Hydrocracking catalyst composition

FIELD: chemistry.

SUBSTANCE: unsupported catalyst composition for hydrocracking contains one or more group VIb metals, one or more group VIII base metals, one or more zeolites and optionally heat-resistant oxide material. The said composition is obtained through deposition of group VIb metals, group VIII base metals and optionally heat-resistant oxide material in the presence of a zeolite. The method of preparing the said catalyst composition, in which one or more compounds of group VIb metals are combined with one or more compounds of group VIII base metals, and with zeolite, in the presence of a proton-containing liquid and an alkaline compound, and the catalyst composition is extracted after deposition.

EFFECT: obtaining a catalyst composition with very high activity during hydrogenation of monoaromatic compounds, significantly better selectivity towards middle distillate products.

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The technical field to which the invention relates.

The present invention relates to compositions of hydrocracking catalyst, its preparation and application in the process of hydrocracking.

The level of technology

Among the many ways of becoming known in the refining sector, hydrocracking becomes more recently become increasingly important as the hydrocracking is provided a flexible refining of crude oil into products combined with quality products.

Significant efforts have been directed to the development of hydrocracking catalysts with a high activity cracking combined with a low ability to excessive cleavage with the formation of light products and, especially, low-gaseous by-products C1-C3and C4. The target products of the hydrocracking process are often kerosene and gasoil (these fractions boil at a temperature in the range from 150 to 370°C, commonly referred to as middle distillates).

The basis of such catalysts hydrocracking is typically molded carrier made from a separate, active craterous component, such as an aluminosilicate, particularly the component of the zeolite, subjected to crushing and extrusion together with the refractory oxide binder material, and infiltrating the connection guide is arousih metals.

Were offered alternative forms of catalysts for use in the processes of hydroconversion, for example, in a refinery. One such group of catalysts is called "solid catalysts". Such catalysts are formed only of the metal compounds, usually using technology coprecipitation, and they do not require a carrier or substrate of the catalyst; see, for example, the document WO 00/42119, US 6162350 and WO 00/41810.

In these publications revealed massive catalysts containing metals from group VIII and group VIb, their preparation and use. In the patent US 6162350 described that such catalysts may contain one or more metals of each type, and as examples of specified solid catalysts are NiMo, NiW and most preferably NiMoW. Binder, if present, is preferably added after preparation of the composition of solid metal and prior to molding.

In the coprecipitation certain amount of dispersed metals embedded in traditional material media by providing actual contact between the compounds of metals and material media, and thus, the metals have the ability to dispergirujutsja in all material media before the operation of molding. This differs from traditional methods of impregnation, in which the possible precipitation only slightly the amount of metals, as has already formed structure molded of media, and there are diffusion and spatial constraints for ions or metal compounds to their dispersion around the catalyst carrier.

In the patent US 6162350 discusses the use of other catalytic components with solid catalysts. Thus, kekirawa components, such as ZSM-5, zeolite and amorphous kekirawa components can be combined with the compositions of solid catalysts. Preferably, this occurs after the formation of the composition and, along with the introduction of a binder material prior to molding in order to obtain the media craterous catalyst in the traditional way.

At the same time the International patent application number PCT/EP 2004/050196, published as WO 2004/073859, disclosed a composition of quasi-solid metal catalyst, in which the binder material is mainly introduced into the composition during deposition. After the formation of this material can also be connected with other components, such as kekirawa components.

Thus, if kekirawa components must be entered in such compositions massive metals, it is recommended that they are preferably introduced by mixing or joint grinding after th the manufacture of the composition of solid metal.

The coprecipitation of the zeolite material and component hydrogenating metal from group VIb with the formation of the hydrocracking catalyst disclosed in the description of the US No. 3853747, in which the method of preparation of a hydrocracking catalyst having superior activity, through a combination of highly dispersed metal link group VIb (e.g., molybdenum), practically insoluble form the basis of the crystalline aluminosilicate in an aqueous medium having a pH value below 6. Formed precipitated zeolite containing metals. The pH value is set below 6 in order to ensure the insolubility of the compounds of the metal and to facilitate the deposition without destroying the crystal structure of the zeolite. The problem of preparation of the catalyst is to ensure that the concentration of metal on the outer surface of the zeolite, avoiding impregnation internal adsorption surface, and to ensure that the crystal structure and the acidity of the zeolite will not disappear at any stage during the preparation of the catalyst due to the use of soluble compounds of molybdenum or tungsten.

In the International application number WO 01/00753 the influence of the distribution of the hydrogenating metals within the pores of the zeolite to obtain hydrocracking catalyst on the selectivity for middle distillate. I think that zoom is the selectivity for middle distillate can be achieved through the introduction of hydrogenating metals inside the pores of the zeolite, for example, by impregnation of the zeolite with the metal prior to the forming medium. Specified broad ranges of content of from 0.1 to 10 wt.% for metals of group VIII (calculated as oxide) and from 0.1 to 10 wt.% for metals of group VIb (calculated as oxide), however, most preferably the entered number is from 0 to 5 wt.% metal of group VIII (calculated as oxide) and from 0.1 to 3 wt.% metal of group VIb (calculated as oxide). However, a certain amount of hydrogenating metals inevitably embedded in the pores of the zeolite during the preparation of traditional catalyst. The inventors have found that, indeed, when traditional methods of preparation of the catalyst by impregnation is the amount of metal of group VIb, such as molybdenum, may be in the hydrocracking catalysts based on zeolite U.

Typically in the prior art, it follows that, although it may be advantageous to introduce hydrogenating metals into the pores of the zeolite materials, the technology of deposition must be used with caution due to the risk of destruction of the crystalline structure of the zeolite.

Disclosure of inventions

In the present invention it has been unexpectedly found that zeolite materials can be introduced into the catalyst without media or precipitated catalyst during the preparation process, and that the resulting composition of the hydrocracking catalyst has the significant advantages in the process of hydrocracking, compared with the composition obtained by co-grinding and extrusion. Such compositions have a very high activity in the hydrogenation of mono-aromatic compounds, and preferred compositions also have significantly better selectivity for products middle distillates. Even when achieving a considerably higher degree of hydrogenation of the aromatic compounds, the amount of consumed hydrogen unexpectedly remains lower than for catalysts traditional cooking.

In contrast to the recommendations of the prior art, it was established the possibility of obtaining such precipitated compositions using precipitated mixtures having a pH from neutral to alkaline, as well as with soluble or partially soluble compounds of metals of group VIb, without destroying the crystal structure of the zeolite, and without loss of activity when the hydrocracking; indeed, such materials may have a higher selectivity for middle distillate hydrocracking than traditional catalysts preparation.

Thus, in the present invention provided the composition of the catalyst without media, which includes one or more metals of group VIb, one or more base metals of group VIII, one or more zeolites, neobyazatelno, one or more refractory oxide materials.

In addition, a method of preparation of the catalytic compositions according to the invention, and its use in the hydrocracking process.

The implementation of the invention

The present invention relates to the hydrocracking of crude oil using the catalyst composition without the media containing the metals of group VIII (especially Ni and/or Co) and group VIB (especially Mo and/or W), zeolite, and optionally an inert refractory oxide.

In the present invention refer to the Periodic table of elements, which are provided on the inner cover sheet physico-chemical Handbook "CRC Handbook of Chemistry and Physics" ('The Rubber Handbook'), 66th edition, and using the notation adopted in CAS.

The term "no carrier" means that the composition is not a traditional catalyst, which has a pre-formed catalyst carrier, which is then applied metals by impregnation or precipitation; the composition also is not of the type in which the metals together with media materials are crushed or unite together under the action of physical forces. In the composition according to the invention the metals, zeolite and optional refractory oxide material are joined together at one point in time using a chemical process in which this comp is position is formed prior to any stage of molding. Usually this chemical combination will occur as a result of precipitation. Thus, the term "no carrier" may be used in this invention interchangeably with the term "besieged", but only in connection with the catalytic composition of the present invention. In contrast to supported catalysts in the composition of the catalyst without any media refractory oxide material is not a separate individual material within the composition; however, the crystalline structure of the zeolite component unexpectedly remains intact. In fact, it was found that metals, mainly metal of group VIb, and especially metal molybdenum, heavily embedded inside the pores of the zeolite.

The metal of group VIII is preferably a one or two base metal chosen from Nickel, cobalt and iron. Preferably the metal of group VIII selected from Nickel, cobalt and combinations of Nickel and cobalt. The most preferred metal of group VIII is Nickel. The metal of group VIb, preferably represents one or two metal chosen from chromium, molybdenum and tungsten. More preferably, the metal of group VIb is selected from molybdenum, tungsten and combinations thereof. The most preferred metal of group VIb is molybdenum. Often in catalic the ical compositions, in which the desired function is hydrogenation, apply noble metals from group VIII, especially the metals platinum and palladium, which are the main metals in the selection of hydrogenation catalysts. However, unexpectedly high activity materials of the present invention in the hydrogenation means that there is no need for the use of these expensive materials.

It is advisable, when the zeolite component is a crystalline molecular sieve, the choice of sieves having pores with the largest diameter of more than 0.6 nm (crystallographically available diameters, calculated according to the Atlas of Zeolite Framework Types", Ch. Baerlocher, W.M. Meier, and O. Olson, 5-e edition, Elsevier, Amsterdam, 2001), of sieves having pores with a diameter of more than 0.6 nm, as determined from the distribution of the Horvath-Kawazoe pore size according to the data of adsorption isotherms of argon or nitrogen, and sit structural type AEL, EUO, PER, MFI, MEL, MTT, MTW, MWW, and TON.

In the context of the present invention, the term "molecular sieve" also includes appropriate (hydrothermal) stable and dealuminated derivatives and such derivatives, which can be obtained by isomorphous substitution and cation exchange. Methods cation exchange (hydrothermal) stabilization, dealumination and isomorphic substitution forefront of the lar sieves are well known in the prior art, and therefore is not further discussed in this invention.

In the description of the present invention, unless otherwise indicated, the molar ratio of silica to alumina in the zeolite is a molar ratio which is determined on the basis of the total or the total quantity of aluminum and silicon (in the frame and out of frame)in the zeolite.

Zeolite component may be formed from a single zeolite material or combination of two or more zeolites of the same or of different types.

Preferably, the zeolite is chosen from one or more crystalline molecular sieves structural type FAU, EMT, -CLO, VFI, AET, CFI, DON, OSO, AFI, AFR, AFS, AFY, ATS, *BEA, BOG, BPH, CON, CZP, DFO, GME, GON, IFR, ISV, LTL, MAZ, MEI, MOR, MTW, OFF, SAO, SBE, SBS, SBT, SFE, ETR, IWR, SSY, USI, UOZ, AEL, EUO, FER, MFI, MEL, MTT, MTW, MWW, TON, representatives of the families with disordered structure beta, SSZ-33, faujasite, MTT/TON, SFF/STF and ZSM-48, which are described in Atlas of Zeolite Framework Types" (see above), as well as in Database ' Database of Zeolite Structure Types" (Ch. Baerlocher and L.B.McCusker, http://www.iza-structure.org/databases/), ITQ-15, ITQ-21, and ITQ-25. More preferably, the zeolite may be one or more of zeolite Y, ZSM-5, ZSM-12, and zeolite beta. Most preferably, the zeolite is a crystalline molecular sieve structure type FAU, for example, ultrastable (with respect zeolite Y (USY) or very ultrastable (with respect zeolite Y (VUSY) the size of the unit cell (a aboutless than 2,440 nm (24,40 angstroms), including less than 2,435 nm (24,35 angstroms), which are known, for example, from the description of the patent EP 247678 and 247679, patent US 4784750, International application WO 2004/047988 and patent US 2002/094931.

Despite the fact that the zeolite USY and VUSY Y are the preferred forms of zeolite component used in the present invention, other forms of Y zeolite are also suitable for use, for example, the known ultrahydrophobic Y zeolites. Can be used more than one form of Y zeolite: for example, two of the zeolite with different size of the unit cell, such as USY zeolite in combination with VUSY zeolite.

Preferred VUSY zeolite according to the patent EP-A-247678 or EP-A-247679 characterized by the size of the unit cell is smaller than from 2.445 nm (24,45 angstroms) or 2,435 nm (24,35 angstroms), adsorption capacity for water at 25°C and the value of R/R0=0,2), at least 8% by weight of the zeolite and a pore volume of at least 0.25 ml/g, and between 10% and 60% of the total pore volume comprises pores having a diameter of at least 8 nm. The most preferred materials are zeolite Y with a small size of the unit cell and a large surface area according to the document WO 2004/047988, Such materials can be described as zeolites parasitol patterns having the size of an elementary cell in diapazonom 2,410 to 2,440 nm (24,10 to 24,40 Å), the ratio of silica to alumina (SAR) greater than 12, and a surface area of at least 850 m2/g, which is measured by the BET method and ATSM D 4365-95 by adsorption of nitrogen at the value of R/R0equal to 0.03.

When the zeolite beta is used as the zeolite component or as part of, then it could be any catalytically active zeolite beta, crystalline zeolite, described in the patent US Re 28341 or known of Atlas "Atlas of Zeolite Structure Types, 3rd edition, published in 1992, on behalf of the Structural Commission of the International zeolite Association. A particularly effective material in compositions for cracking is zeolite beta with a small crystallite size. Preferably, the crystallites of zeolite beta have a size less than 100 nm, for example, up to 99 nm. More preferably, the crystallites have a size in the range from 20 to 95 nm, most preferably 70 nm or less, such as 30, 40 or 50 to 70 nm. It is advisable that the zeolite beta had a molar ratio of silicon dioxide to aluminum oxide is equal to at least 20, preferably at least 25. Optionally, can also be used zeolite beta with a higher molar ratio of silicon dioxide to aluminum oxide, for example, up to and including 60, 80, 100, 120 or 150. Thus, the zeolite beta may have a molar on the wearing of silicon dioxide to aluminum oxide in the range from 20 to 60, 25-60, 20-80, 25-80, 20-100, 25-100, 20-120, 25-120, 20-150 or from 25 to 150. It is also advisable, and may be preferable to use zeolite beta with a high SAR value, such as beta zeolite, which has a value of SAR 150 or more, preferably from 150 to 400, more preferably from 200 to 350, especially 300.

Suitable zeolites beta are industrially available, for example, by PQ Corporation or from Zeolyst International.

If you use a refractory oxide material, it is chosen from aluminum oxide, silicon dioxide, titanium dioxide, magnesium oxide, zirconium dioxide, boron oxide, zinc oxide, zinc hydroxide, natural and synthetic clays and mixtures of two or more such materials. The preferred materials are silicon dioxide, titanium dioxide, amorphous aluminosilicate and alumina. Aluminum oxide and/or amorphous aluminosilicate are traditional binders in the compositions for hydrocracking; however, unexpectedly, were received very good songs that don't use any aluminiumoxide binder.

Used form of aluminum oxide is not limited, and the present invention can be used any type of aluminum oxide or the precursor of aluminium oxide, which is usually applied to media catalysts. Very suitable aluminiumoxide mater what Alami are boehmite, pseudoboehmite, bayerite, alpha-alumina, gamma-alumina, theta-alumina and ETA-alumina.

For amorphous aluminosilicate, the term "amorphous" means the absence of a crystal structure, which is defined in the material using x-ray diffraction, although in some ways it may be the middle order. Amorphous aluminosilicate, suitable for use in the present invention is industrially available. Alternatively, the aluminosilicate can be obtained using joint gelation or vaccinations, which are well known in the prior art. Preferably, the amorphous aluminosilicate contains silicon dioxide in a quantity in the range from 25 to 95 wt.%. More preferably, the amount of silica is more than 35 wt.%, and most preferably at least 40 wt.%. Amorphous silica-alumina product, very suitable for receiving the catalyst carrier, contains 45 wt.% silicon dioxide and 55 wt.% aluminum oxide and is industrially available (from the firm Criterion Catalysts and Technologies, USA).

In nature, titanium dioxide is available in several forms or polymorphic types:

rutile, anatase and brookite. Thermally the most stable form of titanium dioxide is rutile, and at very high temperatures the anatase can PR is vratitsa in rutile. In the catalytic composition of the present invention can be any of these forms of titanium dioxide. The surface area of the applied titanium dioxide, measured by the BET method, is typically in the range from 10 to 700 m2/g, more preferably from 20 to 400 m2/year

Found that the particle size of titanium dioxide can influence and enhance the activity of the final catalyst composition. Although for use in the present invention are suitable for any powders of titanium dioxide, preferably, the powder of titanium dioxide had an average particle diameter of about 50 μm or less, preferably, the particle diameter is 20 μm or less, and especially preferred particle diameter of 5 μm or less. Usually the minimum average diameter of the particles of titanium dioxide is of the order of 0.005 μm. In this invention, the average particle diameter means the diameter of 50% of the particles, which is also denoted by Dv50.

The most suitable raw materials of titanium dioxide available from the company Millenium Chemicals, Degussa and Haishunde. For example varieties Millenium's DT-51D and G5; grade Degussa's P25 and grade Haishunde's FCT010925. In addition, it is suitable industrial mixture of titanium dioxide and other refractory oxide materials, such as mixtures of silicon dioxide with titanium dioxide, such as grade FTS 01 from the company Haishunde.

In particular, most of predpochtitel the tion, especially when the desired high selectivity for middle distillates is the use of amorphous aluminosilicate or one of silicon dioxide, and particularly preferred is the use of one of silicon dioxide. The form used amorphous aluminosilicate or silica is not limited, and the present invention can be used any amorphous aluminum silicate or silicon dioxide, which is normally used in catalytic media. Very suitable siliceous material is Sipernat 50, white powder of silicon dioxide, in which the particles are mostly spherical in shape. It is available in production volume from the company Degussa (Sipernat means a trade mark).

When the main task is deep hydrogenation of mono-aromatic compounds, especially preferred is the use of one of titanium dioxide.

However, even more preferred is that the composition of the present invention contains almost no refractory oxide material.

Depending on the cooking method, which is used to obtain a catalytic composition used in the present invention, there may be a residual amount of ammonia, organic particles and/or water; when using other methods can be razlicicote, as well as the different types of particles. As for water, the amount present in the catalytic composition may also depend on atmospheric conditions. Therefore, in order to ensure the absence of distortions caused by atmospheric conditions or conditions of preparation in the determination of the catalytic composition specified in the description of the aspect ratio, for example, the number in percent, is given in the calculation of the oxide.

In order to establish the composition of the catalyst calculated on an oxide, is carried out elemental analysis of the sample after removal of all volatiles, for example, by careful heating, for example, at temperatures above 400°C, for at least 60 minutes, in accordance with the usual practice in this field of technology.

Quite appropriate, when the total amount of the metals of group VIII and group VIB, expressed in percentage by weight, is in the range from 15 to 99 wt.% as oxides and based on the whole catalyst, but preferably this amount is in the range from 20 to 80%. When there is a refractory oxide, more preferably this amount is in the range from 25 to 70 wt.%, especially from 25 to 60 wt.%.

Quite appropriate, when the molar ratio of the metal (metals) of group VIII to the metal (metals) of group VIb is in the range from 0.5:1 to 3:1, preferably from 0.5:1 is about to 2.0:1, and especially 1:1.

Good results have been obtained when the metal of group VIII is a Nickel, and the metal of group VIb means molybdenum, and the molar ratio of Nickel to molybdenum in the catalyst is in the range from 0.5:1 to 3:1, preferably from 0.5:1 to 2.0:1, and especially 1:1.

It is advisable, when the zeolite is in the range from 1 to 85 wt.%. Effective minimum amount of zeolite is 4 wt.%, preferably 15 wt.%, more preferably 20 wt.%, for example, 25 wt.%, and especially 40 wt.%. The effective maximum number of zeolite, based on the whole composition, 80 wt.% and especially 75 wt.%.

Suitable quantity of refractory oxide material is in the range from 0 to 70 wt.%, preferably from 0 to 50 wt.%, in the calculation of the oxide. More preferred compositions contain from 5 to 40 wt.% this material is based on the oxide. However, most preferably, when the refractory oxide is missing.

Good results have been obtained in the quantitative content of Nickel in the range from 7 to 30 wt.%, preferably from 13 to 26 wt.%, in the calculation of the oxide, in the quantitative content of molybdenum in the range from 14 to 50 wt.%, preferably from 25 to 50 wt.% in the calculation of the oxide; and the rest falls on the VUSY zeolite and silicon dioxide or titanium dioxide, if present. the good results are obtained when the content of VUSY zeolite in the formulation of the catalyst is in the range from 20 to 73 wt.%. When in such formulations is silicon dioxide or titanium dioxide, their numbers are in the range of from 6 to 10 wt.%, preferably from 6 to 9 wt.%. If there is a second zeolite, such as zeolite beta, its preferred amount is in the range from 1 to 10 wt.%.

In the composition of the catalyst used in the present invention, when the assessment is not based on the oxide, there may be residual particles, for example, organic particles, ammonia and/or water, in the range from 0 to 10 wt.%, and most typically from 3 to 8 wt.%, in the calculation on the entire catalyst. The presence of such components and their number can be determined using standard analytical techniques,

The catalytic composition of the present invention can be obtained using any suitable deposition method or an equivalent method. Therefore, the present invention also provides a method for the catalytic compositions according to the invention, which combines one or more compounds of metals of group VIb with one or more compounds of base metals of group VIII, with one or more zeolites, and optionally, with one or more refractory oxide materials, in the presence of protonotaria liquid and optional alkaline link is; moreover, the catalytic composition allocate after deposition.

The method of obtaining can be carried out by the method described in patent US 6162350 or in the application WO 00/41810 where metal compounds dissolved completely or partially in the liquid used, respectively protonotaria liquid, especially water or a liquid containing water, with the addition of an appropriate quantity of zeolite and optional refractory oxide material in one of the source components or the mixture of the starting components.

However, it is most preferable to obtain a catalyst by the method which comprises heating the precursor composition, which is in the form of a suspension, or extracted from the suspension, optionally after aging at a temperature in the range from 20 to 95°C, for at least 10 minutes, and found the suspension is obtained by (co)precipitation at the corresponding temperature and for a sufficient time, one or more compounds of metals of group VIb, one or more compounds of metals of group VIII, one or more zeolites, optionally one or more refractory oxide materials, and alkaline compounds, protonotaria fluid. In this way we obtain a material which has a high crushing strength in molded form, for example, in the ideal of the extrudate. When metal compounds are used in the solid state (and one or more compounds partially dissolve upon contact with protonotaria liquid), the crushing strength of the resulting molded catalyst may increase.

Thus, preferably, the metal compounds used in the method according to the invention, added to protonotaria liquid in the solid state.

Metal compounds and refractory oxide, respectively, are used in amounts (in wt.%), already discussed above.

Decomposition or heating of the precursor is carried out at elevated temperature in the range from 100 to 600°C., preferably from 120 to 450°C., more preferably at a temperature in the range from 250 to 400°C. the Decomposition can take place in an inert atmosphere such as nitrogen atmosphere, any noble gas or mixtures thereof, or in an oxidizing atmosphere, such as oxygen, oxygen-nitrogen, air, or mixtures of one or more of these gases, or in a reducing atmosphere, such as hydrogen, hydrogen sulfide or a mixture thereof. Decomposition can occur during processing of suspension or during subsequent processing compositions used, for example, during extrusion or calcination, before or after molding.

A preferred method of prepara is possible according to the invention includes contacting one or more suspensions of the desired metals in protonotaria fluid (for example, water), in which one or more metal compounds, especially both compounds, both in the solid and dissolved phase, zeolite and optional refractory oxide in the presence of an alkaline compound at a temperature and time sufficient to obtain predecessor. For each type of metal, it is possible that the metal is provided in the form of two metal compounds, one of which is soluble in protonotaria fluid, and the other only partially soluble. In this context, the term "metal" refers not to the metals of the metal phase, and to compounds of metals containing the desired metal ions.

All components can be added to protonotaria fluid simultaneously or sequentially. In addition, it is possible that one or more compounds of metals, zeolite and refractory oxide will be in phase suspension with protonotaria fluid, and that the other components will add to this suspension.

The method according to the invention includes mixing into the suspension phase of a mixture of compounds of metals of group VIb and metals from group VIII in water or other protonotaria fluid, which is mixed at an elevated temperature with a suspension of the zeolite in water or other protonotaria liquid, and then add at elevated temperature alkali the connection and optional refractory oxide material, also in water or other protonotaria fluid. Although the sequence of addition of the individual compounds with the formation of the suspension does not matter for the formation of the catalytic compositions according to the invention, the authors found that the addition of the alkaline compound in the suspension is partially dissolved metals, zeolite and refractory oxide, formed a very effective catalytic materials. However, you can add suspension metals to alkaline compound, when the zeolite and refractory oxide are present in one or the other, or both, and still get an effective catalytic composition.

Mixing or stirring can be performed using traditional means, such as anchor stirrers, or by using high-energy, percussion method, for example, the device Ultra Turrax.

During the process of blending or mixing the components of the suspension (co)deposited with the formation of solids of the composition of the precursor, preferably under the action of an alkaline precipitating agent. The term "coprecipitation" is typically used when two or more dissolved compounds together are precipitated from the solution.

In a preferred method according to the invention, some compounds are not dissolved, and it is possible that one or more of the LCO dissolved components are deposited on the solid component (components). Therefore, the inventors use the term "coprecipitation"when considering the deposition of materials from which at least one is in a partially dissolved state. Accordingly, the method according to the invention is controlled by maintaining an appropriate temperature for the appropriate time in order to obtain the desired catalyst precursor. Determining the appropriate combination of temperature/time in order to obtain the desired product is a standard procedure. The corresponding temperature value can be in the range of from 25 to 95°C, and the time of deposition can be in the range from 10 minutes to 2 hours. Although the regulation of both parameters will practically get the desired end products, it is noted that the process of deposition at elevated temperatures may cause excessive dissolution of the metal components in order to obtain the desired final product; at too low a temperature may be insufficient dissolution.

In a preferred embodiment of the invention seek to obtain an initial suspension concentration in the range from 2 to 40, preferably from 2 to 25 wt.% the actual content of solids. The term actual content of solid substances is tion means the amount of solid substances, added to protonotaria fluid. Preferably, the amount of alkaline compounds such as ammonia, in the suspension is at least to 0.2 mole per mole of metals, based on the oxide, and the largest 50 mol per mol of metal per oxide. The quantity of alkaline material may affect the final form of the catalytic composition. Preferably, the amount of alkaline material such as ammonia, should be at least 0.75 mol, more preferably at least 0.8 times, especially at least 0.9 mol, per mole of metal per oxide. Preferably, the amount of alkaline material is the most 5, more preferably at most 3, and particularly, to a maximum of 2 mol per mole of metal per oxide.

The pH of the final mixture suspensions usually varies from neutral to alkaline, and preferably is at least to 6.0, and more preferably at least about 6.5, Typically the pH of the final mixture is in the range from 6.5 to 9.0, preferably from 6.8 to 8.5. The temperature of the mixture can affect the measured pH value. To accurately estimate the pH of the final mixture heated suspensions, usually select a small sample, cool it to ambient temperature and then measure the pH traditionally the first image. Unlike level information technology was established that at the specified pH of the zeolite material remains crystalline structure, both during deposition and subsequent retrieval operations, drying and calcination.

Suitable metal compounds of group VIII, which partly remain in the solid phase, if the solvent is a water, and are therefore preferred are Nickel carbonate, Nickel oxide, Nickel hydroxide, Nickel phosphate, Nickel formate, Nickel sulfide, Nickel molybdate or a mixture of two or more compounds. Additionally, there may be used a soluble salt, such as nitrate, sulfate or acetate of Nickel, in combination with one or more of these compounds and/or with each other. Also suitable are the corresponding compounds of cobalt or other metal of group VIII. Suitable and preferred compounds of molybdenum (based on similar criteria) are di - or molybdenum trioxide, ammonium molybdate, molybdenum acid, molybdenum sulfide, or mixtures thereof. These materials are industrially available, or they can be obtained using conventional laboratory techniques, for example, by deposition. Also are appropriate corresponding compounds of tungsten or other metals of group VIb.

Except as athelny metals, generally preferred are the starting materials containing the elements C, H and O, because they have less impact on the environment. Therefore, the Nickel carbonate is preferred because it can decompose to the oxide of Nickel, carbon dioxide and water when heated, with regard to the content of carbonate in the source material.

The terms "alkali or alkaline compound used in this invention to refer to compounds that provide in protonotaria liquid pH value at least equal to 6.0 when measured at ambient temperature (20°C).

Apply suitable alkaline compounds selected from hydroxides or oxohydroxides metals, for example, from groups Ia or Ib or hydroxides of metals of groups IIA, or IIb; silicates of metals of groups Ia or IIa; carbonates of metals of groups Ia or Ib or group IIa or IIb; and the equivalent of ammonium compounds; or mixtures of any two or more compounds. Suitable examples include ammonium hydroxide, sodium hydroxide, ammonium silicate, ammonium carbonate and sodium carbonate.

Also suitable for use as alkaline compounds are any basic nitrogen-containing organic compounds, for example selected from aliphatic or aromatic amines and polyimines, type polietilene the ina; derivatives of pyridine; aminoalcohols; salts of amino acids; and derivatives of urea and substituted urea, which when heated in water to produce ammonia or amines.

Preferably, the alkaline compound is a compound that may produce ammonium ions in the solution; these include ammonia, which forms with water as the solvent ammonium hydroxide.

Usually it is preferable to use such terms mixing and deposition, in which solvents are below the boiling temperature, i.e. below 100°C. in the case of water. Usually maintain a natural pH value of the suspensions during the whole process of preparation of the catalyst. However, you can optionally implement an additional pH regulation through the use of suitable acidic or more alkaline compounds, which are known from the prior art.

The resulting suspension is not necessarily maintained at ambient temperature or at an elevated temperature during the period (commonly referred to as aging), after completion of the process of deposition. Typically, the aging period is 10 minutes, mostly 30 minutes, preferably 4 hours; aging temperature is in the range from ambient temperature, for example, from 20, predominantly from 25°C to 95°C, predpochtite the flax from 55 to 90, and especially from 60 to 80°C. After a period of aging is not necessarily followed by a cooling of the mixture.

After optional cooling the suspension obtained can be processed in various ways in order to recover the solids content, and these methods may include filtration, spray drying, thermal drying, evaporation and distillation in vacuum. The term evaporation means any removal process protonotaria liquid such as water, or drying, for example, the process of moisture absorption and distillation. Type of system used will depend on a number of local factors, which include the law on environmental protection, and the availability of an energy source. The most preferred method is spray drying.

Most preferred for use is a combination of the preferred method of preparation of the suspension (using alkaline compounds) together with the spray drying.

The thus obtained solid product is a powder, which has a loss on ignition (SPT) from 5 to 95%, mostly from 10 to 20%, and most preferably from 15%to 20%.

Here the loss on ignition (SPT) material mean relative quantity (mass)measured by heating the material up to 540°C, following the method of the ICA. The sample mixed well to eliminate any discontinuity. The weighted sample is transferred into a pre-annealed and weighed crucible. This crucible placed in an oven, heated to 540°C. for a minimum time of 15 minutes, but usually during 1 hour. The crucible containing the calcined sample is weighed again and determine the loss on ignition by the formula:

SPT (%)=(w-wgood)/w·100%,

where w means the original sample mass, wgoodmeans the mass of the calcined sample after aging in an oven, and both masses determined from the mass of the crucible.

The resulting powder can be dried to an optional additional treatment, especially in case of using a filter to highlight or extract solids. This operation drying or aging can be carried out in any suitable atmosphere, for example in an inert gas, such as nitrogen, noble gases, or mixtures thereof, or in an oxidizing gas, such as oxygen, a mixture of oxygen, nitrogen, air, or mixtures thereof, or in a reducing atmosphere such as hydrogen or a mixture of reductive and inert gases or mixtures thereof, in the presence or in the absence of ammonia and/or moisture of water. Preferably the drying temperature is in the range from about 20, typically from 25 to 200°C., preferably from 55 to 150°C and especially from 70 to 130°C.

This powder can be used for sovan as such or, more preferably, it is used in the form of a molded catalyst.

The resulting powder optionally calcined before molding. Suitable temperature of calcination is in the range from 100 to 600°C., preferably from 120 to 450°C., such as below 400°C and most preferably at 300°C. the Calcination can also be carried out in any suitable atmosphere, for example in an inert gas, such as nitrogen, noble gases or mixtures thereof, or in a reactive atmosphere, such as oxygen, mixtures of oxygen, nitrogen, air, or mixtures of one or more of these gases, or a mixture of inert and reactive gases.

Before molding the resulting powder optionally mixed with additional materials or in solid or in liquid phase. The materials in the solid phase include catalytically active materials, for example, other catalytic materials that are used in the hydrocracking process. Thus, the powder may be combined with additional craterous component, such as a zeolite or other component that promotes hydrocracking, as described above. Certain amorphous aluminosilicate materials have kekirawa ability and can be used.

Of course, if desired, can be added to any other additional materials. About the and include materials, which usually added during the preparation of traditional catalysts. Suitable examples include phosphorus compounds such as phosphoric acid, ammonium phosphate or organic phosphorus compounds, silicon compounds, boron compounds, fluorine-containing compounds, rare earth elements, additional transition metals or mixtures thereof. Phosphorus compounds may be added at any stage of the preparation of the catalyst. For example, if as part of a refractory oxide material you intend to use aluminum oxide, phosphorus compounds can be used for peptization (with nitric acid or without it).

Most often, an additional component may be a diluent or a binder material, introduced to improve the physical properties of the catalyst, such as density, strength, wear and strength crush strength.

Moreover, the added materials may include additives, which are usually referred to in this technical field as "forming agents" or "AIDS molding". These additives may include stearates, surfactants, graphite or mixtures thereof. However, to maximize the strength of the resulting molded material, especially when molding is carried out using an extrusion, preferably smart is the culprit to minimize any conventional accessories molding. Most preferably, the molding is carried out using an extrusion process without adding any auxiliary means of molding.

In the mixture for molding can be added for more suitable materials in the liquid phase, which include protonotaria liquid such as water, polyols, and others, and liquids that do not contain protons, for example hydrocarbons. Protonotaria fluid, for example water, may be added, for example, in order to bring the values of loss on ignition of the mixture to a suitable level for processing.

Usually there is no specific order of mixing of the materials (solid and/or liquid phase).

An important factor is ensuring good mixing of the sample to eliminate the heterogeneity. Preferably, the amount of additional solid and liquid substances added during molding, is in the range from 0 to 95 wt.%, in the calculation of the final mass, and it depends on the requirements of the intended use of the catalyst. Molding can be done in various ways, depending on the application requirements. These methods include, among others, spray drying, extrusion, granulation and/or tableting.

Sulfatirovnie can be conducted with the aim of translating one or more meta is fishing in an active form. If the composition is used in the form of a molded catalyst composition, it may be subject to solifidian before and/or after molding. Usually sulfatirovnie can be carried out by contacting the catalyst or its precursor with sulfur-containing material, such as elemental sulfur, sulfides, disulfides, and others, in the gas or liquid phase. Sulfatirovnie may be conducted at any stage of the molding process, including prior to the first optional stage of drying. However, preferably, when sulfatirovnie is only to molding, with any subsequent stage heat treatment is conducted in a congenial atmosphere, which prevents the conversion of (partial) solifidians phase back in the state of oxide.

Methods sulfatirovnie well known in the prior art, and include, or in-situ sulfatirovnie, at the time of use of the catalyst, or ex-situ sulfatirovnie, which is performed before loading the catalyst into the reactor hydroconversion. Usually both methods is the contacting of the catalyst with elemental sulfur or sulfur-containing compound at a temperature, pressure and for a time sufficient to provide the desired degree of sulfatirovnie or activation of the oxide catalyst particles. The actual temperature is, the pressure and time required can vary depending on the type and amount of catalyst used sulfiding materials and reactor. The specialist in this field of technology can easily select the desired mode using the standard experiments.

Preferably, the phase of sulfatirovnie is performed after stage (stages) molding and after the last stage of annealing, when conducting calcination. Conventional methods of ex-situ process are ACTICAT (firm CRI International, Inc.) and the process SULFICAT process (Eurecat US Inc.). However, preferably, when the last stage of sulfatirovnie is carried out in situ as follows.

The catalyst sulfiderich to translate into active form in the presence of hydrogen, or by contacting the catalyst with a liquid raw material (liquid or partially gas phase), which contains and/or enriched sulfur, and sulfur is present in the form of organic sulfur compounds and/or as elemental sulfur or in the presence of a gas containing sulfur, or mixtures thereof.

Good results have been obtained when using traditional methods of gas-phase sulfatirovnie in situ.

However, particularly advantageous to carry out the traditional sulfatirovnie in situ in the liquid phase using a sulfur-containing fluid, especially gas, and according to the usual method of sulfatirovnie. Convenient to the Yes sulfur-containing liquid is a raw material, designed for processing in the hydrocracking process, which, if necessary, enriched by the addition of sulfur to make sulfatirovnie in the liquid phase. Although the reasons are not entirely clarified, it was found that sulfatirovnie facilitates the movement of particles of molybdenum within the composition, which leads to increased molybdenum content in the pores of the zeolite in comparison with the composition in the oxide form. In addition, we discovered that sulfatirovanne compositions of the present invention have a significantly higher selectivity for middle distillates, as well as increased ability to hydrogenation of mono-aromatic compounds, especially in the case of compositions containing silicon dioxide or not containing refractory oxide material. The highest selectivity for middle distillates have compositions sulfatirovanne in the liquid phase.

For methods of sulfatirovnie as in the gas phase and the liquid phase can be used traditional techniques, which are known from the prior art. Normally, this kind of sulfatirovnie will include the contacting of the catalyst with sulfur or sulfur-containing material at elevated temperature and pressure, preferably at a gradual increase in temperature over time and maintain a constant pressure. Typically, the temperature of the sulfide is in the interim will be in the range of above ambient temperature (20°C) to 400°C, and the time will be in the interval from 1 hour to 48 hours, preferably from 10 to 40 hours.

Preferably, the metals of group VIII and group VIb form x-ray amorphous phase in the form of powder or a molded end product, which is manifested as the absence of any newly formed crystalline phases, in addition to crystalline zeolite or a refractory oxide that can be detected using x-ray powder diffraction.

The catalysts, which include Catholic composition of the present invention have a very high activity in the hydrogenation of mono-aromatic compounds in the process of hydrocracking of hydrocarbons.

The authors believe that without the involvement of any theory of this exceptional activity is a consequence of the high degree of dispersion of the metal throughout the zeolite material, which is achieved by careful control of the process of deposition. This high degree of dispersion should not be confused with uniformity of dispersion; catalytic composition for use according to the invention have a high activity, caused by metals dispergirovannykh around the zeolite material, but not necessarily uniformly dispersed in the material.

However, it appeared that a substantial proportion of the metal of group VIb, especiallyin the case of molybdenum, drawn into the pores of the zeolite material. Usually inside the pores of the zeolite may be molybdenum in the range of 3%, suitably from 4%, preferably from 5%, and more preferably from 8%, for example from 10 to 25 wt.%. Unexpectedly, it was found that after sulfatirovnie sulfide composition contains more molybdenum in the pores of the zeolite than the original oxide form.

Appropriate means of assessing the amount of molybdenum in the pores of the zeolite known to specialists in this field of technology, and the main methods considered in document WO 01/00753: using electron microprobe and transmission electron microscopy using energy dispersive x-ray spectrometer having a detector for identification and quantification of the elements present in the crystals of the zeolite.

In addition, in the present invention, a method of conversion of hydrocarbons in the materials of lower boiling point, which comprises contacting the feedstock with hydrogen at elevated temperature and elevated pressure in the presence of a catalytic composition according to the present invention. Usually this process called hydrocracking.

Examples of such processes include single-stage hydrocracking, two-stage hydrocracking and sequential hydrocracking in the stream. Determine the quiet processes can be found in the book "Introduction to zeolite science and practice" on str and 603 in Chapter 15 (title: "Processing of hydrocarbons in the presence of zeolites"), edited by van Bekkum, Flanigen, Jansen; published by the company Elsevier, 1991.

How hydroconversion of the present invention can be carried out in any conventional reaction apparatus known from the prior art. Thus, these methods can be carried out in a reactor with a fixed or moving bed of catalyst. In addition, the catalyst according to the invention can be used in conjunction with any suitable acetalization or other materials common in this area of engineering. For example, the catalyst according to the invention can be used in a composite layer with one or more other catalysts used in hydroconversion, for example with a catalyst that contains a zeolite catalyst containing fozhazity the zeolite with a different size of the unit cell, with a catalyst containing amorphous media, etc. Various combinations of composite layers proposed in the document WO 99/32582; ER AND-310164; ER AND-310165; and ER AND-428224.

The hydrocarbon feedstock used in the method according to the invention, can have a very wide limits boil. This material includes gas oil atmospheric distillation, the oil coking, gas oil vacuum distillation, the fractions after deasphalting, waxes obtained in the process of the Fischer-Tropsch synthesis, wide and narrow residual fraction, circulating oil, catalytic the ski cracking, the gas oil thermal or catalytic cracking, and synthetic crude oil, optionally originating from tar Sands, shale, processes, improve the quality of residues and biomass. Additionally, there may be used a combination of various hydrocarbon fractions. Typically, the raw materials may include hydrocarbons having a boiling point of at least 330°C. the Normal boiling range can be temperature from about 330 to 650°C., preference is given to raw materials having a boiling range from about 340 to 620°C. This raw material may contain nitrogen, up to 5000 parts per million (weight ppm) and sulfur up to 6 wt.%. Typically, the nitrogen content is in the range from 250 to 2000 parts per million and the sulfur content is in the range from 0.2 to 5 wt.%. It is possible, and sometimes it may be desirable to expose part or all of the raw materials pre-treatment, such as gidrogenizirovanii, hydrodesulphurization unit or hydrodemetallization, all of these methods known from the prior art.

The method according to the invention can be carried out at a temperature in the range from 250 to 500°C., preferably in the range of from 300 to 450°C.

Preferably, the method of the present invention is carried out at the total pressure at the inlet of the reactor) in the range from 3×106up to 3×107PA, more preferably from 4×1062.5×1 7PA and even more preferably from 8×106up to 2×107PA. When the process of hydrocracking is carried out at low pressure, for example from 4×106to 1.2×107PA, this method is usually called "mild hydrocracking".

The partial pressure of hydrogen at the inlet of the reactor) is preferably in the range from 3×106to 2.9×107PA, more preferably from 4×106to 2.4×107PA and even more preferably from 8×106to 1.9×107PA.

Commonly used volumetric feed rate in the range of 0.1 to 10 kg per liter of catalyst per hour (kg·l-1·h-1). Preferably, the volumetric feed rate is in the range from 0.1 to 8, in particular from 0.2 to 5 kg·l-1·h-1.

In the method according to the invention is typically used ratio of gaseous hydrogen to the raw material (total gas flow) in the range from 100 to 5000 nl/kg, but preferably in the range of from 200 to 3000 nl/kg

Now the present invention will be illustrated in the following examples.

EXAMPLES

In these examples, the size of the unit cell determined by x-ray diffraction, using the standard ASTM D 3942-80; surface area determined by BET method (see Brunauer, Emmett and Teller. J. Am. Chm. Soc., 60, 309 (1938)), and according to ASTM D 4365-95 using assessment by a single point nitrogen adsorption at p/p0equal to 0.03. the volume of micropores evaluate method t-graph, using nitrogen as adsorbate, as described in the work Lippens, Linsen and de Boer, Journal of Catalysis, 3-32 (1964),

Preparation of catalyst

The following examples use the same VUSY zeolite for all of the catalysts of this invention and in the reference catalysts C and F. VUSY is an ultrastable (with respect zeolite Y, which is the size of the unit cell 24.32Å, the molar ratio of silicon dioxide to aluminum oxide, equal to 29, the surface area according to BET 893 m2/g, and micropore volume 0,298 ml/year Method of getting VUSY described in document WO 2004/047988.

Example 1. The catalyst NiO/MoO3/SiO2/VUSY zeolite - 13 wt.%/25 wt.%/9 wt.%/53 wt.%.

In a two-liter flask is weighed 557 g of water. Then add the following connections: 54,4 g Nickel carbonate (39.5 wt.% Nickel) and 62.1 g dimolybdate ammonium. Dispersed 133,3 g of zeolite in 796 g of water, is added to a suspension of metal and heated to 80°C under stirring. In addition, prepare another suspension containing 22,5 g of silica (Sipernat 50), 186 g of water and 27.9 g of ammonia solution of 25 wt.%).

When the temperature of the slurry containing the zeolite and the metal will reach 80°C, add the suspension of silicon dioxide in the ammonia solution, and the mixture is heated to 80°C. the Mixture is maintained at a temperature of 80°C for 45 minutes, during this time select the sample cooled to room temperature and determine pH 7.4

The resulting suspension is subjected to spray drying and obtain 190 g of powder, which is extruded, dried and calcined at 300°C in air.

Example 2. The catalyst NiO/WO3/SiO2/VUSY zeolite - 9 wt.%/Mos.%/Mas.%/54 wt.%.

A 5-liter flask was dispersed 238,6 g of zeolite in 3636 g of water using the connected dispersant (apparatus Ultra-Turrax purchased the firm Janke &Kunkel GmbH) for 1 minute. The resulting suspension is heated to 80°C under stirring. After reaching this temperature, water is added to 78.5 per g Nickel carbonate (39 wt.% Nickel), to 140.5 g of metavolume ammonium and of 44.9 g of Sipernat 50. Immediately after this mix of 57.5 g of ammonia solution (ammonia 25 wt.%) with the above suspension. The resulting mixture was kept at 80°C for 30 minutes; the pH of the mixture is equal to 8.3.

After 30 minutes, turn off heat, and emit 349,7 g of solid material by means of spray drying. The powder is extruded, and the resulting crude extrudate is dried and then calcined at 300°C.

Example 3. The catalyst NiO/MoO3/TiO2/VUSY zeolite - 13 wt.%/24 wt.%/9 wt.%/54 wt.%.

A 5-liter flask was dispersed 298,3 g of zeolite in 4476 g of water using the connected disperser Ultra-Turrax for 1 minute. The resulting suspension is heated to 80°C under stirring. After reaching this temperature, add to water the 137,7 g Nickel carbonate (39.5 wt.% Nickel), was 155.3 g dimolybdate ammonium and 51.5 g of titanium dioxide P25 (from the company Degussa). Immediately after this mix 69.7 g of ammonia solution (ammonia 25 wt.%) with the above suspension. The resulting mixture was kept at 80°C for 30 minutes; the pH of the mixture is equal to 7.9.

After 30 minutes, turn off heat and emit 489,6 g of solid material by means of spray drying. The powder is extruded, and the resulting crude extrudate is dried and then calcined at 300°C.

Example 4. The catalyst NiO/WO3/TiO2/VUSY zeolite - 9 wt.%/28 wt.%/9 wt.%/54 wt.%.

A 5-liter flask was dispersed 298,3 g of zeolite in 4474 g of water using the connected disperser Ultra-Turrax for 1 minute. The resulting suspension is heated to 80°C under stirring. After reaching this temperature, add to the water of 98.2 g Nickel carbonate (39,0 wt.% Nickel), covers 175.6 g metavolume ammonium and 51.5 g of titanium dioxide P25 (from the company Degussa). Immediately after this mix to 71.9 g of ammonia solution (ammonia 25 wt.%) with the above suspension. The resulting mixture was kept at 80°C for 30 minutes; the pH of the mixture is equal to 8.3.

After 30 minutes, turn off heat, and emit 465,8 g of solid material by means of spray drying. The powder is extruded, and the resulting crude extrudate is dried and then calcined at 300°C.

Example 5. The catalyst NiO/MoO /SiO2/VUSY zeolite - 7 wt.%/14 wt.%/6 wt.%/73 wt.%.

In a two-liter flask is weighed 557 g of water. Then add the following connections: 55,1 g Nickel carbonate (39 wt.% Nickel) and 62.1 g dimolybdate ammonium. Dispersed 264,4 g of zeolite in 796 g of water, is added to a suspension of metal and heated to 80°C under stirring.

In addition, prepare another suspension containing 22,5 g of silica (Sipernat 50), 186 g of water and 27.9 g of ammonia solution (25 wt.%).

When the temperature of the slurry containing the zeolite and the metal will reach 80°C, add the suspension of silicon dioxide with ammonia, and the mixture is heated to 80°C. the Mixture is maintained at a temperature of 80°C for 45 minutes, and determine pH 7.4. Add 1061 g of deionized water, heated to 80°C., and the mixture is homogenized.

The resulting suspension is subjected to spray drying and receive 252 g of powder, which is extruded, dried and calcined at 300°C in air.

Example 6. The catalyst NiO/MoO3/SiO2/VUSY zeolite - 5 wt.%/19 wt.%/6 wt.%/70 wt.%.

A 5-liter flask was dispersed 417,7 g of zeolite in 4419 g of water using the connected disperser Ultra-Tiggy within 1 minute. The resulting suspension is heated to 80°C under stirring. After reaching this temperature, water is added to 49.8 g Nickel carbonate (39 wt.% Nickel), to 112.4 g dimolybdate ammonium and 33.7 g dioxi is and silica Sipernat 50. Immediately after this mix of 26.6 g of ammonia solution (ammonia 25 wt.%) with the above suspension. The resulting mixture was kept at 80°C for 30 minutes; the pH of the mixture is 6.8.

After 30 minutes, turn off heat, and emit 509,4 g of solid material by means of spray drying. The powder is extruded, and the resulting crude extrudate is dried and then calcined at 300°C.

Example 7. The catalyst NiO/MoO3/SiO2/VUSY zeolite - 20 wt.%/20 wt.%/10 wt.%/50 wt.%.

A 5-liter flask was dispersed 298 g of zeolite in 4444 g of water using the connected disperser Ultra-Turrax for 1 minute. The resulting suspension is heated to 80°C under stirring. After reaching this temperature, water is added to 205,2 g Nickel carbonate (39 wt.% Nickel), 115, 8mm g dimolybdate ammonium and 56.1 g of silica Sipernat 50. Immediately after this mix to 101.1 g of ammonia solution (ammonia 25 wt.%) with the above suspension. The resulting mixture was kept at 80°C for 30 minutes; the pH of the mixture is equal to 8.6.

After 30 minutes, turn off heat and emit 522,5 g of solid material by means of spray drying. The powder is extruded, and the resulting crude extrudate is dried and then calcined at 300°C.

Example 8. The catalyst NiO/MoO3/SiO2/VUSY zeolite - 14 wt.%/26 wt.%/10 wt.%/50 wt.%.

A 5-liter flask di is bergerot 298 g of zeolite in 4475 g of water using the connected disperser Ultra-Turrax for 1 minute. The resulting suspension is heated to 80°C under stirring. After reaching this temperature, water is added to 137,7 Nickel carbonate (39 wt.% Nickel), was 155.3 g dimolybdate ammonium and 56.1 g of silica Sipernat 50. Immediately after this mix 69.7 g of ammonia solution (ammonia 25 wt.%) with the above suspension. The resulting mixture was kept at 80°C for 30 minutes; the pH of the mixture is equal to 8.1.

After 30 minutes, turn off heat and emit 487,7 g of solid material by means of spray drying. The powder is extruded, and the resulting crude extrudate is dried and then calcined at 300°C.

Example 9. The catalyst NiO/MoO3/VUSY zeolite - 17 wt.%/33 wt.%/50 wt.%.

A 5-liter flask was dispersed 298 g of zeolite in 4458 g of water using the connected disperser Ultra-Turrax for 1 minute. The resulting suspension is heated to 80°C under stirring. After reaching this temperature, water is added to 172,1 g Nickel carbonate (39 wt.% Nickel and 194,2 g dimolybdate ammonium. Immediately after this mix is 87.1 g of ammonia solution (ammonia 25 wt.%) with the above suspension. The resulting mixture was kept at 80°C for 30 minutes; the pH of the mixture is equal to 8.1.

After 30 minutes, turn off heat and emit 523,6 g of solid material by means of spray drying. The powder is extruded, and received the Roy extrudate is dried and then calcined at 300°C.

Example 10. The catalyst NiO/MoO3/VUSY zeolite - 26 wt.%/49 wt.%/25 wt.%.

A 5-liter flask was dispersed 143,4 g of zeolite in 4413 g of water using the connected disperser Ultra-Turrax for 1 minute. The resulting suspension is heated to 80°C under stirring. After reaching this temperature, water is added to 258,3 g Nickel carbonate (39 wt.% Nickel), and 291,7 g dimolybdate ammonium. Immediately after this mix of 129.5 g of ammonia solution (ammonia 25 wt.%) with the above suspension. The resulting mixture was kept at 80°C for 30 minutes.

After 30 minutes, turn off heat and emit 540 g of solid material by means of spray drying. The powder is extruded, and the resulting crude extrudate is dried and then calcined at 300°C.

Example 11. The catalyst NiO/MoO3/VUSY zeolite/Beta zeolite - 24 wt.%/45 wt.%/25 wt.%/6 wt.%.

Used in this example, the Beta zeolite has a ratio of silicon dioxide to aluminum oxide of about 300, and zeolite receive from the company Zeolyst International, product code SR-S.

A 5-liter flask was dispersed 143,0 g VUSY zeolite and a 35.8 g of Beta zeolite in 4424 g of water using the connected disperser Ultra-Turrax for 1 minute. The resulting suspension is heated to 80°C under stirring. After reaching this temperature, water is added to 237,8 g Nickel carbonate (39 wt.% Nickel and 268,5 d is of ammonium molybdate. Immediately after this mix to 120.4 g of ammonia solution (ammonia 25 wt.%) with the above suspension. The resulting mixture was kept at 80°C for 30 minutes.

After 30 minutes, turn off heat and allocate 508 g of solid material by means of spray drying. The powder is extruded, and the resulting crude extrudate is dried and then calcined at 300°C.

Test the catalyst activity

Performance of the catalysts according to the invention when the hydrocracking is estimated at some two-stage flow-through test method simulation in comparison with the reference catalysts. Tests are conducted in flow-through installation with a single micro currents, which loads the top layer of the catalyst containing 1 ml of the catalyst-424 (available from industrial firms Criterion Catalyst & Technology Company), diluted with 1 ml of SiC particles size of 0.1 mm, and the bottom layer containing 10 ml of test catalyst diluted with 10 ml of SiC particles size of 0.1 mm, Both catalysts were pre-sulfatirovanne in the layer (in situ) to test one of the two following methods.

Gas-phase sulfatirovnie: preliminary sulfatirovnie carried out at a gauge pressure of 1.5 MPa in the gas phase (5% vol. H2S in hydrogen at a heating rate of 20°C./hour from room temperature (20°C) to 135°C, and incubated for 12 the aces to raise the temperature up to 280°C, and again incubated for 12 hours to raise the temperature to 355°C, and in this case at a rate of 20°C/hour.

Liquid-phase sulfatirovnie: preliminary sulfatirovnie carried out at a gauge pressure of 4.0 MPa, using a mixture of 1.5 vol.% H2S in hydrogen and sulfur gasoil, heating rate 20°C./hour from room temperature (20°C) to 135°C, and incubated for 10 hours to raise the temperature up to 280°C, and again incubated for 10 hours to raise the temperature to 345°C, and in this case at a rate of 20°C/hour.

Each test includes the sequential contacting of hydrocarbons (heavy oil) from the upper layer of the catalyst and then with the lower layer of the catalyst in the mode of single duct under the following operating conditions: feed space velocity of heavy oil 1.5 kg per 1 liter of catalyst per hour (kg·l-1·h-1), with respect to hydrogen gas/heavy oil 1440 nl/kg, the partial pressure of hydrogen sulfide is 5.6×105PA (5.6 ATM and the total pressure of 14×106PA (140 bar).

The Y zeolites used in the reference catalysts a, b, D, and E, are industrially available from the company PQ Corporation of Philadelphia and have the characteristics shown in table 1.

Reference catalysts were prepared by following General methods, using different amounts of zeolite and inorganic is ugolovnogo oxide, usually aluminum oxide, each recipe catalyst, as listed in table 1.

General methods

The catalyst is prepared by mixing zeolite with a refractory inorganic oxide in the desired proportions. Add water and 3 wt.% nitric acid (a solution of 65 wt.%), to get the value of pH in the range from 4.4 to 5.7 and loss on ignition of from 50 to 60 wt.%, and the mixture is milled in a mixer with the runners to obtain a mixture for extrusion. The mixture is then subjected to extrusion together with extrusion additive (Superfloc). The extrudates are dried in static conditions for 2 hours at 120°C and then calcined for 2 hours at 535°C. the thus Obtained catalyst particles have a regular length.

Then enter the connection hydrogenating metals, Nickel and tungsten by means of impregnation of the granules of homogeneous aqueous solution of Nickel nitrate and metavolume ammonium. The impregnated extrudates are dried at ambient conditions in a circulating hot air for 1 hour and then at 120°C for 2 hours and finally calcined at 500°C for 2 hours.

Table 1
Catalyst No.Zeolite, wt.%Size* unit cell, Å Area* surface, m2/gSAR*Volume* micropores, ml/gThe metal content, wt.%
Standard And5024,307249,30,254% Ni; 19% W
Standard7024,307249,30,253.3% of Ni; 16% W
Standard D**1024,307249,30,255% Ni; 21% W
Standard E5024,528175,3no data2.5% of Ni; 9,8% W
* Properties of zeolite
** In addition, the media contains amorphous aluminosilicate

The reference catalyst is a catalyst which is notice metals with silica binder material prepared by the method of (co)deposition using such components which allow to obtain the final number of components, comparable to the compositions of example 1. The formed oxide material is mixed and then milled together with the same zeolite material VUSY, which was used to prepare the catalysts in the examples of the invention given above. The method of preparation is given below:

NiO/Moo3/SiO2/VUSY zeolite - 13 wt.%/26 wt.%/10 wt.%/50 wt.%.

Mix 220,5 g Nickel carbonate (39.5 wt.% Nickel and 256,1 g dimolybdate ammonium and added with stirring to 2250 g of water in a 5-liter autoclave. The mixture is then heated to 80°C.

Preparing a second slurry of 92.2 g of silica (Sipernat 50), 750 g of water and 113 g of ammonia solution (25 wt.%). When the temperature metalloceramic suspension reaches 80°C, add the suspension of silicon dioxide in the ammonia solution, and the mixture was kept at 80°C for 30 minutes under stirring.

The resulting suspension is subjected to spray drying, and the resulting powder is extruded with VUSY zeolite in the form of a 50/50 mixture (calculated on dry weight), dried and calcined at 300°C in air.

Reference catalysts a, b, D and E are subjected to gas-phase solifidian in situ before the test, at a gauge pressure of 1.5 MPa in the gas phase (5% vol. H2S in hydrogen at a heating rate of 40°C./hour from room temperature (20 the C) to 200°C, and incubated for 2 hours to raise the temperature up to 280°C, and again incubated for 2 hours to raise the temperature up to 375°C, and in this case at 40°C/hour. The reference catalyst is subjected to gas-phase solifidian in situ, as the catalysts according to the invention.

Example 12.

In this example, the performance of the catalysts of examples 1-5 at hydrocracking determined with the use of heavy gas oil having the following properties:

The carbon content86,47 wt.%
The hydrogen content13,53 wt.%
The content of nitrogen (N)9 parts/million
Additive n-decylamine12.3 g/kg (equivalent to 1100 parts per million) N)
Total nitrogen (N)1109 parts/million
Density (15/4°C)0,8736 g/ml
Density (70/4°C)0,8394 g/ml
Molecular weight433 g
Point initial boiling point351°C
The boiling point of 50 wt.%451°C
The point end of boil605°C
Faction wikipeida below 370°C3,71 wt.%
Faction wikipeida above 540°C10.0 wt.%

Performance characteristics of the catalyst hydrocracking appreciate when the total degree of conversion between 40 and 90 wt.% for components, raw materials boiling above 370°C. table 2 shows the results obtained, expressed as the temperature required to obtain the total degree of conversion of 65 wt.% for components, raw materials boiling above 370°C.

The increase in selectivity for middle distillates (DM, fraction of product boiling from 150 to 370°C) assess against the reference catalysts a and b, and normalize to the same level of activity as that of the reference catalysts; thus, the reference catalysts act as standards, and therefore have a zero increase in selectivity in the SD. In addition, the data on the degree of transformation of monoaromatic compounds and consumption of hydrogen.

From table 2 it is obvious that all the catalysts of the present invention possess significantly greater activity in the hydrogenation of mono-aromatic compounds, che is all tested reference catalysts. Significantly improves the selectivity to products (middle distillates) and increased activity (as indicated by a reduction to the required temperature in the preferred catalysts in which the metal of group VIII choose molybdenum, and refractory oxide is silicon dioxide. It should be recognized that the increase in selectivity SD 1% may provide an additional output of 20000 tons of DM worldwide industrial hydrocracking units. The preferred use of liquid-phase sulfatirovnie compared to the gas-phase solifidianism provides an even more significant increase in selectivity in the SD and the hydrogenation of mono-aromatic compounds. In addition, reduces the consumption of hydrogen for all of the catalysts according to the invention in comparison with the hydrogen consumption for the reference catalysts.

In addition, in table 2 demonstrated the possibility of developing a catalyst composition of a special purpose by selection of used refractory oxide. For example, when a task of the process of hydrocracking is to increase the selectivity for middle distillates, the use of silicon dioxide provides an additional increase in the selectivity for middle distillates (see the data for catalysts 1, 2 and 2'). When the main task is the high degree of transformation of monoaromatic compounds, it is effective titanium dioxide as a refractory oxide (see data for catalysts 3 and 4).

However, as shown in example 13, it is possible to provide simultaneously high selectivity for middle distillates and high activity in the hydrogenation of mono-aromatic compounds, if absolutely exclude refractory oxide.

Example 13

In this example, evaluate performance for hydrocracking catalysts described in examples 6-11, relative to the reference catalysts b and d and the Determination of the activity carried out in the same manner as described above, but in this case used a few other raw materials - heavy gas oil having the following properties:

The carbon content86,50 wt.%
The hydrogen content13,48 wt.%
The content of nitrogen (N)14 parts per million)
Additive n-decylamine12.3 g/kg (equivalent to 1100 parts per million) N)
Total nitrogen (N)1114 parts/million
Density (15/4°C)0,8757 g/ml
Density (70/4°C)0,8415 g/ml
Molecular weight433 g
Point initial boiling point359°C
The boiling point of 50 wt.%451°C
The point end of boil602°C
Faction wikipeida below 370°Cof 2.86 wt.%
Faction wikipeida above 540°C9.7 wt.%

Reference catalysts b and D are subjected to gas-phase solifidian as previously described, and the catalysts of examples 6-11 are subjected to the liquid-phase solifidian, as described previously.

Table 3 shows that it is possible to further improve the selectivity for middle distillates (more than 5 wt.% raw materials for catalysts containing Nickel and molybdenum, by sulfatirovnie in the liquid phase.

Table 3
CatalystThe necessary temperature, Tnecessary.°CC1-C4, wt.% C4-82°C, wt.%82-150°C, wt.%150-370°C, wt.%Increase** selectivity MD, wt.%The degree of transformation of monoaromatic compounds, wt.%The consumption of hydrogen, wt.%
In375,74,414,624,057,10,039,71,08
D400,73,09,419,168,40,044,01,15
b*NiMoSi375,44,0the 11.622,262,25,3of 57.5 1,13
7*NiMoSi377,04,011,222,062,85,258,71,16
8*NiMoSiUSD 376.63,410,922,563,15,661,71,15
9*NiMoUSD 376.63,111,321,863,86,463,41,17
10*NiMo378,34,011,4of 21.263,55,367,71,17
11*377,13,711,221,064,16,464,81,15
* Methods of sulfatirovnie in the liquid phase
** Increase normalized by linear interpolation or extrapolation of the dependence of selectivity on the SD from the required temperature (Titfor reference catalysts b and D, which leads to the expression:
Selectivity for DM (150-370°C)=0,4549*Tit- 113,87

Example 14

In this example, determine the proportion of molybdenum contained within the pores VUSY zeolite as for the reference catalysts, and various catalysts according to the invention.

The reference catalyst E is the same as previously described. The reference catalyst F contains 3.6 wt.% Nickel and 10,85 wt.% molybdenum, and obtained by impregnation of a carrier containing 48 wt.% the zeolite used in the catalyst according to the invention in combination with alumina and amorphous silica-alumina binder material. The catalyst was prepared by the method of impregnation used for reference rolled is atarov And, B, D and E. Both the reference catalyst is subjected to solifidian in situ in the gas phase, as described above for the reference catalysts. The catalysts according to the invention is subjected to solifidian or in the gas phase or in the liquid phase, as shown in table 4.

To demonstrate the presence of molybdenum in the zeolite used transmission electron microscope equipped with energy dispersive x-ray spectrometer to identify and quantify the elements present in the crystals of the zeolite. In each case investigated fresh sample of the catalyst, i.e. the catalyst in the oxide form, which is not yet subjected to solifidian.

Used for this purpose is the transmission electron microscope JEOL JEM 2010, equipped with energy dispersive x-ray spectrometer Noran Instruments, type Voyager 4.1. The extrudate catalyst is poured resin in order to obtain ultra-thin slices, with a thickness of 100 nm. The resulting slice is fixed on a copper grid covered with a carbon membrane with holes used for preparation of media. These drugs are dried using a lamp with IR-radiation to enter into the camera transmission electron microscope, where they are processed at low vacuum for several minutes and then in a deep vacuum in the course of the study. Using e-ICRI the osprey can reliably identify the zeolite crystals, size of about 0.4 micron dispersed in a matrix of aluminum oxide. Then spend a number (from 10 to 15) local analyses in various areas of the matrix and in different zeolite crystals using a probe having a diameter of 0.1 μm. Used quantitative signal processing in order to obtain the relative concentration of elements (wt.%), with the exception of oxygen.

Performance of hydrocracking catalysts evaluated in units of increasing selectivity in the SD or compared with the characteristics of the reference catalysts a and b, described in example 10, or with the characteristics of the reference catalysts b and D, which are described in example 11, using the same heavy gas oil and the same test conditions that are shown in these examples.

From the results shown in table 4, we can see that when traditional methods, a significant proportion of molybdenum is able to impregnate the pores of the zeolite. However, the preparation method of the present invention provides a much greater amount of molybdenum, which is located in the pores of the zeolite.

The increase in selectivity in the SD for the catalysts of the present invention is significantly greater than in the case of the reference catalyst F, which uses the same zeolite and traditional binders and who made who by impregnation compounds of metals.

Table 4
CatalystAl2O3, wt.%SiO2, wt.%Ni, wt.%Mo in the pores of the zeolite, wt.%The increase in selectivity MD, wt.%
E20,575,72,51,3not tested
F20,584,42,0a 3.90,6**
1NiMoSi3,189,41,95,63,4**
8*NiMoSi3.390,41,44,85#
9*NiMo the 5.784,02,08,46#
* Methods of sulfatirovnie in the liquid phase
** Increase normalized by linear interpolation or extrapolation of the dependence of selectivity on the SD from the required temperature (Titfor reference catalysts a and b, which leads to the expression:
Selectivity for DM (150-370°C)=0,5310*Tit- 138,91
# Increase normalized by linear interpolation or extrapolation of the dependence of selectivity on the SD from the required temperature (Titfor reference catalysts b and D, which leads to the expression:
Selectivity for DM (150-370°C)=0,4549*Tit- 113,87

1. The composition of the catalyst without media for hydrocracking, which includes one or more metals of group VIb, one or more base metals of group VIII, one or more zeolites, and, optionally, the refractory oxide material obtained by precipitation of the metals of group VIb, base metals of group VIII, and, neobythites is but refractory oxide material in the presence of zeolite.

2. The composition of the catalyst according to claim 1, in which the zeolite is an ultrastable (with respect or very ultrastable (with respect zeolite Y, which is present in an amount of from 1 to 85 wt.%, preferably from 15 to 75 wt.%, calculated on the whole composition.

3. The composition of the catalyst according to claim 1 in which the refractory oxide is silica, which is present in an amount of from 0 to 40 wt.%, preferably from 0 to 15 wt.%, calculated on the whole composition.

4. The composition of the catalyst according to claim 1 in which the refractory oxide is titanium dioxide, which is present in an amount of from 0 to 40 wt.%, preferably from 0 to 15 wt.%, calculated on the whole composition.

5. The composition of the catalyst according to any one of claims 1 to 4, in which the present metals are Nickel and molybdenum in a molar ratio of Nickel to molybdenum is from 0.5:1 to 2.5:1.

6. The composition of the catalyst according to claim 5, in which the amount of molybdenum, which is located in the pores of the zeolite is in the range from 4, preferably from 5 to 25 wt.%, in the calculation of the oxide form of the composition.

7. The method of obtaining the composition of the catalyst according to any one of claims 1 to 6, in which one or more compounds of metals of group VIb unite with one or more compounds of base metals of group VIII and with the zeolite in risotti protonotaria liquid and alkaline compounds and after the deposition of the extract composition of the catalyst.

8. The method according to claim 7, in which during the deposition of the mixture components has a pH value of at least 6,0.

9. The method according to claim 7, in which at least one of the compounds of the metal is partially solid and partially dissolved.

10. The method according to claim 9, which comprises heating the precursor composition, which is in the form of a suspension or extracted from the suspension optional after aging at a temperature in the range from 20 to 95°C, for at least 10 min, and the specified suspension obtained by (co)precipitation at the corresponding temperature and for a sufficient time, one or more compounds of metals of group VIb, one or more compounds of base metals of group VIII, one or more zeolites, optionally one or more refractory oxide materials and alkali compounds in protonotaria liquid.

11. The method according to any of claims 7 to 10, in which the composition of the catalyst allocate using spray drying.

12. The composition of the catalyst obtained by the method according to claim 7.

13. The method of conversion of hydrocarbons in the materials of lower boiling point, which comprises contacting the feedstock at elevated temperature in the presence of a catalyst composition according to any one of claims 1 to 6, 12 or composition of catalysis is ora, obtained by the method according to any of claims 7-11.

14. The method according to item 13, in which the catalyst composition is subjected to solifidian using the reagent sulfatirovnie in the liquid phase.

15. The use of a composition of the catalyst according to any one of claims 1 to 6 and 12 in the method of hydrocracking.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: stable composition for application for catalyst carrier impregnation in order to obtain catalytically active solid substance includes: (A) water; (B) catalytically active metals, which are in form of and containing: (1) at least, one component, ensuring, at least, one metal of group VIB of Periodic system; and (2) at least, one component, ensuring, at least, one metal of group VIII of Periodic system, selected from group consisting of Fe, Co and Ni; and (i) said metal of group VIII is supplied with, in fact, insoluble in water component; (ii) molar ratio of said metal of group VIII and metal of group VIB constitutes approximately from 0.05 to approximately 0.45, on condition that amount of said metal of group VIII is sufficient for promoting catalytic impact of said metal of group VIB; (iii) concentration of said metal of group VIB, expressed as oxide, constitutes, at least, from approximately 3 to approximately 50 wt % of said composition weight; and (C) at least, one, in fact, water-soluble phosphorus-containing acid component in amount, insufficient for dissolving said metal of group VIII at room temperature, and sufficient for ensuring molar ratio of phosphorus and metal of group VIB from approximately 0.05 to less than approximately 0.25. Described is method of obtaining described above composition, including addition to suitable water amount of: (A) at least, one in fact water-insoluble component based on metal of group VIII, selected from group consisting of Fe, Co and Ni; and (B) at least, one in fact water-soluble phosphorus-containing acid component in amount insufficient for causing dissolution of said component based on metal of group VIII, with obtaining suspension, and combining suspension with: (C) at least, one component based on metal of VIB group; and (D) mixing of combinations (A), (B) and (C), and heating mixture during time and to temperature sufficient for formation of solution by (A), (B) and (C); and (E) adding supplementary amount of water, if necessary, in order to obtaining concentrations of solution of, at least, one said metal of group VIII, at least, one said metal of group VIB and phosphorus, suitable for impregnation of said carriers; group VIB and VIII refer to groups of periodic system of elements. Described is catalyst obtained by carrier impregnation with stable composition, suitable for hydrocarbon raw material processing.

EFFECT: increase of conversion degree of sulphur, microcarbon residue.

23 cl, 3 ex

The invention relates to the field of oil refining and catalysis of processes of production of heavy hydrocarbons hydrocarbon fractions used for the production of liquid motor fuels and as raw materials for the production of solvents containing aromatic compounds

The invention relates to processes deep oil processing by the conversion of petroleum fractions in the presence of hydrogen

FIELD: oil and gas industry.

SUBSTANCE: methods and systems of treatment of heavy oil raw material with hydrogen producing enriched material consists in implementation of colloid or molecular catalyst dispersed in heavy oil raw material, also in implementation of hydraulic cracking and hot separator. Colloid or molecular catalyst catalyses reactions of hydraulic cracking and reactions of other treatment utilising hydrogen in the hydraulic cracking reactor. Catalyst preferably is associated with pyrobitumen in heavy oil raw material facilitating reactions of enrichment including pyrobitumen to a higher degree, than to forming coke precursor and sediment. Colloid or molecular catalyst solves problems relevant to porous catalysts on a carrier during enriching heavy oil raw material, particularly inability of such catalysts to efficiently process pyrobitumen molecules.

EFFECT: decreased equipment clogging, increased level of conversion and more efficient utilisation of catalyst on carrier if used in combination with colloid or molecular catalyst.

36 cl, 5 tbl, 25 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to promoter catalysts on a combined zeolite/aluminosilicate substrate with low content of macropores and to methods of hydrocracking/hydroconversion and hydrofining, in which said catalysts are used. The catalyst contains at least one hydrogenating-dehydrogenating element, selected from a group comprising group VIB and group VIII elements, a promoter element in a controlled amount, selected from phosphorus oxide, and a substrate based on zeolite Y, defined by constant a of the unit cell of the crystal lattice, ranging from 24.40·10-10 m to 24.15·10-10 m, and based on aluminosilicate, containing silicon dioxide (SiO2) in amount exceeding 5 wt % and less than or equal to 95 wt %. The catalyst has the following characteristics: average pore diametre, total pore volume, BET specific surface area, volume of pores of different diametre, characterised by X-ray diffraction pattern and packing degree of the catalyst.

EFFECT: catalyst provides for suitable selectivity of middle distillates, ie fractions with initial boiling point of at least 150°C and final boiling point which reaches initial boiling point of residue, for example below 340°C or 370°C.

28 cl, 4 tbl, 21 ex

FIELD: physics.

SUBSTANCE: invention relates to a method of producing crude material. When crude material is brought into contact with one or more catalyst, a total product is obtained, which contains a crude product. Crude material has residue content of at least 0.2 grams per 1 gram of crude material. The crude product is a liquid mixture at 25°C and 0.101 MPa. One or more properties of this crude product can be altered at least 10% from corresponding properties of the crude material. In some versions of the invention, gas is obtained after bringing crude material with one or more catalysts. These methods allow for obtaining crude material with improved characteristics.

EFFECT: invention also relates to a crude product or a mixture or a method of producing transport fuel.

22 cl, 27 ex, 4 tbl, 12 dwg

FIELD: chemistry.

SUBSTANCE: description of the elongated mould particles is provided, the particles have two asperities which start from and end at the central position where it aligns the longitudinal axis of the particle, and the cross-section of the particle takes the space, that is surrounded by peripheral edge of six circles which are located around the central circle; each of the six circles contacts two adjacent circles, while two interlacing circles are located at the equal distance from them the central circle and can be connected to the central circle; at that, two circles adjacent to the interlacing circles (but not the common circle) contact the central circle, except for the space taken by four remained external circles, and four remained interstitial areas; the elongated mould particles have complementary one to four asperities which are connected, preferably one or two, to the existing end asperity in a way specified above, and the complimentary asperity is specified as described above, while existing end asperity becomes a new central circle and the initial central circle becomes another asperity; also, the description is provided for the mould catalyst or its precursor for hydrocarbon synthesis by Fischer-Tropsch, mould carrier, method for producing the mould carrier, matrix disk, method for producing the hydrocarbons and method for producing the fuel and basic oil from hydrocarbons.

EFFECT: method for producing hydrocarbons is improved.

14 cl, 1 tbl, 2 dwg, 4 ex

FIELD: chemistry, organic, processing of hydrocarbons.

SUBSTANCE: invention is related to an improved method for hydroprocessing of hydrocarbon raw stock containing sulphur- and/or nitrogen-bearing contaminants. The method comprises the first contact interaction of hydrocarbon raw stock with hydrogen in the presence of at least one first catalyst based on VIII group metals on an acidic carrier, the carrier being selected from the group of zeolites and zeolite-bearing carriers, and then the flow leaving the first catalyst directly contacts hydrogen in the presence of at least one second catalyst based on a VIII group metal on a less acidic solid carrier, said solid carrier being selected from the group of carriers based on silicon dioxide-aluminium oxide and other solid carriers that are not zeolites. Said combination of two catalyst layers allows processing of raw stock with a high content of contaminating impurities without high-level cracking that involves the use of highly acidic carriers.

EFFECT: processing of hydrocarbon raw stock with contaminating impurities without high-level cracking.

14 cl, 1 ex

FIELD: petroleum processing.

SUBSTANCE: catalyst is characterized by that content of rare-earth elements in crystalline lattice of Y-zeolite, based on RE2O3, is 4 to 15 wt %, initial size of elementary cell is 2.450 to 2.458 nm, and size of equilibrium structure of elementary cell after its treatment with 100% steam at 800°C for 17 h exceeds 2.430 nm. Also described is a method for preparation of above catalyst for hydrocarbon cracking comprising (1) drying Y-zeolite with rare-earth element ions to water level below 10%, then, at a weight ratio SiCl4/Y-zeolite, interacting zeolite with gaseous SiCl4 supplied with dry air at 150-600°C for a period of time from 5 min to 2 h after reaction followed by removing residual soluble by-products in zeolite by washing with decationized water; (2) mixing and suspending 10-50% Y-zeolite with rare-earth element ions prepared in step (1), 10-60% binder, and 2-75% clay followed by forming catalyst by spray drying and using it.

EFFECT: increased catalytic activity, hydrothermal stability, degree of heavy oil conversion, and selectivity with respect to gasoline, dry gas, and coke, and considerably reduced content of olefin in produced gasoline.

33 cl, 3 dwg, 17 tbl, 36 ex

FIELD: petroleum processing.

SUBSTANCE: invention relates to technologies of obtaining feedstock sources such as crude oil, high-boiling petroleum fractions, petroleum residues, coal liquefaction and by-product-cock plant products, spent lubricating oils, household and industrial wastes of various hydrocarbon fuels, and hydrocarbon raw materials for basic and petrochemical synthesis. Method according to invention comprises: provision and/or synthesis hydrogen donors; hydrocarbon, hydrogen donor, and catalyst stirring step; separation of resulting mixture; isolation of light and heavy fractions; and recycling of heavy fraction together with catalyst to mixing step and hydrogenation of light fraction followed by recovering synthesized hydrogen donors, which are also directed to mixing step.

EFFECT: enhanced process efficiency.

9 cl, 1 dwg, 4 ex

FIELD: petroleum processing.

SUBSTANCE: petroleum feedstock hydrocracking catalyst is prepared by compounding zeolite Y with aluminonickel(cobalt)-molybdenum(tungsten) oxide system. Specifically, low-alkalinity zeolite Y having silicate modulus 5.5-7.0 and crystallinity at least 70% is mixed with aluminum hydroxide having pseudoboehmite structure in proportion (1-9):1. Thus obtained mix is molded, dried, and calcined under water steam atmosphere to give molded thermally treated zeolite. The latter is impregnated with aqueous Ni(Co) and Mo(W) salt solutions or ground and compounded with aluminonickel(cobalt)-molybdenum(tungsten) oxide system by mixing with aluminum hydroxide and Ni(Co) and Mo(W) salts, after which follow molding and impregnation with aqueous Ni(Co) and Mo(W) salt solutions.

EFFECT: expanded catalyst preparation possibilities.

2 cl, 5 tbl, 4 ex

FIELD: petrochemical processes.

SUBSTANCE: group of inventions relates to processing of hydrocarbon feedstock having dry point from 140 to 400°C and is intended for production of fuel fractions (gasoline, kerosene, and/or diesel) on solid catalysts. In first embodiment of invention, processing involves bringing feedstock into contact with regenerable catalyst at 250-500°C, pressure 0.1-4 MPa, and feedstock weight supply rate up to 10 h-1, said catalyst containing (i) crystalline silicate or ZSM-5 or ZSM-14-type zeolite having general empiric formula: (0.02-0.35)Na2O-E2O3-(27-300)SiO2-kH2O), where E represents at least one element from the series: Al, Ga, B, and Fe and k is coefficient corresponding to water capacity; or (ii) silicate or identically composed zeolite and at least one group I-VIII element and/or compound thereof in amount 0.001 to 10.0 % by weight. Reaction product is separated after cooling through simple separation and/or rectification into fractions: hydrocarbon gas, gasoline, kerosene, and/or diesel fractions, after which catalyst is regenerated by oxygen-containing gas at 350-600°C and pressure 0.1-4 MPa. Hydrocarbon feedstock utilized comprises (i) long hydrocarbon fraction boiling away up to 400°C and composed, in particular, of isoparaffins and naphtenes in summary amount 54-58.1%, aromatic hydrocarbons in amount 8.4-12.7%, and n-paraffins in balancing amount; or (ii) long hydrocarbon fraction boiling away up to 400°C and composed, in particular, of following fractions, °C: 43-195, 151-267, 130-364, 168-345, 26-264, 144-272. In second embodiment, feedstock boiling away up to 400°C is processed in presence of hydrogen at H2/hydrocarbons molar ratio between 0.1 and 10 by bringing feedstock into contact with regenerable catalyst at 250-500°C, elevated pressure, and feedstock weight supply rate up to 10 h-1, said catalyst containing zeolite having structure ZSM-12, and/or beta, and/or omega, and/or zeolite L. and/or mordenite, and/or crystalline elemento-aluminophosphate and at least one group I-VIII element and/or compound thereof in amount 0.05 to 20.0 % by weight. Again, reaction product is separated after cooling through simple separation and/or rectification into fractions: hydrocarbon gas, gasoline, kerosene, and/or diesel fractions, after which catalyst is regenerated by oxygen-containing gas at 350-600°C and pressure 0.1-6 MPa.

EFFECT: improved flexibility of process and enlarged assortment of raw materials and target products.

12 cl, 3 tbl, 22 ex

FIELD: petroleum processing and petrochemistry.

SUBSTANCE: catalyst (water-soluble silicon compound) solution is added to hydrocarbons, which are then subjected to cracking in presence of hydrogen at temperature and overpressure providing explosive transfer of catalyst solution into vapor phase. Motor fuel components are predominantly obtained. Yearly processing of 0.5 to 1.0 million ton petroleum is thus envisaged.

EFFECT: simplified process, increased yield of commercial products, and enabled creation of mediate-scale cracking plants.

5 cl, 2 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: present invention relates to a method of producing a catalyst or procatalyst, to catalysts for producing alkenylalkanoates and a method of producing alkenylalkanoates. A method is described for making a catalyst or procatalyst, suitable for use together to produce alkenylalkanoates, involving bringing palladium-, gold- and rhodium-containing precursors into contact with carrier material, calcination in a non-reducing atmosphere, reduction of the palladium-, gold- and rhodium-containing precursors as a result of bringing reducing medium into contact with carrier material and bringing acetate of an alkali metal into contact with reduced carrier material. Described is a catalyst composition for producing alkenylalkanoates which contains: carrier material, which contains at least palladium, rhodium, gold and acetate of alkali metal which are brought into contact with the carrier material, obtaining a catalyst or procatalyst for producing alkenylalkanoates, where at least palladium and rhodium are calcined in a non-reducing atmosphere. Also described is a method of producing alkenylalkanoates, involving bringing initial material, which contains alkene, alkane acid and oxidising agent into contact with the above described catalyst or procatalyst.

EFFECT: increased activity and selectivity of catalyst for producing alkenylalkanoates.

41 cl, 6 tbl,12 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing a catalyst which is used for converting hydrocarbon material to hydrogen and hydrogen-containing gases. A method is described for producing a catalyst for vapour conversion of methane-containing hydrocarbons based on spinel-containing carrier, distinguished by that, the carrier is obtained by depositing inorganic components from solutions from acid etching vermiculite ore with alkali liquor with subsequent calcination of the obtained residue at temperature which allows for obtaining complex spinel of the type Mg [Al, Fe]2O4, where the solutions from acid etching vermiculite ore and the alkali are taken in amounts which provide for content of oxides of magnesium, iron and aluminium in the ready catalyst in mass ratio of 1:0.6:1. The carrier is separated, granulated, dried and calcined, after which nickel is deposited in amount of 6 to 15 wt % in the ready catalyst and calcined again.

EFFECT: wider raw material base for producing a catalyst for vapour conversion of methane-containing hydrocarbons.

1 cl, 7 ex, 3 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to chemistry and can be used for catalytic hydrogenation and oxidation. A method is described for producing a palladium-containing catalyst through extraction of bivalent palladium from an initial solution and deposition of reduced palladium onto a carrier. The method is distinguished by that, the initial compound used is palladium (II) chloride. Reduction of palladium (II) to palladium (0) and deposition onto a carrier is done using iron (II) sulphate. The carrier used is carbon or aluminium silicate materials.

EFFECT: simpler technology of producing a desired catalyst and provision for safety of the process by replacing hard to produce tetraaquapalladium (II) perchlorate and reducing agent.

1 cl, 4 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing Cu/Zn/Al catalysts, to a catalyst produced using this method, as well as to its use in methanol synthesis, methanol reforming and for low-temperature conversion of carbon monoxide. A method is described for preparing Cu/Zn/Al catalysts, involving preparation of a first aqueous solution which contains at least copper formate and zinc formate, preparation of a second solution which contains a precipitation agent, wherein the first and/or second solution contains an aluminium hydroxide sol/gel mixture, combining both solutions, separating the obtained precipitate from the aqueous phase which forms waste water, washing the precipitate until an alkali content, based on a catalyst which calcined at 600°C, of not less than 500 parts per million is attained, and drying. A catalyst prepared using this method is described, and its use in methanol synthesis, methanol reforming and conversion of carbon monoxide.

EFFECT: simpler technology of producing catalyst and increased activity of the catalyst.

32 cl, 5 tbl, 8 ex

FIELD: chemistry.

SUBSTANCE: method of hydrocarbon aromatisation includes: a) contacting of alkane containing from 2 to 6 carbon atom in molecule with at least one catalyst consisting virtually of platinum applied to zeolite MFI which lattice consists virtually from gallium, silicon and oxygen and b) separation of aromatic products. The preparation method for platinum-gallium zeolite catalyst used for hydrocarbon aromatisation is described, it includes: preparation of gallium zeolite containing silicon and gallium; precipitation of the platinum to said zeolite; and c) zeolite calcination. In the said method the said gallium zeolite catalyst consists virtually of platinum applied to zeolite MFI which lattice consists virtually from gallium, silicon and oxygen. The platinum- gallium zeolite catalyst for hydrocarbon aromatisation containing: a) gallium-silicon zeolite and b) platinum precipitated to gallium-silicon zeolite is also described. In the said method the said platinum-gallium zeolite catalyst consists virtually of platinum applied to zeolite MFI which lattice consists virtually from gallium, silicon and oxygen.

EFFECT: enhancing of the catalyst selectivity in transforming of lower alkanes to aromatic hydrocarbons.

30 cl, 3 dwg, 4 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: method of Fischer Tropsch synthesis of hydrocarbons includes the stage of carbon monoxide and hydrogen mixture interreaction in presence of catalyst in the form of particles containing homogenous mixture of cobalt and aluminium compounds at atomic ratio cobalt/aluminium in the range from 10:1 to 2:1 which after reducing at 425°C has cobalt surface area measured with hydrogen chemosorption at 150°C at least 30 m2 per 1 g of catalyst. The catalyst preparation includes the stages: (i) of precipitation of unsoluble cobalt compound from water cobalt salt solution with excess of alkali precipitator; (ii) adding of soluble aluminium compound; (iii) aging of obtained precipitate in suspended form; (iv) extracting and drying of catalyst composition; (v) catalyst activation by its reducing with hydrogen-containing gas.

EFFECT: catalysts obtaining with high cobalt content and high cobalt surface area used for hydrogenating of unsaturated compounds in Fischer Tropsch synthesis.

15 cl, 4 ex, 10 tbl

FIELD: chemistry.

SUBSTANCE: catalysts for preparation of biofuel by reesterification of vegetable oil with alcohol represent composition based on hexaaluminate (MAl12O19) having magnetoplumbite or β-Al2O3 whereat: M - Ba or Sr, or La, or having spinel structure (MR2O4) whereat: M - Ca or Sr, or Ba, whereat R contains Y or La, or composition based on MgO+R2O3+solid solution R2-xMgxO3 with hexagonal structure whereat R contains Y or La, x=0.05÷0.12. The method for catalysts preparation includes precipitation of mixed solution of M and Al nitrates whereat M contains Ba or Sr, or La at constant values of pH 7.5-8.0 and temperature with water solution of NH4HCO3, or precipitation of mixed solution of M and R whereat M = Ca or Sr, or Ba, R contains Y or La at constant values pH equal to 9.9÷11.9 and temperature with water solution of KOH, or precipitation mixed solution of Mg and R nitrates at constant values of pH equal to 9.0-9.5 and temperature with water solution of KOH followed with stages of filtration, washing, drying and calcination. The method of biofuel preparation involves the reesterification of vegetable oil with alcohol implemented in the presence of the catalyst described above.

EFFECT: high level of the vegetable oil conversion.

13 cl, 1 tbl, 18 ex

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