Method of pour point improvement of hydrocarbon raw material produced by fischer-tropsch process using zeolite zbm-30 based catalyst

FIELD: physics.

SUBSTANCE: dewaxing procedure of raw material produced by Fischer-Tropsch method implies that processed raw materials contact with catalyst containing at least one zeolite ZBM-30, synthesised with triethylene tetramine, at least one hydrogenating- dehydrogenating element preferably selected from elements of group VIB and group VIII of periodic table, and at least one inorganic porous matrix.

EFFECT: good recovery of raw material, raised pour point.

13 cl, 5 ex, 1 dwg

 

The present invention relates to a method of improving the temperature loss of mobility of the hydrocarbons produced in the Fischer-Tropsch process, in particular, in order to turn with a good yield of raw materials with high temperature loss of mobility, in at least one fraction having a low temperature loss of mobility and high viscosity index base oils, passing it over the catalyst for catalytic hydrodewaxing containing at least one zeolite (molecular sieve) ZBM-30, synthesized in the presence of a particular structuring agent, such as Triethylenetetramine at least one porous inorganic matrix, at least one hydrogenating-dehydrating element, preferably selected from elements of group VIB and group VIII of the Periodic system of elements.

Prior art

Lubricants of high quality are of paramount importance for successful operation of modern machinery, cars and trucks. However, the quality of paraffins obtained directly from crude oil, raw and have the appropriate properties to create a good lubricant, very low from the point of view of increasing requirements in this industry.

To obtain the base oil of good quality, neobhodimosti heavy oil fractions with a high content of linear or often weakly branched paraffins, moreover, with the best outputs, using the way having to remove linear or very little branched paraffins from raw materials, which will then be used as base oils or as kerosene or jet fuel (jet fuel).

Indeed, the paraffins of high molecular masses, which are linear or very slightly branched and which are present in oils, kerosene or jet fuel, lead to high temperatures, loss of mobility and, thus, to the phenomena of thickening when using at low temperature. To reduce the temperature loss of mobility, these linear or very little branched paraffins must be fully or partially removed.

This operation can be carried out by extraction with solvents, such as propane or methyl ethyl ketone (MEK), then talk about dewaxing propane or methyl ethyl ketone. However, these methods are costly, time-consuming and not always easy to implement.

Another way is selective cracking longest linear paraffin chains, which leads to the formation of compounds with lower molecular weights, some of which can be removed by distillation.

Given the selectivity of their form, more often than other catalysts used zeolites. The predominant reason for their COI is whether - it is a fact that there are zeolite structure, in which the pore size is such that they allow to enter their micropores long linear or very little branched paraffins, but exclude the entrance branched, naphthenic and aromatic paraffins. Thus, this phenomenon leads to selective cracking linear or very malorazmernyj paraffins.

The use of such catalysts based on zeolites having an intermediate pore size, such as ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35 and ZSM-38 described in particular in patents US 3894938; US 4176050; US 4181598; US 4222855; US 4229282 and US 4247388.

Mixtures of zeolites with large pores and these zeolites with intermediate pores, suitable dewaxing process described in patent WO 02088279.

In addition, it argues that the ways of using these zeolites (ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35 and ZSM-38), allow to obtain oil cracking feedstock containing linear or very often weakly branched paraffins in a quantity of less than 50 wt.%. However, for materials containing higher amounts of these compounds, it appeared that they were cracking leads to the formation of a large number of products with lower molecular weights, such as butane, propane, ethane and methane, which significantly reduces the yield of desired products.

To correct these shortcomings, the authors filed research efforts on the development of the method of the improvement of the temperature loss of mobility of hydrocarbons, obtained in the Fischer-Tropsch process using catalysts containing at least one zeolite ZBM-30, at least one hydrogenating-dehydrating element, preferably selected from elements of group VIB and group VIII of the Periodic system of elements. The authors found that the use of a catalyst containing at least one zeolite ZBM-30, synthesized with a particular structuring agent such as Triethylenetetramine, reduces temperature loss of mobility of the raw material, thus obtaining a high viscosity index (VI) and maintaining a good yield of the desired products. Indeed, it was unexpectedly found that the catalyst prepared with zeolite ZBM-30, synthesized in the presence of a structuring agent Triethylenetetramine has activity and selectivity for dewaxing (improved temperature loss of mobility)greater than the solids on the basis of ZBM-30, synthesized with other structuring agents, and the catalytic forms-based zeolites, known from the prior art.

The present invention provides a catalytic method for reducing the temperature of the mobility on the basis of such catalysts.

The object of the invention

In more detail, the invention relates to a method of improving the temperature loss of mobility couples who renovage raw materials, obtained by Fischer-Tropsch synthesis, in which the processed raw material is brought into contact with a catalyst containing at least one zeolite ZBM-30, synthesized with a particular structuring agent such as Triethylenetetramine at least one hydrogenating-dehydrating element, preferably selected from elements of group VIB and group VIII of the Periodic system of the elements, at least one inorganic porous matrix. This method of dewaxing is conducted at a temperature of from 200 to 450°C, a pressure of from 0.1 to 25 MPa and specific volume hourly flow rate from 0.05 to 30 h-1in the presence of hydrogen at the rate of 50 to 2000 normal liters of hydrogen per liter of feedstock (nl/l).

Synthesis of zeolite ZBM-30 described in the patent EP-A-46504.

It was unexpectedly found that the catalyst has higher activity and selectivity in the process of dewaxing (improved temperature loss of mobility of the raw material obtained in the Fischer-Tropsch process)than catalytic forms on the basis of zeolite (molecular sieve), known from the prior art.

Favorably, this method allows you to turn raw materials with high temperature loss of mobility in a product with lower temperature loss of mobility, and allows to obtain a base oil having good low-temperature properties and high is th viscosity index, and oils of good quality.

Raw materials that can be processed according to the method of the invention is favorably fractions having a relatively high temperature, loss of mobility, the values of which it is desirable to reduce.

Typical raw materials that can be favorably processed according to the invention has, as a rule, the temperature loss of mobility above 0°C. the Products obtained as a result of processing according to this method, have a temperature loss of mobility below 0°C and preferably below about -10°C.

The method according to the invention under the conditions described above allows, in particular, to obtain a good output products with low temperature loss of mobility and a high viscosity index in the case of most heavy fractions, which are processed in order to obtain base oils.

A detailed description of the invention

The method according to the invention uses a catalyst that contains at least one zeolite ZBM-30, synthesized with a particular structuring agent such as Triethylenetetramine at least one hydrogenating-dehydrating element, preferably selected from elements of group VIB and group VIII of the Periodic system of elements, and at least one inorganic porous matrix.

Synthesis of zeolite ZBM-30 described in the patent EP-A-4504.

Zeolite ZBM-30 was synthesized according to the methods described in the patent EP-A-46504, by the way, using a structuring agent of Triethylenetetramine.

The total ratio Si/Al zeolites included in the catalyst composition according to the invention, as well as the chemical composition of the samples determined by x-ray fluorescence and atomic absorption spectroscopy.

Relations Si/Al zeolites described above are relations, obtained by synthesis according to the methods described in the above documents, or obtained after synthesis by removing the aluminum - processing, well known to the person skilled in the art, such as, without limitation, gidrodermabrasy with or without subsequent acid etching or direct etching solutions of inorganic or organic acids.

Zeolites included in the catalyst composition method according to the invention can be calcined and subjected to ion exchange by at least one treatment with a solution of at least one ammonium salt to obtain the ammonium form of the zeolites that during annealing leads to the hydrogen form of the zeolite.

Zeolites included in the catalyst composition method according to the invention are at least partially and preferably practically completely, in acid form, then eats is in the hydrogen form (H +). The atomic ratio Na/T usually below 10%, preferably below 5% and even more preferably below 1%.

On the other hand, the catalyst contains at least one hydrogenating-dehydrating element, preferably selected from elements of group VIB and group VIII (i.e., the metal or compound) of the Periodic system of elements, and at least one inorganic porous matrix.

When the element is at least one metal of group VIII, preferably refers to at least one noble metal and favorably noble metal selected from the group formed by platinum and palladium, it can be introduced into the zeolites, for example, "dry" impregnation, ion exchange, or any other method known to the expert, or he can also be entered into the matrix.

According to the first embodiment, before forming the zeolite described previously, his cause at least one metal of group VIII, preferably selected from the group formed by platinum and palladium.

Then the zeolite shape by any method known to the person skilled in the art. He may, in particular, to be mixed with a matrix, usually amorphous, for example with wet powder gel alumina. The mixture is formed into the shape of, for example, by extrusion through a Spinneret.

The shaping can be carried out on the natives matrices other than alumina, such as, for example, magnesium oxide, amorphous aluminosilicates, natural clays (kaolin, bentonite, thick, attapulgite), silicon oxide, titanium oxide, boron oxide, Zirconia, aluminum phosphate, titanium phosphates, zirconium phosphates, coal, and mixtures thereof. It is preferable to use a matrix containing aluminum oxide, in all forms known to the specialist, and even more preferably alumina, such as gamma-alumina. Can also be used not only extrusion, but other methods, such as tableting or drazhirovanie.

You can also benefit from a mixture of aluminum oxide and silicon oxide, a mixture of aluminum oxide and aluminum silicate.

The resulting catalysts are moulded in the form of grains of different shapes and sizes. They are usually used in the form of a cylindrical or multipartite extrudates, such as two, three, multipartite in a straight or curved form, but in certain cases they can be produced and used in the form of crushed powder, tablets, rings, balls, wheels.

After the stage of forming the resulting product is subjected to a stage of drying, and then the stage of calcination.

When hydrogenating metal belongs to group VIII and preferably is platinum and/or palladium, it can also favorably be applied N. the substrate after forming the zeolite, not containing metals, in any way known to the person skilled in the art and allowing the deposition of metal on a molecular sieve. In this case, the substrate obtained by the method similar to that described previously.

Hereinafter, the term substrate denote zeolite (containing metals) plus matrix after forming, drying and calcination, such as obtained previously.

To precipitate metal on the zeolite, it is possible to use the method of competitive cation exchange, in which the competitor is preferably ammonium nitrate, with respect to competition is at least about 20 and favorably ranges from about 30 to 200. In the case of platinum or palladium typically use complex tetraamine platinum or complex tetraamine palladium: these last almost completely deposited on the zeolite. This method of cation exchange can also be used for the direct deposition of metal powder molecular sieves, prior to its possible mixing with the matrix.

For deposition of the metal (or metals) of group VIII should usually annealed in air or in oxygen atmosphere, typically at a temperature of from 300 to 600°C for 0.5 to 10 hours, preferably from 350 to 550°C for 1 to 4 hours. Then you can conduct recovery in hydrogen atmosphere usually at a temperature of from 300 to 600°St for 1 to 10 hours, preferably operate in the range of from 350 to 550°C for from 2 to 5 hours.

You can also apply a platinum and/or palladium is not directly on the zeolite and the matrix (for example, aluminum bonding) substrate, before or after the stage of forming, using anionic exchange hexachloroplatinic acid, hexachloroplatinic acid and/or palladium chloride in the presence of a competing agent, for example hydrochloric acid. Usually after deposition of platinum and/or palladium catalyst, as previously, is subjected to calcination, then restore in hydrogen atmosphere as described above.

The substrate of the catalyst catalytic dewaxing according to the present invention usually contains the following percentage amounts of matrix and zeolites:

from 5 to 95 wt.%, preferably from 10 to 90 wt.%, even more preferably from 15 to 85 wt.% and very preferably from 20 to 80 wt.% zeolite ZBM-30,

from 5 to 95%, preferably from 10 to 90%, even more preferably from 15 to 85% and very preferably from 20 to 80 wt.% at least one inorganic porous matrix, amorphous or nizkoglikemichesky, oxide type.

The content of noble metal(s)may also enter(s), expressed in wt.% from the total mass of the catalyst, usually below 5%,preferably below 3%, even more preferably below 2% and usually below 1 mA is.%.

When the hydrogenation catalyst contains a metal of group VIII, preferably a noble metal and a positive platinum and/or palladium, the catalyst usually recover in a reactor in the presence of hydrogen under conditions well known to the specialist in this field.

When the hydrogenating metal is a noble metal elements VIB and VIII groups, if necessary, is introduced into the catalyst according to the invention can be present completely or partially in the form of metal and/or oxide and/or sulfur compounds.

From the elements of group VIB preferred molybdenum and tungsten.

Sources of the elements of group VIB, which can be used are well known to the specialist. For example, as sources of molybdenum and tungsten can be used oxides and hydroxides, molybdenum and tungsten acid and their salts, in particular ammonium salts such as ammonium molybdate, heptamolybdate ammonium, ammonium tungstate, posteromarginal acid, rostroventrally acid and their salts. Preferably used oxides and ammonium salts such as ammonium molybdate, heptamolybdate ammonium and ammonium tungstate.

The dewaxing catalyst according to the present invention may contain a base metal of group VIII, preferably cobalt and Nickel. Favorably, when used with ewusie combination of base elements VI and VIII groups: Nickel-molybdenum, cobalt-molybdenum, iron-molybdenum, iron-tungsten, Nickel-tungsten, cobalt-tungsten, the preferred combinations are: Nickel-molybdenum, Nickel-tungsten. You can also use a combination of the three metals, for example Nickel-cobalt-molybdenum.

The sources of elements of group VIII, which can be used are well known to the specialist. For example, use nitrates, sulphates, phosphates, halides, for example chlorides, bromides and fluorides, carboxylates, for example acetates and carbonates.

When the hydrogenating function is provided precious metal of group VIII or a combination of the base metal of group VIII and a metal of group VIB,

structure of a substrate formed of at least one matrix and zeolites described in the invention, the same as the structure described previously, and

the relative weight percent of at least one element selected from the base elements of group VIB and group VIII, is from 0.1 to 60%, preferably from 1 to 50% and even more preferably from 2 to 40%.

Typically, to complete the preparation of the catalyst, wet the solid material is incubated in a humid atmosphere at a temperature of from 10 to 80°C, then dry the obtained wet material at a temperature of from 60 to 150°C and finally calcined obtained solid at a temperature of from 150 to 800°C, usually from 250 to 600°C.

Katal is the congestion of the method of the present invention may optionally be subjected to culturali, to convert, at least partially metallic substances in sulfur compounds before bringing them into contact with the processed raw materials. This activation is well known to the expert and may be submitted by any of the methods already described in the literature.

In the case of base metals classic method of sulfuration, well known to the specialist, is heated in the presence or in the flow of the mixture of hydrogen/hydrogen sulfide or also in pure hydrogen sulfide at a temperature of from 150 to 800°C, preferably from 250 to 600°C, usually in the reaction zone penetrating the layer.

Raw materials

Hydrocarbon raw materials processed according to the method of the invention is the product of the Fischer-Tropsch synthesis, a positive fractions having a relatively high temperature, loss of mobility, the value of which it is desirable to reduce.

Generally speaking, at least part of the compounds having a boiling point higher than or equal to 340°C, is processed according to the invention.

During Fischer-Tropsch synthesis gas (CO+H2) catalytically converted into oxygenated products and almost linear hydrocarbons in the gaseous, liquid or solid form. These products usually do not contain heteroatomic impurities, such as, for example, sulfur, nitrogen or metals. They also turn the key do not contain or contain very little aromatic compounds, naphthenes and generally cycles, in particular, in the case of cobalt catalysts. On the contrary, they may contain nepreoborimoe amount of oxygen products, which, being expressed in weight of oxygen, typically less than 5 wt.%, and an unsaturated compound (usually olefinic products) in an amount of usually less than 10 wt.%. However, these products, mainly consisting of normal paraffins cannot be used as is, especially because of their low-temperature properties, poorly compatible with a normal exploitation of oil fractions. For example, the temperature loss of mobility of the linear hydrocarbon containing 20 carbon atoms in the molecule (boiling point of about 340°C, which often comes in the middle distillate fraction), is about +37°C, making its use impossible, because the technical requirements for gasoil be -15°C. the Hydrocarbons produced by the method of Fischer-Tropsch, most of them contain n-paraffins, which should translate into more valuable products, such as, for example, gasoil, kerosene, which receive, for example catalytic reactions of hydroisomerization.

Typical raw materials that can be favorably processed according to the invention usually has a temperature loss of mobility above 0°C. the Products obtained after processing according to the method, the ima is t the temperature loss of mobility below 0° C, preferably below about -10°C.

In hydrocarbon raw materials that come into contact with a catalyst based on ZBM-30 (which can be obtained from oil and possibly distillates of high quality) is preferably at least 50 wt.% the feedstock has a boiling point of at least 340°C, even more preferably at least 60 wt.% and better still at least 80 wt.% the feedstock has a boiling point of at least 340°C, preferably above at least 370°C and more preferably above at least 380°C. This does not mean, for example, that the boiling point equal to 380°C and more, but it means 380°C or more.

Thus, most of the raw materials is normal paraffins.

Typically, raw materials, suitable for obtaining oils have an initial boiling point above at least 340°C, even better above at least 370°C and even better above at least 380°C.

The use of the catalyst according to the invention under the conditions described below, allows, in particular, to obtain products with low temperature loss of mobility with good yield and with high viscosity index in the case of the heavy fractions, which are processed in order to obtain base oils.

Working mode

Operating mode in which carry out the process of catalytic de is arabinitol according to the invention, the following:

the reaction temperature is from 200 to 450°C, preferably from 200 to 420°C, positive 250-410°C;

- the pressure is from 0.1 to 25 MPa, preferably from about 0.1 to 20 MPa;

- specific volumetric hourly rate (obobo, expressed as the amount of raw material that passes through a unit volume of catalyst per hour) is from about 0.05 to about 30, preferably from about 0.1 to about 20 h-1and even more preferably from about 0.1 to about 10 h-1.

The contact between the feedstock and the catalyst is carried out in the presence of hydrogen. The share of hydrogen, expressed in liters of hydrogen per liter of feedstock is from about 50 to about 2000 liters of hydrogen per liter of feedstock and preferably from 100 to 1500 liters of hydrogen per liter of feedstock.

Methods of implementation

In the first preferred method of implementing the process of catalytic dewaxing according to the invention may be preceded by a stage of hydroisomerization-hydroconversion in the presence of a catalyst containing at least one noble metal deposited on an acidic amorphous substrate.

This stage of hydroisomerization-hydroconversion optionally preceded by a step of Hydrotreating to remove heteroatoms (oxygen), and stage Hydrotreating can follow the intermediate section the population.

Stage hydroisomerization-hydroconversion takes place in the presence of hydrogen and in the presence of a bifunctional catalyst containing acidic amorphous substrate (preferably amorphous aluminosilicate), in which the hydrogenating function is dehydrating metal provides at least one noble metal of group VIII.

The substrate and the catalyst, is called amorphous, when it does not contain molecular sieves, and, in particular, zeolite. Acidic amorphous substrate is favorably an amorphous aluminosilicate, but can also be applied to other substrates. When speaking about the aluminosilicate, the catalyst usually contains no added Halogens, except those that could be introduced by impregnation, for example, a noble metal. The aluminosilicate can be obtained by any means known to the person skilled in the art, such as methods of co-deposition, co-gelation, etc.

At the stage of hydroisomerization-hydroconversion molecules of the processed raw materials, such as n-paraffins, in the presence of a bifunctional catalyst are subjected to isomerization, then if necessary, hydrocracking, to lead to the formation of respectively isoparaffins and lighter products of cracking, such as gas oils and kerosene. Conversion products having a boiling point greater than or equal to the existing boiling point of raw material, which is equal to at least 340°C, even 370°C or better still, at least 380°C, into products with boiling points below the initial boiling point of raw material is usually from 5 to 90%, preferably from 5 to 80%, but is usually preferably below 80% and, even better, below 60%.

In more detail, the characteristics of the catalyst hydroisomerization-hydroconversion as follows.

The preferred substrate used for the preparation of the catalyst pre-treatment by hydroisomerization-'ve got a hydro conversion described in this application consists of silicon oxide SiO2and aluminum oxide Al2O3. The content of silicon oxide in the substrate, expressed in mass percent, usually from 1 to 95%, a positive even from 5%to 95%, preferably from 10 to 80%, even more preferably from 20 to 70% and from 22%to 45%. Is the content of silicon oxide is perfectly measured using x-ray fluorescence.

For this particular type of reaction, metal plays the role of a noble metal of group VIII of the Periodic system of elements, more particularly platinum and/or palladium.

The content of noble metal in the catalyst, expressed in wt.% metal is from 0.05 to 10 and more preferably from 0.1 to 5.

The distribution of the noble metal is a dispersion of the metal within the grain cat who lyst moreover, the metal can be well or poorly dispersed. It is also possible to get badly distributed platinum (such as that found in the crust, the thickness of which is considerably lower than in the field of grain), but well dispergirovannoyj, i.e. all atoms of platinum in the crust available for reagents. In this case, the distribution of platinum is good, that is, the profile of platinum measured using microprobe Castaing, has a distribution coefficient higher than 0.1, and preferably above 0.2.

The specific surface according to BET of the substrate is from 100 to 500 m2/g, preferably from 250 to 450 m2/g, and substrates on the basis of aluminosilicate even more preferably from 310 to 450 m2/year

Preparation and molding of the substrate, in particular, the silicate is carried out by conventional methods, well known to the person skilled in the art. Favorably before impregnation of the metal to expose the substrate to annealing, for example, heat treatment at 300-750°C (preferably at 600°C) for 0.25 to 10 hours (preferably 2 hours) 0-30% vol. water vapor (aluminosilicate preferably of 7.5 %).

Salt of the noble metal is injected by conventional means, used for the deposition of metal (preferably platinum and/or palladium, and platinum are preferable) on the surface of the substrate. One of predpochtite the selected methods is the "dry" impregnation, which consists in the introduction of the metal salt in the solution volume equal to the pore volume of the mass of the impregnated catalyst. Before restoring the catalyst can be subjected to annealing, for example treatment in dry air at 300-750°C (preferably 520°C) for 0.25 to 10 hours (preferably 2 hours).

Before use in the reaction of hydroisomerization-hydroconversion metal contained in the catalyst, should be restored. One of the preferred methods of metal recovery is treatment with hydrogen at a temperature of from 150 to 650°C and a pressure of from 0.1 to 25 MPa. For example, the recovery is at the plateau of 150°C for 2 hours, then the temperature is increased to 450°C with a speed of 1°C/min, then plateau for 2 hours at 450°C; during this phase of the recovery flow rate of hydrogen is 1000 liters of hydrogen per liter of catalyst. Note also that fit all recovery methodsex-situ.

Operating mode in which the phase of hydroisomerization-hydroconversion described below.

Pressure support level from 2 to 25 MPa, preferably from 3 to 20 MPa and favorably from 2 to 18 MPa, specific volume hourly rate is from 0.1 to 10 h-1preferably from 0.2 to 10 h-1and favorably from 0.5 to 5.0 h-1. The proportion of hydrogen sostav the et from 100 to 2000 liters of hydrogen per liter of feedstock, preferably from 150 to 1500 liters of hydrogen per liter of feedstock.

The temperature used in this step is from 200 to 450°C, preferably from 250 to 450°C, favorably from 300 to 450°C and even more favorably above 340°C, for example 320-450°C.

When the stage Hydrotreating precedes the stage of hydroisomerization-hydroconversion, the two stage Hydrotreating and hydroisomerization-hydroconversion can be carried out on two types of catalysts in various (two or more reactors and/or at least two catalytic layers that are installed in the same reactor.

The use of the catalyst described above, at the stage of hydroisomerization-hydroconversion aims to increase the share of isomerization of the heavy fraction (340°C+ or even 370°C+ or better still, 380°C+) and to reduce its temperature loss of mobility. Usually argue that the processing at the stage of hydroisomerization-hydroconversion will then allow you to get the best outputs deparaffinizing oil fractions, which are obtained at the stage catalytic dewaxing, and to obtain the desired viscometric properties (viscosity and viscosity index IV).

In one embodiment, the product emerging from the stage of hydroisomerization-hydroconversion can be processed entirely in the dewaxing process according to izopet the tion. This option, together with the supply to the catalytic dewaxing the entire product obtained in stage hydroconversion-hydroisomerization, is of interest from an economic point of view, because at the end of the process uses a single distillation unit. Moreover, the final distillation (after catalytic dewaxing or subsequent treatment) receive gas oil with very good low temperature properties.

In another embodiment, the flow coming from the stage of hydroisomerization-hydroconversion may be split at least a portion (and preferably at least mostly) light gases that contain hydrogen and it is also possible hydrocarbon compounds with not more than 4 carbon atoms. Hydrogen can be removed in advance.

Favorably in another embodiment, the stream exiting the stage hydroisomerization-hydroconversion, is distilled to separate light gases and also to separate at least one residual fraction containing compounds with a boiling point above at least 340°C. It is preferably about distillation at atmospheric pressure.

Can favorably to distillation to obtain several fractions (e.g., gasoline, kerosene, gas oils) with a boiling point of not more than 340°C and one faction (called OS is enough) with an initial boiling point above at least 340° C and better 350°C and preferably at least 370°C or 380°C.

This fraction (residual) is then treated at the stage catalytic dewaxing, that is, without distillation in vacuum. But in another embodiment it is possible to use the distillation in vacuum.

Generally speaking, middle distillates in this text referred to as the fraction(s) with an initial boiling point of at least 150°C and end up to the boiling point of the residual fraction, that is usually up to 340°C, 350°C or preferably below 370°C or 380°C.

The stream obtained at the stage of hydroisomerization-hydroconversion may be subjected, before or after distillation, other types of processing, such as extraction of at least part of the aromatic compounds.

Generally speaking, at least a portion of the product obtained at stage hydroisomerization-hydroconversion, the product may be subjected to separation or treatments described above, then subjected to catalytic dewaxing according to the invention.

Note that compounds boiling above at least 340°always subjected to catalytic dewaxing.

At the end of the process is the catalytic dewaxing according to the invention the flow of positively fed to the distillation, which preferably combines the stretch is at atmospheric pressure and distillation under vacuum, the purpose of which is to separate the conversion products with a boiling point below 340°C, preferably below 370°C (including, in particular, those formed at the stage catalytic hydrodewaxing), and to separate the fraction containing the base oil, the initial boiling point which is above at least 340°C and preferably above or equal to 370°C.

In addition, this section of the distillation under vacuum allows to separate the oil of varying quality.

Preferably before distillation stream coming from the stage catalytic dewaxing, at least partially, and preferably completely, is the catalyst for Hydrotreating (hydrofinishing) in the presence of hydrogen, in order to carry out the hydrogenation under pressure of aromatic compounds may still present, which degrades the stability of oils and distillates. However, the acidity of the catalyst should be sufficiently low so as not to lead to the formation of the product of cracking with a boiling point below 340°C, in order not to reduce the final outputs, in particular oils.

The catalyst used in this step of Hydrotreating contains at least one metal of group VIII and/or at least one element of group VIB of the Periodic system. Possessing valuable properties of metals: platinum and/or palladium, or a combination of Nickel-tungsten, Nike is ü-molybdenum, will be favorably used to effect the hydrogenation of aromatic compounds under pressure.

These metals are precipitated and distributed on a substrate of amorphous or crystalline oxide such as, for example, aluminum oxide, silicon oxide, aluminum silicates.

The Hydrotreating catalyst (HDF) may also contain at least one element of group VIIA of the Periodic system of elements. Preferably, these catalysts contain fluorine and/or chlorine.

Bulk metal content is from 10 to 30% in the case of base metals and below 2%, preferably from 0.1 to 1.5%, even more preferably from 0.1 to 1.0% in the case of noble metals.

The total number of halogen is from 0.02 to 30 wt.%, favorably from 0.01 to 15% or even more favorably 0.01 to 10%, preferably from 0.01 to 5%.

Of catalysts that can be used at this stage Hydrotreating and that result in excellent performance, in particular for medical oils include catalysts containing at least one noble metal of group VIII (e.g., platinum and palladium and at least one halogen (chlorine and/or fluorine), preferably a combination of chlorine and fluorine.

Operating mode, in which the step of Hydrotreating the following if necessary, process kataliticheski the second dewaxing, the following:

the reaction temperature is from 180 to 400°C and preferably from 210 to 350°C, positive 230-320°C;

- the pressure is from 0.1 to 25 MPa and preferably from 1.0 to 20 MPa;

- specific volumetric hourly rate (obobo, expressed as the amount of raw material that passes through a unit volume of catalyst per hour) is from about 0.05 to about 100, preferably from about 0.1 to about 30 h-1.

The contacting of the feedstock and catalyst occurs in the presence of hydrogen. The proportion of the applied hydrogen, expressed in liters of hydrogen per liter of feedstock is from about 50 to about 2000 liters of hydrogen per liter of feedstock, preferably from 100 to 1500 liters of hydrogen per liter of feedstock.

Favorably, when the temperature of the stage Hydrotreating (HDF) is lower than the temperature of the phase catalytic dewaxing (HDPC). The difference between THDPC-THDFis usually from 20 to 200°C, preferably from 30 to 100°C.

At the end of HDF thread is held on the stage of distillation.

In the first preferred embodiment of the method according to the invention, comprising a step prior hydroconversion/hydroisomerization, the obtained base oil will have a temperature loss of mobility below -10°C, YVES higher than 95, preferably above 110 and more preferably above 120, a viscosity of at least a 3.0 cSt at 100°C, the color of the item is ASTM below 1 and the stability to UV such the increase ASTM colour ranges from 0 to 4, preferably from 0.5 to 2.5.

Another advantage of this variant of the method according to the invention is that it is possible to obtain a very low aromatic content (less than 2 wt.%, preferably below 1 wt.% and better below 0.05 wt.%) and to even go to get light oils of medical quality, containing less than 0.01 wt.% aromatics. These oils have values of the absorption coefficient of the ultraviolet wavelength 275, 295 and 300 nm, respectively, lower than 0.8, and 0.4 and 0.3 (method ASTM D2008) and color of Sabato from 0 to 30.

Thus, a particularly interesting method according to the invention allows to obtain bright medical oil. Bright medical oils are mineral oils obtained by pressure cleaning oil, their quality is determined by various regulations, which aim to guarantee their safety for pharmaceutical applications, they are non-toxic and differ in density and viscosity. Bright medical oils contain mainly saturated hydrocarbons, they are chemically inert and content of aromatics is low. Special attention is given to aromatic compounds and, in particular, 6 polycyclic aromatic hydrocarbons (abbreviated P.A.H.). polycyclic aromatic hydrocarbons), which are toxic and present the light oils in concentrations of one mass part of the aromatic compounds mass per billion parts light oil. Control total content of aromatic compounds can be carried out according to the method of ASTM D 2008. This test UV absorption at a wavelength of 275, 292 and 300 nanometers allows you to control the absorption coefficient below respectively of 0.8, 0.4 and 0.3 to (that is, light oils contain less than 0.01 wt.% aromatic compounds). These measurements are carried out at concentrations of 1 g of oil per litre, cell 1 see commercially Available light oils have a viscosity, as well as for their origin, which may be paraffinic or naphthenic, these two parameters indicate the difference simultaneously physico-chemical properties of the considered light oils and their chemical composition.

In the second variant of the preferred embodiment of the method of dewaxing of the present invention is favorably carried out in sequence the following steps:

- processed raw materials share (D1) at least one light fraction 3 with a boiling point below 380°0 and at least one heavy fraction 4 (residual);

- specified light fraction 3, if necessary gidrirovannoe on the stage of the hydraulic control treatment (IPF HDT), is subjected to hydroisomerization (HISM);

- specified heavy fraction 4 is subjected to stage hydrocracking (HCK) in the presence of hydrogen, and then subjected to distillation (D2) to obtain at least one light fraction (13) and the end is th least one heavy fraction (10);

the mixture obtained after hydroisomerization (HISM), fractionary (D3) together with at least part of the light fraction 13, obtained from the distillation of D2 to obtain middle distillates having excellent low-temperature properties and/or high cetane number, and/or low allocation of contaminants;

- heavy fraction with stage D2 is subjected to stage dewaxing (DWX), so that after separation of the volatile products formed to receive liquid samaritane products, suitable as base oils of high quality;

and the way dewaxing is the method according to the invention.

This is particularly preferred form of the sequence comprising the method according to the present invention, is shown schematically in the drawing.

Liquid stream 1, consisting of a mixture of linear hydrocarbons obtained in the process of the Fischer-Tropsch synthesis, also containing unsaturated products (linear olefins), in the amount of up to 10 wt.%, preferably from 2 to 5 wt.%, and oxygen compounds (primarily alcohol) in an amount up to 10 wt.%, preferably from 2 to 7 wt.%, share in the distillation column D1 on one light fraction 3 with a boiling point below 380°C, component preferably from 260 to 360°C, and one heavy fraction 4, which forms the residue from the distillation. Pereg the NCA on D1 preferably is carried out in one stage (flash) and can be preceded by differential selection of two fractions immediately after the reactor Fischer-Tropsch synthesis.

Preferably the mass ratio of the two fractions 3 and 4 lies in the range from 0.5 to 2.0, more preferably from 0.8 to 1.5.

Light fraction 3 is the power set hydroisomerization (HISM). However, especially when there are heteroatoms or unsaturated groups, in particular, oxygen compounds, which can be uncomfortable for proper operation of the catalyst in this stage, the fraction 3 is powered preferably installed hydrogenation (HDT), in which it comes into contact with hydrogen (line 2) in the presence of a suitable catalyst, under conditions that can minimize and even lead to the absence of the hydrocracking reaction.

Installation hydrogenation (HDT) can be performed by conventional methods and includes preferably the reactor under pressure, comprising a fixed bed of the catalyst, selected so as to satisfy the above conditions. Typical hydrogenation catalysts, adapted to the conditions above, contain one hydrogenating metal such as Nickel, platinum or palladium deposited on a solid inert support such as alumina, silica, aluminosilicate, zeolite or molecular sieve. It is possible that during the hydrogenation reaction occurs hydroisomerization and partial hydrocracking, usually limited coverseaming 15% of the total weight of given fractions. A minor fraction of volatile compounds (150°C-) and water possibly formed may optionally be separated by distillation.

Light fraction, gidrirovanny or not, in the second place, then served on stage hydroisomerization (HISM) in line 6, which reacts in the presence of hydrogen, under normal conditions, to allow the isomerization under pressure and a partial rupture of linear hydrocarbon chains. The conditions selected for isomerization, are widely cited in the prior art, and an extensive list of suitable catalysts.

Part, usually below 50%, preferably from 0 to 25%, of the specified light fraction may optionally be selected through the line 7 to the stage of isomerization and mixed again with the specified heavy fraction from line 4, for transmission to the hydrocracking.

In this phase isomerization is usually a mixture of hydrocarbons complement hydrogen (line 5) in an amount of from 150 to 1500 normal liters per liter of the liquid phase and is passed over a fixed bed of a suitable catalyst, preferably based on a noble metal, with a specific volumetric flow rate of from 0.1 to 10 h-1and temperature from 300 to 450°C at a pressure of from 1 to 10 MPa.

Samaritano mixture entering through line 14 to column fractionation D3 with the light fraction 13 from the column D2 distillation of heavy tails is AI, last hydrocracking. Upon exit from the column D3 in accordance with this embodiment receive middle distillate, optionally selected at two different levels to separate kerosene (line 17) from gasoil (line 18)having excellent low-temperature properties, high cetane number, preferably above 50, and a lower allocation of contaminants.

On leaving the distillation column and the column fractionation D3 also receive a reduced amount of low molecular weight products, in particular through line 15 - gaseous fraction C1-C5relatively minor, generally along the line 16 is the fraction of light hydrocarbons, preferably having a boiling point below 150°C (nafta).

According to one particularly advantageous aspect of this variant implementation of the present invention, the number of such volatile fractions are significantly less than in the similar methods of the prior art, preferably less than 20%, even more preferably less than 15 wt.% from the initial feed line 1.

Fraction (line 4) hydrocarbons with a high boiling point and low content of oxygen and unsaturated compounds add the required amount of hydrogen (line 8) and nourish the hydrocracking (HCK), made in the usual way. The resulting product is the itania, on line 9, the installation of distillation and fractionation, which preferably operates to separate the hydrocarbon mixture mainly into two fractions. Light fraction having a boiling temperature below 380°C, preferably below 350°C, and containing less than 10 wt.% volatile compounds (150°C), forming a product having an increased concentration isoparaffins supplied via line 13 to the power stage fractionation of the light fraction, samaritano on stage HISM. This Union of the two obtained at different stages in different, but complementary conditions flows in one feed stream allows beneficial to get a fraction of the kerosene and gas oil with excellent properties mentioned earlier. In this case, a portion, preferably less than 50 wt.%, the mixture obtained in stage distillation D2, enter on line 19 to the input of the phase isomerization (HISM)to further improve the quality and composition of isomerized fractions and to control the relative amount of gas oil and kerosene.

The residual fraction from the distillation of D2 consists of a mixture of hydrocarbons with a high boiling point, with a surprisingly low content of waxes in comparison with the products obtained with other catalysts of the prior art in similar conditions. This residual fraction can also be used as such persons in the x applications, but preferably it is in the power (line 10) phase catalytic dewaxing, or dewaxing (DWX), before using as a base grease. According to a preferred variant it is partially returned to the stage hydrocracking (HCK) in line 12 to regulate the performance of the process or change the degree of isomerization depending on the needs of production.

According to the method of the present invention, the specified stage of dewaxing (DWX) is carried out in the presence of a catalyst suitable for the desired purpose. Partially samaritana mixture reacts further in the presence of hydrogen and a suitable solid catalyst, such as described previously, in terms of the method according to the invention.

Favorably, when the number of linear paraffins lowered, stage dewaxing process of this variant implementation can be carried out in a particularly favorable conditions in terms of contact time and the output of the base grease.

At the end of this stage dewaxing share the resulting volatile products (usually below 3 wt.%), extract (line 11) liquid isomerized product with excellent low temperature properties and high viscosity, having an initial boiling point above 350°C, preferably above 360°C, which has an optimum composition for the use of the Finance as the base grease of high quality.

The following examples illustrate the invention, but not limit it.

Example 1: preparation of catalyst C1 dewaxing corresponding to the invention

Catalyst C1 contains zeolite ZBM-30. This catalyst obtained by the method described below.

Zeolite ZBM-30 was synthesized according to the BASF patent EP-A-46504 with organic structuring agent Triethylenetetramine.

Raw zeolite ZBM-30 synthesis is subjected to calcination at 550°C in a stream of dry air for 12 hours.

Obtained zeolite H-ZBM-30 (acid form) has a ratio Si/Al equal to 45. Zeolite mix with gel alumina type SB3 set by society Condéa. Mixed pasta then push through a die plate with a diameter of 1.4 mm, So the resulting extrudates calcined at 500°C for 2 hours in air. Weight fraction of H-ZBM-30 to 80 wt.%.

Then extruded substrate is subjected to dry impregnation aqueous solution of platinum salt Pt(NH3)42+,2OH-. The weight percentage of platinum in the obtained catalyst C1 is equal to the value of 0.52%.

Example 2: preparation of catalyst dewaxing C2, is not relevant to the invention

The catalyst C2 contains zeolite ZBM-30. This catalyst obtained by the method described below.

Zeolite ZBM-30 was synthesized according to the BASF patent EP-A-46504 with organic structuring agent of triethylene what Eremina.

Raw zeolite ZBM-30 synthesis is subjected to calcination at 550°C in a stream of dry air for 12 hours.

Obtained zeolite H-ZBM-30 (acid form) has a ratio Si/Al equal to 54. Zeolite mix with gel alumina type SB3 set by society Condéa. The mixed paste is then forced through a die plate with a diameter of 1.4 mm Obtained extrudates calcined at 500°C for 2 hours in air. Weight fraction of H-ZBM-30 to 80 wt.%.

Then extruded substrate is subjected to dry impregnation aqueous solution of platinum salt Pt(NH3)42+,2OH-. Mass fraction of platinum in the so-obtained catalyst C2 is equal to 0.53%.

Example 3: the use of catalysts C1 and C2 for improved temperature loss of mobility of the raw material obtained in the process of the Fischer-Tropsch synthesis

Catalysts C1 and C2, the preparation of which is described in examples 1 and 2, are used to improve the temperature loss of mobility of the raw materials constituting the waxes obtained by Fischer-Tropsch synthesis, in order to obtain oil. For this purpose, and without limiting the scope of this example, the wax is Fischer-Tropsch derived in the plant for the production of paraffins, is distilled to obtain a fraction 370°C+. Main characteristics of the thus obtained raw materials as follows:

on the real point 356°C
point 5%370°C
point 10%383°C
point 30%399°C
point 50%424°C
point 80%509°C
point 90%568°C
point 95%631 °C
temperature loss of mobility+83°C
density (20/4)0,789

Test the catalytic apparatus consists of a reactor with a fixed bed, with upward circulation of raw materials ("up-flow"), which entered 80 ml of catalyst C1 or C2. The catalyst is placed in an atmosphere of pure hydrogen at a pressure of 10 MPa to ensure recovery of platinum oxide in metal is platinum, then served raw. The total pressure is 10 MPa, the flow rate of 1000 liters of hydrogen gas of hydrogen per liter of injected materials, specific volumetric hourly rate of 1.1 h-1and a reaction temperature of 340°C. After the reaction output stream fractionary on light products (gasoline HT-150°C), middle distillates (150-370° (C) and residual fraction (370°C).

Table 1 shows the outputs for the various factions and characteristics of oils obtained directly from the raw materials and products, hydroisomerization catalyst C1 (according to cstuuyxm invention) and then passed through the catalytic dewaxing.

Table 1
Corresponds to the inventionDoes not correspond to the invention
CatalystC1C2
Gross conversion fraction 370°C (wt.%)63,964,1
Division on fractions
The output of the HT-370°C (wt.%):63,964,1
Output 370°C+(wt.%)36,135,9
The quality of the oil (fraction 370°C+)
Temperature loss of mobility (°C)-9-3
IV (viscosity index)145141
Viscosity at 100°C (cSt)5,55,6

Note, it is obvious that the raw materials processed by the catalyst (C1) according to the invention leads to oil fraction (370°C+) the best quality; the lower the temperature loss of mobility and a higher viscosity index than that of the catalyst (C2), is not relevant to the invention, with close values of the conversion of raw materials into the product is, having a boiling point below 370°C.

Example 4: preparation of catalyst C3 pre-treatment with hydroisomerization raw materials received by the CFT process and subjected to dewaxing

Catalyst C3 pre-treatment by hydroconversion-hydroisomerization prepared, based on the aluminosilicate substrate used in the form of extrudates. It contains 40 wt.% silicon oxide SiO2and 60 wt.% aluminium oxide Al2O3. The aluminosilicate, which added to the noble metal has a surface 332 m2/g and a complete pore volume of 0.82 ml/year

Catalyst C3 obtained by impregnation of the noble metal substrate. Salt of platinum H2PtCl6dissolved in a volume of solution corresponding to the total pore volume, which is impregnated with. The solid material is then calcined for 2 hours in air at 500°C. the Content of platinum equal to 0.48 wt.%. The measured specific surface according to BET of the catalyst is equal to 310 m2/year Distribution of platinum measured by titration of H2/O2that is equal to 75%.

Example 5: application of catalyst C1 (corresponding to the invention) to improve the temperature loss of mobility paraffin feedstock for the Fischer-Tropsch process, the pretreated catalyst C3 (hydroisomerization-hydroconversion)

The catalyst (C3), preparation, whom of which is described in example 4, used to hydroisomerization paraffin feedstock obtained by Fischer-Tropsch synthesis, in order to obtain oil. Paraffin feedstock used in this example, the same as used and described in example 3.

Test the catalytic apparatus consists of a reactor with a fixed bed with upward circulation of raw materials ("up-flow"), which entered 80 ml of catalyst C3. The catalyst is placed in an atmosphere of pure hydrogen at a pressure of 10 MPa to ensure recovery of platinum oxide in metal is platinum, then served raw. The total pressure is 10 MPa, the flow rate of hydrogen to 1000 liters of hydrogen gas per liter of introduced raw specific volume hourly rate equal to 1.0 h-1and the reaction temperature 350°C. After the reaction output stream fractionary on light products (gasoline HT-150°C), middle distillates (150-370° (C) and residual fraction (370°C).

The residual fraction (370+° (C) is then treated to reduce its temperature loss of mobility, in the second reactor with an ascending circulation of raw materials ("up-flow"), which entered 80 ml of catalyst C3. The catalyst was then injected into the atmosphere of pure hydrogen at a pressure of 10 MPa to ensure recovery of platinum oxide in metal is platinum, then served raw. The total pressure is 10 MPa, the flow rate of hydrogen is 1000 liters of hydrogen gas nality served raw materials, specific volumetric hourly rate equal to 1.1 h-1and the reaction temperature is equal to 335°C. After the reaction outflows fractionary in light products (gasoline HT-150°C), middle distillates (150-370°C) and the fraction of oil (370+°C).

The measured characteristics of the oil.

Table 2 shows the outputs of the various factions and characteristics of oils obtained directly from the raw materials and products, pre-treated catalyst C3, and then past the dewaxing catalyst C1, corresponding to the invention.

Table 2
Hydroisomerization productThe flow past the hydroisomerization and catalytic dewaxing at C3
CatalystC3 (pre-processing)C1
Gross conversion fractions 370°C-(wt.%)40,532,1
The separation into fractions
The output of the HT-370°C (wt.%):40,532,1*
Output 370°C+(wt.%)59,567,9*
The quality of the oil (fraction 370°C+)
Temperature loss of mobility (°C) +42-21
IV (viscosity index)/147
Viscosity at 100°C(cSt)/6,3

*The outputs of the phase catalytic dewaxing.

Note, it is obvious that pre-treatment of raw materials on the catalyst hydroisomerization-hydroconversion C3 followed by treatment of the catalyst C1 (corresponding to the invention) allows to reach temperatures loss of mobility significantly lower than those obtained using only the catalyst pre-treatment (C3) or only catalyst C1 (see table 1). On the other hand, you can also see that the use of a pre-processing step before the catalyst C1, corresponding to the invention allows to obtain the fraction of oil 370°C+, with a temperature loss of mobility -21°C, with access to 40.4% by weight, while the use of catalyst C1 (corresponding to the invention) does not allow to obtain an oil fraction from such a low temperature loss of mobility (it is only -9°C), and the yield of oil fraction lower, 36,1% (cf. table 1). Finally, the viscosity index YVES oil fraction obtained by applying a pre-processing step and the catalyst C1 corresponding to the invention, more than in the absence of pre-processing is I.

1. Method of dewaxing raw material obtained by the method of Fischer-Tropsch process, in which the processed raw material is brought into contact with a catalyst containing at least one zeolite ZBM-30, synthesized in the presence of Triethylenetetramine at least one hydrogenating-dehydrating element and at least one inorganic porous matrix.

2. The method according to claim 1, in which the hydrogenating-dehydrating element selected from elements of group VIB and group VIII of the Periodic system of elements.

3. The method according to claim 2, in which the hydrogenating-dehydrating element of group VIB is molybdenum and/or tungsten.

4. The method according to claim 2 or 3, in which the hydrogenating-dehydrating element of group VIII is a noble metal of group VIII.

5. The method according to claim 1, in which the hydrogenating-dehydrating element of group VIII is platinum and/or palladium.

6. The method according to one of claims 1, 3 or 5, in which the processed raw material contains at least 50 vol.% compounds boiling above 340°C.

7. The method according to one of claims 1, 3 or 5, in which the operating mode is as follows:

the reaction temperature from 200 to 450°C

pressure from 0.1 to 25 MPa,

specific volume hourly flow rate (obobo, expressed as the amount of raw material passing through a unit volume of catalyst per hour) is from about 0.05 to about 30 h-1.

8. The method is about one of claim 1 or 5, in which the raw material is first subjected to hydroisomerization-hydroconversion.

9. The method according to claim 8, in which the flow coming from the stage of hydroisomerization-conversion is performed directly on the stage dewaxing.

10. The method according to one of claims 1 or 5, in which the stage of hydroisomerization-hydroconversion is preceded by the step of Hydrotreating.

11. The method according to claim 10, in which the step of Hydrotreating should the intermediate division.

12. The method according to one of claims 1 to 5, in which the flow coming from the stage catalytic dewaxing at least partly carried out on the catalyst Hydrotreating.

13. The method according to one of claims 1, 3 or 5, which are implemented in the following stages:

processed raw materials share (D1) at least one light fraction 3 with a boiling point below 380°and at least one heavy fraction 4 (residual fraction);

the specified light fraction 3, if necessary gidrirovanny on the stage of the hydraulic control treatment (IPF HDT)was subjected to hydroisomerization (HISM);

the specified weight fraction 4 is subjected to a step of hydrocracking (NSC) in the presence of hydrogen, and then subjected to distillation (D2) to obtain at least one light fraction (13) and at least one heavy fraction (10);

the mixture resulting from hydroisomerization (HISM), fractionary (D3) together with at the ore part of the light fraction 13, obtained at the stage distillation D2 to obtain middle distillates having excellent low-quality and/or high cetane number, and/or low allocation of contaminants;

the heavy fraction is discharged with stage D2, is subjected to the step of dewaxing (DWX) to obtain, after separation of the volatile products formed, liquid isomerized products, suitable as base lubricants of high quality.



 

Same patents:

FIELD: oil and gas industry.

SUBSTANCE: here is disclosed group of inventions related to versions of two-stage method of calalytic hydro-treatment of heavy oil hydrocarbons with high content of metals, total sulphur, pyrobitumens and total nitrogen, containing less, than 80% for volume of distillates extracted at 538°C and possessing density API lower, than 32°. According to the first version at the first stage hydrocarbons hydro-metallisation and hydrogen cracking of pyrobitumens are carried out, and at the second stage hydrocarbons hydro-desulphurisation and hydro-denitrogenation are performed; at that both stages of process are performed in a reactor with an immovable layer of catalyst. The second version includes: a) passing hydrogen and hydrocarbon raw material of heavy oil with specific mass (density) less, than 32° API and contents of distillates extracted at 538°C less, than 80% of volume through to the first stage of reaction for hydro-treatment of the said raw materials; at that the said first stage of reaction is performed in the reactor with the immovable layer of catalyst, containing a catalyst of hydro-demetallization and facilitating operation under pressure from 40 to 130 kg/cm2, at temperature from 320° to 450°C, at a volume speed (LHSV) from 0.2 to 3.0 hr-1 and at ratio of hydrogen/hydrocarbon (H2/HC) from 350 to 1.200 In/I with the result of production of hydro-treated heavy hydrocarbons; b) passing hydrogen and the said hydro-treated heavy hydrocarbons through to the second stage of reaction for hydro-treatment in the reactor with the immovable layer of catalyst containing hydro desulphurisation catalyst and facilitating operation under pressure from 40 to 130 kg/cm2, at temperature from 320° to 450°C, at a volume speed (LHSV) from 0.2 to 3.0 hr-1 and at ratio of hydrogen/hydrocarbon (H2/HC) from 350 to 1.200 In/I, at that the amount of sediments formed at each the said first and second stages of reaction is less 0.65% from weight of hydro-treated hydrocarbons. Also one of the inventions of the group refers to the product produced by the method according to the second variant. Employing of the said variant of the method facilitates high degree of metals, sulphur, nitrogen and pyrobitumens extraction and also limits formation of sediments which provides receiving the product after hydro-treatment with improved characteristics.

EFFECT: facilitating high degree of metals, sulphur, nitrogen and pyrobitumens extraction and also limits formation of sediments which provides receiving product after hydro-treatment with improved characteristics.

10 cl, 26 tbl, 10 ex, 1 dwg

FIELD: chemistry, organic, processing of hydrocarbons.

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

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

14 cl, 1 ex

FIELD: chemistry.

SUBSTANCE: catalyst material, which contains microporous zeolites on inorganic oxide mesoporous carrier, where mesopores account for at least 97% (vol.) of total micropore and mesopore volume, is described. Method to manufacture the said catalyst material, which implies preparation of laminar zeolite, where preparation consists in laminar zeolite delamination and intercalation, is described, as well as method for hydrocarbon material treatment.

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43 cl, 4 tbl, 12 dwg, 19 ex

FIELD: petroleum processing.

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3 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.

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18 cl, 6 dwg, 3 tbl, 5 ex

FIELD: petrochemical industry; other industries; methods of production of the sweet oil middle-distillate fractions with the improved low-temperature characteristics.

SUBSTANCE: the invention is pertaining to the method of production of the sweet oil middle-distillate fractions with the improved low-temperature characteristics by their treatment in the hydrogen medium at the increased pressure and temperature in the presence of the catalysts or the catalytic systems characterized by the fact, that the fractions with the temperature of the boiling end of 210-280°С are treated with the catalysts or the catalytic systems intended predominantly for transformation of the hetero-organic compounds; the fractions with the temperature of the boiling point of 210-280°С are treated with the catalytic systems consisting of the catalysts of transformation of the hetero-organic compounds and the n-paraffinic hydrocarbons; at that the catalysts of the preferable transformation of the hetero-organic compounds represent the alumonickel(cobalt) molybdenum oxide catalysts; the catalytic systems of the preferential transformation of the hetero-organic compounds represent the catalytic systems consisting of the indicated catalysts, and the catalysts of transformation of the n-paraffin hydrocarbons contain the alumosilicate compounds of the crystalline structure in the form of zeolites of the pentasil type and the active hydrogenating components in the form of the nickel oxide or the mixture of nickel oxides and molybdenum.

EFFECT: the invention ensures production of the sweet oil middle-distillate fractions with the improved low-temperature characteristics.

3 cl, 8 tbl, 17 ex

FIELD: petroleum processing.

SUBSTANCE: invention, in particular, relates to development and improvement of the processes of hydrofining and catalytic dewaxing of petroleum oil components. Petroleum base oil production process is discloses wherein hydrofining and catalytic dewaxing of hydrocarbon stock is carried out via bringing the latter into contact with catalytic system at elevated temperature and pressure in presence of hydrogen, said catalytic system consisting of hydrofining catalyst, containing active alumina-supported nickel and molybdenum, and dewaxing catalyst containing middle-silica zeolite. Specifically, process is conducted at 330-370°C, pressure 24.0-26.0 MPa, volumetric feed supply velocity 0.2-1.5 h-1, hydrogen-containing gas-to-feed ratio 1000-1500 nm3/m3. Catalytic system contains, summarily at least 20% nickel and molybdenum on active alumina and consists of alternating beds of hydrofining catalyst (70-55%) and dewaxing catalyst, which contains up to 60% middle-silica zeolite.

EFFECT: increased yield of desired fraction, reduced freezing temperature, and improved viscosity characteristics at low-temperature dearomatization of base oil.

1 tbl, 5 ex

FIELD: petroleum processing.

SUBSTANCE: heavy crude oil feed is subjected to two-stage hydrogen treatment at elevated temperature and pressure in presence of oxide catalyst in the first stage and oxide zeolite-containing catalyst in the second stage, whereupon gasoline fraction, diesel fraction and upgraded residue are recovered from the catalytic reaction product. Diesel fraction is combined with starting feedstock in amount ranging from 2 to 45 wt %. Volume ratio of first-stage catalyst to second-stage catalyst varies between 1:1 and 1:3.

EFFECT: increased quality of target products.

3 cl, 3 ex

FIELD: petrochemical processes.

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EFFECT: simplified technology without loss in quality of target products.

11 cl, 2 dwg

FIELD: petroleum processing.

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EFFECT: improved purification degree of residue and enabled involvement of heavy vacuum distillate.

2 cl, 3 ex

FIELD: oil and gas industry.

SUBSTANCE: here is disclosed group of inventions related to versions of two-stage method of calalytic hydro-treatment of heavy oil hydrocarbons with high content of metals, total sulphur, pyrobitumens and total nitrogen, containing less, than 80% for volume of distillates extracted at 538°C and possessing density API lower, than 32°. According to the first version at the first stage hydrocarbons hydro-metallisation and hydrogen cracking of pyrobitumens are carried out, and at the second stage hydrocarbons hydro-desulphurisation and hydro-denitrogenation are performed; at that both stages of process are performed in a reactor with an immovable layer of catalyst. The second version includes: a) passing hydrogen and hydrocarbon raw material of heavy oil with specific mass (density) less, than 32° API and contents of distillates extracted at 538°C less, than 80% of volume through to the first stage of reaction for hydro-treatment of the said raw materials; at that the said first stage of reaction is performed in the reactor with the immovable layer of catalyst, containing a catalyst of hydro-demetallization and facilitating operation under pressure from 40 to 130 kg/cm2, at temperature from 320° to 450°C, at a volume speed (LHSV) from 0.2 to 3.0 hr-1 and at ratio of hydrogen/hydrocarbon (H2/HC) from 350 to 1.200 In/I with the result of production of hydro-treated heavy hydrocarbons; b) passing hydrogen and the said hydro-treated heavy hydrocarbons through to the second stage of reaction for hydro-treatment in the reactor with the immovable layer of catalyst containing hydro desulphurisation catalyst and facilitating operation under pressure from 40 to 130 kg/cm2, at temperature from 320° to 450°C, at a volume speed (LHSV) from 0.2 to 3.0 hr-1 and at ratio of hydrogen/hydrocarbon (H2/HC) from 350 to 1.200 In/I, at that the amount of sediments formed at each the said first and second stages of reaction is less 0.65% from weight of hydro-treated hydrocarbons. Also one of the inventions of the group refers to the product produced by the method according to the second variant. Employing of the said variant of the method facilitates high degree of metals, sulphur, nitrogen and pyrobitumens extraction and also limits formation of sediments which provides receiving the product after hydro-treatment with improved characteristics.

EFFECT: facilitating high degree of metals, sulphur, nitrogen and pyrobitumens extraction and also limits formation of sediments which provides receiving product after hydro-treatment with improved characteristics.

10 cl, 26 tbl, 10 ex, 1 dwg

FIELD: chemistry.

SUBSTANCE: invention refers to method of base oil processing with viscosity index within 80 to 140, made of charge stock in the form of vacuum distillate or asphalt-free oil and resulted from hydrogen contact of charge stock with catalyst containing group VIB metal and group VIII base metal on amorphous carrier, followed by dewaxing cycle. Method of base oil processing with viscosity index within 80 to 140 is made of charge stock in the form of vacuum distillate or asphalt-free oil by the following stages: caused hydrogen contact of charge stock with sulphided unfluorinated hydrosulphur removal catalyst containing nickel and tungsten on carrier based on acid amorphous silicon dioxide - aluminium oxide. Then pour point for product of stage (a) is lowered, and base oil is produced. Hydrosulphur removal catalyst is produced by method implying that nickel and tungsten are applied on the carrier based on acid amorphous silicon dioxide - aluminium oxide consequently from chelator impregnation.

EFFECT: developed processing method of base oil with viscosity index.

16 cl, 7 dwg, 3 tbl, 6 ex

FIELD: petrochemical processes.

SUBSTANCE: major amount of hydrocarbon stock is brought into countercurrent contact with hydrogen in first reaction zone under hydrogenation reaction conditions in presence of hydrogenation catalyst in at least first catalyst bed wherein liquid leaving stream comes out of the bottom of the first reaction zone and hydrogen-containing gas stream comes out of the top of the first reaction zone. After that, insignificant part of hydrocarbon-containing stock comes into contact with above-mentioned hydrogen-containing gas stream in the second reaction zone accommodating catalyst bed disposed in such a way as to receive hydrogen-containing stream from the first reaction zone.

EFFECT: enabled production of product with ultralow content of sulfur using simple processing flowsheet.

19 cl, 7 dwg

FIELD: production of super-low-sulfur diesel fuel; oil and gas producing industry.

SUBSTANCE: proposed method consists in stage-by-stage catalytic hydraulic cleaning of diesel fraction in presence of hydrogen-containing gas at elevated temperature and increased pressure. At the first stage of process, starting material - diesel fuel fraction at temperature of 180-260C is subjected to hydraulic cleaning. At hot separation of hydrogenation product obtained at the first stage, vapor phase and liquid phase - fractions boiling-off at temperature above 330C are obtained; liquid phase of hydrogenation product of the first stage is subjected to hydraulic cleaning at the second stage, thus obtaining the hydrogenation product of the second stage; then, both products are combined with vapor phase of the first stage hydrogenation product.

EFFECT: improved quality of product; low cost of process; increased life of catalyst.

1 tbl, 3 ex

FIELD: petroleum processing.

SUBSTANCE: diesel distillates are passed through "filtering" bed composed by ceramic ball bed, which occupies 0.2 to 5.0% of reaction space. Feed is then subjected (i) to hydrofining in presence of catalyst present in the form of contact bed containing alumina-supported molybdenum oxide (2-10%) occupying 0.5 to 10% of reaction space and (ii) to hydrogenation in presence of alumino-nickel-molybdenum and/or alumino-cobalt-molybdenum catalyst. Process is conducted at 340-400 C, pressure 4-10 MPa, volumetric feed supply rate 0.5-3.0 h-1, and hydrogen-containing gas-to-feed volume ratio 400-1200. Invention allows level of sulfur to be lowered to 0.005 wt % or below with amount of polycyclic aromatics being below 11 wt %.

EFFECT: simplified technology and improved quality of product containing negligible quantities of sulfur.

2 cl, 4 ex

FIELD: oil refining industry.

SUBSTANCE: initial olefin-containing hydrocarbon material is brought in contact with catalyst of olefin modification in zone of reaction under conditions making it possible to obtain intermediate product having low degree of olefin non-saturation as compared with initial material which is measured by means of bromine number. Then, intermediate product is divided into at least three fractions at different volatility. First fraction whose boiling point is lowest is brought in contact with hydro-desulfurizing catalyst in presence of hydrogen under conditions which make it possible to convert at least part of sulfur to hydrogen sulfide. Fraction at intermediate boiling point is brought in contact with catalyst of selective hydraulic purification in presence of hydrogen under conditions which make it possible to convert at least part of sulfur to hydrogen sulfide.

EFFECT: improved quality of target product.

19 cl, 1 dwg, 6 tbl, 2 ex

FIELD: petroleum processing.

SUBSTANCE: cracked naphtha stream is separated into three fractions: light cracked ligroin, intermediate cracked ligroin, and heavy cracked ligroin. The latter is subjected to desulfurization in first desulfurization reactor. Stream leaving the first reactor is combined with intermediate cracked ligroin and resulting mixture is subjected to desulfurization in second desulfurization reactor. Stream leaving the second reactor can be combined with low-boiling naphtha to form a new naphtha with wide boiling temperature range, which contains on the whole much less sulfur than starting materials. Mercaptans in low-boiling naphtha can be removed either via thioetherification reaction before separation or by washing with alkali after separation.

EFFECT: enhanced sulfur removal efficiency due to olefin preserving treatment procedure.

11 cl, 2 dwg, 2 ex

FIELD: oil production particularly to produce petroleum solvents of sulfur-bearing oil having low aromatic hydrocarbon content.

SUBSTANCE: method involves obtaining fraction with initial boiling temperature of 140-195°C at one stage of oil refining operation; hydrofining of obtained fraction by passing thereof through two serially arranged reactors under temperature of not more than 300°C, wherein volumetric ratio between hydrogen containing gas and raw material is not less than 150 nm3/m3; stabilizing thereof under temperature of upper column part of not less than 150°C and temperature of bottom column part of not less than 180°C, wherein aluminum-nickel-molybdenum or nickel-molybdenum or aluminum-nickel-cobalt-molybdenum catalysts are used.

EFFECT: simplified technology, reduced power inputs and costs of petroleum solvent production.

2 cl, 5 tbl

FIELD: petroleum refining industry.

SUBSTANCE: the invention is pertaining to the field of petroleum refining industry, in particular, to the methods of production of an ecologically pure diesel fuel. Substance: carry out hydraulic purification of a mixture of a virgin diesel fraction and distillate of carbonization and a catalytic cracking. The layers of the catalysts are located in the following way. The first on a course of traffic of a gas-raw material stream protective layer of wide-porous low-percentageNi-Co-Mo/Al2O3 catalyst is made in the form of the hollow cylinders. The second layer - the catalyst with a diameter of granules of 4.5-5.0 mm. The third - the basic catalyst made in the form of granules with a diameter of 2.0-2.8 mm. The basic catalyst has a surface of 250-290 m2 /g, a pore volume - 0.45-0.6 cm3 / g, in which - no less than 80 % of poremetric volume is formed by the through internal pores predominary of a cylindrical shape with a diameter of 4.0-14.0 nanometers. The last layer on a course of raw material traffic layer is organized analogously to the second layer. Loading of 2-4 layers is performed by a method of a tight packing. The technical result - production of the diesel fuel with improved ecological performances and with a share of sulfur less than 350 ppm from the mixture of the virgin run fraction and distillates of a carbonization and a catalytic cracking containing up to 1.3 % mass of sulfur, at a low hardness of the process and a long time interrecovery cycle.

EFFECT: the invention ensures production of the diesel fuel with improved ecological performances and with a share of sulfur less than 350 ppm.

7 cl, 2 tbl, 2 ex

FIELD: petroleum chemistry.

SUBSTANCE: invention relates to microcrystalline paraffin obtained by catalytic hydroisomerization at temperature more than 200°C from FT paraffin having from 20 to 105 carbon atoms. Microcrystalline paraffin is non-liquid at 25°C, but at least pasty with needle penetration less than 100x10-1, measured according to DIN 51579. Disclosed is method for production of microcrystalline paraffin.

EFFECT: microcrystalline paraffin free from naphthenes and aromatics.

17 cl, 1 dwg, 1 tbl, 3 ex

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