DE2154592C3 - Process for the hydrocracking of hydrocarbons - Google Patents

Description

Liquid flow rate 0.5 to 10, especially 1 to 10, and the maximum catalyst temperature 177 to 343 C. The operating pressures are usually 15 to 137 atmospheres. In many cases, especially with hydrocarbon feeds from the lighter gas boiling range, the working pressure can be 35 to 69 atmospheres and the hydrogen cycle ratio 535 to 1780 parts by volume of gas per part of liquid and the liquid space velocity at 2 to 10 without impairing the life of the catalyst or the product quality If the pressure in the reaction zone is 15 to 35 atmospheres. so butanes are produced to a greater extent, with the amount of methane, ethane and propane increasing slightly but measurably at the same time. The inventive method provides a butane concentrate of 70 his 80 volume percent isobutane, which is extremely rv _e. is desired.

The addition of 1 to 20 percent by weight of a leather-molecular olefin, such as ethylene, propylene, butylene or pentenes, to the hydrocarbon flow leads to a reduction in butane formation and the conversion of the C ₄ carbonium ions on the catalyst with the olefins. The reaction products formed are then formation of paraffins with a higher molecular weight hydrogenated Suitable alumina carrier for the catalyst pickling a bulk density from 0.30 to 0.70 e / cm ^3, • .iien average pore diameter of 20 ■, s 300 A, a pore volume vnn 0.1 to 1 ml / g and. ■ me inner surface of 100 to 500 m ² / g. The carrier material can have been activated before use, for example by drying, calcining or water inoculation, and can have any desired shape.

As a further component, the catalyst contains nickel or a noble metal from group VIII des Periodic table of the elements, such as platinum, palladium, rhodium, ruthenium, osmium or iridium, etc. Platinum, palladium and nickel are preferred. The Group VIII noble metal can be in the catalyst also exist as a compound, such as an oxide, sulfide or halide, but is usually in elemental form in it State present. The precious metals

35 the catalyst is generally holds in a Mcnpe from 0.1 to 2 percent by weight, nickel in an amount of I to 10 weight percent, based on the weight of the finished catalyst. These metal constituents can be incorporated into the catalyst by co-precipitation with the carrier material or by impregnation, expediently with a water-soluble compound of the metal in question. For example, an aqueous solution of chloroplatinic acid can be used to incorporate platinum. Ammonium chloroplatinate, platinum chloride or dinitrodiaminoplatinum, a solution of chloropalladic acid or palladium chloride can be used to incorporate palladium and a solution of nickel nitrate hexahydrate can be used to incorporate nickel. In general, the support is impregnated with the metal constituent after calcining in order to keep metal losses as low as possible, and the catalyst is then dried, calcined again and generally reduced with hydrogen at elevated temperature.

The combination with the Friedel-Crafts metal halide takes place by sublimation only afterwards, since the bond created in the process —Al — 0 — AlCl _{2 is} sensitive to moisture. The sublimation or vapor deposition of the metal halide onto the support is carried out while heating it to a temperature above about 300 ° C. for a sufficiently long time to remove any unreacted metal halide, so that the finished catalyst no longer contains any free Friedel-Crafts metal halide. The alumina carrier increases in weight by about 2 to 25, preferably about 5 to 20%.

In addition, the Aufsublimieren or vapor deposition is carried out at the sublimation point of the corresponding metal halides up to a temperature which is not higher than 100 ⁰ C above the sublimation point. The sublimation can be carried out under pressure and also in the presence of a diluent such as an inert gas.

If the Friedel-Crafts metal halide is aluminum chloride, the finished catalyst has groups of the formula —Al — O — AlCl ₂ , which can be linked to one another as follows:

..- Al - O - Al - O - AICI ₂

I ο

Al-O-AlCl ₂

CI ₂ AI - 0 — Al -

As Friedel-Crafts metal halides, for example, aluminum chloride, aluminum bromide, antimony pentachloride, Beryllium chloride, iron (III) bromide, iron (III) chloride, gallium trichloride, tin (IV) biomide, Tin (IV) chloride, titanium tetrabromide, titanium tetrachloride, Zinc bromide, zinc chloride and zirconium chloride can be used. Are particularly preferred Aluminum chloride and aluminum fluoride, not only because of the ease of their manufacture, but also, as they give the catalyst a surprisingly high hydrocracking activity.

It is also possible instead of direct sublimation of the metal halides in the preparation of the catalyst to proceed in such a way that a non-metallic Halogen compound, which reacts with the alumina to form aluminum halide, with the alumina reacts, the aluminum halide thus formed then reacting with further alumina

5 6

and forms the - Al - O - AICI "groups. Such crane. To counter this harmful influence

non-metallic halogen compounds are harmful, a high-boiling organic chloride,

for example CCI ₄ , SCI ₃ and SOCI ₂ . such as nonyl chloride, decyl chloride, undecyl chloride, do-

Before hydrocracking, the catalyst will be reduced to decyl chloride, alkyl chlorobenzene, alkylbenzyl chlorides to get a more uniform distribution of 5 or chlorinated alkylcyclohexanes, the fresh black metal constituents. For this purpose, an amount of approximately 100 to 500 ppm of the weight of the fresh charge is used as a reducing agent, practically pure and dry hydrogen is used.
this hydrogen usually at one temperature

to 650 ⁰ C for half 427-10 hours behan- io Example 1
ddt.

The hydrocracking process is often improved. The catalyst consisted of alumina with about when the catalyst after reducing is up to 0.4 weight percent palladium and about 5.0 percent by weight Content of 0.05 to 0.5 percent by weight of aluminum fluoride, which is then based on sulfur, calculated as an element that is sulfided. This 15 had been sublimed and containing the palladium Treatment takes place in the presence of hydrogen alumina had reacted.

and a suitable sulfur-containing compound The objective was die'Erzeugung maximum such as hydrogen sulphide or low molecular weight mer- amounts of a jet fuel light oil fraction with mercaptans, advantageously using a mixture of 10 mol of an initial boiling point vn about 150 ⁰ C and a hydrogen per mole of hydrogen sulfide at a 20 final boiling point from about 288 to 290 ° C and a temperature of 10 to 600 ° C with a heavy gasoline fraction that is practically light in water. Charging exempt conditions. sat a specific gravity of 0.933, an initial

The hydrocarbon feed is preferably boiling at 139 ° C, a distillation temperature free of water and oxygenated compounds. at 50.0 percent by volume of 385 ° C, at 90.0 volume-The catalyst can be as a fixed layer, as 25 percent of 479 ⁰ C and an end boiling point of agitated bed, fluidized bed or in a batch, about 510 ° C, a Content of 1.2 percent by weight can be brought into operation. While generally sulfur and about 3038 ppm by weight nitrogen. The use of the system with a fixed layer of charging was initially preferable in an amount of about, but is recommended for more than 181 m ³ / hour. containing catalyst at a maximum temperature usually heavy feedstock compositions, the ^non-r 30 of about 413 C, a combined Einspeisverdestillierbare asphalts and asphaltenes, ratio of 1.0 and an hourly liquid inlet fluidized bed system. When working with. fixed space velocity of about 0.1 with a water-lying layer, a hydrogen-rich gas material cycle rate of about 1070 parts by volume of gas is heated and the charge mass is heated to the desired reactivity of 15 ° C and 1 at per part of oil at 15 ° C of a purification temperature Conversion zone 35 subjected. The pressure is initiated in the reaction zone. _ψ The latter can be one or more totaled around 103 atü. The total effluent was introduced with separate reactors with suitable interposed a temperature of about 43 ° C in a high pressure equipment, which included the desired conversion low temperature separator, from which the temperature at the entrance to each reactor ensure proportion of butanes and higher hydrocarbons. The reactants can remove the catalyst as a liquid product. Including the sator layer either in the upstream, in the downstream or the hydrogen consumption, the feed preferably passed through in radial flow. In addition, for the subsequent hydrocracking zone, the reactants can represent 99.72 percent by weight and 110.45 percent by volume of the fresh catalyst in vapor or liquid or as feed. The feed for the hydromixed liquid vapor phase is present. 45 cracking zone comprised 1.73 percent by volume butane, 1.25 percent by volume

Since hydrocracking reactions are exothermic, lum percent pentanes, 1.43 vol percent hexanes,

the temperature in the catalyst layer. The 2.46 percent by volume of a fraction of heptane up to

Kalalysatorhöchsttemperatur to 175-345 ° C 149 ^C loading C, 39.98 volume percent of a fraction of 149

carry. When hydrocracking a heavy coal up to 288 ° C and 63.60 percent by volume hydro

hydrogen material is that part of the product, 50 substance material, which boiled above 288 ° C. Because

that above the final boiling point of the desired volumetric increase to 110.45 percent by volume

Product is boiling, to combine with the fresh was the "fresh feed" to the hydrocracking zone

Hydrocarbon feed recycled. In sol- about 200 m ³ / hour. This was with about 66 m ³ / hour.

In these cases, the combined feed fluid is combined to form a combined

ratio, d. H. Raiim parts of the total liquid loading 55 to give an enema ratio of about 1.33. The

Each part of the volume of fresh liquid mixture sent to the reaction zone was about 1250 parts by volume

Feed to the reaction zone, within the hydrogen per volume of oil mixed and the mixture

rei-. ; s range from 1.1 to 6.0. heated to about 302 ^{° C.} The liquid enema streaked

■ '. a few cases, where the high-boiling points through the catalyst with a liquid space

Loads of metallic impurities and 60 speed of about 1.55, based on fresh

Contain asphalt, the catalyst can run in, ur.d the hydrocracking zone pressure was about

Aromatics with strongly condensed rings poisoned 98 atm. A common hydrogen quench stream of

graze. Apparently these aromatics are solid about 450 parts by volume per part by volume of oil was used to

adsorbed before hydrocracking occurs. Since even the maximum temperature at the reactor outlet is 330 ° C

a previous hydrofining treatment to keep this flavor. Subsequent to the product separation,

Mat is not sufficiently hydrated, especially if the approximately 66 m ³ / hour. of the 288 ° C + liquid to the

if the feeds are higher boiling point, the inlet to the hydrocracking zone is recycled. The fol-

If the catalyst mass finally changes its action table shows the product yield:

Table I.
Product yield and distribution

component

yield

Ammonia 0.37 percent by weight

Hydrogen sulfide ... 1.28 weight percent

Methane 0.15 percent by weight

Ethane 0.27 percent by weight

Propane 1.65 percent by weight

Butane 10.94 percent by volume

Pentane 9.80 percent by volume

Hexanes 8.34 percent by volume

Heptane up to 149 ⁰ C .... 22.33 percent by volume

149 to 288 ° C 70.02 percent by volume

Total liquid

excluding 123.43 percent liquid volume

In the second reaction zone, the hydrogen consumption was 1.42 percent by weight, based on fresh feed to the first reaction zone, or 157 parts by volume per part of oil. For the whole process the total hydrogen consumption was thus 3.68 percent by weight or 406 parts by volume per part of space Liquid inlet.

The butane product was approximately 75.0% Isobutanes and about 90.0% of the pentane product are isopentanes. The combined pentane and hexane possessed a specific gravity of 0.657, an octane number from 85.0 clear and from 99.0 leaded. The heavy gasoline fraction from heptane to boiling point 149 ° C had an octane number of 68.0 clear and 86.0 leaded with a specific gravity of about 0.759. This Heavy gasoline contained about 1.0 percent by volume of aromatics, about 82.0 percent by volume of naphthenes and only about 17.0 percent by volume paraffins. The desired jet fuel luminous oil fraction had a specific one Weight of 0.808, contained 5.0 percent by volume aromatics and had an IPT smoke point of 27 mm. The heavy gasoline fraction, which was about 82.0 volume percent naphthenic, was an excellent one Charging mass for a catalytic reformer.

Example 2

In this example the catalyst consisted of alumina with 5 weight percent nickel. After drying, calcination and reduction in hydrogen, about 7.5 percent by weight of aluminum chloride was sublimed on in order to react with the clay. The catalyst was used to convert an unchanged vacuum gas oil with the aim of producing a maximum amount of a heavy gasoline fraction of heptane up to a boiling point of ^{193 c C.} The fresh feed had a specific gravity of 0.904, an initial boiling point of about 321 ° C, a distillation temperature for 50.0 volume percent liquid of about 416 ° C and a final boiling point of about 552 ° C, and contained 1.70 weight percent sulfur and 760 weight percent ppm nitrogen.

The mass was initially in an amount of about 49.5 m ³ / hour at a maximum temperature of the catalyst ^{layer of about 400 °} C., a liquid space velocity of 1.05, a hydrogen cycle ratio of about 1780 parts by volume of gas per part by volume of liquid feed and a pressure of about 103 atü subjected to a purge. All of the product discharge from the cleaning zone was fed into the hydrocracking zone. The hydrogen consumption in the first reaction zone was about 166 parts per volume of liquid feed or 1.56 percent by weight of the fresh feed. On a weight basis, the normally liquid feed to the hydrocracking zone consisted of about 1.09% butanes, 0.90% pentanes, 1.09% hexanes, 10.71% of a fraction of heptane bis

ίο Boiling point 193 ° C and 84.97% hydrocarbons boiling above 193 ° C excluding the return flow. The pressure in the hydrocracking zone was about 110 atm, and the combined inlet ratio was about 1.68 at a cycle of about 33.7 m ³ / hr. Hydrocracked product outlet with a boiling range above 193 ° C. The maximum temperature of the catalyst layer was kept at about 305 ° C. with 695 parts by volume of quenching hydrogen per part by volume of liquid feed. The temperature rise in the catalyst ^{layer was about 11 °} C. The liquid space velocity was 0.62, based on the fresh feed alone. Following the product separation, the material boiling above 193 ° C. was recycled. The product yield can be found in the following table.

Table II

Product yields and distribution
Ingredient yield

Ammonia 0.09 percent by weight

Hydrogen sulfide ... 1.81 percent by weight

Methane 0.34 percent by weight

Ethane 0.48 percent by weight

Propane 3.41 weight percent

Butanes, ... 22.10 percent by volume

Pentanes 14.42 percent by volume

Hexanes 18.64 percent by volume

Heptane to 193 ⁰ C, 70.75 volume percent

In the hydrocracking zone, the hydrogen consumption was 178 parts by volume per part by volume of liquid feed or 1.67 percent by weight with a total consumption of 3.23 percent by weight. The 11.0 m ³ / hour Butane consisted of about 80.0% isobutaries and the 7.2 m ³ / hour. About 93.0% pentane from isopentanes. The combined pentane-hexane stream had a clear octane number of 84.0. The 35.1 m ³ / hour the fraction of heptane up to a boiling point of 193 ° C. consisted of about 83.0% naphthenes, 11.0% paraffins and about 6.0% aromatics, based on the volume of the liquid.

Example 3

The catalyst consisted of alumina with about 5.0 weight percent nickel and about 7.5 weight percent aluminum fluoride which had been sublimed onto the alumina-nickel mass. The specific weight of the charge was about 0.845, the initial boiling point 168 ° C, the distillation temperature at 50.0% liquid volume 291 ° C and the final boiling point about 427 ° C. The charge contained 0.57 weight percent sulfur and 130 weight-ppm nitrogen . The feed was in an amount of 132 m ³ / hour. first a cleaning at a maximum temperature of the catalyst ^{layer of about 400 0} C, a combined inlet ratio

409607/404

9 10

of 1.0 and a liquid space velocity - Table III

of about 2.54 with a hydrogen cycle ratio _. . ,,,

of about 1780 parts of volume per part of volume liquid product yields and distribution

subject to inflow. The pressure in the reaction zone constituent yield

was et'-va 42 atü. The total product outflow from ammonia 0.02 percent by weight

of the purification zone was fed into the hydrocracking zone hydrogen sulfide ... 0.61 weight percent

brought in. The hydrogen consumption in the first methane 0.39 percent by weight

The reaction zone was about 1.02 weight percent or ethane was 0.56 weight percent

102 room parts per room part liquid inlet. Before propane, 3.82 percent by weight

When entering the hydrocracking zone, the product butane was 10.61 percent by volume

outlet from the cleaning zone with el; wa 6.0 Ge Pentane 15.00 percent by volume

weight percent propylene mixed. The usually hexanes 23.65 percent by volume

liquid feed to the hydrocracking zone contained heptane up to 177 ° C 69.05 percent by volume

about 2.04% butanes, 1.50% pentanes, 1.68% hexanes,

9.95% fraction of heptane up to boiling point 177 ⁰ C 15 In the hydrocracking zone, the hydrogen

and 86.72% coal consumption boiling above about 177 ° C, 1.40 percent by weight or 139 parts by volume

Hydrogen, based on the volume of liquid, from the liquid inlet for each part of the space. The hydrogen

finally rewind. The hydrocracking zone consumption in the overall process was 2.41 weight percent

kept under a pressure of about 33.4 atmospheres, and or 240 parts of volume per part of volume of liquid inlet,

the ratio of the combined feed was about ao. The pentane-hexane fraction had a specific one

1.59, which results from the return flow of about 78.1 m ³ / hour. Weight of 0.663 and an octane number of 83.8 clear

The result was the hydrocracked product boiling above 177 ° C and 98.0 remained. The heavy gasoline fraction had

The inlet temperature of the hydrocracking zone was 0.752 specific gravity and contained 54.9%

about 288 ° C, and to maintain the maximum paraffins, 30.6% naphthenes and 14.5% aromatics

temperature of about 315 ° C in the catalyst layer 25 (the liquid volume) and was a suitable one

about 535 parts of space per part of space liquid feed for a catalytic reformer,

Quenching hydrogen inlet used. The liquid octane number was 62.5 clear and 81.3 leaded,

Capacity space velocity, based on fresh feed, when propylene is added to the hydrocracking charge

was about 0.99. The product obtained was decomposed, the butane yield would be 23.11%. the pentane-hexane

sets, and the material boiling above 177 ° C was 30 yield 34.60% and the heavy gasoline yield

returned. The product yields are found in heptane up to boiling point 177 ° C 61.05 (of the liquid

the following table. volume).

Claims (7)

chloride, which does not fall into the group of Friede! -Crafts patent claims: metal halides. From U.S. Patent 2,900,425 and British Patent 898,972 1. Process for hydrocracking coal, on the other hand, isomerization processes are known Hydrogen by converting the hydrocarbons 5 which catalysts are used on a substances with hydrogen in the presence of a nickel alumina carrier platinum and a Friedel-Crafts metal or a noble metal from group VIII of the periohalide. On the one hand, there is it The system of elements on an alumina carrier is a different type of process, and on the other hand containing catalyst, characterized in these cases the Friedel-Crafts metal halo, that one io genid a catalyst by soaking a solution of the same in one used, its carrier from a reactive organic solvent or by dry product Mix of alumina and a sublime incorporated into the catalyst. In both Friedel-Crafts metal halide. In some cases, only a low level of cracking is obtained. 2. The method as claimed in claim 1, characterized in that the invention is based on that one understands a catalyst to mean using new kata in hydrocracking, at which the Friedel-Crafts-Metallhalosatoren work, the milder Hydrocrackbegenid made of aluminum halide, preferably aluminum conditions, such as operating temperatures and pressures, aluminum chloride or aluminum fluoridef. enable and greater selectivity towards 3. The method according to claim 1, thereby yielding hydrocracking catalysts previously used, indicates that a catalyst is used. during its production the halide for the cracking of hydrocarbons by reaction Reaction with the alumina, the hydrocarbons have been sublimed with hydrogen in the presence is. a nickel or a Group VIII noble metal 4. The method according to claim 1, characterized in the periodic table of the elements on a tone, that a catalyst containing a catalyst is used det, in the manufacture of which the sublimed halo is characterized in that a catalyst is used, genid with alumina, which is the noble metal or nickel whose carrier is a reaction product of tonais Contains component has been implemented. earth and a sublime Friedel Crafts metal 5. The method according to claim 1, characterized in that there is halide. indicates that a catalyst is used, if the greatest possible amount of carbon is used to form aluminum halide, which reacts with the alumina with the hydrocarbon fraction boiling in the gasoline range was further reacted with alumina to form the reaction hydrogen products in the propane-butane boiling range, sublimated 35 wants to have,
has been. With regard to interest in unleaded petrol 6. The method according to any one of claims 1 to 5, the method is particularly suitable for the hydro, characterized in that the conversion cracks of heavy gasoline fractions, since it is very reactive with a hydrogen cycle ratio little methane or ethane is generated, propane cone of 535 to 3560 parts by volume of gas 15 ° C, 1 at 40 centrate for later alkylation or isopropyl per volume of liquid feed at 15 ° C, an alcohol production arises, the paraffin hydrocracking hourly liquid space velocity, on relatively large amounts of butane, which is rich in fso-1 to 10 and a catalyst maximum temperature butane, supplies, the resulting pentane-hexane cone from 177 to 343 ⁰ C is carried out. . centrate has a strongly branched constitution and to 7. The method according to claim 1, characterized in that it is suitable for direct use in the gasoline indicates that the hydrocarbon feed is and the heptane and heavier heavy petrol 1 to 20 percent by weight of a low molecular weight product is rich in naphthenes and is ideal kular olefin is mixed. Represents feed mass for catalytic reforming. Heavy loading masses include 50 luminous oils in the boiling range from 149 to 343 ⁰ C, light Gas oils in the boiling range from 260 to 400 "C and heavy gas oils in the boiling range up to about 510 ⁰ C. Hydrocarbon feeds can also be used It is known to use hydrocarbons with hydrogen in a boiling range up to about 566 ° C in the presence of a nickel or a noble metal of 55. When the hydrocarbon feed Group VIII of the Periodic Table of the Elements on sulfur and nitrogen compounds as appropriate a catalyst containing alumina to also metallic components and insoluble asphalt hydrocrackers, to contain practically saturated, generally tene, it becomes habitual before hydrocracking boiling, normally liquid or gas borrowed hydrogenated or hydrofined. to get shaped hydrocarbon products. 60 In the inventive method succeeds in this case had relatively sharp operating conditions, the required hydrocracking temperatures will maxi be applied, such as to reduce temperatures in the range times 177-343 ° C, and in some of about 370-510 ⁰ C and relatively high pressures. In cases, pressures as low as 15 to Die USA.-Patent 3,000,813 and the German 3 * atü are sufficient. Auslegeschrift 1080 717 relate to the production 65 In a preferred embodiment of the Vcrvon Reforming or hydroforming catalysts from driving, the hydrogen cycle ratio is 535 a platinum group metal on an alumina carrier up to 3560 cubic centimeters of gas at 15 ° C and one atmosphere with water-based aluminum impregnation for each part of the room, liquid inflow at 15 ° C, the hourly