Promotor silica-alumina catalyst and improved method of processing hydrocarbon material

FIELD: chemistry.

SUBSTANCE: invention relates to promoter catalysts on aluminosilicate carriers with defined content of macropores and to hydrocracking/hydroconversion and hydroprocessing methods which use these catalysts. A catalyst is described, which contains at least one hydro-dehydrogenating element chosen from a group consisting of elements of groups VIB and VIII of the periodic table of elements, 0.6 to 2.5% phosphorous. The said catalyst has total volume of pores of 0.35 to 0.74 ml/g, measured using mercury porosimetry and a non-zeolite carrier based on aluminosilicate, with the following characteristics: percentage content of silicon oxide 5 to 95 wt %; content of sodium less than 0.03%; total volume of pores, measured using mercury prosimetry, ranging from 0.45 to 0.96 ml/g; porosity, for which: i) volume of mesopores with diametre ranging from 40 to 150 Å and average pore diametre from 80 to140 Å ranges from 40 to 70% of the total volume of pores, measured using mercury porosimetry; ii) volume of macropores with diametre greater than 500 Å ranges from 30 to 60% of total volume of pores, measured using mercury porosimetry; BET specific surface area ranging from 100 to 550 m2/g; diffraction pattern in X-rays, which contains at least main characteristic bands of at least one of the transition modification aluminosilicates, which is part of a group which consists of alpha, rho, xi, eta, gamma, kappa, theta aluminosilicate modifications. Also described is a method of hydrocracking/hydroconverting hydrocarbon material, using a catalyst in one of the paragraphs described above. A method is also described for hydroprocessing hydrocarbon material, using a catalyst in accordance with one of the paragraphs described above.

EFFECT: design of a hydrocracking catalyst with high catalytic activity and selectivity.

41 cl, 16 ex, 2 tbl

 

The scope of the invention

The present invention relates to promoted catalysts on silica-alumina carrier and to a method of hydrocracking, hydroconversion and hydrobromide using these catalysts.

The level of technology

The hydrocracking of heavy hydrocarbon fractions is a very important refining process of petroleum products, allowing you to get from bad-recyclable residues lighter fractions such as gasoline, jet fuel and light gas oil, in which the interested manufacturer, seeking to Orient their production to the market demands. Some of the ways hydrocracking allow also to obtain highly purified residue, which can serve as an excellent basis for oils. Compared to catalytic cracking advantage of catalytic hydrocracking is possible to obtain middle distillates, jet fuel and gasoil very high quality. And, on the contrary, produced by hydrocracking gasoline gives a lower octane number than the gasoline obtained by catalytic cracking.

Hydrocracking is a way, flexibility is provided by three main factors, namely the working conditions of its implementation, the nature of the used catalysts and the fact that hydrocracking the hydrocarbon can be done in one or two stages.

All the hydrocracking catalysts used in the methods of hydrocracking, are bifunctional type, combining an acid function with hydrogenise function. The acid function is performed by the media, the surface of which is usually 150-800 m2·g-1and characterized in that have a superficial acidity, such carriers are, for example, halogenated aluminum oxide (in particular chlorinated or fluorinated), combinations of oxides of boron and aluminium, amorphous silica-alumina carriers and zeolites. Hydrogeneous the function of one or more metals of group VIII of the periodic system of elements or Association, at least one metal of group VIB of the periodic system and at least one metal of group VIII.

The balance between the two functions, acid and hidrogenesse, is one of the parameters that affect the activity and selectivity of the catalyst. Low acid function and high hydrogeneous function lead to less active catalysts, operating typically at a higher temperature (above or equal to 390-400°C) and at a lower space velocity of the raw materials (speed VVH, expressed in volume of processed raw materials per unit volume of catalyst per hour, usually equal to or less than 2), but with very good selek what ewnetu in relation to middle distillates. Conversely, a strong acid function and a weak hydrogeneous function lead to active catalysts, but with less than satisfactory performance in terms of selectivity in relation to middle distillates (jet fuel and gasoil).

Typical catalysts, hydrocracking catalysts based on amorphous media with moderate acidity, such as, for example, silica-alumina carriers. These catalytic systems used to produce middle distillates good quality and possibly bases for oils. These catalysts are used, for example, in the two-stage methods.

International patent application WO 02/055192 describes the catalyst used in the methods of hydrocracking a hydrocarbon feedstock containing at least one aluminosilicate,moreover, the specified aluminosilicate has a mass content of silicon oxide is from 10 to 60%, the mass content of Na is below 300 ppm wt., total pore volume of from 0.5 to 1.2 ml/g, measured by the method of mercury porometry, while the porosity of the aluminum silicate is as follows: the volume of mesopores having a diameter of from 40 to 150 Å, and the average diameter of from 80 to 120 Å, is 30-80% of the total pore volume, and the volume of macropores whose diameter is greater than 500 Å is 20-80% of the total pore volume, specific surface WET above 200 m2/g, and at least one hydro-dehydrogenation is selected from the group formed by the elements of group VIB and group VIII of the periodic system. This catalyst optionally contains at least one element selected from the group formed by phosphorus, boron and silicon, an element of group VIIA element of group VIIB and VB. Using this type of catalyst for hydrocracking of hydrocarbon raw materials allows to achieve high degrees of conversion download and satisfactory selectivity in respect of interest of middle distillates.

Another document EP 0686687 describes the catalyst used in the method for mild hydrocracking of heavy hydrocarbons. The catalyst contains 2 to 6 wt.% oxide of an element of group VIII, 12-25 wt.% molybdenum oxide and 0-3 wt.% oxide of phosphorus, and the specified catalyst deposited on a porous carrier made of alumina, containing 4-30% of silicon oxide. The catalyst has a specific surface area BET, equal to 150-250 m2/g, total pore volume, equal to 0.75 to 0.92 cm3/g and the pore distribution in which pores with diameter less than 10 nm represent 20-40% of the total volume of pores, the pores having a diameter of from 10 to 16 nm, consists of 28.4-34.1 per cent of the total volume of pores, the pores with diameters greater than 16 nm account for 30-50% of the total volume of pores and macropores having diameters exceeding 25 nm, constitute 25-40% of the total pore volume. The use of such catalyst in the soft way hydro is racinga allows to avoid the formation of insoluble precipitated products able to block the reactor located downstream from the installation, achieving a high degree of conversion.

The performance of these catalysts is closely related to their physicochemical characteristics, more specifically, with their structural characteristics. It is advisable to reduce the density of the catalysts in order to minimize their cost, while maintaining high catalytic performance. In this sense, prefer to use catalysts in which the total pore volume due to the presence of macropores (under the macropores refers to pores with a diameter above 500 Å). Despite the fact that the total pore volume higher, remains satisfactory catalytic activity and at the same time reduces the cost of the catalyst.

Although satisfactory performance can be achieved with improved structural characteristics, the performance of these catalysts also depend on the nature hydrogenise phase. Hydrogeneous activity, therefore, will play a role in the reactions of hydrodesulfurised (HDS), gidrogenizirovanii (HDN), hydrodearomatization (HAD) and affect the stability of the catalyst.

To solve these problems, the applicant came to the need to develop catalysts for hydrocracking, which would be suitable to process the content of the mA is Roper and improved hydrogeneous function in order to achieve improved catalytic performance in hydrocracking processes. The applicant has unexpectedly found that the addition of a controlled amount of the promoting elements to catalysts having these structural characteristics, leads to unexpected catalytic performance in the hydrocracking/hydroconversion and hydrobromide.

More specifically, the invention relates to promoted hydrocracking catalyst on a carrier, having a given content of macropores, and to a method of hydrocracking/hydroconversion and hydrobromide using this catalyst.

Specifications

In the further description of the invention under specific surface understand the specific surface according to BET, determined by nitrogen adsorption in accordance with ASTM D 3663-78, see BRUNAUER, EMMETT, TELLER, The Journal of American Society, 60, 309, (1938).

In the further description of the invention under mercury displacement of carriers and catalysts understand the volume measured by the mercury method of Parametrii in accordance with ASTM D 4284-83 at a maximum pressure of 4000 bar with respect to the surface tension of 484 Dyne/cm and the contact angle of silica-alumina carrier, equal to 140°. One of the reasons why I prefer to use media as a base to determine the distribution of the pores, is that after impregnation of the metals, the contact angle of mercury is changing, and this change occurs depending on clause is the Herods and the type of metals. The contact angle is assumed equal to 140°, following the recommendations outlined in the work of Jean Charpin and Bernard Rasneur “Techniques de l ingénieur, traité analyse et caractérisation,” p. 1050-5.

In order to achieve the greatest accuracy, determine the value of the mercury volume in ml/g, given in the further description that represents the value of the total mercury volume (total pore volume, measured by the method of mercury porometry) in ml/g, obtained after measurement of the sample minus the value of the mercury volume in ml/g, obtained after measuring the same sample at a pressure corresponding to 30 psi (2 bar). Also determine the “average mercury diameter as the diameter at which all the pores having a size smaller than this diameter constitute 50% of the total mercury pore volume.

In order to more accurately characterize the pore distribution, establish the following criteria for the distribution of mercury in the pores: the volume V1', which is the volume of macropores having a diameter greater than 500 Å, and the volume V2', which is the volume of macropores with a diameter of above 250 Å, and corresponds to the volume contained in pores with a diameter above 250 Ǻ.

Finally, in order to more accurately characterize the distribution of the pore, set the following criteria for the distribution of mercury in the pores: the volume V1 corresponds to the volume contained in pores with a diameter below average diameter minus 30 Å. Volume V2 soo the same volume, contained in pores with diameters greater than or equal to the average diameter minus 30 Å and below the mean diameter plus 30 Å. Volume V3 corresponds to the volume contained in pores with a diameter higher than or equal to the mean diameter plus 30 Å. Volume V4 corresponds to the volume contained in pores with a diameter below average diameter minus 15 Å. Volume V5 corresponds to the volume contained in pores with diameters greater than or equal to the average diameter minus 15 Å and below average diameter plus 15 Å. Volume V6 corresponds to the volume contained in pores with diameters greater than or equal to the average diameter plus 15 Å.

The pore distribution measured by nitrogen adsorption, was determined on the model of the Barrett-Joyner-Halenda (bjh's). Isotherm adsorption-desorption of nitrogen, obtained using the bjh's model, described in The Journal of American Society, 73, 373, (1951) authors E.P.Barrett, L.G.Joyner and P.P.Halenda. In the following text under the amount of nitrogen adsorption understand volume, measured at R/R0=0.99, and the pressure at which it is assumed that the nitrogen fills all the pores. Express the average diameter of desorption of nitrogen as the diameter at which all pores smaller than this diameter constitute 50% of the pore volume (Vp)measured on the curve desorption isotherms of nitrogen.

Beneath the surface adsorption understand the surface, measured by the curve of the adsorption isotherms. In this regard, we can refer to, for example, article ALecloux “Memoires Societe Royale des Sciences de Liège, 6emesérie, Tome I, fasc.4, pp.169-209 (1971)”.

The sodium content measured by atomic absorption spectrometry.

The x-ray diffraction is a method that can be used to characterize the media and catalysts according to the invention. In the following description, x-ray diffraction analysis carried out on the powder using a diffractometer Philips PW 1830, working with reflection and is equipped with a rear monochromator using radiation Juice(alpha) (λα1=1,7890 Ǻ, λ1Kα2=1,793 Å, the ratio of the intensity of the Kα1/Kα2=0,5). To obtain a diffraction pattern in x-rays, gamma-alumina, using the database ICDD, section 10-0425. In particular, two of the most intense peak is located at the position corresponding to the value of d in the range of 1.39 to 1.40 Å and from 1.97 to 2.00 Å. The symbol d represents the interplanar distance, which is calculated from the angular position using the Bragg equation (2 d(hk1)·sin (θ) = n·θ). Under gamma-aluminum oxide understand in the future, for example, alumina, a member of the group consisting of cubic gamma-oxide, pseudo-cubic gamma-oxide, tetragonal gamma-oxide, or bad nizkochastotnogo gamma oxide, and gamma-oxides with large surface, gamma-oxides with low surface,gamma oxides obtained the C coarse boehmite, gamma-oxides derived from cristallino of boehmite, gamma-oxides derived from poorly or nizkochastotnogo of boehmite, gamma-oxides obtained from a mixture cristallino of boehmite and amorphous gel, gamma-oxides derived from an amorphous gel, gamma-oxides, passing in the Delta modification. As for the position of diffraction peaks of aluminum oxide modifications this, Delta and theta, you can refer to the article B.C. Lippens, J.J. Steggerda in the journal Physical and Chemical aspects of adsorbents and catalysts, E.G. Linsen (Ed.), Academic Press, London, 1970, pp. 171-211.

As for carriers and catalysts according to the invention, a diffraction pattern in x-rays detects blurred characteristic peak, indicating the presence of amorphous silica.

In addition, in the further description of the connection of the aluminum oxide may contain amorphous fraction, hard-to-detect methods DRX. Therefore, further description imply that the compounds of aluminum oxide may contain amorphous or nizkorentabelnuju faction.

Carriers and catalysts according to the invention was analyzed by spectroscopy solid-state NMR MAS27Al with a spectrometer firm Brüker, type MSL 400 with a diameter of 4 mm sensing the Speed of rotation of the sample about 11 kHz. Potentially, the NMR spectrum of aluminum allows us to distinguish three types of aluminum, the chemical shifts of which p is Evegeny below:

From 100 to 40 ppm: tetracoordinated aluminum, marked Aliv

From 40 to 20 ppm: pentacoordinated aluminum, marked Alv

From 20 to -100 ppm: hexacoordinated aluminum, marked Alvi

The aluminum atom has quadrupolar the core. Under certain conditions analysis (field, with a low radio frequency: 30 kHz, a small corner of momentum: π/2 and the sample saturated with water), the spectral method of NMR spectroscopy with the rotation of the magic angle (MAS) is quantitative. The decomposition of the MAS NMR spectra allows to determine directly the number of different elements. The spectrum is recorded in the form of chemical shift relative to a 1M solution of aluminium nitrate. The signal aluminium is taken as zero shift (0 ppm). Were combined signals from 100 to 20 ppm, related to the Alivand Alvthat corresponds to an area of 1, and the signals from 20 to -100 ppm, related to the Alvithat corresponds to area 2. In the further text the content of octahedral Alviis the ratio: area 2/(area 1 + area 2).

The coordination environment of the atom of silicon in the silicate was studied using NMR spectrum29Si. Tables of chemical shifts depending on the degree of condensation were borrowed from the work of G. Engelhardt and D. Michel, “High resolution solid-state NMR of silicates and zeolites” (Wiley), 1987.

An NMR spectrum29Si shows the chemical is the cue shifts of various structures of silicon, such as Q4(-105 ppm to about 120 ppm), Q3(-90 ppm to -102 ppm) and Q2(-75 ppm up to -93 ppm). The fragments with a chemical shift to -102 ppm may represent fragments of type Q3or Q4who called fragments Q3-4. The fragments expressed as follows:

the fragments Q4: Si associated with 4Si (or Al),

the fragments Q3: Si associated with 3Si (or Al) and 1 OH,

the fragments Q2: Si associated with 2Si (or Al) and 2OH.

The silicates according to the invention are compounds of silicon type Q2, Q3, Q3-4and Q4. Most of the structures apparently refers to the type of Q2and approximately of the order of 10-80%, more 20-60%, preferably 20-40%. The share structures of type Q3and Q3-4also significant, is approximately of the order of 5-50%, preferably 10-40% for both structures.

The coordination environment of the silicon atoms were studied by means of the NMR spectrum CF MAS1H->29Si (300 MHz, the speed of rotation of 4000 Hz). In this case, only the silicon atom associated with IT-the groups should answer. As a table of chemical shifts was used table Kodakari et al., Langmuir, 14, 4623-4629, 1998. The distribution was as follows: -108 ppm (Q4), -99 ppm (Q3/Q4(1Al), -91 ppm, (Q3/Q3(1Al), -84 ppm (Q2/Q 3(2Al), -78 M.L.(Q1/Q2(3Al) and -73 ppm (Q1/Q2(3Al).

Method of characterizing the media and catalysts according to the invention may be a transmission electron microscope (METH). For this study using an electronic microscope (type Jeol 2010 or Philips Tecnai 20F, possibly with scanning), equipped with a spectrometer with energy dissipation (EDS) for x-ray analysis (e.g., Tracor or Edax). The EDS detector must make the determination of light elements. The combination of these two devices, the MET and EDS, allows you to adjust the image and local chemical analysis with satisfactory spatial resolution.

For this type of analysis samples of dry finely pulverized in a mortar; the powder is then combined with resin to obtain ultrathin sections with a thickness of about 70 nm. These sections are collected on copper grids covered with a film of amorphous carbon with holes, serving as a substrate. Then the slices are placed under the microscope for observation and analysis under secondary vacuum.The image under the microscope easily distinguished areas with a sample from areas with resin. Proceed then to a specific number of tests at least 10, preferably 15 to 30 analyses on various areas of industrial design. The size of the electron beam for analysis zones (which is approximately the size and elizerbeth zones) is a maximum of 50 nm in diameter, preferably 20 nm, more preferably 10, 5, 2 or 1 nm in diameter. In scan mode the analyzed area will depend on the size of the scanned area, and not on the size of the beam, which is usually narrow.

Semi-quantitative processing of x-ray spectra, obtained using a spectrometer (EDS, allows to obtain the relative concentration of Al and Si (in % of the atoms) and the ratio of Si/Al for each subject area. You can then calculate the mean value of the ratio Si/Almand standard deviation θ of all of these measured values. In the examples, not limiting the further description of the invention, a probe with a diameter of 50 nm probe is used to describe the media and catalysts according to the invention, unless otherwise specified.

The density of pressing (DRT) is measured by the method described in “Applied Heterogeneous Catalysis” J.F. Le Page, J. Cosyns, P. Courty, E. Freund, J-P. Franck, Y. Jacquin, D. Juguin, C. Marcilly, G. Martino, J. Miquel, R. ontarnal, A. Sugier, H. Van Landeghem, Technip, Paris, 1987. Cylinder, graduated to the appropriate size, is filled with the catalyst by sequentially input portions; between each addition of the catalyst was pressed, shaking the cylinder to establish a constant volume. This measurement is usually carried out at 1000 cm3catalyst compressed in the cylinder, and whose ratio of height to diameter of about 5:1. This is the measurement can be carried out preferably by automatic devices, such as Autotap®, manufactured by Quantachrome®.

The acidity of the matrix was measured by the method of infrared spectrometry (IR). Spectra IR were recorded on the interferometer Nicolet type Nexus-670 with a resolution of 4 cm-1with Apodization type Happ-Gensel. The sample (20 mg) was extruded in the form of a self-supporting circular plates, then placed in a cell for in situ analysis (25°C-550°C, furnace, sending a beam of infrared,secondary vacuum of 10-6 mbar). The diameter of the plate 16 mm.

The sample was pre-treated as described below in order to remove physically absorbed water and partially dehydrosilybin the surface of the catalyst and to obtain a characteristic picture of the acidity of the catalyst in the mode:

- temperature rise from 25°C to 300°C for 3 hours,

- keeping the temperature at 300°C for 10 hours,

- lowering the temperature from 300°C to 25°C for 3 hours.

Probe alkaline nature (pyridine) then adsorbing at the saturation pressure at the temperature of 25°C, then desirerable when heated, by following temperature regime:

25°C for 2 hours in a secondary vacuum,

100°C for 1 hour in a secondary vacuum,

200°C 1 hour with the secondary vacuum,

300°C 1 hour with the secondary vacuum.

The spectrum was recorded at 25°C at the end of the pre-treatment and at each temperature level desorption m the mode of transmission when the accumulation time of 100 sec. Spectra are correlated with ISO-weight (i.e. assuming ISO-thickness) (exactly 20 mg). The number of plots Lewis proportional to the square of the peak, the maximum of which is located near 1450 cm-1including any shoulder.The number of sites of Bronsted proportional to the square of the peak maximum which is around 1545 cm-1. The ratio of the number of sites Branstad to the number of parcels Lewis B/L is equal to the ratio of the areas of the two peaks described above. Usually use the surface peaks at 25°C. This ratio B/L is usually calculated on the basis of the spectrum recorded at 25°C at the end of the pre-processing.

If you enter the promoting element R and possibly and/or Si, the distribution and localization can be determined by methods such as the use of microprobe Casting (distribution profile of the various elements), transmission electron microscopy in combination with x-ray analysis of the components of the catalysts, or by creating a cartographic picture of the distribution of elements present in the catalyst, by electronic microprobe. These methods allow to detect the presence of these exogenic items added after synthesis of aluminosilicate according to the invention.

The overall composition of the catalyst can be determined by x-ray fluorescence the analysis on the catalyst in powdered state or atomic absorption spectrometry after acid etching of the catalyst.

Measurement of the local structure at the micron scale in contrast to the overall composition of the catalyst may be carried out by electronic microprobe. This measurement can be carried out by determining the metal content on the sites in a few cubic microns along one diameter of the catalyst particles, which are called units. This measurement allows to estimate the macroscopic distribution of the elements within the particles. It can be supplemented by measurements on the nanometer scale using STEM (Scanning Transmission Electron Microscopy (Transmission electron microscopy with scanning)).

Tests conducted using electron microprobe of CAMEC S100 (with 5 spectrometers with scattering wavelength) (preferred device) or perhaps on the instrument JEOL 8800R (4 spectrometer). The required parameters are as follows: the acceleration voltage of 20 kV, a current of 80 or 200 and the integration time is 10 seconds or 20 seconds, depending on the concentration level. Particles coated with resin, and then polished to their diameter.

It should be noted that the term "diameter" refers not only to the shape of a ball or extruded pellets, but, more broadly, to any form particles; in fact, the diameter is called the characteristic length of the particle being measured.

Measurements carried out on the sample, not only the next layer or batch of catalyst, designed for catalytic layer. It is believed that the tests should be made not less than 5 particles with not less than 30 measurements on the particle made uniformly in diameter.

Local concentration (expressed in %) molybdenum, Nickel, tungsten and phosphorus indicated respectively Smo, Ni, CW and CF.

You can also Express the concentration in atomic % at the same relative fluctuations.

It is of interest to obtain catalysts, in which the concentration of Smo, Ni, CW and CF are evenly distributed along the granules. Also of interest is the preparation of catalysts in which the concentration of Smo, Ni, CW and CF are concentrated in the centre and in the periphery of the granules. These catalysts have a profile of the concentration distribution called "Cup-shaped" or "domed". Another option allocation refers to allocation type “skin”, where the elements of the active phase are concentrated in the surface layer.

Detailed description of the invention

More specifically, the invention relates to catalysts containing:

at least one hydro-dehydrogenase element selected from the group formed by the elements of group VIB and group VIII of the periodic system,

is 0.01-6% phosphorus, as promoterwise element (in combination, perhaps, with boron and/or silicon,

while specified catalyst has a total pore volume, measured by the method of mercury porometry, from 0.35 up to 0.74 ml/g,

and neoreality based media aluminosilicate,

moreover, the specified aluminosilicate has the following characteristics:

- the percentage of silicon oxide is 5 to 95 wt.%, preferably 10-80%, more preferably 20-60%, even more preferably, the percentage of silicon oxide is necessarily above 25% and below 50%, and even more preferably necessarily above 25% and below 42%,

- the sodium content below 0.03 wt.%,

- total pore volume, measured by the method of mercury porometry, from 0.45 to 0.96 ml/g,

when the porosity is such that:

i) the volume of mesopores with a diameter of 40-150Ǻ and with an average pore diameter of 80-140Ǻ (preferably, 80-120Ǻ) is 30-80% of the total pore volume, measured by the method of mercury porometry,

ii) the volume of macropores with a diameter above 500Ǻ is 15-80% of the total pore volume, measured by the method of mercury porometry,

iii) mainly, the volume of pores with a diameter above 250 Å is 20-80% of the total pore volume, preferably 25-60% of the total pore volume, more preferably not less than 30% of the total pore volume,

- specific surface according to BET is 100-550 m2/g, preferably

150-500 m2/g, more preferably below 350 m2/g, even more preferably below 50 m 2/g

- diffraction pattern in x-rays contains at least the main characteristic bands at least one of transition alumina included in the group formed by the oxides of aluminum alpha, Rho, XI, ETA, gamma, Kappa, theta and Delta modification.

The invention relates also to a method of hydrocracking/hydroconversion and to method of hydrobromide of hydrocarbons with the use of these catalysts.

Characteristics of the catalyst carrier according to the invention

The aluminosilicate used in the catalyst according to the invention, preferably a homogeneous aluminosilicate particles of micron size, in which the content of cationic impurities (for example, Na+below 0.1 wt.%, preferably below 0.05 wt.%, even more preferably below to 0.025 wt.%, and the content of anionic impurities (for example, SO42-, Cl-below 1 wt.%, preferably below 0.5 wt.%, even more preferably below 0.1 wt.%.

Thus, to obtain the media according to the invention any acceptable method of synthesis of aluminosilicate, known to the specialist, which leads to the homogeneous aluminosilicate micron size, in which the content of cationic impurities (for example, Na+below 0.1 wt.%, preferably below 0.05 wt.%, even more preferred is entrusted below to 0.025 wt.%, and the content of anionic impurities (for example, SO42-, Cl-) can be reduced to less than 1 wt.%, preferably less than 0.05 wt.%.

The catalyst carrier according to the invention is neoreality based media aluminosilicate (i.e. contains aluminum oxide and silicon oxide) when the mass content of silicon oxide (SiO2) higher than 5% and less than or equal to 95 wt.%, often, 10-80 wt.%, the preferred content of silicon oxide is higher than 20 wt.% and below 60 wt.%, more preferably, the percentage of silicon oxide is necessarily above 25% and below 50%, even more preferably above 25% and below 42%.

The percentage of silicon oxide affects the acidity of the catalyst and, consequently, on its conversion activity.

So, if hydroconversion more specifically, when the hydrocracking conversion of hydrocarbon molecules occurs on acidic centers. The interface between silicon oxide and aluminum oxide are the basis of the acidity of aluminosilicates. Indeed, the active site is the hydroxyl proton, forming a bridge connection between silicon and aluminum. Thus,total acidity will depend on the number of proton centers. This acidity increases with increasing content of silica, because it increases the total area of the boundary surfaces of the silicon oxide is the oxide of aluminum.

According to a preferred variant of the invention, the catalyst carrier consists only of aluminosilicate.

According to another variant of the invention, the media contains 1-40 wt.% the binder. In this case, the media is a product of mixing of silicate and at least one binder selected from the group formed by silicon oxide, aluminum oxide, clay, titanium oxide, boron oxide and zirconium oxide.

The coordination environment of the atom of silicon in the silicate was studied by using an NMR spectrum29Si. The silicates according to the invention consist of silicon types Q2, Q3, Q3-4and Q4. The largest structure is the type of Q2approximately of the order of 10-80%, more 20-60%, preferably 30-50%. The share structures of Q3and Q3-4also significant, approximately of the order of 5-50%, preferably 10-40% for both structures.

Preferably, the aluminosilicate contains 30-50% of structural fragments Q2in which one silicon atom is linked to two atoms of Si or Al, and with two groups, and also contains 10-30% of structural fragments Q3in which one silicon atom is linked to three atoms of Si or Al, or with one group IT.

The coordination environment of silicon atoms was studied by using an NMR spectrum CF MAS 1H->29Si (300 MHz, Corot rotation 4000 Hz). In this case, only the silicon atom associated with IT, should give the answer. As tables with chemical shifts were used table Kodakari et al., Langmuir, 14, 4623-4629, 1998. The distribution was as follows: -108 ppm (Q4), -99 ppm (Q3/Q4(1Al)), -91 ppm, (Q3/Q3(1Al)), -84 ppm (Q2/Q3(2Al)), -78 ppm (Q2/Q3(3Al)and -73 ppm (Q1/Q2(3Al)).

The silicates according to the invention are generally represented in the spectrum of several superimposed arrays. The main peak of these arrays is mainly at the level of -110 ppm

Spectra of solid-state NMR MAS27Al media and catalysts according to the invention give two arrays with distinct peaks. The first type of aluminum, a maximum of the resonance is about 10 ppm, is stretched in the interval from -100 to 20 ppm, the Position of the maximum means that these structures are mainly structures of type AlVI(octahedral). The second smallest type of aluminum, a maximum of the resonance which is about 60 ppm, stretched in the range of from 20 to 110 ppm, This array can be decomposed, at least two areas. The largest area of this array, apparently, corresponds to the atoms of AlIV(tetrahedral). Carriers and catalysts according to the invention contain predominantly the proportion of atoms of AlVIin the octahedral positions above 50%, predpochtitel is but above 60%, even more preferably above 70%.

According to a variant embodiment of the invention the silicate contains at least two silica-alumina zones, and these zones values relations Si/Al lower or higher values of the correlation Si/Al, determined by x-ray fluorescence. Thus, the carrier having a ratio Si/Al = 0.5, includes, for example, two silica-alumina zones, one zone has a ratio Si/Al, as defined by the MET, below 0.5, and the other zone has a ratio Si/Al, as defined by the MET, from 0.5 to 2.5. According to another variant of the invention, the aluminosilicate contains only one aluminosilicate zone, and this zone has a ratio Si/Al equal to the total ratio Si/Al, determined by x-ray fluorescence and is less than 2,3.

The acidity of the catalyst according to the invention is measured mainly (not this narrowing scope of the invention) observation of the infrared spectrum of thermodesorption of pyridine. Usually, the ratio B/L, as described above, in the carrier according to the invention is 0.05 to 1, preferably from 0.05 to 0.7, even more preferably of 0.05-0.5.

The diffraction pattern of the silicates according to the invention, obtained by x-ray diffraction, correspond to a mixture of silicon oxide and aluminum oxide with some transformation in gamma-aluminum oxide and silicon oxide in may the STI on the content of SiO 2in the samples.

Structural characteristics of the aluminosilicate used in the catalyst according to the invention, as follows:

- specific surface WET from 100 to 550 m2/g, more 150-500 m2/g, preferably below 350 m2/g, more preferably below 250 m2/g

- total pore volume, measured by the method of mercury porometry, from 0.45 to 0.96 ml/g,

the porosity of this, in which:

i) the volume of mesopores with a diameter ranging from 40 Å to 150 Å, and the average diameter of which varies from 80 to 140 Å, preferably from 80 to 120 Å)is 30-80% of the total pore volume, as specified above, preferably 40-70%;

ii) the volume of macropores with a diameter greater than 500 Å, preferably 1000 Å-10000 Å, is 15-80% of the total pore volume, preferably 30-60% of the total pore volume, more preferably the volume of macropores is not less than 35% of the total pore volume;

iii) heavy, pore volume, the diameter of which exceeds 250 Å is 20-80% of the total pore volume, preferably 25-60% of the total pore volume, more preferably not less than 30% of the total pore volume.

Characteristics of the catalyst according to the invention

Therefore, the catalyst according to the invention contains:

cationic impurities, the contents of which are mostly below 0.1 wt.%, preferably below 0.05 wt.%, even more preferably, below of 0.025 wt.%. P is d content of cationic impurities understand the total content of alkali metals.

- anionic impurities, the contents of which are mostly below 1 wt.%, preferably below 0.5 wt.%, even more preferably below 0.1 wt.%,

at least one hydro-dehydrogenase element selected from the group formed by the elements of group VIB and group VIII of the periodic system;

- metal (metals) of group VIB in the metallic form or in the form of oxide, the mass content of which is preferably 1-50%, preferably 1.5 to 35%, even more preferably 1.5 to 30%,

- metal (metals) of group VIII in the metallic form or in the form of oxide, the mass content of which is 0.1-30%, preferably 0.2 to 25%, even more preferably 0.2 to 20%,

is 0.01-6% of phosphorus as the promoting element applied to the catalyst (under the promoting element see element introduced after the preparation of aluminosilicate carrier described above), possibly in combination with boron and/or silicon. Thus, it can be used as the promoting elements combination of phosphorus and boron, or a combination of phosphorus, boron and silicon. If present in the catalyst elements boron and/or silicon, the mass content of boron and silicon, calculated on their oxide form, are from 0.01 to 6%, preferably 0.1 to 4%, even more preferably 0.2 to 2.5%,and

perhaps at least one element from group VIIB (e.g., before occhialino, manganese) when the mass content of 0-20%, preferably 0-10% of the compound in the form of oxide or metal

probably at least one item from a VB group (for example, and preferably, niobium) when the mass content of 0-40%, preferably 0-20% of the compound in the form of oxide or metal.

The catalyst according to the invention has a total pore volume, measured by the method of mercury porometry, equal to 0.35-of 0.74 ml/g, preferably 0.4 to 0.6 ml/g

The reduction in total pore volume results in an increase of the density of the catalyst, it allows to increase the filling of the reactor and, therefore, increase the capacity of the plant for processing. In addition, it is proved that it is advantageous to use a catalyst having a higher density, smaller plants. The use of this catalyst also allows you to remove the bottlenecks of existing facilities so that a higher number of load was converted.

The catalyst according to the invention mainly contains no fluorine.

The density of pressing of the catalyst is typically greater than 0.7 g/cm3, preferably 0.7-0.9 g/cm3depending on the porous characteristics of the catalyst.

Neoreality based media aluminosilicate and aluminosilicate has the following characteristics:

- the percentage of the oxide is silicon is 5 to 95 wt.%, preferably 10-80%, more preferably 20-60%, very preferably the percentage of silica necessarily above 25% and below 50%, and even more preferably is necessarily higher than 25% and less than 42%;

- the sodium content below 0.03 wt.%,

- total pore volume, measured by the method of mercury porometry is from 0.45 to 0.96 ml/g,

the porosity of this, in which:

i) the volume of mesopores with a diameter ranging from 40 Å to 150 Å, and the average diameter of which varies from 80 to 140 Å, preferably from 80 to 120 Å) is 30-80% of the total pore volume, as specified above, preferably 40-70%;

ii) the volume of macropores with a diameter greater than 500 Å, preferably 1000 Å-10000 Å, is 15-80% of the total pore volume, as specified above, preferably 30-60% of the total pore volume, more preferably the volume of macropores is not less than 35% of the total pore volume;

iii) heavy, pore volume, the diameter of which exceeds 250 Å is 20-80% of the total pore volume, preferably 25-60% of the total pore volume, more preferably not less than 30% of the total pore volume.

- BET specific surface is 100-550 m2/g, preferably 150-500 m2/g, more preferably below 350 m2/g, even more preferably below 250 m2/g

- diffraction pattern in x-rays contains at least the main characteristic is not, at least one of transition alumina included in the group formed by the oxides of aluminum, Rho, Chi, Kappa, ETA, gamma, theta and Delta modification, preferably contains at least the main characteristic bands at least one of transition alumina included in the group consisting of alumina, gamma, ETA, theta, and Delta modification, more preferably contains at least the main characteristic bands of gamma and ETA-alumina, and more preferably contains peaks at d equal to 1,39-of 1.40 Å, and d equal 1,97-2,00 Ǻ.

The phosphorus content is preferably 0.01 to 4 wt.% based on the oxide, preferably from 0.01 to 2.5 wt.% in the calculation of the oxide.

Preferably, the catalyst is based on Nickel, molybdenum and tungsten and/or Nickel and tungsten.

The preferred catalyst according to the invention contains the Association of Nickel-tungsten and contains phosphorus in an amount of 0.01-4 wt.% in the calculation of the oxide.

Particularly preferred catalyst according to the invention contains the Association of Nickel-tungsten and contains phosphorus in an amount of 0.01-2.5 wt.% in the calculation of the oxide.

Preferably, the aluminosilicate contains 30-50% of structural fragments Q2in which one Si atom is linked to two atoms of Si or Al, and with two groups, and also contains 10-30% of the structure is to become fragments of Q 3in which the Si atom is linked to three atoms of Si or Al, and with one group IT.

According to a preferred variant of the invention, the catalyst carrier consists only of aluminosilicate.

According to another variant of the invention, the media contains 1-40 wt.% the binder. In this case, the carrier can be obtained by mixing the silicate and at least one binder selected from the group formed by silicon oxide, aluminum oxide, clay, titanium oxide, boron oxide and zirconium oxide.

In the catalyst, the content of AlVIoctahedral determined using spectra of solid-state NMR MAS27Al usually exceeds 50%.

The catalyst may also contain a small amount of at least one promoting element selected from the group formed by zirconium oxide and titanium.

Preferably, the catalyst is subjected to hydrothermal treatment after synthesis, as will be described later.

Preferably, the catalyst is subjected to sulfonation, as will be described later.

Standard test activity: evaluation of the catalysts according to the invention

The acidity and the rate of hydrogenation catalysts according to the invention can be evaluated according to the catalytic test is carried out with a mixture of compounds, taken as a fashion and: hydrogenation of toluene and isomerization of cyclohexane.

Catalytic test, allows you to control the hydrogenation process and the acidity of the catalysts is carried out in accordance with the following Protocol.

Catalysts sulferous in situ dynamics in a tubular reactor with a fixed layer in the transverse direction of the flow in the pilot installation type catatest (design Vinci Technologies), and recirculating flows are directed from the top down. Measurement hydrogenise and isomerizing activity carried out immediately after sulfonation under pressure, without air,using hydrocarbon loading, which was carried out by sulfonation catalyst.

Download for sulfonation and for the test consists of: 5.8 wt.% dimethyl disulfide (DMDS), 20 wt.% toluene and 74.2 wt.% cyclohexane. Now, measure the catalytic activity stabilized in equal amounts of catalysts in hydrogenation reactions of toluene. Monitoring the isomerization of cyclohexane, diluted with toluene, to determine the acidity of the catalysts.

The conditions under which measured the acidity, the following (assuming the full evaporation and using the law of perfect gases):

Total pressure: 6,0 MPa

The pressure of toluene: 0,38 MPa

The pressure of cyclohexane: 1,55 MPa

The hydrogen pressure: 3,64 MPa

Pressure H2S: 0,22 MPa

Amount of catalyst: 40 cm3

Consumption, load: 80 cm3per hour

Hourly spatial speed: 2 l/l/h-1

The flow rate of hydrogen: 36 l/h

The temperature of sulfonation and the dough: 350°C (3°C/min)

Samples of liquid effluent analyzed by chromatography in the gaseous phase. Determine the molar concentration of unconverted toluene (T) and the concentration of products of hydrogenation: methylcyclohexane (MSS), ethylcyclopentane (EtCC5) and dimethylcyclopentane (DMCC5)that allows to calculate the degree of gidrogenizirovanii toluene XHYDexpressed by the ratio:

XHYD(%)=100·(MS+EtCC5+DMCC5)/(T+MS+EtCC5+DMCC5)

The degree of isomerization of cyclohexane XISOcalculated in the same way, based on their concentrations of unconverted cyclohexane and its reaction product: Methylcyclopentane. Based on the fact that the reaction gidrogenizirovanii toluene and isomerization of cyclohexane is a first order reaction in these test conditions, and taking the reactor as a perfect piston reactor, expect hydrogeneous activity AndHYDand isomerizing activity

AISOcatalysts, using the formula:

Ai=In(100/(100-Xi))

Mainly, the catalyst according to the invention in a standard test activity is the activity of aHYD>0.7 and the activity of aISOM>0,1, preferably AHYD>0.9 and AISOM/sub> >to 0.12, more preferably AHYD>1.2 and AISOM>0,13, even more preferably AHYD>1.4 and AISOM>0,13.

Attitude hydrogenise activity for isomerizing activity N/a And AHYD/AISO.

Attitude hydrogenise activity for isomerizing activity N/a is mainly 6,5-30, preferably 7-30, very preferably 7.5 to 25, more preferably about 8.5-20, and more preferably 9.5 to 15.

Ways to get

The catalysts according to the invention can be obtained in accordance with any well-known specialist of ways.

The preferred method of preparation of the catalyst according to the invention includes the following stages :

According to a preferred version get direct predecessor forming one of the aluminosilicate or forming silicate together with at least one binder, and then carry out the drying and calcination. Elements VIB and/or VIII group and possibly elements selected from phosphorus, boron, silicon, and possibly elements of VB and VII groups enter, if necessary by any method known to the expert, before or after molding and before or after calcination of the precursor or catalyst.

Hydrogenise element can be introduced at any point of receipt, preferably by mixing, or that very preference is sustained fashion, after molding. After molding carry out the annealing, and hydrogenating agent may be introduced before or after this annealing. The receiving end usually by annealing at a temperature varying between 250 and 600°C. Another of the preferred methods according to the invention consists in the formation of aluminosilicate without a binder, and then mixing with the latter, then passing the resulting paste through a die plate to produce pellets with a diameter of 0.4 to 4 mm, Then hydrogenise item can be entered only partially (for example, in the case of associations of metal oxides VIB and VIII groups) or completely at the stage of mixing. This element can also be introduced by one or more ion exchange operations on the calcined carrier comprising at least one aluminosilicate, perhaps molded together with a binder, using solutions containing salt precursors selected metals, if they belong to group VIII. It can also be introduced by one or more impregnation molded and calcined carrier with a solution of precursors of oxides of metals of group VIII (in particular cobalt and Nickel)when the precursors of oxides of metals VIV groups (in particular molybdenum or tungsten) have been previously entered at the stage of mixing media. And finally, it can be entered according to a very PR is doctitle version by one or more impregnation of calcined carrier, comprising at least one aluminosilicate according to the invention and possibly at least one binder, solutions containing precursors of oxides of metals of the VI and/or VIII group, and the precursors of oxides of metals of group VIII is preferably introduced after the precursors of oxides of metals VIV groups or simultaneously with the latter.

Preferably, the carrier is impregnated with the aqueous solution. The impregnation of the support is preferably carried out by impregnation method called "dry", a well-known specialist. Impregnation can be performed for a single phase solution containing a collection of elements, the components of the final catalyst.

Thus, the catalyst according to the invention may contain at least one element of group VIII, such as iron, cobalt, Nickel, ruthenium, rhodium, palladium, Osmi, iridium or platinum. From metals of group VIII prefer to use a metal selected from the group formed by iron, cobalt, Nickel, platinum, palladium and ruthenium. The catalyst according to the invention may also contain at least one element of group VIB, preferably tungsten and molybdenum. Mostly use Association the following metals: Nickel-molybdenum, cobalt-molybdenum, iron-molybdenum, iron-tungsten, Nickel-tungsten, cobalt-wolf who am, platinum-palladium, the preferred associations are Nickel-molybdenum, cobalt-molybdenum, cobalt-tungsten, and more preferably platinum-palladium and Nickel-tungsten. You can also use the Association of the three metals, for example Nickel-cobalt-molybdenum, Nickel-molybdenum-tungsten, Nickel-cobalt-tungsten. Mostly use Association the following metals: Nickel-niobium-molybdenum, cobalt-niobium-molybdenum, iron-niobium-molybdenum, Nickel-niobium-tungsten, cobalt-niobium-tungsten, iron-niobium-tungsten, the preferred associations are Nickel-niobium-molybdenum, cobalt-niobium-molybdenum. You can also use the Association of the four metals, for example Nickel-cobalt-niobium-molybdenum. You can also use the Association containing a noble metal, for example, ruthenium-niobium-molybdenum, or ruthenium-Nickel-niobium-molybdenum.

At least one of the following elements: phosphorus and possibly boron and/or silicon and possibly the element(s)selected(s) group(s) VIIB and VB, is introduced into the catalyst at any stage of its receipt in accordance with any method known to the expert.

A preferred method according to the invention is that cause the selected(s) promoting(s) element(s) on calcined or ' green ' predecessor, preferably calcined. For applied what I for example, boron is prepared an aqueous solution of at least one boron salt such as Deborah ammonium or pentaborate ammonium, alkaline medium and in the presence of hydrogen peroxide, carry out the so-called dry impregnation, which is filled pore volume of the precursor solution, containing, for example, boron. If applied, for example, silicon, is used, for example, a solution of the silicon compound silicone or a silicone oil emulsion.

Application of boron and silicon can also be carried out simultaneously using, for example, a solution containing a salt of boron and silicon compound silicone type. For example, if the predecessor is the catalyst type Nickel-tungsten deposited on the silicate, it is possible to impregnate this precursor with an aqueous solution of diborate ammonium and silicone Rhodosil EIP company Rhodia, to carry out drying at a temperature of, for example, 120°C., then to impregnate with a solution of ammonium fluoride, to carry out drying at a temperature of, for example, 120°C, and, for example, be subjected to calcination, preferably, the layer with the cross-directional air flow,for example, at 500°C for 4 hours.

The promoting element selected from the group formed by phosphorus, silicon and boron, as well as from elements of group VIIB, VB, can be entered by one or more operations of impregnation about Lenogo predecessor excessive amount of solution.

If you enter at least one of the promoting element R and possibly and/or Si, the distribution and localization can be determined by methods such as the use of microzide Castaing (distribution profile of the various elements), transmission electron microscopy in combination with x-ray analysis of the catalyst components, or by making cartograms distribution of elements present in the catalyst using the electron microprobe. These methods allow to detect the presence of these exogenous elements that were introduced after synthesis of aluminosilicate according to the invention.

Interest preparation of catalysts in which the concentration of CMoCNiCWand CPevenly distributed along the granules. Is also interested in the preparation of catalysts in which the concentration of CMoCNiCWand CPconcentrated in the centre and in the periphery. These catalysts have profiles, called "covetously" or "domed". Another type of distribution refers to the distribution type "peel"when the elements of the active phase are located in the surface layer.

Typically, the concentration ratioMoCNiCWand CPcore/edge is 0.1-3. Under option the image is placed, this ratio is 0.8-1.2. According to another variant, the ratio of concentrations WithMoCNiCWand CPcore/edge is 0.3-0.8.

The preferred source of phosphorus is orthophosphoric acid, H3RHO4but well its salts and esters, for example the ammonium phosphates. Phosphorus can be introduced, for example, in the form of a mixture of phosphoric acid and organic compounds of an alkaline nature, containing nitrogen, such as ammonium hydroxide, primary and secondary amines, cyclic amines, compounds of the family of pyridines and quinoline and connections of the family of pyrrole. Can also be used tungsten-phosphorus-or tungsten-molybdenum acid.

The phosphorus content is set so (without limiting the scope of the invention)to form a mixed compound in solution and/or media, such as a tungsten-phosphorus or molybdenum-tungsten-phosphorus. These mixed compounds may represent heteropolyanions. These compounds may represent, for example, heteropolyanions Anderson. Mass content of phosphorus is calculated on the oxide form of P2About5and is 0.01-6%, preferably 0.01 to 4%, very preferably from 0.01 to 2.5%.

The boron source can be boric acid, preferably orthoboric acid, H3IN3Deborah and the and pentaborate ammonium, boron oxide, esters of boric acid. Boron may be introduced, for example, in the form of a mixture of boric acid, hydrogen peroxide and organic compounds of an alkaline nature, containing nitrogen, such as ammonium hydroxide, primary and secondary amines, cyclic amines, compounds of the family of pyridines and quinoline and connections of the family of pyrrole. You can enter boron, for example, in the form of a solution of boric acid in a mixture of water/alcohol.

As for silicon, can be used numerous sources. So, you can use utilitarian Si(OEt)4, siloxanes, polysiloxanes, silicones, silicone emulsions, halogenoalkane, such as forcricket ammonium (NH4)2SiF6or forcricket Na2SiF6. Can also be used successfully criminalistica acid and its salts, cranioleuca acid and its salts. Silicon can be introduced, for example, by impregnation of the ethyl silicate, dissolved in a mixture of water/alcohol. Silicon can be introduced, for example, by impregnation of a silicon compound silicone type or suspension of silicic acid in water.

The metals of group VIB and group VIII of the catalyst according to the invention can be partially or completely in the metallic form and/or in the form of oxide and/or sulfide. For example, from the sources of molybdenum and tungsten can IP alsowhat oxides and hydroxides, molybdenum or tungsten acid and their salts, in particular ammonium salts such as ammonium molybdate, heptamolybdate ammonium, ammonium tungstate, posteromarginal acid, rostroventrally acid and their salts, criminalistica acid, cranioleuca acid and their salts.

The sources of elements of group VIII, which can be used in this invention are well known to the specialist. For example, the introduction of base metals use nitrates, sulfates, hydroxides, phosphates, halides, for example chlorides, bromides and fluorides, carboxylates, for example acetates and carbonates. For the introduction of noble metals used halides, for example chlorides, nitrates, acids, such as chloroplatinate acid, oxychloride, such as ammonium ruthenium oxychloride.

Preferably, do not add other Halogens, in addition, which is entered when the impregnation, and this halogen is preferably chlorine.

Getting media

The carrier may be pure aluminum silicate or the product of the mixing of the aluminosilicate with a binder, such as silicon oxide (SiO2), aluminum oxide (Al2O3), clay, titanium oxide (TiO2), boron oxide (B2O3) and zirconium oxide (ZrO2and any mixture of the above binder. Preferred binders are silica and xed aluminum, more preferred is aluminum oxide in all its well-known specialist modifications, for example gamma alumina. The mass content of the binder in the catalyst carrier is 0-40%, more preferably 1-40%, more preferably 5-20%. However, the catalysts according to the invention, in which the carrier is only the aluminosilicate without any binders are preferred.

The media can be obtained by forming aluminosilicate in the presence of a binder or without him according to the method known to the expert.

When all the above methods, you may want to add on one of the stages of their implementation minor amount of at least one promoting element selected from the group consisting of zirconium oxide, and titanium.

Forming carriers and catalysts

The media can be obtained by forming silicate of any well-known specialist way. Molding can be carried out, for example, by extrusion, pelletizing, the method of coagulation in a drop of oil-drop), granulation with a rotating plate or any other means well known to the specialist.

Shaping can also be carried out in the presence of various catalyst components obtained by extrusion of mineral paste, tabla is the key, the molding in the form of beads in a rotary pelleting machine or dryer, coagulation in a drop of oil-drop method oil-up or any other known method agglomerative powder containing aluminum oxide and possibly other ingredients selected from the above.

The catalysts used according to the invention, have the form of spheres or extruded pellets. However, it is preferable that the catalyst was in the form of extruded granules with a diameter of from 0.5 to 5 mm, more preferably 0.7 to 2.5 mm They may take the form of a cylinder (hollow or not hollow), twisted cylinder, multilobe cylinder (2, 3, 4 or 5 petals) and be in the form of rings. The cylindrical shape is preferred, although other shapes can be used.

In addition, these carriers to be used according to the invention can be processed with additives known to a person skilled way to improve formemost and/or improve the final mechanical properties of silica-alumina carriers. Examples of such additives can be, in particular, cellulose, carboxymethylcellulose, karboksimetilcelljuloza, tall oil,xanthan resins, surfactants, flocculosa agents such as polyacrylamides, carbon black, starches, stearic acid, polyacrylic acid, polyvinyl KIS the PTA, biopolymers, glucose, polyethylene glycols, etc.

Regulation of the porous characteristics of the media according to the invention takes place partly during this phase, forming particles of the media.

Molding may be carried out by methods known to the expert in forming catalysts, such as extrusion, drazhirovanie, spray drying or tableting.

You can add or remove water to bring the viscosity of the paste suitable for extrusion. This step can be performed at any time at the stage of mixing. In the case of aluminosilicate media it is recommended to reduce the amount of water in the pasta to make pasta mechanical strength. This operation is usually accompanied by a decrease in the total volume at the optimum content of acid.

To bring the content of solids in the extrudable paste suitable for extrusion, you can also add the connection that this is the most solid, preferably an oxide or hydrate. Prefer to use hydrate, more preferably a hydrate of aluminum. Losses during the combustion of the hydrate exceed 15%.

The content of acid added with stirring before forming, below 30%, preferably 0.5-20 wt.% from the anhydrous mass of cu oxide is mnia and aluminum oxide, involved in the synthesis.

Extrusion can be carried out using any suitable equipment available for sale. The paste obtained after mixing, extruded through the die plate, for example, by a piston or single-screw or twin-screw extruder. This operation of the extrusion can be performed by any known specialist way.

Extruded granules media according to the invention typically have a resistance to crushing of at least 70 N/cm, preferably higher than or equal to 100 N/see

The annealing medium

Drying is carried out according to any known specialist method.

To obtain the media corresponding to the invention, prefer to carry out annealing in the presence of molecular oxygen, for example, by blowing air at a temperature below or equal to 1100°C. Can be performed, at least one annealing at the end of any stage of the cooking medium. This annealing can be performed, for example, in the layer in the transverse direction of the flow of air in the layer in the longitudinal direction of the air flow or in a static atmosphere. For example, used kiln for calcination may be a rotary furnace or a vertical furnace with a radial layers in the transverse direction of air flow. Conditions procelian the I: temperature and duration depend mainly on the maximum temperature of the catalyst. The calcination conditions are the temperature and duration of annealing, depending mainly on the maximum temperature of the catalyst. The preferred calcination conditions are burning more than 1 hour at 200°C and less than one hour at 1100°C. the Annealing can be carried out in the presence of water vapor. The final annealing is possible in the presence of acid or alkaline vapors. For example, the calcination may be conducted at a partial pressure of ammonium hydroxide.

Processing after synthesis

Processing after synthesis can be carried out in order to improve the properties of the media, in particular, to improve its homogeneity, which was described above.

According to a preferred variant implementation, the processing after synthesis means hydrothermal processing. Hydrothermal treatment is carried out by any method known to the expert. Under hydrothermal processing understand introduction to contact mixed media at any stage of its receipt of water in vapor or liquid state. Under hydrothermal processing can be understood, in particular, maturation, steaming (steaming), autoclaving, roasting in a humid atmosphere, rehydration. Without limiting the scope of the invention, it is possible to say that such processing will riday mobility silicon component.

According to the invention maturation can be performed before or after molding. According to a preferred variant of the invention, the hydrothermal treatment is carried out by steam treatment in a furnace in the presence of water vapor. Temperature during steam treatment may be in the range of 600-1100°C., preferably above 700°C, during the time from 30 minutes to 3 hours. The content of water vapor above 20 g of water per 1 kg of dry air, preferably above 40 g of water per kg of dry air, more preferably above 100 g of water per 1 kg of dry air. Such processing may, if necessary, to replace all or part of the annealing operation.

Mostly the media may be subjected to hydrothermal treatment in a closed atmosphere. Under hydrothermal treatment in a closed atmosphere understand the treatment by passage through the autoclave in the presence of water at a temperature above room temperature.

During this hydrothermal treatment molded aluminosilicate can be processed in different ways. Thus, it is possible to impregnate the aluminosilicate acid before passing through the autoclave, and the autoclave aluminosilicate either in the vapor or in the liquid phase and the liquid or vapor phase may be acidic or not acidic. This impregnation before autoclaving can the t to be acidic or not acidic. This impregnation before autoclaving can be carried out dry or by immersing the aluminum silicate in an aqueous acid solution. Under the dry impregnation understand the contacting of the alumina with a solution that is lower than or equal to the total porous volume of aluminum oxide. Prefer to carry out the impregnation dry.

The autoclave is preferably an autoclave with a rotating basket, such as the one described in the patent application EP-A-0387109.

Temperature during autoclaving can be equal to 100-250°C for a period of time from 30 minutes to 3 hours.

A method of processing hydrocarbon material according to the invention

In General, the catalysts according to the invention used for treatment of hydrocarbon fractions, performed usually in the presence of hydrogen, at temperatures above 200°C and pressures above 1 MPa, while the spatial velocity is 0.1-20 h-1and hydrogen is injected in an amount such that the volume ratio of a liter of hydrogen per liter of hydrocarbon was 80-5000 l/l

The catalysts according to the invention is mainly used for hydrocracking/hydroconversion hydrocarbon fractions.

The catalysts according to the invention can also be used for hydrobromide hydrocarbon, individually or upstream from p is Ogadenia hydrocracking/hydroconversion with a hydrocracking catalyst based on a zeolite or aluminosilicate, containing, preferably, Nickel and tungsten.

Sulfonation catalyst

Before injection of the feedstock, the catalyst used in the method according to the invention, is preferably subjected to sulfureuse processing, allowing to transform, at least partially, the metal elements in sulfides prior to their contact with the processed raw materials. This activating treatment method of sulfonation well known to the expert and can be carried out in any described in the literature in a manner or in situ, i.e. inside the reactor, or outside ex-situ.

The classic way of sulfonation, well-known specialist, is heated in the presence of hydrogen sulphide (pure or in the form of a stream of a mixture of hydrogen/hydrogen sulfide) at a temperature of 150-800°C., preferably varying between 250 and 600°C, usually in the reaction zone in the layer in the transverse direction of the stream.

Raw materials

The methods according to the invention, described above, can process a variety of raw materials, as a rule, it contains not less than 20 vol.%, more often not less than 80% vol. compounds having a boiling point above 340°C.

The raw material can be, for example, LCO (light cycle oil (light oil from the catalytic cracking unit), the products of the atmospheric distillation of crude oil, products of vacuum distillation of crude oil, such as gas oils, arriving after the direct PE Agency crude oil or from units conversion such as FCC, kokoulina installation or reduce the viscosity, as well as raw materials from plants extraction of aromatic compounds from bases for lubricating oils or from installations of deparaffinization with solvent bases for lubricating oils or distillates, coming after processes desulfuromonas or hydroconversion in a fixed bed or fluidized bed RAT (the residue of atmospheric distillation) and/or RSV (residue vacuum distillation) and/or desacralizing oils or raw materials can be desacralization oil, or any mixture of these raw materials. This list is not restrictive. Paraffin hydrocarbons, coming after the way the Fischer-Tropsch process, is an exception. In General, the hydrocarbon feedstock has a boiling point T5 above 340°C., preferably above 370°C, ie 95% of the compounds present in the raw materials have a temperature T5 boiling above 340°C., preferably above 370°C.

The nitrogen content in the raw materials processed by the methods according to the invention, usually above 500 ppm, preferably 500-10000 ppm wt., more preferably 700-4000 ppm wt., even more preferably 1000-4000 h/million sulfur Content in the raw materials processed by the methods according to the invention is usually 0.01 to 5 wt.%, preferably 0.2 to 4%, even more preferably 0.5 to 2%.

Raw materials can sod the rust metals. The total content of Nickel and vanadium in raw materials, processed by the methods according to the invention, preferably below 1 ppm wt.

The content of asphaltenes usually below 3000 ppm, preferably below 1000 ppm, even more preferably below 200 h/million

The protective layer

When the raw material contains the connection type resins and/or asphaltenes, it is recommended that the raw material is pre-skip through the layer of catalyst or adsorbent that is different from the catalyst hydrocracking or hydrobromide.

Protective catalysts or layers used according to the invention have a spherical shape or form of extruded pellets. It is considered desirable that the catalyst was in the form of extruded granules with a diameter of 0.5 to 5 mm, more preferably 0.7 to 2.5 mm They have the shape of a cylinder (hollow or not hollow), the form of the twisted cylinder, multilobe cylinder (for example, 2, 3, 4 or 5 petals), the shape of the rings. The preferred cylindrical form, although you may be used and other forms.

In order to get rid of the presence of toxic substances or poisons in the downloadable raw materials, protective catalysts according to another preferred variant implementation can be more specific geometric shape to increase the proportion of the hollow volume. The share of the hollow volume in these kata is isatori is 0.2 to 0.75. The outer diameter of the catalysts may be in the range from 1 to 35 mm Of the possible specific forms include, without limitation, hollow cylinders, hollow, ring process, the hollow cylinder with the teeth of the hollow gear cylinders, the shape of the five-section wheel carts, cylinders with numerous holes. These catalysts can be impregnated or not impregnated with the active phase. Preferably the catalyst to impregnate hydro-dehydrogenase phase. More preferably, use phase SOMO or NiMo.

These catalysts may contain macropores. The protective layers sells firm Norton-Saint-Gobain, for example, protective layers Mashuga®. The protective layers may be issued by the company Axens series AST: AST, AST, AST or NMS, NMS, NMS or NMS.

Especially, it is preferable to put these catalysts at each other, at least two different layers of different heights. Catalysts having a higher percentage of voids, it is preferable to use in the first or in the first catalytic layer at the inlet to the catalytic reactor. It is also advisable to use at least two different reactor for these catalysts.

Preferred protective layers according to the invention are trademarks of NMS and AST.

Conditions of implementation of operations

Conditions of implementation of operations such as that the temperature value, pressure, the degree of recirculation of hydrogen, spatial hour speed change substantially depending on the nature of the downloadable raw materials, the quality of target products and facilities available at the refinery. The hydrocracking catalyst/hydroconversion or hydrobromide usually enter into contact in the presence of hydrogen with the above-mentioned raw materials at temperatures above 200°C, more frequently when 250-480°C, mostly in 320-450°C, preferably at 330-435°C, under a pressure above 1 MPa, more 2-25 MPa, preferably 3 to 20 MPa, while the spatial velocity is 0.1-20 h-1, preferably 0.1 to 6 h-1, more preferably 0.2 to 3 h-1and the amount of hydrogen such that the volumetric ratio of 1 l of hydrogen/1 liter of hydrocarbon was 80-5000 l/l, more 100-2000 l/l

These operating conditions used in the methods according to the invention, can usually be achieved in a single pass conversion to the formation of products having a boiling point below 340°C., often below 370°C, in the amount higher than 15%, preferably 20-95%.

Options exercise

How hydrocracking/hydroconversion using the catalysts according to the invention, implemented in a wide pressure ranges and conversion, starting with mild hydrocracking to hydrocracking at high Yes is the process. Under mild hydrocracking understand the hydrocracking occurring at medium conversion, usually representing less than 40%, and carried out at low pressure, usually with 2-6 MPa.

Can be used in typical conditions, the method and modes of carrying out traditional hydrocracking and high pressure, but they do not limit the scope of the invention. Depending on the requirements regarding product quality and conversion rates can be divided into two large groups method, the main characteristics of which are presented in the following table:

The mild hydrocrackingTraditional hydrocracking
High pressure
MethodOne stageOne or two stage
Conversion, wt.%20-4070-100
Temperature, °C350-430350-430
H2pressure, MPa3-810-20
LHSV, h-10,3-1,5 0,2-2,0
H2/download, N3/m3300-1000800-2000

Method for mild hydrocracking is an improved method of hydrobromide to achieve a relatively low conversion rates (20-40%) at low pressure (total pressure of about 6, even 8 MPa). A method of hydrocracking a high pressure leads to high conversion (70-100 wt.%) vacuum distillates at high pressure (10-20 MPa).

The catalyst according to the invention can be used individually in the form of one or more catalytic layers fixed layer, in one or more reactors that operate on single-stage hydrocracking, with liquid recirculation of the unconverted fraction, or without it, possibly in conjunction with a Hydrotreating catalyst, located upstream from the catalyst according to the present invention.

The catalyst according to the invention can be used individually in one or more reactors with a fluidized bed, working on a single stage hydrocracking liquid recycling of the unconverted fraction, or without it, possibly in conjunction with a Hydrotreating catalyst, which is located in the reactor with a fixed or fluidized bed upstream from the catalyst is according to the present invention.

During operation of the fluidized bed are separated used catalyst and daily add fresh catalyst to maintain the catalyst activity.

At the two-stage hydrocracking process, providing for interim allocation of product between the two reaction zones at a certain stage, the catalyst according to the invention can be used in one or two reactors in combination with a Hydrotreating catalyst or without, located upstream from the catalyst according to the invention.

One-step method

Hydrocracking, called single-stage hydrocracking, includes, first and foremost, a deep Hydrotreating, which aims to carry out effectively gidrogenizirovanii, desulfuromonas hydrocarbon before it will be sent to the contact with the hydrocracking catalyst, in particular, in the case where the catalyst contains a zeolite. Such deep Hydrotreating hydrocarbon loading leads only to limited conversion of hydrocarbons to more light fractions, which is not enough, therefore requires additional processing with a more active catalyst. However, it should be emphasized that between contact with these two types of catalysts is e exercise of any branch of the product. The entire effluent from the reactor stream is to be served is the catalyst for hydrocracking and only then carry out the separation of the products formed. This scheme hydrocracking, called “Once Through”, includes an implementation option, which recycle unconverted fraction in the reactor in order to carry out a deeper conversion download.

One way fixed bed

If the catalyst according to the invention is used above in the course of the stream from the zeolite hydrocracking catalyst, for example, based on zeolite Y, we use mainly the catalyst, which has a high weight percent of silicon oxide, namely the mass content of silicon oxide in the carrier included in the composition of the catalyst is 20-80%, preferably 30-60%. It might also be useful the use of this catalyst in combination with a Hydrotreating catalyst, the latter feature upstream of the catalyst according to the invention.

If the catalyst according to the invention is used upstream from the catalyst hydrocracking based on aluminosilicate or zeolite in the same reactor and in different catalytic layers or in different reactors, conversion usually (or preferred) is less than 50 wt.%, preferably less than 40%.

Catalysis is the PR according to the invention may be located above or downstream from the zeolite catalyst. If it is below from the zeolite catalyst, it is cracking HPA. Under NDA refers to polyaromatic hydrocarbons, such as those described, in particular, in Hydrocracking, Science and Technology” J.Scherzer, Editions M.Dekker Incorporated, 1996.

One way fluidized bed

The catalyst according to the invention can be used individually in one or more reactors. In this way it can be appropriate to use multiple consecutive reactors, the reactor or reactors with fluidized bed containing the catalyst according to the invention, installed in front of one or more reactors containing at least one Hydrotreating catalyst in a fixed bed or fluidized bed.

If the catalyst according to the invention is located downstream from the Hydrotreating catalyst, the conversion of hydrocarbon fractions occurring on this Hydrotreating catalyst, usually (or preferred) is less than 30 wt.%, preferably less than 25%.

One-step method with a fixed layer with intermediate separation of the product

The catalyst according to the invention can also be used in the method of hydrocracking, called single-stage, containing a Hydrotreating zone, a zone in which partially removes ammonia, for example, the R, under the action of the flash heating, and a zone containing hydrocracking catalyst. This method of hydrocracking a hydrocarbon downloads in one stage for the production of middle distillates and possibly bases for oils containing at least one first reaction zone, carrying out Hydrotreating, and at least one second reaction zone, which is the hydrocracking of at least part effluent leaving the first reaction zone. This method also includes incomplete excretion of ammonia from effluent coming from the first zone. This selection it is advisable to carry out by means of an intermediate flash-heating. Hydrocracking occurring in the second reaction zone is carried out in the presence of ammonia in a quantity less than the quantity in the boot, preferably less than 1500 ppm wt., more preferably less than 1000 ppm wt., even more preferably below 800 ppm based on the nitrogen. The catalyst according to the present invention is preferably used in the reaction zone hydrocracking in combination with a Hydrotreating catalyst or without a disposable upstream from the catalyst according to the invention. The catalyst according to the invention can be used above or below the flow from the zeolite catalyst. If it is below from the zeolite catalyst is performed, in particular, the conversion of the NRA or their predecessors.

The catalyst according to the invention can be used either in the first reaction zone, in which there are pre-conversion, individually or in combination with classical Hydrotreating catalyst located upstream of the catalyst according to the invention, in one or more catalytic layers, in one or more reactors.

One method of hydrocracking with a preliminary Hydrotreating catalyst of low acidity

The catalyst according to the invention can be used in the method of hydrocracking, including:

the first reaction zone of the hydrotreatment, in which the load is in contact with at least one Hydrotreating catalyst, showing the standard test on the activity degree of conversion of cyclohexane is below 10 wt.%.

the second reaction zone hydrocracking, in which at least part effluent coming from the stage Hydrotreating, contacts, at least one zeolite hydrocracking catalyst, showing the standard test on the activity degree of conversion of cyclohexane, above 10 wt.%, moreover, the catalyst according to the invention is at least one of the two reaction zones.

A catalytic amount of catalyst for Hydrotreating ordinary who is 20-45% of the total catalytic volume.

Effluent leaving the first reaction zone, at least partially, preferably completely injected into the second reaction zone of this method. Intermediate separation of gas can be carried out as described above.

Effluent leaving the second reaction zone, is subjected to the so-called final separation (for example, by atmospheric distillation, possibly followed by distillation under vacuum) for separating gaseous products. Receive at least one liquid residual fraction containing mainly products boiling temperature which is usually higher than 340°C., which can at least partially be recycled upstream from the second reaction zone method according to the invention, preferably above hydrocracking catalyst based on aluminosilicate order to obtain middle distillates.

Conversion of obtaining products having a boiling point below 340°C or below 370°C is not less than 50 wt.%.

Dsuchstudies way

Two-stage hydrocracking includes the first stage, which, as in the way of "one-stage" is intended for Hydrotreating hydrocarbon loading, and also to achieve a conversion of this load up to about 40-60%. Effluent leaving the first stage is directed to the separation (distillation), called the controls most often as an intermediate division, which is aimed at separating the conversion products from the unconverted fraction. In the second stage of two-stage hydrocracking process unconverted in the first stage fraction. This separation makes the two-stage method of hydrocracking a more selective in respect of the middle distillate (kerosene + diesel) in comparison with the one-stage method. Thus, the intermediate separation of the conversion products eliminates the "super-cracking" to light fractions and gas to the second stage hydrocracking catalyst. However, it should be noted that the unconverted fraction of the load that is being processed in the second stage, contains a small number of NH3and nitrogen organic compounds, usually less than 20 ppm wt., and even less than 10 ppm wt.

This catalytic layer in the form of a stationary layer or fluidized bed can be used in the first stage, the so-called two-stage scheme, when the catalyst is used individually or in combination with classical Hydrotreating catalyst. The catalyst according to the invention can be used above or below the flow from the zeolite catalyst. Location below from zeolite catalyst allows, in particular, to implement the conversion NDA or predecessors of the NRA.

In ways, called one who tadenuma, and in the first stage of two-stage methods of the preferred hydrocracking catalysts according to the invention are promoted catalysts based on non-noble metals of group VIII, more preferably the catalysts based on Nickel and tungsten, and preferred the promoting element is phosphorus.

The catalysts used in the second stage of two-stage methods, hydrocracking, preferably are promoted catalysts based on noble metals of group VIII, more preferably the catalysts based on platinum and/or palladium, and the promoting element is preferably phosphorus.

The following examples illustrate the present invention without limiting its scope.

Examples

Example 1: retrieving the catalyst C1 is not relevant to the invention

The media And is an aluminosilicate, which has the following chemical composition by weight: Al2O360% and SiO240%. Attitude in him Si/Al is 0.6. The content of sodium is about 100-120 ppm wt. Extruded pellets are cylindrical in shape with a diameter of 1.6 mm, a Specific surface equal to 320 m2/g Total pore volume of the carrier measured by the method of mercury porometry equal 0,81 cm3/, bimodal pore Distribution. In the area of the mesopores nabludaetsa the maximum thickness of 4 to 15 nm with a maximum at 7 nm on the curve of pore distribution dV/dD, and the average diameter of pores is determined by the method of mercury porometry, is 105 Å. The volume of mesopores with a diameter of from 40 to 150 Å is 0.48 cm3/g and the volume is about 59% of the total pore volume. The volume of macropores in the media, the diameter of which is greater than 500 Å, 0,26 cm3/g, and this volume is 32% of the total pore volume. The volume of pores in the carrier, the diameter of which more than 250 Å, equal to 0.29 cm3/g, and this volume is about 36% of the total pore volume.

The catalyst C1 is obtained by dry impregnation of the carrier And having the form of extruded granules with the above characteristics, an aqueous solution comprising salts of tungsten and Nickel. Salt of tungsten is metabolomic ammonium (NH4)6H2W12O40·4H2O and Nickel salt is Nickel nitrate Ni(NO3)2·6H2O. After ripening at room temperature in an atmosphere saturated with water vapor, impregnated granules are dried at 120°C overnight, and then calcined at 500°C in an atmosphere of dry air. The final content of NiO is 3.5 wt.%. The final contents of WO325 wt.%.

Example 2: obtain the catalyst C2, is not relevant to the invention

The catalyst C2 is produced by soaking dry catalyst C1 solution containing Deborah ammonium [(NH4)2B4O7·4H2 O)] and a silicone oil emulsion Rhodorsil EP1 company Rhodia. After ripening at room temperature in an atmosphere saturated with water vapor, impregnated granules are dried at 120°C overnight, and then calcined at 500°C in an atmosphere of dry air. The final content of NiO is of 3.32 wt.%. The final contents of WO3is 23.7 wt.%. The final contents of the2About3is 3.2 wt.%. The final contents of the SiO2after the second impregnation is 2.1 wt.%.

Example 3: obtaining the catalyst C2, is not relevant to the invention

Catalyst C3 is produced by soaking dry catalyst C1 solution containing Deborah ammonium [(NH4)2B4O7·4H2O)]. After ripening at room temperature in an atmosphere saturated with water vapor, impregnated granules are dried at 120°C overnight, and then calcined at 500°C in an atmosphere of dry air. The final content of NiO is 3.4 wt.%. The final contents of WO3is of 24.25 wt.%. The final contents of the2About3is 3.2 wt.%.

Example 4: Obtaining catalyst C4, not relevant to the invention

Catalyst C4 is produced by soaking dry catalyst C1 silicone oil emulsion Rhodorsil EP1 company Rhodia. After ripening at room temperature in an atmosphere saturated with water vapor, p is upitannie granules are dried at 120°C during the night, then calcined at 500°C in an atmosphere of dry air. The final content of NiO is 3.4 wt.%. The final contents of WO3is of 24.25 wt.%. The final contents of the SiO2after the second impregnation is 2.1 wt.%.

Example 5: Receiving catalyst C5, corresponding to the invention of

The catalyst C5 is obtained by dry impregnation of the carrier And having the form of extruded granules with the above characteristics, an aqueous solution comprising salts of tungsten and Nickel and phosphorous acid, H3RHO4. Salt of tungsten is metabolomic ammonium (NH4)6H2W12O40·4H2O and Nickel salt is Nickel nitrate Ni(NO3)2·6H2O. After ripening at room temperature in an atmosphere saturated with water vapor, impregnated granules are dried at 120°C overnight, and then calcined at 500°C in an atmosphere of dry air. The final content of NiO is 3.5 wt.%. The final contents of WO325 wt.%. The final contents of the P2About5is 1.9 wt.%. Total pore volume of the catalyst, measured by the method of mercury porometry, is 0.45 ml/g Volume of pores with a diameter greater than 500 Å in the catalyst, measured by the method of mercury porometry, is 0.10 ml/g Volume of pores with a diameter above 250 Å in the catalyst, measured by the method of mercury porometry and, is 0.13 ml/year Indicator DRT is 0,808 g/cm3.

Example 6: obtain the catalyst C6, corresponding to the invention of

The catalyst C6 is produced by soaking dry catalyst C5 solution containing Deborah ammonium [(NH4)2B4O7·4H2O)] and a silicone oil emulsion Rhodorsil EP1 company Rhodia. After ripening at room temperature in an atmosphere saturated with water vapor, impregnated granules are dried at 120°C overnight, and then calcined at 500°C in an atmosphere of dry air. The final content of NiO is of 3.32 wt.%. The final contents of WO3is 23.7 wt.%. The final contents of the P2About5is 1.8 wt.%. The final contents of the2About3is 3.2 wt.%. The final contents of the SiO2after the second impregnation is 2.1 wt.%. Total pore volume of the catalyst, measured by the method of mercury porometry is of 0.44 ml/g Volume of pores with a diameter greater than 500 Å in the catalyst, measured by the method of mercury porometry, is 0.10 ml/g Volume of pores with a diameter above 250 Å in the catalyst, measured by the method of mercury porometry, is 0.13 ml/year Indicator DRT is 0.83 g/cm3.

Example 7: obtain a catalyst C7, corresponding to the invention of

The catalyst C7 is produced by soaking dry catalyst C5 solution provided is Deborah ammonium [(NH 4)2B4O7·4H2O)]. After ripening at room temperature in an atmosphere saturated with water vapor, impregnated granules are dried at 120°C overnight, and then calcined at 500°C in an atmosphere of dry air. The final content of NiO is 3.4 wt.%. The final contents of WO3is of 24.25 wt.%. The final contents of the P2About5is of 1.84 wt.%. The final contents of the2About3is 3.2 wt.%. Total pore volume of the catalyst, measured by the method of mercury porometry is of 0.44 ml/g Volume of pores with a diameter greater than 500 Å of the catalyst, measured by the method of mercury porometry, is 0.10 ml/g Volume of pores with a diameter higher than 250 Å, the catalyst was measured using mercury porometry, is 0.13 ml/year Indicator DRT is 0.82 g/cm3.

Example 8: obtain a catalyst C8 corresponding to the invention of

The catalyst C8 is produced by soaking dry catalyst C5 silicone oil emulsion Rhodorsil EP1 company Rhodia. After ripening at room temperature in an atmosphere saturated with water vapor, impregnated granules are dried at 120°C overnight, and then calcined at 500°C in an atmosphere of dry air. The final content of NiO is 3.4 wt.%. The final contents of WO3is 24 wt.%. The final contents of the P2About5was 1.82 wt.%. End the obsession SiO 2after the second impregnation is 2.1 wt.%. Total pore volume of the catalyst, measured by the method of mercury porometry is of 0.44 ml/g Volume of pores with a diameter greater than 500 Å of the catalyst, measured by the method of mercury porometry, is 0.10 ml/g Volume of pores with a diameter above 250 Å of the catalyst, measured by the method of mercury porometry, is 0.13 ml/year Indicator DRT is 0.81 g/cm3.

Example 9: Obtaining catalyst C9, is not relevant to the invention

The catalyst C9 obtained by dry impregnation of the carrier And having the form of extruded granules with the above characteristics, an aqueous solution comprising salts of tungsten and Nickel and phosphorous acid, H3RHO4. Salt of tungsten is metabolomic ammonium (NH4)6H2W12O40·4H2O and Nickel salt is Nickel nitrate Ni(NO3)2·6H2O. After ripening at room temperature in an atmosphere saturated with water vapor, impregnated granules are dried at 120°C overnight, and then calcined at 500°C in an atmosphere of dry air. The final contents of WO325 wt.%. The final content of NiO is 3.5 wt.%. The content of P2About5is 7 wt.%.

Example 10: obtain the catalyst C10 corresponding to the invention of

The catalyst C10 obtained by impregnation of OSHA media And having the form of extruded granules with the above characteristics, an aqueous solution comprising salts of tungsten and Nickel and phosphorous acid, H3RHO4. Salt of tungsten is metabolomic ammonium (NH4)6H2W12O40·4H2O and Nickel salt is Nickel nitrate Ni(NO3)2·6H2O. After ripening at room temperature in an atmosphere saturated with water vapor, impregnated granules are dried at 120°C overnight, and then calcined at 500°C in an atmosphere of dry air. The final content of NiO is 3.5 wt.%. The final contents of WO325 wt.%. The final contents of the P2About5is 0.6 wt.%. Total pore volume of the catalyst, measured by the method of mercury porometry is of 0.44 ml/g Volume of pores with a diameter greater than 500 Å of the catalyst, measured by the method of mercury porometry, is 0.10 ml/g Volume of pores with a diameter above 250 Å of the catalyst, measured by the method of mercury porometry, is 0.13 ml/year Indicator DRT is 0,808 g/cm3.

Example 11: obtain a catalyst C11 corresponding to the invention of

The catalyst C11 obtained by dry impregnation of the carrier And having the form of extruded granules with the above characteristics, an aqueous solution comprising salts of tungsten and Nickel and phosphorous acid, H3 RHO4. Salt of tungsten is metabolomic ammonium (NH4)6H2W12O40·4H2O and Nickel salt is Nickel nitrate Ni(NO3)2·6H2O. After ripening at room temperature in an atmosphere saturated with water vapor, impregnated granules are dried at 120°C overnight, and then calcined at 500°C in an atmosphere of dry air. The final content of NiO is 3.5 wt.%. The final contents of WO325 wt.%. The final contents of the P2About52.5 wt.%. Total pore volume of the catalyst, measured by the method of mercury porometry, is 0.45 ml/g Volume of pores with a diameter greater than 500 Å of the catalyst, measured by the method of mercury porometry, is 0.10 ml/g Volume of pores with a diameter above 250 Å of the catalyst, measured by the method of mercury porometry, is 0.13 ml/year Indicator DRT is 0.81 g/cm3.

Example 12: obtain the catalyst C12 corresponding to the invention of

The catalyst C11 obtained by dry impregnation of the carrier And having the form of extruded granules with the above characteristics, an aqueous solution comprising salts of tungsten and Nickel and phosphorous acid, H3RHO4. Salt of tungsten is metabolomic ammonium (NH4)6H2W12O40·4H2O and Nickel salt is Nickel nitrate Ni(NO )2·6H2O. After ripening at room temperature in an atmosphere saturated with water vapor, impregnated granules are dried at 120°C overnight, and then calcined at 500°C in an atmosphere of dry air. The final content of NiO is 3.5 wt.%. The final contents of WO325 wt.%. The final contents of the P2About5is 2.6 wt.%. Total pore volume of the catalyst, measured by the method of mercury porometry, is 0.46 ml/g Volume of pores with a diameter greater than 500 Å of the catalyst, measured by the method of mercury porometry, is 0.10 ml/g Volume of pores with a diameter above 250 Å of the catalyst, measured by the method of mercury porometry, is 0.13 ml/year Indicator DRT is 0.83 g/cm3.

Example 13: obtain the catalyst S13 corresponding to the invention of

The catalyst C11 obtained by dry impregnation of the carrier And having the form of extruded granules with the above characteristics, an aqueous solution comprising salts of tungsten and Nickel and phosphorous acid, H3RHO4. Salt of tungsten is metabolomic ammonium (NH4)6H2W12O40·4H2O and Nickel salt is Nickel nitrate Ni(NO3)2·6H2O. After ripening at room temperature in an atmosphere saturated with water vapor, impregnated granules are dried at 120°C overnight, then p is kaliwat at 500°C in an atmosphere of dry air. The final content of NiO is 3.5 wt.%. The final contents of WO325 wt.%. The final contents of the P2About5is 3.5 wt.%. Total pore volume of the catalyst, measured by the method of mercury porometry is of 0.44 ml/g Volume of pores with a diameter greater than 500 Å of the catalyst, measured by the method of mercury porometry, is 0.10 ml/g Volume of pores with a diameter above 250 Å of the catalyst, measured by the method of mercury porometry, is 0.13 ml/year Indicator DRT is 0.83 g/cm3.

Example 14: Obtaining catalyst C14 corresponding to the invention of

The media is an aluminosilicate, which has the following chemical composition by weight: Al2O370% and SiO230%. Attitude in him Si/Al is 0.37. The content of sodium is about 100 ppm wt. Extruded pellets are cylindrical in shape with a diameter of 1.6 mm, a Specific surface equal to 300 m2/g Total pore volume, measured by the method of mercury porometry equal to 0.7 cm3/, bimodal pore Distribution. In the area of mesopores there is a maximum thickness of 4 to 15 nm with a maximum at 7 nm on the curve of pore distribution dV/dD, and the average diameter of pores defined by the method of mercury porometry is 90 Å. The volume of mesopores with a diameter of from 40 to 150 Å is 0,51 cm3/g and the volume is about 72% of the total pore volume. The volume of the m macropores in the media, the diameter of which is greater than 500 Å, is 0.145 cm3/g and this amount is 20% of the total pore volume. The volume of pores in the carrier, the diameter of which more than 250 Å, equal to 0.17 cm3/g and the volume is about 24% of the total pore volume.

The catalyst C14 obtained by dry impregnation of the carrier, having the form of extruded granules with the above characteristics, an aqueous solution comprising salts of tungsten and Nickel and phosphorous acid, H3RHO4. Salt of tungsten is metabolomic ammonium (NH4)6H2W12O40·4H2O and Nickel salt is Nickel nitrate Ni(NO3)2·6H2O. After ripening at room temperature in an atmosphere saturated with water vapor, impregnated granules are dried at 120°C overnight, and then calcined at 500°C in an atmosphere of dry air. The final content of NiO is 3.5 wt.%. The final contents of WO325 wt.%. The final contents of the P2About5is 1.9 wt.%. Total pore volume of the catalyst, measured by the method of mercury porometry is of 0.44 ml/g Volume of pores with a diameter greater than 500 Å of the catalyst, measured by the method of mercury porometry, is 0.10 ml/g Volume of pores with a diameter above 250 Å of the catalyst, measured by the method of mercury porometry, is 0.13 ml/year Indicator DRT is 0.82 g/cm3.

Use the 15: Obtaining catalyst C15, corresponding to the invention of

The media is an aluminosilicate, which has the following chemical composition by weight: Al2O381% and SiO219%. Attitude in him Si/Al is 0.2. The content of sodium is about 100 ppm wt. Extruded pellets are cylindrical in shape with a diameter of 1.6 mm, a Specific surface equal to 300 m2/g Total pore volume, measured by mercury porometry equal to 0.61 cm3/, bimodal pore Distribution. In the area of mesopores there is a maximum thickness of 4 to 15 nm with a maximum at 7 nm on the curve of pore distribution dV/dD, and the average diameter of pores defined by the method of mercury porometry, 85 Å, the Volume of mesopores with a diameter of from 40 to 150 Å is 0.45 cm3/g and the volume is about 74% of the total pore volume. Macropores volume of the medium, the diameter of which is greater than 500 Å, is 0.10 cm3/g and this amount is 16% of the total pore volume. The pore volume of the carrier, the diameter of which more than 250 Å, equal to 0.13 cm3/g and the volume is about 21% of the total pore volume.

The catalyst 15 is obtained by dry impregnation of the carrier With having the form of extruded granules with the above characteristics, an aqueous solution comprising salts of tungsten and Nickel and phosphorous acid, H3RHO4. Salt of tungsten is metabolomic ammonium (NH4) 6H2W12O40·4H2O and Nickel salt is Nickel nitrate Ni(NO3)2·6H2O. After ripening at room temperature in an atmosphere saturated with water vapor, impregnated granules are dried at 120°C overnight, and then calcined at 500°C in an atmosphere of dry air. The final content of NiO is 3.5 wt.%. The final contents of WO325 wt.%. The final contents of the P2About5is 2 wt.%. Total pore volume of the catalyst, measured by the method of mercury porometry is 0.4 ml/g pore Volume of the catalyst with a diameter greater than 500 Å, measured by the method of mercury porometry, is 0.10 ml/g Volume of pores with a diameter above 250 Å of the catalyst, measured by the method of mercury porometry, is 0.13 ml/year Indicator DRT is 0.82 g/cm3.

The final mass of the contents of WO3, NiO, P2O5, SiO2and In2About3the catalysts are presented in table 1.

Table 1
Mass content of WO3, NiO, P2O5, SiO2and In2About3in the catalysts C1-C15
C1C2C3C4C5C7C8
NiO(wt.%)3,53,323,43,363,53,323,43,36
WO3(wt.%)2523,724,25242523,724,2524
P2O5(wt.%)00001,91,81,841,82
In2About3(wt.%)03,23,2003,23,20
SiO2(wt.%) printed on the media0 2,102,002,102,1

C9C10C11C12C13C14C15
NiO(wt.%)3,53,53,53,53,53,53,5
WO3(wt.%)25252525252525
P2O5(wt.%)70,62,52,63,51,92
In2About3(wt.%)0 000000
SiO2(wt.%) printed on the media0000000

Example 16: Evaluation of catalysts C1-C15

Catalysts C1-C15, which are described in examples 1-15, is used for the hydrocracking of a vacuum distillate, the main characteristics of which are given below:

Nature downloadVacuum distillate
Density at 20°C0,904
Sulfur, wt.%2,2
Nitrogen ppm wt.620
Model distillation
MD: initial temperature °C345
MD: 05 wt.% °C368
MD: 10 wt.% °C375
MD: 50 wt.% °C402
MD: 90 wt.% °C428
MD: the final temperature °C467

Catalysts C1-C15 used in accordance with the method according to the invention on a pilot plant containing 1 reactor with a porous layer with cross-directional flow, streams circulate from bottom to top (up-flow).

Before test hydrocracking catalysts were subjected to sulfonation at a pressure of 140 bar and a temperature of 350°C using gasoil direct distillation, to which is added 2% DMDS.

After sulphurization of the catalytic tests were carried out under the following conditions:

The total pressure14 MPaT=400°C

The spatial velocity (VVH)of 0.65 h-1

Catalytic properties expressed in a net conversion of forming products having a boiling point of below 380°C, a net selectivity in respect of the middle distillate fraction 150-380°With respect to the output of gasoil/ output of kerosene in the faction of the middle distillate. These characteristics revealed the stone results obtained on the model of distillation.

Net conversion (CN) has been taken equal to:

CN 380°C=[(% of 380°C-affluent)-(% 380°C-download)]/[100-(% 380°C-download)],

where % 380°C-affluent= mass content of compounds having a boiling point of below 380°C, affluence,

% 380°C-download= mass content of compounds having a boiling point of below 380°C. in the download.

The gross selectivity for middle distillate (SB) has been taken equal to:

SB definition = [(fraction of 150-380affluent)]/[(% 380°C-affluent)]

Table 2
The results of single-stage catalytic hydrocracking at high pressure
CatalystThe temperature at 80%net conversionSB wt.% middle distillate (DM)The Ratio Of Th./Coeur. wt.%/wt.%
C1398691,50
C2(BSi)394691,40
C3(B)396 691,45
C4(Si)396691,47
C5(P)39270,51,50
C6(PBSi)38870,51,40
C7(PB)39070,51,45
C8(PSi)39070,51,47
C9(P)398691,47
C10(P)39270,51,50
C11(P)39270,51,50
C12(P)394691,45
C13(P)394691,40
C1439270,51,50
C15396691,45

Identify the benefits associated with the use of phosphorus as promoting

It is interesting to note that the catalysts C3 and C4, which contain, respectively, only boron and only silicon as the promoting element have selectivity for middle distillates is lower than the catalyst C5 containing only phosphorus as the promoting element. In addition, the fraction of middle distillates attitude Gasoil/Kerosene lower than the ratio obtained with the catalyst C5.

However, when using catalyst C2, which contains a combination of boron and silicon, the observed decrease of the ratio of gasoil/kerosene and, consequently, a decrease in the selectivity for gasoil in middle distillates compared to a catalyst containing phosphorus.

Thus, the results of the study of catalysts show that the catalyst C5 on the media from a special aluminum silicate according to the invention, in the composition of the active phase of which is set according to the invention the amount of phosphorus shows high convert the th activity and mainly high selectivity for middle distillates. In addition, the fraction of middle distillates get high gasoil/kerosene. This means that the catalyst C5 is a selective primarily to the oil of the middle distillates. Therefore, the catalyst C5 is selective to the middle distillates, and mainly to the gasoil fraction, in which particularly interested manufacturers. Characteristics of catalyst C5 associated with extreme acidity of the catalyst C5, which is printed on a special silica-alumina carrier. Thus, the use of silicate as a carrier has special advantages for obtaining highly active catalysts for hydrocracking, which is the high selectivity to middle distillates.

Consequently, the use of phosphorus as the promoting element is preferable to use boron, silicon, and use a combination of boron/silicon.

It should be emphasized that the catalysts C6, C7 and C8, obtained on the basis of catalyst C5 adding, respectively, In, Si, B and Si, have improved activity compared to catalyst C5. The selectivity to middle distillates they are identical, however, the catalysts C6, C7 and C8 attitude gasoil/kerosene is slightly different from the same ratio in the catalyst C5. When increasing the activity of these catalysts decrease the relationship gasoil/kerosene and therefore, the reduction of selectivity in respect of oil in middle distillates, which is the target fraction, compared with a catalyst having a low content of phosphorus.

Identify the benefits of using a catalyst with a limited content of phosphorus

Table 2 shows the selectivity to middle distillates (70,5 wt.%), as well as a higher gasoil/kerosene (1,5) catalysts C5, C10 and C11 according to the invention with respect to the catalysts C12 and C13, which themselves contain only phosphorus and, therefore, correspond to the invention.

This implies that these catalysts C5, C10 and C11, in which the phosphorus content is in the preferred range from 0.01% to 2.5 wt.% in the calculation of the oxide promoting item, show superior catalytic properties and are best suited for the production of middle distillates in accordance with the purpose of the invention.

In addition, the results of the test catalyst C9 show the deterioration of the conversion, if the content of phosphorus in the catalyst (7 wt.% P2About5) does not correspond to the invention.

Identify the benefits of using a catalyst in which the carrier contains silicon oxide in the specified range

Table 2 shows that the catalysts in which the medium contains silicon oxide in quantity is as, selected from a range between a value above 25% and below 50%, has an improved catalytic properties from the point of view of selectivity and relationships gasoil/kerosene and, therefore, very well suited for the production of middle distillates in accordance with the purpose of the invention.

1. The catalyst containing at least one hydro-dehydrogenase element selected from the group formed by the elements of group VIB and group VIII of the Periodic system of elements, 0.6 to 2.5% phosphorus, with the specified catalyst has a total pore volume, measured by the method of mercury porometry, 0,35-of 0.74 ml/g and neoreality based media aluminosilicate having the following characteristics:
the percentage of silicon oxide 5-95 wt.%
the sodium content below 0.03%and
total pore volume, measured by the method of mercury porometry, 0,45-to 0.96 ml/g, '
porosity, in which:
i) the volume of mesopores with a diameterand with an average pore diameter of
is 40-70% of the total pore volume, measured by the method of mercury porometry;
ii) the volume of macropores with a diameter aboveis 30-60% of the total pore volume, measured by the method of mercury porometry;
specific surface area by BET is 100-550 m2/g
diffraction pattern in x-rays, which contains, at the ore, the main characteristic bands at least one of aluminum silicates transitional modification, a member of the group consisting of aluminosilicates alpha, Rho, XI, ETA, gamma, Kappa, theta and Delta modification.

2. The catalyst according to claim 1, in which the percentage of silica necessarily above 25% and below 50%.

3. The catalyst according to claim 2, in which the percentage content of silicon oxide is necessarily higher than 25% and less than 42%.

4. The catalyst according to one of claims 1 to 3, in which the total pore volume of the catalyst, measured by the method of mercury porometry, is 0.4-0.6 ml/year

5. The catalyst according to one of claims 1 to 3, in which the density of pressing above 0.7 g/cm3.

6. The catalyst according to one of claims 1 to 3, in which the phosphorus content is 0.01-4 wt.% in the calculation of the oxide.

7. The catalyst according to claim 6, in which the phosphorus content is 0.01-2.5 wt.% in the calculation of the oxide.

8. The catalyst according to one of claims 1 to 3 or 7, which also contains boron and/or silicon.

9. The catalyst according to one of claims 1 to 3 or 7 on the basis of molybdenum and tungsten.

10. The catalyst according to one of claims 1 to 3 or 7 on the basis of Nickel and tungsten.

11. The catalyst according to one of claims 1 to 3 or 7, in which the proportion of octahedral AlVIdetermined by the spectra of solid-state NMR MAS27Al, above 50%.

12. The catalyst according to one of claims 1 to 3 or 7, in which the aluminosilicate sod is RIT 30-50% of structural fragments Q 2in which the Si atom is linked to two atoms of Si or Al and two OH groups, and also contains 10-30% of structural fragments Q3in which the Si atom is linked to three atoms of Si or Al or one OH group.

13. The catalyst according to one of claims 1 to 3 or 7, in which the carrier is made of aluminum silicate.

14. The catalyst according to one of claims 1 to 3 or 7, in which the medium contains 1-40 wt.% the binder.

15. The catalyst 14 in which the carrier is a product of mixing of silicate and at least one binder selected from the group formed by silicon oxide, aluminum oxide, clay, titanium oxide, boron oxide and zirconium oxide.

16. The catalyst according to one of claims 1 to 3, 7 or 15, in which the carrier has a porosity, in which the volume of pores with a diameter aboveis not less than 30% of the total pore volume.

17. The catalyst according to one of claims 1 to 3, 7 or 15, which contains at least one element of group VIIB.

18. The catalyst according to one of claims 1 to 3, 7 or 15, which contains at least one element of group VB.

19. The catalyst according to one of claims 1 to 3, 7 or 15, in which a diffraction pattern in x-rays contains at least the main characteristic bands at least one of aluminum silicates transition modification selected from the group consisting of aluminosilicates this, te is a, Delta and gamma modification.

20. The catalyst according to one of claims 1 to 3, 7 or 15, in which the surface of the BET is 150-500 m2/year

21. The catalyst according to one of claims 1 to 3, 7 or 15, in which the carrier includes at least two silica-alumina zones, having a ratio Si/Al higher or lower than the General relations Si/Al, determined by x-ray fluorescence.

22. The catalyst according to one of claims 1 to 20, in which the medium contains only one aluminosilicate zone having a ratio Si/Al equal to the total ratio Si/Al, determined by x-ray fluorescence and having a value below a 2.3.

23. The catalyst according to one of claims 1 to 3, 7 or 15, containing a small amount of at least one promoting element selected from the group formed by zirconium oxide and titanium oxide.

24. The catalyst according to one of claims 1 to 3, 7 or 15, subjected sulfureuse processing.

25. The catalyst according to one of claims 1 to 3, 7 or 15, subjected to hydrothermal processing.

26. Method of hydrocracking/hydroconversion hydrocarbon download using the catalyst according to one of claims 1 to 25.

27. Method of hydrocracking/hydroconversion on p carried out according to the method, called one-step.

28. Method of hydrocracking/hydroconversion on p, including at least one first reaction zone of the hydrotreatment and at least one second reaction zone, including hydrocracking, at least part effluent coming from the first zone and including an incomplete separation of ammonia from effluent coming from the first zone.

29. Method of hydrocracking/hydroconversion one of p or 28, including:
the first reaction zone of the hydrotreatment, in which the load is in contact with at least one Hydrotreating catalyst, showing the standard test activity, the degree of conversion of cyclohexane, below 10 wt.%.
the second reaction zone hydrocracking, in which at least part effluent coming after Hydrotreating, contacts, at least one zeolite hydrocracking catalyst, showing the standard test activity, the degree of conversion of cyclohexane, above 10 wt.%.

30. Method of hydrocracking/hydroconversion on p carried out according to the method, called two-stage.

31. The method according to one of p or 28, which is carried out in the presence of hydrogen at temperatures above 200°C and pressures above 1 MPa, while the spatial velocity is 0.1-20 h-1and the amount of hydrogen such that the volume ratio of 1 l of hydrogen/1 liter of hydrocarbon was 80-5000 l/l

32. Method of hydrocracking/hydroconversion one of p or 28, which is carried out at a pressure of 2 to 6 MPa and achieve the conversions below 40%.

33. The method according to one of p or 28, carried out with a fixed layer.

34. The method according to one of p or 28 carried fluidized bed.

35. How hydrobromide hydrocarbon download using the catalyst according to one of claims 1 to 25.

36. The method according to p, included upstream method of hydrocracking.

37. The method according to p, which use the hydrocracking catalyst based on Nickel and tungsten.

38. The method according to p, in which hydrocarbons are selected from the group which consists of LCO (light oils coming from catalytic cracker), products of the atmospheric distillation products of vacuum distillation, the products coming from plants extraction of aromatic compounds from bases for lubricating oils or leaving after dewaxing solvent bases for lubricating oils, distillates, coming after methods desulfuromonas or hydroconversion in a fixed or fluidized bed of the RAT (the remains of the atmospheric distillation) and/or RSV (vacuum residues) and/or deasphalting oils, DisasterRecovery oils, alone or as a mixture.

39. The method according to p, in which the pre-loading is passed through a bed of the catalyst or adsorbent that is different from the catalyst hydrocracking/hydroconversion or hydrobromide.

40. The method according to clause 37, in which carbohydrate is the same raw materials are selected from the group which includes LCO (light oils coming from catalytic cracker), products of the atmospheric distillation products of vacuum distillation, the products coming from plants extraction of aromatic compounds from bases for lubricating oils or leaving after dewaxing solvent bases for lubricating oils, distillates, coming after methods desulfuromonas or hydroconversion in a fixed or fluidized bed of the RAT (the remains of the atmospheric distillation) and/or RSV (vacuum residues) and/or deasphalting oils, DisasterRecovery oils, alone or as a mixture.

41. The method according to clause 37, in which the pre-loading is passed through a bed of the catalyst or adsorbent that is different from the catalyst hydrocracking/hydroconversion or hydrobromide.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: mould catalyst for hydrocracking contains at least zeolite Y and inorganic high-melting oxide with monomodal pores distribution (by mercury porosimetre) whereat at least 50% of total volume is represented with pores having diametre in the range from 4 to 50 nm and the volume at least 0.4 ml/g. The method for carrier preparation and the carrier obtained with this method are described; the said method includes moulding of the mixture containing at least zeolite Y and high-melting oxide with calcinations losses in the range (LIR) from 55 to 75%. The catalytical composition for hydrocracking includes said carrier, at least one component of hydrogenating metal selected from the metal of groups V1B and group V111 and optionally at least one promoting element selected from silicon boron in the case when carrier virtually does not contain the alumosilicate zeolite. The method for catalytical composition preparation and composition obtained with this method are described; the said method includes optional calcinations of the said carrier, precipitation of the at least one hydrogenating metal selected from described above ones in the corresponding amount; the said precipitation is carried out by impregnation with solution containing organic compound having at least two functional groups selected from carboxyl, carbonyl and hydroxyl groups. The hydrocracking method with application of the aforementioned catalytical composition is described.

EFFECT: enhancing of the catalytical composition activity, selectivity and hydrogenation ability.

18 cl, 5 tbl

FIELD: chemistry.

SUBSTANCE: invention refers to method of aromatic compound and olefin hydrogenation in hydrocarbon flows. Method concerns hydrogenation of incoming hydrocarbon flow containing unsaturated components, which involves: a) formation of the catalyst including at least one metal of group VIII on noncrystalline mesoporous inorganic oxide support with at least 97 vl % of interconnected mesopores in relation to mesopores and micropores with "БЭТ" surface area at least 300 m2/g and pore space at least 0.3 cm3/g; and b) interaction of incoming hydrocarbon flow and hydrogen with the specified catalyst added in reaction hydrogenation zone in hydrogenation environment to make product with lowered content of unsaturated components. Herewith hydrogenation conditions include hourly volume liquid velocity (HVLV) within approximately more than 0.33 h-1 to approximately 10.0 h-1 and hydrogen circulation rate within approximately 500 SCF/barrel to approximately 20000 SCF/barrel.

EFFECT: development of effective method of aromatic compound and olefin hydrogenation in hydrocarbon flows.

23 cl, 14 ex, 2 tbl

FIELD: petroleum processing.

SUBSTANCE: invention consists in that petroleum stock is brought into contact with hydrogen-containing gas at elevated temperature and pressure in presence of catalyst, said petroleum stock being secondary-process gas oils containing no less than 50 wt % of aromatic hydrocarbons. Process is carried out in a system of reactors with separated reaction zones filled with nickel-tungsten or nickel-molybdenum catalyst in sulfide form. At least 30 vol % of hydrogen is supplied to be mixed with petroleum stock and the rest of hydrogen is distributed in 12-21 reaction zones of reactors. Desired product recovered is fraction boiling within a boiling range 190 to 280°C. Process parameters: temperature 330-450°C, pressure 26-30 MPa, volumetric flow rate 0.3-1.0 h-1, and hydrogen-to-petroleum stock 1500-3000 nm3/m3.

EFFECT: simplified process flowsheet and improved performance characteristics of product.

2 cl, 3 ex

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

The invention relates to a method for producing a catalyst composition comprising bulk catalyst particles containing at least one base metal of group VIII and at least two metals of group VIB, including the integration and interaction of at least one component made of base metal of group VIII with at least two components of metals of group VIB in the presence of proton fluid, and at least one metal component remains at least partly in the solid state throughout the method, where the metals of groups VIII and VIB range from about 50 to about 100 wt.% in terms of oxides, of the total weight of the specified volume of the catalytic particles, and the solubility of the component metals of these groups, which are at least partly in the solid state during the reaction, is less than 0.05 mol/100 ml water at 18aboutWith

FIELD: chemistry.

SUBSTANCE: invention relates to a catalyst for converting hydrocarbons, which contains zeolite, method of making said catalyst and method of converting hydrocarbon petroleum products on the catalyst. The zeolite-containing catalyst for converting hydrocarbons, which contains zeolite, heat resistant inorganic oxide and optionally clay, is distinguished by that, the said zeolite has MFI structure, which contains phosphorous and transition metals, or a mixture of said zeolite with MFI structure, containing phosphorous and transition metals, with macroporous zeolite, which contains 75 to 100 wt % of the said zeolite with MFI structure in terms of mass of the mixture, containing phosphorous and transition metals, and 0 to 25 wt % macroporous zeolite; wherein the said zeolite with MFI structure, containing phosphorous and transition metals, in terms of mass of oxide, has the following chemical formula without taking water into account: (0 to 0.3)Na2O·(0.03 to 5.5)Al2O3·(1.0 to 10)P2O5·(0.7 to 15)M1xOy·(0.01 to 5)M2mOn·(0.5 to 10)RE2O3·(70 to 97)SiO2 I or (0 to 0.3)Na2O·(0.3 to 5)Al2O3·(1.0 to 10)P2O5·(0.7 to 15)MpOq·(0.5 to 10)RE2O2·(70 to 98)SiO2 II in which M1 is a transition metal, which is chosen from Fe, Co and Ni, M2 is a transition metal, which is chosen from Zn, Mn, Ga and Sn, M is a transition metal, which is chosen from Fe, Co, Ni, Cu, Zn, Mo or Mn, and RE is a rare-earth metal; x is equal to 1 or 2, where if x equals 1, y equals half the valency of transition metal M1, and when x equals 2, y equals valency of transition metal M1; m equals 1 or 2, when m equals 1, n equals half the valency of transition metal M2, and when m equals 2, n equals valency of transition metal M2; p equals 1 or 2, when p equals 1, q equals half the valency of transition metal M, and when p equals 2, q equals valency of transition metal M; the catalyst also contains an auxiliary component, one or more of which are chosen from a group consisting of IVB group metals, group VIII base metals and rare-earth metals of the period table of elements; in terms of catalyst mass, the said catalyst contains 1 to 60 wt % zeolite, 0.1 to 10 wt % auxiliary component of the catalyst, 5 to 98 wt % heat resistant inorganic oxide and 0 to 70 wt % clay in form of oxides. The method of preparing the catalyst involves mixture and suspension of all or part of the heat resistant inorganic oxide and/or its precursor, water and optionally clay, addition of zeolite and drying the obtained suspension, addition of auxiliary compound before addition of zeolite and before or after addition of clay, addition of acid to establish pH of the suspension equal to 1 to 5, ageing at 30 to 90°C for 0.1 to 10 hours and addition of the remaining heat resistant inorganic oxide and/or its precursor after ageing.

EFFECT: obtained catalyst has high activity and stability and is highly capable of converting petroleum hydrocarbons with high output of propylene, ethylene and lower aromatic hydrocarbons.

20 cl, 24 ex, 5 tbl

The invention relates to the refining of oil, in particular, to the hydrofining of petroleum fractions

The invention relates to a method for the catalytic dewaxing of lubricating oils

The invention relates to a method of hydrocracking a hydrocarbon feedstock with the aim of obtaining basic component of the lubricating oil

The invention relates to the refining, in particular, to methods for nitrosative oils, hydraulic fluids, diesel and aviation fuels

FIELD: chemistry.

SUBSTANCE: claimed invention relates to catalyst of olefin monomers trimerisation. Described is catalytic composition for olefin monomers trimerisation, which contains a) source of chrome, molybdenum or tungsten; b) ligand if general formula (I), in which X stands for bivalent organic group, selected from substituted or non-substituted alkylene groups, in case of substituted groups, substituents represent hydrocarbon groups; R1 and R3 represent cycloaromatic groups, which do not contain polar substituents in none of orto-positions; R2 and R4 are independently selected from obligatory substituted cycloaromatic groups, each of R2 and R4 having polar substituent in at least one orto-position; and c) cocatalyst. Also described is method of olefin monomers trimerisation, including interaction of at least one olefin monomer in conditions of trimerisation reaction with said above catalytic composition.

EFFECT: selective obtaining 1-hexagen from ethylene, reducing level of formation of by-products, especially C10.

10 cl, 2 tbl, 12 ex

FIELD: chemistry.

SUBSTANCE: invention relates to the catalyst for synthesising the 2- and 4-picolines, method for its producing and the method for producing the 2- and 4-picolines. The catalyst which can be used in synthesis of 2- and 4-picolines containing the heteropolyacid from the group containing the silicon tungsten acid, phosphorus tungsten acid and the vanadium tungsten acid applied upon the silica gel substrate with the particles size of 6-14 mesh, is described. The method for producing the catalyst is also described, which includes the dissolution of heteropolyacid in distilled water, stirring the obtained mixture with the needed amount of the silica gel to obtain the suspension; mixing the suspension till even impregnation, air drying the suspension at 200-250°C up to 1.5 hour; following heating the suspension at 300 to 400°C within 0.5 to 1.5 hours and cooling the obtained product till the room temperature in the exiccator to obtain the needed catalyst. The method for producing the of 2- and 4-picolines is described which includes the interaction of acetaldehyde and ammonium hydrate at heating in presence of the said catalyst.

EFFECT: stable highly selective and active catalyst is available.

14 cl, 3 ex

FIELD: petrochemical processes and catalysts.

SUBSTANCE: invention concerns catalytic process for obtaining isooctane fractions via alkylation of isobutane with butylene fractions. Process involves catalytic complex having following composition: MexOy*aAn-*bCnClmH2n+2-m, wherein Me represents group III-IV metal, x=1-2, y=2-3, and An- anion of oxygen-containing acid selected from sulfuric, phosphoric, molybdenic, and tungstenic acid, or mixture thereof in any proportions; a=0.01-0,2, b=0.01-0.1; bCnClmH2n+2-m is polychlorine-substituted hydrocarbon with n=1-10 and m=1-22, dispersed on porous support and containing hydrogenation component. Alkylation process is carried out at temperature not exceeding 150°C, mass flow rate of starting mixture not higher than 3 g/g cat*h, pressure not higher than 40 atm, and in presence of 10 mol % hydrogen.

EFFECT: increased catalyst stability and selectivity.

5 cl, 3 tbl, 20 ex

FIELD: petrochemical processes and catalysts.

SUBSTANCE: invention provides catalyst composed of heteropolyacid: phosphorotungstic acid and/or phosphoromolybdenic acid, at least one precious metal deposited on essentially inert inorganic amorphous or crystalline carrier selected from group including titanium dioxide, zirconium dioxide, aluminum oxide, and silicon carbide, which catalyst retains characteristic structure of heteropolyacid confirmed by oscillation frequencies of the order 985 and 1008 cm-1 recorded with the aid of laser combination scattering spectroscopy and which has specific surface area larger than 15 m2/g, from which surface area in pores 15 Å in diameter is excluded. Method of converting hydrocarbon feedstock containing C4-C24-paraffins in presence of above-defined catalyst is likewise described.

EFFECT: increased catalyst selectivity and enhanced hydrocarbon feedstock conversion.

5 cl, 7 tbl, 7 ex

FIELD: petrochemical process catalysts.

SUBSTANCE: invention relates to catalytic methods of isomerizing n-paraffins and provides catalyst constituted by catalytic complex of general formula MexOy*aAn-*bCnXmH2n+2-m, where Me represents group III and IV metal, x=1-2, y=2-3, An- oxygen-containing acid anion, a=0.01-0.2, b=0.01-0.1; CnXmH2n+2-m is polyhalogenated hydrocarbon wherein X is halogen selected from a series including F, Cl, Br, I, or any combination thereof, n=1-10, m=1-22, dispersed on porous carrier with average pore radius at least 500 nm and containing hydrogenation component. Method of preparing this catalyst is also disclosed wherein above-indicated catalytic complex is synthesized from polyhalogenated hydrocarbon CnXmH2n+2-m wherein X, n, and m are defined above, group III and IV metal oxide, and oxygen-containing acid anion, and dispersed on porous carrier with average pore radius at least 500 nm, hydrogenation component being introduced either preliminarily into carrier or together with catalytic complex. Process of isomerizing n-paraffins utilizing above-defined catalyst is also described.

EFFECT: lowered isomerization process temperature and pressure and increased productivity of catalyst.

17 cl, 3 tbl, 25 ex

FIELD: petrochemical process catalysts.

SUBSTANCE: invention relates to catalytic methods of isomerizing n-butane into isobutane and provides catalyst constituted by catalytic complex of general formula MexOy*aAn-*bCnXmH2n+2-m, where Me represents group III and IV metal, x=1-2, y=2-3, An- oxygen-containing acid anion, a=0.01-0.2, b=0.01-0.1; CnXmH2n+2-m is polyhalogenated hydrocarbon wherein X is halogen selected from a series including F, Cl, Br, I, or any combination thereof, n=1-10, m=1-22, dispersed on porous carrier with average pore radius at least 500 nm and containing hydrogenation component. Method of preparing this catalyst is also disclosed wherein above-indicated catalytic complex is synthesized from polyhalogenated hydrocarbon CnXmH2n+2-m wherein X, n, and m are defined above, group III and IV metal oxide, and oxygen-containing acid anion, and dispersed on porous carrier with average pore radius at least 500 nm, hydrogenation component being introduced either preliminarily into carrier or together with catalytic complex. Process of isomerizing n-butane into isobutane utilizing above-defined catalyst is also described.

EFFECT: lowered butane isomerization process temperature and pressure and increased productivity of catalyst.

13 cl, 1 tbl, 24 ex

The invention relates to a method of continuous hydration of ethylene, propylene or mixtures thereof with water in the vapor phase to the corresponding alcohols in the presence of salts heteroalicyclic as a catalyst at a molar ratio of water to olefin passing through the reactor, in the range of 0.1 to 3.0, an average hourly rate of gas supply water/olefin through the catalytic system 0,010 - 0.25 g/min/cm3concentrations of heteroalicyclic 5 to 60 wt.% from the total mass of the catalytic system, at a temperature of 150 - 350oC and a pressure ranging from 1000 to 25000 kPa

The invention relates to a catalyst based on aluminum, which contains, calculated on the weight content of the oxide 2-10 wt.% of cobalt oxide COO, 10-30 wt.% molybdenum oxide of Moo3and 4-10 wt.% oxide of phosphorus P2ABOUT5with a surface area by BET method in the range of 100 - 300 m2/g crushing strength CSH more than 1.4 MPa and an average diameter of pores in the range of 8-11 nm, the volume of pores of diameter greater than 14 nm is less than 0.08 ml/g, volume of pores with a diameter of less than 8 nm is not more than 0.05 ml/g and a volume of pores with a diameter of 8 to 14 nm in the range 0,20 - 0,80 ml/g

The invention relates to catalysts and methods of hydroperiod of crude oil
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