DE1198952B - Process for the catalytic conversion of hydrocarbon distillates into lower-boiling products - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. α .:

Clog

German class: 23 b-1/04

Number: 1198 952

File number: C 23141IV d / 23 b

Filing date: January 11, 1961

Opening day: August 19, 1965

In the known process for hydrocracking petroleum fractions, in which these are first hydrofiniert to remove nitrogen and sulfur-containing impurities and then passed together with hydrogen over a catalyst which contains hydrogenating and active cracking components, it is found that the aromatic compounds present in primary products with 1 or 2 and in some cases 3 fewer carbon atoms than the corresponding starting compounds. Is z. B. a heavy petroleum with a boiling range of about 182 to 233 ⁰ C, which contains about 40% aromatic products, exposed to a number of hydrofining and hydrocracking stages, it can be seen that the ^{synthetic fractions boiling below about 182 0} C are rich in aromatic compounds having 9 carbon atoms and containing a relatively minor amount of compounds such as benzene, toluene or xylene (or their naphthene equivalents), which are preferred gasoline admixtures both because of their octane number and their volatility.

The invention relates to a process for the catalytic conversion of hydrocarbon ^{distillates which boil above about 149 °} C. and can be catalytic cycle oils, have a low nitrogen content and contain aromatic hydrocarbon fractions, which is characterized in that the starting material optionally

Process for the catalytic conversion of coals to hydrogen distillates in low boiling products

Applicant:

California Research Corporation, San Francisco, Calif. (V. St. A.)

Representative:

Dr. W. Beil, A. Hoeppener and Dr. H. J. Wolff, lawyers, Frankfurt / M.-Höchst, Adelonstr. 58

Named as inventor:

Robert Harry Kozlowski, Harold Frederick Mason, Berkeley, Calif .; John Walter Scott Jr., Ross, Calif. (V. St. A.)

Claimed priority:

V. St. v. America January 14, 1960 (2363) - -

light and heavy catalytic cycle oils. Various of these products come from unprocessed first hydrofinished and then the products in them, others, however, are aromatic hydrocarbons with water from distillate fractions from various processing methods, e.g. fuel in the presence of a hydrogenation catalyst, coking plants or other cracking plants, e.g. B. hydrogenated under elevated temperatures and pressures thermal or catalytic cracking plants. Further, whereupon the hydrogenated product in the presence of suitable starting materials are the proportions boiling over about 149 of hydrogen and an acidic catalyst at 35 to 163 ° C from a catalytic hydrogenation properties and high cracking reforming plant, e.g. B. Products that are usually speed at temperatures of about 177 to 370 ⁰ C and are produced in such a way that unprocessed, heat pressures of at least 28 atmospheres are hydrocracked cracked and / or catalytically cracked petroleum and optionally from the product of the hydro fractions together with hydrogen under reforcing a gasoline fraction and a higher boiling 40 mierbedingungen is obtained via a platinum-alumina or fraction and the gasoline fraction passes under a molybdenum-alumina catalyst. Further aromatization of the naphthenes catalytically reformed suitable starting materials are concentrates, which is. are rich in aromatic hydrocarbons and

The starting products of the process of the invention by extracting various hydrocarbon dung are especially hydrocarbon distillates which contain 45 fractions with sulfur dioxide, furfural or gearomatic compounds with at least 9 carbon mixtures from different polyethylene and polystyrene atoms in the molecule and are obtained via propylene glycols, for example.
Boil 149 ⁰ C. Examples of such starting products However, starting products are also used

are those that are generally considered to be heavy petroleum derived from other sources, e.g. B. distillates with a boiling range of about 149 to 50 slate, gilsonite or coal. In general, before-246 are referred to ⁰ C, light and heavy gas however Trains t products in which at least oils, light and heavy Verkokungsdestillate and the 10% - or 90% distillation of ASTM

509 657/392

3 4

D-86, D-158 or D-1160 can be returned within a Beieiches finishing machine. In the separator

fall from about 177 to 510 ^{° C.} two liquid phases arise, an upper carbon

The content of the starting products of aromatic hydrogen phase and a lower aqueous phase, the

Compounds is not critical for the process, the existing ammonia and some sulfur

it can also be used for products that contain hydrogen in the form of ammonium sulfide,

those indicated above, in which the content of the aqueous phase is withdrawn from the system

aromatic substances between about 1 and 100 Vo- and discarded,

can be lum percent. The hydrocarbon layer is then

Starting products of the type described usually contain in a purification or distillation process a considerable amount of nitrogen was passed through the column, from the rest of the column containing sulphurous water as well as sulphurous impurities. When the substance, ammonia and water are removed overhead Processing of raw materials of this type will be carried out.

Accordingly, the initial product in a first As the next process stage, the hydro-stage of a Hydrofinierbehandlung is subjected to lined product with added hydrogen under its nitrogen content is preferably from 0 to 0.001%, ¹ S elevated temperatures and pressures over a expressed as total nitrogen content, reduced. Hydrogenation catalyst passed, whereby a considerable amount of this can be done in such a way that part of the raw material present in the charge is saturated with at least 8.9 cbm of matic substances as a compensator. In most cases hydrogen per hectolitre with one sulfur a saturation of at least 50% is achieved. The constant hydrogenation catalyst at about 233 to 20 hydrogen is introduced in an amount which is 426 ° C., pressures of at least 21 atmospheres and flow rates at least sufficient to bring about these saturation rates per hour of about 0.3 to 5. Preferably an excess of is contacted. As used in Hydrofinierverfahren hydrogen, at least a portion is the common for the removal of nitrogen-containing and sulfur erforderhaltigen during the subsequent hydrocracking stage ingredients that condi- are to provide ² 5 loan amount in which also hydrogen, the Hydrofinierstufe conditions chosen so that one is consumed. The entire flow of saturation of the aromatic constituents in general from the saturation zone directly into the hydrocracking zone can thus only be carried out to a limited extent and that, except for the ones. With most of the starting materials, the nitrogen- and sulfur-containing compounds, only required saturation of both the aromatics and a slight cracking of the feed takes place. At 3o the cracked products also reach, if the process according to the invention, any of the sulfur-resistant hydrogenation catalysts known as the saturation zone for the aromatics can be used at least 35.7 cm ³ H ₂ per generators. The preferred catalyst hectoliters of charge and preferably at least catalysts of this type contain 53.55 emm ³ H ₂ per hectolitre as the main active ingredient,
constituent one or more oxides or sulphides of the 35 The conditions prevailing in the saturation zone for the aromatic transition metals such as cobalt, molybdenum, nickel substances are generally or tungsten, or the corresponding reduced substances the same as those used in the hydrofining stage, but substances. These products can be used in a large area, the temperatures are a little lower here, i. h, they number of combinations with or without using lie at 149-370 ⁰ C, preferably at 205 to various known stabilizing or activated 40 344 ° C. The Katalyvierungsmittel used in the second stage use. The catalysts can sator is a sulfur-active catalyst of the kind used either alone or in conjunction with various first or hydrofinishing stages, or conventional carrier materials such as charcoal, fuller's earth, it consists of metals and / or metal oxides of kieselguhr, silica gel, alumina, or bauxite Ma- elements of groups VI, VII and VIII of the magnesium earth are used. An effective hydrodynamic system. It can use Raneynickel finierungskatalysator consists z. B. from a clay as well as other catalysts, z. B. Molyberdeträger and contains molybdenum and / or tungsten denoxide, platinum, palladium, rhodium, rhenium, in sulfide or oxide form in an amount of about nickel or cobalt on alumina, silica gel, 5 to 25% (expressed as Mo or W) and Oxides diatomaceous earth or other similar carriers with low levels or sulfides of cobalt and / or nickel, with the 50 cracking effectiveness and large surface area. For the latter products in amounts from about 1 to saturation of aromatics, more preferably 20% (expressed as Ni or Co) are present. Catalyst consists of about 0.1 to 20% or more

The stream of metallic platinum coming from the hydrofining stage on an alumina carrier. the

is treated by known processes so that the catalysts can also contain 0.1 to 2 percent by weight

Ammonia and any sulfur halogen, e.g. B. fluorine or chlorine, and contain

hydrogen can be removed. A preferred resolution, therefore, is currently used in catalytic

removal process consists of injecting platinum and others used by reforming processes

Water in the total stream from the hydrofining catalysts.

plant, whereupon the mixture obtained in a The stream from the saturation stage for the aromatics

High pressure separator is passed under such 60 (i.e. the hydrogenation) can be done in several ways

Temperature and pressure conditions works (e.g. process. He can e.g. a gas-liquid

38 ⁰ C and 66.5 atm), that a gas flows off overhead, separators are fed to a hydrogen

which consists mainly of H ₂ and normally a rich gas stream can be obtained with fresh,

some hydrogen sulfide and light hydrocarbons - additional hydrogen via the hydrogenation catalyst

contains substance. This gas flowing overhead can be returned to the generator. The remaining part

optionally after a cleaning treatment for the stream is then passed on for further treatment

Removal of nitrogen and sulfur compounds from the hydrocracking catalyst in a storage tank

fertilize with the addition of hydrogen fed into the hydro. Another possibility is to

5 6

the mentioned remainder to certain fractions to fractionate the cracking components of the hydrocracking catalyst, the remainder subsequently using sators can be various solid or liquid products with good cracking efficiency. Fixed pro is headed. In this embodiment of the products of this type, for. B. the various silicon processes, the hydrogenation catalyst is normally 5 oxide-containing cracking catalysts, also those, kept in a separate reaction vessel. In the case of alumina chemically aligned with aluminum chloride, the preferred embodiment of the invention, magnesium oxide or aluminum chloride, the entire flow is bound by the hydrogenation catalyst, and in particular those which are in the pores of a carrier such as charcoal, if necessary together with added amounts the hydrogen - to reduce _{the AlCl 3} evaporation directly via a hydrocracking catalyst. Examples of headed sator. As a result, the hydrogenation liquid catalysts of this type are hydrogen catalysts in the same equipment casing as fluoride-boron trifluoride mixtures, titanium trichloride and the hydrocracking catalyst, but on an aluminum chloride, which together with HCl in a place where the required saturation of the aro- suitable hydrocarbons are used,
matic substances within the above-mentioned casing 15 It is generally preferred to find a solid catalyst containing silicon oxide as cracking compost before the stream flows over the hydrocracking component of the catalyst. On the other hand, it goes without saying, material. It can e.g. B. Components with silica that the hydrogenation catalyst in this process can be kept in earth-alumina, silica-magnesia, silica-as well as in the above-mentioned process in an alumina-zirconia, acid-treated clays and the like reaction equipment used by the 20 as well as synthetic metal aluminum plant silicates used for the hydrocracking catalyst, e.g. B. synthetic chabazite that is mole separated. are known. Particularly preferred si-

The catalyst components used in the hydrocracking plant, containing silicon oxide, are syn-

Sator is an acidic material with hydrogenation inherently produced silica-alumina products with

shafts and high cracking effectiveness. It consists of a silica content between about 40 and 99 ge

from a hydrogenation component and a percentage by weight.

product that has high cracking efficiency per se or in particularly good results in terms of a high combination with the conversion per working day as the hydrogenation component, even with the ratio of the catalyst used. The moderately low working temperatures used here in connection with the term "high cracking efficiency - 30 _m / high iso-normal ratios and ability" are intended to designate the catalysts whose effectiveness, with repeated regeneration, only has a cat.A value of at least 25 or to show a moderately small decrease in effectiveness, a quinoline number of at least 20 corresponds can be achieved with catalysts that overall (Journal Am. Chem. Society, 72, p. 1554 [1950]). About 0.1 to 35 percent by weight of at least catalysts which do not withstand the conditions used in such experiments using a compound such as cobalt sulfide or nickel sulfide can be included, these compounds being synthetically produced at the generally comparable minimum cracking activity Silica alumina values are deposited by other known processes. From these catalysis agents. Sators, those containing nickel sulphide showed the highest

The hydrogenation component of the catalyst can have an effectiveness of 4 °.

The following hydrocracking catalysts are compounds of metals of groups I (B), II (B), play for those who use the method according to the invention V, VI, VII or VIII of the Periodic Table can be used with the carrier standing. However, if, as in a preferred embodiment, a synthetic fraction of the silica-alumina product consists in any case of a synthetically produced guide, which contains about 87 to hydrocracking zones with such a ratio of 90% silica and a Cat.-A- Value of Iso- to Normal Paraffin Ingredients Delivered 46 Owns. In the context of the dynamic equilibrium values according to the invention, no protection is claimed for the production of the catalysts used, which is far above the theoretical thermolysers,
applied temperatures is used as 5o
Hydrogenation component of the catalyst one or

several of the various metal compounds that make up nickel sulfide (3.6 ° / ₀ Ni) on silica-alumina
count to the aforementioned groups and under the

Reduction prevailing in the hydrocracking zone The preparation of this catalyst (No. 425-2) was not followed by the corresponding metals 55 being grossly reduced by impregnating 111 one. Such silica-alumina mixtures ground in the hydrocracking zone with compounds that are not easily reducible are oxides 2896.9 g Ni (NO ₃ ) ₂ · 6 H ₂ O, which have been dissolved in sufficient water and sulphides of molybdenum, tungsten, chromium, rhe were to bring the total solution to nium or zinc as well as the sulfides of cobalt, nickel, 88CO cm ³ . Then the spheres became copper or cadmium. More Hydrierungskataly- ^6o kept for 24 hours at 21 ⁰ C. Then, the catalysts were in this group are dried and various metals of the groups mentioned, for example, the complexes of the calcined comparable catalyst for 10 hours at 121 ⁰ C then 10 hours at 538 ⁰ C. The calcined cobalt-chromium and nickel-chromium. If appropriate, product was reduced in a hydrogen atmosphere at more than one hydrogenation component present - 303 ° C. and 84 ° C. and the resulting product can be present. The amount of hydrogenation component 65 nickel-containing catalyst in an atmosphere sulcan fidied within relatively wide limits, which contained 8% H ₂ S in hydrogen at 84 atmospheres and between about 0.1 and 35% or more, based on 303 ° C, whereby essentially the entire weight of the entire catalyst, will vary. Nickel was converted into nickel sulfide.

7 8

Nickel sulfide (2.5% Ni) on silica-alumina cobalt sulfide (2% Co) and chromium sulfide (3.53% Cr)

τλ · γτ Ii λ · π ι / XT -> i ^ on silica-alumina

The preparation of this catalyst (No. 316) was carried out by impregnating 111 of a coarse The preparation of this catalyst (No. 174-5) ground silica-alumina mixture with a 5 was followed by preparing an aqueous slurry solution, which was followed by mixing 1500 cm ^{3 of} water and mung with 1130 g of the chelate of chromium and ethylene-500 cm ^{3 of} ammonium hydroxide solution with 1082 g of ethyl diamine tetraacetic acid and the addition of 196 g of cobalt lenediaminetetraacetic acid and 469 g of nickel carbonate carbonate to the slurry, after which the solution had been prepared, the solution was stirred with water until the bubble formation was filled to a total of 4000 cm ³ . That im- io heard, and was filled up ^{to 1779 cm 3.} This product was prägnierte 24 hours at 21 ⁰ C overall solution was heated to 60 ⁰ C and added to 2280 cm ³ of the hold, and then centrifuged for 10 hours in coarsely ground SiO ₂ -Al ₂ O ₃ added solvent mixture. The air calcined at 538 ° C. to convert the nickel chelate into the product obtained was then converted to nickel oxide for 24 hours. Subsequently, the 60 ⁰ C was maintained, then centrifuged and calcined for 10 hours at the catalyst in a hydrogen atmosphere at 344 ° C 15 538 ⁰ C. The calcined product was reduced in atm and 84 and in place in the reactor an atmosphere of hydrogen under 84 atm at 356 ⁰ C tion vessel by using a stream sulfided, reduced. Then the cobalt and that of a catalytic cycle oil (49 volume chromium metals by treating with an over percent aromatic substances), the 0.1 volume amount of a solution of 10 volume percent dimethyl disulfide at a pressure of 84 atü 20 percent dimethyl disulfide in hexane mixtures under and in the presence of about 115.83 cm ³ H ₂ per 84 atm at 356 ° C converted into the sulfides, wherein hectoliters feed was added. Hydrogen was present per hectolitre feed in an amount of 116 cm ^3.

Nickel sulfide (2.5% Ni) on silica-alumina

² S molybdenum sulfide (2% Mo) on silica-alumina

This catalyst (No. 353) was produced by impregnating about 7.5 l of a coarsely _{ground SiO 2 -Al 2} O ₃ mixture, which was 530 cm ^{3 of} an ammoniacal mixture in air ver-solution for 24 hours at 205 ⁰ C was dried with 2183.7 g applies that contained 41.4 g ammonium molybdate. Ni (NO ₃ ) ₂ · 6 H ₂ O, which was dissolved in water, and this solution was then filled with the previously 24 hour filling to a total of 7760 cm ³ . The the dried at 205 ⁰ C, coarsely ground SiO ₂ -Al ₂ O ₃ -impregnated base material was thereafter, so that one mixture kept for 24 hours in sufficient amount to a at 21 ⁰ C and calcined for 10 hours at 538 ° C. dried product was obtained that contained the equivalent of Thereafter the catalyst was treated in 2% by weight of Mo. After 24 hours a hydrogen atmosphere, sulfided that at 84 atm at 21 ⁰ C 35 linger the impregnated product and 304 ° C, containing 8% of hydrogen sulfide. centrifuged and calcined at 538 ° C for 5 hours.

After that it was in a hydrogen atmosphere

Cobalt sulfide (4% Co) on silica-alumina reduced below 84 atmospheres at 344 ° C and then in place and

Body by treatment with a hydrofined

The preparation of this catalyst (No. 248-2) was 40 circulation oil (49% aromatics), which was followed by 1 volume percent by impregnating 2000 cm ^{3 of} a coarse dimethyl sulfide, with the same temperature-milled _{SiO 2 -Al 2} O ₃ mixture 1500 cm ^{3 of} a conditions and hydrogen pressure sulphided.
aqueous solution, dje 172.5 cm ³ ammonium hydroxide solution and 373 g ethylenediaminetetraacetic acid and

Contained 168 g cobalt carbonate. Here, the 45 nickel sulfide (1% Ni) and molybdenum sulfide

The solution is heated until the formation of bubbles (1% Mo) on silica-alumina

heard; then it was added to the silica-alumina material added to the previously for 24 hours at this catalyst (no. 296) was was dried at 205 ⁰ C the following. Prepared according to the impregnation method: 28.6 cm ^{3 of} ammonia were centrifuged with the catalyst and 50 80 cm ^{3 of} water were mixed for 4 hours and calcined to 49.3 g of ethylene at 538 ° C. The result was a product whose diamine tetraacetic acid was added. This solution had a cobalt oxide content of 2.2 percent by weight of Co. added to the 22.3 g of nickel carbonate. After using 150.2 g of cobalt carbonate, heating to develop carbon dioxide, 334 g of ethylenediaminetetraacetic acid and 154 cm ^{3 of} Am- the solution were mixed with another solution; , 7 g of ammonium molybdate in writing a second impregnation solution prepared a mixture of 80 cm ^{3 of} ammonium hydroxide and added to the catalyst. After a dwell and 80 cm ^{3 of} water had been produced. After a period of 24 hours at 21 ^° C. , the catalyst was made up to 480 cm ³ with water, which was centrifuged and ^{calcined at 538 3} ° C. for 10 hours. The solution for impregnating 600 cm ^{3 of} the roughly prepared calcined product was then used with 60 milled SiO ₂ -Al ₂ O ₃ mixture. After 538 ⁵ C and 84 atm alternately reduc- 24stündigetn in hydrogen dwell at 21 ⁰ C was imziert and oxidized in air, repeated five times prägnierte material was centrifuged and 10 hours at. Subsequently, the catalyst was maintained by 538 ⁰ C. Thereafter, it was treated in a water with an excess of a mixture of substance atmosphere below 84 atmospheres at 344 ° C reduced 10 percent by volume dimethyl disulfide in hexane mixtures 65 and then sulfided at the same temperature below 84 atmospheres at 356 ⁰ C, with hydrogen conditions and the same hydrogen pressure with sulfided in an amount of about 115.83 cm ³ per hectolitre of a solution containing 10 percent by volume of di-feed was present. methyl disulfide contained in hexane mixtures.

The resulting saturated product with a low nitrogen content is cm (z. B. Both fresh and circulatory feed) ³ hydrogen per hectolitre total charge regardless of the nature of the preceding Hydrofinier- and saturation levels in mixture with at least 8.9 at temperatures of about 177-370 ⁰ C and passed over a hydrocracking catalyst at pressures of at least 28 atm. In the hydrocracking reaction zone at least

10

example 1

To find out the difference between hydrocracking an aromatic compound with corresponding Molecular weight obtained products and those obtained in a similar process Show products in which the same compound is first saturated and then hydrocracked, became hexamethylbenzene (nitrogen free) at one

4.45 cm ³ and usually about 8.9 to 26.7 cm ³ IO average temperature of 344 ° C, a pressure of hydrogen per hectolitre of total charge of 84 atmospheres and a throughput rate per consumption which is converted into products, ie in hours of 8.0 along with 120.5 cm ^{3 of} H ₂ per those boiling below the initial boiling point of the hectoliters of hexamethylbenzene via a hydrocracking feed to this zone. catalyst made of nickel sulfide (3.6 wt.

The pressures applied in the hydrocracking zone 15 percent Ni) on a synthetically produced pebble lie above 28 atmospheres and can even consist of up to 210 atmospheres earth-alumina carriers. In this process or more, preferably about 35 to 140 atmospheres, the conversion per operation was wear. 97.8% ^a n products below the initial

In general, one can boil the feed to the boiling point of the feed compound. As the hydrocracking zone with a throughput rate ao of about 0.2 to 5 volumes of coal per hour results from the data listed in Table I, a large part of the feed is in aerohydrogen (calculated as liquid) per upper matic compounds with 10 and 11 Introduce carbon surface volume catalyst, preferably atoms per molecule converted,
at about 0.5 to 3. A similar procedure was then carried out using

One of the greatest advantages of the invention consists of application 25 of the corresponding saturated compound in the fact that the mean reaction temperature (Hexamethylcyclohexan) as a starting compound the hydrocracking catalyst below about 370 ⁰ C overall. This was kept nitrogen-free. At such a low temperature, sending at a pressure of 82.95 atmospheres, a long operating time that extends over many hundreds of temperatures of 288 ° C and a throughput rate of 8 hours per hour with an extremely low output, along with 116, 6 cm ³ H ₂ yields of Q-Cg light gases and in the per hectolitre charge passed over a hydrocracking production of a synthetic product with isocatalyst, the nickel sulfide (6 weight to normal paraffin ratios far above the thermopiozentNi) on one synthetic silica clay dynamic equilibrium values, earth cracking carriers contained. This catalyst was possible. In the preferred embodiment of FIG. 35, somewhat more effective than that used in the conversion of the invention, the temperature at which the hydrohexamethylbenzene was used, but this active cracking reaction was initiated with the introduction of a fresh catalyzer in terms of the data of the described versator into the stream, kept as low as only equal work steps only insofar as important as possible (to the same extent as the up- it allowed a lowering of the temperatures from 344 to the maintenance of appropriate conversion 40 288 ° C, while the other conditions,

quantities per operation). The lower the starting temperature, the longer the operating time. at for any given conversion, the allowable exit temperature is a function of catalyst efficiency insofar as the more effective catalysts (i.e. those which, under the given working conditions can bring about a relatively high conversion per operation) the operation of the Allow installation at lower starting temperatures than would otherwise be the case. Preferred Initial temperatures are between about 177 and 344 ° C; it should be noted that the generated Saturated products are less heat-resistant methane than those that were previously not saturated and are ethane therefore let hydropropane crack at significantly lower temperatures than would otherwise be possible. Isobutane

A petrol η-butane fraction and a higher-boiling fraction isopentane can be obtained from the hydrocracked product and the gasoline fraction (e.g. a fraction boiling between n-pentane about 82 and 205 ° C) catalytically 60 isohexanes to be reformed. Products in the stream from the hydrocracking process that are above that desired Boiling end point of the gasoline fraction can be used in whole or in part for jet propulsion or other fuel purposes use.

The benefits that can be obtained by applying the invention are provided by the data the following examples:

z. B. the conversion per operation, remain essentially the same. The transformation in this Process was 99.8% per pass. Table I shows the product distribution achieved.

Table I.

Mole of product per
Mole charge

n-Hexane C ₆ -Naphthenes C ₇ -Naphthenes C ₈ -Naphthenes 65 C ₉ -Naphthenes C ₁₀ -Naphthenes C _u -Naphthenes C ₁₂ -Naphthenes

feed

Hexa-

methyl-

cyclo-

hexane

Hexamethyl
benzene

10.3
4.0
7.7

37.3
5.9

11.8
1.4
7.0
0.5
4.2
8.8

15.7
8.4
2.2
0.8
0.1

0.14

0.16

7.80

58.68

2.28

22.75

0.39

13.28

0.23

3.62

17.86

62.26

3.71

no

no

no

657/392

Table I (continued)

Mole of product per
100 moles of feed

Xylenes

Mesitylene

Pseudocumene

Hemimellitol

Durol, isodurol

Prehnitol

Aromatic C ₁₀ compounds

Pentamethylbenzene

Hexamethylbenzene

feed

Hexa-

methyl-

cyclo-

hexane

Hexamethyl benzene

0.2 0.9 3.4 0.7

21.2 2.7 0.5

19.3 2.2

no no no no no no no no no

It can be seen from the data in the table above that by saturating an aromatic compound prior to hydrocracking, the resulting naphthene is hydrocracked in a greater proportion into a naphthene which contains 4 fewer carbon atoms than the starting compound. The data also show that the saturated starting material provides a much higher yield of the desired light isoparaffin compounds having 4 to 6 carbon atoms in the molecule, while at the same time there is a corresponding decrease in the amounts of undesirable lighter gases and normal C ₄ -C _e paraffins . Furthermore, it can be seen from the data in Table II, which are derived from the data listed in Table I, that the ratio of iso- to normal components in the case of the saturated starting material is many times higher than that achieved using hexamethylbenzene and is far is above the iso-normal ratio calculated from thermodynamic equilibrium ratios.

Table II

Hexamethyl cyclohexane 288 ° C

Example 2

In this process, a catalytic cycle oil, which consists of a with a Californian crude catalytic cracking plant was used. This showed the following Data:

Specific gravity 0.9013

Aniline point, ⁰ C 24

Sulfur, weight percent 0.98

Nitrogen,% 0.01

Aromatic substances, volume percentage ... 58

Olefins, volume percent 10

Paraffins + naphthenes, percent by volume 32

iC ₄ / nC ₄
iC ₅ / nC ₅
iQ / nC _e *

* Based on species with only a single branch, such as. B. arise during the hydrocracking stage.

D-158 distillation, ⁰ C.

Initial boiling point 210

10% 237

50% 249

90% 266

End boiling point 288

The above starting material was hydrofined, taking it along with 53.5 cm ^{3 of} H ₂ per

ίο hectoliters of feed was passed at 50.4 atmospheres, 388 ⁰ C and a throughput rate per hour of 1.0 over a hydrofining catalyst which contained 10.4 percent by weight of molybdenum oxide and 3.6 percent by weight of cobalt oxide, while the remainder consisted of alumina. The resulting product was then treated to remove hydrogen, hydrogen sulfide, ammonia, other gases and water-soluble compounds, leaving a hydrofined product with the following data:

Specific gravity 0.8789

Aniline point, ⁰ C 86

Nitrogen content,% 0.00021

Content of aromatic substances,

Volume percentage 55

Paraffins, volume percentage 12

Naphthenes,% by volume 33

Freezing point, ⁰ C -34

Pour point, ⁰ C -41

ASTM D-158 Distillation, ⁰ C

Initial boiling point 193.5

10% 224

50% 244

90% 263

End boiling point 272

This hydrofined product was then divided into two parts, one part of which was saturated and then hydrocracked, while the other part was only hydrocracked. The hydrogenation of the first of these samples was carried out by passing, together with 116 cm ³ H ₂ per hectolitre of feed at 344 ° C atmospheres below 84 and a throughput speed per hour of 2.0 over a platinum catalyst on alumina (0.75 percent by weight Pt, 0, 8 percent by weight halogen). This saturation process, which required a hydrogen consumption of approximately 196.3 cm ³ per hectolitre of feed, resulted in a product with the following data:

specific weight

Aniline point, ⁰ C

Paraffins + naphthenes,

Volume percentage

Aromatic substances, volume percentage

Freezing point, ⁰ C

Smoke point, mm

0.8423 64

90
10

-37.2
21

Hydrocracking of the hydrogenated product was then carried out by passing it - along with 214.4 cm ^{3 of} H ₂ per hectolitre of feed - over a catalyst comprised of nickel sulfide (2.6% Ni) on a synthetic cracked silica (90%) clay , at an average temperature of 279 ⁰ C, a pressure of 84 atü and a throughput rate per hour of 1.1. At these ratios the conversion to

a boiling below 182 ⁰ C product about 59 volume percent per pass. The following yields were achieved in this process:

Weight percent 0.0

The properties of the product from the hydrocracking zone boiling above 182 ° C were as follows:

C ₁ .
C ₂ .
C ₃ .
iC ₄

nC ₄

0.3 0.9 6.3 0.7

C ₅ -82.2 ° C fraction 9.9

82.2 to 182 ° C fraction 42.7

182 ⁰ C 40.3

Hydrogen consumption per hectolitre converted charge 11.83 cm ³

The fraction boiling at 82 to 182 ° C, the 4% aromatic Compounds containing 77% naphthenes and 19% paraffins were a gasoline admixture product represents, which after passing through a catalytic reforming vessel to a leaded octane value of 100 to 103 improved. The fraction boiling above 182 ° C provided good material for the mixture with jet fuels and had the following properties:

Specific gravity 0.8198

Aniline point, ⁰ C 67

Freezing point, ⁰ C -35

Pour point, ⁰ C -40

Smoke point, mm 24

Content of aromatic substances, ^3ü

Volume percentage 5

When the procedure described using the catalyst of Example 1 and without intervention of a hydrogenation step, it was found that the temperature of the hydrocracking catalyst had to be increased to about 298 ⁰ C under otherwise identical conditions in order to achieve a comparable conversion per pass. The following yields were achieved in this process:

Weight percent ... 0.0 ... 0.8 ... 1.7 ... 4.4 2.1

specific weight

Aniline point, ⁰ C

Composition, percent by volume

Paraffins + naphthenes

Aromatic substances

Freezing point, ⁰ C

Smoke point, mm

0.8319 52

71
29

-32.8
16

45

C ₁

C ₂

C ₃

iC ₄

nC ₄

C ₅ -82 ° C fraction 11.2

82-182 ° C fraction 42.01

182 ° C + fraction 40.1

Hydrogen consumption per hectolitre

converted charge 25.40 cm ³

From the data, it is apparent that the ratio of the 1-C 4 to nC ₄ -products here is much lower than that shown in the hydrogenated material value.

Due to its high content of aromatic components, this product is not suitable for Use as an ingredient in jet fuels.

Example 3

In this process, light catalytic cycle oil of Californian origin boiling between 210 and 287 ° C. and containing 0.09% total nitrogen and 55 volume percent aromatics was hydrofined in the manner described in Example 2 and the total nitrogen content was reduced to 0.0002%. The product, along with 214.2 cm ^{3 of} H ₂ per hectolitre of feed, was then passed first over a first and then over a second individual catalyst under a pressure of 84 atmospheres and a flow rate of 3.0. The first catalyst layer containing the catalyst described in Example 2, and the feed stream was taken at about 260 ⁰ C. The entire stream emerging from the bed, which had a temperature of about 354 ° C. due to the exothermic nature of the hydrogenation reaction taking place above the catalyst, was then passed over the catalyst of the second bed, which consists of a hydrocracking catalyst with the same composition as that of the example 2 existed. This procedure was carried out in one pass and resulted in a conversion of 59.7% of the feed (per pass) to a maintaining 182 ° C boiling product. Based on the total charge for the reaction vessel, the result was a product with the following composition:

C ₁

C ₂

C ₃

i-Q

nC ₄

C ₅ -82 ° C fraction 13.4

82 to 182 ° C fraction 42.5

182 ° C + fraction 38.1

Weight percent ... 0.0
... 0.06
... 1.3
... 6.7
1.4

These factions had the following characteristics:

Q-82 ° C 82 to 182 ° C

182 ° C +

specific weight

Aniline point, ⁰ C

Paraffins + naphthenes, percent by volume Aromatic substances, percent by volume

Freezing point, ⁰ C

Smoke point, mm

0.6681

99

0.7765
121.5
92
8th

0.8309
149.5
88
12th
-26
21

Claims (3)

Patent claims: 1. A process for the catalytic conversion of hydrocarbon ^{distillates which boil above about 149 °} C. and can be catalytic cycle oils, have a low nitrogen content and contain aromatic hydrocarbons, characterized in that the starting material is optionally first hydrofined and then the aromatic hydrocarbons present therein with hydrogen are hydrogenated in the presence of a hydrogenation catalyst at elevated temperatures and pressures, whereupon the hydrogenated product is hydrocracked in the presence of hydrogen and an acidic catalyst with hydrogenation properties and high cracking efficiency at temperatures of about 177 to 370 ⁰ C and pressures of at least 28 atm and optionally from the Product of hydrocracking a gasoline fraction and a higher-boiling fraction is obtained and the gasoline fraction below Aromatization of the naphthenes is reformed catalytically. 2. The method according to claim 1, characterized in that the hydrogenated feed over a from at least one of the products nickel sulfide or cobalt sulfide and one synthetically produced High cracking efficiency silica-alumina carrier hydrocracked existing catalyst will. ίο 3. The method according to claim 1 and 2, characterized characterized in that a starting material with a nitrogen content above 0.001% is used is hydrofined and while reducing the total nitrogen content to a value below 0.001% is, whereupon the hydrofined product together with added hydrogen in an amount that at least sufficient to saturate the aromatic compounds present, over one Platinum catalyst hydrogenated on an alumina support ao and hydrocracking the hydrogenated feed in the presence of at least 89.2 cm ^{3 of} H ₂ per hectolitre of feed. 509 657/392 8.65 © Bundesdruckerei Berlin