The catalytic composition based on a mixture of metals, its preparation and use

 

The invention relates to a method for producing a catalyst composition comprising bulk catalyst particles containing at least one base metal of group VIII and at least two metals of group VIB, including the integration and interaction of at least one component made of base metal of group VIII with at least two components of metals of group VIB in the presence of proton fluid, and at least one metal component remains at least partly in the solid state throughout the method, where the metals of groups VIII and VIB range from about 50 to about 100 wt.% in terms of oxides, of the total weight of the specified volume of the catalytic particles, and the solubility of the component metals of these groups, which are at least partly in the solid state during the reaction, is less than 0.05 mol/100 ml water at 18aboutC. the Invention also relates to a catalytic composition obtained by the above method, and to a method of hydrobromide. The resulting catalysts have high activity. 4 C. and 15 C.p. f-crystals, 1 Il., table 2.

The scope of the invention

The invention relative to the ski particles, containing at least one base metal of group VIII and at least two metals of group VIB, obtained in this way catalytic compositions and to the use of specified composition as catalyst in the processes of hydrobromide.

Background of the invention

In the processes of hydrobromide hydrocarbon feedstock is subjected to Hydrotreating and/or hydrocracking in the presence of hydrogen. Processes hydrobromide cover 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 mild pressure conditions, which is usually referred to as mild hydrocracking.

In General, catalysts hydrobromide consist of a carrier with a metal component of group VIB and besieged it base metal component of group VIII. Typically, such catalysts obtained by impregnation of the support with aqueous solutions of compounds of these metals, followed by one or more stages of drying and effective technology for producing the above-mentioned catalysts are described in U.S. patent No. 4113605, where, for example, Nickel carbonate interacts with, for example, of Moo3with the formation of crystalline molybdate Nickel, which is then mixed and ekstragiruyut with alumina.

This method is described in DE No. 3029266, where the Nickel carbonate is mixed with WO2and the resulting composition is mixed with alumina, impregnated, for example, Nickel nitrate and ammonium tungstate.

Because the media itself has no catalytic activity or has a very low catalytic activity, the activity containing the above-mentioned carrier catalysts for hydrobromide is rather moderate. Therefore, the aim of the present invention is to provide a catalyst which can be applied without a carrier. These do not contain catalysts, generally referred to as “bulk catalysts”.

Getting bulk catalysts are known, for example from GB No. 836936 and EP No. 0014218. The catalyst, for example, EP No. 0014218 get a spray drying aqueous suspension of potassium carbonate, potassium dichromate, vanadium oxide, iron oxide, Portland cement, methyl cellulose and graphite.

It is noted that all the above-mentioned catalysts contain one base metal of group VIII and one metal graphene - to provide catalysts with high catalytic activity.

A more recent improvement is the use of catalysts containing one base metal of group VIII and the two metals of group VIB.

Such catalysts are described, for example, in JP No. 09000929, in U.S. patents№ 4596785, № 4820677, № 3678124, № 4153578 and international patent application no prepublication WO No. 9903578.

The catalyst JP No. 09000929, which is containing the carrier of the catalyst is obtained by impregnation of inorganic media with cobalt or Nickel as the base metal of group VIII and molybdenum and tungsten as the metal of group VIB.

The catalyst for U.S. patent No. 4596785 includes disulfides at least one base metal of group VIII and at least one metal of group VIB. The catalyst for 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, a polydentate ligand such as Ethylenediamine. In both references the catalyst was prepared by coprecipitation of water-soluble sources of the same base metal of group VIII and the two metals of group VIB in the presence of a hundred means, for implementation of this method requires complicated methods. In addition, because this method coprecipitation there are huge amounts of sewage.

Therefore, another objective of the present invention is to propose a method, which is technically simple and sustainable, which does not require any operations in an inert atmosphere during the preparation of the catalyst and in which it is possible to avoid the formation of huge amounts of sewage.

U.S. patent No. 3678124 describes the oxidic bulk catalyst for use in oxidative dehydrogenation of paraffin hydrocarbons. The catalysts obtained by coprecipitation of water-soluble components of the respective metals. Application of coprecipitation method again leads to huge amounts of wastewater.

The catalyst for U.S. patent No. 4153578 is a Nickel Raney catalyst for use in the hydrogenation of butynediol. The catalyst was prepared by contacting of Raney Nickel, optionally containing, for example, tungsten, molybdenum component in the presence of water. Molybdenum is adsorbed on the Raney Nickel under stirring the resulting suspension at room temperature.

Finally, at medunet sources of Nickel, molybdenum and tungsten in the absence of sulphides.

Brief description of the invention

It was found that all the above objectives can be achieved in a way that enables the integration and interaction of at least one component made of base metal of group VIII with at least two components of metals of group VIB in the presence of proton fluid, and at least one metal component remains at least partly in the solid state throughout the process.

Another aspect of the present invention is a new catalyst composition.

Another aspect of the present invention is the use of the above compositions for hydrobromide hydrocarbons.

Detailed description of the invention

The method according to the invention

(A) Obtaining volumetric catalytic particles

The present invention is directed to a method of obtaining a catalyst composition comprising bulk catalyst particles containing at least one base metal of group VIII and at least two metals of group VIB, including the integration and interaction of at least one component made of base metal of group VIII, p is, one of the metal component remains at least partly in the solid state throughout the process.

Essential to the method according to the invention, therefore, is that at least one metal component remains at least partly in the solid state throughout the process according to the invention. This method includes the integration and interaction between the metal components. More specifically, the method comprises adding metallic components to each other and at the same time, and/or after their interaction. Therefore, essential for the method according to the invention is that at least one metal component is added at least partly in the solid state and that this metal component remains at least partly in the solid state throughout the reaction. The term "at least partly in the solid state" in this context means that at least part of the metal component is present in the form of a solid metal component and, optionally, another portion of the metal component is present in the form of a solution of this metal component in the proton fluid. The type is at least partially is present in the form of solids and, optionally, partially dissolved in the surrounding liquid.

It is possible to first obtain a suspension of the metal component in the proton fluid and add, at the same time or one after another, the solution (solutions) and/or additional suspension (slurry) containing dissolved and/or suspended in proton liquid metal component(s). It is also possible to combine first solution either simultaneously or one after the other and then add, at the same time or one after another, additional suspension (slurry) and, optionally, the solution (solutions).

In all these cases, the suspension containing the metal component can be obtained by suspension of solid metal component in the proton fluid.

However, it is also possible to obtain a suspension (co)deposition of one or more metal components. The suspension obtained can be used as such in the method according to the invention, i.e. the resulting suspension add additional metal components in solution, in suspension or as such. The resulting suspension can also be applied after separation of solid/liquid and/or after neobyzantine in proton fluid. Instead of the metal suspension component can be used a metal component in wet or dry condition.

It should be noted that the above alternative methods are just a few examples of the metal components in the reaction mixture. In General, any order of introduction. Preferably simultaneously combine all the components of the base metals of group VIII and integrate all components of metals of group VIB, and then the two resulting mixture combine.

Up until at least one metal component is at least partly in the solid state during the process according to the invention, the number of metal components, which, at least partially, are in the solid state, is not critical. Therefore, it is possible that all metal components are combined in the method according to the invention, can be used at least partly in the solid state. Alternatively, a metal component that is at least partly in the solid state, can be combined with a metal component, which is in a dissolved state. For example, one and preferably two metallic component type in a dissolved state. In another embodiment of the invention, the two metallic component type (type), at least partly in the solid state and at least one and preferably one metal component is introduced into the dissolved state.

What metal component add "dissolved" means that the entire quantity of this metal component is added in the form of a solution of this metal component in the proton fluid.

Not wishing to be bound by any theory, it is assumed that the metal components that are added during the method according to the invention, interact, at least partially: the proton fluid responsible for the transport of dissolved metal components. Due to such transfer of metal components come into contact with each other and can communicate. It is believed that this reaction can occur even if all components are virtually entirely in the solid state. Due to the presence of the proton fluid a small part of the metal components may dissolve and then to interact, as described above. The presence of the proton fluid through the usual methods, such as infrared spectroscopy or Raman spectroscopy (Raman spectroscopy). In this case, the reaction manifests itself by a change of the signal. In some cases, you can monitor the progress of the reaction by controlling the pH of the reaction mixture. In this case, the reaction is manifested in the change of the pH value. In addition, the completeness of the reaction can be monitored by x-ray diffraction. This will be described in more detail in the section "Catalytic composition according to the invention".

It should be clear that it is unacceptable to first get the solution containing all components necessary for obtaining a certain catalytic compositions, and then choosedate these components. Unacceptable to the method according to the invention to add metal components, at least partly in the solid state and to select the process conditions, such as temperature, pH or proton number of the liquid, so that all added metal components are present in full in a dissolved state, at least at some stage. On the contrary, as indicated above, at least one of the metal components, which is added at least partly in the solid state, occhialino, at least 1 wt.%, more preferably at least 10 wt.% and even more preferably at least 15 wt.% the metal component is added in the solid state in the course of the method according to the invention relative to the total mass of all components of the metals of group VIB and base metals of group VIII, calculated as metal oxides. If it is desirable to obtain a high yield, i.e. a large number of the final catalytic composition, the preferred method may be the use of metallic components, a large number of which remains in the solid state during the entire method according to the invention. In this case, small amounts of metal components remain dissolved in the mother solution, and the amount of metal components that go into the waste water for subsequent separation of the solid/liquid decreases. You can completely avoid any loss of metal components, if recycling of the mother liquor produced during the separation of solid/liquid, in the method according to the present invention. It is noted that a particular advantage of the method according to the present invention in comparison with obtaining catalyst, based on the coprecipitation method is tomellini components, preferably, at least 0.01 wt.%, more preferably, at least, of 0.05 wt.% and most preferably at least 0.1 wt.% all metal components originally used in the method according to the invention (relative to the total weight of all metal components, calculated as metal oxides), add in the form of a solution. This provides a suitable contact metal components. If the reactivity of a particular added metal component is low, it is recommended to add a large quantity of this metal component in the form of a solution.

Proton fluid used in the method according to the present invention, can be any proton fluid. Examples are water, carboxylic acids and alcohols, such as methanol, ethanol or mixtures thereof. Preferably as a proton fluid in the method according to the present invention using a liquid containing water, such as a mixture of alcohol and water, and more preferably water. In addition, in the method according to the present invention can be used concurrently by different proton fluid. For example, you can add a suspension of the metal component in ethanol to bodnant, which dissolves in its own water of crystallization. In this case, crystallization water acts as a proton fluid. Of course, you must choose proton liquid, which does not affect the reaction.

In the method according to the invention is used, at least one component made of base metal of group VIII and at least two of the component metals of group VIB. Suitable metals of group VIB include chromium, molybdenum, tungsten or mixtures thereof, and a combination of molybdenum and tungsten is the most preferred. Suitable base metals of group VIII include iron, cobalt, Nickel or mixtures thereof, preferably cobalt and/or Nickel. Preferably in the method according to the invention use a combination of metal components, including Nickel, molybdenum and tungsten, or Nickel, cobalt, molybdenum and tungsten, or cobalt, molybdenum and tungsten.

Preferably, the Nickel and cobalt was at least 50 wt.% from the sum of the components of the base metal of group VIII, in terms of oxides, more preferably at least 70 wt.% and even more preferably at least 90 wt.%. It may be particularly preferred when the component base metal of groups is at least 50 wt.% from the sum of the components of the metal of group VIB in terms trioxide, more preferably at least 70 wt.% and even more preferably at least 90 wt.%. It may be particularly preferred when the component metal of group VIB consists essentially of molybdenum and tungsten.

The molar ratio of the metals of group VIB to base metals of group VIII used in the method according to the invention, is typically in the range of 10:1-1:10, preferably 3:1-1:3. The molar ratio of the various metals of group VIB to each other is usually not critical. The same is true when using more than one base metal of group VIII. When the metals of group VIB apply molybdenum and tungsten, the molar ratio of molybdenum:tungsten is preferably in the range of 9:1-1:19, more preferably 3:1-1:9, most preferably 3:1-1:6.

If proton fluid is water, the solubility of the components of the base metals of group VIII and components of metals of group VIB, which are at least partly in the solid state in the course of the method according to the invention is typically less than 0.05 mol/100 ml water at 18C.

If proton fluid is water Verdon state in the course of the method according to the invention, include the components of the base metals of group VIII of low solubility in water, such as citrates, oxalates, carbonates, hydroxycarbonate, hydroxides, phosphates, phosphides, sulfides, aluminates, molybdates, wolframates, oxides or mixtures thereof. Preferably the components of the base metals of group VIII, which are at least partly in the solid state during the method according to the invention, contain, and more preferably consist essentially of oxalates, carbonates, hydroxycarbonate, hydroxides, phosphates, molybdates, wolframates, oxides or mixtures thereof, and hydroxycarbonate and carbonates are the most preferred. Usually the molar ratio of hydroxyl groups and carbonate groups in hydroxycarbonate is in the range of 0-4, preferably 0-2, more preferably 0-1 and most preferably of 0.1 to 0.8. Most preferably component base metal of group VIII, which is located at least partly in the solid state in the course of the method according to the invention is a salt made of base metal of group VIII.

If proton liquid is water, suitable components of Nickel and cobalt, which are at least partly in the solid is e as oxalates, citrate, aluminates, carbonates, hydroxycarbonate, hydroxides molybdates, phosphates, phosphides, sulfides, wolframate, oxides or mixtures of these compounds Nickel and/or cobalt. Preferably Nickel or cobalt component include oxalates, citrates, carbonates, hydroxycarbonate, hydroxides molybdates, phosphates, wolframate, oxides or mixtures of these compounds Nickel and/or cobalt, and more preferably essentially consists of, and hydroxycarbonate Nickel and/or cobalt hydroxide of Nickel and/or cobalt, carbonate of Nickel and/or cobalt, or mixtures thereof are most preferred. Usually the molar ratio of hydroxyl groups and carbonate groups in hydroxycarbonate Nickel or cobalt or Nickel/cobalt is in the range of 0-4, preferably 0-2, more preferably 0-1 and most preferably of 0.1 to 0.8. Suitable components of iron that are at least partly in the solid state in the course of the method according to the invention, is the citrate of iron (II) carbonate, hydroxycarbonate, hydroxide, phosphate, phosphide, sulfide, iron oxide or mixtures thereof, and citrate of iron (II) carbonate, hydroxycarbonate, hydroxide, phosphate, phosphide, iron oxide or mixtures thereof are preferred.

what Nisha least in part, in the solid state during contacting, include components of metals of group VIB of low solubility in water, such as di - and trioxide, carbides, nitrides, aluminum salts, acids, sulfides or mixtures thereof. Preferred components of metals of group VIB, which are at least partly in the solid state during contacting, include di - and trioxide, acids or mixtures thereof, and preferably essentially consist of them.

Suitable molybdenum components, which are at least partly in the solid state during contacting, include water-insoluble molybdenum components, such as di - and trioxide of molybdenum, molybdenum sulfide, molybdenum carbide, molybdenum nitride, aluminum molybdate, molybdenum acid (e.g., N2Moo4), phosphomolybdate ammonium or mixtures thereof, and molybdenum acid and di - and trioxide of molybdenum are preferred.

Finally, suitable tungsten components which are at least partly in the solid state during the method according to the invention include water-insoluble compounds of tungsten, such as di - and trioxide, tungsten, tungsten sulfide (WS2and WS3), carbide volts or polyvalent), phospholipase ammonium or mixtures thereof, and orthovalerate acid and di - and trioxide of tungsten are preferred.

All of the above components are typically commercially available or can be obtained, for example, deposition. For example, hydroxycarbonate Nickel can be obtained from a solution of the chloride, sulfate or nitrate of Nickel by adding the appropriate quantity of sodium carbonate. Usually experts in this field know how to choose deposition conditions so as to obtain the desired morphology and texture.

In General, the preferred metal components, which in addition to metal mostly contain C, O and/or N, since they are less harmful to the environment. Carbonates and hydroxycarbonate base metals of group VIII are preferred metal components to add at least partly in the solid state, because when using a carbonate or hydroxycarbonate, outstanding CO2and positively affects the pH of the reaction mixture. In addition, since the carbonate is converted to CO2and misses the waste water, the waste water can be recycled. In addition, in this case is not required StudioLine components of the base metals of group VIII to add in the dissolved state include water-soluble salts of base metals of group VIII, such as nitrates, sulfates, acetates, chlorides, formate, hyposulfite and mixtures thereof. Examples include water-soluble Nickel and/or cobalt components, for example, soluble salts of Nickel and/or cobalt, such as nitrates, sulfates, acetates, chlorides, formate, or mixtures of these compounds Nickel and/or cobalt, and hyposulphite of Nickel. Appropriate components of iron to add in the dissolved state include the acetate, chloride, formate, nitrate, ferric sulfate, or a mixture thereof.

Appropriate components of metals of group VIB to add in the dissolved state include water-soluble salts of metals of group VIB, such as normal monopolarity or wolframite ammonium or alkali metal, and water-soluble isopoliteia molybdenum and tungsten, such as methanolmaria acid, or water soluble heteropolysaccharide molybdenum or tungsten, optionally including, for example, P, Si, Ni or Co, or combinations thereof. Suitable water-soluble versions, displacements contour plots and heteropolysaccharide shown in Molybdenum Chemicals, Chemical Data Series, Bulletin Cdb-14, February 1969 and Molybdenum Chemicals, Chemical Data Series, Bulletin Cdb-12a-revised, November 1969. Suitable water-soluble chromium compounds are, for example, normal chromates, versions, displacements contour plots is oxycarbonate and/or carbonate base metal of group VIII, such as hydroxycarbonate and/or carbonate of Nickel or cobalt, a metal oxide of group VIB and/or acid of a metal of group VIB, such as a combination of tungsten acid and molybdenum oxide, or a combination of molybdenum trioxide and tungsten trioxide, or hydroxycarbonate and/or carbonate of a metal of group VIII, such as hydroxycarbonate and/or carbonate of Nickel or cobalt salt of a metal of group VIB, such as dimolybdate ammonium, heptamolybdate ammonium and metabolomic ammonium. The additional choice of suitable combinations of metal components is within the competence of a specialist.

It was found that the morphology and texture of the metal component or components that remain at least partly in the solid state throughout the method according to the invention, can be stored in the course of the method according to the present invention. Therefore, applying particles of a metal component with a specific morphology and texture, can, at least to some extent to control the morphology and the texture of the bulk catalyst particles contained in the final catalytic composition. “Morphology and texture in the context of the present invention relate to the pore volume, u the Itza”, contained in the final catalytic composition will be disclosed in the section “the Catalytic composition of the present invention”.

Typically, the surface area oxidic bulk catalyst particles is at least 60%, preferably at least 70% and more preferably at least 80% of the surface area of the metal component, which remains at least partly in the solid state throughout the method according to the invention. Surface area is expressed in this case as the surface area to the mass of this metal component, calculated as the metal oxide. Further, the average pore diameter (determined by nitrogen adsorption) of the oxidic bulk catalyst particles is usually at least 40% and preferably at least 50% of the average pore diameter of the metal component, which remains at least partly in the solid state throughout the method according to the invention. In addition, the pore volume (determined by nitrogen adsorption) of the oxidic bulk catalyst particles is usually at least 40% and preferably at least 50% of the pore volume of the metal component, which remains at least frequent the SSA of this metal component, calculated as the metal oxide.

The conservation of particle size usually depends on the degree of mechanical damage to the oxidic bulk catalyst particles during processing, especially during these stages, as mixing or kneading. Particle diameter can be saved to a large extent, if such processing are long and soft. In this case, the average diameter of the oxidic bulk catalyst particles is usually at least 80% and preferably at least 90% of the average particle diameter of the metal component, which remains at least partly in the solid state in the course of the method according to the invention. The particle size can also be affected by such processes, such as spray drying, especially if there are additional materials. The selection of the suitable conditions to monitor the distribution of particle size in such treatments is within the competence of a specialist.

It is believed that if the selected metal component, which is added at least partly in the solid state and which has a large average particle diameter, the other metal components will interact only with the outer layer of large particles of metal componentdata morphology and texture of the metal component (components) can be provided either by the use of suitable pre-formed metal components or receipt of such metal components by means of the above-described deposition, or recrystallization, or by any other method known in the art, under these conditions, to obtain a suitable morphology and texture. Appropriate selection of the conditions of deposition may be carried out in the usual experiments.

In order to obtain a final catalyst composition with high catalytic activity, it is preferable that the metal component or components that are at least partly in the solid state during the method according to the invention, were porous metal components. It is desirable that the total pore volume and the distribution of pore sizes of these metal components were similar to those indicators for conventional catalysts hydrobromide. Traditional catalysts hydrobromide typically have a pore volume of 0.05-5 ml/g, preferably 0.1 to 4 ml/g, more preferably 0.1 to 3 ml/g and most preferably 0.1 to 2 ml/g as determined by mercury or water parametria. In addition, traditional catalysts hydrobromide usually have a specific surface area of at least 10 m2/g, more preferably at least 50 the particle diameter of the metallic component or components, which are at least partly in the solid state during the method according to the invention, preferably is in the range of at least 0.5 micron, more preferably at least 1 μm, most preferably at least 2 μm, but preferably not more than 5000 μm, more preferably not more than 1000 μm, even more preferably not more than 500 μm and most preferably not more than 150 μm. Even more preferably, the average particle diameter is in the range of 1-150 μm, and most preferably in the range of 2-150 microns. Typically, the smaller the particle size of the metal components, the higher their reactivity. Therefore, the metal components with a particle size below the preferred lower limit in principle are the preferred implementation of the present invention. However, from the point of view of health, safety and environmental factors work with such small particles requires special precautions.

Next will be described the preferred conditions of the method join phase metal components and (subsequent) reaction stage.

a) Combining a metal component

Terms of the way in time bring the tour to the environment at their natural pH values (if apply a suspension or solution). In the General case, of course, it is preferable to maintain the temperature of the added metal components below the boiling point of the reaction mixture at atmospheric pressure in order to ensure easy handling of the components during their add. However, if required, can also be used temperature above the boiling point of the reaction mixture at atmospheric pressure or different pH values. If the reaction stage is carried out at elevated temperature, the suspension and, optionally, solutions which are added to the reaction mixture, generally can be pre-heated to elevated temperature, which may be equal to the reaction temperature.

As mentioned above, the addition of one or more metal components can also be implemented at a time when the combined metal components interact with each other. In this case the combination of metal components and their reactions are superimposed on each other and constitute a single stage of the way.

b) Reaction stage

During and/or after the addition of metal components are usually mixed at a certain temperature for a certain period of time, �tp://img.russianpatents.com/chr/176.gif">S, more preferably 50-300With even more preferably 70-200°C. and most preferably in the range of 70-180C. If the temperature is below the boiling point of the reaction mixture at atmospheric pressure, the method is usually carried out at atmospheric pressure. Above this temperature, the method is usually carried out at elevated pressure, preferably in an autoclave and/or static mixer.

Usually the mixture during the reaction stage is supported at its natural pH value. The pH value is preferably in the range of 1-12, more preferably 1-10 and more preferably in the range of 3-8. As indicated above, must be taken in order to find the pH and temperature so that not all metals are dissolved during the reaction stage.

The reaction time usually ranges from 1 min to several days, more preferably in the range from 1 min to 24 hours and most preferably in the range from 5 minutes to 20 hours. As mentioned above, the reaction time depends on the temperature. After the reaction stage, if necessary, the solid can be separated from the liquid, for example, by filtration.

The method according to the infusion of the Xia, during the above preparation of the bulk catalyst particles or the particles after their receipt can be added to a material selected from the group of binder materials, conventional catalysts hydrobromide, kekirawa components or mixtures thereof, as will be explained below. Details relating to such materials below in section (B).

For this the method you have the following options: components of metals of group VIB and base metals of group VIII can be combined with any of the above materials before or during the reaction of the metal components. They can be, for example, added to the material or simultaneously or one after the other. Alternatively, the components of metals of group VIB and base metals of group VIII can be combined, as described above, and then the material can be added to the combined metal components. In addition, you can combine the components of metals of group VIB and base metals of group VIII, either simultaneously or one after the other, then add the material, and finally add the rest of the components of metals of group VIB and base metals of group VIII, either simultaneously or one after the greater least in part, in the solid state during the method according to the invention, may be first mixed and, if necessary, molding materials, and then to not necessarily formed of the mixture you can add additional component (s) of metals of group VIB and/or base metals of group VIII. However, you can also combine the material with the component(s) of metals of group VIB and base metals of group VIII dissolved and then add the metal component at least partly in the solid state. Finally, the simultaneous addition of metal components and material.

As indicated above, the material to be added during the preparation of the bulk catalyst particles, may be a bonding material. The connecting material according to the present invention means a binder and/or its predecessor. If the precursor is added in the form of a solution, you should take measures to binder moved to the solid state in the course of the method according to the invention. This can be done by adjusting the pH conditions so that was the precipitation of the binder. Conditions suitable for the deposition of binder known in the art and require no further explanation. If quantity is of the solid-liquid.

In addition, during the preparation of the bulk catalyst particles may be added additional materials, such as phosphorus-containing compounds, boron compounds, silicon compounds, fluorine-containing compounds, additional transition metals, rare earth metals or mixtures thereof, in the same manner described for the above materials. Details regarding these additional materials below.

It is noted that regardless of whether at the time of receipt of the particles added to any of the above (additional) materials, particles obtained by the above-described (A) of the method will be outlined in the present invention as “three-dimensional catalytic particles”.

(C) Subsequent stage of the method,

Preferably surround the catalytic particles either as such or containing any of the above (additional) materials are exposed to one or more of the following process steps:

(i) mixing with a material selected from the group of binder materials, conventional catalysts hydrobromide, kekirawa components or their mixtures;

(ii) spray drying, quick drying, grinding, tameshiwari heat treatment, and

(v) acarnania.

These process steps will be explained in more detail later.

Technological stage (i)

Material may be added in the dry state, either heat-treated or not, in wet and/or suspended state, and/or in the form of a solution.

Material can be added during the preparation of the bulk catalyst particles (see above), after obtaining three-dimensional catalytic composition, but before any stage (ii) and/or during and/or after any stage (ii), but before any stage of the molding (iii).

Preferably the material is added after the preparation of the bulk catalyst particles and before spray drying or any alternative way, or if not used for spray drying or alternative methods, before forming. Optional volumetric catalytic composition obtained as described above can be subjected to separation of solid-liquid before mixing with the material. After separation of solid-liquid can be optionally included stage of leaching. In addition, the possible heat treatment of the bulk catalyst composition after optional separation of solid-liquid phase drying and before the Pach is eskay song material” means, that material is added to surround the catalytic composition, or Vice versa, and the resulting composition is mixed. The mixing is preferably carried out in the presence of liquid ("wet mix"). This increases the mechanical strength of the final catalytic composition.

It was found that the mixing of the bulk catalyst particles with the material and/or introduction of material during preparation of the bulk catalyst particles gives a volumetric catalytic compositions particularly high mechanical strength, in particular, if the average size of the volume of the catalytic particles is in the range of at least 0.5 micron, more preferably at least 1 μm, most preferably at least 2 μm, but preferably not more than 5000 μm, more preferably not more than 1000 μm, even more preferably not more than 500 μm and most preferably not more than 150 μm. Even more preferably, the average particle diameter is in the range of 1-150 μm, and most preferably in the range of 2-150 microns.

The mixing of the bulk catalyst particles with the material results in a bulk catalyst particles embedded in the material, or Vice versa. Typically, the morphology of the bulk catalytically the t to be selected from a binder material, conventional catalyst hydrobromide, craterous component or mixtures thereof. Such materials will be described in more detail below.

The applied binder material can be any material commonly used as a binder in the catalyst of hydrobromide. Examples are silica, silica-alumina, such as a conventional silica-alumina, alumina-coated silica, and silica-coated alumina, aluminum oxide, such as (pseudo)boehmite or gibbsite, titanium oxide, aluminum oxide coated titanium oxide, zirconium oxide, cationic or anionic clays such as saponite, bentonite, kaolin, thick or hydrotalcite, or mixtures thereof. Preferred binders are silica, silica-alumina, alumina, titanium oxide, aluminum oxide coated titanium oxide, zirconium oxide, bentonite, or a mixture thereof. Data binding can be used as such or after peptization.

You can also use the predecessors of such binders which turn into any of the above binder in the course of the method according to the invention. Suitable precursors are, for example, anusuya on the basis of silicon dioxide), a mixture of aluminates of alkali metals with liquid glass (to obtain a binder based on silica-alumina), a mixture of sources of two-, three - and/or tetravalent metal, such as a mixture of water-soluble salts of magnesium, aluminum and/or silicon (for cationic clay and/or anionic clay), chlorodrol aluminum, aluminum sulfate, aluminum nitrate, aluminum chloride, or a mixture thereof.

If necessary, a binder material may be constituted (mixed) with a compound containing a metal of group VIB and/or a compound containing base metal of group VIII, before compiling with the bulk catalyst composition and/or before adding in the course of its receipt. Mixing a binder with any of those containing metal compounds can be carried out by impregnation of the binder of these materials. Suitable impregnation methods known to experts in this field. If a binder parisiano can also be peptization in the presence of compounds containing a metal of group VIB and/or base metal of group VIII.

If the binder is applied aluminum oxide, specific surface area aluminum oxide is typically in the range of 50-600 m2/g and preferably 1-1,5 ml/g, as determined by adsorption of nitrogen. Before defining characteristics of aluminum oxide it is subjected to heat treatment at 600C for 1 hour.

Typically, the binder material to be added in the method according to the invention, has a lower catalytic activity than the bulk catalyst composition, or no 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 increase in the mechanical strength of the final catalytic composition. Therefore, the amount of binder added in the method according to the invention generally depends on the desired activity and/or the required mechanical strength of the final catalytic composition. May be appropriate quantity of binder 0-95 wt.% of the total composition depending on the intended use of the catalyst. However, in order to benefit from the unusually high activity of the composition of the present invention, the number of added binders are typically in the range of 0-75 wt.% on the whole composition, predpochtite, for example, the catalysts of hydrodesulfurization, hydrodenitrogenation or hydrocracking catalysts. These catalysts can be added to used fresh, regenerated or solifidianism condition. If required, the conventional catalyst hydrobromide can be crushed or processed in any other conventional manner prior to use in the method according to the invention.

Craterous component according to the present invention is any conventional krakeroy component, such as cationic resins, anionic resins, crystalline kekirawa components such as zeolites, for example ZSM-5 (extremely stable); zeolite Y, zeolite X, ALPOs, SAPOs, MCM-41, amorphous kekirawa components such as silica-alumina or mixtures thereof. It should be clear that some materials can act at the same time as the binder and krakeroy component. For example, silica - alumina can be performed simultaneously and cretinous, and mediating functions.

If you krakeroy component may be mixed with the metal of group VIB and/or base metal of the group VIII before mixing with the bulk catalyst composition and/or before adding in the course of its receipt. CME is Ananta such materials.

It usually depends on the intended use of the final catalytic composition, which are added if added, the above kekirawa components. Crystal krakeroy component is preferably added, if the resulting composition should be used for hydrocracking. Other kekirawa components such as silica - alumina or cationic clay preferably add, if final catalytic composition should be used when hydroacustic or mild hydrocracking. The number of added craterous material depends on the desired activity of the final composition and intended application and, therefore, can vary from 0 to 90 wt.% relative to the total weight of the catalytic 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 metals, rare earth metals or mixtures thereof.

As phosphorus-containing compounds may be used ammonium phosphate, phosphoric acid or organic phosphorodithioate at the stage of molding and/or after the stage of forming. If the binder material Patision, phosphorus-containing compounds can also be used for peptization. For example, a binder on the basis of aluminum oxide can be parisiano by contact with phosphoric acid or with a mixture of phosphoric and nitric acids.

As the boron compounds can be used, for example, boric acid or heteropolysaccharide boron and molybdenum and/or tungsten, as well as 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. Additionally, there may be used compounds such as kremneftoristogo acid, forborne acid, dipterofauna acid or hexaphosphoric acid, if required combination of F with Si, and P, respectively.

Suitable additional transition metals are, for example, rhenium, manganese, ruthenium, rhodium, iridium, chromium, vanadium, iron, platinum, palladium, titanium, zirconium, niobium, cobalt, Nickel, molybdenum or tungsten. These metals can be added at any stage of the method according to the present invention to the mi of the final catalytic composition. Thus, the final catalytic composition can be impregnated with an impregnating solution containing any of these metals.

Technological stage (ii)

Volumetric catalytic particles, optionally containing any of the above (additional) materials, may be subjected to spray drying, quick drying, grinding, kneading, mixing suspensions, dry or wet mixing, or their combinations, and the combination of wet mixing and kneading or mixing the slurry and spray drying is preferred.

These methods can be applied either before or after you add (if you add) any of the above (additional) materials, after separation of solid-liquid, before or after heat treatment and after re-wetting.

Preferably surround the catalytic particles are mixed with any of the above materials, and subjected to any of the methods described above. It is believed that the use of any of the above methods, spray drying, quick drying, grinding, kneading, mixing suspensions, dry or wet mixing, or combinations thereof to improve the IMO to cases when the material is added before and after applying any of the methods described above. However, in the General case, it is preferable to add the material in front of stage (ii). If the material is added after stage (ii), the resulting composition is preferably thoroughly mixed by any known method before any of the additional process steps, such as forming. Dignity, for example, spray drying is that this method does not generate wastewater flows.

Spray drying is usually carried out at a temperature in the range of 100-200With and preferably 120-180C.

Dry mixing means mixing volume of the catalytic particles in the dry state with any of the above materials in a dry condition. The wet mixture includes, for example, mixing the wet filter cake, comprising bulk catalyst particles and, optionally, any of the above materials, in the form of powders or wet filter cakes to obtain a homogeneous paste.

Technological stage (iii)

If required, the bulk catalyst, optionally comprising any of the above (additional tableting, preparation of beads and/or spray drying. It should be noted that, if the catalytic composition should be used in the suspension-type reactors, fluidized bed, moving bed or a soft layer, typically used for spray drying or cooking beads. For use in fixed bed or fluidized bed usually catalytic composition ekstragiruyut, tabletirujut and/or prepare beads. In the latter case, at any stage before the stage of molding or can be added any additives that are usually used in order to facilitate molding. Such additives may include aluminum stearate, surfactants, graphite, starch, methylcellulose, bentonite, polyethylene glycols, polyethylene oxides, or mixtures thereof. In addition, if the binder is used, the alumina may be desirable to add at the stage of forming acid, such as nitric acid, to increase the mechanical strength of the extrudates.

If the molding includes extrusion, preparation of beads and/or spray drying, it is preferable to carry out the stage of forming in the presence of a fluid, such as water. It is preferable to extrusion and/p>If necessary, you can use a coaxial extrusion of any of the above materials with a bulk catalyst particles, optionally including any of the above materials. More specifically, the two mixtures can be coextrudable, and in this case, the bulk catalyst particles, optionally including any of the above materials are present in the inner extrusion environment, while any of the above materials without the bulk catalyst particles present in the outer extrusion environment, or Vice versa.

Stage (iv)

After an optional stage of drying, preferably above 100With the obtained molded catalytic composition may be, if necessary, subjected to a heat treatment. However, thermal processing is not essential for the method according to the invention. “Thermal treatment” according to the present invention relates to the processing carried out at a temperature of, for example, from 100 to 600C, preferably from 150 to 550S, more preferably from 150 to 450With in a period of time ranging from 0.5 to 48 hours, in an inert gas is carried out in the presence of water vapor.

At all the above stages of the method the amount of fluid must be monitored. If, for example, before the catalytic composition is subjected to spray drying, the amount of liquid is too low, should be added incremental fluid. On the other hand, if, for example, the amount of liquid before extrusion catalytic composition is too large, the amount of liquid should be reduced by, for example, separation of solid-liquid, for example, filtration, decantation or evaporation, and, if necessary, the resulting material can be dried and then re-hydrated to a certain extent. For all the above stages of the method corresponding to the control amount of water is within the competence of a specialist.

Technological stage (v)

The method according to the present invention may further include stage acarnania (sulfatirovnie). Acarnania usually carried out by contacting the volumetric catalytic particles immediately after their receipt or after any of steps (i)-(iv) with sulfur-containing compound, such as elemental sulfur, hydrogen sulfide, DMDS or polysulfides. Stage acarnania can be carried out in the liquid and in the gas f is the donkey stage (i), but before stage (ii), and/or after stage (ii), but before stage (iii), and/or after stage (iii), but before stage (iv), and/or after stage (iv). Preferably, acarnania not performed before any stage of the method, in which the resulting sulfides of metals are returned to their oxides. These stages of the process are, for example, thermal treatment or spray drying, or any other high-temperature processing, if it is carried out in oxygen-containing atmosphere. Therefore, if the catalytic composition is subjected to spray drying and/or another alternative method or heat treatment in an oxygen-containing atmosphere, acarnania preferably carried out after the application of any of these methods. Of course, if such methods are used in an inert atmosphere, acarnania can also be carried out before these methods.

If the catalytic composition used in processes with a fixed layer, acarnania preferably carried out after the stage of forming and, if it applies, after the last heat treatment in an oxidizing atmosphere.

Acarnania in the General case can be done in situ and/or ex situ. Preferably acarnania carried out ex situ, i.e., acarnania proveable. In addition, preferably, the catalytic composition username and ex situ and in situ.

The preferred method according to the present invention includes the following sequential process steps: obtaining volumetric catalytic particles, as described above; mixing the suspension obtained volumetric catalytic particles, such as; spray drying the resulting composition, re-hydration, mixing, extrusion, drying, calcining, acarnania. Another preferred implementation of the invention includes the following sequential process steps: obtaining volumetric catalytic particles, as described above, the allocation of particles by filtration; the wet mixture of filter cakes with a material such as a binder; mixing, extrusion, drying, calcining, acarnania.

The catalytic composition according to the invention

Further, the invention relates to a catalytic composition obtained in the above way. Preferably the invention relates to a catalytic composition obtained process stage (A) and, optionally, one or more process stages B(i)-(iv) above.

In the preferred implementation of izobretaia component (component), located at least partly in the solid state during the way, is stored in the catalytic composition. This preservation of morphology are described in detail in the Method according to the invention".

(a) an Oxide catalyst composition

The invention further relates to a catalyst composition comprising bulk catalyst particles which contain at least one base metal of group VIII and at least two metals of group VIB, where the metals are present in the catalytic composition in their oxide state, and where the characteristic full width at half maximum does not exceed 2.5if the metals of group VIB is molybdenum, tungsten, and, optionally, chromium, or does not exceed 4.0if the metals of group VIB is molybdenum and chromium or tungsten and chromium.

As described in the section "Methods of research", the characteristic full width at half maximum is determined on the basis of the peak located at 2=53,6(±0,7if the metals of group VIB is molybdenum, tungsten, and, optionally, chromium and if the metals of group VIB are Wolfram and chrome), or when 2

Preferably the characteristic full width at half maximum does not exceed 2.2more preferably 2.0 toeven more preferably 1.8 toand most preferably does not exceed 1.6(if the metals of group VIB is molybdenum, tungsten, and, optionally, chromium), or not more than 3.5more preferably 3,0even more preferably 2,5and most preferably 2.0 to(if the metals of group VIB is molybdenum and chromium or tungsten and chromium).

Preferably radiograph shows two peaks at positions 2=38,7(±0,6) and 40.8(±0,7) (these peaks will be referred to as a doublet P) and/or two peaks at positions 2=61,1(±1,5) and 64.1(±1,2) (these peaks will be referred to as a doublet Q), if the metals of group VIB is molybdenum, tungsten, and, optionally, chromium.

From the characteristic full width at paloncha least one of the two doublets P and Q, we can conclude that the microstructure of the catalyst of the present invention is different from the microstructure of the corresponding catalysts prepared by coprecipitation as described in WO No. 9903578 or in U.S. patent No. 3678124.

Typical radiographs disclosed in the examples.

X-ray volumetric catalytic particles preferably do not contain any peaks, characteristic of metallic components introduced into the reaction. Of course, if you want, you can also select the number of metal components so as to receive a volume of the catalytic particles, characterized by the x-rays which include one or more of the peaks characteristic of at least one of these metal components. If, for example, to add a large amount of the metal component, which is at least partly in the solid state during the method according to the invention or if you add this metal component in the form of large particles, small amounts of this metal component can be seen in the radiograph obtained volumetric catalytic particles.

The molar ratio of the metals of group VIB to base metals of group VIII usually n the relations, of course applicable to the metals that are in the shell. The ratio of the metals of group VIB to each other is usually not critical. The same is true if you use more than one base metal of group VIII. In cases where as metals of group VIB are molybdenum and tungsten, the ratio of molybdenum:tungsten is preferably in the range of 9:1-1:19, more preferably 3:1-1:9, most preferably 3:1-1:6.

Volumetric catalytic particles include components, at least one base metal of group VIII and at least two metals of group VIB. Suitable metals of group VIB include chromium, molybdenum, tungsten or mixtures thereof, and a combination of molybdenum and tungsten is the most preferred. Suitable base metals of group VIII include iron, cobalt, Nickel or mixtures thereof, preferably Nickel and/or cobalt.

Preferably surround the catalytic particles according to the invention contain a combination of metals, including Nickel, molybdenum and tungsten, or Nickel, cobalt, molybdenum and tungsten, or cobalt, molybdenum and tungsten.

Preferably, the Nickel and cobalt was at least 50 wt.% from the sum of the components of the base is) at least 90 wt.%. It may be particularly preferred that the component base metals of group VIII consisted essentially of Nickel and/or cobalt.

Preferably, the molybdenum and tungsten were at least 50 wt.% from the amount of component metals of group VIB in the calculation of trioxide, more preferably at least 70 wt.%, even more preferably, at least 90 wt.%. It may be particularly preferred that the component metals of group VIB consisted essentially of molybdenum and tungsten.

Preferably oxidic bulk catalyst particles contained in these catalytic compositions have a specific surface according to BET of at least 10 m2/g, more preferably at least 50 m2/g, even more preferably at least 80 m2/g as determined by BET method.

If during the preparation of the bulk catalyst particles do not add none of the above (additional) materials, such as binders, krakeroy component or basic catalyst hydrobromide, volumetric catalytic particles will contain about 100 wt.% metals of group VIB and base metals of group VIII. If at the time of getting about is to win 30-100 wt.%, more preferably 50-100 wt.% and most preferably 70-100 wt.% metals of group VIB and base metals of group VIII and the balance is any of the above (additional) materials. The number of metals of group VIB and base metals of group VIII may be assigned by TEM-EDX, AAS or ICP.

The average diameter of pores (50% of the pore volume is below this diameter and the remaining 50% higher) of the oxidic bulk catalyst particles is preferably 3-25 nm, more preferably 5-15 nm (determined by adsorption of N2).

Total pore volume of the oxidic bulk catalyst particles is preferably at least 0.05 ml/g and more preferably at least 0.1 ml/g, as determined by the adsorption of N2.

It is desirable that the size distribution of the pore volume of the catalytic particles was approximately the same as that of conventional catalysts hydrobromide. More specifically, the bulk catalyst particles preferably have an average pore diameter of 3-25 nm, as determined by adsorption of nitrogen.

In addition, these bulk catalyst particles preferably have an average particle size in the range of at least 0.5 micron, more preferably at least 1 μm, most is 1000 μm, even more preferably not more than 500 μm and most preferably not more than 150 μm. Even more preferably, the average particle diameter is in the range of 1-150 μm, and most preferably in the range of 2-150 microns.

As mentioned above, using the method according to the invention, can be obtained, if required, the volume of the catalytic particles to the structure of the core-shell. In such particles, at least one of the metals anisotropic distributed in the bulk catalyst particles. The concentration of the metal, the metal component of which is at least partly in the solid state in the course of the method according to the invention, is generally higher in the inner part, i.e. in the kernel of finite volume catalytic particles than in the outer part, i.e. in the shell finite volume of the catalytic particles. Typically, the concentration of this metal in the shell finite volume of the catalytic particles is not more than 95% and in most cases not more than 90% of the concentration of this metal in the core of the finite volume of the catalytic particles. It was further found that the metal of the metal component, which is used in a dissolved state in the course of the method according to the invention, also anisotropic distributed in a finite volume of catalic usually lower than the concentration of this metal in the shell. More specifically, the concentration of this metal in the core of the finite volume of the catalytic particles is not more than 80%, usually not more than 70% and often not more than 60% of the concentration of this metal in the shell. It should be noted that the above-described anisotropic metal distribution, if any, can be detected in the catalytic compositions according to the invention regardless of whether the catalytic composition is subjected to a heat treatment and/or acarnania or not. In the above cases, the shell usually has a thickness of 10-1000 nm.

Although the method according to the invention can achieve the above-described anisotropic distribution of metals, usually metals of group VIB and base metals of group VIII is distributed homogeneously in the bulk catalyst particles. This embodiment is generally preferred.

Preferably, the catalytic composition further comprises a suitable binder material. Suitable binders are those that have been described above. The particles are usually embedded in a binder material, which works as a glue, holding the particles together. Preferably the particles are uniformly distributed inside the light of the composition. Typically, the catalytic composition according to the invention has a mechanical strength, defined as the lateral crushing, at least 0,454 kg/mm and preferably at least 1.36 kg/mm (measurement extrudates with a diameter of 1-2 mm).

The amount of binder depends, among other things, on the desired activity of the catalytic composition. May be appropriate quantity of binder 0-95 wt.% of the total composition depending on the intended catalytic applications. However, in order to take advantage of the unusually high catalytic activity of the composition of the present invention, the amount of binding are usually in the range of 0-75 wt.% of the total composition, preferably 0-50 wt.%, more preferably 0-30 wt.%.

If required, the catalytic composition may contain suitable krakeroy component. Suitable cretinously components preferably are those that have been described above. The number craterous component preferably is in the range of 0-90 wt.% calculated on the total weight of the catalytic composition.

In addition, the catalytic composition may contain conventional catalysts hydrobromide. Traditional to the clients. Hydrogenating metals of traditional catalyst hydrobromide usually contain metals of group VIB and base metals of group VIII, such as combinations of Nickel or cobalt with molybdenum or tungsten. Suitable conventional catalysts hydrobromide are, for example, catalysts for Hydrotreating or hydrocracking. Such catalysts can be used, recycled, fresh or sulfurized condition.

In addition, the catalytic composition may contain any additional material, which is usually present in the catalysts of hydrobromide, such as phosphorus-containing compounds, boron compounds, silicon compounds, fluorine-containing compounds, additional transition metals, rare earth metals or mixtures thereof. Details on these additional materials listed above. Transition or rare earth metals are usually present in oxide form, if the catalytic composition is thermally treated in an oxidizing atmosphere, and/or sulfurized form, if the catalytic composition was subjected to acarnania.

To obtain a catalytic composition with high mechanical strength, it may be desirable, h is Adelino by the intrusion of mercury, the contact angle of 130) is preferably less than 30% of the pore volume of the catalytic composition, more preferably less than 20%.

The oxide catalyst composition of the present invention typically 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 with respect to the total weight of the catalytic composition based on oxides of metals.

It is noted that the catalyst obtained by stepwise impregnation of the carrier based on alumina with solutions of metals of group VIB and base metals of group VIII, as described in JP No. 09000929, does not contain any bulk catalyst particles and, therefore, has a morphology that is completely different from the morphology of the present invention.

(b) Sulfurized catalyst composition

If required, the catalytic composition of the present invention may be subjected to acarnania. Therefore, the present invention relates to catalytic compositions containing sulfide bulk catalyst particles which contain at least one base metal of group VIII and men who CSOs, the present invention relates to catalytic compositions containing sulfide bulk catalyst particles which contain at least one base metal of group VIII and at least two metals of group VIB, where the degree of acarnania under conditions of use not in excess of 90% and where the catalytic composition does not contain sulfurized form the compounds of formula NibMocWdO2with the values of b/(c+d) being in the range of 0.75 to 1.5, or even 0.5 to 3 and the values of c/d in the range of 0.1 to 10, or even equal to or higher than 0.01 and z=[2b+6(c+d)]/2, or where the catalytic composition does not even contain any sulfurized forms of Nickel molybdate in which at least part of the molybdenum, but not all of the molybdenum is replaced by tungsten, as described in international patent application no prepublication WO No. 9903578.

It should be clear that the above sulfurized catalyst composition can contain any of the above (additional) materials.

The present invention further relates to molded and sulfurized catalyst composition containing:

(i) sulfide bulk catalyst particles containing at least one base metal of group VIII and at least two of the th from the group of binder materials, conventional catalysts hydrobromide, kekirawa components or mixtures thereof.

It is essential that the degree of acarnania volumetric sulfide catalyst particles under conditions of use does not exceed 90%. Preferably the degree of acarnania in the terms of use is in the range of 10-90%, more preferably 20-90%, and most preferably 40-90%. The degree of acarnania determine, as described in "research Methods".

If in the method according to the present invention apply the usual methods of acarnania, the degree of acarnania volumetric sulfide catalyst particles before using essentially identical degree of acarnania in the terms of use. However, if you use very specific methods acarnania, it may be possible that the degree of acarnania before use of the catalyst is higher than when it is used as while using part of sulfides or elemental sulfur is removed from the catalyst. In this case, the degree of acarnania is that which is received during use of the catalyst, but not before using it. Usage conditions are those described below in the section "Application for the invention". What a catalyst is iodine-time, long enough so that the catalyst has reached equilibrium with the reaction medium.

In addition, preferably, the catalytic composition of the present invention would be essentially free from disulfide base metals of group VIII. More specifically, base metals of group VIII are preferably present in the base metal of the group VIII)ySxand x/y is in the range of 0.5-1.5.

It is noted that sulfide catalytic composition of the present invention have a much better catalytic performance than the catalysts comprising one base metal of group VIII and only one metal of group VIB.

Molded and sulfurized particles of the catalyst can have many different forms. Suitable shapes include spheres, cylinders, rings and symmetric or asymmetric polylobate, for example, three - and quadrilobate. Particles obtained by extrusion, manufacture beads or pelletizing, typically have a diameter in the range of 0.2-10 mm, and their length is similar is in the range of 0.5-20 mm Particles obtained by spray drying, typically have an average particle diameter in the range of 1-100 microns.

Details of binder materials, kekirawa compo is Evegeny above. In addition, the details belonging to the VIB group metals and base metals of group VIII contained in the sulfurized catalyst compositions and their quantities above.

It is noted that the above-described oxide for catalytic composition the structure of the core-shell does not collapse due to acarnania, i.e., sulfurized catalyst composition may also contain a structure of core-shell.

Further noted that the sulfurized catalysts are, at least partially crystalline materials, i.e., the x-ray volumetric sulfide catalyst particles typically includes several crystalline peaks characteristic of the sulphides of the metals of group VIB and base metals of group VIII.

As for the oxide catalytic compositions, preferably less than 30% and more preferably less than 20% of the pore volume of sulfide catalytic composition accounted for by pores with a diameter above 100 nm (determined by mercury intrusion, contact angle 130).

Typically the average diameter volumetric sulfide catalyst particles identical to those listed above for the oxidic bulk catalyst particles.

The use according to the invention

The catalytic composition on from the article in widely varying reaction conditions, for example, at temperatures in the range of 200-450C, hydrogen pressures in the range from 500 to 30,000 kPa and volume velocity (average velocity of the fluid) in the range of 0.05 to 10 h-1. The term "hydrobromide" in this context encompasses 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 mild pressure conditions, which is usually 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. You can apply the usual process conditions, such as temperature in the range of 250-450With pressure in the range from 5000-25000 kPa, flow rate in interdelta strength at lateral crushing

First measure the length, for example particles of the extrudate, and then the particle extrudate is subjected to a load compression (11.3 kg in 8.6 sec) by means of a moving piston. Measure the force required to crush the particle. The procedure is repeated with at least 40 samples part of the extrudate and calculate the average value as the force (kg) unit length (mm). The method previously used for shaped particles with a length not exceeding 7 mm

2. Determination of pore size on adsorption of N2

Measurement of the adsorption of N2were performed as described in Ph.D. thesis J. CF. Broekhoff (Delft University of Technology, 1969).

3. The amount of added solid metal components

Qualitative determination. The presence of solid metal components during the method according to the invention can be easily detected by visual inspection, at least when metal components are present in the form of particles with a diameter larger than the wavelength of visible light. Of course, in order to ensure that at any time during the method according to the invention all metals will not be dissolved, may also be applied by methods such as quasi-elastic light scattering (RATE) is the metallic components, which is added at least partly in the solid state, add in suspension (suspension), the amount of solid metal components added in the course of the method according to the invention, can be determined by filtering the added suspension (add suspensions) under the conditions that apply during add (temperature, pH, pressure, amount of liquid), so that all the solid material contained in the suspension (suspensions), collected in the form of a solid filter cakes. By mass of the solid and dried filter cakes can be by standard methods to determine the mass of solid metal components. Of course, if the filter cake in addition to solid metal components present additional solid components, such as solid binder, the mass of solid and dried binder should be subtracted from the mass of the solid and dried filter cakes.

The amount of solid metal components in the filter cake can also be determined by standard methods, such as atomic absorption spectroscopy (AAS), XRF, wet chemical analysis or ICP (plasma-chemical analysis).

If the metal components to the Oia is usually impossible. In this case, the mass of solid metal components are considered equal to the mass of the corresponding original metal components, calculated on the dry matter. Total weight of all metal components represents the number of all original metal components, calculated on the dry matter, in terms of oxides of the metals.

4. The characteristic full width at half maximum

The characteristic full width at half maximum for oxide catalysts is determined on the basis of radiographs catalysts, using a linear relationship:

(a) if the metals of group VIB is molybdenum and tungsten: the characteristic full width at half maximum is the full width at half maximum (based on) peak at 2=53,6(±0,7);

(b) if the metals of group VIB is molybdenum and chromium: the characteristic full width at half maximum is the full width at half maximum (based on) peak at 2=63,5(±0,6);

(c) if the screens full width at half maximum (based on) peak at 2=53,6(±0, 7);

(d) if the metals of group VIB is molybdenum, tungsten and chromium: the characteristic full width at half maximum is the full width at half maximum (based on 2) peak at 2=53,6(±0,7).

To obtain x-rays, you can use a standard powder diffractometer (e.g., Phillips PW1050), equipped with a graphite monochromator. Conditions of analysis can be selected, for example, the following:

the parameters of the x-ray generator: 40 kV and 40 mA

wavelength: 1,5418 Angstrom

divergence and anti-scattering slit: 1

the gap detector: 0.2 mm

the step value: 0,04 (2)

time/step: 20 seconds

5. The degree of acarnania

Any sulfur contained in sulphide bulk catalyst composition, are oxidized in a stream of oxygen by heating in an induction furnace. The resulting sulfur dioxide analyzed using an infrared cell with a detection system based on thermal characteristics of sulfur dioxide. For predece on standard, well-known substances. Then calculate the degree of acarnania as the ratio of the number of sulphur in sulphide bulk catalyst particles, the amount of sulfur, which would be contained in the bulk catalyst particles, if all the metals of group VIB and base metals of group VIII is present in the form of their disulfides.

Professionals should be clear that the catalyst, which determine the degree of acarnania, should be kept in an inert atmosphere to determine the extent of acarnania.

The invention will be further explained by the following examples.

Example 1

17,65 g Heptamolybdate ammonium (NH4)6Mo7O24·4H2O (0,1 mole of Mo, from Aldrich) and 24.60 g metavolume ammonium (NH4)6H2W12O40(of 0.1 mol W, from Strem Chemicals) was dissolved in 800 ml of water, getting a solution with a pH of approximately 5.2 at room temperature. After this, the solution is heated to 90With (solution A). 35,3 g Hydroxycarbonate Nickel 2NiCO3·3Ni(OH)2·4H2About (from 0.3 mol of Ni, from Aldrich) suspended in 200 ml of water and this suspension is heated to 90With (suspension). Hydroxycarbonate Nickel has a specific surface area by BET 239 m2/g (=376 m2/g NiO), objerr particles of 11.1 microns.

Then the suspension To add to the solution a for 10 min and the resulting suspension is maintained at 90C for 18-20 h with continuous stirring. At the end of this period, the suspension is filtered. The obtained solid is dried at 120C for 4 h and then calcined at 400C. the Yield is about 92% based on the calculated weight of all metal components are converted into their oxides.

Oxidic bulk catalyst particles have a specific surface area by BET 167 m2/g (=486 m2/g NiO=128% from the corresponding specific surface area of hydroxycarbonate Nickel), pore volume of 0.13 cm3/g (=0,39 cm3/g NiO=63% of the volume of pores hydroxycarbonate Nickel), the average pore diameter of 3.4 nm (=55% of the average diameter of the pores hydroxycarbonate Nickel), and the average particle diameter of 10.6 μm (=95% of the average particle diameter hydroxycarbonate Nickel).

Radiograph obtained after the stage of annealing, as shown in the drawing. The characteristic full width at half maximum is defined as 1,38(on the basis of the peak at 2=53,82).

Following this, the catalyst is subjected to UserMenu: 1,5 who t into the furnace Lindberg (Lindberg). The temperature was raised to 370C for about 1 h at a flow of 50 ml/min nitrogen, and the flow continued for 1.5 h at 370C. the Supply of nitrogen block and then into the reactor served at a speed of 20 ml/min 10% H2S/H2. The temperature was raised to 400C and maintained at this level for 2 hours and Then heating is shut off and the catalyst was cooled in a stream of H2S/N2up to 70Since at this point the purge is interrupted and the catalyst is cooled to room temperature under nitrogen.

Sulfurized catalyst is estimated at 300-ml modified periodic reactor CARBERRY (Carberry), designed for continuous flow of hydrogen. The catalyst tabletirujut and screened to 20/40 mesh and 1 g load in a stainless steel basket, placing between layers of beads made of mullite. To the autoclave was added 100 ml of a liquid raw material containing 5 wt.% studied (DBT) decline. Through the reactor flow flow 100 ml/min of hydrogen and maintain the pressure at 3150 kPa, using back pressure regulator. The temperature was raised to 350With speeds of 5-6C/min, and the experience leading up to, until or not converterparameter (GC). The rate constants for total conversion count as described in M. Daage and R. R. Chianelli (J. Catal., 149, 414-427 (1994).

Complete conversion DB (defined as the rate constant) at 350totalwas 138·1016molecules/ (g·s).

Comparative example a

The catalyst was prepared as described in example 1, except that used only one component of a metal of group VIB: the catalyst was prepared as in example 1, using 35,3 g heptamolybdate ammonium (NH4)6Mo7O24·4H2O (0,2 mol Mo) and 35.3 g of hydroxycarbonate Nickel 2NiCO3·3Ni(OH)2·4H2About (from 0.3 mol of Ni). The yield is about 85% relative to the calculated weight of all metal components are converted into their oxides. The catalyst is subjected to acarnania and experience as described in example 1. Complete conversion DB (defined as the rate constant) at 350With (total) has accounted for 95.2·1016molecules/(g·s) and, thus, was significantly lower than in example 1.

Comparative example

The catalyst was prepared as described in example 1, except that used only one component metal W12O40(of 0.2 mol W) and 35.3 g of hydroxycarbonate Nickel 2NiCO3·3Ni(OH)2*4H2O (0,3 mol of Ni). The yield is about 90% relative to the calculated weight of all metal components, turned into metal oxides. The catalyst is subjected to acarnania and experience as described in example 1. Complete conversion DB (defined as the rate constant) at 350With (total) was 107·1016molecules/(g·s) and, thus, was significantly lower than in example 1.

Example 2

28.8 g of Moo3(0,2 mol of Mo, from Aldrich) and 50.0 g of tungstic acid (H2WO4(of 0.2 mol W, from Aldrich) suspended in 800 ml of water (suspension A) and heated to 90C. 70,6 g Hydroxycarbonate Nickel 2NiCO3·3Ni(OH)2·4H2O (0,6 mol of Ni, from Aldrich) suspended in 200 ml of water and this suspension is heated to 90With (suspension).

Suspension To add to the suspension And for 60 min and the mixture was incubated at 90C for 18 h under continuous stirring. At the end of this period, the suspension is filtered, the obtained solid is dried at 120C for 4-8 h and calcined at 400

Oxidic bulk catalyst particles have a specific surface area by BET 139 m2/g (=374 m2/g NiO=99% from the corresponding specific surface area of hydroxycarbonate Nickel), pore volume of 0.13 cm3/g (=0,35 cm3/g NiO=56% of the volume of pores hydroxycarbonate Nickel), the average pore size of 3.7 nm (=60% of the average diameter of the pores hydroxycarbonate Nickel), and the average particle diameter of 14.5 μm (=131% from the average particle diameter hydroxycarbonate Nickel).

Radiograph of the oxidic bulk catalyst particles comprises peaks at 2=23,95 (very wide), 30,72 (very wide), 35,72, 38,76, 40,93, 53,80, 61,67 and 64,23. The characteristic full width at half maximum defined for the calcined catalyst composition as 1,60(determined on the basis of the peak at 2=53,80).

The catalyst is subjected to acarnania and catalytic characteristics are examined as in example 1.

Complete conversion at 350With (total) amounted to 144·1016molecules/(g·s).

The degree of acarnania under conditions of use amounted to 62%.

Example 3

Repeat the 2W12O40. The output is approximately 96% relative to the calculated weight of all metal components are converted into their oxides.

Example 4

Repeat example 2 with varying amounts of Nickel. Output and the characteristic full width at half maximum (determined on the basis of peaks in the interval 2=53,66-53,92are given in table 1.

Example 5

Example 4 is repeated with different ratios of molybdenum:tungsten.

Output and the characteristic full width at half maximum (determined on the basis of peaks in the interval 2=53,80-53,94°) are shown in table 2.

Example 6

The catalytic composition was prepared in the same manner as described in example 1. The resulting mixture was subjected to spray drying. The powder after spray drying contains of 43.5 wt.% NiO, of 20.1 wt.% Moo3and to 34.7 wt.% WO3. Pore volume bulk catalyst particles after spray drying is 0.14 ml/g measurement by nitrogen adsorption and a specific surface area by BET is 171 m2/,

Bulk catalyst particles are mixed with wet mixed with 20 wt.% the mixture is brought to such to obtain a compression mixture, after which the mixture ekstragiruyut. After the extrusion, the extrudate is dried at 120C and annealed at 385C. the Obtained catalyst composition has a specific surface area by BET 202 m2/g, pore volume, measured by mercury porometry 0.25 ml/g, and lateral crushing 2,46 kg/mm

Part of the resulting catalyst is subjected to acarnania using the straight-run gas oil (PIP) with the addition of dimethyl disulfide (DMDS) to obtain the total content of S to 2.5 wt.% S at 3000 kPa (average hourly feed rate of the liquid 4 h-1; N:oil=200). The catalytic Converter temperature increase from room temperature to 320With using the lifting speed of 0.5C/min, and support at 320C for 10 h and Then the sample is cooled to room temperature.

The degree of acarnania sulfurized catalyst composition under conditions of use is 52%.

Another part of the catalyst is subjected to acarnania raw materials with the addition of DMDS. Sulfurized thus the catalyst was then tested on a light crakereanda cyclic oil (LCCM). The relative volumetric activity guide is spruce and molybdenum, is 281.

Example 7

The catalytic composition was prepared similarly to the procedure described in example 1. After completion of the reaction patinirovannuyu alumina (15 wt.% relative to the total weight of the catalytic composition) suspendered with the bulk catalyst particles and the suspension is subjected to spray drying. The resulting catalyst contains up to 13.2 wt.% Al2O3, to 33.9 wt.% NiO, to 20.5 wt.% Moo3and 30.2 wt.% WO3. The volume of the pores of the oxide catalyst composition of 0.17 ml/g measurement by nitrogen adsorption and a specific surface area by BET is 114 m2/year of Particles after spray drying is mixed with such a quantity of water to obtain a compression mixture. The resulting mixture ekstragiruyut, the extrudate is dried at 120C and annealed at 385C. the Obtained catalyst composition has a specific surface according to BET of 133 m2/g, pore volume by mercury porometry of 0.24 ml/g and lateral crushing 2,42 kg/mm

Part of the resulting catalyst is subjected to acarnania using a mixture of 10 vol.% H2S in H2at atmospheric pressure (hourly average gas flow rate of approximately 8700 nm3·m-3·h-1C/min, and support for 400C for 2 hours Then the samples are cooled down to room temperature in a mixture of N2S/N2.

The degree of acarnania sulfurized catalyst composition under conditions of use is 64%.

Another part of the catalyst is subjected to acarnania raw materials with the addition of DMDS. Sulfurized thus the catalyst was then tested on a light crakereanda cyclic oil (LCCM). The relative volumetric activity when hydrodenitrogenation compared with the industrial catalyst on a carrier of aluminum oxide containing Nickel and molybdenum, is 235.

Claims

1. The method for the catalytic composition comprising bulk catalyst particles containing at least one base metal of group VIII and at least two metals of group VIB, including the integration and interaction of at least one component made of base metal of group VIII with at least two components of metals of group VIB in the presence of proton fluid, and at least one metal component remains at least partly in the solid state throughout Proca mass specified volume of catalytic particles, and the solubility of the component metals of these groups, which are at least partly in the solid state during the reaction, is less than 0.05 mol/100 ml water at 18aboutC.

2. The method according to p. 1, in which at least one of the metal components is at least partly in the solid state and at least one of the metal components is in a dissolved state during the incorporation of metal components.

3. The method according to p. 1, in which all metal components are at least partly in the solid state during the incorporation of metal components.

4. The method according to any of the preceding paragraphs, in which the proton fluid includes water.

5. The method according to any of the preceding paragraphs, in which the base metal of the group VIII includes cobalt, Nickel, iron or mixtures thereof.

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

7. The method according to any of the preceding paragraphs, in which the metal of group VIB includes at the greater least 50 wt.% from the sum of the components of the metal of group VIB in terms trioxide, preferably at least 70 wt.%, more preferably at least 90 wt.%.

9. The method according to any of the preceding paragraphs, which at the time of Association and/or interaction of metal components add material selected from the group of binder materials, conventional catalysts hydrobromide, kekirawa components or mixtures thereof.

10. The method according to any of the preceding paragraphs, in which bulk catalyst particles are subjected to one or more of the following process steps: (i) mixing with a material selected from the group of binder materials, conventional catalysts hydrobromide, kekirawa components or mixtures thereof; (ii) spray drying, quick drying, grinding, kneading, mixing suspensions, dry or wet mixing, or combinations thereof; (iii) formation; (iv) drying and/or thermal treatment, and (v) acarnania.

11. The method according to p. 10, comprising the following stages: Association and interaction of at least one component made of base metal of group VIII with at least two components of the metal of group VIB in the presence of proton liquid, where at least one of the components of metals remains, at least partially, in your, selected from the group of binder materials, conventional catalysts hydrobromide, kekirawa components or mixtures thereof; optionally forming; not necessarily acarnania.

12. The method according to p. 10, comprising the following stages: Association and interaction of at least one component made of base metal of group VIII with at least two components of the metal of group VIB in the presence of proton liquid, where at least one of the components of metals remains at least partly in the solid state during the entire process, from material selected from the group of binder materials, conventional catalysts hydrobromide, kekirawa components or mixtures thereof, present during the reaction; optional drying and/or washing; optional molding; not necessarily acarnania.

13. The method according to p. 11 or 12, in which the stage of formation.

14. Catalyst composition comprising bulk catalyst particles which contain at least one base metal of group VIII and at least two metals of group VIB, where the metals are present in their oxide and/or sulfide state, the metals of group VIII and group VIB constitute from about 50 wt.% to premenstruum in the catalytic composition in their oxide state, the catalytic composition has an x-ray, in which the characteristic full width at half maximum does not exceed 2.5°, if the metals of group VIB is molybdenum, tungsten, and, optionally, chromium, or does not exceed 4.0°, if the metals of group VIB is molybdenum and chromium, or tungsten, and chromium, and where sulfurized catalyst composition is at least partially crystalline material.

15. The catalytic composition according to p. 14, in which the characteristic full width at half maximum does not exceed 2.0°, if the metals of group VIB is molybdenum, tungsten, and, optionally, chromium, or not larger than 3.0°, if the metals of group VIB is molybdenum and chromium or tungsten and chromium.

16. The catalytic composition according to p. 14, which contains sulphide bulk catalyst particles which contain at least one component made of base metal of group VIII and at least two component metal of group VIB, the catalytic composition is essentially free from disulfide base metal of group VIII.

17. The catalytic composition according to p. 16, in which the base metals of group VIII are present in the base metal of the group VIII)ySxwhere x:we have the ical particles, which contain at least one component made of base metal of group VIII and at least two component metal of group VIB, and where the degree of acarnania under conditions of use does not exceed 90%.

19. How hydrobromide hydrocarbons in the presence of a catalytic composition according to any one of paragraphs.14-18.

 

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