DE3013154A1 - HYDRO TREATMENT CATALYST, METHOD FOR PRODUCING AND USE THEREOF - Google Patents

Description

The invention relates to an improved VIb metal / VIII metal / support catalyst which is used for hydrotreating Hydrocarbon materials is suitable, on processes for the preparation of the catalyst as well as on its use for Hydrotreatment of hydrocarbon materials.

Hydrobehar.diung describes the process of hydrodesulphurisation, Hydrodenitrogenation and denetalation of hydrocarbon feeds. The invention is particularly directed to the production of a catalyst composite having superior hydrotreating activity aimed at removing sulfur and nitrogen from high boiling hydrocarbon materials. Examples of such high-boiling materials are whole crude oil, crude distillate residues, atmospheric and Vacuum gas oils and cycle oils.

Crude oil and high-boiling hydrocarbon fractions and / or -Distillates that come from the raw materials contain components such as nitrogen, sulfur and metal contents. These impurities can be present in heteroatoms of compounds and are often present in relatively large amounts. Such impurities can be caused by the catalysts used for upgrading petroleum fractions in reforming or cracking steps poison or alter. Are nitrogen and sulfur

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also therefore disruptive / because the combustion of hydrocarbons fuels containing these impurities, nitrogen and releases sulfur oxides. Such gases as by-products are poisonous, corrosive and bring a number of problems in the field of air pollution.

The removal and / or conversion of these impurities is effected by catalytic hydrotreatment, in which a A feed containing sulfur and nitrogen contents with a supported catalyst in the presence of hydrogen comes into contact. The hydrotreatment conditions can include a wide range of temperatures, pressures and space velocities determined by the equipment of the technical Refineries are determined.

Supported catalysts can generally be characterized as having metallic components supported on a refractory inorganic oxide carriers of synthetic or natural origin, have and a medium to high effective Surface and have a well-developed pore structure. Can become metallic components with hydrotreatment activity the metals belong to groups VIb and VIII of the periodic table.

There are numerous publications on methods of manufacture of supported catalysts for hydrotreatment. Catalytically / active metals can be shaped or unshaped Carriers can be applied by one of several impregnation methods known from the art. This usually follows shaping, if still necessary, and calcination to convert the catalytic metal compounds into oxides.

Various proposals for making active hydrotreating catalysts by individual impregnation techniques under

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The use of acid-stabilized solutions of the catalytically active metal components are known.

The US-PS 32 32 887 describes a process for the impregnation of catalyst carriers, in which the impregnating the metals Solution is stabilized with an acidic compound. The acidic stabilizer can be of an organic nature, e.g. gluconic or citric acid, or of an inorganic nature. The preferred acid is phosphoric acid. The acid stabilized solution contains metals of group VIb and VIII, in the case of phosphoric acid the molar ratio of phosphorus to metal of Group VIb, e.g., P / Mo, ranges from 0.25 to 2.5.

The US-PS 32 87 280 describes a process for the preparation of a hydrodesulfurization catalyst by impregnating one shaped alumina carrier with a stabilized phosphoric acid solution made from molybdenum and nickel salts. The solution contains at least about 0.2 mol of phosphoric acid per mol of molybdenum metal and is limited to a P / Mo molar ratio of 0.2 to 0.8 in some cases.

The US-PS 38 17 873 and 37 55 196 describe a stable Metal compound solution, a process for their manufacture, a manufacturing method for a catalyst using the metal compound solution and the obtained catalyst. The solution contains molybdenum, nickel and / or cobalt and an acid containing phosphorus with a P / Mo molar ratio of 0.1 to 0.25.

In US-PS 38 40 472 the production of an impregnation solution described, wherein the promoter solution consists essentially of molybdenum oxide, at least one special metal compound of

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Group VIII metals and phosphoric acid dissolved in water. The solution can range in molar ratios for P / Mo from 0.065 to 2.5.

In addition to the above individual impregnation processes with acid-stabilized Solutions are prior art methods of making hydrotreating catalysts by multiple impregnations and / or staged methods are known for incorporating the active metals into the shaped or unshaped support.

The US-PS 31 14 701 describes a catalytic denitrification process using a catalyst produced by multiple impregnations of a shaped alumina carrier with aqueous solutions of nickel nitrate and ammonium molybdate is produced in such a way that the nickel content of the finished Catalyst in the range of 4-10 wt .-% and the molybdenum metal content on the finished catalyst in the range of 19-30 % By weight, based on the calcined composite.

The US-PS 40 97 413 relates to the production of a desulfurization catalyst, by first tumbling together boehmite aluminum oxide hydrate with an aqueous ammonium molybdate solution is, the resulting mixture is dried and then rolled together with a soluble cobalt salt. The mixture will then squeezed and calcined.

The US-PS 40 49 115 describes a step-by-step process for Manufacture of a desulfurization catalyst, wherein a desulfurization catalyst of an inorganic oxide support material, a metal component of Group VIb and a metal component of Group VIII is prepared by (a) extruding at least 10% of the VIII metal component with the organic oxide support material and (b) impregnating the resulting extrudate with a sufficient amount of VIb- and VIII-

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Metal! Components to get a finished catalyst, which has the required metal component content.

A primary object of the invention is to develop a new hydrotreatment catalyst and process for its manufacture same. It becomes a novel improved hydrotreatment catalyst with high desulfurization and denitrogenation activity aimed at when used as intended. The manufacturing process includes a two-step process Impregnation using a new acid-stabilized solution in at least one stage.

It is general from the art of hydrotreating catalysts It is known that compositions activated by cobalt give better desulfurization selectivity than by Nickel activated compositions, while the reverse is true for denitrogenation. Another object of the invention is therefore also the development of a nickel-molybdenum catalyst ir.it has unexpectedly high desulfurization activity compared to its denitrification activity.

It is known in the hydrotreating catalyst art that by merely increasing the level of catalytically active Metals of a given composition possibly the activity effect can be driven up and that with However, very high metal loadings actually result in a decrease in the Activity begins. An object of the invention is also to propose, by correctly applying a multiple impregnation to achieve extremely effective activity with the use of increased metal loads.

Hydrotreatment catalysts are made in accordance with the invention by using multiple impregnation and a critical VIb metal to VIII metal ratio

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in one or more stages to produce catalysts that show higher than normal activity in removing contaminants from hydrocarbon feedstocks, particularly in removing both sulfur and nitrogen levels, which catalysts also have relatively low or no acidic residues such as P ₂ ⁰ R and allow the use of lower effective operating temperatures for a given percentage of impurities removal, such as 85% removal of sulfur.

The invention also proposes an impregnation solution for impregnation of a catalyst carrier in the manufacture of catalysts for the hydrotreatment of hydrocarbon feedstocks before, which consists essentially of an aqueous solution of compounds of the metals of group VIb and group VIII in such proportions that the molar ratio of the VIb metal to the VIII metal is approximately 3: 1.

The invention also proposes a method for producing a hydrotreatment catalyst in which a Hydrotreating catalyst carrier with a hydrotreating metal is impregnated in several stages, with impregnation with an impregnation solution in at least one stage of the invention is carried out.

The invention also proposes a hydrotreating catalyst which consists essentially of a hydrotreating catalyst carrier consists, which has been impregnated with VIb metals and VIII metals in several substances, the Impregnation in at least one stage with a solution of VIb metals and VIII metals in an approximate molar ratio of 3: 1 is carried out, which solution is a stable

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Sizing acid in a molar ratio of VIb metal to be stabilized May contain acid from 0 to 0.087.

The general method of manufacture used in the present invention a hydrotreatment catalyst comprises the following two-stage impregnation:

a) Two impregnation solutions, "A" and "B", are prepared, with solution "A" being metal compounds of metals of group VIb and group VIII in the case of acid stabilization with very low acid content contains. Solution "B" is a solution of a soluble Group VIII metal salt.

b) An aluminum oxide or alumina carrier or a carrier made of aluminum oxide-silicon dioxide or Γοη-earth-silica material is impregnated with "A" and '"« "metal solutions or their equivalent.

c) The impregnated material from step (b) is after shaped and calcined using a method known from the art.

d) The calcined material from step (c) is impregnated again with solution "A" and calcined a second time.

An essential feature of the invention is the preparation of solution "A". This solution contains about 3 mol of Group VIb metal per 1 mol of VIII metal and an acid stabilization at a low acid level. Generally, the stabilized solution "A" is prepared by mixing the required amounts of the Group VIII and Group Vib metals in water with the acid stabilizer. The mixture is then heated and allowed to react sufficiently to give a clear solution. Usually this takes several hours at 82 ³ C or above. The volume of the solution

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can be adjusted to the desired concentration with water.

Some Group VIII metals suitable for use in the impregnation solution are suitable are the salts of iron, nickel or cobalt. Carbonate salts are preferred. Nickel carbonate is particularly preferred. Suitable Group VIb metals for use in making a stable solution are preferably molybdenum and tungsten oxides. Molybdenum trioxide is most preferred.

Applicable acid stabilizers are carboxylic acids, such as citric acid, Gluconic acid, formic acid and acetic acid, as well as certain inorganic oxidic acidsetv phosphoric acid is special preferred.

The preferred solution "A" is made with nickel carbonate, molybdenum trioxide and phosphoric acid. Ni-Mo solutions of 120 g / 1 ΜοΟ concentration or less were stable for 24 hours without the addition of phosphoric acid. For concentrations higher than 120 g / l MoO-. It is necessary to add a small amount of phosphoric acid to stabilize the solution for 24 hours. The concentration of the metals in this solution "A" can be varied within a range from 17.5 g / l to 340 g / l MoO ₃ with a maximum of 20.1 g / l required for stabilization. This corresponds to a maximum molar ratio of P / Mo of 0.087. As previously indicated, solution "B" is the aqueous solution of a soluble salt of a Group VIII metal. The citrate salt is preferred. Nickel citrate is particularly preferred.

Any aluminum oxide / alumina or silica (silicon dioxide) / Alumina (aluminum oxide) carrier, which is used in technology as for

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Hydrotreatment is known to be suitable for catalyst manufacture be used.

Several methods of impregnating the catalyst support are known in the art (see e.g. US Pat. No. 3,232,887). The preferred method for the first impregnation in catalyst manufacture is carried out hydrothermally. But also other processes, such as pore volume impregnation or the joint Kollern, lie within the concept of the invention · The second-stage impregnation can also be based on technology known methods for dispersing metals on a shaped support. The preferred method for the invention are dipping or pore volume impregnation. The most preferred method is dip impregnation.

The catalyst shaping can be carried out by any method known in the art. Extrusion and spheridization are the preferred methods.

The following examples serve to illustrate the invention Process and the effectiveness of the obtained catalyst in hydrotreatment processes. The analytical and activity test results all of the catalysts in the examples are summarized in Tab.

example 1

This example illustrates the preparation of impregnation solutions.

Solution "A" (288 g / l MoO ₃ , 47.5 g / l NiO and 12.4 g / l P ₃ O ₅ ) was prepared as follows:

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A slurry was made from 9,000 ml of H _? O (21 ⁰ C) with 2,880 g MoO ₃ and 144 ml 75% H ₃ PO. Nickel carbonate (820 g) was added over a period of 15 minutes. The mixture was heated to 93 ° C with agitation and held at that temperature for 2 h. A clear green solution resulted. The solution had a pH of 3.0 and a P / Mo molar ratio of 0.087. The volume of the solution was adjusted to 10 1 with water. The solution was stable indefinitely (at least 6 months at room temperature).

Solution "B" (106 g / l NiO) was prepared as follows: Anhydrous citric acid (80 g) was dissolved in 350 ml of HO (24 ° C.). Nickel carbonate (73.3 g) was then added over a 15 minute period. The slurry was slowly heated to 82 ° C with continued agitation. After 1 hour of reaction at 82 ⁰ C all NiCO was. Gone into solution and the pH 3.8. The volume of the solution was adjusted to 400 ml with water.

Three variants of solutions "A" were prepared in order to determine the required range of phosphoric acid that is used for the Obtaining stable Ni-Mo solutions of various metal concentrations necessary is.

Variant 1 ("A"): A Ni-Mo solution of 120 g / l MoO_ and 19.8 g / l NiO as metal concentration was prepared using method "A" above. No phosphoric acid was added.

During the preparation of the solution, 5,400 ml H · (27 ° C), 720 g MoO ₁ . and 203 g NiCO-. on slurried. The mixture was agitated and heated to 88 ° C. After 2 h at 88 ^° C., a clear green solution was obtained. The volume of the solution was made up with water

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adjusted to 6,000 ml. This solution was stable for about 24 hours, then a green solid precipitated out.

Variant 2 ("A"): This solution was like variant 1, but with the addition of 36 ml of 75% Η-, ΡΟ. made to the final solution of 6,000 ml. This solution (120 g / l MoO, 19.8 g / l NiO and 5.15 g / l PpO _1. ) Was stable for at least 45 days at room temperature. The P / Mo molar ratio of the solution was 0.087.

Variant 3 ("A"): This solution was prepared according to the above procedure for solution "A", but with changing the amount of reactants. The quantities were 900 ml H ₃ O 340 g MoO ₃ , 96 g NiCO ₃ and 17 ml 75% H ₃ PO ₄ . The solution was adjusted to 1,000 ml with water and was stable for at least 45 days. The P / Mo molar ratio of the solution was 0.087. The concentration of the metal components in the final solution was 340 g / l MoO ₃ , 56 g / l NiO and 14.6 g / l P ₂ ⁰ S ^-

Example 2

This example illustrates the manufacture of one according to the invention Catalyst. This example uses solution "A" from Example 1, which contains 288 g / l MoO- and a P / Mo molar ratio of 0.087.

15.23 kg of alumina / silica powder containing 22% solids was slurried in 4 liters of water. The alumina / silica contained 2.8% SiO ₂ on a dry basis, the remainder being essentially Al-O ₃ . The slurry was mixed with 2522 ml of Solution "A" of Example 1 and 844 ml of Solution "B" of Example 1. The slurry was heated to 93 ⁰ C and 1 h kept at 93 ° C. After the impregnation, the slurry was filtered. The filtrate was saved. The filter cake

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was dried at 82 ° C. for 2 hours. The impregnated dried filter cake had a free moisture content of 42%, the free moisture being determined with an O-House moisture meter using a 10 g sample heated at a setting of 75 for 20 minutes. 8.17 kg of the dried filter cake was placed in a Simpson mixer. The filtrate (3800 ml) was added to the mixer. The material was mixed for 20 minutes and then pressed with a 1.85 mm press tool at 55% free moisture. The extrudates were pre-dried for 3 hours at 149 ⁰ C for 2 h and then calcined at 593 ⁰ C. After the first impregnation, the calcined, impregnated extrudates contained 17% MoO. ,, 3.73% NiO and 0.78% P ₇ O ₁ - (in each case percent by weight). 2.27 kg of the above extrudate was immersed in 9,080 ml of solution "A" for 16 hours. After the impregnation, the solution was allowed to run off and the impregnated catalyst was ^{dried at 149 3} C and then calcined ^{at 593 C for 2 hours.}

The finished catalyst contained 28% MoO, 6.4% NiO and 3.1 P ₃ O ₅ (in each case% by weight). The chemical analyzes can be found in Tab.

Example 3

This example serves as a comparison to Example 2, the immersion time being reduced from 16 hours to 1 hour. All other steps for catalyst production are the same as in Example 2. The analytical results can be found in Tab. I.

Example 4

This example shows the effect of lower metal contents after the first impregnation. The catalyst was

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prepared in the same way as the catalysts in Examples 2 and 3, only the metals in the calcined extrudate after the first impregnation were 11.8% by weight MoO ₃ , 3.51% by weight NiO and 0.50% by weight. -% Ρ_0 _ς . After an immersion time of one hour for the second impregnation, the finished catalyst contained 26.2% by weight MoO ₃ , 5.59% by weight NiO and 1.6% by weight PO_. The analysis results are given in Tab.

Example 5

In this example, the metal content is further reduced after the first impregnation, so that the extrudate after the first impregnation is 5.9% by weight MoO, 3.08% by weight NiO and 0.05% by weight P _? 0 "contains. In addition, the metal impregnation of the first stage was carried out by adding the metal compound MoO- ,, NiCo, and citric acid in its solid form instead of solutions "A" and "B". In all other points, the preparation of the finished catalyst followed the procedure described in Examples 3 and 4. The finished catalyst contained 23.6% by weight MoO ₃ , 5.76% by weight NiO and 1.3% by weight P ₃ O ₅ . The analysis results are summarized in tabular form in Tab.

Example 6

This example shows the effect of completely eliminating the Vlb metal from the first impregnation step. The procedure of Example 5 was followed, but only nickel carbonate and citric acid were used to impregnate the alumina-silica carrier. The first-stage impregnated extrudates contained 2.85% by weight NiO and the second-stage impregnated catalyst 22.8% MoO ₃ , 5.85 wt% NiO and 3.4 wt% ^ ₂ ⁰ S '^D; * - ^{e analy sener <} ? ^e b ⁿ i ^s s ^e are shown in Tab.

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given.

Example 7

This example shows the effect of the solution concentration in the final impregnation on the catalyst activity.

The extrudates calcined after the impregnation of the first stage were prepared according to the procedure described in Example 4 manufactured. During the second stage impregnation, 454 g of the calcined extrudate were mixed in 1,816 ml of impregnation solution "A" immersed with a concentration of 200 g / l MoO ^ concentration (instead of the 288 g / l MoO, .- concentration, as in the example 4). The analysis results are given in Tab.

Example 8

This catalyst was prepared by the same method as in Examples 4 and 7, but the concentration was of solution "A" 120 g / l MoO., in the final impregnation step. The analysis results are given in Tab.

Example 9

This example shows the use of pore volume impregnation in the second stage of impregnation. The calcined extrudates obtained after the first stage impregnation were produced by a process similar to Example 2 and gave a material which contained 14.6% by weight MoO. 4.55% by weight NiO and 0.93% by weight P ₂ ° 5 ^{removed .} This carrier (7,302 g) was mixed with 4,554 ml of solution "A" (288 g / l MoO ₃ ) by introducing the Liquid in an evacuated mixed drum bed

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of the extrudate impregnated. The impregnated extrudates were dried for 2 hours at 593 ⁰ C caiziniert. The analysis results are given in Tab.

Example 10

This example illustrates the use of the catalysts of the invention for hydrotreatment. Each of the catalysts of Examples 2 through 9 were tested for hydrotreatment activity. The activities were determined in comparison with a commercially available Ni-Mo hydrotreating catalyst. The analysis of the comparative catalyst is given in Tab. I (Example 10). 60 ml of each of the test catalysts to be evaluated and of the comparative catalyst were tested for desulfurization and denitrogenation activity with a high-boiling vacuum gas oil (API density 20.0; boiling range 394.5-575 ° C.) containing 2.8% by weight of sulfur and contained 1560 ppm nitrogen. The experimental conditions were 357 ⁰ C, 7 MPa (1,000 psig), LHSV 1.5 (volumes of oil / h. Vol. Catalyst) and 0.73 Nir. ^3/1 hydrogen (4,100 scf / bbl). The catalysts were placed in adjacent tubular reactors in an isothermal sand bath.

The comparative catalyst received a standard activity value of 1.00 on a volume basis. The activities of the experimental catalysts are reported as relative values with respect to this standard on a volume basis. The activity results are summarized in Tab.

Example 11

The following example explains how to maintain the superior Activity of the catalyst according to the invention in a

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Comparison with a commercially available Co-Mo catalyst if a Mixture of vacuum gas oil and vacuum residue is desulfurized. This feed is more difficult to handle than vacuum gas oil or lighter distillates alone. The one tested in this example The catalyst of the present invention was prepared by a procedure similar to that in Example 2. The above Catalysts (1.59 mm extrudates) were made with the same volume placed in identical tubular reactors in an electrically heated test facility and subjected to a standardized presulfidation activation treatment and subjected to a stream of the feed mixture described below for desulfurization. The reactor temperatures were raised if necessary to maintain 85% desulfurization and the run continued for 24 days under the conditions given below. Maintaining the superior activity of the Catalyst according to the invention is shown both on the basis of a lower operating temperature and on the basis of a smaller one Temperature rise over the extended period of operation.

Charging properties (mixture)

Density, ⁰ API 25.7

Flash Point, ° C (COC) 152

Ramsbottom carbon, wt% 1.91

Sulfur, wt% 0.62

Nitrogen, wt% 0.114 distillation, ASTM D-1160:

IBP, ⁰ C 214.1

10% 300

50% 399.0

90% 568.5

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Test conditions

Trial start temperature 365.5 C

Reactor pressure. 8,555 MPa (1,225 psig)

(Space velocity of the oil liquid) 1.74

Hydrogen / oil 0.356 Nm ^3/1

(2,000 scf / bbl)

Features d. catalyst according to the invention

MoO ₃ 27% Necessary for 85% desulfurization
Temperature, ⁰ C Comparative catalyst NOK 6.7% Catalyst d. invention 372 P ₂ O ₅ 2.25% 370 378.5 ABD 374 383 376.5 386 378 388 0.92 g / ml (mean bulk density) 378.5 Activity results Days of operation 5 10 15th 20th 24

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- - - 1 1 ,8th 1 1 ,8th 1 4th , 6 2, 85 3 , 51 3 , 51 4th , 55 0, 06 0 , 50 0 , 50 0 , 93

TABLE I

ANALYTICAL AND ACTIVITY RESULTS FOR HYDRO-TREATMENT CATALYSTS Example .23_4567Ö9 10

Metal analysis according to
first impregnation and
Calcination (wt .-%)

MoO ₃ 17.0 17.0 11.8 5.9

_o NiO 3.73 3.73 3.51 3.08

ο P ₃ O ₅ 0.78 0.78 o. 50 0.05

cd metal analysis according to
&> second impregnation

"■ * - (% by weight)
O

2 MoO ₃ 28.0 25.4 26.2 23.6 22.8

"" * NiO 6.41 5.29 5.59 5.76 5.85

P ₂ O ₅ 3.1 1.7 1.6 1.3 1.4

HDS activity

Volume 1.30 1.23 1.39 1.20 1.15 1.43 1.22 1.23 1.00

HDN activity

Volume 1.16 1.19 1.29 1.14 1.09 1.17 1.07 1.0 1.0 J ~

ABP g / ml 0.93 0.89 0.91 0.92 0.86 0.87 0.82 0.85 0.88 ^

23 , 2 2 1 ,1 23 ,8th 1 9 , 9 5 , 24 5 , 0 5 , 61 5 , 4 1 , 5 1 , 2 1 , 7 6th , 3

Evaluation of the results

The examples illustrate several properties of the invention Catalysts that stand alone and solve the problem set according to the invention.

The data in Tab. I show that within a wide range of production conditions, the inventive Catalysts show an activity that of a commercially available nickel-molybdenum catalyst, both in the Denitrogenation as well as desulfurization is superior. In addition, there was the desulfurization activity in each case improved by an additional 4 to 26% compared to the denitrogenation improvement achieved. Example 11 shows a superior one Desulfurization activity even against a commercially available cobalt-molybdenum catalyst.

The content of VIb metal which is added to the catalyst in the first step varies from 0 to 17%, the best improvement in activity being achieved with the higher contents (see Examples 2, 3, 4, 5, 6). The second stage impregnation has been explained on the basis of immersion or pore volume impregnation. In the dipping examples, the time varied from 1 to 16 hours (examples 2 and 3) and the dipping solutions varied _{in their concentrations from 120 g / l MoO 3} to 288 g / l MoO (examples 4, 7 and 8).

In general - as the examples show - these catalysts should preferably contain 21-30% MoO, 5-7% NiO and 1.0-3 / 5% P ₃ O _5. The molar ratio of VIb metal to VIII metal of approximately 3: 1 appears to be critical. The multi-stage impregnation of the catalyst support is also an important factor of the invention when using the impregnation solutions of the type described here. In addition, there is a significant improvement through the use of the diving

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method of impregnation versus other methods, such as the pore volume impregnation has been achieved.

The ability of a catalyst to desulfurize a hydrocarbon feed at a predetermined high desulfurization rate at lower temperatures, such as by
Example 11 demonstrated is a very important factor in processes of this type since the use of lower temperatures results in lower costs.

Dr. Ro / biti, at

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Claims (19)

2901 Butterfield Road, Oak Brock, Illinois 60.5Z ¹ , V. St. A. Claims h e 1 . Impregnation solution for impregnating a catalyst carrier in the production of catalysts for hydraulic treatment consisting of any substantial amount of hydrocarbon feedstocks from an aqueous solution of compounds of the metals of Group VIb and Group VIII in such proportions that the molar ratio of Group VIb metal to Group VIII metal is approximately 3: 1. 2. The solution of claim 1 wherein the Group VIb metal is molybdenum and the Group VIII metal is nickel or cobalt. 3. Solution according to claim 1 or 2, which is stabilized by adding a stabilizing acid. 030066/0611 BATH ORIGINAL 4. Solution according to claim 1, 2 or 3, which by adding Phosphoric acid is stabilized in a small amount that does not exceed the molar ratio of phosphorus to Group VIb metal of 0.08 goes beyond 7. 5. A process for producing a hydrotreatment catalyst, characterized in that a hydrotreatment catalyst support is impregnated with a hydrotreatment metal in several stages, the impregnation with an impregnation solution according to one of claims 1 to 4 being carried out in at least one stage. 6. The method according to claim 5, characterized in that at least one step of the impregnation is carried out hydrothermally with this impregnation solution. 7. The method according to claim 5, characterized in that two impregnations are carried out with this impregnation solution and the second impregnation by immersion in this impregnation solution. 8. The method according to claim 5, 6 or 7, characterized in that an impregnation solution is used which is made from nickel carbonate and molybdenum trioxide dissolved in water, the concentration of the molybdenum trioxide in a range from 17.5 g / l to 340 g / 1 and the solution also contains a stabilizing amount of phosphoric acid when the amount of molybdenum trioxide exceeds 120 g / l of solution, the stabilizing amount of phosphoric acid not exceeding a maximum molar ratio of P / Mo = 0.087. :. -. z $ / Ό 611 BAD ORIGINAL 13154 9. The method of claim d, 6 or 7, characterized in that the impregnating solution used ^contained 283 g / I MoO ₃₄ 47.5 g / l NiO and 12.4 g / l P ₂ ⁰ B · 10. The method according to claim 5, characterized in that the catalyst support is suspended in water and mixed with the impregnation solution, which contains soluble forms of both molybdenum oxide and nickel oxide, and is mixed with a second impregnation solution, which contains solubilized nickel oxide without molybdenum oxide, which Slurry is filtered and dried, the dried impregnated filter cake is mulled with the filtrate and extruded, the extrudate is predried and calcined, the calcined impregnated extrudate is immersed in the impregnation solution, which contains soluble forms of both molybdenum oxide and nickel oxide, and the impregnated one obtained The catalyst is predried and calcined. 11. Hydrotreatment catalyst, consisting essentially of a hydrotreatment catalyst carrier in several Steps -with metals of group VIb and group VIII ir.-has been impregnated, the impregnation in at least a stage with a solution of Group VIb and Group VIII metal compounds in an approximate molar ratio of 3: 1, based on the metals, was carried out, which solution has a stabilizing acid in a Moi ratio of Group VIb metal to be stabilized acid of 0 to 0.087. 12. The catalyst of claim 11, wherein the remainder of the stabilizing acid is Ρ-, ^ο ς. Γ / 0 6 1 1 13. Catalyst according to claim 11 or 12, wherein the metal of Group VIb is molybdenum and the Group VIII metal is Nikkei or cobalt. 14. The catalyst of claim 11, 12 or 13, which ^entnält 21-30 wt .-% MoO _3, 5-7 wt .-% NiO, and 1.0-3.5 wt .-% P ₃ O ₅ · 15. Catalyst according to claim 14, containing approximately 26.1 wt .-% MoO ₃ , 6.41 wt .-% NiO and 3.1 wt .-% P ₃ O ₅ . 16. Catalyst according to claim 14, containing approximately 26.1 wt .-% MoO, 5.59 wt .-% NiO and 1.6 wt .-% P ₂ ⁰ S " 17. Catalyst according to claim 14, containing approximately 2 5.4 wt .-% MoO ₃ , 5.29 wt .-% NiO and 1.7 wt .-% P ₂ ⁰ S * 18. Catalyst according to claim 14, containing approximately 23.2 wt .-% MoO ₃ , 5.24 wt .-% NiO and 1.5 wt .-% P ₃ ⁰ - 19. A process for the hydrotreatment of hydrocarbon feeds for the purpose of removing one or more of the components sulfur, nitrogen and metals, characterized in that these feeds are subjected to a catalytic conversion in the presence of a catalyst according to any one of claims 11 to 18. U-300G6 / 081 1