of thumb, it can be said that the conditions for almost all heavy petroleum fractions are at or above the reforming threshold if the temperature is above 370 ° C and the hydrogen partial pressure is lower than to prevent the formation of more than 10% aromatics from perydrophenanthrene Balance is required, which is also shown in the drawing. The process conditions which are therefore used in the process of the present invention can generally be expressed as the conditions encompassing the area below and to the right of the curve shown in the drawing. However, the total pressure should be at least 70 kg / cm ² in order to achieve a satisfactory life of the catalyst with a low pollution rate. The temperature is also preferably maintained at at least about 400 ° C in order to achieve economical conversion rates. In a particularly advantageous embodiment of the process, the reaction conditions are at a temperature between 415 and 440 ° C, and the hydrogen partial pressure is between 84 and 140 kg / cm ² for at least 1000 hours, during which time the feedstock is brought into contact with the catalyst . It was found that these conditions apply to almost everyone in the process

usable feedstocks are close to or above the reforming threshold.

Catalytic hydrodealkification is a type of hydrocracking that initially leads to the long side chains of the condensed ring structures being broken up. A typical Hydrodealkylierungsumsetzung, which takes place in the present process is the conversion of a C ₂₆ -Tricycloparaffins, the ^c 370-427 C boiling, to a

ίο C ₁₆ tricycloparaffin, which boils between 288 and 343 ° C, and a C ₁₀ paraffin. In the presence of a suitable hydrodealkylation catalyst, the desired hydrocracking reactions take place under process conditions such as e.g. B. the temperatures between 370 and 482 ° C, pressures 70 to 280 kg / cm ^2, space velocities between 0.3 and 5 parts by volume of the liquid feed per volume of catalyst per hour and of a few VorHegen least 356.701 hydrogen per hardening HektoHter

ao material instead of supplying the hydrogen consumed in the reactions as well as sufficient excess hydrogen so that the hydrogen partial pressure represents the predominant part of the total pressure.

Suitable hydrodealky production catalysts used in the process of the invention are in the presence of substantial concentrations of sulfur and nitrogen compounds effective and have a hydrogenation-dehydrogenation action and a cracking action. These properties are usually found in catalysts that have a sulfactive metal as the active component VI. Group of the Periodic Table, e.g. B. molybdenum and / or tungsten. Improved effectiveness, Selectivity for the desired conversions and resistance to contamination or Deactivation can be achieved if the catalyst consists of a combination of a MetaH of VI. group with a metal from Group VIII and a porous metal oxide, alumina or magnesia, preferably in Combination with silica. The preferred MetaHe of Group VIII are nickel and the Precious metals. Strongly acidic catalysts, such as catalysts made from only one metal of the VIII.

Group or its sulphide on a carrier consisting of a mixture of silica and alumina, the contains a larger proportion of silica than alumina, characteristically cause the formation of unusually large amounts of isobutane. Such acidic catalysts are common with nitrogen compounds sensitive. If they are poisoned by nitrogen or other bases, they can die Hydrodealkification in the same way as the catalysts used in the process of the invention favor, but then they are usually less effective and therefore unsatisfactory.

An example of a preferred hydrodealkylation catalyst is the combination of potassium sulfide- Molybdenum sulphide - alumina - silica, the ratio of alumina to silica being between 0.5 and 10 parts by weight. In this catalyst, nickel can be used in place of palladium.

Another preferred hydrodealky hardening catalyst consists of the combination of nickel sulfide-WoHramsulfid-magnesia-silica, where the ratio "of magnesia to silica is between 0.2 and 0.5 parts by weight. Molybdenum can in this catalyst on the control of tungsten

are present. The preferred catalysts contain silica in addition to alumina and / or magnesia, there, for example, nickel sulfide-molybdenum sulfide-alumina catalysts, although selective dehydroalkylation effect, are less effective and not used for so long at the high temperatures as is necessary for good effectiveness.

The metals of the VIII. Group and metal components of the catalyst of metals of the VI. group can initially be present as metals or as metal compounds such as oxides or sulfides. While however, the hydrodealkylation of sulfur-containing feedstocks becomes these metal components converted into the sulphides, if they are not already present as such. It is therefore preferred that the To sulfide the catalyst prior to use in order to achieve the desired activity from the start of the process to have. The components of the metals of the VIII, and VI. Groups can be present in equal or unequal amounts, but preferably exceeds the Weight percentage of the component of the metal of VI. Group that of Group VIII metal, and the total amount of the two components is between 10 and 60 percent by weight, based on the Catalyst.

The catalysts can be prepared by a variety of known methods including simultaneous or successive impregnation or deposition of the metals of the VI. and VIII. Groups a previously prepared carrier, simultaneous deposition with clay or magnesia and / or silica, Mixed gelation and the like can be prepared.

The hydrocarbon oil feed materials suitable for the process according to the invention are hydrocarbon distillates, their residues and fractions which boil over the entire boiling range of the desired lubricating oil. That is, the initial boiling point of the feed should be at least nearly as high as the desired initial boiling point of the lubricating oil and that the end boiling point of the feed cannot be lower than the end boiling point of the desired lubricating oil. The initial boiling point of the feed, however, can be substantially below the initial boiling point of the desired lubricating oil while the final boiling points are substantially the same. Likewise, the initial boiling points can be substantially the same, but the final boiling points of the feedstock can be substantially higher than the final boiling point of the desired lubricating oil. In the same way, in the case of an input material without a fixed end point, such as e.g. B. a deasphalted residue, the initial boiling point will not be significantly above that of the desired lubricating oil, but can itself be a residue such as a bright stock material.

The feedstock is preferably an impure oil or a crude oil that contains impurities such as sulfur and nitrogen compounds. Preferred feedstocks contain about 10 to 40 percent by weight Polycycloparaffins, as the yield of high quality lubricating oil is very low, if necessary an inappropriate amount of polycycloparaffins to achieve a recognized high viscosity index to convert the product into lower-boiling compounds. If the input material is less than 10% Contains polycycloparaffins, the process can

are mainly used to convert aromatics into lower-boiling aromatics. The expression "Cycloparaffins" is used with special reference to dicycloparaffins and tricycloparaffins as well as saturated ones Compounds with more than three condensed rings used. Monocycloparaffins and paraffins become a different one with respect to the way in which they are dealt with in the procedure Group counted. In order to more precisely identify the preferred feedstocks, the ratio of Paraffins to tricycloparaffins must be greater than 1. If .this ratio is less than 1, then Product obtained lubricating oil usually has a viscosity index below 100, even if the ratio is significantly higher in the product.

The term "naphthenes" is sometimes used in the petroleum industry to refer to saturated ring compounds having fewer than 6 carbon atoms in the ring, as well as those having 6 and more than 6 carbon atoms in the ring. When used in this way, the terms "naphthenes" and "cycloparaffins" have the same meaning.

In the selective conversion according to the invention, the hydrodealkylation removes polycycloparaffins from the feed boiling range, many of which are again called lower-boiling polycycloparaffins appear in the part of the product just below the initial boiling point of the Feed boils. Therefore, the products that are just below the initial boiling point of the Boiling feedstock, often less suitable lubricating oils than the original feedstock itself.

Between about 30 and 70 percent by weight of the feed boiling in the lubricating oil range will be converted into lower boiling distillates that boil below the lubricating oil boiling range. The received Distillates can be described as aromatics in the sense that they are more aromatic than that Feed material, since aromatics are selectively converted into lower-boiling aromatics and not fully hydrogenated. Be in a similar fashion Polycycloparaffins in the feed are selectively converted to lower boiling compounds. Of the Most of the polycycloparaffins are only hydrodealkylated to form compounds such as Perhydrophenanthrene, which is concentrated in the boiling range between 260 and 370 ° C. To such materials To exclude from the lubricating oil, the recovered lubricating oil product is said to have an initial boiling point of above about 343 ° C, preferably at least 370 ° C. The feedstock is at least boiling sometimes at over 427 ° C.

According to one embodiment of the invention, the reaction products boiling in the lubricating oil boiling range and the products boiling above the initial boiling point of the feedstock in different fractions, at least two, separated with a relatively narrow boiling range, for example is essentially no greater than 55 ° C. It is therefore possible to use special lubricating oil distillates to obtain desired properties. According to a particular embodiment, the feedstock has even a fairly narrow boiling range which does not substantially exceed 55 ° C, with a Lubricating oil distillate is obtained in which there is a possibility of remaining fragments of hydrodealkylation of much higher-boiling polycycloparaffins and aromatics to a minimum

is reduced, since almost all the products of the selective conversion in the lower-boiling distillate fractions appear,

The selective hydrodealkyhering cracking of aromatics and polycycloparaffins leads to paraffins and cycloparaffins ₃ that boil below the lubricating oil boiling range. Some of the highest boiling paraffins and monocycloparaffins in the feed are also cracked, but the selective nature of the process is characterized in that these conversions do not occur on a large scale. Therefore, the product boiling in the lubricating oil boiling range is highly enriched in paraffins and the concentration of the monocycloparaffins can increase as a result of the removal of the polycycloparaffins and aromatics. In many cases the lubricating oil product must be de-waxed if a low pour point of the product is desired, but this will largely be determined by whether or not the original feedstock is waxy. Where wax removal is required or desired, it is preferred not to remove wax from the entire product, rather the reaction products are distilled to obtain the desired lubricating oils and then wax the lubricating oil fractions separately, as required by the various fractions is.

In some instances, the aromatics content of the hydrocarbon oil feed can be so high that a substantial amount of unconverted aromatics remains in the lubricating oil range. This is due to the fact that according to the invention, in contrast to previously known processes in which such aromatics were hydrogenated during the hydrocracking, the aromatics are not strongly hydrogenated, but rather are removed by the mechanism of hydrodealkylation. Therefore, in order to avoid having more than about 70% of the feed converted to lower boiling distillates by the hydrocracking process, it is preferred to use a feed which contains less than 40% aromatics. In order to remove the remaining aromatics and / or to obtain a lubricating oil with an extremely high resistance to oxidation, one embodiment of the invention provides for the hydrogenation of the lubricating oil, preferably after removal of the wax, if desired, under mild conditions, so that only one hydrogenation takes place with the exclusion of hydrocracking. For example, the lubricating oil can be passed over a hydrogenation catalyst such as platinum or nickel at a low temperature of 150 to 315 ° C. under a pressure of 49 to 140 kg / cm ^8.

The most economical way to run the process continuously is to preheat the oil feed and hydrogen under pressure and then pass it through one or more stationary layers of catalyst particles in a high pressure reactor. The material flowing out of the reactor containing the reaction products is then cooled, excess hydrogen is removed and the lower boiling distillates are then separated from the lubricating oil fractions by distillation at lower pressures. By-products such as B. gas, including normally gaseous hydrocarbons, H ₂ S and NH ₃ , are preferably separated from the reaction products. The aromatic distillates can be obtained directly by distillation for further use or for mixing with fuel oil products such as gasoline, kerosene or diesel oil. In many cases, they are preferably further treated in order to remunerate them or to convert them into more valuable products, such as high octane gasoline, by known processes.

Parts of the material flowing out during the conversion that are not used as lubricating oil or as low-boiling Distillates obtained can be combined with the catalyst for further treatment be returned with the feedstock. Although the recycling of part of the lubricating oil material can be used to provide quantitative conversion of the hydrocarbon oil feed To achieve the desired products, it should be noted that the conversions indicated above refer to one-time conversions or one conversion per pass and that the space velocities relate to the primary fresh feed.

The invention is illustrated by the following example of producing high viscosity index lubricating oil from an untreated distillate of crude oil explained.

example 1

An untreated gas oil with a boiling range of 355 and 530 ° C was mixed with 107 0101 hydrogen per hectare of oil and passed through a reactor containing a palladium-molybdenum-alumina-silica catalyst ^{at 434 ° C and 84 kg / cm 2 with a space flow rate of 1,} 5 per hour. The catalyst consisted of 2 parts of palladium sulfide, 10 parts of molybdenum sulfide, 63 parts of alumina and 25 parts of silica. It was produced by mixing palladium, molybdenum, aluminum and silica compounds and then calcining and sulphiding to convert the palladium and molybdenum components into sulphides. This catalyst has a high selective activity for the hydrodeaIherung of polycycloparaffins and aromatics and has a low deactivation rate and excellent temperature resistance at only moderately high hydrogen partial pressures without rapid coke formation or contamination. The reaction products, by which all hydrocarbons flowing out of the reactor are understood, were cooled, hydrogen and other gases (e.g. the by-product H ₂ S and NH ₃ ) were separated and the liquid reaction products were then used to recover various fractions distilled. Table I below compares the properties of the feedstock with the properties of the lubricating oil fractions of the reaction products which in some of the cases indicated have been de-waxed.

From the information below it can be seen that polycycloparaffins and aromatics in the process were selectively converted, causing an increase in the concentration of compounds with a higher average viscosity index in the lubricating oil range compared to that in the hydrocarbon oil feed present connections is achieved.

9 10

Table I

- Input material fraction
Lubricating oil,
that between 371
and boils at 432 ° C Lubricating oil,
that between 432 '
and boils at 488 ° C Yields obtained from the feed, 28 10.5 Composition, percent by volume 33.4 45.8 ^: 48.8 "\ A η Ti r \ ί * \ 7 r * 1 r \ Y \ a r a f π η 16.8 19.8 24.7 Dicycloparaffins 10.5 8.6 9.3 18.3 10.8 5.6 9.3 2.9 4.0 Indanes / Tetrahydronaphthalenes.: ..... ... 4.2 2.7 1.9 2.2 0.7 0.4 2.8 2.9 2.8 Benzomdane / Benzotetrabydronaphthalenes ... 2.4 2.8 2.6 between 409 and 427 ° C boiling fraction Viscosity at 38 ° C, SSU 133.4 63.51 97.47 Viscosity at 99 ° C, SSU 41.65 35.84 40.27 88 113 139 Wax removed Wax removed 64 '129 10.2 20.2 18.7 5.6

* Persistence A is the time it takes for a given volume of oil to absorb 11 oxygen from the air, which is blown through the oil at 171 ° C. The durability B is the time determined in the same way when 3.7% by weight a commercially available oxidation inhibitor can be added and the oxidation by added iron and copper contaminants is catalyzed. This is a measure of the response of the lubricating oil to the additive, since the amount of metal oxidation catalyst added would be sufficient to produce essentially immediate discoloration of the oil in the absence of an inhibitor.

Table II below presents an analysis of the major ones obtained by the procedure of Example 1 lower-boiling distillate fractions.

. TabeUeII

distillate
82 to 160 ° C fraction
distillate
160 to 288 ° C distillate
288 to 343 ° C Yield obtained from the feed, Ge 13th 20th 16 Composition, percent by volume 32.1 25.2 22.9 42.0 11.5,. 3.7 Dicycloparaffins 2.8 9.3 17.3 Tricycloparaffins 4.3 .. 20.4 23.0 16.0 10.9 Indanes / tetrahydronaphthalenes 21.5 7.2 2.6 ' 3.8 5.7 3.5 3.8 10.2

Thus, by the above process, the feedstock was divided into two main amounts of product, which consists of a lower-boiling distillate part with a high aromatic ring content and an im Lubricating oil boiling part with high viscosity index passed. Particularly noteworthy is that high aromatic content of the low-boiling de-. stillats and the increase in the concentration of polycycloparaffins between 288 and 343 ° C.

The following Table III, which was calculated on the basis of the above and other analyzes, further summarizes the results of the above example

together and shows in particular the increase in aromatics in the total product compared to the total input material. In addition, the selective conversion of the polycycloparaffins is clearly emphasized. The selectivity of the process is expressed by the ratio of paraffins to tricycloparaffins in the product divided by the ratio of paraffins to tricycloparaffins in the feed. For the above example, the selectivity was 4.7 based on a boiling 432-482 ° C .The product, and for the whole, above boiling from 343 ⁰ C product 2.8.

Table III

Mole Total stake Products under Products that are about material Total product Boil 343 ⁰ C Boil 343 ° C Tricycloparaffins 20th 11.5 6th 5.4 Dicycloparaffins 11 13th 8.5 4.3 Monocycloparaffins 16 30th 19th 11 Paraffins 31 60 37 23 Aromatics 22nd 44 37 7th

The following example illustrates the practice of the invention at a higher pressure, which is in the Is close to or above the reforming threshold.

Example 2

The same feedstock was subjected to hydrodealkinking cracking with the same catalyst as in Example 1, but at a higher pressure of 120 kg / cm ² and a slightly higher temperature of 436 ° C. A lubricating oil fraction was obtained from the reaction products which had the following properties:

Table IV

Between 432 and
512 ° C boiling
Lubricating oil composition 39.1 Monocycloparaffins 26.7 Dicycloparaffins 13.5 Tricycloparaffins 8.2 Alkylbenzenes 4.9 Indanes / Tetrahydronaphthalenes .. 2.4 Benzodicycloparaffins 0.5 2.3 Benzoindane / Benzotetrahydro- naphthalenes 2.4 Removal of wax Viscosity at 38 ° C 147.2 Viscosity at 99 ° C 44.3 Viscosity index 126 Resistance B, hours 6.1

From the foregoing, it appears that the selectivity, as previously stated, was 2.6, indicating that the process operating at higher pressures near and above the reforming threshold is also highly selective for the desired conversion.
The following example illustrates the practice of the invention using a different catalyst and using a cycle process.

Example3.

40 In this example, the feedstock was a simple distillate of the same crude petroleum oil which was used in Examples 1 and 2 and boiled in this case between about 357 and 550 ° C and had a specific gravity of 0.9142. The catalyst used consisted of nickel sulfide, tungsten sulfide, silica and magnesia and was obtained by impregnating a commercially available silica-magnesia cracking catalyst containing 30% by weight of magnesia with nickel nitrate and ammonium tungstate, calcining and sulfiding. The catalyst contained about 15 weight percent nickel and about 15 weight percent tungsten. The feed and 115,9271 H ₂ per hectare were passed over the catalyst at a pressure of 140 kg / cm ² , a space flow rate of 0.6 per hour, based on the fresh feed, and at 427 to 453 ° C. About 53% of the feed was converted into lower boiling ^{distillates that boil below 371 ° C.} The majority of the higher-boiling products, which are in the lubricating oil range, were returned to the reactor together with the feedstock for further conversion. Another part of that in the lubricating oil business

65 ' boiling products, about 10%) was drawn off, distilled into lubricating oil fractions with a boiling range of about 55 ° C and freed from wax to give lubricating oils with the following properties:

Table V

fraction Lubricating oil, Lubricating oil, Lubricating oil, Uaa ä WloUJCIl j I j Uab UCi UUCl and boils at 432 ° C and boils at 483 ° C Boils 483 ° C Yield obtained from the lubricant part, weight jo J ₁ J Composition, percent by volume 41.2 Monocyclic paraffins 29.6 ' Dicycloparaffins 11.4 5.4 Alkylbenzenes .... 4.5 .2.4 Benzodicycloparaffins 0.6 2.2 Benzoindanes / Benzotetrahydronaphthalenes 82/67 2.6 132.9 285.2 Viscosity at 99 ^° C. 38.37 43.48 55.20 125 131 122 Wax removed, weight percent 15.3 20.3 • 39.4 4.9 5.7 5.9

The selectivity for the conversion of tricycloparaffins was, as indicated above, about 4, based on the ^{fraction boiling between 432 and 483 °} C. compared to the fresh feed. Using this catalyst, a high selectivity for removing polycycloparaffins and aromatics was therefore achieved under the reaction conditions corresponding to Example 2. In the above example, the selectivity and the scaling oil properties in the fraction boiling at 432 to 482 ° C. were better than in the fraction obtained in Example 2 because of the lower space velocity of 0.6 compared to the space velocity of 1.5 used there, with additional treatment time allowed to achieve a more complete selective conversion.

The following example illustrates an embodiment of the invention resulting from a combination of the following Process steps consist of: hydrodealkylation, obtaining a lubricating oil with a high viscosity index, removing wax and hydrogenating for improvement of constancy.

Example 4

The lubricating oil obtained in Example 3, freed from wax and boiling between 432 and 483 ° C, was hydrogenated by treating it with hydrogen and a catalyst consisting of 0.55 percent by weight of platinum-on-silica at 232 ° C, 84 kg / cm ² and a space velocity of 1 per hour. The wax freed, hydrogenated. Oil recovered directly in quantitative yields after this treatment had essentially the same viscosity and viscosity index as the de-waxed lubricating oil feedstock. It showed an improved oxidation resistance of 7.7 hours compared to the oxidation resistance of 5.7 hours of the de-waxed oil prior to hydrogenation.

The following example provides a comparison between an above reform threshold and a ■ processes operating below the reforming threshold, d. H. a process in which the Conditions lead to hydrogenation of the aromatics.

Example 5

The same feedstock and the same catalyst as in Example 3 were brought together at 140 kg / cm ² with 10 7 O 1 of hydrogen per hectohter. In an experiment (A) the temperature was 460 ° C. and the hourly space air velocity was 0.6. In the other experiment (B) the temperature was 388 ° C and the hourly space air velocity was 0.8. The differences in the reactions with regard to their selectivity emerge from the following comparison of the hydrogen consumption and the properties of the lower-boiling products.

attempt (A) (B) Temperature, ° C 460 388 Consumed hydrogen, 1 / hl .. 21 759 30 676 Fraction with boiling point between
62 and 160 ° C, percent by volume Aromatics 12th 3.4 Fraction with boiling point between
160 and 288 ° C 34.5 12.5 Fraction with boiling point between
288 and 371 ° C 23 10

From the above data it can be seen that at the lower temperature of 388 ° C there are no aromatics formed and a large part of the aromatic fragments from hydrocracking were hydrogenated, while aromatics were formed at the higher temperatures. The large hydrogen consumption

460 ° C in spite of the increase in the aromatic concentration, the hydrogenation of nitrogen, sulfur and .._ Oxygen compounds, the hydrogenation of olefinic compounds and the hydrogenation of hydrodealkylation fragments to be led back. The difference between this and the much higher hydrogen consumption at 388 ° C shows this extensive hydrogenation of aromatics at the lower temperature. By avoiding this hydrogen The process according to the invention achieves considerable economic efficiency with the consumption of the reaction without deterioration in product quality.

The following example illustrates the effect of the feed properties on the results obtained. As already mentioned, the preferred feedstocks contain 10 to 40% polycycloparaffins and more paraffins than tricycloparaffins. Polycycloparaffins and aromatics are selectively converted so that the product obtained in the lubricating oil sector has a greater paraffin concentration with respect to the feedstock, while the monocycloparaffin concentration increases only slightly. The total conversion is between 30 and 70%. It can be seen that the most preferred feedstocks contain a total amount of paraffins plus monocycloparaffins which is greater than the total amount of polycycloparaffins plus aromatics in the lube oil boiling range. This example shows the inferior results obtained with a feed that does not have the preferred distribution of the various hydrocarbon groups. ⁰

Example 6

A heavy gas oil distillate, which boils between about 316 and 593 ° C and comes from a crude oil rich in cycloparaffins, was with 107 OlO 1 hydrogen per hectare with the nickel-tungsten-silica-magnesia catalyst at a space flow rate of 1.0 per hour 416 ° C and below 127 kg / cm ^a . The properties of the feed and the lubricating oils obtained from the products boiling above 371 ° C are shown in Table VI below, in which the viscosity index determination was also carried out on fractions of the feed which boil in the same ranges as the lubricating oil fractions obtained as product.

Table VI

Mission-
filial 'Lubricating oil
with boiling point
between 371 and
427 ° C fraction
Lubricating oil
with boiling point
between 427 and
482 ° C Lubricating oil
with boiling point
between 482 and
585 ° C
(Wax removed) Yield based on that above 371 ° C 15th 10 10 end input material,% ··· ■ '* composition Paraffins 16.1 21.6 18.4 21.4 28.7 29.4 Dicycloparaffins 17.5 17.8 19.4 Tricycloparaffins 34.1 24.3 25.1 Alkylbenzenes 1.0 1.3 1.5 Indanes / tetrahydronaphthalenes 3.7 3.2 3.3 Benzodicycloparaffins, 2.5 1.5 1.6 Naphthalenes 2.4 0.8 0.7 Benzoindane / Benzotetrahydro- naphthalenes 1.4 0.7 0.7 Viscosity index of the product 80 89 74 Viscosity index of the part of the feedstock rials that has the same boiling range ... 43 53 37 (Wax removed)

Although the viscosity index had increased sharply in each EaU, the unusually high polycycloparaffin content of the feed prevented a viscosity index above 100 from being reached. It should be noted that the feed contained greater than 50% polycycloparaffins and more tricycloparaffins than paraffins. Therefore, the conditions of this example steUen for carrying out the invention almost boundary conditions are. If the temperature is lowered from 416 to 399 ⁰ C, then Hegt the viscosity index of boiling 427-482 ° C product only 63. Better results can at temperatures above 427 ⁰ C can be obtained.

It should be noted that the less useful feedstock of Examples 6 and above also the more preferred feed of Example 1

60

65 both contain more tricycloparaffins than dicycloparaffins. The inferior lubricating oil product of Example 6 contains even more tricycloparaffins than dicycloparaffins, whereas the superior lubricating oil product of Example 1 contained more dicycloparaffins than tricycloparaffins.

A particular advantage of the process according to the invention is that it can be used with many crude gas oil distillates as a product yields a high viscosity index lubricating oil of the kind that is produced by thermal diffusion of solvent treated lubricating oils. With a thermal Diffusion process is liquid oil in a very narrow, perpendicular pipe between a relatively hot and a relatively cold surface, creating longer-chain molecules

Claims (5)

up to relatively concentric, d. H. more polycyclic molecules diffuse. The following table compares the overhead fraction obtained by thermal diffusion of a neutral oil 150 (88 V I) with the products boiling above 377 ° C. obtained in Example 1. Percentage by volume in the productDuring product thermal after diffusionExample 1Product obtainedParaffins 48.229.8Monocycloparaffins 25.135.2Dicycloparaffins 9.316.3Tricycloparaffins 5.68.4Total content of aromatics11.810.1Viscosity at 38 ° CViscosity at 3815.6Viscosity at 38 ° C 990C 39.2539.3 Viscosity index 123123 25 The analyzes of the compositions given in the preceding examples were carried out with the mass spectrometer. Compounds other than the listed types of groups may also be present in the feedstock and in the products; for example, the feed may contain tetracycloparaffins, but this does not change the interpretation of the values. Patent claims: 1. Process for the simultaneous production of high viscosity index lubricating oil and lower boiling distillates by combining a heavy oil feed with low Viscosity index that boils in the lubricating oil range with hydrogen and a sulfur-active catalyst at elevated temperatures and pressures for a time sufficient to produce a substantial Conversion to lower-boiling distillates achieve, and. Separation of a lubricating oil with a high viscosity index and a distillate containing hydrocarbons boiling below the lubricating oil range from the reaction product, characterized in that a heavy oil feed is used which at least partially boils above 427 ° C and contains between 10 and 40 percent by weight polycycloparaffins and below 40 percent by weight aromatics, that one uses a sulfur-active hydrogenation catalyst which is a hydrodealkylation catalyst, the metals of the group. VI and VIII of the Periodic Table of the Elements and a porous oxide carrier, and that the reaction is carried out at 370 to 482 ° C and hydrogen pressures of 70 to 280 kg / cm ² close to or above the reforming threshold of this charge, so that the total content of aromatics in the reaction product is at least 90 mole percent of the aromatics in the feed. 2. The method according to claim 1, characterized in that a heavy oil charge is used, which have more paraffins than cycloparaffins, more tricycloparaffins than dicycloparaffins and contains more paraffins plus monocycloparaffins than polycycloparaffins plus aromatics. 3. The method according to claim 1, characterized in that the temperature and pressure during the reaction be chosen so that the hydrogen pressure-temperature ratio in the range below the equilibrium curve shown in the drawing. 4. The method according to claim 1, characterized in that there is a hydrodealkylation catalyst used, 'containing alumina, silica and molybdenum as well as nickel or palladium, the ratio of alumina to silica in parts by weight being between 0.5 and 10. 5. The method according to claim 1, characterized in that there is a hydrodealkylation . uses a catalyst that contains silica, magnesia and nickel as well as molybdenum or tungsten, the ratio of magnesia to silica in parts by weight being between 0.2 and 0.5. Considered publications:
U.S. Patent No. 2,787,582. 10 A priority document was displayed when the registration was announced. 1 sheet of drawings 709 619/588 7.67 ® BundesdruckeieiBeilin