Zeolite catalysts with controlled content of promoter element and improved method of processing hydrocarbon fractions

FIELD: chemistry.

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

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

28 cl, 4 tbl, 21 ex

 

The technical field to which the invention relates

The present invention relates to promoted catalysts on substrates based on silica-alumina matrix and based on zeolite Y, defined constantathe unit cell of the crystal lattice component from 24,40·10-10m to 24,15·10-10m, and to a method of hydrocracking, hydroconversion and Hydrotreating, in which they are used.

The objective of the method is mainly obtain middle distillates, i.e. fractions with an initial boiling point of at least 150°C and end, reaching values of initial boiling point residue, for example, below 340°C or 370°C.

Prior art

The hydrocracking of heavy petroleum fractions is a very important cleaning method, which produces excessively heavy and low fractions of lighter fractions such as gasoline, jet fuel and light gas oils, which makes the owners of oil companies to adapt their production to the structure of the query. Some of the ways hydrocracking allow you to get highly purified residues, which can be an excellent basis for oils. Compared to catalytic cracking benefit from catalytic hydrocracking is receiving environments is their distillates, jet fuel and gas oil of very good quality. On the contrary, the resulting gasoline has a much lower octane number than the gasoline produced by catalytic cracking.

Hydrocracking is a way that attracts the flexibility of its three main components: applied operating conditions, the types of catalysts and the fact that the hydrocracking of hydrocarbon fractions can be implemented in one or two stages.

The hydrocracking catalysts used in hydrocracking processes, can be any bifunctional catalysts of the type combining an acid function with a hydrogenating function. The acid function are the substrate, the surface of which varies generally from 150 to 800 m2/g and which have a surface acidity, such as halogenated aluminum oxide (in particular chlorinated or fluorinated), combinations of oxides of boron and aluminium, amorphous aluminosilicates and zeolites. Hydrogenating function are one or more metals of group VIII of the Periodic system of elements, or a combination of at least one metal of group VIB of the Periodic system with at least one metal of group VIII.

The balance between these two, acid and hydrogenating functions is one of the parameters that control the activity and selectionist the Yu catalyst. A weak acid function and a strong hydrogenating function give low activity catalysts, operating typically at elevated temperatures (greater than or equal to 390-400°C) and low bulk feed speed (VVH expressed in workload for processing per unit volume of catalyst per hour, usually less than or equal to 2), but give a very good selectivity for middle distillates. Conversely, a strong acid function and a weak hydrogenating function give active catalysts, but with less good selectivity for middle distillates (jet fuel and gasoil).

One type of conventional hydrocracking catalysts are catalysts based on amorphous, moderately acidic substrates, such as aluminosilicates. These systems are used to obtain middle distillates good quality and possibly base oils. These catalysts are used, for example, in two-stage processes.

The behavior of these catalysts is closely related to their physico-chemical characteristics and, in particular, with their textural characteristics. So, generally speaking, the presence of macropores in the catalyst containing the aluminosilicate (as described, for example, in patent US 5370788) is a disadvantage. Under the macropores are defined as pores with a diameter greater than 500 Å. Advantageous to increase the density of filling of Katalizator is, in order to improve their catalytic properties. In this regard beneficial to use catalysts with a small full time. This way when the same total volume of pores get the best catalytic activity.

Also, the behavior of the catalysts is closely correlated with their structure, amorphous or crystalline. With regard to catalysts containing a zeolite or mixture of zeolites, they have a higher catalytic activity than the catalysts with amorphous silicates, but have a higher selectivity for light products.

Although good performance can be obtained with improved textural characteristics, the behavior of these catalysts is also associated with nature hydrogenating phase. Thus, the hydrogenating activity will play a role in the reactions hydrodesulphurization (HDS), gidrogenizirovanii (HDN), hydrodearomatization (HDA) and affect the stability of the catalyst.

In an effort to resolve these problems, the applicant has discovered, and in an unexpected way, that the introduction of a matrix with a low content of macropores certain zeolites, alone or together with components with improved hydrogenating function provide a catalyst exhibiting improved catalytic performance in hydrocracking processes. The applicant has unexpectedly found that the addition of controlling the constituent (adjustable) content promoting elements in the catalysts, with such texture characteristics, leads to unexpected catalytic performance in the hydrocracking/hydroconversion and Hydrotreating.

More precisely, the invention relates to promoted hydrocracking catalyst on the substrate based on zeolite Y, defined constantathe unit cell of the crystal lattice component from 24,40·10-10m to 24,15·10-10m, and based on the aluminosilicate matrix with reduced content of macropores, and to a method of hydrocracking/hydroconversion and Hydrotreating, in which it is used.

Characterization methods

In the further description of the invention under the specific surface area refers to the specific surface according to BET, determined by nitrogen adsorption according to ASTM D 3663-78, based on the method of brunauer-Emmett-teller described in the journal "The Journal of American Society", 60, 309, (1938).

In the further description of the invention under the volume on mercury substrates and catalysts refers to the volume measured by the mercury method of porosimetry by pushing ASTM D4284-83 at a maximum pressure of 4000 bar, when using the surface tension of 484 Dyne/cm and a contact angle of 140° to amorphous silica-alumina substrates. The average diameter of mercury is defined as such a diameter that all pores with a size smaller than this diameter constitute 50% of the pore volume (Vsub> Hg), in the range of 36' up to 1000'. One of the reasons why it is preferable to use the substrate as a basis to determine the distribution of the pores, is that the contact angle of mercury changed after impregnation of the metals, and depending on the nature and type of metals. The contact angle is assumed equal to 140°, following the recommendations of the work "Techniques de l ingénieur, traité analyse et caractérisation (Engineering methods, processing, analysis and characterization)", P. 1050-5, authors Jean Charpin and Bernard Rasneur.

To get the best accuracy, the volume of mercury in ml/g, the following text corresponds to the value of the full volume of mercury (total pore volume, measured by the indentation on mercury porosimetry) in ml/g, measured on the sample, minus the value of the amount of mercury in ml/g, measured on the same sample at a pressure corresponding to 30 pounds per square inch (about 2 bar). The average diameter of mercury can also be defined as such diameter that all pores smaller than this diameter constitute 50% of the total pore volume by mercury.

Finally, to better oharakterizovat a pore distribution, determined by the following criteria of pore distribution on mercury: the volume V1 that corresponds to the volume contained in pores with a diameter less than the average diameter minus 30 Å. Volume V2 corresponds to the volume contained in pores of diameter greater than or equal to the average is yameru minus 30 Å and smaller mean diameter plus 30 Å. Volume V3 corresponds to the volume contained in pores of diameter greater than or equal to the mean diameter plus 30 Å. Volume V4 corresponds to the volume contained in pores with a diameter less than the average diameter minus 15 Å. Volume V5 corresponds to the volume contained in pores of diameter greater than or equal to the average diameter minus 15 Å and less than the mean diameter plus 15 Å. Volume V6 corresponds to the volume contained in pores of diameter greater than or equal to the average diameter plus 15 Å.

The pore distribution measured by nitrogen adsorption, is determined by the model of the Barrett-Joyner-Halenda (bjh's). The isotherm of adsorption-desorption of nitrogen on the model of bjh's described in the journal "The Journal of American Society", 73, 373, (1951) authors E.P.Barrett, L.G.Joyner and P.P.Halenda. In the further description of the invention under the amount of nitrogen adsorption is the amount measured for P/P0=0,99 - pressure for which it is assumed that nitrogen filled all the pores. The average diameter of desorption of nitrogen is defined as such a diameter that the pores with diameters less than 50% of the pore volume (Vp)measured on branches desorption isotherms of nitrogen.

Under the adsorption surface is meant the surface, calculated from the adsorption branch of the isotherms. We will refer, for example, article A.Lecloux in "Memoires Societe Royale des Sciences de Liège, 6éme série, Tome I, fasc. 4, pp.169-209 (1971)".

The sodium content measured by atomic-absorbtion the Noah spectrometry.

X-ray diffraction is a method that can be used to characterize the substrates and catalysts according to the invention. Further x-ray analysis is carried out with a powder diffractometer Philips PW 1830, working in reflected rays and is equipped with a rear monochromator, using radiation CoKalpha (λα1=1,7890 Å, λα2=1,793 Å, the ratio of the intensity of the Kα1/Kα2=0,5). For x-rays oxide gamma-aluminum sent to the database ICDD card 10-0425. In particular, two of the most intense peak is located at the position d, the average of 1.39 to 1.40 Å, and d, constituting from 1.97 Å to 2.00 Å. The value of d is called the interplanar distance inside the lattice, which is calculated from the angular position using a ratio called Bragg (2d(hkl)·sin(θ)=n·λ). Under the oxide gamma-aluminum in further text refers to, among other things, for example, alumina, a member of the group consisting of oxides of aluminum cubic gamma, gamma pseudokoningii, tetragonal gamma, gamma bad or makristathis, gamma with a large surface, low gamma surface, γ, obtained from bumitaw, gamma, obtained from crystallized boehmite, gamma, obtained from low - or poorly crystallized boehmite, gamma, obtained from a mixture of cu is stellitano of boehmite and amorphous gel, gamma obtained from an amorphous gel, gamma in the evolution of the Delta. With regard to the position of the diffraction peaks of oxides of aluminum, this, Delta and theta, you can refer to the article B.C. Lippens, J.J. Steggerda in Physical and Chemical aspects of adsorbents and catalysts, E.G. Linsen (Ed.), Academic Press, London. 1970, p.171-211.

For the substrates and catalysts according to the invention the x-ray showed a broad peak characteristic of the presence of amorphous silica.

In addition, throughout the following text, the connection of the aluminum oxide may contain amorphous fraction, poorly detectable by the methods of RD. Thus, hereinafter, it is understood that the connection of the aluminum oxide used or described in the text, may contain amorphous or poorly crystallized fraction.

Matrix catalysts according to the invention were analyzed by solid-state method27Al NMR VMF spectrometer firm Brüker type MSL 400, with probe 4 mm, the rotation speed of the samples was about 11 kHz. Potentially, NMR aluminum allows us to distinguish three types of aluminum, chemical shifts are listed below:

from 100 to 40 ppm: aluminum type Tetra-coordinated, denoted AlIV,

from 40 to 20 ppm: aluminum type Penta-coordinated, denoted AlV,

from 20 to -100 ppm: aluminum type hexa-coordinated, denoted AlVI.

The aluminum atom has a quadrupole the draw. In certain conditions analysis (weak RF field: 30 kHz, small angle momentum: π/2 and the sample saturated with water) the NMR method with rotation under magic angle (VMF) is a quantitative method. Decomposition of NMR spectra VMF allows you to directly associate with a number of different components. The spectrum is calibrated with respect to the chemical shift of a 1M solution of aluminium nitrate. The signal aluminium is taken as zero. The inventors decided to sum the signals between 100 and 20 ppm for AlIVand AlVthat corresponds to square 1, and between 20 and -100 ppm for AlVIthat corresponds to area 2. In the further description of the invention under octahedral share of AlVIrefers to the following size 2/(area 1+area 2).

The environment of silicon aluminosilicates investigated using29Si-NMR. Tables of chemical shifts as a function of the degree of condensation were removed in the work G.Engelhardt and D.Michel: "High resolution solid-state NMR of silicates and zeolites (Solid state high resolution NMR of silicates and zeolites)" (Wiley), 1987.

29Si-NMR shows the chemical shifts of the different States of silicon, such as Q4(-105 ppm to 120 ppm), Q3(-90 ppm to -102 ppm) and Q2(from -75 ppm to 93 ppm). Centers with a chemical shift -102 ppm can be centers of type Q3or Q4will call them centers Q3-4. Determination of the following is relevant:

centers Q4: Si is connected with 4Si (or Al),

centers Q3: Si is connected with 3 Si(or Al) and 1 OH,

centers Q2: Si is connected with 2 Si(or Al) and 2-OH.

The silicates according to the invention are compounds of silicon type Q2, Q3, Q3-4and Q4. Many of the components will be of type Q2approximately of the order of 10-80%, preferably from 20 to 60% and preferably from 20 to 40%. The proportion of species Q3and Q3-4also great about the order of 5-50%, preferably from 10 to 40% for both species.

The environment of silicon was studied by NMR CP/VMF1H→29Si (300 MHz, rotation speed: 4000 Hz). In this case, to respond only silicon, coupled with the constraints of OH. Table used chemical shifts is a table Kodakari and others, Langmuir, 14, 4623-4629, 1998. Match the following: -108 ppm (Q4), -99 ppm (Q3/Q4(1 Al)), -91 ppm (Q3/Q3(1 Al)), -84 ppm (Q2/Q3(2Al), -78 ppm (Q2/Q3(3 Al) and -73 ppm Q1/Q2(3 Al).

The silicates according to the invention is presented in the form Superpole multiple arrays. The main peak of these arrays is usually located near -110 ppm.

One of the methods of characterization of the substrates and catalysts according to the invention, which can be used is transmission electron microscopy (TEM). This is done using an electron microscope (type Jeol 2010 or Philips Tecnai20F, enabled the scanning), equipped with an energy dispersive spectrometer (EDS) for x-ray analysis (e.g., Tracor or Edax). EMF detector should allow to detect light elements. The combination of these two tools, TEM and EDS, allows you to combine image processing and local chemical analysis with high spatial resolution.

For this type of analysis samples of finely pulverized by a dry process in a mortar; then the powder is introduced into the resin to obtain the ultrafine fraction of a thickness of about 70 nm. These fractions are collected in arrays of Cu covered with a film of amorphous carbon with holes, serving as a substrate. Then they are introduced into the microscope for observation and analysis in a secondary vacuum. In this case, when the image analysis zone of the sample is readily distinguishable from the resin. Then spend a certain number of tests, at least 10, preferably 15 to 30, in different areas of industrial design. The size of the electron beam for analysis zones (which is about the size of the analyzed zones) is a maximum diameter of 50 nm, preferably 20 nm, more preferably 10, 5, 2 or 1 nm in diameter. In scan mode the analyzed area is a function of the size of the scan area and not exceed the size of the beam, usually reduced.

Semi-quantitative processing of x-ray spectra obtained with the Spectro is the ETP EMF, allows you to determine the relative concentration of Al and Si (atomic %) and the ratio of Si/Al for each subject area. In this case, it is possible to calculate the average ratio Si/Almand standard deviation for this set of measurements. In the following non-limiting examples describe the invention by the probe used for characterizing the substrates and catalysts according to the invention, unless otherwise specified, is the probe 50 nm.

Zeolites are used for preparation of catalysts for hydrocracking, differ in several parameters, such as molar ratio of SiO2/Al2O3in the matrix, the stability of the crystal lattice, the pore distribution, specific surface area, the ability to absorb sodium ions, and the ability to adsorb water vapor.

The level peaks and the proportion of the crystalline fractions are important parameters for consideration. The level peaks and the proportion of the crystalline fractions are determined by x-ray diffraction relative to the standard zeolite using a procedure derived from method ASTM D3906-97 "Determination of the relative intensities of x-ray diffraction for the type of materials containing vorasit". You can refer to this method as regards the General conditions of application of this procedure and, in particular, for the preparation of samples and standards.

Radiograph of SOS is the RTO of the characteristic lines of the crystalline fraction of the sample and background, caused mainly by the diffusion of amorphous or microcrystalline fraction of the sample (weak signal from diffusion associated with equipment, air, sample holder and so on) the Level of the peaks of the zeolite is in a given angular zone (usually for 2θ from 8 to 40°, when using radiation Kαcopper, λ=0,154 nm), the square of the spectral lines of zeolite (peaks) to complete the square in x-rays (peaks+background). This ratio peaks/(peaks+background) is proportional to the amount of crystalline zeolite material. To evaluate the crystalline fraction of the sample of zeolite Y, compare the level of the peaks of the sample of the zeolite with the standard that is considered to be crystalline at 100% (for example, NaY). The level of the peaks of zeolite NaY, perfectly crystallized, is of the order of 0.55 to 0.60.

Density padding (DRT) is measured by the method described in "Applied Heterogeneous Catalysis", the authors J.F. Le Page, J. Cosyns, P. Courty, E. Freund, J-P. Franck, Y. Jacquin, B. Juguin, C. Marcilly, G. Martino, J. Miquel, R. Montarnal, A. Sugier, H. Van Landeghem, Technip, Paris, 1987. A graduated cylinder of appropriate sizes fill the catalyst by successive supplements and between each addition of the catalyst compacted by shaking the cylinder to achieve a constant volume. This measurement is usually performed with 1000 cm3catalyst, compressed in the cylinder, and whose ratio of height to diameter close to 5:1. This measurement can be carried out pre is respectfully in an automated device, such as Autotap®, available in sale Quantachrome®.

The acidity of the matrix is measured by infrared spectrometry (IR). IR spectra are recorded by the interferometer Nicolet, type Nexus-670 with a resolution of 4 cm-1with Apodization type Happ-Gensel. The sample (20 mg) is pressed in the form of a solid plate, then placed in a cell for the analysis of in-situ (25-550°C, oven, closed from infrared rays, secondary vacuum of 10-6 mbar). The diameter of the plate is 16 mm.

The sample is processed as follows to remove physically adsorbed water and partially dehydrosilybin the surface of the catalyst, to obtain an image characteristic acidity of the catalyst during operation:

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

plateau at 300°C for 10 hours,

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

Then basically the probe (pyridine) adsorbed at saturating pressure at 25°C, then thermodesorber according to the following stages:

- 25°C for 2 hours in a secondary vacuum,

- 100°C for 1 hour in a secondary vacuum,

- 200°C for 1 hour in a secondary vacuum,

- 300°C for 1 hour in a secondary vacuum.

The spectrum recorded at 25°C at the end of the pre-treatment and at each stage of desorption in the transition mode when the accumulation time of 100 C. the Spectra are converted to ISO-weight (which implies the same thickness) (exactly 20 mg). The number of centres Lewis p is oportional of the peak area, a maximum which is located at 1450 cm-1, and included all of the adjunction. The number of centers Branstad proportional to the square of the peak, the maximum of which is located at 1545 cm-1. The ratio of the number of centers Branstad among centers Lewis, B/L, is estimated as the ratio of the two areas described above peaks. Usually use the area of the peaks at 25°C. This ratio B/L is usually calculated from the spectra recorded at 25°C, at the end of the pre-processing.

When they enter the promoting element P and/or b and/or Si, its distribution and location may be determined by such means as the microprobe Castanha (distribution profile of the various elements), transmission electron microscopy in combination with x-ray analysis of the catalyst components, or by Cartaromana distribution of elements present in the catalyst, using electron microprobe. These methods allow to prove the presence of these exogenous elements added after synthesis of aluminosilicate according to the invention.

The full composition of the catalyst can be determined by x-ray fluorescence on the catalyst in a spray or by atomic absorption after etching of the catalyst acid.

Measurement of the local structure on the micron scale, in contrast to the full composition of the catalyst, MoE, what should be done by means of the electron microprobe. This measurement can be made by determining the metal content in areas the size of a few cubic microns on the length of the diameter of the catalyst particles, which are called units. This measurement allows to estimate the macroscopic distribution of elements within the particles. In certain cases it can be implemented on the scale of nanometers method STEM (Scanning Transmission Electron Microscopy (transmission and scanning electron microscopy)).

The analyses are carried out by electron microprobe CAMECA SX100 (spectrometers equipped with 5 wave dispersion) (preferred apparatus) or perhaps on a JEOL 8800R (4 spectrometer). The acquisition parameters as follows: the acceleration voltage 20 kV, a current of 80 or 200 and a read time of 10 s or 20 s depending on the concentration level. Particles coated with resin, and then polished to their diameter.

It should be noted that the name of the diameter refers not only to the particles in the form of a ball or extrudate, but, more generally, to any form particles; in fact, the diameter is called the characteristic size of the particles, which is measured.

The measurements are performed on the sample, which is a layer or part of the catalyst to be used in the catalytic layer. It is believed that the tests should be made at least 5 particles with at least 30 measurements on the particle,evenly distributed along the length of the diameter.

Denote CMo, CNi, CW and CP concentrations (expressed in%), respectively, molybdenum, Nickel, tungsten and phosphorus.

You can also Express the concentration in atomic %, and the relative deviation will be the same.

It is interesting to prepare catalysts with homogeneous concentration CMo, CNi, CW and CP along the length of the extrudate. It is also interesting to obtain catalysts having different concentrations CMo, CNi, CW and CP in the center and the periphery. These catalysts have a distribution profile, called a "cell" or "dome". Another type of distribution is Korotkova distribution, where the elements of the active phase are distributed on the surface.

Detailed description of the invention

More precisely, the invention relates to a catalyst containing:

at least one hydrogenating-dehydrating element selected from the group formed by the elements of group VIB and group VIII of the Periodic system,

- from 0.01 to 5.5% of the promoting element selected from phosphorus, boron and silicon, preferably boron or phosphorus, and more preferably phosphorus,

- and substrate-based zeolite Y, defined constantathe unit cell of the crystal lattice component from 24,40·10-10m to 24,15·10-10m, and on the basis of aluminosilicate containing silicon oxide (SiO2) in an amount greater than 5% weight. and less iliamna 95% weight.,

with the specified catalyst has the following characteristics:

- the average pore diameter, measured by mercury porosimetry ranges from 20 to 140 Å,

- total pore volume, measured by mercury porosimetry is 0.1 ml/g to 0.5 ml/g, preferably less than 0.45 ml/g and more preferably less than 0.4 ml/g,

- total pore volume, measured by nitrogen porosimetry is 0.1 ml/g to 0.5 ml/g, preferably less than 0.45 ml/g and more preferably less than 0.4 ml/g,

- specific surface area by BET ranges from 100 to 600 m2/g, preferably less than 500 m2/g, very preferably less than 350 m2/g and even more preferably less than 250 m2/g

- pore volume, measured by mercury porosimetry produced pores with a diameter higher than 140 Å, of less than 0.1 ml/g,

- pore volume, measured by mercury porosimetry produced pores with a diameter higher than 160 Å, of less than 0.1 ml/g,

- pore volume, measured by mercury porosimetry produced pores with a diameter above 200 Å, less than 0.1 ml/g, preferably less than 0.075 ml/g and more preferably less than 0.05 ml/g,

- pore volume, measured by mercury porosimetry produced pores with a diameter greater than 500 Å, is strictly larger than 0.01 ml/g and less than 0.1 ml/g, more preferably of 0.02 ml/g or less of 0.07 ml/g and even more preferably greater of 0.03 ml/g and less of 0.07 ml/g,

- radiograph, the content is based on at least the main characteristic of at least one of transition alumina, a member of the group consisting of oxides of aluminum alpha, Rho, Chi, ETA, gamma, Kappa, theta and Delta,

the density of the packing of the catalyst is higher than 0.75 g/cm3preferably above 0,85 g/cm3very preferably higher than 0.95 cm3/g and even more preferably above 1,05 g/cm3.

Based on the proportion of zeolite radiograph of the catalyst usually contains also the main characteristic of the selected zeolite or zeolites.

The invention relates also to a method of hydrocracking and/or hydroconversion and to a method of Hydrotreating a hydrocarbon fractions with the use of these catalysts.

Characteristics of the substrate of the catalyst according to the invention

The substrate of the catalyst according to the invention is a substrate made of zeolite Y, defined constantathe unit cell of the crystal lattice component from 24,40·10-10m to 24,15·10-10m, based on the aluminosilicate (i.e. containing aluminum oxide and silicon oxide) with a mass fraction of silicon oxide (SiO2) more than 5% weight. and less than or equal to 95 wt%, preferably component of from 10 to 80 wt%, preferably, the proportion of silicon oxide is higher than 20 wt%. and below 80% weight., even more preferably higher than 25 wt%. and below 75% weight. The proportion of silicon oxide substrate is favorably 10 to 50 wt%.

Matrix

Netseal the percentage matrix based on aluminum silicate, used in the substrate of the catalyst according to the invention, preferably an aluminosilicate, homogeneous in micron scale, in which the proportion of cationic impurities (for example, Na+) below 0.1 wt%, preferably below 0.05 wt%. and even more preferably below 0.025% wt., while the proportion of anionic impurities (for example, SO42-, Cl-below 1 wt%, preferably below 0.5 wt%. and even more preferably below 0.1 wt%.

Thus, to obtain substrates objects of the invention are suitable all methods of synthesis of aluminosilicate, known to the specialist, which lead to the aluminosilicate, homogeneous on the micrometer scale, in which the cationic impurities (for example, Na+) can be brought to a level less than 0.1%, preferably below 0.05% weight., even more preferably below 0.025% wt., and in which the anionic impurities (for example, SO42-, Cl-) can be brought to a level below 1% and more preferably below 0.05% of the weight.

The environment of silicon aluminosilicates investigated using29Si-NMR. The silicates according to the invention contain compounds of silicon type Q2, Q3, Q3-4and Q4. Many centres will have type Q2approximately of the order of 10-80%, preferably from 20 to 60% and preferably from 20 to 40%. The proportion of centers Q3and Q3-4also great about over the and 5-50%, preferably from 10 to 40% for both species.

The environment of silicon was studied by NMR CP/VMF1H→29Si (300 MHz, rotation speed: 4000 Hz). In this case, to respond only silicon, coupled with the constraints of OH. Table used chemical shifts is a table Kodakari and others, Langmuir, 14, 4623-4629, 1998. Match the following: -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 is represented as a superposition of multiple arrays. The main peak of these arrays usually is around -110 ppm

Spectra of solid-state27Al NMR MVD of the matrix according to the invention show two different array of peaks. The first type of aluminum, the maximum of which is located near 10 ppm, gives a signal in the range from -100 to 20 ppm, the Position of the maximum implies that these centres are mainly in the type of AlVI(octahedral). The second non-primary type of aluminum, the maximum of which is close to 60 ppm, gives a signal in the range from 20 to 110 ppm, This array can be decomposed at least two components. The predominant component of this array corresponds to the atoms of AlIV(tetrahedral). For the substrates and catalysts according to the present invention favorably to share staedtische Al VIwas above 50%, preferably above 60%, and even more preferably above 70%.

In one embodiment of the invention, the catalyst includes a matrix containing at least two silica-alumina zones, and these zones have relations Si/Al is less than or more full relationship Si/Al, determined by x-ray fluorescence. For example, the matrix having a ratio Si/Al = 0.5, contains two silica-alumina zones, and each zone has a ratio Si/Al, as determined by TEM, is less than 0.5, and the other zone has a ratio Si/Al, as determined by TEM, comprising from 0.5 to 2.5.

In another embodiment of the invention, the catalyst includes a matrix containing only one aluminosilicate zone, and this zone has a ratio Si/Al, is equal to the total ratio Si/Al, determined by x-ray fluorescence, and below 2,3.

Zeolite

Zeolite Y according to the invention is characterized by the constantathe unit cell of the crystal lattice component from 24,40·10-10m to 24,15·10-10m, preferably from 24,38·10-10m to 24,24·10-10m

Full weight fraction of zeolite in the catalyst is usually from 0.1% to 30%, favorably from 0.2% to 25%, preferably from 0.3% to 20%, very preferably from 0.5% to 20%, even more preferably from 1% to 10%.

Depending on the entered in the share of the zeolite is an x-ray of the substrate or the catalyst usually contains also the main characteristic line of the selected zeolite or zeolites.

Zeolite Y according to the invention can also be a zeolite Y, subjected to secondary processing, such as USY, VUSY, SDUSY.

Zeolite Y used in the substrate of the catalyst according to the invention, at least partially is hydrogen or an acid (H+) or ammonia (NH4+or in cationic form, with the specified cation selected from the group formed by groups IA, IB, IIA, IIB, IIIA, IIIB (including the rare earths), Sn, Pb and Si, preferably it is at least part is in the form of H+or it can also be used at least in part in cationic form (as defined above).

The acidity of the substrate (matrix + zeolite) according to the invention can be favorably (without limiting the scope of invention) measured IR control of thermodesorption of pyridine. Usually the ratio B/L, such as described above for the substrate according to the invention amounts to more than 0.07, more preferably 0.125 and very preferably greater than 0.25.

Characteristics of the catalyst according to the invention

Thus, the catalyst according to the invention contains:

- substrate-based zeolite Y, defined constantathe unit cell of the crystal lattice component from 24,40·10-10m to 24,15·10-10m, and based on aluminosilicate (that e is th containing aluminum oxide and silicon oxide) with a mass fraction of silicon oxide (SiO 2) more than 5% weight. and less than or equal to 95 wt%, preferably component of from 10 to 80 wt%, preferably, the proportion of silicon oxide is higher than 20 wt%. and below 80% weight. and even more preferably higher than 25 wt%. and below 75% wt., moreover, the proportion of silicon oxide is favorably 10 to 50 wt%,

cationic impurity content is preferably less than 0.1 wt%, preferably less than 0.05 wt%. and even more preferably less than 0.025 wt%. Under the share cationic impurities is a complete share of alkalis,

- anionic impurities is preferably in the content below 1 wt%, preferably below 0.5 wt%. and even more preferably below 0.1 wt%,

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

preferably, the mass fraction of the metal(s) of group VIB in the form of metals or in the form of oxide is from 1 to 50 wt%, preferably from 1.5 to 35% and even more preferably from 1.5 to 30%,

- preferably the mass fraction of metals of group VIII in the form of metals or in the form of oxide is from 0.1 to 30 wt%, preferably from 0.2 to 25% and even more preferably from 0.2 to 20%,

at least one of the promoting element deposited on the catalyst (under the promoting element refers to the element that is entered after receiving the aluminosilicate substrate description the Noah earlier) and selected from the group formed by phosphorus, boron and silicon, preferably phosphorus and/or boron, more preferably phosphorus. Mass fraction of phosphorus, boron, silicon, calculated in their oxide form, are from 0.01 to 5.5%, preferably from 0.5 to 2.5% and even more preferably from 4 to 5%,

- if necessary, at least one element of group VIIB (for example and preferably, magnesium), weight fraction comprising from 0 to 20%, preferably from 0 to 10% of the compound in the form of oxide or metal

- if necessary, at least one element of group VB (for example and preferably, niobium), the weight proportion of which is from 0 to 40%, preferably from 0 to 20% of the compound in the form of oxide or metal

- the average pore diameter, measured by mercury porosimetry ranges from 20 to 140 Å, preferably from 40 to 120 Å, even more preferably from 50 to 100 Å,

preferably the ratio of the volume V2, measured by mercury porosimetry, corresponding to diameters of Daverage-30 Å to Daverage+30 Å, to the total pore volume, measured by mercury porosimetry, is more than 0.6, preferably more than 0.7, and even more preferably above 0.8,the

preferably, the volume V3 compiled by pores with a diameter above Daverage+30 Å, measured by mercury porosimetry, less than 0.1 ml/g, preferably less than 0.06 ml/g and even more predpochtite is) less than 0.04 ml/g,

preferably the ratio of the volume V5 corresponding to the diameters of Daverage-15 Å to Daverage+15 Å, measured by mercury porosimetry, to volume V2, corresponding to diameters of Daverage-30 Å to Daverage+30 Å, measured by mercury porosimetry above to 0.6, preferably higher than 0.7, and even more preferably above 0.8,the

- preferably the volume V6, compiled by pores with a diameter above Daverage+15 Å, measured by mercury porosimetry, less than 0.2 ml/g, preferably less than 0.1 ml/g and even more preferably less than 0.05 ml/g,

- total pore volume, measured by mercury porosimetry is 0.1 ml/g to 0.5 ml/g, preferably less than 0.45 ml/g and more preferably less than 0.4 ml/g,

- total pore volume, measured by nitrogen porosimetry is 0.1 ml/g to 0.5 ml/g, preferably less than 0.45 ml/g and more preferably less than 0.4 ml/g,

- specific surface area by BET ranges from 100 to 600 m2/g, preferably less than 500 m2/g, very preferably less than 350 m2/g and even more preferably below 250 m2/g

- preferably the surface adsorption is such that the ratio of surface adsorption to the surface by the BET will be above 0.5, preferably above 0.65 and more preferably above 0.8,the

- pore volume, measured by mercury porosimetry prepared pore diameter is trom above 140 Å, less than 0.1 ml/g, preferably less than 0,07 ml/g and even more preferably less than 0.05 ml/g,

- pore volume, measured by mercury porosimetry produced pores with a diameter higher than 160 Å, of less than 0.1 ml/g, preferably less than 0,07 ml/g and even more preferably less than 0.05 ml/g,

- pore volume, measured by mercury porosimetry produced pores with a diameter above 200 Å, less than 0.1 ml/g, preferably less than 0.075 ml/g and more preferably less than 0.05 ml/g,

- pore volume, measured by mercury porosimetry produced pores with a diameter greater than 500 Å, is strictly larger than 0.01 ml/g and less than 0.1 ml/g, more preferably of 0.02 ml/g or less of 0.07 ml/g and even more preferably greater of 0.03 ml/g and less of 0.07 ml/g,

- x-ray, which contains at least the main characteristic of at least one of transition alumina included in the group formed by the oxides of aluminum, Rho, Chi, Kappa, ETA, alpha, gamma, theta and Delta, which preferably contains at least the main characteristic of at least one of transition alumina included in the group consisting of alumina, gamma, ETA, theta, and Delta, and more preferably that contains at least the main characteristic of aluminum oxide and gamma this, and even more preferably which contains peaks d, average of 1.39 to 1.40 Å, and d, constituting from 1.97 Å to 2.00 Å,

the density of the packing of the catalyst is higher than 0.75 g/cm3preferably above 0,85 g/cm3very preferably higher than 0.95 g/cm3and even more preferably above 1,05 g/cm3,

The total weight fraction of zeolite Y catalyst is usually from 0.1% to 30%, favorably from 0.2% to 25%, preferably from 0.3% to 20%, very preferably from 0.5% to 20% and even more preferably from 1% to 10%.

Based on the proportion of zeolite radiograph of the catalyst usually contains also the main characteristic of the selected zeolite or zeolites.

Zeolite Y according to the invention can also be a zeolite Y, having passed the secondary processing, such as USY, VUSY, SDUSY.

Zeolite Y according to the invention is characterized by the constantathe unit cell of the crystal lattice component from 24,40·10-10m to 24,15·10-10m, preferably from 24,38·10-10m to 24,24·10-10m

Zeolite Y used in the catalysts according to the invention, at least part is in the hydrogen or acid form (H+) or ammonium form (NH4+) or cationic, with the specified cation selected from the group formed by groups IA, IB, IIA, IIB, IIIA, IIIB (including the rare earths), Sn, Pb and Si, preferably it is less than the least part is in the form of H +or it can also be used at least in part in cationic form (such as defined above).

When the promoting element is phosphorus, the phosphorus content is favorably from 0.01 to 5.5%, according to the first preferred variant, from 0.5 to 2.5%, according to the second preferred variant, from 4 to 5%.

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

The preferred catalyst according to the invention contains a combination of Nickel-tungsten, and the phosphorus content is from 0.01 to 4 wt%. oxide.

Very preferred catalyst according to the invention a combination of Nickel-tungsten, and the phosphorus content is from 0.01 to 2.5 wt%. oxide.

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

The catalyst according to the invention has better activity without loss of selectivity for middle distillates. Not wishing to be bound by any theory, I believe that this particularly high activity without significant loss of selectivity of the catalysts of the present invention due to the synergistic effect between the zeolite, silica-alumina matrix and improved hydrogenating phase.

The standard is first tested for activity: evaluation of the catalysts according to the invention

Acidity and options when for hydrogenation catalysts according to the invention can be evaluated in the catalytic test mixture model molecules: the hydrogenation of toluene and isomerization of cyclohexane.

Catalytic test that allows to adjust the hydrogenation and the acidity of the catalysts is carried out in the following order.

Catalysts sulferous in situ under dynamic conditions in a tubular reactor with a transverse fixed bed pilot plant catatest (design Vinci Technologies), and the environment circulates from top to bottom. Measuring activity in hydrogenation and isomerization is carried out immediately after the sulfonation under pressure without return air with hydrocarbon fractions, which are used to sulfurylase catalysts.

Download for sulfonation and testing consists of 5.8% of dimethyl disulfide (DMDS), 20% toluene and 74.2% of cyclohexane by weight. In this way measure stabilised catalytic activity equal volumes of the catalysts in the reaction of hydrogenation of toluene. Regulation isomerization of cyclohexane by dilution with toluene allows to estimate the acidity of the catalysts.

Conditions measuring the activity of the following (assuming complete evaporation and 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

Feed rate: 80 cm3/h

Hourly volumetric rate: 2 l/l/h

The flow rate of hydrogen: 36 l/h

The temperature of sulfonation and testing: 350°C (3°C/min).

Sample liquid out-flow is analyzed by gas chromatography. Determination of the molar concentrations of unreacted toluene (T) and concentrations of products of hydrogenation: methylcyclohexane (MCC6), ethylcyclopentane (EtCC5) and dimethylcyclopentane (DMCC5) allows us to calculate the degree of hydrogenation of toluene XHYDdefined as

XHYD(%)=100·(MCC6+EtCC5+DMCC5)/(T+MCC6+EtCC5+DMCC5).

The degree of isomerization of cyclohexane XISOis calculated in the same way, based on the concentrations of unreacted cyclohexane and its reaction product, Methylcyclopentane. As hydrogenation reactions of toluene and isomerization of cyclohexane are used in test conditions the reactions of the first order and the reactor is a reactor of ideal displacement, the activity of the catalyst in the hydrogenation of AHYDand the isomerization of AISOis calculated using the formula Ai=ln(100/(100-Xj)).

Favorably, the catalyst according to the invention is in the standard test the activity of aHYD>to 0.7, preferably AHYD>to 0.9, more preferably AHYD >1.2 and more preferably AHYD>1,4.

Ways to get

The catalysts according to the invention can be obtained by any means known to the expert.

Getter

Matrix

The applicant has found that a substrate of zeolite Y having a controlled constantathe unit cell of the crystal lattice component from 24,40·10-10m to 24,15·10-10m, based on the aluminosilicate matrices obtained from the mixing, at any stage, compounds of aluminum oxide, partially dissolved in the acidic environment, with a mix of silicon oxide, is completely dissolved, or with a combination of fully dissolved aluminum oxide and hydrated silicon oxide, molded after hydrothermal or thermal treatment to homogenize on the micron scale and even on the nanometer scale, allow to obtain the catalyst is particularly active in hydrocracking processes. Under partial dissolution in acidic environment the applicant has in mind that bringing in the contact connections of aluminum oxide prior to any addition of compounds of silicon oxide (usually completely soluble) or combination with an acid solution such as nitric acid or sulfuric acid, will cause partial dissolution.

Sources of silicon oxide

Compounds of silicon oxide is, used according to the invention, can be selected from the group formed by silicic acid, colloidal solution or powder of silicic acid, a water-soluble alkali metal silicates, cationic salts of silicon, for example, gidratirovannym sodium metasilicate, Ludox® ammonium or alkaline form, the Quaternary ammonium silicates. Silicasol can be obtained in one of the well-known specialist of ways. Preferably prepare a solution decationizing orthosilicic acid on the basis of water-soluble alkali metal silicate by ion exchange resin.

Sources completely soluble silicates

Completely soluble hydrated silicates used according to the invention, can be obtained true coprecipitation managed in stationary operating conditions (pH, concentration, temperature, average time of stay) by reaction of a basic solution containing silicon, for example, in the form of sodium silicate, possibly aluminum, for example, in the form of sodium aluminate, with an acidic solution containing at least one aluminium salt such as aluminium sulphate. In the reaction medium, if necessary, may be added at least one carbonate or CO2.

Under the true coprecipitation the applicant understands the process, which at least one is Obedinenie aluminum, completely soluble in basic or acidic medium, what is described below, and at least one compound of silicon, what is described below, brought into contact, simultaneously or sequentially, in the presence of at least one precipitating and/or sookidega connection, to obtain a mixed phase consisting mainly of hydrated aluminosilicate, which is essentially homogenized by intensive mixing, shear, grinding in a colloid mill or a combination of these individual operations. For example, these hydrated aluminosilicates can be obtained according to the descriptions of the American patent US 2908635; US 3423332, US 3433747, US 3451947, US 3629152, US 3650988.

Complete dissolution of compounds of silicon oxide or combination thereof was measured by how close to the next method. A fixed number (15 g) compounds of silicon oxide or hydrated combination is introduced into the environment at a predetermined pH. Preferably the concentration of the added solid phase per liter of suspension is 0.2 mole per liter. the pH of the dispersion solution is at least 12 and can be obtained by using a source of alkali. Preferably, it is advantageous to use NaOH. Then the mixture is mechanically stirred with a turbine stirrer delocalised type for 30 minutes at a speed of 800 rpm As the only mixing is terminated, the mixture is centrifuged for 10 minutes at a speed of 3000 Rev/min the Precipitate was separated from the settled liquid. The solution is filtered through a filter with a porosity of 4 with a diameter of 19 cm followed by drying and thereafter calcining the two factions at 1000°C. Then define the relation R, is equal to the private from division clarified the mass of the solid mass of the suspension. Under the complete dissolution is the ratio R is at least higher than 0.9.

Sources of aluminum oxide

Compounds of aluminium oxide used according to the invention, are partially soluble in an acid environment. They are selected in whole or in part, from the group consisting of aluminum oxide of General formula Al2O3·nH2O. Can, in particular, to use hydrated compounds of alumina, such as: hydro-argillite, gibbsite, bayerite, boehmite, pseudoboehmite, and gels of aluminum oxide, amorphous or substantially amorphous. You can also use digidrirovannye forms of these compounds, which consist of transition alumina and which contain at least one of the phases belonging to the group: Rho, Chi, ETA, gamma, Kappa, theta, and Delta in a significantly different organization of their crystalline structure. Alumina alpha, commonly called corundum, may be injected into the substrate according to the invention in a minor proportion.

This property is a partial solution is tion is the desired property of the invention, it is applied to the powder of hydrated aluminum oxide, crushed powder of hydrated aluminum oxide, dispersions or suspensions of hydrated aluminum oxide or any combination thereof, prior to any addition of compounds containing the whole or part of the silicon.

Partial dissolution of compounds of aluminum oxide was estimated by the method close to the next method. The exact number of connections of aluminum oxide powder or in suspension is introduced into the environment at a predetermined pH. Then the mixture is mechanically stirred. After mixing, the mixture is left without stirring for 24 hours. Preferably, the concentration in the solid phase Al2O3per liter of suspension, 0.5 mol per liter. the pH of the dispersion solution is equal to 2 and is obtained by using either HNO3or HCl, or HClO4. Preferably, it is advantageous to use HNO3. The distribution of precipitated and dissolved fractions govern by the dosage of aluminum by the absorption of UV. Emergent liquid is passed through an ultra-filter (membrane from polyethersulfone, Millipore NMWL: 30000) and insist in the concentrated acid. The amount of aluminum in the fluid is ejected neozhidannomu connection of aluminum oxide and dissolved aluminum, and ultrafiltration faction - only rest Renamo aluminum. The quantity of precipitated particles is calculated from theoretical concentration of aluminum in the variance (assuming that you have filled in all the hard phase is dispersed) and the number actually dispersed boehmite and aluminum in solution.

The precursor of aluminium oxide used according to the present invention, differ, therefore, from precursors used in the case of true co-precipitation, which are completely soluble in the acidic environment: cationic salt of alumina such as aluminum nitrate. The methods that are part of the invention, differ from the true co-precipitation, as one of the elements in the presence of aluminum compounds soluble part.

To obtain the aluminum oxide can be used all compounds of aluminum oxide of the General formula Al2O3·nH2O. Their specific surface area is from 150 to 600 m2/, it is Possible, in particular, to use hydrated compounds of alumina, such as: hydro-argillite, gibbsite, bayerite, boehmite, pseudoboehmite and gels of aluminum oxide, amorphous or essentially amorphous. You can also use digidrirovannye forms of these compounds, which consist of transition alumina and which contain at least one of the phases belonging to the group: Rho, Chi, ETA, gamma, Kappa, theta, Delta and alpha significantly different'or what enisala of the crystal structure. During heat treatment of these different forms can evolve into each other, in accordance with a complex relationship, which depends on working conditions. You can also use in metered proportions of alumina alpha, usually called corundum.

More preferably used a hydrate of aluminum Al2O3·nH2About is boehmite, pseudoboehmite and gels are amorphous or essentially amorphous alumina. May also be a mixture of these products in any combination.

Boehmite is usually described as an aluminum monohydrate of the formula Al2O3·nH2O that covers the reality of a large variety of materials with different degrees of hydration and structure with more or less defined borders: gel boehmite, the most hydrated, with n, which can exceed 2, pseudoboehmite or microcrystalline boehmite with n components from 1 to 2, then crystalline boehmite and, finally, a well-crystallized boehmite in large crystals with n close to 1. Morphology of aluminum monohydrate can vary widely between extreme forms acicular or prismatic. Between these two forms can be used with any combination of different shapes, chains, boats, twisted records.

Obtaining and/or molding of the aluminum hydrate is I may be the first step to finding these catalysts. Many patents associated with obtaining and/or molding of the substrate on the basis of the transition alumina derived from aluminum monohydrate: US 3520654; US 3630670; US 3864461; US 4154812; US 4313923; DE 3243193; US 4371513.

Relatively pure hydrates of aluminium can be used in the form of amorphous or crystalline powders or crystallized containing amorphous part. The hydrate of aluminum can also be given in the form of aqueous suspensions or dispersions. Aqueous suspension or dispersion of aluminum hydrate, used according to the invention, can be gel-like or coagulating. Aqueous dispersions or suspensions can also be obtained, as is well known to the specialist, by peptization hydrates of aluminium in water or acidified water.

The dispersion of aluminum hydrate may be performed by any known specialist method: periodic reactor, the mixing reactor with a continuous action, a mixer, a colloidal mill. Such mixing may also be implemented in a flow reactor displacement and, in particular, in the static mixer. You can call reactors Lightnin.

In addition, as the source of aluminum oxide can also use aluminum oxide subjected to pre-processing, can improve the degree of dispersion. For example, the dispersion of the source of aluminum oxide can be improved is to build a preliminary homogenizing treatment. As homogenization can be used at least one type of homogenizing processing, described later in the text.

The aqueous dispersions or suspensions of aluminum oxide, suitable for use are, in particular, aqueous suspension or dispersion of fine or ultrafine bumitaw, consisting of particles with sizes in the colloidal sphere.

Thin or ultra-thin Amity used in the present invention can be obtained, in particular, according to French patent FR 1261182 and FR 1381282 or the application for the European patent EP 15196.

You can also use aqueous suspension or dispersion obtained from pseudoboehmite, gels, amorphous alumina, gel, aluminum hydroxide or ultra-thin hydrargillite.

Monohydrate aluminum can be purchased from many commercial sources of aluminum oxide, such as, in particular, as PURAL®, CATAPAL®, DISPERAL®, DISPAL®, manufactured in the sale by the company SASOL, or HIQ®, manufactured sale in ALCOA, or get methods known to the expert: it can be obtained by partial dehydration of three-hydrate of aluminum by conventional methods or can be obtained by precipitation. When these aluminum oxide are in the form of a gel, they are dispersed in water or acidified solution. In the case of deposition, the source of acid may be selected from, for example, on minicamera one of the following compounds: aluminium chloride, aluminum sulfate, aluminum nitrate. The main source of aluminum may be selected from the basic aluminum salts, such as sodium aluminate and potassium aluminate.

As of precipitators may be used sodium hydroxide, sodium carbonate, potassium carbonate and ammonia. Precipitators are selected so that the source of aluminum oxide according to the present invention and these precipitators are deposited together.

Depending on the acidic or basic nature of the initial compounds based on aluminum, the aluminum hydrate is precipitated with a base or acid, selected from, for example, hydrochloric acid, sulphuric acid, soda, or basic or acidic aluminum compounds, such as what is listed above. Both types of reagent can be aluminium sulphate and sodium aluminate. For example, obtaining monohydrate, alpha-aluminum using aluminum sulfate and sodium aluminate can be referenced, in particular, in patent US 4154812.

Pseudoboehmite can be obtained, in particular, by the method described in the American patent US 3630670, interactions solution of alkali metal aluminate with a solution of inorganic acid. It can also be obtained as described in the French patent FR 1357830.

Gels are amorphous aluminum oxide can be obtained, in particular, the methods described in the article "Alcoa paper n°19 (1972), p. 9-12" and, in particular, the reaction of the aluminate to the slots or aluminium salts or by hydrolysis of aluminum alcoholate, or by hydrolysis of the basic aluminum salts.

Gels of aluminum hydroxide can be, in particular, the gels obtained according to the methods described in the American patent US 3268295 and US 3245919.

Gels of aluminum hydroxide can be obtained, in particular, the methods described in patent WO 00/01617, by mixing the acidic source of aluminum and a base or main source of aluminum and acid to precipitate the monohydrate of alumina, and the following steps will be:

2) maturation

3) filtering

4) rinse and

5) drying,

these methods are characterized in that the mixing in step 1 is carried out without back-mixing.

Ultra hydro-argillite can be obtained, in particular, by the method described in patent US 1371808 by evolution, when the temperature of from ambient temperature up to 60°C, the gels of aluminum oxide in the form of honeycombs containing, based on alumina, 0,1 acidic monovalent ions per molecule of Al2O3.

You can also use aqueous suspension or dispersion of ultrafine boehmite or pseudoboehmite obtained by the method in which carry out the reaction of the alkali metal aluminate with carbon dioxide to form a precipitate of amorphous hydroxycarbonate aluminum, the obtained precipitate was separated by filtration, then washed it(the way described, in particular, in the American patent US 3268295).

Then:

a) at the first stage, mixing the washed precipitate amorphous hydroxycarbonate aluminum with a solution of acid, base or salt, or mixtures thereof; this mixing is carried out, pouring the solution onto hydroxycarbonate, and pH educated so the environment is less than 11,

b) in the second stage formed so reaction medium is heated to a temperature below 90°C for at least 5 minutes

c) at the third stage, the environment, obtained in the second step, is heated to a temperature component from 90°C to 250°C.

Dispersion or suspension of boehmite and pseudoboehmite obtained in this way have an alkali content, expressed as weight ratio "oxide of the alkali metal/Al2O3below 0,005%.

When you want to get a very clean substrate catalysts, preferably by use of a suspension or dispersion of ultrapure bumitaw or pseudoboehmite, which were obtained as described above, or gel, aluminum hydroxide, which were obtained by hydrolysis of aluminum alcoholate according to the method of the type described in the American patent US 2892858.

Hereinafter will be briefly described by way of the obtain, which leads to such gels, aluminum hydroxide type boehmite obtained as a byproduct in the production of alcohol by hydrolysis of the alcoholate or alkoxide of aluminum (si is TEZ Ziegler). The synthesis reaction of alcohols by Ziegler described, in particular, in the American patent US 2892858. According to this method, first get triethylaluminium from aluminum, hydrogen and ethylene, and the reaction is carried out in two stages with partial recirculation of triethylaluminum.

At the stage of polymerization add ethylene and then the resulting product is oxidized to aluminum alcoholate, and the alcohols obtained by hydrolysis.

Gels of aluminum hydroxide can also be gels, which were obtained by the methods described in the American patent US 4676928-A and US 6030599.

Hydrated aluminum oxide, obtained as a by-product of the reaction Ziegler described, in particular, in the Bulletin of the firm CONOCO dated January 19, 1971.

The particle size of the alumina-forming source of aluminum oxide, may vary within wide limits. It is usually from 1 to 100 microns.

Methods of obtaining matrix

The matrix can be favorably obtained by one of the following methods.

As an example, one method of producing aluminum silicate, forming part of the invention is to prepare, on the basis of water-soluble alkali metal silicate, solution of orthosilicic acid (H2SiO4·H2O), decationizing by ion exchange, followed by the simultaneous addition of solution of cationic aluminium salts, e.g. the measures nitrate, and ammonia under controlled operating conditions; or by adding a solution of orthosilicic acid to cationic aluminium salts in solution and the coprecipitation of the obtained solution of ammonia under controlled operating conditions, resulting in a homogeneous product. This aluminosilicate hydrogel is mixed with a powder or slurry of hydrate of aluminum. After filtration and washing, drying, molding and then calcining, preferably in air, in a rotary kiln at an elevated temperature and for a time sufficient to facilitate the interaction between aluminum oxide and silicon oxide, usually at least 2 hours, get the matrix, corresponding to the characteristics of the invention.

Another way to get the aluminosilicate according to the invention consists in the precipitation of the hydrate of aluminum oxide, as above, filtering and washing, and then mixed with aqueous solution of orthosilicic acid to obtain a suspension, which deeply homogenized by intensive mixing and shearing. You can use the turbine Ultraturrax or turbine Staro, as well as colloid mill such as a colloid mill Staro. Then a homogeneous suspension is spray dried as above, and then calcined at a temperature of from 500 to 1200°C for at least 3 hours, and get aluminosilicate matrix, suitable for when the change in the method according to the invention.

Another way, which is part of the invention is to obtain, as described above, decationizing solution of orthosilicic acid, then adding to it, simultaneous or sequential, the compounds of alumina, for example, of aluminum hydrate in powder or in acidified suspension. To increase the diameter of pores in the final aluminosilicate substrate, in a reaction medium, you can add at least one primary connection. After a highly effective homogenization of the suspension by mixing, matching, possibly filtered, dry matter content, and then if necessary, re-homogenization, the product is dried with simultaneous or subsequent molding, then calcined as described above.

Another way, also part of the invention consists in the obtaining of aqueous suspensions or dispersions of alumina, such as aluminum monohydrate, then in addition thereto, simultaneously or sequentially, the compound of silicon oxide, such as sodium silicate. To increase the diameter of pores in the final aluminosilicate matrix, in the reaction environment, you can add at least one primary connection. The matrix is obtained by filtering and washing, it is possible leaching of ammonium solution to be extracted by ion exchange of the residual sodium, drying with simultaneous and subsequent molding. After drying, molding, and then annealing, as described above, receive the substrate, corresponding to the characteristics of the invention. The particle size of the used alumina is preferably from 1 to 100 microns, in order to obtain good homogenization of the aluminosilicate substrate according to the invention.

To increase the diameter of the mesopores in the silica-alumina matrix can be particularly advantageous, as it follows from the American patent US 4066574, to obtain aqueous suspension or dispersion of alumina, such as aluminum monohydrate, and then to neutralize the basic solution such as ammonia, then add, simultaneously or sequentially, the compound of silicon oxide, for example decationizing solution of orthosilicic acid. After a highly effective homogenization of the suspension by intensive mixing, installation, possibly filtered, dry matter content and then re-homogenization of the product is dried with simultaneous or subsequent molding, then calcined as described above. This method also forms part of the means used according to the invention.

In the description of the above-mentioned methods use homogenization to describe the translation in a solution of the product containing a solid fraction, for example, a suspension, a powder, the filter cake, and then his dispergirovany is under vigorous stirring. The homogenization of the dispersion is a process well known to the specialist. This homogenization can be carried out by any method known to the person skilled in the art: for example, in the periodic reactor, the reactor mixing of continuous operation, the mixer. Such mixing can be implemented in the reactor of complete exclusion and, in particular, in a static reactor. You can call reactors Lightnin. Can be used turbine Ultraturrax® or turbine Staro®, as well as colloid mill such as a colloid mill Staro. Can also be used commercially available colloidal mill IKA®.

In all the above methods in certain cases it may be desirable to add at any stage receive a small proportion of at least one stabilizing element selected from the group formed by zirconium and titanium. The stabilizing element is preferably added in the form of soluble salts.

The acidity of the matrix according to the invention can be favorably measured, without limiting the scope of the invention, by IR control of thermodesorption of pyridine. In General, the ratio B/L in the matrix according to the invention is from 0.05 to 1, preferably from 0.05 to 0.7, very preferably from 0.06 to 0.3, and even more preferably of 0.075 to 0.15.

Zeolite

Zeolites profitable glanymor fact, that improves the parameters of catalyst in the conversion. Any zeolites, known for its behavior in the hydrocracking and/or hydroconversion can be used in the substrates and catalysts, which are the objects of the invention.

According to one implementation variant of the invention, but not limiting, however, the scope of the invention are zeolites Y parasitol structure (Zeolite Molecular Sieves Structure, Chemistry and Uses, D.W. Breck, J.WILLEY and Sons, 1973), which may be in the hydrogen form or subjected to partial exchange with metal cations, for example, with cations of alkaline earth metals and/or rare earth metals with atomic numbers 57-71 inclusive. Zeolites Y, the last secondary processing, are also part of the invention. Under the secondary processing means, in particular, the process described: "Hydrocracking, Science and Technology", J.Scherzer, A.J.Gruia, 1996 or R.J.Beyerlein. The zeolite Y prepared, for example, by techniques commonly used in dealumination.

The Y zeolites, which are often used in hydrocracking catalysts, obtained by modification of zeolite Na-Y, commercially available. This modification allows you to result in zeolites, called stabilised, ultrastability (USY), very stabilised (VUSY) or dealumination (SDUSY). This symbol is often found in the literature, but it is, nevertheless, not limited icepay characteristics of the zeolites of the present invention in such a name. This modification is carried out by combining three types of transactions well-known specialist: hydrothermal treatment, ion exchange and acid pickling. Hydrothermal processing is ideally determined by a combination of such operating parameters as temperature, duration, total pressure and partial pressure of water vapor. This processing has the effect of extract of aluminosilicate zeolite matrix atoms of aluminum. The consequence of this treatment is to increase the molar relationship SiO2/Al2O3in the matrix, and decrease the parameter crystal cell.

Ion exchange takes place usually by immersing the zeolite in an aqueous solution containing ions that can bind to the centers of cation-exchange capacity of the zeolite. In this way remove sodium cations present in the zeolite after crystallization.

Surgery for acid etching is the alignment of the zeolite in contact with the aqueous solution of inorganic acid. The degree of etching acid is determined by the concentration of the acid, the temperature and duration. Held over zeolite hydrothermal treated, this treatment leads to the removal of aluminum components extracted from the matrix, which clog the micropores of the solid substance.

In addition, a special hydrothermal processing, such as described in patent US 560179, has the consequence of increasing mesoporosity zeolite Y, USY, VUSY and SDUSY, i.e. zeolites, particularly advantageous in combination with the above-described amorphous matrix.

Can be used in various zeolites Y.

Acidic zeolite H-Y according to the invention is characterized by different parameters: constantathe unit cell of the crystal lattice is 24,40·10-10m to 24,15·10-10m and preferably from 24,38·10-10m to 24,24·10-10m; the total molar ratio of SiO2/Al2O3is from about 10 to 70, preferably from about 12 to 50; the proportion of sodium determined on zeolite calcined at 1100°C, less than 0.15 wt%; the ability to absorb sodium ions (CNa), expressed in grams of Na per 100 grams of modified zeolite, neutralized, and then calcined above about 0.85; the specific surface area determined by BET method, above about 400 m2/g and preferably above 550 m2/g, the capacity to adsorb water vapor at 25°C for a partial pressure of 2.6 Torr (or 34.6 MPa) higher than about 6%, and favorably, the zeolite has a pore distribution, determined by physical adsorption of nitrogen, in which from 5 to 45%, preferably from 5 to 40% of the total pore volume of the zeolite is contained in pores with a diameter constituting from 20·10-10m to 80·10-10m, and in which from 5 to 45%, preferably from 5 to 40 total volume of the pores of the zeolite is contained in pores with a diameter of more than 80·10 -10m and typically less than 1000·10-10m, and the rest of the pore volume consists of pores with a diameter of less than 20·10-10m

The preferred catalyst ktoroy used this type of zeolite, aluminosilicate contains a matrix, at least one dealuminated zeolite Y having a constantacrystal lattice component from 24,40·10-10m to 24,15·10-10m, preferably from 24,38·10-10m to 24,24·10-10m, the total molar ratio of SiO2/Al2O3above 10, such proportion of the cations of alkaline earth or alkali metals and/or cations of rare earth metals, the atomic ratio (nxMn+)/Al lower than 0.8, preferably below 0.5 or below 0.1, specific surface area, determined by BET method, above 400 m2/g, preferably above 550 m2/g, and the ability to adsorb water at 25°C and the value of P/P0=0,2, above 6 wt%, with the specified catalyst also contains at least one hydrogenating-dehydrating the metal and silicon deposited on the catalyst.

In one advantageous variant implementation of the invention using partially amorphous zeolite Y.

Under partially amorphous zeolite Y understand a solid phase containing:

i) the level of the peaks, which is below 0,40 preferably below about 0,30;

ii) a crystalline fraction, determined by x-ray diffraction and expression is directly in relation to the standard zeolite Y in soda form (Na), below about 60%, preferably below about 50%.

Preferably partially amorphous zeolites Y, solids included in the composition of the catalyst according to the invention have at least one (and preferably all) of the following other characteristics:

iii) total ratio Si/Al higher than 15, preferably above 20 and below 150,

iv) the ratio of Si/AlIVin the matrix is greater than or equal to the full ratio Si/Al,

v) pore volume equal to at least of 0.20 ml/g of solid substance, part of which is from 8% to 50%, is formed by pores with a diameter of at least 5 nm (nanometers), i.e., 50 Å;

vi) specific surface 210-800 m2/g, preferably 250-750 m2/g and a positive 300-600 m2/year

The level peaks in the classical zeolite USY is from 0.45 to 0.55, the proportion of crystals in it in relation to the perfectly crystallized NaY is from 80 to 95%. The level of the peaks of a rigid body, which is the object of the present description, below 0.4 and preferably below 0,35. Thus, its crystalline fraction is less than 70%, preferably less than 60%.

Partially amorphous zeolites get methods, which are often used to dealumination based on a commercially available zeolite Y, that is, having generally a higher degree of crystallinity (at least 80%). More General, it can be assumed zeolites having a share crystallite least 60% or at least 70%.

The Y zeolites, which are often used in hydrocracking catalysts, obtained by modification of zeolites Na-Y, commercially available. This modification allows you to result in zeolites, called stabilised, ultrastability or dealumination. This modification is performed by at least one of the methods dealumination, for example, hydrothermal treatment, acid pickling. Preferably this modification is a combination of three types of processing, well-known specialist: hydrothermal treatment, ion exchange and acid pickling.

In another preferred method of the invention, the substrate contains a zeolite, as described in the patent application US 5601978. These zeolites are described, in particular in the column 30, lines 48-64. Their volume of mesopores are equal, in particular, more 0,313 cm3/g for a constant cell component of 24.3 to 24.4 Å.

Receiving and handling or processing, as well as the formation of the zeolite can also be one step of receiving these catalysts.

The introduction of the zeolite can be performed by any method known to the expert, upon receipt of a matrix or the molded substrate.

Obtaining catalyst

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

Preferred with the persons receiving the catalyst according to the present invention includes the following steps.

The zeolite can be introduced by any method known to the specialist, and at any stage of the receiving substrate or catalytic Converter.

According to a preferred method for producing a zeolite can be introduced during synthesis of the precursors of the matrix. The zeolite may be, without limitation, for example, in the form of a powder, milled powder, suspension, and the suspension felt desagglomeration processing. For example, the zeolite can be transferred to the suspension was acidified or not, at a concentration consistent with the final content of the zeolite provided for the substrate. This suspension is called a slip, then mixed with precursors of the matrix at any stage of the synthesis, as described above.

According to another preferred method for producing a zeolite can be introduced during formation of the substrate with the elements that make up the matrix, possibly with at least one binder. The zeolite may, without limitation, be in the form of a powder, the crushed powder, suspension, and the suspension is subjected to desagglomeration processing.

The elements of groups VIB and/or VIII, and possibly elements selected from phosphorus, boron, silicon, and possibly elements of groups VB and VIIB may optionally be introduced at this stage of the preparation of the catalyst by any known specialist way. They can also in titsa after molding of the substrate and after or before drying and calcination of the substrate.

Hydrogenating element can be introduced at any point of receipt, preferably during the mixing or, very preferably, after forming. If the molding is followed by a calcination, hydrogenating element can also be given before or after the calcination. Obtaining usually ends with annealing at a temperature of from 250 to 600°C. Another preferred method according to the present invention consists in forming aluminosilicate without binder after mixing the latter, then the transmission-obtained paste through a die plate to form extrudates with a diameter of 0.4 to 4 mm Hydrogenating function can be introduced in this case only partially (for example, a case of a combination of oxides of metals of groups VIB and VIII) or fully, in the moment of mixing. It can be entered for one or more ion exchange operations on the calcined substrate, comprising at least one aluminosilicate, perhaps molded with a binder, using solutions containing precursor salts of the selected metals when they belong to the group VIII. It can be entered for one or more operations of impregnation molded and calcined substrate with a solution of precursors of oxides of metals of group VIII (in particular cobalt and Nickel)when the precursors of the oxides of the metal is in group VIB (in particular, molybdenum or tungsten) have been previously entered at the time of mixing of the substrate. It can be put, very preferably also one or more operations of impregnation of the calcined substrate, comprising at least one aluminosilicate according to the invention and possibly of at least one binder, solutions containing precursors of oxides of metals of groups VI and/or VIII, and the precursors of oxides of metals of group VIII is preferably introduced after the precursors of oxides of metals of group VIB or at the same time with these last.

Preferably the substrate is impregnated with the aqueous solution. Substrate treatment is preferably carried out by impregnation method called "dry", a well-known specialist. The impregnation can be carried out in one step with a solution containing all components of the final catalyst.

Thus, the catalyst of the present invention may contain at least one element of group VIII, such as iron, cobalt, Nickel, ruthenium, rhodium, palladium, osmium, iridium or platinum. From metals of group VIII is preferably used a metal selected from the group consisting of iron, cobalt, Nickel, platinum, palladium and ruthenium. The catalyst according to the invention may also contain at least one element of group VIB, preferably the tungsten and molybdenum. Favorable use combinations of the following metals: Nickel-molybdenum, cobalt-molybdenum, iron-molybdenum, iron-tungsten, Nickel-tungsten, cobalt-tungsten, platinum-palladium, and the preferred combinations are: Nickel-molybdenum, cobalt-molybdenum, cobalt-tungsten, and, still more favorably, platinum-palladium and Nickel-tungsten. You can also use a combination of the three metals, for example Nickel-cobalt-molybdenum, Nickel-molybdenum-tungsten, Nickel-cobalt-tungsten. Favorable use combinations of the following metals: Nickel-niobium-molybdenum, cobalt-niobium-molybdenum, iron-niobium-molybdenum, Nickel-niobium-tungsten, cobalt-niobium-tungsten, iron-niobium-tungsten, and the preferred combinations are: Nickel-niobium-molybdenum, cobalt-niobium-molybdenum. You can also use a combination of the four metals, for example Nickel-cobalt-niobium-molybdenum. You can also use the combination comprising a noble metal, such as ruthenium-niobium-molybdenum, or ruthenium-Nickel-niobium-molybdenum.

At least one of the following elements: phosphorus and/or boron and/or silicon and perhaps an element or elements selected from groups VIIB and VB, are introduced into the catalyst at any stage of receipt and according to any method known to the expert.

One preferred method according to the ACLs to the invention consists in the deposition of one or more selected promoting elements, for example, a pair of boron-silica, calcined or ' green ' predecessor, preferably calcined. To do this, prepare an aqueous solution of at least one boron salt such as biborate ammonium or pentaborate of ammonia in alkaline medium in the presence of hydrogen peroxide, and proceed to the impregnation called dry, which fill the pore volume of the precursor solution, containing, for example, boron. When precipitated, for example, silicon, is used, for example, a solution of the silicon compound type silicone or silicone oil emulsion.

The deposition of boron and silicon can also be conducted simultaneously using, for example, a solution containing a salt of boron, and silicon compound type silicone. For example, in the case where the precursor is a catalyst type Nickel-tungsten deposited on the silicate, it is possible to impregnate this precursor with an aqueous solution of biborate ammonium and silicone Rhodorsil E1P company Rhodia, turning to drying, for example, at 120°C, and then impregnating with a solution of ammonium fluoride, followed by drying, for example, at 120°C and going to the annealing, for example, preferably in air in a transverse layer, for example, at 500°C for 4 hours.

The promoting element selected from the group formed by phosphorus, silicon and boron, as well as elements of group VIIB and VB, can be entered n the fact one or more operations of impregnation of the calcined precursor in excess mortar.

When they enter the promoting element P and/or B and/or Si, its distribution and localization can be determined by methods such as electron microprobe Castanha (distribution profile of the various elements), transmission electron microscopy in combination with x-ray analysis of the catalyst components, or by Cartaromana distribution of elements present in the catalyst, using electron microprobe. These methods allow to prove the presence of these exogenous elements added after synthesis of aluminosilicate according to the invention.

It is interesting to obtain catalysts having a uniform concentration CMoCNiCWand CPalong the length of the extrudate. It is also interesting to obtain catalysts having different concentrations CMoCNiCWand CPin the center and the periphery. These catalysts have a distribution profile, called a "cell" or "dome". Another type of distribution is Korotkova distribution, where the elements of the active phase are distributed on the surface.

Generally speaking, the ratio of the concentrations of the core/edge CMoCNiCWand CPis from 0.1 to 3. In one embodiment of the invention it is from 0.8 to 1.2. In another embodiment of the invention the ratio of the core/center of concentration CPranges from 0.3 to 0.8.

The preferred East is cinecom of phosphorus is orthophosphoric acid (H 3PO4, but also its salts and esters, as the ammonium phosphates. Phosphorus can be introduced, for example, in the form of a mixture of phosphoric acid and a basic organic compound containing nitrogen, such as ammonia, primary and secondary amines, cyclic amines, compounds of the family of pyridine and quinoline and connections of the family of pyrrole. Can be applied tungsten-phosphorus-or tungsten-molybdenum acid.

The phosphorus content is selected, without limiting the scope of the invention so as to form a mixed compound in solution and/or on the substrate, for example, tungsten-phosphorus or molybdenum-Wolfram-phosphorus. These mixed compounds can be heteropolyanions. These compounds can be, for example, heteropolyanions Anderson. The weight percent of phosphorus, calculated in the form of P2About5is from 0.01 to 5%, preferably from 0.1 to 4% and more preferably from 0.2 to 2%.

The boron source can be boric acid, preferably orthoboric acid (H3BO3biborate or pentaborate ammonium, boron oxide, boric esters. Boron may be introduced, for example, in the form of a mixture of boric acid, hydrogen peroxide and a basic organic compound containing nitrogen, such as ammonia, primary and secondary amines, cyclic amines, compounds of the family of pyridine and quinoline and connection of the foster family of pyrrole. Boron may be introduced, for example, by introducing a solution of boric acid in a water-alcohol mixture.

Can be used many sources of silicon. So, you can use orthosilicate ethyl Si(OEt)4, siloxanes, polysiloxanes, silicones, silicone emulsions, halogenoalkane as forcricket ammonium (NH4)2SiF6or forcricket Na2SiF6. Can also favorably be used silicomolybdic acid and its salts, siliconvalley acid and its salts. Silicon can be added, for example, by impregnation of ethyl silicate dissolved in water-alcohol mixture. Silicon can be added, for example, by impregnation of the silicon compounds of the type of silicone or silicic acid suspended in water.

The metals of group VIB and group VIII in the catalyst according to the present invention may be entirely or partially in the form of metal and/or oxide and/or compounds of sulfur.

For example, from the sources of molybdenum and tungsten can be used oxides and hydroxides, molybdenum and tungsten acid and their salts, in particular ammonium salts such as ammonium molybdate, heptamolybdate ammonium, ammonium tungstate, phosphomolybdic acid, fotovoltaica acid and their salts, silicomolybdic acid, siliconvalley acid and their salts.

The sources of elements of group VIII, which is s can be applied, well-known specialist. For example, for base metals are nitrates, sulfates, hydroxides, phosphates, halides, for example chlorides, bromides and fluorides, carboxylates, for example acetates and carbonates. For noble metals will be used halides, for example chlorides, nitrates, acids, such as platinochloride acid, oxychloride, such as ammoniacal ruthenium oxychloride.

Preferably other Halogens, except that introduced by impregnation, do not add, and this halogen is preferably chlorine.

For all the above-mentioned methods in certain cases it may be desirable to add at any stage receive a small proportion of at least one stabilizing element selected from the group consisting of zirconium and titanium.

Forming substrates and catalysts

The substrate can be molded by any method known to the expert. Molding can be implemented, for example, by extrusion, pelletizing, the method of coagulation of droplets (oil drop), the granulation on a rotating plate or any other means well known to the specialist.

Molding can be carried out in the presence of different components of the catalyst and the extrusion of the resulting mineral paste, by tableting, molding in the form of beads by rotating rezervace device or drum, coagulation of droplets, oil drop, oil-up or any other known method, sintering powder containing aluminum oxide and possibly other ingredients, selected from those mentioned above.

The constituent elements of the matrix substrate may also be implemented partially or fully in the form of powder.

The catalysts used according to the invention, have the form of spheres or extrudates. However, the advantage that the catalyst was in the form of extrudate diameter, comprising from 0.5 to 5 mm, in particular from 0.7 to 2.5 mm Shapes are cylindrical (cylinders can be hollow or not), a cylindrical woven, mnogotochechnymi (for example, 2-, 3-, 4 - or 5-lobed), the ring. Preferably, a cylindrical shape, but may be any other form.

In addition, these substrates obtained according to the present invention can be processed, as is well known to the specialist, additives to facilitate the formation and/or to improve the final mechanical properties of aluminosilicate substrates. As examples of additives include, in particular, cellulose, carboxymethylcellulose, carboximetilzellulozu, tall oil, xanthan gum, surfactants, flocculants, as polyacrylamides, carbon black, starches, stearic acid, polyacrylic alcohol, polyvinyl alcohol, biopolymers, glucose, polietileno the Oli etc.

Regulation of the characteristic porosity of the substrates according to the invention is carried out partially at this stage of the forming particles of the substrate.

Molding can be carried out using methods of forming catalysts known to the specialist, such as extrusion, drazhirovanie, spray drying or tableting.

To set the viscosity of the extrudable paste, you can add or take away water. This step can be conducted at any stage of phase mixing. In the case of aluminosilicate substrates may be advantageous to reduce the amount of water in the paste, in order to increase the mechanical force applied to the paste. This action is expressed usually in the decrease in the total volume for optimum proportion of acid.

To establish the content of solids in the extrudable paste, to make it suitable for extrusion, you can also add the connection is mostly solid and preferably oxide or hydrate. Preferably applies hydrate, even more preferably a hydrate of aluminum. The loss on ignition of this hydrate is higher than 15%.

The proportion of acid added during the mixing up of molding, is less than 30%, preferably from 0.5 to 20 wt%. calculated on the anhydrous weight of silicon oxide and aluminum oxide, are involved in the synthesis.

Extrusion can be carried out by any of the traditional device, available on the market. Paste after mixing extruded through the die plate, for example, by using a piston or single-screw or twin-screw extruder. This stage of the extrusion process can be implemented in any manner known to the expert.

The extrudates of the substrate according to the invention typically have a compressive strength of at least 70 N/cm, preferably greater than or equal to 100 N/a see

The annealing of the substrate

Drying is carried out by any method known to the expert.

To obtain the substrate of the present invention it is preferably calcined, preferably in the presence of molecular oxygen, for example, by blowing air at a temperature of less than or equal to 1100°C. At least one annealing may be performed after any of the stages. This processing may be performed, for example, in a cross-layer design in a sleek layer or in a static atmosphere. For example, used the oven can be a rotary furnace or a vertical furnace with a transverse radial layers. Conditions of annealing temperature and duration mainly depends on the maximum temperature of the catalyst. The preferred calcination conditions are in the range of more than an hour at 200°C to less than one hour at 1100°C. the Annealing can be carried out in the presence of water vapor. Konecne the s annealing may be carried out in the presence of vapors of acids or bases. For example, the calcination may be conducted under a partial pressure of ammonia.

Processing after synthesis

Processing after synthesis can be carried out to improve the properties of the substrate, in particular, its homogeneity, as defined above.

According to one preferred implementation variant, the processing after synthesis is a hydrothermal treatment. Hydrothermal processing is carried out by any method known to the expert. Under hydrothermal processing means bringing into contact, no matter at what stage of obtaining the mixed substrate with water in the vapor phase or in liquid phase. Under hydrothermal processing can be understood, in particular, maturation, steaming (steam treatment), the treatment in the autoclave, calcining in moist air, rehydration. Without limiting the scope of the invention, such processing leads to the fact that the silicon oxide becomes mobile.

According to the invention maturation can take place before or after molding. According to one preferred variant of the invention, the hydrothermal treatment is made by steaming (steam treatment) in a furnace in the presence of water vapor. Temperature during steaming (steam treatment) may range from 600 to 1100°C, preferably to be above 700°C for a period of from 30 minutes to hours. The content of water vapor exceeds 20 g of water per kg of dry air, preferably above 40 g water per kg dry air and more preferably above 100 g water per kg dry air. If necessary, this treatment can completely or partially replace the annealing treatment.

Also, the substrate can with advantage be subjected to hydrothermal treatment in a closed atmosphere. Under hydrothermal treatment in a closed atmosphere refers to the autoclave in the presence of water at a temperature above the ambient temperature.

During this hydrothermal treatment can be different ways to handle molded aluminosilicate or molded substrate (matrix+zeolite). Thus, it is possible to impregnate the substrate or aluminosilicate acid for the autoclave, and the autoclave is carried out either in vapor phase or in the liquid phase and the vapour or liquid phase of the autoclave may be acidic or not. This impregnation to the autoclave may be acidic or sour. This impregnation before treatment in the autoclave can be carried out by a dry process or by immersing the aluminum silicate or substrate in an aqueous acid solution. Under dry impregnation refers to the bringing into contact of aluminum oxide with a volume of solution, less than or equal to the total pore volume of the treated alumina. Preferably provideproduct using a dry method.

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

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

Methods of processing hydrocarbon fractions according to the invention

Generally speaking, the catalysts according to the invention are used for treatment of hydrocarbon fractions, usually in the presence of hydrogen, at temperatures above 200°C, at a pressure above 1 MPa, and the space velocity is from 0.1 to 20 h-1and quantity of the injected hydrogen is such that the volume ratio of litres of hydrogen/litres of hydrocarbon" is from 80 to 5000 l/l

The catalysts according to the invention are used favorably for hydrocracking and/or hydroconversion hydrocarbon fractions.

The catalysts according to the invention can be used for Hydrotreating hydrocarbon fractions or only previously hydrocracking/hydroconversion passing the hydrocracking catalyst based on a zeolite or aluminosilicate, preferably containing Nickel and tungsten.

Sulfonation catalyst

Before the introduction of loading the catalysts used in the method according to the present invention, preferably are first education is ode sulphurization, allows you to convert, at least partially, the metal components in the sulfur compound prior to their contact with the treated load. This activating treatment sulphurization well known to the expert and can be carried out in any already described in the literature, fashion, or in situ, i.e. in the reactor, or ex situ.

The classic way of sulfonation, well known to the specialist, is heated in the presence of hydrogen sulphide (pure or, for example, in the form of a stream of a mixture of hydrogen/hydrogen sulfide) to the temperature component from 150 to 800°C, preferably from 250 to 600°C, usually in the reaction zone with a cross-layer.

Boot

In the above-described methods according to the invention can be processed very different load, and they usually contain at least 20% of the volume, often at least 80% of the volume of compounds boiling above 340°C.

The load may be, for example, LCO (Light Cycle Oil (light gas oil from a catalytic cracking unit)), atmospheric distillates, vacuum distillates, such as gas oils from the direct distillation of crude oil or units conversion, such as cracking with a fluidized bed of catalyst, gumming or decreasing the viscosity, and the fractions coming from plants extraction of aromatics from lubricating base oils, or coming from the dewaxing lubricating base mA is eaten in the solvent, or the distillate coming from the processes of desulfurization or hydroconversion RAT (atmospheric residues)and/or RSV (vacuum residues)and/or deasphalting oil in a fixed bed or fluidized bed, the download can be also deasphalting oil, and any mixture of the above fractions. The above list is not limiting. Paraffins from the Fischer-Tropsch process are excluded. Typically, fractions have a boiling point T5 above 340°C and better still, above 370°C, 95% of the compounds present in the download, have a boiling point above 340°C and better still, above 370°C.

The nitrogen content in the fractions that are processed in the processes according to the invention, generally exceeds 500 mln, preferably from 500 to 10000 weight mlnd, more preferably from 700 to 4000 weight mlnd and even more preferably from 1000 to 4000 mind sulfur Content in the fractions that are processed in the processes according to the invention is usually from 0.01 to 5 wt%, is preferably from 0.2 to 4%, even more preferably from 0.5 to 2%.

Download may in certain cases contain metals. The total proportion of Nickel and vanadium in the fractions that are processed in the processes according to the invention, typically below 1 weight mlnd the Content of asphaltenes usually below 3000 mlnd, preferably below 1000 mlnd, more pre is respectfully below 200 mlnd

The protective layers

When the download contains the connection type resins and/or asphaltenes, it is advantageous first to download through the layer of catalyst or absorbent, non-catalyst hydrocracking or Hydrotreating.

Protective catalysts or layers used according to the invention, have the form of spheres or extrudates. However it is advantageous if the catalyst is in the form of extrudates with a diameter of 0.5 to 5 mm, more accurately, from 0.7 to 2.5 mm Shapes are cylindrical (cylinders can be hollow or not), a cylindrical woven, mnogotochechnymi (for example, 2-, 3-, 4 - or 5-lobed), the ring. Preferably, a cylindrical shape, but may be any other form.

To prevent the presence of impurities and/or poisons in the boot, protective catalysts can, in another preferred implementation, to be more specific geometric shape, to increase their share of the pores. The proportion of pores in these catalysts is from 0.2 to 0.75. Their outer diameter can vary from 1 to 35 mm Of the possible special forms in this non-limiting list includes: hollow cylinders, hollow, ring process, the hollow toothed cylinders, serrated hollow cylinders, rings PAL with five jumpers, cylinders, with many channels and so on

These catalysts can the be impregnated or not impregnated with the active phase. Preferably the catalysts are impregnated hydrogenating-dehydrating phase. Very preferably used phase CoMo or NiMo.

These catalysts may have macropores. The protective layers can be layers manufactured by the Norton company Saint-Gobain, for example, protective layers MacroTrap®. It can be protective layers from the family ACT: ACT077, ACT935, ACT961 produced in the sale of the company Axens, or layers HMC841, HMC845, HMC941 or HMC945.

Can be especially beneficial to stack these catalysts in at least two different layers with different height. Catalysts with a higher proportion of the pores are preferably used in the first or the first catalytic layer at the inlet of the catalytic reactor. Can also be advantageous to use at least two different reactor for these catalysts.

Preferred protective layers according to the invention are layers HMC and TACT961.

Working conditions

Working conditions, such as temperature, pressure, degree of recirculation of hydrogen, an hourly space velocity, can be very different depending on the nature of the load, the desired quality of products and installations owned by the owner of the oil company. The hydrocracking catalyst/hydroconversion or Hydrotreating is usually given in the contact, in the presence of hydrogen, with the previously described factions, when temperature is re above 200°C, often component from 250 to 480°C, a positive component from 320 to 450°C, preferably from 330 to 435°C, at a pressure above 1 MPa, often comprising from 2 to 25 MPa, preferably from 3 to 20 MPa, and the space velocity is from 0.1 to 20 h-1preferably from 0.1 to 6 h-1, preferably 0.2 to 3 h-1and quantity of the injected hydrogen is such that the volume ratio of litres of hydrogen/litres of hydrocarbon" is from 80 to 5000 l/l, usually from 100 to 2000 l/l

These operating conditions used in the process according to the invention, can usually be achieved in a single pass conversion to products having a boiling point below 340°C, and preferably below 370°C, more than 15%, even more preferably constituting from 20 to 95%.

Implementation options

The process of hydrocracking and/or hydroconversion that employ catalysts according to the invention covers the field of pressure and conversion coming from pressure and mild hydrocracking conversion to high pressure hydrocracking. Under mild hydrocracking understand hydrocracking, leading to moderate conversions, usually below 40%, and operating at low pressure, usually from 2 MPa to 6 MPa.

The catalyst according to the present invention can be used alone, in one or more catalytic layers in a fixed bed, in one or more reactors, in the scheme of g is of dragracing, called single-stage, with or without recycling of unconverted liquid fractions, possibly in conjunction with a Hydrotreating catalyst in the diagram above, the catalyst according to the present invention.

The catalyst of the present invention may be used alone, in one or more reactors with a fluidized bed, in the hydrocracking scheme called single-stage, with or without recycling of unconverted liquid fractions, possibly in conjunction with a Hydrotreating catalyst placed in the reactor with a fixed bed or fluidized bed above the catalyst according to the present invention.

Fluidized bed operates at removing spent catalyst and the daily addition of new catalyst to keep the catalyst is stable.

In the hydrocracking scheme called two-stage, with intermediate separation between the two reaction zones, at a given stage, the catalyst of the present invention can be used in one or two reactors in combination with or without combination with a Hydrotreating catalyst, which is located above the catalyst according to the present invention.

The method, called one-step

Hydrocracking, called single-stage, includes a first and in a more General way, a highly effective Hydrotreating with C is poured to conduct effective hydrodenitrification and the desulfurization load before as it will be held on the catalyst itself hydrocracking, in particular, in the case when it contains zeolite. This highly effective Hydrotreating download only leads to limited conversion download in the lighter fraction, which remains insufficient and, therefore, should be completed on a more active hydrocracking catalyst. However, it should be noted that no separation between these two types of catalysts does not occur. The entire stream exiting the reactor, is fed to the catalyst itself hydrocracking and only then is the separation of the formed products. This version of hydrocracking, called "Once-Through (single pass)"has a variant that includes the return of the unconverted fraction in the reactor for a higher conversion download.

The method, called one-step in a fixed bed

For catalysts with a low content of silicon oxide weight fraction of silicon oxide substrate, which is included in the catalyst composition ranges from 5 to 30%, preferably from 5 to 20%.

For catalysts with a high content of silicon oxide weight fraction of silicon oxide substrate, which is included in the catalyst composition ranges from 20 to 80%, preferably from 30 to 60%.

When the catalyst according to the present invention is applied to zeolite is in utilizator hydrocracking, for example, based on zeolite Y, favorably used is a catalyst having a small weight fraction of silicon oxide, such as previously defined. It can also favorably be used in combination with a Hydrotreating catalyst, the latter is according to the scheme above, the catalyst according to the present invention.

When the catalyst according to the present invention is applied to the hydrocracking catalyst based on aluminum silicate, or on the basis of the zeolite, in the same reactor in other catalytic layers or in other reactors, conversion usually (or preferred) is less than 50 wt%, preferably less than 40%.

The catalyst according to the invention can be used before or after the zeolite catalyst. After zeolite catalyst it allows you to cruciality HPA. Under HPA understand polyaromatic hydrocarbons, such as described in particular in "Hydrocracking, Science and Technology", J.Scherzer, Editions M.Dekker Incorporated, 1996.

A process called single-stage fluidized bed

The catalyst according to the invention can be applied in one or more reactors.

As part of this process can be beneficial to use several successive reactors, and reactor or reactors with fluidized bed containing the catalyst according to the invention, is preceded by one or more reactor is in, containing at least one Hydrotreating catalyst fixed bed or fluidized bed.

When the catalyst according to the present invention is applied after the Hydrotreating catalyst, the conversion of part of the load, the resulting catalyst Hydrotreating, usually (and preferably) below 30 wt%, and preferably below 25%.

A process called single-stage, fixed bed with intermediate division

The catalyst according to the present invention can also be used in the hydrocracking process, called one-step, including the area of the Hydrotreating zone, allowing to partially eliminate ammonia, for example, by instantly heating, and a zone containing hydrocracking catalyst. This single-stage hydrocracking of hydrocarbon fractions to obtain middle distillates, and possibly base oil comprises at least one first reaction zone, including Hydrotreating, and at least one second reaction zone, in which the hydrocracking is carried out at least part of the stream leaving the first reaction zone. This method also includes incomplete separation of ammonia from a stream coming from the first zone. This division is favorably carried out using intermediate instant heat. The hydrocracking is carried out in the second reaction the Ohe, is carried out in the presence of ammonia in a quantity below the amounts present in the load, preferably below 1500 weight mlnd, more preferably below 1000 weight mlnd, and even more preferably below 800 weight mlnd nitrogen. The catalyst of the present invention is preferably used in the reaction zone hydrocracking in combination with or without combination with a Hydrotreating catalyst located before the catalyst according to the present invention. The catalyst according to the invention can be applied before or after the zeolite catalyst. After zeolite catalyst it allows, in particular, to convert HPA or predecessors HPA.

The catalyst according to the invention can be used in the first reaction zone prior to the conversion processing, alone or in combination with classical Hydrotreating catalyst located before the catalyst according to the invention, in one or more catalytic layers, in one or more reactors.

Method of hydrocracking, called single-stage, with a preliminary Hydrotreating on weak acid catalyst.

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

the first reaction zone of the hydrotreatment, in which the load is brought into contact with at least one kata is Isadora Hydrotreating, detecting in the standard test the activity degree of conversion of cyclohexane is below 10% by weight;

the second reaction zone hydrocracking, in which at least part of the flow coming from the stage Hydrotreating, is brought into contact with at least one zeolite hydrocracking catalyst, detecting in the standard test the activity degree of conversion of cyclohexane is above 10% by weight, and the catalyst according to the invention is present in at least one of the two reaction zones.

The share of the catalytic volume of the Hydrotreating catalyst is usually from 20 to 45% of the total catalyst.

The stream exiting the first reaction zone, at least partially, and preferably completely, is introduced into the second reaction zone of the specified process. Intermediate separation of gases can be carried out as described above.

The flow released from the second reaction zone, is subjected to separation, called final (for example, by distillation at atmospheric pressure, for which you may want distillation in vacuum)to separate gases. Receive at least one residual liquid fraction, containing mainly products with a boiling point generally above 340°C, which can at least partially be returned to the process according to the invention above the Torah reaction zone, and preferably above the hydrocracking catalyst based on aluminum silicate, in order to obtain middle distillates.

Conversion into products with a boiling point below 340°C or below 370°C is at least 50% of the weight.

A process called two-step

Two-stage hydrocracking includes the first stage, the purpose of which, as in "one-step" process is to carry out the hydrotreatment of the load, but also to achieve the conversion of the load is usually around 40-60%. The stream coming from the first stage, then subjected to separation (distillation), often called the intermediate division, the purpose of which is to separate the conversion products from the unreacted fraction. In the second stage of two-stage hydrocracking process is handled only part of the boot is not reacted in the first stage. This separation allows the two-stage process of hydrocracking to be more selective for middle distillates (kerosene + diesel)than single-stage process. Indeed, the intermediate separating the conversion products prevents their excessive kikirevenge in naphtha and gas at the second stage on the hydrocracking catalyst. In addition, it should be noted that the unconverted portion of the load to be processed in the second stage, usually contains a very small proportion of NH3and organic is such nitrogen compounds, typically less than 20 weight mlnd, and even less than 10 weight mlnd

In the first stage of the scheme, called two-stage, can be used the same configuration of the catalytic layers, as fixed bed or fluidized bed, so that the catalyst was used alone or in combination with classical Hydrotreating catalyst. The catalyst according to the invention can be applied before or after the zeolite catalyst. After zeolite catalyst it allows, in particular, to convert HPA or predecessors HPA.

For processes, called single-stage, and for the first stage of two-stage hydrocracking preferred catalysts according to the invention, are promoted catalysts composed of base elements of group VIII, more preferably, the catalysts based on Nickel and tungsten, preferably the promoting element is phosphorus.

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

The following examples illustrate the present invention in no way is grunicheva its volume.

Example 1: retrieving the catalyst C1 (invention)

Synthesis of aluminosilicate matrix AS1

Matrix AS1 obtained as follows.

Preparing a hydrate of aluminum oxide on the recommendations of the patent US 3124418. After filtering freshly prepared precipitate is mixed with a solution of silicic acid obtained by the exchange for decationizing resin. The proportions of the two solutions are chosen in order to achieve the final composition of the aluminosilicate matrix 70% Al2O3- 30% SiO2calculated on the anhydrous product. This mixture is rapidly homogenized commercial colloid mill in the presence of nitric acid, so that the proportion of nitric acid in the slurry at the outlet of the mill was 8% of the solid mixture of silica - alumina. Then, the suspension is dried classic by the atomizer, usually at a temperature of from 300°C to 60°C.

Zeolite Z1

Use zeolite Z1 type USY with the ratio Si/Al, measured by x-ray fluorescence equal to 14.7, the ratio Si/Al in the matrix, the measured NMR equal to 19, fractional sodium 260 mlnd, cella=24,29 Å, a degree of crystallinity of 88% and a BET surface equal to 838 m2/year

The molding of the substrate S1

Then mixed with 5 g zeolite Z1 and 95 g of aluminosilicate matrix AS1, supplemented solids, such as described above. This mixture conducting the before introduction into the extruder. The zeolite powder is then ground, then add to the powder aluminosilicate matrix in the presence of 66%nitric acid (5% weight. acid per gram of dry gel). The resulting mixture was stirred for 15 minutes. Then mixing the resulting paste is carried out through a die plate with a cylindrical hole of diameter equal to 1.4 mm, Then the extrudates are dried for one night in air at 120°C, and then calcined at 550°C in air and then calcined at 700°C in the presence of water vapor.

In this way receive a substrate S1 containing 5% zeolite Z1 calculated on the anhydrous mass. The mass content of the anhydrous product in the substrate S1 is 66.5% of Al2O3and 33.5% SiO2.

Getting hydrocracking catalyst C1 according to the invention

Catalyst C1 obtained by dry impregnation of the substrate S1 in the form of an extrudate with an aqueous solution containing salts of tungsten and Nickel and phosphoric acid (H3PO4. Salt of tungsten is metavolumes ammonium (NH4)6H2W12O40·4H2O, and the Nickel salt is Nickel nitrate Ni(NO3)2·6H2O. After ripening at ambient temperature in an atmosphere saturated with water, the impregnated extrudates are dried at 120°C overnight, and then calcined at 500°C in dry air. Mass content of WO3, NiO, P2O5in to the talesfore C1 are respectively 24,7%, 3.6% and 2%.

Characteristics of catalyst C1 the following:

The surface on BET equal to 245 m2/year

Total pore volume, measured by nitrogen adsorption, is 0.37 ml/year

Total pore volume, measured by mercury porosimetry, is about 0.34 ml/year

The average diameter of pores measured by mercury porosimetry equal to 75 Å.

The ratio of the volume V2, measured by mercury porosimetry, corresponding to diameters of Daverage-30 Å to Daverage+30 Å, to the total pore volume, measured by mercury porosimetry is 0,87.

The volume V3, measured by mercury porosimetry produced pores with a diameter above Daverage+30 Å, equal of 0.045 ml/year

The volume V6, measured by mercury porosimetry produced pores with a diameter above Daverage+15 Å, equal to 0.05 ml/year

Pore volume, measured by mercury porosimetry produced pores with a diameter higher than 140 Å, equal 0,040 ml/year

Pore volume, measured by mercury porosimetry produced pores with a diameter higher than 160 Å, equal 0,0385 ml/year

Pore volume, measured by mercury porosimetry produced pores with a diameter above 200 Å, equal 0,038 ml/year

Pore volume, measured by mercury porosimetry produced pores with a diameter greater than 500 Å, equal to 0.032 ml/year

Radiograph contains:

the main characteristic of the oxide gamma-aluminum and, in particular, it contains the peaks at d, sostavlyayet of 1.39 to 1.40 Å, and d, constituting from 1.97 Å to 2.00 Å,

the main characteristic of zeolite Z1 type USY. The content of atomic sodium is 190+/-20 mind the Content of atomic sulfur is 800 mlnd

Example 2: obtain the catalyst C2 (not according to invention)

Aluminosilicate matrix used to obtain the catalyst C2 is aluminosilicate matrix AS1 defined in example 1.

Zeolite Z2

Use zeolite Z2 type USY, such as described in patent application US 5601798. This zeolite is prepared according to the method described in example 52, table 16. The obtained volume of mesopores is 0.36 cm3/,andcell is 24,34 Å, a degree of crystallinity equal to 75%.

Forming the substrate S2

Then mixed with 5 g zeolite Z2 and 95 g of aluminosilicate matrix AS1, supplemented solids, such as described above. Forming the substrate S2 is identical to the molding of the substrate 31 of example 1.

In this way receive a substrate S2, containing 5% zeolite Z2 is calculated on the anhydrous mass. The mass content of the anhydrous product in the substrate S2 is 66,7% Al2O3and 33.3% of SiO2.

Getting hydrocracking catalyst C2 is not according to the invention

The catalyst C2 obtained by dry impregnation of the substrate S2. The method of producing catalyst C2 is identical to the method of preparation of the catalyst C1 of example 1. Mass content of the project WO 3, NiO, P2O5the catalyst C2, respectively 24,9%, 3.8% and 2%.

Characteristics of catalyst C2 the following:

The surface on BET equal to 250 m2/year

Total pore volume, measured by nitrogen adsorption, is 0.36 ml/year

Total pore volume, measured by mercury porosimetry, 0.33 ml/year

The average diameter of pores measured by mercury porosimetry equal to 75 Å.

The ratio of the volume V2, measured by mercury porosimetry, corresponding to diameters of Daverage-30 Å to Daverage+30 Å, to the total pore volume, measured by mercury porosimetry is 0,87.

The volume V3, measured by mercury porosimetry produced pores with a diameter above Daverage+30 Å, equal of 0.045 ml/year

The volume V6, measured by mercury porosimetry produced pores with a diameter above Daverage+15 Å, equal to 0.05 ml/year

Pore volume, measured by mercury porosimetry produced pores with a diameter higher than 140 Å, equal 0,040 ml/year

Pore volume, measured by mercury porosimetry produced pores with a diameter higher than 160 Å, equal 0,0375 ml/year

Pore volume, measured by mercury porosimetry produced pores with a diameter above 200 Å, equal to 0.037 ml/year

Pore volume, measured by mercury porosimetry produced pores with a diameter greater than 500 Å, equal 0,030 ml/year

Radiograph contains:

the main characteristic is xida gamma-aluminum and in particular, it contains the peaks at d average of 1.39 to 1.40 Å, and d, constituting from 1.97 Å to 2.00 Å,

the main characteristic of zeolite Z2 type USY.

The content of atomic sodium is 190+/-20 mind the Content of atomic sulfur is 800 mlnd

Example 3: Obtaining catalyst C3 (invention)

Aluminosilicate matrix used to obtain the catalyst C3 is aluminosilicate matrix AS1 defined in example 1.

Zeolite Z3

Use zeolite Z3 type USY with a ratio Si/Al, measured by x-ray fluorescence, equal to 73, fractional sodium 102 mlnd, cella=24,15 Å, a degree of crystallinity of 44% and a BET surface equal to 783 m2/year

Forming the substrate S3

Then mix 25 g of zeolite Z3 and 75 g of aluminosilicate matrix AS1, supplemented solids, such as described above. Forming the substrate S3 is identical to the molding of the substrate S1 of example 1.

In this way receive the substrate S3, containing 25% zeolite Z3 calculated on the anhydrous mass. The mass content of the anhydrous product substrate S3 is 52.6% of Al2O3and 47.4% SiO2.

Getting hydrocracking catalyst C3 according to the invention

Catalyst C3 obtained by dry impregnation of the substrate S3. The method of producing catalyst C3 is identical to the method of preparation of the catalyst C1 PR is a measure of 1. Mass content of WO3, NiO, P2O5in the catalyst C3, respectively 26,0%, 4.0% and 2%.

Characteristics of catalyst C3 the following:

The surface on BET 365 m2/year

Total pore volume, measured by nitrogen adsorption, is of 0.38 ml/year

Total pore volume, measured by mercury porosimetry, 0.32 ml/year

The average diameter of pores measured by mercury porosimetry equal to 77 Å.

The ratio of the volume V2, measured by mercury porosimetry, corresponding to diameters of Daverage-30 Å to Daverage+30 Å, to the total pore volume, measured by mercury porosimetry is 0,87.

The volume V3, measured by mercury porosimetry produced pores with a diameter above Daverage+30 Å, equal of 0.045 ml/year

The volume V6, measured by mercury porosimetry produced pores with a diameter above Daverage+15 Å, equal to 0.05 ml/year

Pore volume, measured by mercury porosimetry produced pores with a diameter higher than 140 Å, equal 0,040 ml/year

Pore volume, measured by mercury porosimetry produced pores with a diameter higher than 160 Å, equal 0,038 ml/year

Pore volume, measured by mercury porosimetry produced pores with a diameter above 200 Å, equal to 0.037 ml/year

Pore volume, measured by mercury porosimetry produced pores with a diameter greater than 500 Å, equal 0,031 ml/year

Radiograph contains:

- basic ha is acteristically line oxide gamma-aluminum and in particular, it contains the peaks at d average of 1.39 to 1.40 Å, and d, constituting from 1.97 Å to 2.00 Å,

the main characteristic of zeolite Z3 type USY.

The content of atomic sodium is 190+/-20 mind the Content of atomic sulfur is 800 mlnd

Example 4: Obtaining catalyst C4 (not according to invention)

Aluminosilicate matrix used to obtain the catalyst C4, is a silica-alumina matrix AS1 defined in example 1.

Zeolite Z4

Use zeolite Z4 type Y with the ratio Si/Al, measured by x-ray fluorescence, is 2.6, fractional sodium 1400 mind, cella=24,53 Å and a surface on BET equal to 750 m2/year

Forming the substrate S4

Then mixed with 5 g zeolite Z4 and 95 g of aluminosilicate matrix AS1, supplemented solids, such as described above. Forming the substrate S4 is identical to the molding of the substrate S1 of example 1.

In this way receive the substrate S4, containing 5% zeolite Z4 calculated on the anhydrous mass. The mass content of the anhydrous product in the substrate S4 is 66.5% of Al2O3and 33.5% SiO2.

Getting hydrocracking catalyst C4 not according to the invention

Catalyst C4 obtained by dry impregnation of the substrate S4. The method of producing catalyst C4 is identical to the method of preparation of the catalyst C1 of example 1. Mass content is WO 3, NiO, P2O5in the catalyst C4, respectively 25,9%, 3.9% and 2%.

Characteristics of catalyst C4 the following:

The surface on BET equal to 210 m2/year

Total pore volume, measured by nitrogen adsorption, 0.33 ml/year

Total pore volume, measured by mercury porosimetry, 0.32 ml/year

The average diameter of pores measured by mercury porosimetry equals 75 Å.

The ratio of the volume V2, measured by mercury porosimetry, corresponding to diameters of Daverage-30 Å to Daverage+30 Å, to the total pore volume, measured by mercury porosimetry is 0,87.

The volume V3, measured by mercury porosimetry produced pores with a diameter above Daverage+30 Å, equal of 0.045 ml/year

The volume V6, measured by mercury porosimetry produced pores with a diameter above Daverage+15 Å, equal to 0.05 ml/year

Pore volume, measured by mercury porosimetry produced pores with a diameter higher than 140 Å, equal 0,040 ml/year

Pore volume, measured by mercury porosimetry produced pores with a diameter higher than 160 Å, equal 0,038 ml/year

Pore volume, measured by mercury porosimetry produced pores with a diameter above 200 Å, equal to 0.036 ml/year

Pore volume, measured by mercury porosimetry produced pores with a diameter greater than 500 Å, equal 0,030 ml/year

Radiograph contains:

the main characteristic if the AI oxide gamma-aluminum and in particular, it contains the peaks at d average of 1.39 to 1.40 Å, and d, constituting from 1.97 Å to 2.00 Å,

the main characteristic of zeolite Z4 type Y.

The content of atomic sodium is 265+/-20 mind the Content of atomic sulfur is 800 mlnd

Example 5: Receiving catalyst C5 (invention)

Synthesis of aluminosilicate matrix AS2

Matrix AS2 obtained as follows.

Powder of aluminum hydroxide was prepared according to the method described in patent WO 00/01617. The average particle size of aluminum hydroxide, measured by laser grain size distribution is 40 microns. This powder is mixed with silicates received by the exchange for decationizing the resin, then filtered through the resin porosity 2. Concentration silicates and powder of aluminum hydroxide choose to obtain the final content of the anhydrous product in the aluminosilicate matrix, 60% Al2O3and 40% SiO2. Then the suspension is filtered to reduce the amount of water in the mixed precipitate on the filter.

Zeolite Z1

Use zeolite Z1 defined in example 1.

Forming the substrate S5

Then mixed with 5 g zeolite Z1 and 95 g of aluminosilicate matrix AS2, supplemented solids, such as described above. Forming the substrate S5 is identical to the molding of the substrate S1 of example 1.

In this way receive the Ute substrate S5, containing 5% zeolite Z1 calculated on the anhydrous mass. The mass content of the anhydrous product in the substrate S5 is 57% Al2O3and 43% of SiO2.

Getting hydrocracking catalyst C5 according to the invention

The catalyst C5 obtained by dry impregnation of the substrate S5. The method of producing catalyst C5 identical to the method of preparation of the catalyst C1 of example 1. Mass content of WO3, NiO, P2O5in the catalyst C5 are respectively 24,7%, 3.6% and 2%.

Characteristics of catalyst C5 the following:

The surface on BET equal to 235 m2/year

Total pore volume, measured by nitrogen adsorption, is 0.36 ml/year

Total pore volume, measured by mercury porosimetry, is about 0.34 ml/year

The average diameter of pores measured by mercury porosimetry equal to 72 Å.

The ratio of the volume V2, measured by mercury porosimetry, corresponding to diameters of Daverage-30 Å to Daverage+30 Å, to the total pore volume, measured by mercury porosimetry, is 0.9.

The volume V3, measured by mercury porosimetry produced pores with a diameter above Daverage+30 Å, equal 0,072 ml/year

The volume V6, measured by mercury porosimetry produced pores with a diameter above Daverage+15 Å, equal 0,087 ml/year

Pore volume, measured by mercury porosimetry produced pores with a diameter higher than 140 Å, equal to 0.055 ml/year

Pore volume, measured by mercury porosimetry produced pores with a diameter higher than 160 Å, equal 0,053 ml/year

Pore volume, measured by mercury porosimetry produced pores with a diameter above 200 Å, equal 0,051 ml/year

Pore volume, measured by mercury porosimetry produced pores with a diameter greater than 500 Å, equal of 0.045 ml/year

Radiograph contains:

the main characteristic of the oxide gamma-aluminum and, in particular, it contains the peaks at d average of 1.39 to 1.40 Å, and d, constituting from 1.97 Å to 2.00 Å,

the main characteristic of zeolite Z1 type USY.

The content of atomic sodium is 190+/-20 mind the Content of atomic sulfur is 800 mlnd

Example 6: obtain the catalyst C6 (invention)

Aluminosilicate matrix used to obtain the catalyst C6 is aluminosilicate matrix AS2 defined in example 5.

Zeolite Z2

Use zeolite Z2, defined in example 2.

Forming the substrate S6

Then mixed with 5 g zeolite Z2 and 95 g of aluminosilicate matrix AS2, supplemented solids, such as described above. Forming the substrate S6 is identical to the molding of the substrate S1 of example 1.

In this way receive the substrate S6 containing 5% zeolite Z2 is calculated on the anhydrous mass. The mass content of the anhydrous product in the substrate S6 is 57% Al2 O3and 43% of SiO2.

Getting hydrocracking catalyst C6 according to the invention

The catalyst C6 obtained by dry impregnation of the substrate S6. The method of producing catalyst C6 is identical to the method of preparation of the catalyst C1 of example 1. Mass content of WO3, NiO, P2O5in the catalyst C6 are respectively 24,6%, 3.6% and 2%.

Characteristics of catalyst C6 the following:

The surface on BET equal to 210 m2/year

Total pore volume, measured by nitrogen adsorption, is 0.35 ml/year

Total pore volume, measured by mercury porosimetry, 0.33 ml/year

The average diameter of pores measured by mercury porosimetry equal to 70 Å.

The ratio of the volume V2, measured by mercury porosimetry, corresponding to diameters of Daverage-30 Å to Daverage+30 Å, to the total pore volume, measured by mercury porosimetry, is 0.9.

The volume V3, measured by mercury porosimetry produced pores with a diameter above Daverage+30 Å, equal 0,072 ml/year

The volume V6, measured by mercury porosimetry produced pores with a diameter above Daverage+15 Å, equal 0,087 ml/year

Pore volume, measured by mercury porosimetry produced pores with a diameter higher than 140 Å, equal to 0.055 ml/year

Pore volume, measured by mercury porosimetry produced pores with a diameter higher than 160 Å, equal 0,053 ml/year

Pore volume, serenitynow porosimetry, compiled by pores with a diameter above 200 Å, equal 0,051 ml/year

Pore volume, measured by mercury porosimetry produced pores with a diameter greater than 500 Å, equal 0,044 ml/year

Radiograph contains:

the main characteristic of the oxide gamma-aluminum and, in particular, it contains the peaks at d average of 1.39 to 1.40 Å, and d, constituting from 1.97 Å to 2.00 Å,

the main characteristic of zeolite Z2 type USY.

The content of atomic sodium is 190+/-20 mind the Content of atomic sulfur is 800 mlnd

Example 7: obtain a catalyst C7 (invention)

Aluminosilicate matrix used to obtain the catalyst C7 is aluminosilicate matrix AS2 defined in example 5.

Zeolite Z3

Use zeolite Z3 defined in example 3.

Forming the substrate S7

Then mix 25 g of zeolite Z3 and 75 g of aluminosilicate matrix AS2, supplemented solids, such as described above. Forming the substrate S7 is identical to the molding of the substrate S1 of example 1.

In this way receive the substrate S7, containing 25% zeolite Z3 calculated on the anhydrous mass. The mass content of the anhydrous product in the substrate S7 is 45% Al2O3and 55% SiO2.

Getting hydrocracking catalyst C7 according to the invention

The catalyst C7 obtained by dry impregnation of the substrate S7. SP is a way to obtain catalyst C7 identical to the method of preparation of the catalyst C1 of example 1. Mass content of WO3, NiO, P2About5in the catalyst C7, respectively 24,5%, 3.5% and 2%.

Characteristics of the catalyst C7 following:

The surface on BET equal to 360 m2/year

Total pore volume, measured by nitrogen adsorption, is of 0.38 ml/year

Total pore volume, measured by mercury porosimetry, is 0.35 ml/year

The average diameter of pores measured by mercury porosimetry equal to 75 Å.

The ratio of the volume V2, measured by mercury porosimetry, corresponding to diameters of Daverage-30 Å to Daverage+30 Å, to the total pore volume, measured by mercury porosimetry, is 0.9.

The volume V3, measured by mercury porosimetry produced pores with a diameter above Daverage+30 Å, equal 0,072 ml/year

The volume V6, measured by mercury porosimetry produced pores with a diameter above Daverage+15 Å, equal 0,087 ml/year

Pore volume, measured by mercury porosimetry produced pores with a diameter higher than 140 Å, equal to 0.055 ml/year

Pore volume, measured by mercury porosimetry produced pores with a diameter higher than 160 Å, equal 0,052 ml/year

Pore volume, measured by mercury porosimetry produced pores with a diameter above 200 Å, equal 0,050 ml/year

Pore volume, measured by mercury porosimetry produced pores with a diameter greater than 500 Å, equal 0,042 ml/year

Radiograph contains:

- basic x is racteristics line oxide gamma-aluminum and in particular, it contains the peaks at d average of 1.39 to 1.40 Å, and d, constituting from 1.97 Å to 2.00 Å,

the main characteristic of zeolite Z3 type USY.

The content of atomic sodium is 180+/-20 mind the Content of atomic sulfur is 800 mlnd

Example 8: obtain a catalyst C8 (invention)

Aluminosilicate matrix used to obtain the catalyst C8 is aluminosilicate matrix AS2 defined in example 5.

Zeolite Z4

Use zeolite Z4 defined in example 4.

Forming the substrate S8

Then mixed with 5 g zeolite Z4 and 95 g of aluminosilicate matrix AS2, supplemented solids, such as described above. Forming the substrate 38 is identical to the molding of the substrate 31 of example 1.

In this way receive the substrate 38, containing calculated on the anhydrous weight, 5% zeolite Z4. The mass content of the anhydrous product in the substrate 38 is equal to 57% of Al2O3and 43% of SiO2.

Getting hydrocracking catalyst C8 according to the invention

The catalyst C8 obtained by dry impregnation of the substrate 38. The method of producing catalyst C8 identical to the method of preparation of the catalyst C1 of example 1. Mass content of WO3, NiO, P2O5in the catalyst C8 are respectively 24,5%, 3.5% and 2%.

Characteristics of the catalyst C8 following:

Surface B Is T equal to 210 m 2/year

Total pore volume, measured by nitrogen adsorption, is of 0.38 ml/year

Total pore volume, measured by mercury porosimetry, is 0.35 ml/year

The average diameter of pores measured by mercury porosimetry equal to 76 Å.

The ratio of the volume V2, measured by mercury porosimetry corresponding to a diameter of Daverage-30 Å to Daverage+30 Å, to the total pore volume, measured by mercury porosimetry, is 0.9.

The volume V3, measured by mercury porosimetry produced pores with a diameter above Daverage+30 Å, equal 0,072 ml/year

The volume V6, measured by mercury porosimetry produced pores with a diameter above Daverage+15 Å, equal 0,087 ml/year

Pore volume, measured by mercury porosimetry produced pores with a diameter higher than 140 Å, equal to 0.055 ml/year

Pore volume, measured by mercury porosimetry produced pores with a diameter higher than 160 Å, equal 0,052 ml/year

Pore volume, measured by mercury porosimetry produced pores with a diameter above 200 Å, equal 0,050 ml/year

Pore volume, measured by mercury porosimetry produced pores with a diameter greater than 500 Å, equal of 0.045 ml/year

Radiograph contains:

the main characteristic of the oxide gamma-aluminum and, in particular, it contains the peaks at d average of 1.39 to 1.40 Å, and d, constituting from 1.97 Å to 2.00 Å,

the main characteristic is Eolica Z4 type USY.

The content of atomic sodium is 260+/-20 mind the Content of atomic sulfur is 800 mlnd

Example 9: Obtaining catalyst C9 (not according to invention)

Synthesis of aluminosilicate matrix AS3

Matrix AS3 obtained as follows.

Aluminosilicate gels are prepared by mixing sodium silicate and water, directing the mixture to ion exchange resin. A solution of uranyl aluminofluoride in the water add to decationization silicasol. To obtain the gel, add ammonia, and then the precipitate is filtered and hold the rinse solution of water and concentrated ammonia until the conductivity of the wash water does not become constant. The gel obtained at this stage is mixed with powder of boehmite Pural so that the final composition of the aluminosilicate matrix anhydrous product, at this stage of the synthesis, corresponded to 70% of Al2O3- 30% SiO2. This suspension is carried out in a colloid mill in the presence of nitric acid. The amount of added nitric acid is chosen so that the percentage of nitric acid at the outlet of the mill was 8% by weight of the mixed solid oxide. Then the mixture is filtered to reduce the amount of water in the mixed precipitate on the filter.

Zeolite Z1

Use zeolite Z1 defined in example 1.

Forming the substrate S9

Then mix 5g of zeolite Z1 and 95 g of aluminosilicate matrix AS3 supplemented solids, such as described above. Forming the substrate S9 identical to the molding of the substrate S1 of example 1.

In this way receive the substrate 39, containing 5% zeolite Z1 calculated on the anhydrous mass. The mass content of the anhydrous product in the substrate S9 is 66.5% of Al2O3and 33.5% SiO2.

Getting hydrocracking catalyst C9 not according to the invention

The catalyst C9 obtained by dry impregnation of the substrate S9. The method of producing catalyst C9 identical to the method of preparation of the catalyst C1 of example 1. Mass content of WO3, NiO, P2O5in the catalyst C9, respectively 24,7%, 3.6% and 2%.

Characteristics of the catalyst C9 following:

The surface on BET equal to 205 m2/year

Total pore volume, measured by nitrogen adsorption, 0.33 ml/year

Total pore volume, measured by mercury porosimetry, 0.32 ml/year

The average diameter of pores measured by mercury porosimetry equal to 69 Å.

The ratio of the volume V2, measured by mercury porosimetry, corresponding to diameters of Daverage-30 Å to Daverage+30 Å, to the total pore volume, measured by mercury porosimetry, is 0.95.

The volume V3, measured by mercury porosimetry produced pores with a diameter above Daverage+ 30 Å, equal 0,018 ml/year

The volume V6, measured by mercury porosimetry, the composition of aemy pores with a diameter above D average+15 Å, equal 0,021 ml/year

Pore volume, measured by mercury porosimetry produced pores with a diameter higher than 140 Å, equal to a 0.012 ml/year

Pore volume, measured by mercury porosimetry produced pores with a diameter higher than 160 Å, equal 0,010 ml/year

Pore volume, measured by mercury porosimetry produced pores with a diameter above 200 Å, equal to 0,006 ml/year

Pore volume, measured by mercury porosimetry produced pores with a diameter above 500 Å 0.002 ml/year

Radiograph contains:

the main characteristic of the oxide gamma-aluminum, and, in particular, it contains the peaks at d average of 1.39 to 1.40 Å, and d, constituting from 1.97 Å to 2.00 Å,

the main characteristic of zeolite Z1 type USY.

The content of atomic sodium is 190+/-20 mind the Content of atomic sulfur is 800 mlnd

Example 10: obtain the catalyst C10 (invention)

Synthesis of aluminosilicate matrix AS 4

Matrix AS 4 is an aluminosilicate powder having a weight chemical composition of the anhydrous product: 60% Al2O3and 40% SiO2. The proportion of sodium in it is about 100-120 weight mind Its specific surface area is equal to 520 m2/year Full pore volume, measured by mercury porosimetry equal 0,83 cm3/, bimodal pore Distribution. In the area of mesopores observed a broad peak between 4 and 15 nm with Macs is imonom at 7 nm. Macropores in the substrate, the diameter of which is greater than 50 nm, approximately 40% of the total pore volume.

Zeolite Z1

Use zeolite Z1 defined in example 1.

Forming the substrate S10

Then mixed with 5 g zeolite Z1 and 95 g of aluminosilicate matrix AS4, supplemented solids, such as described above. Forming the substrate S10 is identical to the molding of the substrate S1 of example 1.

In this way receive the substrate S10 containing 5% zeolite Z1 calculated on the anhydrous mass. The mass content of the anhydrous product in the substrate S10 is 57% Al2O3and 43% of SiO2.

Getting hydrocracking catalyst C10 according to the invention

The catalyst C10 obtained by dry impregnation of the substrate S10. The method of producing catalyst C10 identical to the method of preparation of the catalyst C1 of example 1. Mass content of WO3, NiO, P2O5in the catalyst C10 respectively equal to 24.7%, 3.6% and 2%.

Characteristics of the catalyst C10 the following:

The BET surface 255 m2/year

Total pore volume, measured by nitrogen adsorption, of 0.85 ml/year

Total pore volume, measured by mercury porosimetry, is 0.83 ml/year

The average diameter of pores measured by mercury porosimetry equal to 85 Å.

The ratio of the volume V2, measured by mercury porosimetry, corresponding to diameters of Daverage-30 Å to Denvironments the s +30 Å, to the total pore volume, measured by mercury porosimetry, is 0.4.

The volume V3, measured by mercury porosimetry produced pores with a diameter above Daverage+30 Å, equal of 0.41 ml/year

The volume V6, measured by mercury porosimetry produced pores with a diameter above Daverage+15 Å, 0,43 ml/year

Pore volume, measured by mercury porosimetry produced pores with a diameter higher than 140 Å, equal to 0.37 ml/year

Pore volume, measured by mercury porosimetry produced pores with a diameter higher than 160 Å, equal to 0.35 ml/year

Pore volume, measured by mercury porosimetry produced pores with a diameter above 200 Å, equal to 0.34 ml/year

Pore volume, measured by mercury porosimetry produced pores with a diameter greater than 500 Å, equal to 0.33 ml/year

Radiograph contains:

the main characteristic of the oxide gamma-aluminum and, in particular, it contains the peaks at d average of 1.39 to 1.40 Å and d, constituting from 1.97 to 2.00 Å,

the main characteristic of zeolite Z1 type USY.

The share of atomic sodium equal to 110 +/- 20 mlnd the Share of atomic sulfur is 800 mlnd

Example 11: obtain a catalyst C11 (invention)

Aluminosilicate matrix used to obtain the catalyst C11 is aluminosilicate matrix AS1 defined in example 1.

Zeolite Z1

Use zeolite Z1, determination is hydrated in example 1.

Forming the substrate S11

Then mixed with 5 g zeolite Z1 and 95 g of aluminosilicate matrix AS1, supplemented solids, such as described above. Forming the substrate S11 is identical to the molding of the substrate S1 of example 1.

In this way receive the substrate S11, containing, calculated on the anhydrous weight, 5% zeolite Z1. The mass content of the anhydrous product in the substrate S11 is 66.5% of Al2O3and 33.5% SiO2.

Getting hydrocracking catalyst C11 according to the invention

The catalyst C11 obtained by dry impregnation of the substrate S11. The method of producing catalyst C11 identical to the method of preparation of the catalyst C1 of example 1. Mass content of WO3, NiO, P2O5in the catalyst C11, respectively 24,7%, 3.6% and 0,5%.

Characteristics of the catalyst C11 following:

The surface on BET equal to 252 m2/year

Total pore volume, measured by nitrogen adsorption, is of 0.38 ml/year

Total pore volume, measured by mercury porosimetry, is 0.35 ml/year

The average diameter of pores measured by mercury porosimetry equal to 75 Å.

The ratio of the volume V2, measured by mercury porosimetry, corresponding to diameters of Daverage-30 Å to Daverage+30 Å, to the total pore volume, measured by mercury porosimetry is 0,87.

The volume V3, measured by mercury porosimetry, compiled by then di is a meter above the D average+30 Å, equal of 0.045 ml/year

The volume V6, measured by mercury porosimetry produced pores with a diameter above Daverage+15 Å, equal to 0.05 ml/year

Pore volume, measured by mercury porosimetry produced pores with a diameter higher than 140 Å, equal 0,040 ml/year

Pore volume, measured by mercury porosimetry produced pores with a diameter higher than 160 Å, equal 0,0385 ml/year

Pore volume, measured by mercury porosimetry produced pores with a diameter above 200 Å, equal 0,038 ml/year

Pore volume, measured by mercury porosimetry produced pores with a diameter greater than 500 Å, equal to 0.032 ml/year

Radiograph contains:

the main characteristic of the oxide gamma-aluminum and, in particular, it contains the peaks at d average of 1.39 to 1.40 Å and d, constituting from 1.97 Å to 2.00 Å,

the main characteristic of zeolite Z1 type USY.

The content of atomic sodium is 190+/-20 mind the Content of atomic sulfur is 800 mlnd

Example 12: obtain the catalyst C12 (invention)

Aluminosilicate matrix used to produce the catalyst C12 is aluminosilicate matrix AS1 defined in example 1.

Zeolite Z1

Use zeolite Z1 defined in example 1.

Forming the substrate S12

Then mixed with 5 g zeolite Z1 and 95 g of aluminosilicate matrix AS1, complemented by solid substances is AMI, such as described above. Forming the substrate S12 is identical to the molding of the substrate 31 of example 1.

In this way receive the substrate S12 containing 5% zeolite Z1 calculated on the anhydrous mass. The mass content of the anhydrous product in the substrate S12 is 66.5% of Al2O3and 33.5% SiO2.

Getting hydrocracking catalyst C12 according to the invention

The catalyst C12 obtained by dry impregnation of the substrate S12. The method of producing catalyst C12 identical to the method of preparation of the catalyst C1 of example 1. Mass content of WO3, NiO, P2O5in the catalyst C12 are respectively 24,7%, 3.6% and 5%.

Characteristics of the catalyst C12 following:

The surface on BET equal to 240 m2/year

Total pore volume, measured by nitrogen adsorption, is 0.37 ml/year

Total pore volume, measured by mercury porosimetry, is 0.35 ml/year

The average diameter of pores measured by mercury porosimetry equal to 74 Å.

The ratio of the volume V2, measured by mercury porosimetry, corresponding to diameters of Daverage-30 Å to Daverage+30 Å, to the total pore volume, measured by mercury porosimetry is 0,87.

The volume V3, measured by mercury porosimetry produced pores with a diameter above Daverage+30 Å, equal of 0.045 ml/year

The volume V6, measured by mercury porosimetry produced pores with a diameter above D +15 Å, equal to 0.05 ml/year

Pore volume, measured by mercury porosimetry produced pores with a diameter higher than 140 Å, equal 0,040 ml/year

Pore volume, measured by mercury porosimetry produced pores with a diameter higher than 160 Å, equal 0,0385 ml/year

Pore volume, measured by mercury porosimetry produced pores with a diameter above 200 Å, equal 0,038 ml/year

Pore volume, measured by mercury porosimetry produced pores with a diameter greater than 500 Å, equal 0,031 ml/year

Radiograph contains:

the main characteristic of the oxide gamma-aluminum and, in particular, it contains the peaks at d average of 1.39 to 1.40 Å and d, constituting from 1.97 Å to 2.00 Å,

the main characteristic of zeolite Z1 type USY.

The content of atomic sodium is 190+/-20 mind the Content of atomic sulfur is 800 mlnd

Example 13: obtain the catalyst C13 (not according to invention)

Aluminosilicate matrix used to produce the catalyst C13 is aluminosilicate matrix AS1 defined in example 1.

Zeolite Z1

Use zeolite Z1 defined in example 1.

Forming the substrate S13

Then mixed with 5 g zeolite Z1 and 95 g of aluminosilicate matrix AS1, supplemented solids, such as described above. Forming the substrate S13 identical to the molding of the substrate S1 of example 1.

In this way receive the spoon S13, containing, calculated on the anhydrous weight, 5% zeolite Z1. The mass content of the anhydrous product in the substrate S13 is 66.5% of Al2O3and 33.5% SiO2.

Getting hydrocracking catalyst C13 according to the invention

The catalyst C13 obtained by dry impregnation of the substrate S13. The method of producing catalyst C13 identical to the method of preparation of the catalyst C1 of example 1. Mass content of WO3and NiO in the catalyst C13, respectively 24,7% and 3.6%. Mass content of P2O5in the catalyst C13 is 0%.

Characteristics of the catalyst C13 following:

The surface on BET equal to 248 m2/year

Total pore volume, measured by nitrogen adsorption, is 0.37 ml/year

Total pore volume, measured by mercury porosimetry, is 0.35 ml/year

The average diameter of pores measured by mercury porosimetry equal to 74 Å.

The ratio of the volume V2, measured by mercury porosimetry, corresponding to diameters of Daverage-30 Å to Daverage+30 Å, to the total pore volume, measured by mercury porosimetry is 0,87.

The volume V3, measured by mercury porosimetry produced pores with a diameter above Daverage+30 Å, equal of 0.045 ml/year

The volume V6, measured by mercury porosimetry produced pores with a diameter above Daverage+15 Å, equal to 0.05 ml/year

Pore volume, measured by mercury porosimetry, SOS is supplied pores with a diameter higher than 140 Å, equal 0,040 ml/year

Pore volume, measured by mercury porosimetry produced pores with a diameter higher than 160 Å, equal 0,0385 ml/year

Pore volume, measured by mercury porosimetry produced pores with a diameter above 200 Å, equal 0,038 ml/year

Pore volume, measured by mercury porosimetry, est compiled by pores with a diameter greater than 500 Å, equal 0,031 ml/year

Radiograph contains:

the main characteristic of the oxide gamma-aluminum and, in particular, it contains the peaks at d average of 1.39 to 1.40 Å and d, constituting from 1.97 Å to 2.00 Å,

the main characteristic of zeolite Z1 type USY.

The content of atomic sodium is 190+/-20 mind the Content of atomic sulfur is 800 mlnd

Example 14: Obtaining catalyst C14 (not according to invention)

Aluminosilicate matrix used to produce the catalyst C14 is aluminosilicate matrix AS1 defined in example 1.

Zeolite Z1

Use zeolite Z1 defined in example 1. Forming the substrate S14

Then mixed with 5 g zeolite Z1 and 95 g of aluminosilicate matrix AS1, supplemented solids, such as described above. Forming the substrate S14 identical to the molding of the substrate S1 of example 1.

In this way receive the substrate S14 containing 5% zeolite Z1 calculated on the anhydrous mass. The mass content of the anhydrous product in the substrate S1 is 66.5% of Al 2O3and 33.5% SiO2.

Getting hydrocracking catalyst C14 not according to the invention

The catalyst C14 obtained by dry impregnation of the substrate S14. The method of producing catalyst C14 identical to the method of preparation of the catalyst C1 of example 1. Mass content of WO3, NiO, P2O3in catalyst C14 are respectively 24.7 per cent, 3.6 per cent and 6.5 per cent.

Characteristics of the catalyst C14 following:

The surface on BET equal to 230 m2/year

Total pore volume, measured by nitrogen adsorption, is 0.37 ml/year

Total pore volume, measured by mercury porosimetry, is 0.35 ml/year

The average diameter of pores measured by mercury porosimetry equal to 73 Å.

The ratio of the volume V2, measured by mercury porosimetry, corresponding to diameters of Daverage-30 Å to Daverage+30 Å, to the total pore volume, measured by mercury porosimetry is 0,87.

The volume V3, measured by mercury porosimetry produced pores with a diameter above Daverage+30 Å, equal of 0.045 ml/year

The volume V6, measured by mercury porosimetry produced pores with a diameter above Daverage+15 Å, equal to 0.05 ml/year

Pore volume, measured by mercury porosimetry produced pores with a diameter higher than 140 Å, equal 0,040 ml/year

Pore volume, measured by mercury porosimetry produced pores with a diameter higher than 160 Å, equal 0,0385 ml/year

Objerror, measured mercury porosimetry produced pores with a diameter above 200 Å, equal 0,038 ml/year

Pore volume, measured by mercury porosimetry produced pores with a diameter greater than 500 Å, equal to 0.032 ml/year

Radiograph contains:

the main characteristic of the oxide gamma-aluminum and, in particular, it contains the peaks at d average of 1.39 to 1.40 Å and d, constituting from 1.97 Å to 2.00 Å,

the main characteristic of zeolite Z1 type USY.

The content of atomic sodium is 190+/-20 mind the Content of atomic sulfur is 800 mlnd

Example 15: Obtaining catalyst C15 (invention)

Aluminosilicate matrix used to produce the catalyst C15 is aluminosilicate matrix AS1 defined in example 1.

Zeolite Z3

Use zeolite Z3 defined in example 3.

Forming the substrate S15

Then mixed with 5 g zeolite Z3 and 95 g of aluminosilicate matrix AS1, supplemented solids, such as described above. Forming the substrate S15 identical to the molding of the substrate S1 of example 1.

In this way receive the substrate S15 containing 5% zeolite Z3 calculated on the anhydrous mass. The mass content of the anhydrous product in the substrate S15 is 66,5,6% Al2O3and 33.5% SiO2.

Getting hydrocracking catalyst 15 according to the invention

Produce the p C15 obtained by dry impregnation of the substrate S3. The method of producing catalyst C15 identical to the method of preparation of the catalyst C1 of example 1. Mass content of WO3, NiO, P2About5catalyst C15, respectively 26,0%, 4.0% and 2%.

Characteristics of the catalyst C15 following:

The surface on BET 365 m2/year

Total pore volume, measured by nitrogen adsorption, is of 0.38 ml/year

Total pore volume, measured by mercury porosimetry, 0.32 ml/year

The average diameter of pores measured by mercury porosimetry equal to 77 Å.

The ratio of the volume V2, measured by mercury porosimetry, corresponding to diameters of Daverage-30 Å to Daverage+30 Å, to the total pore volume, measured by mercury porosimetry is 0,87.

The volume V3, measured by mercury porosimetry produced pores with a diameter above Daverage+30 Å, equal of 0.045 ml/year

The volume V6, measured by mercury porosimetry produced pores with a diameter above Daverage+15 Å, equal to 0.05 ml/year

Pore volume, measured by mercury porosimetry produced pores with a diameter higher than 140 Å, equal 0,040 ml/year

Pore volume, measured by mercury porosimetry produced pores with a diameter higher than 160 Å, equal 0,038 ml/year

Pore volume, measured by mercury porosimetry produced pores with a diameter above 200 Å, equal to 0.037 ml/year

Pore volume, measured by mercury porosimetry compiled what ora diameter greater than 500 Å, equal 0,031 ml/year

Radiograph contains:

- main charactistics line oxide gamma-aluminum and, in particular, it contains the peaks at d average of 1.39 to 1.40 Å and d, constituting from 1.97 Å to 2.00 Å,

the main characteristic of zeolite Z3 type USY.

The content of atomic sodium is 190+/-20 mind

The content of atomic sulfur is 800 mlnd

Example 16: Obtaining catalyst C16 (invention)

Aluminosilicate matrix used to obtain the catalyst C16 is aluminosilicate matrix AS2 defined in example 5.

Zeolite Z3

Use zeolite Z3 defined in example 3.

Forming the substrate S16

Then mixed with 5 g zeolite Z3 and 95 g of aluminosilicate matrix AS2, supplemented solids, such as described above. Forming the substrate S16 identical to the molding of the substrate S1 of example 1.

In this way receive the substrate 316, containing, calculated on the anhydrous weight, 5% zeolite Z3. The mass content of the anhydrous product in the substrate S16 is 66.5% of Al2O3and 33.5 %SiO2.

Getting hydrocracking catalyst C16 according to the invention

The catalyst C16 obtained by dry impregnation of the substrate S16. The method of producing catalyst C16 identical to the method of preparation of the catalyst C1 of example 1. Mass content of WO3, NiO, P2O5the catalyst C16, respectively 24,5%, 3.5% and 2%.

Characteristics of the catalyst C16 following:

The surface on BET equal to 360 m2/year

Total pore volume, measured by nitrogen adsorption, is of 0.38 ml/year

Total pore volume, measured by mercury porosimetry, is 0.35 ml/year

The average diameter of pores measured by mercury porosimetry equal to 75 Å.

The ratio of the volume V2, measured by mercury porosimetry, corresponding to diameters of Daverage-30 Å to Daverage+30 Å, to the total pore volume, measured by mercury porosimetry, is 0.9.

The volume V3, measured by mercury porosimetry produced pores with a diameter above Daverage+30 Å, equal 0,072 ml/year

The volume V6, measured by mercury porosimetry produced pores with a diameter above Daverage+15 Å, equal 0,087 ml/year

Pore volume, measured by mercury porosimetry produced pores with a diameter higher than 140 Å, equal to 0.055 ml/year

Pore volume, measured by mercury porosimetry produced pores with a diameter higher than 160 Å, equal 0,052 ml/year

Pore volume, measured by mercury porosimetry produced pores with a diameter above 200 Å, equal 0,050 ml/year

Pore volume, measured by mercury porosimetry produced pores with a diameter greater than 500 Å, equal 0,042 ml/year

Radiograph contains:

the main characteristic of the oxide gamma-aluminum, and, in particular, it contains the peaks at d, sostavlyajushie is of 1.39 to 1.40 Å, and d, constituting from 1.97 Å to 2.00 Å,

the main characteristic of zeolite Z3 type USY. The content of atomic sodium is 180+/-20 mind the Content of atomic sulfur is 800 mlnd

Example 17: Obtaining catalyst C17 (not according to invention)

Aluminosilicate matrix used to obtain the catalyst R17 is aluminosilicate matrix AS1 defined in example 1.

Zeolite Z1

Use zeolite Z1 defined in example 1.

Forming the substrate S17

Then mixed with 5 g zeolite Z1 and 95 g of aluminosilicate matrix AS1, supplemented solids, such as described above. Forming the substrate S17 identical to the molding of the substrate S1 of example 1.

In this way receive the substrate S17 containing 5% zeolite Z1 calculated on the anhydrous mass. The mass content of the anhydrous product in the substrate S17 is 66.5% of Al2O3and 33.5% SiO2.

Getting hydrocracking catalyst C17, not according to the invention

The catalyst C17 obtained by dry impregnation of the substrate 317 in the form of an extrudate with an aqueous solution containing a platinum salt and phosphoric acid (H3PO4. Salt of platinum is hexachloroplatinic acid, H2PtCl6. After ripening at ambient temperature in an atmosphere saturated with water, the impregnated extrudates are dried at 120°C during the night, ZAT is calcined at 500°C in dry air. Mass content PtO2and R2About5in the catalyst C17 respectively of 0.58% and 1%.

Characteristics of the catalyst C17 following:

The BET surface 290 m2/year

Total pore volume, measured by nitrogen adsorption, equal of 0.49 ml/year

Total pore volume, measured by mercury porosimetry, equal to 0.47 ml/year

The average diameter of pores measured by mercury porosimetry equal to 70 Å.

The ratio of the volume V2, measured by mercury porosimetry, corresponding to diameters of Daverage-30 Å and Daverage+30 Å to the total pore volume, measured by mercury porosimetry is 0,87.

The volume V3, measured by mercury porosimetry produced pores with a diameter above Daverage+30 Å, equal of 0.045 ml/year

The volume V6, measured by mercury porosimetry produced pores with a diameter above Daverage+15 Å, above 0.05 ml/year

Pore volume, measured by mercury porosimetry produced pores with a diameter higher than 140 Å, equal 0,040 ml/year

Pore volume, measured by mercury porosimetry produced pores with a diameter higher than 160 Å, equal 0,038 ml/year

Pore volume, measured by mercury porosimetry produced pores with a diameter above 200 Å, equal to 0.036 ml/year

Pore volume, measured by mercury porosimetry produced pores with a diameter greater than 500 Å, equal 0,030 ml/year

Radiograph contains:

the main characteristics the s line oxide gamma-aluminum and in particular, it contains the peaks at d average of 1.39 to 1.40 Å, and d, constituting from 1.97 Å to 2.00 Å,

the main characteristic of zeolite Z1 type USY.

The content of atomic sodium is 190+/-20 mind the Content of atomic sulfur is 800 mlnd

Example 18: Obtaining catalyst C18 (not according to invention)

Aluminosilicate matrix used to produce the catalyst C18 is aluminosilicate matrix AS1 defined in example 1.

Zeolite Z1

Use zeolite Z1 defined in example 1.

Forming the substrate S18

Then mixed with 5 g zeolite Z1 and 95 g of aluminosilicate matrix AS1, supplemented solids, such as described above. Forming the substrate S18 identical to the molding of the substrate 31 from example 1.

Thus obtained substrate S18, containing, calculated on the anhydrous weight, 5% zeolite Z1. The mass content of the anhydrous product in the substrate S18 is 66.5% of Al2O3and 33.5% SiO2.

Getting hydrocracking catalyst C18 (not according to invention)

The catalyst C18 obtained by dry impregnation of the substrate S18 in the form of an extrudate with an aqueous solution containing a platinum salt. Salt of platinum is hexachloroplatinic acid, H2PtCl6. After ripening at ambient temperature in an atmosphere saturated with water, saturated extrude the s dried at 120°C during the night, then calcined at 500°C in dry air. Mass content PtO2in the catalyst C16 is 0.58%. Mass content of P2O5in the catalyst C16 is 0%.

Characteristics of the catalyst C18 following:

The BET surface is 292 m2/year

Total pore volume, measured by nitrogen adsorption, equal of 0.49 ml/year

Total pore volume, measured by mercury porosimetry, is 0.47 ml/year

The average diameter of pores measured by mercury porosimetry is 70 Å.

The ratio of the volume V2, measured by mercury porosimetry, corresponding to diameters of Daverage-30 Å and Daverage+30 Å, to the total pore volume, measured by mercury porosimetry is 0,87.

The volume V3, measured by mercury porosimetry produced pores with a diameter above Daverage+30 Å, equal of 0.045 ml/year

The volume V6, measured by mercury porosimetry produced pores with a diameter above Daverage+15 Å, equal to 0.05 ml/year

Pore volume, measured by mercury porosimetry produced pores with a diameter higher than 140 Å, equal 0,040 ml/year

Pore volume, measured by mercury porosimetry produced pores with a diameter higher than 160 Å, equal 0,038 ml/year

Pore volume, measured by mercury porosimetry produced pores with a diameter above 200 Å, equal to 0.036 ml/year

Pore volume, measured by mercury porosimetry prepared pore diameter is use 500 Å, equal 0,030 ml/year

Radiograph contains:

the main characteristic of the oxide gamma-aluminum and, in particular, it contains the peaks at d average of 1.39 to 1.40 Å, and d, constituting from 1.97 Å to 2.00 Å,

the main characteristic of zeolite Z1 type USY.

The content of atomic sodium is 190+/-20 mind the Content of atomic sulfur is 800 mlnd

Example 19: Evaluation of catalysts C1-C16 in the hydrocracking of a vacuum distillate phase high pressure

Catalysts C1-C16, which are described in examples 1-16 was used for carrying out the hydrocracking of a vacuum distillate, the main characteristics of which are given below:

The type of downloadVacuum distillate
Density at 15°C0,9219
Sulfur, % weight.2,52
Nitrogen, weight mlnd880
Simulated distillation
DS: 05%p°C367
DS: 10%p°C380
DS: 50%p°C 443
DS: 90%p°C520
DS: end point°C690

Catalysts C1-C16 was used according to the method according to the invention using the pilot plant, including 1 reactor with a transverse fixed bed, and the environment circulates upwards (upward flow).

Prior experience in hydrocracking catalysts were sulfurously at 120 bar and 350°C by direct distillation gas oil, with the addition of 2 wt%. DMDS.

After sulfonation, the catalytic tests were carried out under the following conditions:

Total pressure: 14 MPa.

Space velocity (VVH) equal to 0.7 h-1.

The temperature required to achieve 70% net conversion (net of conversion).

Catalytic characteristics are expressed net conversion into products having boiling points below 370°C, a net selectivity for middle distillate fraction 150-370°C and attitude "exit gasoil/output kerosene" in the middle distillate fraction. They are derived from the results of the simulated distillation.

Net conversion (CN) has been taken equal to:

CN 370°C=[(%of 370°C-output stream)-(%of 370°C-download)]/

[100-(%of 370°C-download)],

where %370°C-output stream= mass fraction in the output stream with the joining with boiling points below 370°C,

%370°C-download= mass fraction loading of compounds with boiling points below 370°C.

The gross selectivity for middle distillates (SB) is equal to:

SB by definition=[(fraction of 150-370C-output stream)]/

[(%of 370°C-output stream)].

The output of gasoil/output kerosene" (the ratio of Gas./Coeur.) in the middle distillate fraction is calculated as:

The Ratio Of Gas./Coeur.=output fractions (250°C-370°C) output flow /output fraction (150°C-250°C) in the output stream.

The obtained catalytic characteristics are listed below in table 1.

Table 1
The results of the catalysis for single-stage hydrocracking, high pressure
CatalystVVH (h-1)
Surround
speed·h-1
T required for 70% (wt%) CN in the faction 370°CSB (% wt.) for middle distillates (DM)
C10,7395°C73,9
C20,7394°C73,8
C3 0,7393°C73,9
C40,7398°C71,0
C50,7395°C73,8
C60,7394°C73,7
C70,7392°C73,7
C80,7398°C71,1
C90,7397°C73,7
C100,7400°C73,7
C110/7395°C73,8
C120/7396°C73,7
C130,7397°C73,9
C140,7398°C73,6
C150,7398°C73,6
C160,7398°C73,6

The examples show that the introduction of USY zeolite according to the invention and controlled additive promoting phosphorus according to the invention allows to obtain a significant gain in activity without loss of selectivity for middle distillates.

Thus, the catalysts C1 and C5, corresponding to the invention, have the best catalytic performance compared with catalysts C9 not according to the invention, having a volume of pores produced pores with a diameter greater than 500 Å, respectively, 0.002 ml/g catalysts C1 and C5 allows to obtain a conversion of 70% at less high temperature than is required when using C9. The catalysts C1 and C5 are particularly suitable to obtain middle distillates in accordance with the invention.

Catalysts C1, C3, C15, C5, C6, C7 and C16 corresponding to the invention, have the best catalytic performance compared with catalysts C4 and C8 are not according to the invention, having a permanent elementarnoi cell of the crystal lattice, equal 24,53 Å.

It is interesting to note that the catalysts C1, C5 and C6, with constant and unit cell of the crystal lattice lying in a preferred range from 24,38·10-10m to 24,24·10-10m, have the best catalytic performance compared with catalysts C15 and C16, also relevant to the invention, and are particularly suitable to obtain middle distillates in accordance with the invention.

Catalysts C1, C5, C11 and C12, responsive to the invention, have the best catalytic performance compared with catalysts C13 and C14 is not according to the invention with the content of the promoting element (phosphorus), respectively 0 and 6/5% weight.

Thus, the preceding examples show all the benefits of the use of the catalyst according to the invention for carrying out the hydrocracking of hydrocarbon fractions. Indeed, the combination of the substrate, combining the silica matrix with controlled share of macropores, type zeolite Y having a controlled constantandthe unit cell of the crystal lattice, and optimized hydrogenating phase allows you to get high conversion download and best selectivity for middle distillates.

Example 20: Evaluation of catalysts C17 and C18 in conditions simulating the operation of the second reactor hydrocracking called what about the two-step

Download the second stage is the product of the Hydrotreating of vacuum distillate on the Hydrotreating catalyst produced in sale Axens, in the presence of hydrogen, at a temperature of 395°C and at a volumetric hourly rate of 0.55 h-1. Conversion into products 380°C is approximately 50% weight. After phase separation fraction 380°C+collect and send the power to the second stage. Physico-chemical characteristics of this load are presented in table 2:

Table 2
Load characteristics in the second stage
Density (20/4)0,853
Sulfur (weight mlnd)2,5
Nitrogen(weight mlnd)1,4
Simulated distillation
The starting point322°C
Point 5%364°C
Point 10%383°C
Point 50%448°C
Point 90%525°C
Endpoint589°C

This download is introduced in the test setup of the second hydrocracking stage containing a reactor with a fixed bed, in ascending circulation load ("thermal"), which introduced the catalyst according to the invention. Before the introduction of loading the catalyst restore in an atmosphere of pure hydrogen at 450°C for 2 hours.

Operating conditions of the test setup are as follows:

The total pressure14 MPa
Catalyst50 ml
Temperature370°C
Space velocity (vvh)h-11,1

Catalytic characteristics obtained under these conditions are described below in table 3 of this example.

Table 3
Catalytic results
CatalystVVH (h-1)
The volumetric rate·h-1
CN 370°C-the % weight.SB (% wt.) for middle distillates (DM)
C17 1,180,071,8
C181,178,272,0

Thus, these results show all the benefits of the use of the catalyst according to the invention for carrying out the hydrocracking of hydrocarbon fractions. Indeed, they allow to obtain high conversion download and best selectivity for middle distillates.

Example 21: Evaluation of catalysts C1-C16 in the single-stage hydrocracking of a vacuum distillate at moderate pressure (mild hydrocracking)

Catalysts C1-C16, which are described in examples 1-16 was used to conduct single-stage hydrocracking of a vacuum distillate at moderate pressure (mild hydrocracking). The main characteristics of the vacuum distillate below:

The type of downloadVacuum distillate
Density at 15°C0,9219
Sulfur, % weight.2,52
Nitrogen, weight mlnd880
M is delawanna distillation
DS: 05%p°C367
DS: 10%p°C380
DS: 50%p°C443
DS: 90%p°C520
DS: end point°C690

Catalysts C1-C16 was used according to the method according to the invention, using pilot plant containing 1 reactor with a transverse fixed bed, and the environment circulates upwards (upward flow).

To test the hydrocracking catalysts were sulfurously at 120 bar and 350°C by direct distillation gas oil with the addition of 2 wt%. DMDS.

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

The total pressure5.5 MPaT=405°C
General VVH0.8 h-1
Space velocity (VVH) is equal to 0.8 h-1.

Catalytic characteristics are expressed in net conversion to products boiling below 370°C, the net selective behaviour is awn faction of middle distillates 150-370°C and relative exit gasoil/output kerosene" in the middle distillate fraction. They are derived from the results of the simulated distillation, and definitions are the same as made in example 19.

The obtained catalytic characteristics are shown below in table 4.

Table 4
Catalytic results for mild hydrocracking under moderate pressure
CatalystVVH (h-1)
Surround
speed·h-1
CN 370°C-the % weight.SB (% wt.) for middle distillates (DM)
C10,849,881,2
C20,849,880,9
C30,8to 49.980,8
C40,848,078,0
C50,849,681,2
C60,849,8 80,9
C70,850,080,7
C80,848,178,1
C90,848,180,6
C100,847,080,7
C110,849,681,2
C120,849,681,2
C130,84980,5
C140,849,180,6
C150,84880,5
C160,84880,5

Interpretation of results table 4 shows, therefore, how interpretacija results of table 1, benefit from the use of the catalyst according to the invention for the conduct of hydrocracking of hydrocarbon fractions. Indeed, the combination of the substrate, combining the silica matrix with controlled share of macropores, type zeolite Y having a controlled constantathe unit cell of the crystal lattice, and optimized (in particular, in regard to the content of the promoting element) hydrogenating phase, allows to obtain high conversion download and best selectivity for middle distillates.

1. The catalyst containing at least one hydrogenating-dehydrating element selected from the group formed by the elements of group VIB and group VIII of the Periodic system, from 0.5 to 2.5 wt.% oxide of phosphorus, which is the promoting element, and the substrate on the basis of zeolite Y, defined constant and unit cell of the crystal lattice component from 24,40·10-10to 24,15·10-10m, and on the basis of aluminosilicate containing silicon oxide (SiO2in excess of 5 wt.% and less than or equal to 95 wt.%, with the specified catalyst has the following characteristics:
the average diameter of pores measured by mercury porosimetry ranges from 20 to 140 Å,
total pore volume, measured by mercury porosimetry is from 0.1 to 0.5 ml/g, '
total pore volume, measured by nitrogen the second porosimetry, is from 0.1 to 0.5 ml/g, '
specific surface area by BET ranges from 100 to 600 m2/g
pore volume, measured by mercury porosimetry produced pores with a diameter higher than 140 Å, of less than 0.1 ml/g, '
pore volume, measured by mercury porosimetry produced pores with a diameter higher than 160 Å, below 0.1 ml/g, '
pore volume, measured by mercury porosimetry produced pores with a diameter above 200 Å, less than 0.1 ml/g, '
pore volume, measured by mercury porosimetry produced pores with a diameter greater than 500 Å, is strictly greater of 0.03 ml/g and less than 0.1 ml/g
radiograph of which contains at least the main characteristic of at least one of transition alumina included in the group consisting of oxides of aluminum alpha, Rho, Chi, ETA, gamma, Kappa, theta and Delta,
the density of the packing of the catalyst is higher than 0.75 g/cm3.

2. The catalyst according to claim 1, in which the pore volume, measured by mercury porosimetry produced pores with a diameter greater than 500 Å, more of 0.03 ml/g and less of 0.07 ml/year

3. The catalyst according to claim 1 on the basis of molybdenum and tungsten.

4. The catalyst according to claim 1 on the basis of Nickel and tungsten.

5. The catalyst according to claim 1, which contains from 0.1 to 30 wt.% zeolite Y.

6. The catalyst according to claim 1, wherein the substrate is a substrate on the basis of zeolite Y, defined constant and unit cell of the crystal lattice, costall the ment from 24,38·10 -10to 24,24·10-10m

7. The catalyst according to claim 1, which additionally contains at least one element of group VIIB.

8. The catalyst according to claim 1, which additionally contains at least one element of group VB.

9. The catalyst according to claim 1 with such a pore distribution that the ratio of the volume V2, measured by mercury porosimetry, corresponding to diameters of Daverage-30 Å to Daverage+30 Å, to the total pore volume, measured by mercury porosimetry, is more than 0.6; the volume V3, measured by mercury porosimetry compiled pores of diameter greater than Daverage+30 Å, is less than 0.1 ml/g;
the volume V6, measured by mercury porosimetry produced pores with a diameter above Daverage+15 Å, is less than 0.2 ml/g

10. The catalyst according to one of claims 1 to 9, such that the x-ray contains at least the main characteristic of at least one transition alumina included in the group consisting of oxides of aluminum, this, theta, Delta and gamma.

11. The catalyst according to one of claims 1 to 9, in which the surface according to BET below 350 m2/year

12. The catalyst according to one of claims 1 to 9, optionally containing a small proportion of at least one stabilizing element selected from the group formed by zirconium and titanium.

13. Method of hydrocracking and/or hydroconversion hydrocarbon fractions, use the Mering catalyst according to one of the preceding paragraphs.

14. Method of hydrocracking and/or hydroconversion on 13 held in a process called single-stage.

15. Method of hydrocracking and/or hydroconversion on item 13, including at least one first reaction zone of the hydrotreatment and at least one second reaction zone with a hydrocracking at least part of the flow coming from the first zone and including an incomplete separation of the ammonia from the stream coming from the first zone.

16. Method of hydrocracking and/or hydroconversion one of p or 15, including:
the first reaction zone of the hydrotreatment, in which the load is brought into contact with at least one Hydrotreating catalyst, detecting in the standard test the activity degree of conversion of cyclohexane is below 10% by weight,
the second reaction zone hydrocracking, in which at least part of the flow coming from the stage Hydrotreating, is brought into contact with at least one zeolite hydrocracking catalyst according to one of claims 1 to 12, detecting in the standard test the activity degree of conversion of cyclohexane is higher than 10% by mass.

17. Method of hydrocracking and/or hydroconversion indicated in paragraph 13 in a process called two-stage.

18. The method according to item 13, carried out in the presence of hydrogen at temperatures above 200°C and at a pressure above 1 MPa, and the volumetric rate of the leaves from 0.1 to 20 h -1and amount of the hydrogen such that the volume ratio of litres of hydrogen/litres of hydrocarbon" is from 80 to 5000 l/l

19. Method of hydrocracking and/or hydroconversion on 13 carried out at a pressure of from 2 to 6 MPa and held until the conversion is below 40%.

20. The method according to item 13, carried out in a fixed bed.

21. The method according to item 13, carried out in a fluidized bed.

22. The method of Hydrotreating a hydrocarbon fractions, using the catalyst according to one of claims 1 to 12.

23. The method according to item 22, undertaken prior to hydrocracking.

24. The method according to item 23, in which the hydrocracking catalyst is a catalyst based on zeolite.

25. The method according to item 23, in which the hydrocracking catalyst is a catalyst based on aluminum silicate.

26. The method according to one of p-25, in which the hydrocracking catalyst is a catalyst based on Nickel and tungsten.

27. The method according to item 13, in which the hydrocarbon fraction selected from the group consisting of LCO (Light Cycle Oil, light gas oils, obtained by catalytic cracking), atmospheric distillates, vacuum distillates, fractions on the setting of the extraction of aromatics from lubricating base oils or obtained in solvent dewaxing lubricating base oils, distillates, obtained in the process of desulfurization or hydrocone the AI RAT (atmospheric residues), and/or RSV (vacuum residues)and/or deasphalting oil in a fixed bed or fluidized bed, deasphalting oils, individually or in a mixture.

28. The method according to item 13, in which the load passes first through a layer of catalyst or absorbent, non-catalyst hydrocracking/hydroconversion or Hydrotreating.



 

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18 cl, 2 dwg, 4 tbl, 3 ex

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12 cl, 3 tbl, 22 ex

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.

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18 cl, 5 tbl

FIELD: mining.

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4 cl, 2 ex

FIELD: chemistry.

SUBSTANCE: invention refers to the method of the reduction of hydrogenisation catalyst by the way of serial operations of 1) hydrocarbon desorption from the surface of the spent catalyst located in the stationary layer in the media of hydrogen-containing gas at temperature 200-400°C; 2) passivation of the catalyst surface by its treatment with oxygen-containing gas (oxygen content is 0.02-0.5 vol. %) in the stationary layer at temperature 100-120°C; 3) burn-off of the hydrocarbon condensation products in the oxygen-containing gas flow at temperature 400-550°C; 4) catalyst conversion from oxide to presulphide form by their contacting with elemental sulphur in the air or inert gas flow. The burn-off of the hydrocarbon condensation products and catalyst transforming are implemented in the moving-bed catalyst with burn-off temperature being regulated with the oxygen-containing gas temperature and volume ratio oxygen-containing gas :catalyst in the range (15-30):1.

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3 cl, 5 tbl, 2 ex, 2 dwg

FIELD: oil and gas industry.

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EFFECT: development of efficient method of hydro-fining oil fractions.

3 cl, 1 tbl

FIELD: chemistry.

SUBSTANCE: catalyst is processed with sulphiding agent, which includes sulphur-organic compound and oil fraction, in particular 1.0-2.0%-solution of dimethyldisulphide in Diesel fuel, dimethyldisulphide being introduced into Diesel fuel step-by-step; thermoprocessing of catalyst being carried out as step-by-step increase of temperature within the interval 160-340°C, after which temperature is reduced to 28-290°C, with general activation duration 20-30 hours.

EFFECT: reduction of equipment corrosion with sulphur oxides, obtaining ecologically pure, low-sulphureous Diesel fuel, polycyclic aromatic hydrocarbons in small amount, increasing degree of unlimited hydrocarbons and reduction of gumming-up of main hydropurification catalyst.

3 cl, 6 ex, 1 tbl

FIELD: chemistry.

SUBSTANCE: invention concerns method of hydrotreating catalyst activation containing metal oxide of group VIB and metal oxide of group VIII containing contacting catalyst, acid and organic additive with boiling point within 80-500°C and water solubility, at least, 5 gram per litre (20°C, atmospheric pressure), optionally with following drying in the environment providing at least, 50% of the additive remains in the catalyst. There are disclosed hydrotreating catalyst produced by the method described above, and method of hydrotreating raw hydrocarbons there after applied.

EFFECT: higher activity of both raw hydrotreating catalyst, and utilized hydrotreating catalyst being regenerated.

20 cl, 8 ex

FIELD: chemistry.

SUBSTANCE: invention describes method of obtaining aggregated catalyst for hydrogen treatment of oil fractions. The catalyst is a composition of components in the form of compounds of one VIII group metal and two VIB group metals. Method involves mixing and chemical interaction of components, producing active complex by mechanic and chemical activation of components, which remain in solid state during the whole process performed in aggregates of mechanic and/or hydrodynamic effect, preferably in planetary centrifugal mill, at room temperature for 5-30 minutes, with free pass distance of milling bodies equal to 4.0-5.0 cm, relative collision speed of milling bodies equal to 17-34 m/s, reaction layer thickness for component mix on the surface of milling bodies equal to (0.4-2.6)·10-2 cm, with further drying, tempering and sulfidation. Active complex is dried for 10-15 minutes.

EFFECT: high-grade purification of oil products from sulfur.

1 cl, 1 tbl, 2 dwg, 5 ex

FIELD: chemistry.

SUBSTANCE: invention refers to high metal catalyst compositions, production and application thereof in hydrotreating, specifically in hydrodesulfurisation and hydrodenitrogenating. Described is carrier-free catalyst composition containing one or more metals of VIb group, one or more metals of VIII group and refractory oxide material which contains at least 50 wt % of oxide-based titanium dioxide. Described is production method of catalyst compositions implying that one or more compounds of metal of VIb group is combined with one or more compounds of metal of VIII group and with refractory oxide material containing titanium dioxide with proton liquid and optionally alkaline compound; and catalyst composition is recovered by following precipitation. Described is application of composition described above or produced by method described above, moulded and sulphided if necessary, in hydrotreating of hydrocarbon raw materials.

EFFECT: higher activity of catalyst composition.

15 cl, 8 tbl, 16 ex

FIELD: chemistry.

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

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

23 cl, 3 ex

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