The method for the catalytic compositions by coprecipitation, the catalytic composition and method of hydrobromide hydrocarbons

 

(57) Abstract:

The present invention relates to a method for producing a catalytic composition for hydrobromide hydrocarbon feedstock to a catalytic composition obtained by the above method, and to a method of hydrobromide in the presence of the specified catalyst composition in hydrobromide. This method includes the stage of Association and interaction of at least one component made of base metal of group VIII in the solution and at least two metal components VIB group in the solution in the reaction mixture to obtain a precipitate, stable to oxygen, and sulfatirovnie sediment. The method for the catalytic composition is technically simple and does not require any manipulation in an inert atmosphere during the preparation of the catalytic composition. The resulting catalytic composition has a high activity. 3 N. and 19 C.p. f-crystals.

The invention relates to a method for producing a catalyst hydrobromide, to a catalytic composition obtained by the above method, and to use this catalytic composition in hydrobromide.

When hydrobromide hydrocarbon e the CI covers all processes, in which the hydrocarbon reacts with hydrogen at elevated temperature and elevated pressure, including processes such as hydrogenation, hydrodesulfurization, hydrodenitrogenation, hydrodemetallization, hydrodearomatization, hydroisomerization, hydrodeparafinisation, hydrocracking, and hydrocracking under conditions of medium pressure, commonly referred to as mild hydrocracking.

In General, the catalysts of hydrobromide consist of media deposited on the component metal of group VIB and component base metal of group VIII.

Typically, such catalysts obtained by impregnation of the carrier with aqueous solutions of compounds of these metals, this is followed by one or several stages of drying and calcination. This method of preparation of the catalyst are described, for example, in U.S. patent No. 2873257 and in document EP 0469675.

Another possibility for the preparation of the catalyst is in the coprecipitation of the material of the carrier with one component of a metal of group VIB and one component of the base metal of group VIII, such as disclosed in U.S. patent No. 3280040.

Because the media, as such, has a low catalytic activity (or none) activity ukca of the present invention is the development of a catalyst, which can be used without a carrier. Such catalysts without the media usually referred to as bulk catalysts.

Getting bulk catalysts are known, for example, from Europatent 0379433, which together are deposited one component base metal of group VIII and one component of the metal of group VIB.

It is noted that all of the above catalysts contain one component base metal of group VIII and one component of the metal of group VIB. Such catalysts have only moderate activity when hydrobromide. Therefore, the present invention is the development of catalysts with high catalytic activity.

More modern development is the use of catalysts which contain one base metal of group VIII and two metal VIB group.

Such catalysts are described, for example, in Japan patent 09000929, U.S. patent No. 4596785, 4820677, 3678124 and unpublished (preliminary) international patent application WO 9903578.

The catalyst according to the Japan patent 09000929, which is a catalyst on the carrier are impregnated inorganic carrier cobalt or Nickel as disadvantages is under U.S. patent No. 4596785 contains disulfides, at least one base metal of group VIII and at least one metal of group VIB. The catalyst according to U.S. patent No. 4820677 is an amorphous sulfide containing iron as the base metal of group VIII and a metal selected from molybdenum, tungsten or mixtures thereof as the metal of group VIB, and polydentate ligand such as Ethylenediamine. In both references catalysts receive by co-precipitation of water-soluble compounds of one base metal of group VIII and the two metals of group VIB in the presence of sulfides. Sulfide precipitate out, dried and calcined. All process steps must be carried out in an inert atmosphere, this means that you must use sophisticated techniques to implement this method in order sulfides of the metals are not turned into the corresponding oxides.

Therefore, an additional objective of the present invention is to develop a method which is technically simple and clear and which do not require any manipulation in an inert atmosphere during the preparation of the catalyst.

In U.S. patent 3678124 described volumetric oxide catalysts, which can apply storymy components of the respective metals.

Finally, in an unpublished (preliminary) international patent application WO 9903578 catalysts obtained by coprecipitation of certain quantities of compounds of Nickel, molybdenum and tungsten in the absence of sulphides.

It has been unexpectedly found that the above problems can be solved using the method of preparation of the catalyst, which includes stages of Association and interaction of at least one component made of base metal of group VIII in the solution and at least two metal components VIB group in the solution in the reaction mixture to obtain a precipitate, stable to oxygen, and the stage at which the residue is subjected to solifidian. Accordingly, the present invention relates to that method of producing a catalyst, the resulting catalyst composition and to its use in hydrobromide.

The present invention relates to a method for the catalytic compositions containing sulfide particles volume of catalyst containing at least one base metal of group VIII and at least two metal VIB group, which comprises the following process stages:

i) the Association and interaction, n is now metal of group VIB in the solution, in the reaction mixture to obtain a precipitate, stable to oxygen, and

ii) sulfatirovnie sediment.

In addition, the present invention relates to a method for the catalytic compositions containing sulfide particles volume of catalyst containing at least one base metal of group VIII and at least two metal VIB group, which includes the following stages:

i) the Association and interaction of at least one component made of base metal of group VIII in the solution and at least two metal components VIB group in the solution in the reaction mixture to obtain a precipitate, stable to oxygen, and

ii) sulfatirovnie sludge in which the sludge to be processed in stage ii), does not contain the compounds of formula NibMOcWdOzin which the value of b/(c+d) is in the range of 0.75 to 1.5, or even 0.5 to 3, and the value of c/d is in the range of 0.1 to 10, or even equal to or more than 0.01, and z=[2d+6(c+d)]/2, or in which the sludge to be processed in stage ii), even it does not contain any Nickel molybdate in which at least a portion but less than all of the molybdenum is replaced by tungsten, as described in an unpublished preliminary MEA of the present invention, what components are completely dissolved metals, when subjected to the Association and/or interaction with the sediment. It is possible, for example, to combine the components of metals when they are already dissolved, and then call their interaction with the sediment. However, it is also possible the combination of one or more components of the metals, which are partly or fully in the solid state, with additional metal components. In other words, at least once during the process stage i) all metal components must be entirely in solution. In cases where metal components are combined partially or completely in the solid state, these active components are dissolved in the reaction mixture, for example by mixing, increasing the quantity of solvent variation of solvent, temperature changes or changes in pH, or addition complexes agent that leads to the formation of soluble complex of the metal.

As noted above, the reaction mixture interacts with sediment, stable against oxygen. The deposition may be caused, for example:

a) changing the pH of the environment in vie;

b) adding complexes agent during or after combining the solutions of the components of the metal, which forms a complex with one or more metals in order to prevent the precipitation of metals, and then change the reaction conditions, such as temperature or pH, so that the metals were separated from the complex to precipitate;

c) temperature control during or after combining the solutions of the component metals to such values, in which there is deposition;

d) decreasing the amount of solvent during or after combining the solutions of the component metals, so began the deposition;

e) the introduction of prestorage additives during or after combining the solutions of the component metals to begin the precipitation of these components, and nerastvorim additive is a liquid in which the precipitate is practically not dissolved;

f) adding an excess of any of the components in such quantity that began precipitation.

Regulation of pH values, for example, in variants a) or b) can be carried out by adding to the reaction mixture a base or acid. However, it is also possible dobavleniya respectively increase or decrease the pH value. Examples of compounds that when the temperature will decompose and thereby cause an increase or decrease of the pH of the medium, are urea, nitrite, ammonium cyanate, ammonium hydroxide and ammonium carbonate.

As can be clear from the above, you can add the base metal of group VIII component and the metal of group VIB in a variety of ways: at different values of temperature and pH in solution, in suspension, in hydrated or anhydride condition, simultaneously or sequentially. Five ways deposition will be described in more detail:

1. Simultaneous precipitation at a constant pH value, in this way, at least one component made of base metal of group VIII in solution, or as such, is added slowly into the reaction vessel, which contains the proton fluid, the temperature of which is maintained constant, and the pH value is kept constant by adding a base containing solution component metal of group VIB. The pH value should be installed (at the chosen reaction temperature) at which deposition occurs.

2. Simultaneous deposition, during which the base metal of the VIII gr is derzhitsja proton fluid and substance which decomposes at higher temperature, resulting in a pH value increases or decreases. After adding the components of the metal temperature of the reaction vessel is maintained equal to the decomposition temperature of the specified substances, resulting in deposition due to changes in pH values.

3. Deposition, in which the component base metal of group VIII is added slowly into the reaction tank, which contains a metal of group VIB, dissolved in the surrounding liquid (or Vice versa), and a substance which will decompose at higher temperature, resulting in a pH value increases or decreases. After adding the component base metal of group VIII, the temperature of the reaction vessel is maintained equal to the decomposition temperature of the specified substances, resulting in deposition due to changes in pH values.

4. Precipitation at a constant pH value, in this way the component base metal of group VIII is added slowly into the reaction tank, which contains a metal of group VIB, dissolved in the surrounding liquid, or Vice versa. By adding acid or base in the reaction tank pH value set which authorized the reaction temperature) is deposited.

5. The dissolution of metal components in their own water of crystallization with subsequent evaporation of water for the purpose of the deposition. In this way mixed component base metal of group VIII and a metal component VIB group in the reaction vessel and heated. After the dissolution of the components of metals evaporated water, optionally under vacuum, in order to cause precipitation.

As described above, the metal components can be added to the reaction mixture in solution, in suspension, in hydrated or anhydride condition. Of course, if these components are added in the form of a suspension in moist or anhydride condition, they must dissolve in the reaction mixture. Preferably the components of the metals added in dissolved form.

As a solvent in the above method, you can use any proton fluid, such as water, carboxylic acids, lower alcohols, such as ethanol, propanol or mixtures thereof. Of course, you need to select a proton liquid, which prevents deposition reaction.

In the method of this invention applies at least one component made of base metal VIII groupable, Nickel, iron or mixtures thereof, preferably cobalt and/or Nickel. Suitable metal components VIB group include molybdenum, tungsten, chromium or mixtures thereof, and preferably a combination of molybdenum and tungsten. Preferably use a combination of Nickel/molybdenum/tungsten, cobalt/molybdenum/tungsten or Nickel/cobalt/molybdenum/tungsten. These types of precipitation have more surface area than precipitation, derived from a single base metal of group VIII and one metal of group VIB.

It is preferable that the Nickel and cobalt was at least 50 wt.% from the sum of the components of the base metal of group VIII in the calculation of the oxides, more preferably at least 70 wt.% and even more preferably at least 90 wt.%. May be particularly preferred that the component base metal of the VIII group consisted essentially of Nickel and/or cobalt.

It is preferred that the molybdenum and tungsten were at least 50 wt.% from the sum of the components of the metal of group VIB, per trioxide, more preferably at least 70 wt.% and even more preferably at least 90 wt.%. May be particularly preferred to compononent base metal of group VIII include water-soluble salts of non-precious metal of group VIII. Examples include nitrates, hydrated nitrates, chlorides, hydrated chlorides, sulfates, hydrated sulfates, formate, acetate or hypophosphite. Examples include water-soluble components of Nickel and/or cobalt, for example soluble salts of Nickel and/or cobalt, such as nitrates, chlorides, sulfate, formate, acetate of Nickel and/or cobalt, or mixtures thereof, as well as hypophosphite Nickel. Appropriate components of iron that can be added in a dissolved state, include nitrate, chloride, sulfate, formate, acetate or mixtures thereof.

Suitable metal components VIB groups include the water-soluble salt of a metal of group VIB, such as normal monopolarity and wolframite ammonium or alkali metal, and water-soluble isopoliteia molybdenum and tungsten, such as methanolmaria acid, or water soluble heteropolysaccharide molybdenum or tungsten, optionally containing, for example, P, Si, Ni or Co, or combinations thereof. Suitable water-soluble isoprinosine and heteropolysaccharide given in the publications Molybdenum Chemicals, Chemical data series, Bulletin Cdb-14 February 1969 and Molybdenum Chemicals, Chemical data series, Bulletin Cdb-12a-edited, November 1969. Suitable administers the water-soluble metal salts, which are soluble only at elevated temperatures, are, for example, heteropolysaccharide molybdenum or tungsten, which additionally contain, for example, cobalt or Nickel, or metal components containing so much water of crystallization that when the temperature component of the metal will dissolve in their own water of crystallization.

The molar ratio of the metal of group VIB to the base metal of group VIII usually varies from 10:1 to 1:10, preferably from 3:1 to 1:3. Usually the ratio between the different metals of group VIB does not matter. This is also true in the case of multiple base metals of group VIII. In those cases, when the metal VIB group contains molybdenum and tungsten, preferably the ratio of molybdenum to tungsten is in the range from 9:1 to 1:19, more preferably from 3:1 to 1:9 and most preferably from 3:1 to 1:6.

It is essential that during the reaction, the reaction mixture was kept in the liquid phase. To ensure this, the values of temperature and pressure are selected accordingly.

The reaction can be conducted at ambient temperature. Resumee atmospheric pressure, to ensure ease of operations components. Preferably the temperature is chosen in the range between ambient temperature and the boiling point at atmospheric pressure. If desired, you can also use a temperature above the boiling point of the reaction mixture at atmospheric pressure. Usually at a temperature above the boiling point of the reaction mixture at atmospheric pressure the reaction is carried out at elevated pressure, preferably in an autoclave or in a stationary mixer.

As stated above, during phase i) deposition is invoked, for example, by changing the pH. Suitable pH value, at which the deposited metal components will be known to the specialist.

For the method according to the invention it is essential that the precipitate obtained in stage i), was stable against oxygen. This means that the sediment does not react with oxygen under the conditions of the method of the present invention, if oxygen is present. The precipitate containing any sulfides or teocoli, is not stable against oxygen and, thus, the method of obtaining such sediment is eliminated in the present invention.

The fact that stage i) of this izaberete the subsequent technological operations can be carried out in oxygen-containing atmosphere, such as air, in contrast to, for example, the method of U.S. patent 4596785, 4820677. This makes the method of the present invention is technically simple and clear.

Optionally, during the above-described receiving sediment (technological stage i)) you can add a material selected from the group of binder, traditional catalysts hydrobromide, kekirawa components or mixtures thereof. These materials are disclosed in more detail.

For realization of this method are available from the following options: typically, the components of the metal of group VIB and non-precious metal of group VIII can contact any of the above materials while merging metals. For example, they can be added to these materials simultaneously or alternately.

Alternatively, the components of the metal of group VIB and non-precious metal of group VIII can be combined, as described above, and then any of the above materials may be added to the combined metal components, before or simultaneously with the deposition. In addition, it is possible that some components of the base metal of group VIII and VIB metal groups were combined simultaneously or alternately, to subsequently add material at the same time, or alternately.

As noted above, the material can be added during stage (i) obtaining a precipitate, can be a binder. According to the invention the binder is a binder or its predecessor. If the precursor is added in the form of a solution, it is necessary to observe safety precautions to binder moved to the solid phase in the course of the method according to the invention. This can be done by regulating the pH conditions so that proceeded the precipitation of the binder. Conditions suitable for the deposition of the binder known to the specialist and further explanation is not required. If the amount of liquid in the resulting catalytic composition is too large, it can hold an optional separation of liquid and solids.

In addition, during phase deposition (i) can be supplemented by additional materials, such as phosphorus-containing compounds, boron compounds, silicon compounds, fluorine-containing compounds, additional transition metal compounds, compounds of rare earth elements and mixtures thereof, in the same way as described for the above materials. Below is the detail will overhaul solifidian at an appropriate stage. Before solifidianism usually precipitate is separated from the liquid. You can use any traditional methods, such as filtration, centrifugation, decantation or spray drying (see below). Sulfatirovnie can be carried out in the gas or liquid phase. Sulfatirovnie usually carried out by contacting the precipitate with a sulfur-containing compound, such as elemental sulfur, hydrogen sulfide, dimethyl disulfide, or polysulfides. Sulfatirovnie usually carried out in situ and/or ex situ. Preferably sulfatirovnie carried out ex situ, i.e. sulfatirovnie carried out in a separate reactor to download sulforophane catalyst install hydrobromide. Moreover, preferably, the catalytic composition was sliderule, both ex situ and in situ.

FURTHER OPTIONAL STAGES OF THE METHOD

The method of the present invention may include one or more further optional stages of the method:

a) stage of drying and/or heat treatment, stage of drying and/or stage of leaching,

b) compounding with a material selected from the group of binder materials, conventional catalysts for hydrogenation refining, kekirawa components is eshiwani or mixing in suspension, dry or wet mixing, or combinations thereof, or

d) molding.

OPTIONAL PROCESS STAGE a)

Stage heat treatment and/or washing is preferably used if the sediment contains dangerous compounds such as ammonium nitrate, in order to remove these dangerous compounds, prior to compounding with any of the above materials (stage b)), before application of spray drying or other alternative methods (stage C)) and/or to the formation (stage d)). This stage of thermal treatment and/or washing is preferably applied immediately after precipitation. In addition, this stage of thermal treatment and/or washing is especially preferable if the method according to the invention includes a spray drying (stage C)).

Stage of drying and/or heat treatment can (optionally) be used, for example, after stage b), after stage C) and/or after stage (d). Preferably the stages of drying and heat treatment is used after the stage of formation (d).

Typically, drying is carried out in oxygen-containing atmosphere such as air. Suitable are all traditional methods of drying, such as A heat treatment, such as annealing (if any) is usually carried out in oxygen-containing atmosphere such as air or water vapor. Specified heat treatment is preferably carried out at a temperature between 100 and 600°C, preferably between 150 and 500°C, more preferably between 150 and 450°C for a time of 0.5 to 48 hours

OPTIONAL TECHNOLOGICAL STATION b)

Residue as such or containing any of the above (additional) materials, compendiums with a material selected from the group of binder materials, conventional catalysts for hydrogenation refining, kekirawa components or mixtures thereof. This material can be added in dry form, or thermally processed, or raw, moist and/or suspended form, and/or in the form of a solution. The material is preferably added after precipitation, or after the stage of drying and/or heat treatment, and/or stage of leaching).

The term "compounding sediment material" means that the above materials added to the precipitate (or Vice versa), and the resulting composition is mixed. The mixing is preferably carried out in the presence of a liquid (wet mixture). This Imponderabilia sediment with the above materials and/or the introduction of these materials during phase deposition (i) leads to a massive catalytic compositions with particularly high mechanical strength.

As noted above, the material may be selected from a binder material, traditional catalyst hydrobromide, craterous component or mixtures thereof. These materials will be described in detail below.

Binder materials that will be used can be any material used as a binder for the catalyst of hydrobromide. Examples are silicon dioxide, aluminium silicate, such as traditional aluminosilicate, alumina-coated silica, and silica-coated aluminum oxide, aluminum oxide, such as (pseudo)boehmite or gibbsite, titanium dioxide, aluminum oxide, coated with titanium dioxide, Zirconia, cationic clays or anionic clays such as saponite, bentonite, kaolin, thick or hydrotalcite, or mixtures thereof. Preferred binders are silicon dioxide, aluminium silicate, aluminium oxide, titanium dioxide, aluminum oxide, coated with titanium dioxide, zirconium dioxide, bentonite, or a mixture thereof. These binders can be applied as such or after peptization.

You can also use the predecessors of these binders, which in the course of the method according to the invention into any of the above binder placed aluminiumoxide binder), liquid glass (to obtain dioxidine binder), a mixture of aluminates of alkali metals and liquid glass (to obtain a silica-alumina binder), a mixture of sources of two-, three - and/or tetravalent metals, such as a mixture of water-soluble salts of magnesium, aluminum and/or silicon (to obtain cationic clay and/or anionic clay), chlorodrol aluminum, aluminum sulfate, aluminum nitrate, aluminum chloride, or mixtures thereof.

Optionally, the binder material may compoundrelated with a compound containing a metal of group VIB, and a compound containing base metal of group VIII, prior to compounding with sediment and/or to add in the course of its receipt. Compounding the binder material with any of these compounds containing the metal can be carried out by impregnation of the binder of these materials. Suitable impregnation techniques known to the expert. If a binder peptidases, you can also spend peptization in the presence of compounds containing a metal of group VIB and/or base metal of group VIII.

If the binder is applied to the aluminum oxide, the surface area is typically in the range of 50-600 m2/g and preferably 100-450 mis in the range of 0.1 to 1.5 ml/g, which is measured by nitrogen adsorption. To determine the characteristics of aluminum oxide, it is thermally treated at a temperature of 600°C for 1 h

In General, the binder material, which may be in the method of this invention has a lower catalytic activity than the bulk catalyst composition obtained from the precipitate, as such, or in General does not possess catalytic activity. Therefore, adding a binder material, the volumetric activity of the catalytic composition may be reduced. Also, adding a binder material leads to a significant enhancement of the mechanical strength of the final catalytic composition. Therefore, the amount of binder that can be added in the method of this invention, generally depends on the desired activity and/or from the desired mechanical strength of the final catalytic composition. Depending on the intended use of the catalyst may be appropriate quantity of binder is from 0 to 95% by weight of the entire composition. However, for unusually high activity of the composition of the present invention typically the amount of binder that can be added, nahadisainerina catalysts of hydrobromide, you can add to catalytic compositions are, for example, traditional catalysts hydrodesulfurization, hydrodenitrogenation or hydrocracking. These catalysts can be added to used, regenerated, fresh or solifidianism condition. Optionally, the traditional catalyst hydrobromide you can grind or process any other traditional way, before use in the method of the invention.

Krakeroy component that can be added to the catalytic composition of the present invention, is any traditional krakeroy component, such as cationic clays, anionic clays, crystalline kekirawa components such as zeolites, for example ZSM-5 (ultrastable (with respect), zeolite Y, zeolite X, various ALPO and SAPO, MCM-41, amorphous kekirawa components, such as aluminum silicate, or mixtures thereof. It seemed clear that some materials can simultaneously perform the role of binder and craterous component. For example, the aluminosilicate can simultaneously play the role of binder and craterous component.

Optionally, krakeroy component can compoundrelated with the metal of group VIB and Blagosostoyanie craterous component with any of these metals may be in the form of impregnation craterous component of these materials.

In General the type described above is added kekirawa components (if they are added) depends on the intended catalytic application of the final catalytic composition. Preferably the crystalline krakeroy component is added if the resulting composition will be used in the hydrocracking. Other kekirawa components, such as aluminosilicate or cationic clay, preferably add, if final catalytic composition will be used in the processes for hydrogenation treatment or mild hydrocracking. The number craterous material that is added depends on the desired activity and intended use of the final catalytic composition and thus can vary from 0 to 95% by weight of the entire catalyst composition.

In the catalytic composition can be introduced optional additional materials such as phosphorus-containing compounds, boron compounds, silicon compounds, fluorine-containing compounds, additional transition metal compounds, compounds of rare earth elements, or mixtures thereof.

As phosphorus-containing compounds moderada compounds can be added at any stage of the method of the present invention, to the stage of forming and/or after the stage of forming. If the binder material peptidases, phosphorus-containing compounds can also be used for peptization. For example, aluminiumoxide binder material may patinirovanija result in contact with phosphoric acid or with a mixture of phosphoric acid and nitric acid.

As the boron compounds can be used, for example, boric acid or heteropolysaccharide boron and molybdenum and/or tungsten as a fluorine-containing compounds can be used, for example, ammonium fluoride. Typical silicon-containing compounds are liquid glass, silica gel, tetraethylorthosilicate or heteropolysaccharide silicon with molybdenum and/or tungsten. In addition, there may be used compounds such as ferrania acid, forborne acid, dipterofauna acid or hexaphosphoric acid, if it is desirable combination of fluorine, respectively, silicon, boron and phosphorus.

Suitable additional transition metals are, for example, rhenium, manganese, ruthenium, rhodium, iridium, chromium, vanadium, iron, platinum, palladium, niobium, titanium, zirconium, cobalt, Nickel, molybdenum or an ox and molding. In addition to these metals in the course of the method according to the invention can also or compound their final catalytic composition. Thus, it is possible to impregnate the final catalytic composition impregnating solution containing any of these metals.

OPTIONAL PROCESS STAGE C)

The residue, which optionally contains any of the above (additional) materials, in addition, may be subjected to spray drying, spray (instant) drying, milling, kneading, or mixing in suspension, dry or wet mixing, or their Association, and preferred is a combination of wet mixing and kneading or mixing in a slurry and spray drying.

Stage C) is particularly attractive when there is any of the above materials (binder, traditional catalyst hydrobromide, krakeroy component) in order to ensure a high degree of mixing between the precipitate and any of these materials. This is especially true when stage C) is applied after the introduction of any of these materials (stage (b)).

Typically, the spray drying is carried out in oxygen Prov./P>

Dry mixing means mixing of sediment in the dry state with any of the above materials in a dry condition. Wet mixing, for example, involves mixing wet the filter residue obtained after separation of the precipitate by filtration, with any of the above materials in the form of powders or wet residue on the filter with the formation of a homogeneous paste of these components.

OPTIONAL PROCESS STAGE d)

If desired, the residue, optionally containing any of the above (additional) materials, may be subjected to molding, optionally after stage C) and up to the stage of sulfatirovnie ii). The molding includes extrusion, tableting, granulation and/or spray drying. It should be noted that, if the catalytic composition will be used in the suspension-type reactors, fluid layers moving layers or spreading layers, it is usually used tableting or spray drying. For use in fixed bed or fluidized bed catalytic usually the composition is subjected to extrusion, pelletizing and/or pelletizing. In the latter case, at any stage before fone molding. These additives may include aluminum stearate, surfactants, graphite, starch, methylcellulose, bentonite, polyethylene glycols, polyethylene oxides, or mixtures thereof. In addition, when the binder is alumina, it may be desirable to add acid, such as nitric acid, to the stage of molding, in order to increase the mechanical strength of the extrudates.

If the stage of the molding process includes extrusion, granulation and/or spray drying, it is preferable that stage molding was carried out in the presence of a fluid, such as water. For the extrusion and pelletizing the amount of fluid in the molding of the mixture, expressed as loss on ignition (LOI), is preferably in the range of 20-80%.

If desired, you can apply coaxial extrusion of any of the above materials with the sediment, not necessarily containing any of the above materials. More specifically, it is possible to conduct a joint extrusion of the two mixtures, and in this case the residue, optionally containing any of the above materials, present in the inner extrusion environment, while any of the above materials outside the presence of sediment is necessary to control the amount of liquid. If, for example, before the catalytic composition is subjected to spray drying, the amount of liquid is too low, you must add an additional amount of fluid. If, on the other hand, for example, prior to extrusion of the catalytic composition, the amount of liquid is too large, it is necessary to remove a small amount of liquid, for example, by separation of the liquid and solid phases, for example, by filtering, decanting or evaporation, and if necessary, the resulting material can be dried and re-hydrated to a certain extent. For all the above stages of the method is properly controlled amount of liquid is within the competence of a specialist.

Thus, the preferred method of the present invention includes the following sequential process steps:

i) obtaining a precipitate, which is described above, optionally in the presence of any of the above (optional) materials and isolation of the resulting precipitate,

a) optional drying, heat treatment and/or washing of selected sediment, in particular, in order to remove hazardous materials

b) optional compounded subjecting the resulting composition processing by any of the methods, spray drying, (instant) drying, milling, kneading, mixing in suspension, dry or wet mixing, or combinations thereof,

d) optional formation of the catalytic composition,

and') optionally drying and/or heat treatment of the molded catalyst composition, and

ii) sulfatirovnie catalytic composition.

A typical method involves successive stages of obtaining a precipitate, which is described above, the suspension mixing the precipitate with a bonding material, spray drying, re-moistening, kneading, extrusion, drying, calcination and sulfatirovnie. Another typical example of the method of the present invention includes the sequential stages of the sediment, which is described above, separation of the resulting precipitate by filtration, the wet mixing of the residue on the filter with a bonding material, kneading, extrusion, drying, calcination and sulfatirovnie.

THE CATALYTIC COMPOSITION ACCORDING TO THE INVENTION

The present invention additionally relates to a catalytic composition which can be obtained according to the method of the present invention.

In addition, the present invention otnositel, at least one component made of base metal of group VIII and at least two component metal of group VIB and in which the degree of sulfatirovnie in the conditions of use does not exceed 90%.

In addition, the present invention relates to catalytic compositions containing sulfatirovanne particle volume of the catalyst, which contains at least one component made of base metal of group VIII and at least two component metal of group VIB in which the degree of sulfatirovnie in the conditions of use does not exceed 90% and in which the catalytic composition does not contain solifidian forms of the compounds of formula NibMocWdOzin which the value of b/(c+d) is in the range of 0.75 to 1.5, or even 0.5 to 3, the value of c/d is in the range of 0.1 to 10, or even equal to or greater than 0.01 and z=[2d+6(c+d)]/2, or in which the catalytic composition even does not contain any solifidian forms of Nickel molybdate in which at least a portion but less than all of the molybdenum is replaced by tungsten, as described in unpublished (pre) international patent application WO 9903578.

It is noted that the catalytic composition of the present invention has a much better katako one component of a metal of group VIB.

It is essential that the degree of sulfatirovnie solifidian particles of solid catalyst under conditions of use does not exceed 90%. Preferably the degree of sulfatirovnie applications is in the range of 10-90%, more preferably 20-90%, and most preferably 40-90%, the Degree of sulfatirovnie determined as described in the section "Methods of characterization".

If the method of the present invention uses traditional methods of sulfatirovnie, the degree of sulfatirovnie solifidian particle volume of catalyst to use almost identical degree of sulfatirovnie in the application. However, if you are very specific techniques sulfatirovnie, it is possible that the degree of sulfatirovnie catalyst before it is used is higher than in the conditions of use of the catalyst, since during the operation of the portion of the sulfides or elemental sulfur is removed from the catalyst. In this case, the degree of sulfatirovnie is determined according to the data obtained during operation of the catalyst, but not before it is used. Conditions of use described below under "Use according to the invention". The term "catalyst nahoditsya time period, to the catalyst came into equilibrium with the reaction medium.

In addition, preferably, the catalytic composition of the present invention is substantially free disulfides base metal of group VIII. More specifically, base metals of group VIII are preferably present in the form of (non-precious metal of group VIII)ySxand the ratio x/y is in the range of 0.5-1.5.

Typically, the materials have a characteristic x-ray diffraction. For example, in x-ray diffraction pattern of the catalyst according to the invention containing Nickel as the base metal of group VIII and molybdenum, and tungsten as the metal of group VIB, usually there are peaks at the following angles 2=13,1-14,9°, 27,0-27,6°, 30,9-31,5°, 33,1-34,0°, 50,2-50,8°, 50,6-51,2°, 55,2-55,8°, 58,1-59,7°, moreover, peaks at 2=50,2-50,8° and 50.6-51,2° overlap. Based on this x-ray diffraction pattern, we can conclude that the metals present in the catalyst in the form of sulfide Nickel (Ni7S6), molybdenum disulfide and tungsten disulfide.

In x-ray diffraction pattern of the catalyst according to the invention containing cobalt as the base metal of the VIII G3,1-14,9°, 29,5-30,1°, 33,1-34,0°, 47,2-47,8°, 51,7-52,3° and 58,1-59,7°. Based on this x-ray diffraction can be concluded that cobalt, molybdenum and tungsten are present in the form of a sulfide of cobalt (Co9S8), molybdenum disulfide and tungsten disulfide.

In x-ray diffraction pattern of the catalyst according to the invention containing iron as the base metal of group VIII and molybdenum, and tungsten as the metal of group VIB, usually there are peaks at 2=13,1-14,9°, 29,7-30,3°, 33,1-34,0°, 33,6-34,2°, 43,5-44,1°, 52,8-53,4°, 56,9-57,5° and 58,1-59,7°, moreover, peaks at 2=33,1-34,0° and 33.6-34.2 in° overlap. Based on this x-ray diffraction can be concluded that iron, molybdenum and tungsten are present as sulphide of iron (Fe1-xS, in which x is about 0.1), molybdenum disulfide and tungsten disulfide.

In x-ray diffraction pattern of the catalyst according to the invention containing Nickel as the base metal of group VIII and molybdenum and chromium as the metal of group VIB, usually there are peaks at 2=13,1-14,9°, 30,0-30,6°, 33,1-34,0°, 45,2-45,8°, 53,3-53,9° and 58,1-59,7°. Based on this x-ray diffraction can be concluded that Nickel, molybdenum and the rum.

In x-ray diffraction pattern of the catalyst according to the invention containing Nickel as the base metal of group VIII and tungsten and chromium as the metal of group VIB, usually there are peaks at the following angles 2=13,1-14,9°, 30,0-30,6°, 33,1-34,0°, 45,2-45,8°, 53,3-53,9° and 58,1-59,7°. Based on this x-ray diffraction can be concluded that Nickel, tungsten and chromium are present (among other things) in the form of sulfide Nickel (Ni7S6), tungsten disulfide and sulfides of chromium.

The molar ratio of the metal of group VIB to the base metal of group VIII usually varies from 10:1 to 1:10 and preferably from 3:1 to 1:3. Usually the ratio between the different metals of group VIB does not matter. This is also true in the case of multiple base metals of group VIII. In those cases, when the metal VIB group contains molybdenum and tungsten, preferably the ratio of molybdenum to tungsten is in the range from 9:1 to 1:19, more preferably from 3:1 to 1:9 and most preferably from 3:1 to 1:6.

Sulfide particles volume of the catalyst contain at least one component made of base metal of group VIII and at least deicer combining molybdenum and tungsten is the most preferred. Suitable metals of group VIII include iron, cobalt, Nickel or mixtures thereof, preferably Nickel and/or cobalt. Preferably the catalyst particles contain associations Nickel/molybdenum/tungsten, cobalt/molybdenum/tungsten or Nickel/cobalt/molybdenum/tungsten.

It is preferable that the Nickel and cobalt was at least 50 wt.% from the sum of the components of the base metal of group VIII in the calculation of the oxides, more preferably at least 70 wt.% and even more preferably at least 90 wt.%. May be particularly preferred that the component base metal of the VIII group consisted essentially of Nickel and/or cobalt.

It is preferred that the molybdenum and tungsten were at least 50 wt.% from the sum of the components of the metal of group VIB in the calculation of trioxide, more preferably at least 70 wt.% and even more preferably at least 90 wt.%. May be particularly preferred that the component base metal of the VIII group consisted essentially of molybdenum and tungsten.

If none of the above materials (binder, traditional catalyst hydrobromide, krakeroy kolokolo 100 wt.% base metal of group VIII and VIB metals of the group in the calculation of the total mass of particles of volume of catalyst based on metal oxides. If any of these materials added during the stage of deposition (i), the formed particles of bulk catalyst preferably contain 30-100 wt.%, more preferably 50-100 wt.%, most preferably 70 to 100 wt.% base metals of group VIII and VIB metals of the group in the calculation of the total mass of particles of volume of catalyst based on metal oxides, and the remainder falls on any of the above (additional) materials added during the stage of deposition of the i). The number of VIB metals of the group and base metals can be determined by transmission electron microscopy with rentgenostrukturnoe console, atomic absorption spectroscopy or inductively coupled plasma (TEM-TDX, AAS or ICP).

The average particle size sulfatirovannah volume of catalyst depends on the deposition method used in stage i). If this is desirable, it is possible to obtain a particle size of 0.05 to 60 μm, preferably 0.1 to 60 μm (measured by a method almost direct light scattering by the method Malvern).

Preferably, the catalytic composition further comprises a suitable binder material. Preferred binders are those described in Aut role glue, keeping a binder or particles together. Preferably the particles are uniformly distributed throughout the binder material. The presence of a binder material generally leads to an increased mechanical strength of the final catalytic composition. In General, the catalytic composition according to the invention has a mechanical strength, expressed as the crushing strength contour equal, at least, 0,454 kg (1 lb)/mm and preferably at least 1.36 kg/mm (measured on the extrudates with a diameter of 1-2 mm).

The amount of binder depends, among other things, on the desired level of catalytic activity of the composition. The amount of binder from 0 to 95% from the total mass of the composition may be suitable depending on the intended use of the catalyst. However, for unusually high activity of the composition of the present invention generally, the amount of the binder is in the range of 0-75% by weight of the entire composition, preferably 0-50 wt.%, more preferably 0-30 wt.%.

Optionally, the catalytic composition may contain suitable krakeroy component. Suitable cretinously components are preferably t is the weight of the entire catalyst composition.

Moreover, the catalytic composition may contain conventional catalysts hydrobromide. Usually traditional catalysts hydrobromide contain any of the above-described binders and kekirawa components. Hydrogenating metals of traditional catalyst hydrobromide usually include the metals of group VIB and base metals of group VIII, such as the Association of Nickel or cobalt with molybdenum or tungsten. Suitable conventional catalysts hydrobromide are, for example, catalysts of hydrobromide or hydrocracking catalysts. These catalysts can be used in used, regenerated, fresh or solifidianism condition.

In addition, the catalytic composition may contain any additional material, which is traditionally present in the catalysts of hydrobromide, such as phosphorus-containing compounds, boron compounds, silicon compounds, fluorine-containing compounds, additional transition metal compounds, compounds of rare earth elements, or mixtures thereof. Above disclosed these additional materials. Usually transition metals or rare earth elements, is raised.

To obtain sulfide catalytic composition with high mechanical strength, it may be desirable for the catalytic compositions according to the invention to have a low macroporosity. Preferably less than 30% of the pore volume of the catalytic composition is in pores of diameter greater than 100 nm (determined by the indentation of the mercury contact angle 130°), more preferably less than 20%.

Typically, the catalytic composition of the present invention contains 10-100 wt.%, preferably 25-100 wt.%, more preferably 45-100 wt.% and most preferably 65-100 wt.% metals of group VIB and base metals of group VIII in the calculation of the total mass of particles of volume of catalyst on snore metal oxides, and the remainder falls on any of the above (additional) materials.

Finally, the present invention relates to a molded catalyst composition comprising (i) sulfatirovanne particles of bulk catalyst comprising at least one component made of base metal of group VIII and at least two component metal of group VIB in which the degree of sulfatirovnie in operating conditions does not exceed 90%, and

ii) made or mixtures thereof.

Binder materials kekirawa components and traditional catalysts hydrobromide, and obtaining catalytic compositions disclosed above.

Molded and sulfatirovanne the catalyst particles can have various shapes. Suitable shapes include spheres, cylinders, rings and symmetric or asymmetric mnogodenek, such as three - and four particles. Particles formed by extrusion, granulation or pelletizing, typically have a diameter in the range from 0.2 to 10 mm, and their length is probably in the range of from 0.5 to 20 mm Particles formed by spray drying, typically have an average diameter in the range from 1 to 100 microns.

THE USE ACCORDING TO THE INVENTION

The catalytic composition according to the invention can be used in almost all processes of hydrobromide to handle variety of raw materials in a wide range of process conditions, for example, at a temperature in the range from 200 to 450°C, the hydrogen pressure in the range from 0.5 to 30 MPa (5 are 300 bar) and at a space velocity of fluid (OSPI) in the range of from 0.05 to 10 h-1. The term "hydrobromide" in this context encompasses all processes in which the hydrocarbon is as hydrogenation, hydrodesulfurization, hydrodenitrogenation, hydrodemetallization, hydrodearomatization, hydroisomerization, hydrodeparafinisation, hydrocracking, and hydrocracking under conditions of medium pressure, commonly referred to as mild hydrocracking. The catalytic composition according to the invention is particularly suitable for Hydrotreating of hydrocarbons. Such Hydrotreating processes include, for example, hydrodesulfurization, hydrodenitrogenation and hydrodearomatization hydrocarbons. Suitable raw materials are, for example, middle distillates, kerosene, naphtha, vacuum gas oils and heavy gas oils. Can be used by the traditional process conditions, for example temperatures in the range from 250 to 450°C., a pressure in the range from 0.5 to 25 MPa (5-250 bar), space velocity in the range from 0.1 to 10 h-1and the ratio of N2/hydrocarbon in the range from 50 to 2000 standards. l/l (nl/l).

METHODS OF CHARACTERIZATION

THE DEGREE OF SULFATIROVNIE

Any sulfur contained in solifidians catalytic composition is oxidized in a stream of oxygen when heated in the induction furnace. The resulting sulfur dioxide is analyzed using infrared (IR) cell and systems, toadies to sulfur dioxide, is correlated with the signals obtained from the known calibration standard samples. Then calculate the degree of sulfatirovnie as the ratio between the amount of sulfur contained in solifidian the particle volume of catalyst, and the amount of sulfur that might be contained in solifidian the particle volume of the catalyst, if all the metals of group VIB and base metals of group VIII were present as disulfides metals.

For professionals it is clear that manipulation of the catalyst, which will be measured by the degree of sulfatirovnie, must be carried out in an inert atmosphere to determine the extent of sulfatirovnie.

THE CRUSHING STRENGTH ON A PATH

First measure the length, for example, extruded particles, and then this particle is subjected to a compressive load (25 pounds in 8.6 (C) under the action of the moving piston. Measure the force required for crushing the particles. This procedure is repeated at least 40 extruded particles and calculate the average force (in pounds) per unit length (mm). Preferably this method is used for molded particles with length, not PR is rccoi thesis J. C. P. Broekhoff (Delft University of technology, 1969).

The present invention is further illustrated by the following examples.

EXAMPLE 1

Heptamolybdate ammonium (17,65 g, 0.1 mol Mo) and 24.60 g metavolume ammonium (0.1 mol W) dissolved in 800 ml of water, getting a solution with a pH of about 5.2. To this solution was added to 0.4 mole of ammonium hydroxide (approximately 30 ml), resulting in increased approximately pH to 9.8. This solution is heated to 90°C (solution A). A second solution was prepared by dissolving equal to 58.2 g of cobalt nitrate (0.1 mol) in 50 ml of water. This solution is maintained at a temperature of 90°C (solution). The solution added dropwise to the solution And with the speed of 7 ml/min. and the Resulting suspension stirred for 30 min, while the temperature is maintained at 90°C. the Material was filtered while hot, washed with hot water and dried in air at a temperature of 120°C. Distinguish approximately 48 g of the catalyst.

Next, the resulting catalyst sulfiderich. In a quartz boat placed 1.5-2 g of catalyst, insert it into a horizontal quartz tube, which is heated in the furnace Lindberg. In a stream of nitrogen (50 ml/min) furnace temperature was raised to 370°C for 1 h and continue blowing in the indicate temperatures up to 400°C and maintain it for 2 hours Then the heating is switched off and the catalyst is cooled in a current of H2S/H2up to 70°C; at this point, stop the flow of the mixture and the catalyst is cooled to room temperature in nitrogen.

Sulpicianus the catalyst was tested in a modified reactor CARBERRY with a one-time download, and provided with a constant flow of hydrogen. The catalyst tabletirujut and crushed to a fraction of 20/40 mesh and 1 g of catalyst was loaded into the basket of stainless steel sandwiched between mullite beads (like a sandwich). In the autoclave serves 100 ml liquid raw material containing 5 wt.% studied (DBT) decline. Through the reactor is passed a stream of hydrogen of 100 ml/min and set pressure equal to 3150 kPa, using the pressure regulator (after himself). Increase the temperature to 350°C with a speed of 5-6°C/min and continue testing or to become 50% DBT or before the expiration of 7 hours. Every 30 minutes take a small aliquot of the product and analyzing it by gas chromatography (GC). The values of the rate constants for total conversion count, as described M. Daage and R. R. Chianelli (log J. Catal., so 149, C. 414-427 (1994)).

The total transformation DBT (expressed as rate constants) at 350°C (XEET degree of sulfatirovnie in operating conditions, equal to 58%.

In x-ray diffraction pattern sulforophane catalyst has peaks at 2=13,8; 29,8; 33,5; 47,5; 52,0 and 58.9°. Based on this x-ray diffraction can be concluded that cobalt, molybdenum and tungsten are present in the form of a sulfide of cobalt (Co9S8), molybdenum disulfide and tungsten disulfide.

EXAMPLE 2 (COMPARATIVE)

Get the catalyst, as in example 1, except that use is only one component of a metal of group VIB. The catalyst was prepared as described in example 1, using heptamolybdate ammonium (26,48 g, 0.15 mol Mo), 0,3 mol of ammonium hydroxide (about 23 ml) and 43,66 g of cobalt nitrate (0.15 mol). The total transformation DBT (expressed as rate constants) at 350°C (Xobshaccording to the measurements is a 14.1*1016molecules/(,C) and thus is significantly lower than the corresponding values in example 1.

EXAMPLES 3-6

For examples 3-6 using the following General methods.

a) General method of preparation

Metal components VIB group dissolved and merged into the first reactor. Increase the temperature to 90°C. Salt base metal of group VIII is dissolved in popoluca the main solution. Solution of non-precious metal of group VIII are added dropwise in the first reactor under stirring for approximately 20 minutes After 30 minutes the precipitate is filtered and washed. The precipitate is dried in air overnight at a temperature of 120°C and thermally treated 1 h at 385°C.

b) General method of sulfatirovnie

Catalysts sulfiderich using a mixture of 10% H2S/H2at atmospheric pressure and a space velocity of gas (OPG) approximately 8700 nm3/ (m3*h). Increase the temperature of the catalyst from room temperature up to 400°C, using a heating rate of 6°C/min and maintained at 400°C for 2 hours Then the sample is cooled in a mixture of N2S/N2to room temperature.

EXAMPLE 3

The above General preparation method used for obtaining sediment from dimolybdate ammonium, metavolume ammonium and iron nitrate Fe(NO3)3*N2O. Obtained with a yield of 98% of the sediment contains 41,2 wt.% Fe2O3that is 21.3 wt.% Moo3and 36.9 wt.% WO3. Oxide precipitate has a surface area (by BET method), equal to 76 m2/the Volume of the pores of the oxide precipitate, which measured up to the size of 60 nm using adsorption curve and the which is described above.

Sulpicianus the catalyst has a degree of sulfatirovnie in conditions equal to 39%.

In x-ray diffraction pattern sulfatirovannah catalyst there are peaks, for example, when 2=14,2°, 30,0°, 33,5°, 33,9°, 43,8°, 53,1°, 57,2° and 59,0°, and peaks at 2=33,5 and 33.9° overlap. Based on this x-ray diffraction can be concluded that iron, molybdenum and tungsten are present as sulphide of iron (Fe1-xS, in which x is about 0.1), molybdenum disulfide and tungsten disulfide.

EXAMPLE 4

The above General preparation method is used to obtain a precipitate of Ni(NO3)2*6N2O, (NH4)6Mo7O24*4H2O and (NH4)2Cr2O7. Obtained with a yield of 88% of the sediment contains 52.2 wt.% NiO, to 29.4 wt.% MoO3and 16.6 wt.% CR2ABOUT3. Oxide precipitate has a surface area (by BET method), equal to 199 m2/the Volume of the pores of the oxide precipitate, which measured up to the size of 60 nm using the curve of adsorption of nitrogen is of 0.28 ml/year Then the catalyst sulfiderich using a common methodology sulfatirovnie described above.

Sulpicianus produce the IU sulfatirovannah catalyst there are peaks, for example, when 2=14,2°, 30,3°, 33,4°, 45,5°, 53,6° and 59,0°. Based on this x-ray diffraction can be concluded that Nickel, molybdenum and chromium are present (among other things) in the form of sulfide Nickel (Ni7S6), molybdenum disulfide and sulfides of chromium.

EXAMPLE 5

The above General preparation method is used to obtain a precipitate of Ni(NO3)2*6H2O, (NH4)6H2W12O40and (NH4)2Cr2O7. Obtained with a yield of 90% of the sediment contains to 44.0 wt.% NiO, 42,4 wt.% WO3and 11.8 wt.% Cr2O3. Oxide precipitate has a surface area (by BET method), equal to 144 m2/the Volume of the pores of the oxide precipitate, which measured up to the size of 60 nm using the curve of nitrogen adsorption, is 0.20 ml/year Then the catalyst sulfiderich using a common methodology sulfatirovnie described above.

Sulpicianus the catalyst has a degree of sulfatirovnie in operating conditions, equal to 59%.

In x-ray diffraction pattern sulfatirovannah catalyst there are peaks, for example, when 2=14,2°, 30,3°, 33,4°, 45,5°, 53,6° and 59,0°. Based on this x-ray diffraction can be done bifida tungsten and chromium sulfide.

EXAMPLE 6

The above General preparation method is used to obtain a precipitate of Ni(NO3)2, heptamolybdate ammonium and metavolume ammonium. Aluminum oxide peptizer nitric acid and after completion of the reaction is added to the suspended precipitate in an amount of 10 wt.% in calculating the total weight of the mixture of sludge and aluminum oxide. The mixture is then precipitate aluminum oxide is washed and subjected to extrusion washed sludge mixture with aluminum oxide. After the extrusion, the extrudate is dried and thermally treated as described above in the General method of preparation. Estradot contains approximately 10 wt.% aluminium oxide, to 35.0 wt.% NiO, 20 wt.% Moo3and 35 wt.% WO3. The obtained oxide catalyst has a surface area (by BET method), equal to 119 m2/g, and pore volume, measured by nitrogen adsorption, is equal to 0.14 ml/year

Then part of the catalyst sulfiderich using a common methodology sulfatirovnie described above.

According to measurements sulpicianus the catalyst has a degree of sulfatirovnie in conditions equal to 52%. The surface area solifidians catalytic composition (by BET method) is 66 m2/g is, as described in example 1. Measured that the total transformation DBT (expressed as rate constants) at 350°C (Xows) is 111*1016molecules/(g C).

Another part of the catalyst sulfidic raw material, which is added dimethyl disulfide. Then sulpicianus thus the catalyst was tested with a light kreiranim recirculating oil. According to measurements of the relative volumetric activity in the process of hydrodenitrogenation equal 178 compared to technically accessible deposited on alumina catalyst containing Nickel and molybdenum.

1. The method for the catalytic compositions containing sulfide particles volume of catalyst containing at least one base metal of group VIII and at least two metal V1B group, which comprises the following process stages: I) the Association and interaction of at least one component made of base metal of group VIII in the solution and at least two metal components VIV groups in solution in the reaction mixture to obtain a precipitate, stable to oxygen, and (II) sulfatirovnie sediment.

2. The method according to p. 1, characterized in that the deposition is caused by changed the negative effects of the compounds in the reaction mixture, which when the temperature is decomposed, resulting in a change of pH values.

4. The method according to any of paragraphs.1-3, characterized in that the base metal of group VIII includes cobalt, Nickel, iron or mixtures thereof.

5. The method according to p. 4, characterized in that the Nickel and cobalt are at least 50 wt.% from the sum of the components of the base metal of group VIII in the calculation of the oxides, preferably at least 70 wt.% and more preferably at least 90 wt.%.

6. The method according to any of paragraphs.1-5, characterized in that the metal VIB group includes at least two of the chromium, molybdenum and tungsten.

7. The method according to p. 6, characterized in that the molybdenum and tungsten are at least 50 wt.% from the sum of the components of the metal of group VIB in the calculation of trioxide, preferably at least 70 wt.%, more preferably at least 90 wt.%.

8. The method according to any of paragraphs.1-7, characterized in that the material selected from the group of binder, traditional catalyst hydrobromide, craterous component or mixtures thereof, is added in the reaction mixture in stage (I).

9. The method according to any of paragraphs.1-8, characterized in that the method includes one shall andromania material, selected from the group of binder materials, conventional catalysts hydrobromide, kekirawa components or mixtures thereof; (C) spray drying, spray (instant) drying, milling, kneading, or mixing in suspension, dry or wet mixing, or a combination thereof, and molding.

10. The method according to p. 9, characterized in that it comprises the following stages: Association and interaction of at least one component made of base metal of group VIII in the solution and at least two metal components VIB group in solution in the reaction mixture to obtain a precipitate, stable to oxygen, optional drying and/or washing, compounding sediment from a material selected from the group of binder materials, conventional catalysts hydrobromide, kekirawa components or mixtures thereof, an optional molding, sulfatirovnie.

11. The method according to p. 9, characterized in that it comprises the following stages: Association and interaction of at least one component made of base metal of group VIII in the solution and at least two metal components VIV groups in solution in the reaction mixture to obtain a precipitate, stable to oxygen, with material selected from the gay, which is present during the deposition, an optional drying and/or washing, optional molding, sulfatirovnie.

12. The method according to p. 10 or 11, characterized in that it includes a step of molding.

13. Catalytic composition for hydrobromide hydrocarbons, obtained by any of the preceding paragraphs, which contains sulfide particles volume of catalyst containing at least one component base metal of group VIII and at least two component metal VIB group.

14. Catalytic composition for p. 13, characterized in that as the base metals of group VIII composition comprises cobalt and/or Nickel.

15. The catalytic composition under item 13 or 14, characterized in that the components of group VI are tungsten and molybdenum.

16. The catalytic composition according to any one of paragraphs.13-15, characterized in that it further comprises a binder material selected from silicon dioxide, aluminum silicate, aluminum oxide, titanium dioxide, Zirconia, cationic clays and/or anionic clays.

17. The catalytic composition according to any one of paragraphs.13-16, characterized in that it further comprises krakeroy holds one or more additional materials, selected from phosphorus-containing compounds, boron compounds, fluorine-containing compounds, rare earth metals, additional transition metals or mixtures thereof.

19. The catalytic composition according to any one of paragraphs.13-18, characterized in that it is formed by extrusion, tableting, granulation and/or spray drying.

20. How hydrobromide hydrocarbons, which consists in the processing of hydrocarbon raw materials of the catalyst according to any one of paragraphs.13-19 at a temperature of 200-450°C and a partial pressure of hydrogen in the range of 5 are 300 bar and a space velocity of the feedstock in the range of 0.05-10 h-1.

21. The method according to p. 20, in which the process of hydrobromide is the process of gidrogenizirovanii, hydrodesulfurised, hydrodemetallation, hydrodearomatization, hydroisomerization, hydrobasaluminite, hydrocracking, mild hydrocracking.

22. The method according to p. 20, which are hydrobromide medium distillates, kerosene, naphtha or vacuum gas oil.



 

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