DE2620555A1 - Hydrocracking catalysts contg. noble metals - dispersed in liquid phase of metal fluoride in fluorine-contg. acid - Google Patents

Abstract

Catalysts substantially in a liq. phase, contain (a) a fluoride of Ta, Nb and/or B, (b) HF, 1-4c trifluoroalkyl sulphonic acid or trifluoracetic acid, and (c) a noble metal of Group VIII dispersed on a carrier. (b) is present in at least equimolar ratio to (a), which is at least partly dissolved, and (c) is dispersed in the acid. They are used in the hydrocracking of a wide variety of hydrocarbon materials from petroleum, tar sands, bitumen, coal oils, shale oil, etc. Also for cracking or aromatic hydrocarbons, high mol. wt. paraffins, waxes and polymers into more useful prods. Sulphur-contg. oils may be used, and life of the catalyst is extended since it is not deactivated by coke deposits. Lower hydrogen pressures may be used than with known catalysts.

Description

Hydrocracking Catalyst and Improved Hydrocracking Process Using This Catalyst The invention relates to an improved hydrocracking catalyst and an improved hydrocracking process and relates specifically to hydrocracking using a noble metal hydrogenation component.

A catalyst is generally used for common hydrocracking processes used, the one or more components exhibiting hydrogenation activity either in elemental form or as an oxide or sulfide. Such components are common by impregnation on an inorganic porous carrier material, such as Silica, silica-alumina, crystalline aluminosilicates, and the like existing component deposited. You can work with it very advantageously, but there are nevertheless certain disadvantages. For example, you need high hydrogen pressures such as 1200 to 2000 psig to avoid heavy coke deposits on the catalyst to be avoided (through which the catalyst activity is disruptively reduced). aside from that such catalysts are sensitive to the sulfur content in the feed.

It has been proposed to hydrocrack hydrocarbon feed with one of a metal halide and a proton supplying the system Acid carry out.

The invention is based on the object of a hydrocracking catalyst to propose the one selected from a certain metal halide / protonic acid system exists and one compared to the previous catalysts of this type is greatly improved Service life.

This object is achieved by means of a catalytic converter from the introduction described type in the form of an essentially liquid phase system according to the invention is characterized by the combination of a) a metal fluoride with tantalum, Niobium or boron or a mixture of these metal fluorides, b) a flux, C1 to C4 trifluoroalkyl sulfone, Fluorosulfonic or trifluoroacetic acid, and c) one on a carrier present noble metal hydrogenation component from Group VIII, the acid is present in at least an equimolar ratio to the metal halide, at least a portion of the metal fluoride dissolved in the acid and the hydrogenation component present dispersed in the acid.

According to the invention it has been found that a large number of different Hydrocarbon feedstocks, including feedstocks containing sulfur advantageous at relatively low temperatures and pressures with a long one Hydrocracked catalyst system having a lifetime If the catalyst system is a metal fluoride, one attached to the system Bronsted acid containing proton-donating fluoride and as a hydrogenation component contains a Group VIII noble metal carried on a carrier.

It is essential that the hydrocarbon feedstock in this acid catalyst is relatively insoluble. As a result, if you brings the hydrocarbon feed into contact with the catalyst, the more basic components are preferably extracted into the catalyst phase and be hydrocracked. The products of the hydrocracking reaction, for example paraffins and naphthenes, are then released back into the hydrocarbon phase.

The preparation of the catalyst system is essential for the functioning of the catalyst is important in hydrocracking treatment. So must for example the Bronsted acid must be present in sufficient quantity that at least a portion of the metal fluoride catalyst component is dissolved therein. Based to a metal fluoride should accordingly the Bronsted acid in a molar ratio at least 1: 1 be present in the reaction zone. However, it is recommended generally for the purpose of increasing the activity of the catalyst system, the molar Set the ratio of Bronsted acid to metal fluoride higher (with the maximum amount of Bronsted acid is self-evident from the fact that Bronsted acid is the total acidity of the reaction system). Practically it is the molar ratio of Bronsted acid to metal fluoride expediently at least about 2: 1 and in particular at least 5: 1. The upper limit is not critical per se, since the Bronsted acid acts as a diluent or Solvent able to serve in the reaction. Depending on the relative amount of The materials used make this part of the catalyst a separate phase in the reaction mixture, and at least a portion or the total amount of the metal halide is dissolved in the Bronsted acid. In the invention Metal fluorides that can be used as catalysts are the fluorides of tantalum, niobium and boron. Often, when using tantalum and niobium, these metals are used in the form of a intimate mixture, and accordingly mixtures of tantalum and niobium fluorides used will. Tantalum and niobium are preferred.

The Bronsted Acid component of the catalyst should be a fluoride containing compound capable of delivering protons to the system, a protonic acid. (Materials containing fluoride are useful to prevent undesirable halogen exchange reactions be avoided). Usable acids are, for example, hydrofluoric acid, fluorosulfonic acid, Trifluoromethanesulfonic acid and trifluoroacetic acid. The acids can be used alone or use in a mixture with their corresponding anhydrides. It is preferred to use Hydrogen fluoride.

The third component of the catalyst system according to the invention can generally speaking, a Group VIII noble metal hydrogenation component. Such Components are usually used alone or in conjunction with other materials used for the hydrogenation of unsaturated hydrocarbons. The hydrogenation component should be a metal on a carrier material or an oxide or sulfide of the metal. It can be qin metal from the platinum group (platinum, Osmium, palladium, iridium) or the palladium group (palladium, ruthenium, rhodium) Act.

Platinum, palladium and iridium are the preferred metals, and it is particularly expedient to use palladium and platinum.

The hydrogenation component is advantageously on a solid Support material that does not react with the acidic components of the catalyst system and can be mixed with the acidic components, so that the hydrogenation component similar to a slurry or dispersion in the acidic catalyst phase and not in the hydrocarbon phase. Activated carbon, Charcoal, carbon, coke, fluorinated or sulfonated refractory oxides, Teflon and the like can be used. However, in the present case, the known untreated carrier materials, such as aluminum oxide, silicon oxide, Titanium oxide and other of these heat-resistant oxides are unsuitable as they are resistant to fluoride are sensitive and can be attacked and broken down by fluorides. One a particularly preferred hydrogen-active component is palladium on carbon.

The hydrogenation component of the catalyst system according to the invention is generally available commercially. However, you can do them in a simple way also produce it yourself by bringing the carbon carrier material into contact with an aqueous solution of the metal halide, evaporation of the water and then Reduce with hydrogen for 2 hours at about 3000C. The hydrogenation component can expediently have a particle size of about 38 μm to 25 mm, preferably 75 / by up to 12.5 mm.

The amount of hydrogenation component used is not critical. However, it should be sufficient that it will last for a longer period of time of the catalyst remains effective in the acidic hydrocracking catalyst. The longer one The life of the catalyst begins to have an effect when the content of hydrogenation component at least about 0.0001% by weight, advantageously 0.001% by weight and in particular at least Contains about 0.05% by weight of metal therein, the% by weight of the metal in the Hydrogenation component is calculated based on the acid. By adding higher amounts of the hydrogenation component, the rate of hydrogenation is simply increased.

The complete catalyst combination of the present invention is one Liquid-phase acid containing a precious metal deposited on a carrier material is. As mentioned before, it should be such a carrier material that does not react with the acid. The concentration of the precious metal on the carrier material may be about 0.01 to about 20 wt.%, preferably about 0.2 to about 10 wt.%, based on the carrier material. The metal component present on the carrier can be in the particle size of a fine powder, for example with diameters of 38 / µm to 25 mm. However, the particle size is not critical Size in the manufacture of the catalytic converter (it is sufficient if it is on the carrier material located metal in the form of a dispersion in the acidic catalyst phase present) . The metal present on the carrier material helps to increase the service life of the acidic catalyst, even if only in very small amounts, for example in amounts of about 1.0 x 10% by weight, advantageously 1.0 x 10 3% by weight and in particular 5.0 x 10-2% by weight (% by weight of noble metal, based on the acid) is present. if if the powdered noble metal is added to the acid, it is instantly wetted and forms a dispersion in the acid. As a result, it separates on the carrier metal not present even after repeated extraction with hydrocarbons from the acid. However, you can use the precious metal located on the carrier material separated from the acid by filtration, centrifugation or other conventional methods.

Although the applicant is the underlying of the present invention Theory has not yet examined or clarified in detail, it assumes that the Fluoride-containing acid releases protons to an aromatic substance, where a Carbonium ion is formed. The noble metal then catalyzes the hydrogenation of the carbonium ion to a partially or fully saturated compound, which is subsequently through the acid is cracked.

The catalyst according to the invention gives the possibility of a large number of hydrocarbon feedstocks, those from naturally occurring Crude oil, tar sands, bitumen, coal liquids or shale oils originate from the hydrocracking treatment to undergo. Suitable feed oils are, for example, the typical gas oil cuts (from atmospheric distillation or vacuum distillation), cycle oils, Residual oils and the like. The hydrocracking process can also be used to less complex feed oils in lower molecular weight products or in to convert better removable connections. Accordingly, according to the invention Hydrocarbons such as benzene, toluene, xylene, anthracene, phenanthrene, pyrene, chrysene, high molecular weight paraffins (up to and including waxes and polymers), naphthalenes and the like.

In general, the term "gas oil" is understood to mean numerous different ones Petroleum oils. In the present description, this term is used unless otherwise In other words, to designate any petroleum fraction that has an initial boiling point of at least about 2150C, a 50% point of at least 2600C and an end point of boiling of at least 3150C and between the start of boiling and the end of boiling point boils essentially continuously. The exact boiling range of a gas oil is accordingly determined by the start of boiling, the 50% temperature and the end of boiling. For practical purposes, they are performed under vacuum at temperatures as high as 6950C Petroleum distillations converted to atmospheric pressure.

Accordingly, in the broadest sense, gas oil is a petroleum fraction, which boils continuously in a range from approximately 215 to 6450C and their 50% temperature is at least about 2600C. For example, a gas oil over the entire range from 215 to 6450C or just over an intermediate range, boil for example between 260 and 4800C.

A residual oil is any fraction that does not distill off will. As a result, each fraction, regardless of the start of boiling, is the heavy one Contains soil products such as tars, asphalts and the like as residual oil. It The residual oil may be the portion of the crude oil that is around 6450C has not yet distilled over, or it may be a processing of a gas oil fraction plus the portion that has not yet been distilled over at 645 0C.

The pyrolysis cycle oils are cuts or cracked oils that are above of the gasoline boiling range usually boil between about 215 and about 4500C. Man can use the pyrolysis cycle oils in the process according to the invention together with fresh Use petroleum feed oil or process it on your own.

The hydrocracking reaction can be carried out in bulk, i.e. without any solvent, or in the presence of a solvent or diluent material. Common solvent or diluent compositions are, for example fluorinated acids and / or acid anhydrides, HF and the like. As a reaction diluent hydrofluoric acid is preferred. If you have a solvent or diluent used, it should be used in sufficient quantities that the viscosity of the reaction mixture remains at a certain level. It is typically 0.10 up to 50, advantageously 0.1 to 20 and in particular about 0.3 to 5 volumes of solution or use diluents per volume of hydrocarbon feed.

The hydrocracking process of the present invention can be carried out at one temperature in the range from 0 to 600 ° C, advantageously at 20 to 300 ° C. Very special it is advantageous to carry out the reaction at a temperature between 60 and 2000C. The hydrocracking reaction is carried out at sufficient pressure that the The hydrocarbon feed and the catalyst are essentially liquid Phase. In general, the hydrogen partial pressures are in the reaction zone between about 25 to 3000, preferably between about 100 to 1000 psig. Depending on the size of the reactor can be 0.01 to 5.0 moles, preferably 0.05 to 2.0 moles Hydrogen present per mole of hydrocarbon feed in the reaction zone be.

The reaction time depends on the reaction temperature used, the nature of the feed and the desired products and can vary widely vary. In most cases, the response time is 0.5 minutes to 50 minutes Hours, preferably in the range from 1 minute to 250 minutes.

The hydrogen needed to hydrocrack the feed can come from any source. For a refining treatment one uses generally a raw hydrogen or a contaminated hydrogen stream, as it is obtained from a naphtha reforming process. Alternatively, you can also use hydrogen Develop in situ by using a hydrogen donor during the course of the reaction introduced into the reaction zone. Examples of useful hydrogen donors are Decalin, isobutane, methylcyclohexane and the like. For the most part it is advantageous to introduce elemental hydrogen into the reaction zone.

In a typical refining treatment, the feedstock for the process, hydrogen and an optimal solvent with the catalyst mixed in a substantially liquid phase. Bringing in contact can can be carried out in a large number of series-connected mixing zones. At this The type of process management is the catalyst phase following the reaction and the hydrocarbon phase by, for example, being allowed to settle from one another separated, and the product is made from residual unreacted by conventional distillation methods Feed material released.

The amount of metal halide catalyst component present in the reaction zone is, except if it is a sulfur-containing feedstock, mostly not critical. It can, for example, in the reaction zone per part by weight on feedstock 0.001 to 10, preferably 0.01 to 5.0 parts by weight of metal halide to be available. If, however, sulfur impurities and aromatic components (excluding toluene or benzene) are included in the feed then is If one wants maximum activity of the catalyst, it is advisable to use the metal fluoride component in molar excess relative to that in the reaction zone to any one Time of the amount of sulfur poison present (sulfur-containing compounds) or aromatic ingredients. Compounds containing sulfur and sulfur form, it is believed, complexes with the metal fluoride catalyst component. In the hydrocarbon phase, between the amount of sulfur complex formed is formed and the amount of sulfur in equilibrium. Responds or complexes accordingly not all of the sulfur present with the metal halide catalyst component. It also has the Seems like the complex formation reaction via an equilibrium or a reaction is reversible, so that the concentration of sulfur in the acidic phase can decrease if the catalyst with a sulfur-free material is brought into contact. If it is worked in such a way that a If the catalyst used is supported on a carrier material, the hourly Throughput rate of the reaction liquid (per hour and per volume of catalyst injected volume of liquid) at a level of less than about 200, usually held between about 0.1 and 20.

As already mentioned above, the catalyst system according to the invention not affected by the presence of sulfur compounds. But when If the maximum catalyst activity is desired, the feed oils, diluents and the individual catalyst components before use for the purpose of removing Water to be purified. One can tolerate small amounts of water if one is willing to accept the corresponding drop in activity of the catalyst. The concentration of water within the reaction zone should expediently be 0.01% by weight, based on the total input material, should not be exceeded and preferably not higher than about 10 wppm. Most of the time it is best to have the reaction taking practical to lead anhydrous conditions.

Unless otherwise stated, the following is described in the following Examples use the following general procedure: In a 1 liter, Hasteloy C reactor fitted with a Parr Model 4521 stirrer (or in a 300 cm Hasteloy-C-Autoclave Engineers Autoclave) were tantalum pentafluoride (Ozark-Mahoning Company) as a white powder with a melting point of 97 ° C, and 5% platinum on carbon (Engelhard) as a carrier material entered. The reactor was closed and partially evacuated. Then was hydrogen fluoride added from a container connected directly to it. As a result, the Reactor injected hydrogen, it became the hydrocarbon reaction components and the solvent was added, and the reaction mixture was usually kept at 50.degree stirred at a speed of 600 rpm. It became a liquid sample at 500C removed. For this purpose, an evacuated 10 cm3 stainless steel cylinder was attached to the Connected to the reactor. Then the valves were in the connecting line between the two containers opened, and by a dip piece was due to the pressure difference Liquid aspirated into the smaller container. The fluid sample was on -700C cooled. A sample lot was then placed on a Model 1520 Aerograph Gas Chromatograph analyzed with a DC 200 on a Chromosorb P column (3.18 mm by 9.15 m) at 900C. The reactor was then cooled to room temperature, and all gaseous Components were in an evacuated 100 cm3 with liquid nitrogen cooled stainless steel cylinder collected until the pressure in the Reactor had gone down to 1 atm. This procedure required several Stages; this included a periodic expulsion of the hydrogen at temperatures of liquid nitrogen.

The following examples are the composition of the catalyst and the reaction components as well as the product distribution depending on the respective conversion reaction illustrated.

Example 1 Reaction of cyclohexane in n-hexane at 50 ° C. with TaF5-HF catalyst reaction components ml g moles mol% cyclohexane 16.2 12.6 0.15 10 n-hexane 176.3 116.4 1.35 90 H2 - 0.4 0.2 catalyst TaF5 14.6 69.0 0.25 HF 20 20 1 5% Pt / C - 1 2.56 x 10-4 reaction conditions temperature, ° C 50 # 2 ° time , Hours 5 moles of reaction components 6 moles of catalyst Product distribution range% C1 - C5 2,2-dimethylbutane (2,2-DMC4) 2,5 2,3-dimethylbutane (2,3-DMC4) + 37.7 2- Methylpentane (2-MC5) 31.5 3-methylpentane (3-MC5) 10.4 n-hexane (n-C6) 16.1 methylcyclopentane (MPC) + cyclohexane (CyC) 6 total 100.1 conversions percent rate (hr -1) 80.8 0.29 82.2 0.33 Example 2 Reaction of decalin in n-hexane at 50 ° C. with TaF5-HF catalyst Reaction components ml g mole mole% decalin 23.5 20.7 0.15 10 n -C6 176.3 116.4 1.35-H2 - 1.2 0.6 catalyst TaF5 11.7 55.2 0.20 HF 20 20 1 5% Pt / C - 1 2.56 x 10 -4 reaction conditions temperature, ° C 50 ° # 2 time, hours 5 moles of reaction components 7.5 moles of catalyst Product distribution range C1-C3, C5 2.2 C4 5.4 2.2-DMC4 37.7 2.3 -DMC4 + 2-MC5 31.8 3-MC5 10.0 n-C6 11.4 CyC6 + MCP total 100.0 conversions percent C-speed (hr-1) 53.8 D.15 87.3 D.40 Example 3 Reaction of cyclohexane in n-hexane at 50 ° C with the TaF5-HF catalyst in the presence of naphthalene feed material ml g mole mole% n-C6 208.9 137.9 1, 60 78.43 CyC6 43.2 33.7 0.40 19.61 5.20 0.04 1.36 catalyst TaF5 5.9 27.6 0.10 HF 36 36.0 1.75 H2 1.8 0.9 5% Pt / C - # 0.5 1.28x10- 4 reaction conditions temperature 50 ° C time 5 hours

Moles of reaction components 16 moles of catalyst Example 3 (continued) The results show the following product distributions and conversions: Product distribution range% C1-C5 (minus C4) 1.54 i-C4 + n-C4 1.69 2.2-DMC4 40 .80 2,3-DMC3 + 2-MC5 33.31 3-MC5 11.55 n-C6 6.54 MCP + CyC6 4.53 total 99.96 conversion percent 91.7 76.9 86.2 Example 4 Reaction of polypropylene in Freon 113 at 500C with the HF-TaF5 catalyst Reactor: Autoclave Engineers Autoclave reaction component with a capacity of 300 cm3: 5.0 g polypropylene - average molecular weight 200,000, 20 meshes ( Tyler Sieve Scale), Melt Index 5 3 Solvent: 100 cm Freon 113 Catalyst: TaF (27.6 g, 0.10 moles) HF (31.0 g, 1.55 moles) 5% Pt on C (0.5 g ) Conditions: temperature, ° C 50 initial pH, kp / cm 35.2 (final pH = 17.6 kp / cm 2 2 stirring speed, rpm 600 time, minutes 45 product distribution range% propane 7.32 isobutane 56.65 Normal butane 2.28 isopentane 24.13 normal pentane 3.57 2,3-dimethylbutane + 2-methylpentane 6.86 3-methylpentane 1.55 normal hexane 0.64 84% conversion of the polypropylene in 45 minutes.

Example 5 Reaction of polyethylene in Freon 113 at 50 ° C with the HF-TaF5 catalyst 3 Reactor: 300 cm Autoclave Engineers Autoclave reaction component: 5.0 g polyethylene - average molecular weight 800,000 20 mesh, melt index 0.3 3 Solvent: 100 cm Freon 113 Catalyst: TaF5 (27.6 g, 0.10 mole) HF (41.0 g, 2.05 moles) 5% Pt on C (0.5 g) Conditions: temperature OC 50 initial pressure H kp / cm 35.2 (final pressure H2 = 14, lkp / cm rotary speed rpm 600 time, minutes 22 Product distribution Range% propane 7.30 isobutane 52.09 normal butane 1.15 isopentane 25.47 normal pentane 3.61 2,3-dimethylbutane + 2-methylpentane 7.71 3-methylpentane 1.78 normal hexane 0.89 72% conversion of the polyethylene in 22 minutes.

Example 6 Hydrocracking a feed having a boiling range from 204 to 371 C using an HF / TaF5 catalyst 3 It were in a 300 cm Hasteloy-C autoclave 34.5 g of a hydrocracking feed (82 ppm sulfur, 17.5 ppm nitrogen, 45% paraffins and naphthenes, 55% aromatics) with a boiling range of 204 to 371 ° C., 46.5 g (2.34 moles) of hydrofluoric acid and 55.2 g (0.200 moles) of tantalum pentafluoride was added. Hydrogen got on top of the autoclave applied to a pressure of 500 psig. It was then heated to 80 ° C., whereby the total pressure was maintained at 700 to 900 psig using hydrogen. As the reaction progressed, the autoclave was temporarily cooled and out Any hydrocarbon gases that have formed are vented. It was then in each case fresh feed also added. The hydrocracking reaction of the feed was followed by observing the hydrogen consumption on a measuring device. While a good conversion was observed in the first approach with the feedstock could be, only a small implementation could be seen for the second approach, and in the third approach, no implementation was found at all. The temperature was briefly increased to 80 to 1400C during the reaction to speed up the reaction to increase. After 51 hours the hydrocarbon layer was separated from the acid layer severed. The remaining acid layer was treated with ice. The oil that is from the resulting The two-phase solution was adopted with the remaining hydrocarbon products combined and it was a yield of 78.5 g of oil obtained.

Reaction time temperature- added hydrogen- (hours) range ( C) Input material consumption ~~~~~~~~~~~~ material (g) (millimoles / hour) 0 - 34.5-6 80 34.5 22 27 70 - 100 - 2.9 46.5 120 34.5 4.7 51 140 - 0 In this experiment demonstrate that the acid-HF / TaF5 catalyst has very good hydrocracking activity showed for the first use of input material, but in the subsequent uses was quickly deactivated. This could be seen on the display for the hydrogen consumption recognize; this indicated that the reaction stopped after the second cycle.

Example 7 Hydrocracking ice feed with a boiling range from 204 to 371 C using an HF / TaF5 - Pt / C catalyst In a 300 Hasteloy C autoclaves were 1.83 g of 5% Pt / C, 34.5 g of the hydrocracked feed with a boiling range of 204 to 371 0C, 46.9 g (2.34 moles) Hydrofluoric acid and 55.2 grams (0.200 moles) of tantalum fluoride.

The mixture was pressurized with hydrogen and brought to 80 ° C heated. The reaction was carried out in the same manner as in the foregoing Example described made. The hydrogen pressure was throughout Reaction held between 300 to 1000 psig. After working up the reaction product a yield of 300.2 g of oil was obtained. The analysis is given below.

oC wt.% of input wt.% of the 300.2 g of material that is in yield Product boiled in the range that boiled in the range <-17.8 - 0.7 -17.8 to 204 7.0 41.1 204 to 371 93.0 58.3> 371 Reaction TemperatOr Amount of hydrocarbons Hydrogen time, hours range, C feed samples, g consumption of one millimole / hour.

Set material, g 0 --- 34.5 5 80 - 90 34.5 - 38 23 80 - 90 34.5 - 23 26 100 34.5 55.4 50 30 100 34.5 28.0 49 47 80 34.5 31.8 11 50 110 34.5 35.2 63 53 110 34.5 33.8 66 55 120 34.5 - 95 71 80 --- 70.1 21 This Experiment shows that by adding the Pt / C to the HF / TaF5 hydrocracking catalyst the Activity of the acid catalyst by a factor of 1.7 and the lifetime practically were increased indefinitely. The increase in catalyst activity was determined by Divide the hydrogen consumption in the first hour of the experiment by the Hydrogen consumption in the first hour of the experiment according to Example 6. The increased The life of the catalyst can be seen from the fact that after 8 cycle throughputs further hydrogen was consumed.

In the experiment in Example 6, the hydrogen consumption stopped 2 circuits.

Example 8 Hydrocracking a feed having a boiling range from 204 to 371 C using an HF / TaF5-Pt / C catalyst In a 300 cc Hasteloy C autoclaves were 1.0 g of 5% Pd / C, 34.5 g of the 204 bis 3710C boiling hydrocracking feed, 45.8 g (2.29 moles) hydrofluoric acid, and 55.2 g (0.200 moles) of tantalum pentafluoride were introduced.

Hydrogen pressure was released and the mixture was brought to 80.degree warmed up. The procedure was continued in the same way as in those previously described Try indicated. The hydrogen pressure was maintained during the entire reaction time held between 300 and 900 psig. The final hydrocarbon product was, as in the previous experiment described, separated from the acid and closed the Gas and liquid samples added. In a yield of 244 g it became a light Won oil. The analysis is given below: oC wt.% Of input wt.% Of 244 grams of material made into product that boiled in the area <-17.8 0 1.6 17.8 to 204 7.0 62.1 204 to 371 93.0 36.3 reaction temperature added hydrocarbons hydrocarbons time, hours range, C input material samples, g fabric verrial, g need milimoles / hour.

0 --- 34.5-1.5 80 34.5 --- 188 9 80-90 34.5 --- 30 23 90 34.5 47.2 14 31 90-110 34.5 25.2 17 47 110 34.5 29.4 14 55 110-120 34.5 28.3 30 75 100 34.5 33.0 11 79 130 ---- 32.9 24 This example shows that by adding the Pd / C to the HF / Tats hydrocracking catalyst the activity of the acidic catalyst by a factor of 8.5 (determined by comparing the hydrogen consumption in the first hour in this experiment compared to the corresponding consumption in the example 6) was increased. The life of the catalyst was indefinitely extended. After 7 cycles it was the HF / TaF5-Pd / C system still active while that HF / TaF5 system, Example 6, had lost its activity after 2 cycles.

Example 9 Hydrocracking a feed having a boiling range from 149 to 316 C using an HF / BF3-Pd / C catalyst In a 300 cc Hasteloy C autoclaves containing 1.0 g of 5% Pd / C, 51.0 g of a hydrocracked feed (58 ppm sulfur, 43 ppm nitrogen, 71.45% paraffins and naphthenes, 28.55% aromatics) with a boiling range of 149 to 3160C, 44.8 g (2.24 moles) of hydrofluoric acid and 17.6 g (0.259 moles) of boron trifluoride was charged. The mixture was taken with hydrogen Pressure applied and heated to 1300C.

It was made in the same way as in the examples previously described indicated, worked. The hydrogen pressure was maintained during the entire reaction time held between 500 to 1000 psig. The reaction product was, as indicated above, Worked up and a yield of 281.6 g of oil was obtained. The analysis is given below: ° C% by weight of the input% by weight of the 281.6 g of material that in product that boiled in the area boiling <82 0.78 22.9 82 to 204 5.00 29.6 204 to 316 94.22 27.5 Reaction temperature added hydrocarbons hydrocarbons time, hours range, C input material samples, g material consumption, ~~~~~~~~~~~ rial, g ~~~~~~~~~~~~~ millimoles / hour 0 --- 51.0 1.5 130 51.0 - 91 3.5 130 51.0 43.7 57 5.8 130 51.0 46.7 48 21 30 - 100 51.0 47.8 9 24 130 51.0 49.8 52 25.5 130 ---- 49.1 81 This example shows that the super acid Precious metal system made of HF / BF3 / Pd / C is an active hydrocracking catalyst that is used in repeated throughputs did not become inactive.

Example 10 Effect of Noble Metal Hydrogenation Catalyst on Hydrocracking Anthracene with HF / TaF5 A series of experiments were conducted to determine the effect of adding a noble metal hydrogenation catalyst to a super acidic hydrocracking catalyst. All experiments were carried out in a 300 ccm Hasteloy-C autoclave, in which 1.0 g of the respective noble metal to 5 z on carbon, 17.8 (0.100 moles) anthracene, 103 ml n-pentane, 44 to 66 g ( 2.2 to 2.3 moles) of hydrofluoric acid and 55.2 g (0.20 moles) of tantalum pentafluoride were charged. The mixture was pressurized with hydrogen and heated to 80 ° C. for 6 hours. The course of the reaction was monitored by measuring the hydrogen consumption, and the hydrocarbon layer was analyzed by gas chromatography from time to time. The hydrogen pressure was maintained at 500 to 600 psig throughout the reaction time. After the reaction was complete, the material boiling above 1500 ° C. was separated off and analyzed by gas chromatography and by means of nuclear magnetic resonance spectroscopy. The products from the experiment carried out with palladium were also examined by mass spectroscopy and by carbon / hydrogen analysis. Metal hydrogen consumption 1.0 g 5% / C moles without 0.37 Pt 0.35 Ru 0.45 Rh + 0.56 Pd 1.0 products heavy light 10.0 g anthracene # # # # C2 8.6 g anthracene """ 10.0 g anthracene """ 8.9 g anthracene """ 8.7 g completely """ hydrogenated Anthracene + Reaction temperature = 90 ° C, reaction time = 3 hours These experiments make it clear that palladium is superior to all other noble metals in terms of its effect on hydrogen consumption and the type of products obtained when anthracene is used in a hydrocracking treatment using the super acidic HF / TaF5 catalyst is subjected.

Example 11 Acid Catalyzed Noble Metal Hydrogenations A number of Trials were carried out to illustrate the synergistic effect which one during the hydrocracking reactions as a result of the interaction of HF based super acids and palladium.

Since the palladium in the hydrocracking has the task of Hydrogenating aromatics in the feed became the present reactions carried out at low temperatures, so that the effect of the hydrogenation is unaffected could be observed. This was possible because of the cracking reactions in these Temperatures apparently did not take place yet. All of these attempts were made in one 300 ccm take Hasteloy-C autoclave carried out into which the respective metal Carbon, 12.0 g (0.100 moles) of mesitylene, the acid, and up to a partial pressure of hydrogen of 400 psig were introduced. Hydrogen was supplemented according to consumption. From the rate of hydrogen consumption and the amount of hydrogen consumed Hydrogen was determined to be the time up to which the Half of the Aromatics had been saturated. This time was compared to the time up to when the corresponding noble metal catalyst is used in the absence half of the mesitylene of any acid was saturated. After the reaction is complete expired, the product was poured onto ice and separated. It was gas chromatographed and analyzed by nuclear magnetic resonance spectroscopy. It was the extent the hydrogenation and the formation of trimethylcyclohexane.

Try precious metal acid, g speed increase 5% / C, g for the acid-catalyzed reactions (t acid-noble metal hydrogenation # t1 / noble metal hydrogenation) 3317-65 without HF / TaF5, 48 / 55.2 0 3317-69 Pd / C, 1.0 HF, 46 144 3797-109 Pd / C, 1.0 HF / BF3, 46 / 0.229 3600 3317-67 Pd / C, 1.0 HF / TaF5, 46 / 55.2 2500 3317-59 Pt / D, 1.83 HF / TaF5, 48 / 55.2 16 3317-100 Rh / C, 0.97 HF / TaF5, 46 / 55.2 0 3317-96 Ru / C, 0.50 HF / TaF5, 48 / 55.2 0 3317-94 Pd / C, 1.0 TaF5, 55.2 0 3540-13 Pd / C, 0.5 HBr / AlBr3.77.5 / 27 0 3540-2 Pd / C, 1.0 HCl, 50.2 0 4293-54 Ir / C, 1.80 HF / TaF5, 2.2 / 0.20 153 the end From these examples it can be seen that between the noble metal hydrogenation catalyst Palladium and the HF super acids have a special interaction that exists for others Noble metal hydrogenation catalysts and acids were not detected.

Claims (11)

Claims 1. Catalyst in the form of an essentially liquid phase system, characterized by the combination of (a) a metal fluoride with tantalum, niobium, Boron or mixtures thereof, (b) a river, C1 to C4 trifluoroalkyl sulfone, fluorosulfone or trifluoroacetic acid, and (c) a noble metal hydrogenation component present on a carrier from group VIII, wherein the acid in at least equimolar ratio to the Metal halide is present, at least a subset of the metal fluoride in the Dissolved acid and the hydrogenation component are dispersed in the acid. 2. Catalyst system according to claim 1, characterized in that hydrofluoric acid is present as the acid. 3. Catalyst system according to claim 1 or 2, characterized in that that the molar ratio of acid to metal halide is at least 2: 1. 4. Catalyst system according to claim 1 to 3, characterized in that that tantalum is present as the metal in the metal fluoride. 5. Catalyst system according to claim 1 to 3, characterized in that that niobium is present as the metal in the metal fluoride. 6. Catalyst system according to claim 1 to 5, characterized in that that platinum, palladium or iridium is present as noble metal. 7. Catalyst system according to claim 1 to 6, characterized in that that the precious metal is on a solid support material that does not react with the acid, is applied. 8. Catalyst system according to claim 1 to 7, characterized in that that the hydrogenation component applied to the support material is palladium on carbon is available. 9. Hydrocracking process characterized in that there is a hydrocarbon feedstock in the presence of hydrogen and under hydrocracking conditions with the liquid phase catalyst according to any one of claims 1 to 8. 10. The method according to claim 9, characterized in that one is a Feedstock with an initial boiling point of at least about 2150C is used. 11. The method according to claim 9 or 10, characterized in that the hydrocracking process is carried out at temperatures in the range from about 20 to 3000C.