Method for making medium distillates and lubricant bases relying on synthetic hydrocarbon materials

FIELD: oil and gas industry.

SUBSTANCE: invention refers to method for simultaneous making medium fractions and lubricant bases from synthetic paraffin mixtures, including hydrocracking stage (i) and distillation of product of stage (i), where hydrocracking involves addition of solid bifunctional catalyst including: (A) acidic carrier consisting of catalystically active porous solid substance, including silicon, aluminium, phosphorus and oxygen interlinking so that to form mixed amorphous solid substance, characterised by nuclear ratio Si/Al within 20 to 250, ratio P/Al at least 0.1, but lower that 5, total porous amount within 0.5 to 2.0 ml/g, average pore diameter within 2 nm to 40 nm and specific surface area within 200 to 1000 m2/g; (B) at least one metal with hydrogenation-dehydrogenation activity, selected from groups with 6th on 10th of Periodic systems and distributed over specified carrier (A) in amount within 0.05 to 5 wt % relative to total mass of catalyst.

EFFECT: development of method for simultaneous making medium fractions and lubricant bases from synthetic paraffin mixtures.

25 cl, 26 ex, 5 tbl, 2 dwg

 

This invention relates to a method of producing middle distillates and fundamentals of lubricants on the basis of predominantly paraffinic hydrocarbon synthetic origin.

More specifically this invention relates to a method of simultaneously producing medium fractions and fundamentals of lubricants with a balanced output on the basis of raw materials, consisting mainly of mixtures of n-paraffins, comprising at least one stage of hydrocracking in the presence of a specific bifunctional catalyst.

A mixture mainly of paraffin hydrocarbons, including a significant number of fractions with high boiling point, usually produced as a VAT residue in the processes of refining fuel oil origin. Other mainly paraffin products are, for example, so-called "crude paraffins", which is obtained as a byproduct in the manufacture of bases for lubrication through the process of solvent extraction.

Known also receive hydrocarbon mixtures consisting mainly of n-paraffins, in which a significant fraction has a boiling point above 370°by catalytic synthesis from a mixture of hydrogen and carbon monoxide (synthesis gas) in the so-called processes of Fischer-Tropsch, the names of the image is atela the first synthesis of this type in the thirties.

It is known that the synthesis of Fischer-Tropsch (FT) leads to the formation of products comprising n-paraffins (>90%) (in addition to alcohols and olefins with a lower percentage), which offer a wide range of molecular masses. These products are usually solid or semi-solid (wax) state at room temperature. A feature of the process FT is that it is impossible to synthesize a product with a narrow distribution of molecular masses. Moreover, due to the chemical nature of these products of low-temperature characteristics of the middle distillate are very bad.

Guided by the above mentioned hydrocarbon mixtures, especially of FT paraffins, must be treated to reduce (destruction) and/or increasing chain length (degradacii) to obtain products of greater interest, such as fuel, lubricants, solvents and other derivatives, having the best properties. Currently, improvements in the above-mentioned aspects of reach, putting these paraffins (waxes) more or less complex processes to reduce the chain length in the presence of hydrogen (usually known as the "hydrocracking") and hydroisomerization.

Kerosene and gas oil obtained by hydrocracking of FT-paraffin, have excellent feature is specific as regards the specific requirements for fuels, and because of their low damage to the environment. The absence of heteroatoms such as sulfur, and aromatic structures, leads to a drastic reduction of pollutant emissions, such as particulates and NOx.

At the same time develop catalysts for hydrocracking and/or isomerization to obtain lubricating oils having optimum characteristics from the point of view of composition and degree of isomerization bases for greases, derived from n-paraffin feedstock. These processes hydrocracking is carried out in the presence of a bifunctional catalyst containing a metal with hydro-dehydrogenative activity deposited on the inorganic solid substance, usually composed of oxide or silicate with acid properties.

The hydrocracking catalysts typically contain metals from groups 6 to 10 of the Periodic system of elements (in the form approved by IUPAC and published by CRC Press Inc. in 1989, on which the following are the links), especially Nickel, cobalt, molybdenum, tungsten, or noble metals such as palladium or platinum. While the former are more suitable for processing mixtures of hydrocarbons having a relatively high content of sulfur, noble metals are more active, but poisoned by sulfur and require raw material which is substantially free from it.

Is the guides, which can be used for this purpose are various types of zeolites (β, Y), X-Al2O3(where X can be Cl or F), the silicates, the latter may be amorphous or with different degree of crystallinity, or a mixture of crystalline zeolites and amorphous oxides. A very extensive study of various catalysts, the specific characteristics and different hydrocracking processes based on them can be found, among many available in the literature, publishing J.Scherzer and A.J.Gruia "Theory and technology of hydrocracking" ("Hydrocracking Science and Technology"), Ed. Marcel Dekker, Inc. (1996).

It is also well known that the above-mentioned processes, isomerization, and hydrocracking is carried out at conditions where the degree of conversion on single pass of the high-boiling fraction rarely exceeds 90%, and is normally maintained below 80%, especially in order to reduce the light fractions, representing a low value. Not participating in the transformation of the fraction can be returned recycle to the hydrocracking or separated and used to provide the basics for lubrication. In this case, the high-boiling residue must be subjected to further processing (isomerization and/or dewaxing), the purpose of which is the transformation or separation present in him paraffin fraction.

One of the most significant problems in the process the e hydrocracking mixtures of linear paraffins is the difficulty of simultaneously receiving the same process of middle distillates with good low-temperature characteristics and the fraction of 360+° With acceptable characteristics from the point of view of the average molecular weight and the degree of isomerization to provide the basics of lubricants. If the fraction 150+°To be subjected to hydrocracking using the currently used catalytic systems and to carry out the reaction in such a way as to obtain middle distillates, having good low-temperature characteristics, the remainder 360+°With low molecular weight and, therefore, the basis for the lubricant has a low viscosity. If this reaction, in contrast, be carried out in such a way as to receive the shoulder straps 360+ with a sufficiently high molecular weight, then outputs the basics of lubricants are low because of the presence of the still high number of linear paraffins, which makes it necessary to conduct subsequent stage dewaxing and, in addition, low-temperature properties of middle distillates are unsatisfactory.

Up to the present time, apparently, no solution had been found for all of the above-mentioned problems in relation to known processes and catalysts. Despite the fact that the use as a substrate for a catalyst of some specific amorphous micrometeoritic of silicates, as described in European patent application EP-A 1101813, enables you to provide excellent is ravnovesie between gasoil and kerosene in fractions of the middle distillate, it is apparently not possible to get the faction bases lubricant with optimum characteristics, which give the possibility to use it without any further special treatment.

Now unexpectedly discovered that some amorphous silicates with a low aluminium content, containing some amount of phosphorus associated with the oxide matrix, perfect as an active substrate in combination with one or more metals with hydro-dehydrogenation properties to obtain the catalyst of the refining processes, such as Hydrotreating of hydrocarbons for fuel production and bases for lubricants.

Thus, the objective of the invention is a method for middle distillates and fundamentals of lubricants on the basis of a mixture mainly of paraffin hydrocarbons obtained by a process of synthesis from hydrogen and carbon monoxide, comprising at least 30%, preferably at least 50% of high-boiling fraction having a distillation temperature above 360°including:

(i) at least one stage hydrocracking, in which the hydrocarbon mixture is reacted with hydrogen at a temperature of from 200 to 450°and a pressure of from 0.5 to 15 MPa in the presence of a catalyst for a time sufficient to build the value of at least 40%, preferably from 60 to 95% of the specified high boiling point mixture in a fraction of hydrocarbons that can overtake at temperatures below 360°C;

(ii) at least one stage of distillation of the product of stage (i) to allocate at least part of the middle distillate and at least one VAT residue, suitable for receiving the base of the cutting materials with a boiling point above 340°used, at least partially, for getting the basics of lubricants;

characterized in that the catalyst at this stage hydrocracking (i) includes a catalyst deposited on a solid carrier and includes:

(A) a carrier of acid nature, consisting of a catalytically active porous solids, including silicon, aluminum, phosphorus and oxygen, are related to each other thereby to form a mixed amorphous solid, forming a single phase and characterized by atomic ratio Si/Al from 15 to 250, the atomic ratio of P/Al of at least 0.1, but lower than 5, preferably from 0.3 to 3.5, a total pore volume from 0.5 to 2.0 ml/g, an average pore diameter in the range from 3 nm to 40 nm and a specific surface area in the range from 200 to 1000 m2/g, preferably from 300 to 900 m2/g;

(B) at least one metal with hydro-dehydrogenative activity selected from the group of C6 to 10 of the Periodic system of elements, distributed (dispersed) on the specified media (A) in an amount of from 0.05 to 5 wt.% in relation to the total weight of the catalyst.

The objective of the present invention will become apparent from the following description and claims.

The meaning of some terms used here are defined below to further clarify the description and claims of this patent application and to indicate its scope:

the term "amorphous"is used here in relation to porous catalyst carrier according to this invention and its compounds and applications, indicates significant absence of signals on the x-ray scattering at low angles, as described hereinafter commonly used technique of measurement;

"the distillation temperature relating to a hydrocarbon mixture, indicates, if it is not specifically mentioned, the temperature in the upper part of the column or range of temperatures in a typical distillation columns, in which collected this mixture under normal pressure (0,1009 MPa);

the definition of interval always includes limit values, if it is not specifically mentioned; however, the term "interval includes, within two limit values, refers to any interval between the specified limit values;

the term "hydrocracking" is used here with a total value of high temperature the catalytic treatment of hydrocarbon mixtures preferably comprising fraction with a boiling point above 350°With, in the presence of hydrogen to obtain a mixture with a lower boiling point; processing by hydrocracking typically includes also the so-called processing by hydroisomerization if you get isomerized product having a boiling point lower than the boiling point of the mixture;

the terms "kerosene" and "oil"as used here refer to two hydrocarbon fractions, forming the so-called middle distillate from the distillation temperature of 140 to 280°and from 240 to 380°respectively.

In its most General form acidic media (A) of the catalyst according to this invention essentially includes a homogeneous amorphous phase of mixed oxides of silicon, aluminum and phosphorus, where the phosphorus is in the maximum oxidation state (+5) and is usually associated with a matrix of other oxides through links P-O-Al, as determined by spectroscopic analysis27Al-NMR and31P-NMR. He has an extremely high surface area (determined by BET method), preferably in the range from 300 to 900 m2/g, more preferably from 400 to 800 m2/g, and a pore size within the range of mesopores, preferably with an average diameter (defined by the DFT method) in the range from 5 to 30 nm, more before occhialino from 6 to 25 nm. Porosity (total pore volume in ml/g) is extremely high and can be adjusted within certain limits by using time, temperature and other operating parameters in the formation of gel in the process of obtaining the specified media. The porosity of the amorphous carrier preferably is in the range from 0.7 to 1.7 ml/year

From the point of view of the morphology of the catalytically active amorphous solid of the present invention includes a disordered pore structure with modal, essentially, the size distribution within a relatively wide range. The difference in pore sizes between 10% and 90% of the distribution curve is preferably in the range of diameters from 2 to 40 nm, preferably from 5 to 30 nm. The oxides that form the matrix, in turn, randomly located in a three-dimensional polymer lattice without forming crystalline structures that can be determined by x-ray method.

Specified acidic amorphous media consists mainly of silicon oxide and is characterized by the presence of certain amounts of Al and P, associated homogeneous and dispersed in the oxide matrix, so that the ratio of P/Al is below 5 and at least equal to 0.1. For the ratio P/Al equal to 5 and above, there is significant compression of the porous structure, with a significant reduction properties to the of telesfora and media; for values of P/Al below 0.1 not observed a significant improvement compared to conventional amorphous matrix of silicon oxide and aluminum oxide, which has a similar composition. More preferable results were obtained when the ratio of P/Al in the range from 0.3 to 3.5, and particularly in the range from 0.5 to 2.5.

One of the essential characteristics of the catalyst according to this invention is the selection of the aluminum content in the media (A) within a narrow and quantitatively limited range, which, in turn, determines the range of phosphorus content; the Atomic ratio Si/Al is preferably in the range from 20 to 200, more preferably from 25 to 150.

Specified amorphous media may also include, if necessary, smaller amounts of other components in the mixture or dispersed in the oxide matrix, in particular other metal compounds, especially oxides, non-oxides, which form component (B), and is suitable to impart specific characteristics or catalytic properties. These additional components are usually not more than 20 wt.% amorphous solids, preferably up to 10 wt.%. In particular, the carrier of the catalyst according to this invention may contain a mixture of oxides of phosphorus or phosphate no links with the matrix of amorphous oxides of si and al is MINIA. Other oxides that may be present, represent some oxides of transition metals, especially selected from Ti, Zr, V, Zn, Ga and Sn, while alkaline or alkaline-earth metals are preferably absent or present only in trace quantities. These metals can preferably provide an amorphous solid according to the invention with improved mechanical properties and additional catalytic functions, such as oxidation, which are required for some industrial processes.

Specified amorphous media can be obtained by adapting various typical Sol-gel methods for micro - or mesoporous amorphous aluminosilicates, by adding the required number of suitable phosphorus compounds at any stage prior to the calcination, preferably before the formation of a gel or in the process of its formation. This compound is phosphorus preferably selected from organic or inorganic oxygen-containing compounds capable of forming the oxide of phosphorus or phosphate group after the oxidation heat treatment required for drying and calcination of the gel, more preferably in such a way as to avoid the introduction of unwanted traces of metals in the matrix of the porous oxide obtained after calcination.

Sol-gel methods for the production of amorphous silicates, which can be adapted for this purpose are described, for example, in European patent applications EP-A 160145, EP-A 340868 and EP-A 659478 or in the publication "Journal of Catalysis", v.60 (1969), pp.156-166, the contents of which are incorporated here by reference, without limiting the scope of the present invention mentioned methods.

The preferred method of obtaining this amorphous active substrate (A) comprises receiving at the first stage, a mixture containing of tetraalkylammonium hydroxide, a compound of aluminum and silicon compound that can be hydrolyzed to the corresponding hydroxides, oxygen-containing compound of phosphorus and a sufficient amount of water for dissolution and hydrolysis of these compounds, and specified of tetraalkylammonium hydroxide containing from 1 to 10 carbon atoms in each alkyl group, specified capable of hydrolysis of the compound of aluminium is preferably dialkoxy aluminum containing from 1 to 10 carbon atoms in each alkoxide group specified capable of hydrolysis of the silicon compound is a silicate at least one hydrocarbon residue, preferably tetraalkylammonium containing from 1 to 10 carbon atoms in each alkyl group, and a specified oxygen-containing compound of phosphorus is from the battle salt or phosphate or postnewly ether or the corresponding acid, preferably ammonium salt or a phosphate or postnewly ether in which each alkyl group contains from 1 to 10 carbon atoms.

An aqueous mixture of the above compounds then hydrolyzing and turn into a gel in the second stage by heating in an alkaline medium, preferably at pH above 10, by boiling under reflux in a closed vessel at normal boiling point or higher, or in an open vessel below this temperature, so that essentially there is no exchange of material with the external environment. Thus obtained gel is then subjected to a third stage drying and calcination.

The aqueous mixture at the said first stage can be prepared in water or in a mixture of water and soluble oxygen-containing organic compounds, preferably alcohol having from 1 to 10 carbon atoms, in an amount up to a molar ratio of 1/1 to water. More preferably this oxygen-containing compound is an alcohol with the number of carbon atoms from 2 to 5. During hydrolysis in water. the solvent is released additional amounts of alcohol.

Of tetraalkylammonium hydroxide, which can be used for the purposes of this invention, are selected, for example, hydroxides tetraethyl-, propyl-, isopropyl-, butyl-, isobutyl-, tert-butyl and pentylamine, and from them predpochtitel the YMI are the hydroxides of tetrapropyl-, tetraisopropyl and tetrabutylammonium. Trialled aluminium choose, for example, of triathlete, propylate, isopropylate, butyl, isobutylene and tert-butyl aluminum, and among them, preferred are tripropyl, triisopropyl aluminum. Tetrachlorosilane choose, for example, tetramethyl-, tetraethyl-, propyl-, isopropyl-, butyl, isobutyl, tert-butyl and pentyl-orthosilicate, and among them, preferred is tetraethylorthosilicate.

Oxygen-containing compound of phosphorus is preferably selected from organic or inorganic compounds soluble in the reaction mixture containing phosphate, fotinou or fosfonovoi group. According to one embodiment of the present invention, the connection of phosphorus may also be formed in situ in the reaction mixture, or it can be added to the said mixture in the form of a solution in a suitable solvent, preferably in alcohol or water. Typical phosphorus compounds suitable for this purpose are, for example, phosphoric acid, phosphorous acid, ammonium phosphate, Quaternary ammonium phosphates with organic amines having 1 to 5 carbon atoms in each group connected to the nitrogen atom, organic phosphites and phosphates of alcohols having from 1 to 10, preferably from 1 to 5 carbon atoms, acidic ammonium phosphates or che is vertices ammonium, alkylphosphonate or alkylphosphonate with alkyl groups having from 1 to 10, preferably from 1 to 5 carbon atoms.

Particularly preferred phosphorus compounds are ammonium phosphate, acid phosphate of ammonia and the corresponding Quaternary phosphates with organic amines having 1 to 4 carbon atoms per group, especially in the form of a solution prepared by adding to water phosphoric acid and the corresponding stoichiometric amount of ammonia or amine.

When receiving water mixture indicated the first stage, the order of addition of the various reactants is not particularly critical. The connection of phosphorus can be added to or forming in situ at first, together with the addition of tetraalkylammonium hydroxide, adjusting the amount in accordance with the desired final ratio between atoms and components, or it can be added after the introduction of combinations of Si and Al. The mixture is prepared at room temperature or at a slightly higher its value, preferably between 30 and 80°C. Although the thus obtained mixture preferably is a transparent solution, some compounds, such as aluminum alkoxide, can be partially insoluble, but are completely dissolved under heating and subsequent hydrolysis stage. In some case the s to obtain the solution may take time up to five hours under stirring.

In a preferred embodiment of the method of receipt of amorphous solids of this invention are first obtained an aqueous solution containing a hydroxide of tetraalkylammonium and dialkoxy aluminum, using a temperature that is sufficient to ensure the effective dissolution of aluminum compounds, preferably from 40 to 80°C. To the specified water solution add tetrachlorosilane. If necessary, regulate pH to values above 10, preferably from 11 to 12. This mixture is brought to a temperature which is acceptable to start the hydrolysis reaction. This temperature is related to the composition of the reaction mixture (typically from 60 to 120°). The hydrolysis reaction is exothermic and thus ensures the temperature, if the response has already been activated. The number of components of the mixture are chosen in accordance with the atomic ratios between the elements, which must be received in the catalytically active solid substance at the receiving end; typically, the following atomic or molar ratios: Si/Al from 10/1 to 250/1, (of tetraalkylammonium hydroxide)/Si from 0.05/1 to 0.2/1, H2O/SiO2from 5/1 to 40/1, P/Al from 0.1 to 5.0. The preferred values for these ratios are: Si/Al from 30/1 to 150/1, (of tetraalkylammonium hydroxide)Si from 0.05/1 to 0.2/1, P/Al ranging from 0.5 to 3.5 and H2O/SiO2from 10/1 to 25/1.

Hydrolysis of the reagents and the gelation is preferably carried out, operating at a temperature equal to or higher than the boiling point (at atmospheric pressure) of any alcohol, which is released as a by-product of the specified hydrolysis reaction, without isolation or without a significant selection of these alcohols from the reaction environment. Therefore, the temperature of the hydrolysis and gelation is critical, and it is usually supported at values above about 65°and up to about 110°C. in Addition, for retention within the reaction medium resulting alcohol can work in the autoclave when the system pressure at a given temperature (typically of the order of 0.11-0.15 MPa abs.) or at atmospheric pressure in a reactor equipped with a reflux condenser.

In accordance with a particular case of the complete method hydrolysis and gelation is carried out in the presence of a certain amount of alcohol, having a higher number of carbon atoms than that of alcohol, which is released as a by-product. To this end the free alcohol, preferably ethanol, is added to the reaction mixture in amounts up to the maximum molar ratio between the added alcohol and SiO2equal to 8/1.

The time required to complete the I hydrolysis and gelation of the above conditions, usually from 10 minutes to 3 hours and preferably is on the order of 1-2 hours.

It was also found that it is useful to subject the thus obtained gel aging by keeping the reaction mixture in the presence of alcohol at room temperature in a time of about 1-24 hours

In conclusion, the alcohol is removed from the gel, which is dried, as is customary in the art, thus, to prevent cracking solids and essentially preserving the pore structure. Usually use a reduced pressure, typically from 1 to 20 kPa, preferably from 3 to 6 kPa, together with a temperature in the range from 50 to 120°C, preferably from 100 to 110°C. According to the preferred method of drying is performed with a gradient (or profile) (increasing) temperature and (downward) pressure within the above intervals, to ensure the progressive evaporation of the solvent. The dried gel at the end is subjected to calcination in an oxidizing atmosphere (usually air) at a temperature in the range from 500 to 700°C for 4 to 20 hours and preferably at 500-600°C for 6-10 hours, in this case also, it is preferable to operate at an appropriate temperature gradient.

Thus obtained amorphous media on the basis of silicon, aluminum is I and phosphor has a composition, the appropriate composition of the used reagents, assuming that the reaction goes almost completely. Therefore, the atomic ratio Si/Al in the preferred case varies from 15/1 to 250/1, with the most preferred range is from 20/1 to 150/1, in particular about 100/1. This carrier is obtained essentially amorphous (according to the results of x-ray powder diffraction); it has a surface area of at least 200 m2/g and typically in the range 300-900 m2/g, and pore volume in the range of 0.5-2.0 cm3/g, preferably from 0.6 to 1.8 cm3/year

According to what is known about heterogeneous catalysis, the above amorphous media (A) of the catalyst according to this invention may preferably be mixed and processed with other inert compounds, such as, for example, pseudoboehmite, which, after annealing becomes γ-alumina, suitable for providing improved mechanical and morphological properties that are desirable for industrial applications, especially to improve the consistency and stability of the granules in the catalyst, thus increasing the wear resistance, and to reduce the amount of residual catalyst in the resulting product. Introduction to the basis of the specified catalyst inert component, usually referred to as "binder", which may be implemented as adding it to amorphous media (A) in gel form or after drying or calcination, and adding to the previously obtained catalyst containing a metal (In). The introduction of additives in the media in any case, it is preferable for the purposes of this invention.

Therefore, in accordance with a specific aspect of the present invention, the specified media (A) may, if necessary, to take the form of a composition mixed with an appropriate amount of a binder consisting of an inert inorganic solid substances are usually added to improve mechanical properties, such as, for example, silicon oxide, aluminum oxide, clay, titanium oxide (TiO2) or zirconium oxide (ZrO2), boron oxide (B2O3) or mixtures thereof. In fact, for industrial applications specified solids are generally preferred is its use in granular and not in powder form, and for this it must have a relatively narrow particle size distribution of the particles (size distribution). Moreover, it is preferable to provide a sufficient mechanical resistance to compression and impact in order to prevent its gradual destruction when using due to hydrodynamic and vibration loads, provided the production fluid environments.

Possible binder may be any known binder, suitable for this purpose, as nature is, or synthetic, preferably silicon dioxide and aluminum oxide, especially aluminum oxide in all its known forms, for example gamma alumina.

Specified hardened amorphous solid according to this invention may be obtained using any method of mixing, extrusion and granulation (obtain tablets) for solid materials in the mixture, for example, according to the methods described in European patent applications EP-A 550922 and EP-A 665055 (more preferred is the second), both of which are filed by the applicant and the contents of which are incorporated here by reference.

In particular, according to the preferred method, the gel obtained by hydrolysis and gelation of aqueous mixture of aluminum alkoxide, tetraallylsilane and oxygen-containing phosphorus compounds, prepared as described above are mixed at the stage of annealing (iii) with the desired amount of inorganic binder, usually when the mass ratio, based on the weight of dry matter, between the binder and gel (wet) in the range from 0.05 to 0.5. It is preferable to add a plasticizer selected from known for this purpose, for example, methylcellulose, stearine, glycerine (more preferred is methyl cellulose), to facilitate the formation of a homogeneous mixture, which can be easily processed. This place is idicator usually added in amounts in the range from 5 to 20 g per 100 g binder.

Then add a suitable acidifying the compound selected from organic acids, such as acetic acid or acetic anhydride, oxalic acid, or inorganic acids such as hydrochloric acid or phosphoric acid, the amount is preferably in the range from 0.5 to 8 g per 100 g binder. Especially preferred is acetic acid.

Thus obtained mixture is homogenized by stirring and heating to a temperature in the range from 40 to 90°With partial evaporation of the solvent to form a paste, which is then ekstragiruyut using the appropriate equipment. The extruded product is cut into cylindrical pellets, preferably the size of 2-10 mm in length and 0.5-4.0 mm in diameter. According to an alternative variant of the aforementioned homogeneous paste can also be dried in a suitable granulator to obtain granules having the desired size.

Thus obtained granules are subjected to gradual heating to remove residual amounts of solvent and in the end calcined in an oxidizing atmosphere, usually air stream at a temperature in the range from 400 to 600°within 4-20, preferably 6-12 hours.

So get granular solid acid substance with a desired catalytic and m the mechanical properties and contains the specified inert inorganic binder in an amount of from 1 to 70 wt.%, preferably from 20 to 50 wt.%, while the remaining part consists of amorphous media (A), as described above. This granular solid is preferably in the form of tablets having a size of about 2-5 mm in diameter and 2-10 mm in length.

As the porosity and the surface area of the extruded product are usually average values relative to the values for the individual components of the mixture according to the linear rule of mixtures.

Catalytically active amorphous carrier of the present invention, either by itself or in mixture with other inert materials with acidic characteristics. He boasts an unbeatable combination of pore size and surface area, both of which are relatively high. According to research conducted by the applicant, this combination contributes particularly desirable catalytic selectivity and orientation, especially in Hydrotreating processes of hydrocarbons, in particular paraffins, for example, in the processes of conversion of hydrocarbon fractions, such as hydrocracking, hydroisomerization and dewaxing, with improved activity and selectivity as compared to conventional amorphous silica-alumina gel, especially if you need a range of products from kerosene to basics for lubrication, with the greatest possible reduction in the use with ADI dewaxing, conducted separately or after stage hydrocracking.

According to this invention, the metal component (b) a catalyst selected from the metals having the activity of a hydrogenation-dehydrogenation in the presence of mixtures of hydrogen/hydrocarbons under suitable process conditions. Metals are particularly suitable for this purpose are metals selected from groups 6-10 of the Periodic system. Of particular interest are combinations of Nickel with molybdenum, tungsten and cobalt, and precious metals - platinum or palladium or a mixture thereof, preferably platinum and palladium, more preferably platinum.

Combinations of metals of groups 6, especially tungsten or molybdenum, a metal of group 9, particularly Nickel or cobalt, especially suitable, as is known for other used catalysts suitable for processing hydrocarbons, if the mixture did not contain negligible amounts of sulfur.

According to this invention the specified catalyst can be prepared in a way that includes the contact in the relevant conditions specified active medium (A) with a suitable connection of the specified metal (In). This metal is mainly distributed in the most homogeneous way on the porous media surface to maximize the catalytic surface, which is effective is active. For this purpose it is possible to use various known methods, for example methods described in European patent application EP-A 582347, the contents of which are incorporated here by reference. In particular, according to the method of impregnation (impregnation) of the amorphous media (A), as such or preferably extruded lead in contact with aqueous and/or alcoholic solution of a soluble compound of the desired metal for a period sufficient to ensure uniform distribution of the metal in a solid. This usually requires from several minutes to several hours, preferably under stirring. Soluble salts suitable for this purpose are, for example, H2PtF6H2PtCl6, [Pt(NH3)4]Cl2, [Pt(NH3)4](OH)2and similar salts of palladium; mixtures of salts and other metals, are equally included within the scope of this invention. Usually use the minimum quantity of aqueous liquid (usually water or a mixture of water from the second inert liquid or acid number of less than 50 wt.%), which is sufficient to dissolve the salt and uniform impregnation of the specified carrier, preferably at a mass ratio of the solution/solid is in the range from 1 to 3. The amount of metal is chosen based on its concentration, which should be obtained in katal is the jam, because the metal is fixed on the carrier.

At the end of the impregnation solution is evaporated and the resulting solid is dried and calcined in an inert or reducing atmosphere under conditions in respect of temperature and time, similar to the above for annealing amorphous solid or extruded product.

An alternative method of impregnation is ion exchange. According to the latest amorphous solid silica/alumina/phosphate lead in contact with the aqueous solution of metal salt, as in the previous case, but the application is done through the exchange in alkaline conditions (pH between 8.5 and 11), created by adding sufficient alkali compounds, usually ammonium hydroxide. Then suspended solid matter is separated from the liquid by filtration or decantation and dried and calcined as above.

According to another possible metal salt (C) can be included in a catalytically active carrier at the stage of preparation of the gel, for example, before hydrolysis for the formation of a wet gel or before calcination.

In the end receive the catalyst for Hydrotreating hydrocarbons in accordance with this invention, where the metal M is uniformly distributed in amounts in the range from 0.05 to 5 wt.%, preferably from 0.1 to 2%, more preferred is compulsory from 0.2 to 1 wt.%, in relation to the total weight of the catalyst, particularly if the metal is selected from Pt and Pd.

A typical way to obtain the catalyst in extruded form, including active solid substance according to this invention as a carrier, includes the following stages:

(a) prepare a solution capable of hydrolysis of the components and ammonium phosphate, as described above, in an appropriate amount to obtain the desired final composition;

(b) this solution is heated to 60-70°for the implementation of its hydrolysis and gelation and obtain a gel-like mixture with a viscosity in the range from 0.01 to 100 PA·C;

(c) to this gel-like mixture first, add a binder belonging to the group of bumitaw or pseudoboehmite, in a mass ratio in the same range from 0.05 to 0.5, then, as a plasticizer, methylcellulose in an amount of from 10 to 20 g per 100 g of the specified binder; and finally, a mineral or organic acid in an amount of from 0.5 to 8.0 g per 100 g of the specified binder;

(d) the mixture obtained according to paragraph (C)is heated with stirring to a temperature in the range from 40° to 90°until a homogeneous paste is obtained, which is subjected to extrusion and pelleting;

(e) extruded product obtained in paragraph (d), dried and calcined in an oxidizing atmosphere.

In this way we shall have a granular solid carrier with an acid catalytic activity, containing inert inorganic binder in an amount of from 30 to 70 wt.%, and the rest consists of active porous solids - silicon oxide/aluminum/phosphorus having substantially the same characteristics as porosity, surface area and structure as described above for the same porous solids without binder. Granules usually in the form of tablets having dimensions of approximately 2-5 mm in diameter and 2-10 mm in length.

Stage of deposition of the noble metal on the active granular solid material is carried out using the same procedure as described above.

Before using the thus obtained catalyst is usually subjected to activation in a reducing atmosphere according to one of the known methods suitable for this purpose, which can also be carried out directly in the reactor, the pre-selected for the hydrocracking reaction. A typical method comprises the following steps:

1) 2 hours at room temperature in a stream of nitrogen;

2) 2 hours at 50°in a stream of hydrogen;

3) heating to 310-360°With increasing temperature for 3°C/min in a stream of hydrogen;

4) constant temperature 310-360°C for 3 hours in a stream of hydrogen and cooling to 200°C.

When activated, the pressure in the reactor is supported between a 3.0 and 8.1 MPa (30-80 ATM).

When is ispolzovanie the above-described catalyst in the hydrocracking of hydrocarbons of this invention has unexpectedly become possible to carry out with excellent output the conversion of heavy fractions of paraffins (paraffins with a boiling point above 360+° (C) in middle distillates having good properties at low temperatures, and at the same time get the rest with a high content of, preferably more than 70 wt.%, the basis for lubricants having high viscosity index and a suitable viscosity, especially for use in automotive engines.

The mixture of hydrocarbons fed to the process according to this invention, preferably consists essentially of synthetic linear paraffins and may include a middle distillate fraction in addition to the fractions of high-boiling hydrocarbons (liquid and/or solid at room temperature). According to the method of the present invention, the amount of low-boiling fraction (<150°, nafta and volatile products), even in the presence of supplied raw materials of the middle distillate in the amount of 50%or higher, are usually very limited, preferably below 15%, when the degree of conversion in a single pass about 80 to 90%.

Hydrocarbon mixture suitable for submission as a raw material in the process of this invention generally can include up to 20%, preferably up to 10 wt.% organic meparfynol faction. In particular, it has low sulfur content, preferably below 5000 mln (ppm) by weight of sulfur, it is better if below 1000 ppm or even undetectable amount, and may contain color soderjashie organic compounds, such as alcohols, ethers or carboxylic acid, preferably in an amount of below 5 wt.%.

For optimal operation method according to the invention specified the feed mixture at the stage of hydrocracking is preferably at least 80%, of linear paraffins having from 5 to 80, preferably from 15 to 70, more preferably from 20 to 65 carbon atoms, and an initial boiling point in the range between 45 and 675°With (by extrapolation), preferably between 170 and 630°With (by extrapolation).

According to a particular aspect of this invention specified raw materials supplied to the step (i)includes at least 30 wt.%, preferably from 40 to 80 wt.% the high-boiling fraction, which can overtake at a temperature of >360°and up to 80%, preferably from 20 to 60 wt.% hydrocarbon fractions corresponding to the so-called "middle distillate", which is divided into traditional shoulder straps kerosene and gasoil defined previously.

In accordance with another preferred aspect of this invention, the feed mixture has a boiling point of at least 260°S, more preferably at least 350°C. it Was found that under these conditions, especially if the raw material consists mainly of linear hydrocarbons, can be obtained as middle distillates, and the very foundations for lubrication, having optimal characteristics in the desired relative amounts within a limited source of raw materials.

Processes in which raw materials differs from the preferred compounds mentioned above are not excluded from this invention. A mixture of mainly linear hydrocarbons having intervals of boiling points equal to or higher than 260°With, are solid or semi-solid at room temperature, and for this reason they are commonly referred to as paraffins (waxes).

Typical examples of suitable materials are a mixture of synthetic hydrocarbons obtained by a process using as a feedstock mixture of hydrogen and carbon monoxide (so-called synthesis gas), for example, obtained by the Fischer-Tropsch process.

The latter, in particular, chracterized the absence of sulfur and preferably is composed of more than 70 wt.% of linear paraffins having more than 15 carbon atoms and a boiling point above 260°C. As already mentioned, these compounds are often solid or semi-solid at room temperature and for this reason are referred to as paraffins (waxes). Not all processes of Fischer-Tropsch give a mixture of high-boiling paraffins. In accordance with the conditions and catalyst the Fischer-Tropsch process can give the mixture in the range of several in the of Ermolov temperature distillation, even quite low, if this is desirable. However, it was found that it is more convenient to carry out the synthesis process so as to obtain predominantly high-boiling mixtures or waxes, which can subsequently be subjected to destruction and to fractionate at the desired shoulder straps. It is also well known that the Fischer-Tropsch synthesis side products, consisting primarily of olefins and oxygenated products. The latter are essentially alcohols, and their concentration is below 10 wt.% calculated on the total weight if used cobalt catalyst synthesis.

Stage hydrocracking process according to the invention can in General carried out at known temperatures and pressures of the conventional processes of this type. Temperature is usually chosen between 250 and 450°C, preferably from 300 to 370°C, while the pressure is chosen from 0.5 to 15 MPa, preferably between 1 and 10 MPa, including hydrogen pressure.

Hydrogen is used in large quantities for the implementation of the desired degree of conversion at the desired conditions. The mass ratio between hydrogen and hydrocarbons in the raw materials (and thus their relative pressure) can easily be selected by the specialists in the art depending on other relevant process parameters, such as volume RMSE of the spine, contact time, catalyst activity and temperature to achieve the desired degree of conversion. Usually consider that the initial mass ratio (hydrogen)/(hydrocarbons) from 0.03 to 0.2 is satisfactory for carrying out the process; however, these values are not limiting for the present invention. Under these conditions, consumes only a small part of the originally introduced hydrogen, and the remaining part can be easily separated and retalitate using conventional equipment suitable for this purpose. Generally preferred is the use of essentially pure hydrogen is available commercially at a low price, while in the most General case, does not exclude the use of mixtures of hydrogen with inert gases, such as nitrogen.

Usually as the characteristic function of reactor and process parameters to obtain the desired degree of conversion choose the volume-mass velocity MLA, WHSV (defined as the maximum flow rate in g/h, divided by the mass of catalyst in grams) or contact time (expressed as the reciprocal of the flow rate: 1/MHI) reagents under the reaction conditions of hydrocracking. It is important that the contact time was chosen so that the degree of transformation αcalculated as weight fractions of 360+°in the feedstock is inous mass fraction of 360+° With the products, divided by the mass fraction of 360+°loading [α=(360+entrance-360+outlet)/(360+entrance)], was maintained in the range of values over which largely adverse reactions occur that jeopardize obtaining the desired levels of selectivity for middle distillates and lubricants, for example, due to production of excess amounts of volatile products. Usually choose the contact times, which allow to achieve the degree of conversion α high-boiling fraction (360+° (C) between 60 and 90%, more preferably between 65 and 80%.

In accordance with a typical implementation of the method according to this invention a mixture of hydrocarbons having the above characteristics, pre-heated to a temperature of from 90 to 150°and continuously served after it is pre-mixed with hydrogen in a tubular reactor with a fixed catalyst bed, running at the downstream. The reactor support at a temperature of from 300 to 360°C. the pressure in the reactor support from 3 to 10 MPa. The catalyst was pre-activated, for example, in accordance with a typical method mentioned above, and further it is possible to carry out the hydrocracking process, usually after the stage of stabilization of the catalyst (about 60-100 hours).

Raw material preferably consists of high-boiling compounds which, coming from the synthesis process type Fischer-Tropsch and containing from 30 to 100% paraffins having a boiling point above 360°and up to 5% of oxygen-containing compounds. In the case of raw materials containing alcohols, especially if they are contained in amounts above 5 wt.%, in order to avoid the above disadvantages, experts can expose the feedstock pre-treatment before carrying out stage hydrocracking method of the present invention. This processing may include, for example, in the stage of distillation, which removes the faction with the shoulder strap having a temperature below 360°C, preferably from 260 to 360°in which, as is well known, usually concentrated oxygen-containing products; or the feed mixture can be subjected to the operation of selective hydrogenation in the presence of one of the known catalysts suitable for this purpose, and under conditions which minimize the conversion into products with a lower boiling temperature to remove oxygen-containing groups (such as groups-OH, -COOH, simple or complex esters or ketones) and receive not containing oxygen, hydrocarbons and a small amount of water, which can probably be removed by evaporation or decantation.

According to the typical execution caused the catalyst of this invention is administered in Rea is Thor in granular form, a preferred product is extruded together with a binder, for example, γaluminum oxide, as described above. Metal with activity towards hydrogenation-dehydrogenation is preferably palladium or platinum, especially platinum, and especially in the case of raw materials, obtained by Fischer-Tropsch synthesis. Usually use a fixed bed of catalyst, which receives the mixture of reagents. The contact time is chosen so that the degree of conversion ranged from 60 to 80%. Space velocity is preferably in the range from 0.4 to 8 h-1more preferably from 0.5 to 4 h-1.

The reaction mixture at the outlet of the reactor is continuously analyzed by means of one of the known methods, for example gas chromatography, and sent to the specified stage distillation/separation (and), in the upper part of which receive the product - medium distillate, while the high-boiling residue, suitable for receiving the bases for greases, get in the tail fraction.

The fraction of light hydrocarbons (gas and naphtha)with temperature distillation below 150°With, which is usually produced in quantities below 10 wt.% from the product obtained in stage (ii)is removed by distillation from the upper part of the column and is usually intended for a different use.

According to izaberete is receiving high-boiling residue mainly consists of a mixture of isomerized hydrocarbons, having a high content, preferably above 80%, more preferably greater than 90% or even more preferably essentially consists of a base for lubricants with high viscosity index, low pour point (loss of yield and value of the high-temperature viscosity within a very desirable interval. In particular, the basis for lubrication, which can be obtained in this process has the following desirable characteristics:

the pour point: <-18°

viscosity at 100°With: >4,0 cSt

the viscosity index (VI): >135

Noack: <15%.

If necessary based on the needs of the market, you can retalitate on stage hydrocracking the part of the said residue, preferably not more than 90%, more preferably not more than 50 wt.%, for an additional amount of middle distillate. In this case, it is also possible to improve the degree of isomerization by corresponding regulation of the recycling, as in conventional technologies hydrocracking processes.

Working conditions and equipment for carrying out the process according to this invention can easily determine and optimize the average technical specialist on the basis of this description and the mentioned parameters. Particularly preferred aspect of this process lies in the fact that it can be assetview most cases, and especially when applying a mixture of hydrocarbons, obtained in the Fischer-Tropsch synthesis, essentially from one reaction stage (hydrocracking), usually in combination with one stage of separation and recycling lower process flow stream from the reactor, thus obtaining products of high commercial value, without the need for other combinations of distillation and conversion, except for the possible stages of mild dewaxing high-boiling residue (for example, 360+° (C) and/or separation fractions 550°from this residue by distillation under vacuum to highlight the desired basis for lubrication.

Technicians in this field can make a few obvious variations of this process, without any additional inventive activity.

The above-described solid catalyst can be used in the method of this invention as such, after activation, at the stage hydrocracking process in accordance with the present invention. However, as indicated above, the catalyst preferably reinforce by adding and mixing the required quantity of binder consisting of an inert inorganic solid substances that can improve the mechanical properties.

According to a specific implementation of the present invention suitable for processing mixtures of hydrocarbons containing heteroatom is s, in particular, S, N or O, the specified way to obtain middle distillates, and the basics of lubrication includes a front-stage hydrocracking, hydrogenation treatment under such conditions so as not to get any significant changes in their average molecular weight, to obtain a mixture essentially of saturated hydrocarbons without heteroatoms.

A mixture of the above type usually can be obtained by synthesis, as, for example, a mixture of paraffin obtained by a Fischer-Tropsch synthesis, especially with a catalyst based on cobalt. In particular, such a variant of the process, mainly used for a mixture of essentially linear hydrocarbons containing up to 20%, preferably up to 10 wt.% meparfynol organic fraction, and it is characterized by substantial absence of sulfur. In particular, it nparfenova part consists of oxygen-containing organic compounds, such as alcohols and ethers, typically in amounts from 0.1 to 10%, preferably from 1.0 to 5 wt.%.

The way this hydrogenation treatment is well known and is not particularly critical moments for the method of the present invention, if the decrease in molecular weight of the treated fraction is negligible, in any case not exceeding 15% of the degree of conversion in the products included in a typical faction, called the Yu nafta, having a boiling point of below 150°C. In this case, the stage of hydrogenation should be such that not more than 15%, preferably not more than 10% of the components supplied to the mixture having a boiling point above 150°turned into products having a lower boiling point.

Typical, but not limit the reaction conditions at a stage of hydrogenation are: temperature in the range of 280-380°C, a hydrogen pressure of from 0.5 to 10 MPa, space velocity MLA in the range from 0.5 to 4 h-1. The ratio of hydrogen/feedstock ranges from 200 to 2000 l (N.U.)/kg

The hydrogenation reaction is usually carried out in the presence of a suitable catalyst. The latter, as is known, preferably comprises a metal of groups 6, 8, 9 or 10 of the Periodic system, distributed on storage media, preferably consisting of an inorganic oxide such as aluminum oxide, titanium oxide, aluminum silicate, etc. Preferred hydrogenation catalysts are catalysts based on Nickel, platinum or palladium deposited on alumina, aluminosilicate, fluorinated alumina, with the concentration of the metal, which, depending on the type, ranges from 0.1 to 70%, preferably from 0.5 to 10 wt.%.

During stage hydrogenation reaction can be conducted under such conditions and with such catalyst to p in order to obtain if this is desirable, some degree of isomerization of a hydrocarbon mixture according to known methods.

Thus obtained hydrocarbon mixture is subjected to phase separation by distillation may present gaseous and volatile products (<150°), and even more preferably water and/or other inorganic products obtained during hydrogenation.

According to another implementation of the method of the present invention, stage (i) may be preceded by preliminary separation of low-boiling fractions of the applied mixture. The specified preliminary stage typically may include a compartment by means of a sharp decrease in pressure of the mixture, having a final boiling point of from 150 to 370°C, preferably from 260 to 360°S, which contains the main part of the oxygen-containing compounds possibly present in the case of raw materials, consisting of the products of the Fischer-Tropsch synthesis. Separated thus low-boiling mixture can subsequently be processed in accordance with one of the known methods to obtain middle distillates, and/or fractions suitable for production of gasoline. For example, it can be subjected to a stage of hydrogenation of the previously described type with the subsequent stage isomerization to the corresponding equipment in the presence of a catalyst and under such conditions that the s reaction isomerization prevailed over the cracking reaction, as described, for example, in European patent EP 908231. The desired middle distillate fraction is separated from isomerizing thus the product using conventional fractionation distillation column.

The high-boiling fraction obtained at this preliminary stage, forms the raw material for stage (i), and process it in accordance with the method of the present invention to obtain high-quality medium fraction and foundations for lubrication. Moreover, in accordance with a preferred aspect of the subsequent stage (ii) is distilled under a sudden decrease of pressure to separate the low-boiling fraction containing volatile products (150-° (C) and middle distillate from the high-boiling isomerizing residue, suitable for the formation of foundations for lubrication. Specified low-boiling fraction is then combined with the product of the above stage isomerization and sent further along the stream in the fractionation distillation column or directed, at least in part, on the specified stage isomerization to further improve the quality of the thus obtained medium distillate, especially fractions of kerosene.

Some possible embodiments of the method of the present invention is described below with reference to figures 1 and 2, without limiting in any way the scope of the invention, shown in formalizability.

In particular,

figure 1 schematically depicts a device for implementing the method according to this invention, including stage hydrocracking stage and the distillation of the mixture of products;

figure 2 schematically depicts a special case of the installation of figure 1, where the VAT residue is further treated to improve its behavior as the basis of a lubricant.

According to the setup diagram figure 1 flow 1 is essentially linear and preferably not containing sulfur hydrocarbons obtained, for example, by the method of Fischer-Tropsch, preferably of such a type that does not change the ratio of carbon monoxide and hydrogen ("non-shifting type"), served in the hydrocracking unit (ha) stage (i) of this process, together with the necessary amount of hydrogen through line (pipeline) 2.

Part of the balance 8, preferably having a boiling point above 350°With and extending from the subsequent stage of separation of the middle distillate can also be served in the same unit on line 9 mass ratio is preferably in the range from 0 to 90%, more preferably from 10 to 30% relative to the total amount of VAT residue.

The reaction product stage hydrocracking, consisting of a mixture of hydrocarbons having a degree of isomerization of (nonlinear mass of hydrocarbon per weight of the mixture), preferably above 50%, more p is edocfile above 70%, available on-line 3 phase separation by distillation (PER), preferably in the appropriate column operating at atmospheric pressure or slightly higher, from which selected middle distillates which are suitable according to this invention, as fuel, through line 6 (kerosene) and 7 (gasoil). From block PER figure 1 also receive the following products: on line 4, the gaseous fraction C1-C5, irrelevant, and 5 - light fraction hydrocarbons, preferably having a boiling point of below 150° (nafta), the total number of mostly below 20 wt.%, preferably below 15%, relative to the mixture of hydrocarbons is supplied through line 1.

According to a particularly prominent aspect of the present invention using the above catalyst, deposited on amorphous solid silicon oxide - aluminum oxide - phosphate, at the stage of hydrocracking (i) allows to obtain the average fraction of the distillate of high quality and high yield (low degree of receipt of volatile products 150-° (C)having, in particular, excellent low-temperature properties and a high cetane number, together with the high boiling residue, having unexpectedly low content of linear paraffins, which is particularly suitable to provide the basics for lubrication directly, that is, preferably after treatment with removing paraffins with predominantly reduced contact time and the degrees of conversion.

Particularly preferred implementation of the method of the present invention is shown schematically in figure 2.

The liquid stream 11, consisting of a mixture of light hydrocarbons that originate from a process of the Fischer-Tropsch synthesis, including unsaturated products (linear olefins in an amount up to 10%, preferably from 2 to 5 wt.%, and oxygen-containing products (mainly alcohols) in an amount up to 10 wt.%, preferably from 2 to 7 wt.%, separated in a distillation column D1 light fraction 13 having an end boiling point below 380°C, preferably between 260 and 360°and heavy fraction of 14, consisting of a cubic residue. Distillation in D1 preferably has only one stage (with a sharp decrease in pressure) and can be replaced by a differentiated selection of two fractions directly from the reactor for carrying out the Fischer-Tropsch synthesis.

The mass ratio of the fractions 13 and 14 preferably is in the range from 0.5 to 2.0, more preferably from 0.8 to 1.5.

Light fraction 13 is sent to the unit hydroisomerization (GI). However, it can cause deficiencies in the functioning of the catalyst at this stage, especially in the presence of heteroatoms or unsaturated groups, and especially oxygen-containing products; preferably specified fraction 13 is sent to the hydrogenation unit (G), where it is brought into contact with water is born (line 12) in the presence of a suitable catalyst under such conditions, in order to minimize or eliminate the hydrocracking reaction. The hydrogenation unit (D) can be produced in accordance with known methods and preferably includes a reactor operating under pressure and containing the catalyst in a fixed bed selected from catalysts suitable for the aforementioned purposes. Typical hydrogenation catalysts suitable for this purpose include promoting hydrogenation metal, such as Ni, Pd or Pt deposited on inert or having acid activity of a solid substance, such as aluminum oxide, silicon oxide, aluminum silicate, zeolites or molecular sieves. It may happen that hydrogenation occurs isomerization reactions and partial hydrocracking, usually limited by the degree of transformation below 15 wt.% with respect to the total weight of given fractions. A small proportion of volatile products (150-°) and probably formed water can be separated by distillation. Hydrogenated and dehydrogenation easy flow, according to the occasion, then send the stage hydroisomerization (GI) through line 16, where it reacts in the presence of hydrogen under normal conditions, suitable for extensive isomerization and partial rupture of linear chains of hydrocarbons. Suitable isomerization conditions, together with great colecistopancreatography, described in detail in the literature.

Of a specified light fraction, usually less than 50%, preferably from 0 to 25%, you can remove the front of the stage isomerization on line 17 and again mix with the specified heavy fraction in line 14 to be subjected to hydrocracking.

At this stage isomerization, hydrogen is added to a mixture of hydrocarbons (line 15) in an amount of from 150 to 1500 litres (N.U.) per liter of liquid, and the mixture is served with a bulk velocity from 0.1 to 10 h-1at a temperature in the range from 300 to 450°and a pressure of from 1 to 10 MPa on the stationary layer of a suitable bifunctional catalyst that is active with respect to the hydrogenation-dehydrogenation and preferably composed of extruded product, comprising from 30 to 70 wt.% amorphous micro/mesoporous aluminosilicate and from 0.2 to 1 wt.% platinum or palladium. Stage isomerization is preferably carried out in such a way as to convert at least 60%, preferably at least 80 wt.% linear hydrocarbons in samaritane hydrocarbons, at the same time maintaining the amount of product having a boiling point above 150°and turned into a product with a lower boiling temperature, below 30%, preferably 20 wt.%, to limit the extent of cracking.

Samaritano mixture is sent through line 24 to column fractionation D3, p the following combining at least part of the light fraction 23, coming from the distillation column D2 for heavy fractions subjected to hydrocracking. According to this invention, the average distillate obtained from the column D3, possibly taking on two different levels to separate kerosene (line 27) from gasoil (line 28), which has excellent low-temperature properties, high cetane number, preferably above 50, and reduced secretion of substances that pollute the environment.

In particular, it was found that through this process you can obtain middle distillates, with the following characteristics:

Kerosene (150-250°)
Max. height mecoptera flame>50 mm
Flash>40°
Freezing point<-47°
Aromatic compounds<0,1%
Sulfur<0.1 ppm

Gasoil (250-360°)
B.C.N.>70
Flash>160°
The pour point<-12°
Aromatic compounds <0,1%
Sulfur<0.1 ppm

From the column distillation and fractionation D3 receive a small number of products with a low molecular weight, in particular 25 - gas fraction C1-C5, do not pose a great interest, and in line 26 is a light fraction of hydrocarbons, preferably having a boiling point of below 150° (nafta). According to a particularly advantageous aspect of the present invention, the number mentioned volatile fractions significantly reduced compared to similar known processes, preferably below 20%, more preferably below 15 wt.% in relation to the original raw line 1.

The required amount of hydrogen (line 18) are added to fraction (line 14) high-boiling hydrocarbons with low oxygen content and unsaturated and is sent to the hydrocracking unit (ha) according to stage (i) of the process in accordance with the fact, as already shown for the simplified scheme of figure 1. The resulting product is directed through line 19 to the device D2 for the distillation and fractionation, which preferably operates so as to provide separation of a mixture of hydrocarbons essentially into two fractions:

F1 - light fraction with a boiling point below 380°C, preferably below 360°C, preferably comprising less than 10 wt.% volatile products (150&#HWS), consisting of a product with a high concentration isoparaffins, which is sent through line 23 at the same stage of fractionation, and a light fraction 24, samaritano in GI;

F2 - fraction VAT residue consisting of a mixture of isomerized high-boiling hydrocarbons, suddenly having a low content of paraffins (waxes) in comparison with the products obtained with other known catalysts under similar conditions, in which the initial boiling point above 320°C, preferably above 340°C.

Merging two threads 23 and 24 from the stages carried out with different raw materials and under different conditions, but complementary, allows, after the corresponding distillation in D3 to successfully obtain a fraction of the kerosene and gas oil, which has excellent properties listed above. If necessary, a portion of the mixture F1 coming from the distillation D2, preferably less than 50 wt.%, direct line 29 on the same stage isomerization (GI), in order to further improve the degree and distribution of isomerization and adjust the relative amount of received gasoil and kerosene.

The residual fraction F2 can be used as such for specific applications, or preferably send (line 20) on stage dewaxing (APS) to provide the basics for lubrication. In accordance with the site is titanium aspect of its partially recyclery on stage hydrocracking (HC) in line 22 to regulate the performance of the process or change the degree of isomerization in accordance with the requirements of the products.

The degree of isomerization of the residual fraction is sent to the line 20, is preferably above 85%.

If the number of linear paraffins reduced stage dewaxing, if necessary, can successfully be done in accordance with the method of this invention is particularly advantageous when the contact time and the conditions of obtaining the foundations for lubrication.

The specified stage dewaxing (DP) can be performed in accordance with known methods as with the solvent, and preferably in the presence of a catalyst suitable for this purpose. In this latter case, partially samaritana mixture again reacts in the presence of hydrogen and a suitable solid catalyst, preferably comprising a metal that has activity towards hydrogenation-dehydrogenation, usually a noble metal deposited on a zeolite or other crystalline porous solid.

In this case, in contrast to what happens when dewaxing solvent, where physically separated crystals of paraffin waxes selectively converted into isoparaffin compounds or lighter products of cracking, in accordance with the used catalyst. These products of cracking are mainly low molecular weight paraffins and olefins, partial (up to 50 wt.%) consisting of with the of dinani C5-, while the remaining part is a material having a molecular weight within the range of gasoline.

Used catalytic materials are mainly zeolites with average pore sizes (such as mordenite, ZMS-5, SAPO-11) and, in some cases, materials with larger pore sizes (such as beta-zeolites and HY), but also proposed and other materials.

The catalytic dewaxing can be performed, in accordance with the scope of use at pressures that can vary from 2 to 20 MPa, in the presence of higher operating pressures, the benefits from the point of view of period of use of the catalyst, higher outputs and viscosity indices of products dewaxing. Preferred temperature conditions WABT and the volumetric rate of fluid VSL (LSHV) are typical hydrocracking, while temperature conditions WABT range from 315 to 400°and space velocity VSL from 0.3 to 1.5 h-1.

Further along the stream from stage catalytic dewaxing typically involve the processing of the typical "ennobling" the catalyst for improved color and remove any traces of reactive molecules, such as olefins, to ensure best stability of the product.

At the end of this stage dewaxing, after you remove the last residues (<3 wt.%) volatile products, educated as a result of partial hydrocracking, get liquid isomerized product (line 21), which has excellent properties at low temperatures and high viscosity, having an initial boiling point above 350°C, preferably >360°and distillation temperature (extrapolated) 90% of the mixture (T90) below 700°With (determined by extrapolation).

For a more detailed description of the present invention shows several examples of practical implementation, which, however, are merely illustrative of some specific aspects of this invention and in no way should be construed as limiting the scope of its protection as a whole.

EXAMPLES

The following methods of analysis and characterization were used for practical execution of the invention:

X-ray diffraction on powders (FTEs): this analysis was performed using a vertical diffractometer Philips X'pert equipped with a proportional counter pulse and a secondary curved monochromator from a crystal of graphite; for each sample were conducted by two different dimensions: the first range of angles of 1.5≤2θ<10° 0.05° 2θ and sometimes the accumulation of 20 s/step and a fixed error of 1/6°; the second in the spectral range of 3≤2θ≤53° the step is 0,05° 2θ and accumulation times of 10 s/step and a fixed error of 1°; in both cases used the CuK radiationα (λ=1,54178 A).

Information on the characteristics of the catalyst obtained from the evaluation of the isotherm of adsorption/desorption of N2at the temperature of liquid nitrogen, obtained with the use of the device ASAP 2010 (Micrometrics) and Sorptomatic 1990.

Samples (˜0.3 g) before receiving isotherms were degassed for 16 hours at 350°With under reduced pressure.

The total specific pore volume (Vp) was calculated using the method Gurvich at p/p°=0,995. If adsorption isotherms end of the plateau, you can exclude phenomena associated with macropores or porosity between the particles, therefore, accurate determination of this parameter. If the isotherm is not the end of the plateau, the value of Vp is only indicative.

Measurement of pore size: the average diameter of pores was determined using the method of DFT (density functional theory), the details of which are presented in the publication ..Webb and C.Orr in "Analytical Methods in Fine Particle Technology", Micrometrics Instruments Corp. (1997) ("Analytical methods in the technology of fine particles"), p.81.

Measurement of specific surface area: surface area was estimated by constructing a linear relationship BET with two parameters within the interval R/R° 0.01 to 0.2 s is the label of the method DFT (density functional theory).

The pour point: in accordance with the standards ASTM D97.

Viscosity at 100 cSt: in accordance with the standards ASTM D445.

Viscosity index: in accordance with the standards ASTM D2270.

Reagents and materials.

In the course of the preparations described in the examples used commercial reagents listed below:

The hydroxide of tetrapropylammonium (TPA-OH)SACHEM
Triisopropyl aluminumFLUKA
Tetraethyl silicateDYNAMIT NOBEL
Alumina (VERSAL 250, pseudoboehmite)LAROCHE
Methyl cellulose (METHOCEL)FLUKA
Phosphoric acidCARLO ERBA

The reagents and/or solvents that have been used, but not listed above represent the most commonly used substances, and they can be easily found in conventional commercial vendors specializing in this field.

Example 1: the Catalyst with P/Al=1

239,50 ml of demineralized water, 3,40 g of ammonia solution with a concentration of 30 wt.% and 2.30 g of a solution of phosphoric acid with a concentration of 85 wt.% (equivalent to 0.02 M of diammoniumphosphate (NH4)3PO4) loaded in a three-neck flask equipped with a rod stirrer and a fridge with RA is shiranami. To the thus obtained mixture was added 50,80 g of 40 wt.% an aqueous solution of hydroxide of tetrapropylammonium (TPA-HE, 0.01 mol) and 4,08 g triisopropyl aluminum (0,02 mol). The mixture was maintained under stirring at room temperature for about 60 minutes, until then, until we got a clear solution. To this solution was quickly added 208 g tetraethylorthosilicate (TEOS; 1.00 mol) while bringing the temperature up to 60°and the mixture is generally maintained under stirring under these conditions for 3 hours. In the end observed the formation of gel, which was cooled to room temperature and left to stand for 20 hours. The thus obtained homogeneous gel, characterized by the following molar ratios between its components: Si/Al=51; TPA-OH/Si=0,098; H2O/Si=15; Si/P=50.

Thus obtained gel was first dried in air for about 3 hours and then progulivali by heating in air stream at 550°C for 5 hours. At the end of the obtained amorphous solid according to this invention, identified the following empirical formula: SiAl0,02P0,02O2,08.

The complete absence of crystalline aggregates was confirmed by x-ray diffraction. Using NMR spectroscopy applied to isotopes31P and27Al, it was found that for less than the least 80% of the phosphorus associated with amorphous aluminosilicate matrix links Al-O-P. The results of morphological analysis are summarized below in table 1.

Examples 2 and 3

Repeated the procedure in accordance with the preceding example 1, each time changing the number of diammoniumphosphate received source when mixing ammonia and phosphoric acid in aqueous solution, so that the ratio of P/Al in the gel varied from 0.5 to 2 for examples 2 and 3, respectively.

The results of the morphological analysis and the elemental analysis are shown below in table 1.

Example 4

The procedure of example 1 was repeated exactly, with the only difference that the stages of the hydrolysis and gelation was performed in a mixture of ethanol/water, in which the molar ratio of ethanol/SiO3=8 and H2O/SiO2=8. In the end, using the above methods was determined by the characteristics of the thus obtained product. Data on morphology are shown below in table 1.

Example 5

239,50 ml of demineralized water, to 6.78 g of aqueous ammonia of a concentration of 30 wt.% and 4.59 g of the solution of phosphoric acid with a concentration of 85 wt.% (equivalent 0,040 of moles of diammoniumphosphate (NH4)3PO4) loaded in a three-neck flask equipped with a rod stirrer and a fridge with extensions. To the thus prepared mixture was added 50,8 g of an aqueous solution of hydroxide of tetrapropylammonium with a concentration of 40 wt.% (TPA-HE, of 0.10 mol) and g of 8,13 triisopropyl Alu is INIA (0,04 mol). The mixture was kept under stirring at room temperature for about 60 minutes to obtain a transparent solution. To this solution was quickly added 208 g tetraethylorthosilicate (TEOS, 1.00 mol), and the procedure was the same as in the previous example 1. At the end of the obtained amorphous solid according to this invention, identified by the empirical formula SiAl0,02P0,02O2,08, which was determined using the aforementioned methods. Data on the morphology below in table 1.

The structure of the solid catalyst obtained in accordance with the previous examples 2-5 was determined as for the product, obtained in accordance with example 1, using x-ray diffraction and NMR spectroscopy; it has been proven that these products are completely amorphous solids, in which at least 80% of the phosphorus associated with aluminosilicate matrix through links Al-O-R.

Example 6 (comparative)

The procedure of example 1 was exactly repeated, with the only difference that the ratio of P/Al in the gel was equal to 5 instead of 1.

It was shown that the structure of the thus obtained solid substance was determined using x-ray diffraction and NMR spectroscopy, is similar to the structure of the product of example 1, but the pore structure significantly change the up, with their partial compression, which is evident from the significant reduction in their volume.

Example 7 (comparative)

Was received media of the solid amorphous alumosilicate, not containing phosphorus, by repeating the same procedure as in the previous example 1, but without the introduction of the solution of diammoniumphosphate. The results of determination of the properties listed in the following table 1. There is a significant decrease in the average diameter of the pores.

Table 1
Morphological properties of the catalyst.
ExampleSi/AlP/AlSBET(m2/g)Vp(ml/g)dDFT(nm)
1501,07000,966,1
2500,57200,845,3
3502,05201,6225,0
4502,0760of 1.5713,0
5251,05001,3519,0
6 (EUR.)505800,06 -
7 (EUR.)5007600,492,3

Example 8: extruded catalyst

5 kg of the wet gel obtained by an exact repetition of the procedure of the preceding example 1, but without the stage of drying and calcination, 1,466 kg of aluminum oxide (pseudoboehmite, VERSAL 150), previously dried for 3 hours in air at 150°and 0,205 kg of methyl cellulose loaded into a 10-liter mixer with a paddle stirrer, supported at speeds of 70-80 rpm, and the mixture is left under stirring for about 1 hour. Then add 50 ml of glacial acetic acid, and the temperature of the mixer was adjusted to about 60°continuing the stirring until a homogeneous paste is obtained, having the desired consistency for subsequent extrusion. The mixture is loaded into an extruder type HUTT, ekstragiruyut and cut into cylindrical granules of the desired size (about 2×4 mm). The product is left for aging for about 6-8 hours, and then dried by keeping it in the air flow at 100°C for 5 hours. Finally calcined in a muffle at 550°C for 5 hours in air flow.

Thus obtained extruded porous solid acid characteristics (called hereinafter "extrud the qualified product"), consisting mainly of an amorphous phase of silicon oxide/aluminum oxide/phosphate (60 wt.%, according to x-ray diffraction analysis), and crystalline phase of aluminum oxide (pseudoboehmite), morphological characteristics of which are shown below in table 2.

Examples 9-12 and 13 (comparative)

Repeating the same procedure as in the previous example 8, but replacing amorphous solid prepared according to example 1, the solids obtained in the respective examples, as indicated in the second column of the following table 2.

The thus obtained porous extruded solids, morphological characteristics are shown in table 2.

Table 2
Morphological properties of extruded products
ExampleAmorphous phase (Example no.) P/AlSBET(m2/g)Vp(ml/g)dDFT(nm)
8115400,917,6
9324601,2618,0
10425101,2516,0
1120,5Not ODA.not ODA.not ODA.
12514001,1218,0
13 (EUR.)705900,88<6,0

Example 14: getting hydrocracking catalyst based on platinum

To demonstrate the advantageous properties of amorphous solids of this invention, the catalytically active carrier in Hydrotreating processes of hydrocarbons was obtained hydrocracking catalyst containing platinum as a metal for hydrogenation-dehydrogenation.

For distribution of platinum on the carrier used an aqueous solution hexachloroplatinic acid (H2PtCl6), hydrochloric acid and acetic acid in the following molar ratios: H2PtCl6/HCl/CH3COOH=1/0,84/0,05, with the concentration of platinum 7,69×10-3M 60 ml of this solution was added to 30 g of extruded solid substance obtained in the preceding example 8, so that all solid material was covered with a solution, in order to avoid inhomogeneous distribution of platinum. Thus obtained suspension was maintained under stirring for about an hour, and for the eat was degirolami by suction under vacuum (about 1 kPa) at room temperature. The solvent was then removed by heating to about 70°With air flow. Dry the product at the end was progulivali in the air stream at the following temperature profile: 25-350°C for 2 hours, at 350°C for 2 h, 350-400°With over 50 min, at 400°C for 3 hours

In the end received supported on a carrier, the hydrocracking catalyst having the following characteristics:

to 59.8 wt.% active amorphous solids (molar ratio Si/Al=51, P/Al=1)

to 39.9 wt.% gamma-alumina

0.3 wt.% platinum

Examples 15, 16 and 17 (comparative)

There were obtained three specimens of the hydrocracking catalyst, an exact repetition of the procedure of the preceding example 14, but using extruded products according to examples 9, 10 and 13 (comparative) examples 15, 16 and 17 (comparative), respectively. Characteristics of the composition of the amorphous phase, gamma-alumina and the platinum content in the obtained catalysts are essentially the same as in example 14, while morphological measurements below in table 3.

Table 3
Morphological characteristics of catalysts containing 0.3% platinum.
ExampleP/AlSBET(m2/g) Vp(ml/g)DDFT(nm)
1414900,847,3
1524301,1215,0
1624701,0216,0
17 (EUR.)05100,82Not ODA.

Example 18

120 ml of an aqueous solution hexachloroplatinic acid, used in the previous examples (H2PtCl6/HCl/CH3COOH=1/0,84/0,05, [Pt]=7,69×10-3M), was added to 30 g of extruded solid substance obtained in the preceding example 8, so that all solid material was covered with a solution, in order to avoid inhomogeneous distribution of platinum. Thus obtained suspension was processed in accordance with the procedure described in the preceding example 14, to obtain the at the end, after calcination, supported on a carrier of a hydrocracking catalyst having the following characteristics:

to 59.8 wt.% active amorphous solids (molar ratio Si/Al=51, P/Al=1)

to 39.9 wt.% gamma-alumina

0,59 wt.% platinum

Examples 19, 20 and 21 (comparative)

There were obtained three specimens of hydrocracking catalyst containing 0.6 wt.% platinum by then the aqueous repetition of the process of the preceding example 18, but with the use of extruded products in accordance with examples 11, 12 and 13 (comparative)examples 19, 20 and 21 (comparative), respectively. Characteristics of the obtained catalyst composition in relation to the amorphous phase, gamma-alumina and platinum content are essentially the same as in example 18, while morphological characteristics do not differ significantly from the characteristics of the original active media.

Examples 22-26

Conducted various tests hydrocracking of a mixture of waxes that are solid at room temperature, obtained by Fischer-Tropsch synthesis using catalysts of the preceding examples 18-21.

The hydrocracking tests were carried out in a tubular reactor with a fixed layer having a useful loading capacity 15 ml, corresponding to the height of the layer of catalyst in the isothermal section of approximately 10 cm Reactor equipped with relevant podwodami for continuous simultaneous supply of reagents and removal of the reaction mixture. The hydrogen serves at the desired pressure through the flow meter; a mixture of paraffins support in a liquid state at a temperature of about 110°and served by a pump.

The reactor temperature is controlled using a temperature control system capable of operating up to 400°C. Appropriate analytical instruments Ave is connected to work in online mode for carrying out the process of analysis of the composition of the reaction product.

8 g of the catalyst loaded into the reactor and activated in accordance with the above method.

The raw material used shoulder straps 370+°With a mixture of waxes obtained by the Fischer-Tropsch synthesis and having the following composition:

Fraction <150°0,0
Kerosene (from 150 to 260°)0,3
Gasoil (from 260 to 370°)1,9
Fraction >370°of 97.8

On the specified composition paraffins conducted various tests hydrocracking with a total pressure of about 5 MPa and a mass ratio of hydrogen/(mixture of hydrocarbons) about 0.1. Table 4 below lists the experimental conditions and the catalysts used in examples 22-26. Contact time (1/MHI) regulated in the usual way to obtain at the end of the desired degree of conversion.

Table 4
Process conditions
ConditionsPRPRPRPRPR(*)
Temperature (°)355335345340345
H2/paraffin is (mass./mass.) 0,1050,1050,1050,1050,105
Pressure (MPa)5,05,05,05.05,0
The catalyst (No. of example)PRPRPRPRPR(*)
P/Al (atom/atom)10,510,50
Si/Al (atom/atom)5151255151
MLA (h-1)22222
(*) comparative

The separation into fractions leaving the mixture was performed by gas chromatography analysis, and, based on this measured the degree of conversion of hydrocarbon fractions having more than 22 carbon atoms, With22+corresponding, more or less, the fraction with a boiling point >370°C. the following table 5 presents data on the composition related to the outputs of the various distillation fractions obtained at the end of the process.

Part of the hydrocarbon product is distilled under 360°and determine the content fundamentals of lubrication in the balance in accordance with the method, which is explained below. About who headed the remainder of the 360+ is dissolved at 40° With in a 1/1 by volume mixture of methyl ethyl ketone and toluene. The ratio (solvent)/(remainder 360+) is 4/1 (by volume); an aliquot of the solvent (about 1/8 of the total) is used at the stage of washing paraffin collected on the filter. The temperature of the solution is reduced to -20°at the rate of 1°/min. At the end the mixture is filtered at a temperature of -20°C. Deparaffinizing the product is separated from the solvent by distillation under vacuum and subsequent distillation light ends stream of nitrogen at 80°C.

Measure the amount of the obtained product, in order to determine the content basis for lubrication in the specified residue 360+. Then define the properties of this basis for lubricants by viscosity measurements at 100°and viscosity index. Table 5 below shows the results, which clearly demonstrate the unexpected improvement obtained with the catalytically active carrier of the present invention relative to the silica-alumina carrier having a similar composition but not containing phosphorus. In particular, according to the examples 22-25 in accordance with this invention can be obtained in one stage hydrocracking a high yield of middle distillates (columns 150-260 and 260-370) and high-boiling residue containing more than 80 wt.% the basis for lubrication, has a significantly higher viscosity than the basis for lubrication, obtained by those W the process conditions with a known catalyst (comparative example 26).

In addition to the above, other possible ways to make or equivalent modifications of this invention not specifically identified here are treated just as its variations, and in any case included in the scope of the claims.

Table 5
The composition and properties of the products of hydrocracking
ExampleThe pace.(°)MLA (h-1)The degree of transformationThe output of the products of hydrocracking ( wt.%)The basis for lubrication
C22+(the range of temperature of distillation fractions in °)% output

balance 360+
Viscosity

at 100°s (cSt)
The viscosity index
<150150-260260-370>370
22335280,2723,424,18032,219,3995,23143
23 335263,817,122,71423,97236,034965,97157
24345269,622,620,33226,80830,189875,47145
25340273,319,723,65730,41626,1371005,34148
26 (*)345277,520,926,15130,84221,981864,56142
(*) comparative

1. The method of simultaneous receiving medium fraction and the basis for lubrication on the basis of raw material comprising a mixture mainly of paraffin hydrocarbons obtained by a process of synthesis from hydrogen and carbon monoxide, comprising at least 30%, preferably at least 50%of high-boiling fraction having a distillation temperature above 360°comprising (i) at least one stage hydrocracking, in which the mixture of hydrocarbons is reacted with hydrogen at a temperature of from 200 to 450°and a pressure of from 0.5 to 15 M is as in the presence of the catalyst over time, sufficient to convert at least 40% of the said high-boiling fraction in the fraction of hydrocarbons that can overtake at temperatures below 360°C;

(ii) at least one stage of distillation of the product of stage (i) to allocate at least a fraction of the middle distillate and at least one high-boiling residue, suitable for getting the basics of lubrication, with an initial boiling point equal to or above 340°C, characterized in that the specified stage hydrocracking (i) is conducted in the presence of the applied catalyst containing (A) a carrier of acid nature, consisting of a catalytically active porous solids, including silicon, aluminum, phosphorus and oxygen, are related to each other so that to form a mixed amorphous solid, forming a single phase, characterized by the atomic ratio Si/Al of 20 to 250, the ratio of P/Al of at least 0.1, but lower than 5, the total pore volume in the range from 0.5 to 2.0 ml/g, an average pore diameter in the range from 3 to 40 nm and a specific surface area in the range from 200 to 1000 m2/g; (B) at least one metal from the activity of the hydrogenation-dehydrogenation selected from groups 6 to 10 of the Periodic system, distributed on the specified media (A) in an amount of from 0.05 to 5 wt.% with respect to the total mass produce the RA.

2. The method according to claim 1, wherein said active catalyst carrier has a total pore volume of 0.7 to 1.7 ml/g, a surface area of from 300 to 900 m2/g and an average pore diameter of from 5 to 30 nm, the ratio Si/Al in the range from 20 to 200 and the ratio of P/Al in the range from 0.3 to 3.5.

3. The method according to any of claim 1 or 2, in which the difference between the 10% and 90% on the distribution curve of pore sizes specified active catalyst carrier is enclosed in the interval diameters from 2 to 40 nm.

4. The method according to claim 1, wherein said catalyst comprises in addition to the specified carrier (A) is preferably in a mixture with him binder consisting of inert inorganic solids.

5. The method according to claim 4, in which the specified inert binder selected from silica, alumina, clay, titanium oxide (TiO2) or zirconium oxide (ZrO2), boron oxide (2About3or mixtures thereof.

6. The method according to any of the preceding claim 4 or 5, in which the specified binder is in an amount of from 1 to 70 wt.%, preferably from 20 to 50 wt.%, in calculating the masses of the specified inert binder and the amorphous media (A).

7. The method according to claim 4, wherein said catalyst is in the form of granules having a size of about 2-5 mm in diameter and 2-10 mm in length.

8. The method according to claim 1, wherein said metal in the component (B) rolled atora selected from Nickel, molybdenum, tungsten, cobalt, platinum, palladium and mixtures thereof, preferably platinum and palladium.

9. The method according to claim 1, in which the concentration of the specified metal with the activity of the hydrogenation-dehydrogenation, is in the range from 0.2 to 1 wt.% in relation to the total weight of the specified catalyst.

10. The method according to claim 1, in which specified the feed mixture consists of the product of synthesis type Fischer-Tropsch process.

11. The method according to claim 1, in which at least 80 wt.% this mixture of hydrocarbons consisting of paraffins.

12. The method according to claim 1, in which specified the feed mixture comprises at least 80 wt.% of linear paraffins having from 5 to 80 carbon atoms and an initial boiling point of from 45 to 675°With (by extrapolation).

13. The method according to claim 1, in which specified the feed mixture contains from 40 to 80 wt.% the high-boiling fraction, which can overtake at temperatures of ≥360°and from 20 to 60 wt.% middle distillate.

14. The method according to claim 1, in which specified the feed mixture has an initial boiling point of at least 260°C.

15. The method according to claim 1, in which the specified stage hydrocracking (i) is conducted at a temperature from 300 to 370°and at a pressure of from 1 to 10 MPa, including hydrogen pressure.

16. The method according to claim 1, in which the specified stage hydrocracking (i) is carried out with the initial mass ratio is adored/hydrocarbons from 0.03 to 0.2.

17. The method according to claim 1, in which the degree of conversion at this stage hydrocracking (J) is in the range from 60 to 90%, preferably from 65 to 80%.

18. The method according to claim 1, in which an aliquot of the specified high boiling residue obtained at this stage (ii), recyclart on stage hydrocracking (i).

19. The method according to claim 1, wherein said high-boiling residue, used to provide the basics for lubrication, is subjected to a dewaxing treatment.

20. The method according to claim 19, in which the specified stage dewaxing is catalytic dewaxing.

21. The method according to claim 1, comprising, in addition, processing of raw materials supplied to the specified stage hydrocracking (i)by hydrogenation.

22. The method according to claim 1, in which the front of the stage hydrocracking source light fraction having an end boiling point below 380°C, preferably from 260 to 360°With, separate from said raw materials by distillation before stage hydrocracking.

23. The method according to item 22, which specified light fraction is subjected to processing by the hydroisomerization in the presence of a suitable bifunctional catalyst activity of the hydrogenation-dehydrogenation to obtain samaritano mixture.

24. The method according to item 23, in which the specified light fraction is subjected to a hydrogenation treatment before being processed by hydroisomerization.

Cab according to any one of the preceding p-24, which is obtained from the light fraction product is combined with at least part, preferably with all the specified fraction of the middle distillate, obtained in stage (ii), and direct on stage fractionation to obtain at least one fraction of the middle distillate, preferably gas oil.



 

Same patents:

FIELD: technological processes; chemistry.

SUBSTANCE: method involves reaction of raw material containing organic component with a catalyst composition. Processing method is selected out of alkylation, acylation, hydrotreatment, demetallisation, catalytic deparaffinisation, Fischer-Tropsch process and cracking. Catalyst composition includes mainly mesoporous silicon dioxide structure containing at least 97 vol.% of pores with size in the interval from ca. 15 Å to ca. 300 Å, and at least ca. 0.01 cm3/g of micropores. Mesoporous structure features at least one catalytically and/or chemically active heteroatom in amount of at least ca. 0.02 mass %, selected out of a group including Al, Ti, V, Cr, Zn, Fe, Sn, Mo, Ga, Ni, Co, In, Zr, Mn, Cu, Mg, Pd, Ru, Pt, W and their combinations. The catalyst composition radiograph has one 0.3° to ca. 3.5° peak at 2θ.

EFFECT: highly efficient method of organic compound processing in the presence of catalyst composition without zeolite.

20 cl, 31 ex, 17 tbl, 22 dwg

FIELD: petrochemical processes and catalysts.

SUBSTANCE: middle distillates are obtained, in particular, from paraffin charge prepared by Fischer-Tropsch synthesis wherein hydrocracking/hydroisomerization catalyst is utilized including at least one hydrocracking/hydroisomerization element selected from group constituted by group VIII metals, non-zeolite silica-and-alumina-based carrier (more than 5% and less than or equal to 95% SiO2) and having: average pore size measured by mercury porometry within a range 20 to 140 Å; total pore volume measured by mercury porometry 0.1-0.6 mL/g; total pore volume measured by nitrogen porometry 0.1-0.6 mL/g; specific surface BET between 100 and 550 m2/g; pore volume for pores with diameter above 140 Å measured by mercury porometry less than 0.1 mL/g; pore volume for pores with diameter above 160 Å measured by mercury porometry less than 0.1 mL/g; pore volume for pores with diameter above 200 Å measured by mercury porometry less than 0.1 mL/g; pore volume for pores with diameter above 500 Å measured by mercury porometry less than 0.01 mL/g; x-ray diffraction pattern containing at least principal characteristic lines of at least one transition aluminum oxides (alpha, rho, chi, eta, kappa, teta, and delta). Processes of obtaining middle distillates from paraffin charge obtained ny Fischer-Tropsch synthesis (options) using above indicated procedure are also described.

EFFECT: improved catalytic characteristics in hydrocracking/hydroisomerization processes and improved quality and yield of middle distillates.

18 cl, 6 dwg, 3 tbl, 5 ex

FIELD: petrochemical processes and catalysts.

SUBSTANCE: middle distillates are obtained, in particular, from paraffin charge prepared by Fischer-Tropsch synthesis wherein hydrocracking/hydroisomerization catalyst is utilized including at least one hydrocracking/hydroisomerization element selected from group constituted by group VIII metals, non-zeolite silica-and-alumina-based carrier (more than 5% and less than or equal to 95% SiO2) and having: average pore size measured by mercury porometry within a range 20 to 140 Å; total pore volume measured by mercury porometry 0.1-0.6 mL/g; total pore volume measured by nitrogen porometry 0.1-0.6 mL/g; specific surface BET between 100 and 550 m2/g; pore volume for pores with diameter above 140 Å measured by mercury porometry less than 0.1 mL/g; pore volume for pores with diameter above 160 Å measured by mercury porometry less than 0.1 mL/g; pore volume for pores with diameter above 200 Å measured by mercury porometry less than 0.1 mL/g; pore volume for pores with diameter above 500 Å measured by mercury porometry less than 0.01 mL/g; x-ray diffraction pattern containing at least principal characteristic lines of at least one transition aluminum oxides (alpha, rho, chi, eta, kappa, teta, and delta). Processes of obtaining middle distillates from paraffin charge obtained ny Fischer-Tropsch synthesis (options) using above indicated procedure are also described.

EFFECT: improved catalytic characteristics in hydrocracking/hydroisomerization processes and improved quality and yield of middle distillates.

18 cl, 6 dwg, 3 tbl, 5 ex

FIELD: technological processes; chemistry.

SUBSTANCE: method involves reaction of raw material containing organic component with a catalyst composition. Processing method is selected out of alkylation, acylation, hydrotreatment, demetallisation, catalytic deparaffinisation, Fischer-Tropsch process and cracking. Catalyst composition includes mainly mesoporous silicon dioxide structure containing at least 97 vol.% of pores with size in the interval from ca. 15 Å to ca. 300 Å, and at least ca. 0.01 cm3/g of micropores. Mesoporous structure features at least one catalytically and/or chemically active heteroatom in amount of at least ca. 0.02 mass %, selected out of a group including Al, Ti, V, Cr, Zn, Fe, Sn, Mo, Ga, Ni, Co, In, Zr, Mn, Cu, Mg, Pd, Ru, Pt, W and their combinations. The catalyst composition radiograph has one 0.3° to ca. 3.5° peak at 2θ.

EFFECT: highly efficient method of organic compound processing in the presence of catalyst composition without zeolite.

20 cl, 31 ex, 17 tbl, 22 dwg

FIELD: oil and gas industry.

SUBSTANCE: invention refers to method for simultaneous making medium fractions and lubricant bases from synthetic paraffin mixtures, including hydrocracking stage (i) and distillation of product of stage (i), where hydrocracking involves addition of solid bifunctional catalyst including: (A) acidic carrier consisting of catalystically active porous solid substance, including silicon, aluminium, phosphorus and oxygen interlinking so that to form mixed amorphous solid substance, characterised by nuclear ratio Si/Al within 20 to 250, ratio P/Al at least 0.1, but lower that 5, total porous amount within 0.5 to 2.0 ml/g, average pore diameter within 2 nm to 40 nm and specific surface area within 200 to 1000 m2/g; (B) at least one metal with hydrogenation-dehydrogenation activity, selected from groups with 6th on 10th of Periodic systems and distributed over specified carrier (A) in amount within 0.05 to 5 wt % relative to total mass of catalyst.

EFFECT: development of method for simultaneous making medium fractions and lubricant bases from synthetic paraffin mixtures.

25 cl, 26 ex, 5 tbl, 2 dwg

FIELD: chemistry.

SUBSTANCE: invention refers to the bifunctional catalyst possessing the hydrogenising as well as acid function. The method for the preparation of the catalyst for hydrocarbon conversion includes: (a) obtaining of complex compounds as precursors of non-crystalline inorganic oxide with mesopores disorderedly connected together; (b) usage of the complex compounds from stage (a) for the preparation of the composite containing zeolite incorporated into inorganic oxide with mesopores disorderedly connected together; (c) incorporation of the at least one metal possessing the hydrogenising function to the composite obtained on the stage (b).

EFFECT: obtaining of the catalyst with enhanced operational versatility for control of the acid and hydrogenising functions.

13 cl, 13 ex, 3 tbl, 5 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a method of obtaining middle distillates from paraffin raw material through Fischer-Tropsch synthesis using a hydrocracking/hydroisomerisation catalyst which contains at least one hydro-dehydrogenating element selected from a group comprising group VIB and VIII elements, 0.2-2.5 wt % oxide of a doping element selected from phosphorus, boron and silicon, and a non-zeolite carrier based on silicon dioxide-aluminium oxide, containing silicon dioxide (SiO2) in amount of more than 5 wt % and less than or equal to 95 wt %, whereby the said catalyst has the following characteristics: -average pore diametre measured through mercury porosimetry between 20 and 140 , -overall pore volume measured through mercury porosimetry between 0.1 ml/g and 0.5 ml/g, -overall pore volume measured through nitrogen porosimetry between 0.1 ml/g and 0.5 ml/g, -BET specific surface area between 100 and 500 m2/g, - pore volume measured through mercury porosimetry, included in pores with diametre greater than 140 , less than 0.1 ml/g, -pore volume measured through mercury porosimetry, included in pores with diametre greater than 160 , less than 0.1 ml/g, -pore volume measured through mercury porosimetry, included in pores with diametre greater than 200 , less than 0.1 ml/g, -pore volume measured through mercury porosimetry, included in pores with diametre greater than 500 , strictly greater than 0.01 and less than 0.1 ml/g, - X-ray diffractogram which contains at least main characteristic lines of at least one transition aluminium oxide included in a group comprising alpha-, rho-, chi-, eta-, gamma-, kappa-, theta- and delta-aluminium oxides, -catalyst packing density greater than 0.75 g/cm3, -phosphorus content in the catalyst is between 0.2 and 2.5% of the weight of oxide.

EFFECT: high output of middle distillates.

21 cl, 9 ex, 4 tbl, 4 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing middle distillates from paraffin material obtained via Fischer-Tropsch synthesis, involving, before the hydrocracking/hydroisomerisation step, a step for hydrofining and purifying and/or removing impurities by passing through at least one multifunctional protective layer, where the protective layer contains at least one catalyst saturated with an active hydrogenating-dehydrogenating phase and having the following characteristics: volume of macropores with average diametre of 50 nm determined from mercury is higher than 0.1 cm3/g, the complete volume is greater than 0.6 cm3/g. The method also relates to apparatus for realising the disclosed method.

EFFECT: efficient method of obtaining middle distillates from paraffin material.

16 cl, 5 ex, 2 tbl, 5 dwg

FIELD: oil and gas industry.

SUBSTANCE: paraffin hydrotreating method involves the first stage at which paraffin with content C21 or higher of normal paraffins 70% wt or higher is used as basic material, and paraffin contacts with catalyst at reaction temperature of 270-360 C in presence of hydrogen for hydrocracking, catalyst consisting of metal of group VIII of the Periodic Table, which is put on carrier containing amorphous solid acid; the second stage at which raw material from paraffin is replaced for some time with light paraffin with content C9-20 of paraffins 60% wt or higher, and light paraffin contacts with catalyst at reaction temperature of 120-335 C in presence of hydrogen for hydrocracking; and the third stage at which raw material of light paraffin is replaced with paraffin and paraffin contacts with catalyst at reaction temperature of 270-360 C in presence of hydrogen for hydrocracking. Also, invention refers to method for obtaining material of fuel system, which involves the above method.

EFFECT: use of this invention allows improving activity of hydrocracking catalyst, which deteriorates with time.

6 cl, 1 tbl, 4 ex, 1 dwg

FIELD: oil and gas industry.

SUBSTANCE: invention refers to paraffin hydrotreatment method involving the first stage at which the paraffin produced by means of Fischer-Tropsch synthesis is used as initial raw material, and paraffin contacts with the catalyst containing the metal of group VIII of the Periodic Table, which is applied to the carrier containing zeolite in presence of hydrogen for hydrocracking; the second stage at which initial raw material is converted for some time from paraffin to distilled oil obtained by means of distillation of the mixture containing paraffin hydrocracking product obtained at the first stage and hydrocracking product of fraction of middle distillates, which is obtained by means of Fischer-Tropsch synthesis, and distilled oil contacts with catalyst in conditions with reaction temperature of 160-330C in presence of hydrogen for hydrocracking, and the third stage at which the initial raw material is converted again from distilled oil to paraffin, and paraffin contacts the catalyst in presence of hydrogen for hydrocracking. Invention also refers to base fuel obtaining method.

EFFECT: obtaining base fuel with adequately reduced content of normal paraffins.

3 cl, 3 ex, 1 tbl, 1 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a catalyst composition and its application in the process of hydroprocessing of a heavy hydrocarbon raw material. The catalyst composition for application in the process of hydroconversion of the heavy hydrocarbon raw material contains a molybdenum component, present in the said catalyst composition in a quantity less than 12 wt %, where wt % is taken from the total weight of the said catalyst composition in the supposition that the said molybdenum component is in the form of an oxide independently on its real form, and a nickel component, present in the said catalyst composition in such a quantity, with which the said catalyst composition has a weight ratio of the said nickel component to the said molybdenum component from 0.28 to 0.9, with the said weight ratio being calculated in the supposition, that each of the said nickel component and the said molybdenum component is in the form of oxides independently on their real form, and the material of a carrier, containing aluminium oxide, with the material of the carrier having a median pore diameter in the range from 100 E to 140 E, pores with the diameter larger than 210 E make not more than 5% of its total volume of the pores, and pores with the diameter less than 90 E make less than 10% of the pore volume.

EFFECT: catalyst composition provides high conversion of the resin component of the heavy hydrocarbon raw material.

8 cl, 2 tbl, 13 dwg, 3 ex

FIELD: chemistry.

SUBSTANCE: claimed invention relates to a method of conversion of a paraffinic feedstock, which contains at least 50 wt % of compounds, boiling at a temperature higher than 370C, and in which the content of paraffins constitutes at least 60 wt %, the content of aromatics is less than 1 wt %, the content of naphthenic compounds is less than 2 wt %, the content of nitrogen is less than 0.1 wt % and the content of sulphur is less than 0.1 w t%. The method includes stages, at which the feedstock is supplied into a reaction zone, where it contacts with hydrogen at a temperature in the range from 175 to 400C and under pressure in the range from 20 to 100 bars in the presence of a catalyst, containing from 0.005 to 5.0 wt % of a noble metal of group 8 on a carrier, which contains 0.1-15 wt % of zeolite beta and at least 40 wt % of amorphous alumosilicate counted per the catalyst weight, with the said zeolite beta having a molar ratio silicon dioxide/aluminium oxide equal to at least 50, and the said alumosilicate contains aluminium oxide in the terms of Al2O3 in an amount from 5 to 70%; a discharge flow is output from the reaction zone through an output; the discharge flow is supplied from the reaction zone to the stage of fractioning, at which at least a heavy fraction, an intermediate fraction and a light fraction are formed; and at least a part of the heavy fraction is supplied to an input into the reaction zone.

EFFECT: high conversion of a fraction with the boiling temperature higher than 370C.

10 cl, 3 tbl, 4 ex

Up!