Catalyst system and method for hydrotreatment heavy oils

FIELD: chemistry.

SUBSTANCE: invention relates to a catalyst system for hydrotreatment of heavy oils. Said catalyst system includes a catalyst having a hydrogenation catalyst function and a cocatalyst. Said catalyst having a hydrogenation function is selected from: a catalyst consisting of MoS2 or WS2, or a mixture thereof in form of plates, or an oil-soluble precursor thereof; a catalyst consisting of MoS2 or WS2, or a mixture thereof in form of plates, or an oil-soluble precursor thereof and V, Ni and Fe sulphides; a catalyst consisting of MoS2 distributed in a carbon-containing matrix which includes crystalline domains of V, Ni and Fe sulphides. The cocatalyst includes nano- or microparticles and is selected from cracking and/or denitrification catalysts, where said cocatalyst consists of zeolites and/or supported oxides, or sulphides, or Ni and/or Co sulphide precursors, in a mixture with Mo and/or W. The invention also relates to a method for hydrotreatment of heavy oils using said catalyst system.

EFFECT: disclosed catalyst system has a synergetic effect on the reaction medium.

13 cl, 2 tbl, 5 ex

 

The invention relates to a catalytic system and method of hydroperiod heavy oils in which this system can be applied.

Conversion of heavy hydrocarbons in the distillate is a complex process, which includes the lower molecular weight components of the raw materials and the increasing ratio of H/C, which can be achieved through the removal of carbon (methods with elimination of carbon) or the addition of hydrogen (methods with the accession of hydrogen). Thermal methods mainly characterized by poor selectivity when receiving distillates, because the need to work at high temperatures leads to the formation of large amount of gases, in addition, of course, coke or tar.

When implementing methods hydrogenation conversion of the raw material in the distillate is the result of combined effects of reactions of cracking and catalytic hydrogenation of reactive fragments. This allows you to effectively control the spread of radical reactions, primarily in relation to the reactions of aromatic condensation products, which allows to reduce the formation of coke. Introduction of hydrogen also allows you to saturate aromatic structure and to remove the heteroatoms with the formation of high-quality distillates.

Application applied is of utilizatorul in the way hydroperiod petroleum residues and heavy crude oil in reactors with fixed/fluidized bed is the subject of extensive research. Typically, such catalysts are bifunctional system consisting of aluminum oxide, is used as the ligand, and two active phases, one of which provides catalytic activity in the cracking and can be entered by the impact on the composition of the ligand (SO2-Al2O3or add a second material having acid sites (clay or zeolite), and the second provides the catalytic activity in the transfer of hydrogen and can be obtained by functionalization of media suitable mixture of sulfides of Mo (W)/Co(Ni).

On the other hand, the reactions of cracking, accelerated acid centers zeolites, also increase the rate of formation of coke, which in combination with a high content of metals, asphaltenes and heteroatoms (sulfur, nitrogen, etc.) inevitably leads to a rapid deactivation of the catalyst. In this respect, the use of catalysts in slurry phase, which are less exposed to decontamination, can be a most suitable solution for holding hydrobromide heavy oils.

The use of dispersed catalysts on the basis of sulfides of metals of groups V, VI and VIII (in particular, Fe, Mo and V), the input of raw materials to improve the quality of petroleum residues, heavy oils and bitumens, in the form of oil-soluble precursors (US 5288681), or received in advance exsitu (US 4303634), it is known and is described in detail in the scientific and patent literature.

To date, however, the industrial application of these technologies was driven by the need to improve the catalytic performance and optimization of the operating life of the catalyst, as these factors have a serious impact on the economic efficiency of the method.

For several years, have been proposed and investigated various options related to the use of precursors of various types, and to the synthesis of the catalyst ex-situ with the aim of improving its specific activity.

In most cases, the proposed catalytic system composed of sulfides of one or more metals, contributing to the reactions of hydrogenation/improve product quality, while improving the flow of cracking was achieved through technical improvements and was inevitably linked with the choice of working conditions.

The use of bifunctional systems in the suspension phase, simultaneously with catalytic activity towards hydrogenation and against cracking, can combine the advantages of the catalysts used in a fixed or fluidized bed, with the advantages of the catalysts used in the suspension phase, which leads to catalytic damage to the Oia as a hydrogenation reaction, and cracking, that is, to the maximum catalytic activity and slow deactivation.

Examples of this approach in the patent literature a bit:

WO 02059235 (EXXON). Two-phase suspension method comprising applying the first stage of dispersed catalysts derived from oil-soluble precursors, and the second stage application of Co-Mo, Co-Ni-Mo deposited on Al2About3where the media can be used in combination with US-Y or acid Mironosetsky. The first stage performed at one time, the second stage is carried out with recirculation.

US 6712955 (EXXON). Describes how to obtain catalyst for suspension method hydrobromide heavy raw materials. The system consists of the metals of groups VI and VIII, which can be deposited on a catalytic system for cracking, consisting of zeolite materials (ZSM-5, Y, X, ALPO, SAPO).

WO 0233029 (TEXACO). Suspension method with recirculation to improve the grade of heavy oils, including the use of Co-Mo or Ni-Mo catalysts deposited on Al2About3including promoters, for example, zeolites, halogen, phosphides, oxides of alkaline-earth metals.

US 6755962 (CONOCO). The combination of thermal and catalytic cracking is carried out in a single counterflow suspension reactor. The reactor is divided into three zones; the loading of liquid produced from the top, the mobility of vapor phase; thermal cracking is performed in the intermediate zone in the liquid phase, catalytic cracking is performed in the lower zone, where the suspended catalyst supported in suspension by a stream of hydrogen supplied from the bottom. Unreacted liquid direct recycle to the third area. Used cracking catalyst, which may contain Fe, Co, Ni or Mo on the zeolite.

Heterogeneous catalysts used in the methods with a fixed or fluidized bed of catalyst, generally consist of aluminum oxide, is used as the ligand, and two active phases, one of which provides catalytic activity in the cracking and can be entered by the impact on the composition of the ligand (SiO2-Al2O3or add a second material having acid sites, (clay or zeolite), and the second provides the catalytic activity in the transfer of hydrogen and can be obtained by functionalization of media suitable mixture of sulfides of Mo (W)/Co (Ni). Such systems provide effective activity during hydrocracking, however, do not have sufficient ability to activate molecular hydrogen and blocking free radicals and the formation pitch products, which can cause rapid deterioration of the properties of the catalyst or clogged sections of the installation. Oksanaeroshina has a number of negative consequences: it does not allow recirculation of heavier reaction products and severely limits the possibility of increasing the concentration of solids (i.e. coke and its predecessors, and sulfides of transition metals) in the reaction medium. In the methods using a fluidized bed maximum withholding solids content (determined by the IFG (test filterability in the hot condition)) is less than 0.2%, and for removal of pitch deposits produced in various parts of the installation required frequent stops.

The catalysts used for the implementation of the suspension of ways, usually consist of nanodispersions of layered crystals of molybdenite (MoS2) submicron sizes obtained in situ in the reaction medium or ex-situ by the interaction of a suitable molybdenum compounds with H2S or with an organic sulfide. This material is extremely effectively activates the hydrogen and has optimal properties of the absorber radicals, thereby limiting the formation of pitches or resins from organic compounds with a low ratio of N/S. on the Contrary, molybdenite has a low catalytic activity for cracking, and thus, in the suspension means the activity of cracking is essentially determined by the temperature and, therefore, strictly connected with working conditions that significantly affect the output at each passage. It is also known that in thermal methods of nitrogen removal is not too effective.

The element of novelty is represented by simultaneous use of two catalysts that have complementary functions and are in fine form, along with the technology developed by the applicant in the field of suspension methods of conversion of oil residue, eliminates the main limitations, which were hitherto hindered the industrial implementation of the suspension means. Compared with the methods of the prior art, which use a fixed layers of catalysts for hydrobromide or a single catalyst in a slurry phase with only moisturizing properties, the addition of a second catalyst having acidic properties, or in any way contributing to the cracking and hydrodenitrification, allows to improve the technical characteristics of the reaction system under the same operating conditions (to increase the degree of conversion per pass, to increase the degree of denitrification and desulphurization) or to reduce the rigidity of the conditions of the method with the same technical characteristics.

The use of a catalyst having acid function, in the suspension phase (nanometer size) improves the efficiency of the catalyst compared to its effectiveness in ways where it is in the form of particles of the traditional dimensions (millimeters).

Application of the two catalysts has a synergistic effect on the reaction medium: the first catalyst promotes the flow hydrogenation, which causes the demetalization of raw materials, remove heteroelement (S, N) and reduces the formation of coke and organic compounds that can poison acid catalysts, littering them; the second catalyst contains active phase, which mainly contributes to the occurrence of cracking and denitrification of raw materials.

The catalytic system proposed according to the present invention, which can be applied to hydroperiod heavy oils, characterized in that it includes:

the hydrogenation catalyst containing MoS2or WS2or mixtures thereof in the form of plates, or oil-soluble precursor;

- acetalization containing active phase, which particularly contributes to cracking and/or denitrification of raw materials containing particles of nano-or micron size selected from catalysts cracking and/or denitrification, preferably consisting of zeolites having crystals of small size and low degree of aggregation of the primary particles, and/or oxides or sulfides or predecessors sulfides of Ni and/or Co in a mixture with Mo and/or W may found on the media.

The catalyst may also contain sulfides V, Ni and/or Fe.

The catalytic hydrogenation can be obtained in situ by reaction of the oil-soluble precursor Mo S present in the raw images is of fine plates S 2that the reaction enriched sulfides of transition metals coming from the raw materials.

In working conditions, the catalyst is a complex system consisting of MoS2distributed in the carbon matrix containing crystalline domains sulphides V, Ni and Fe.

The catalyst may be deposited on the aluminum oxide, silicon dioxide, aluminum silicate, talc or mica.

Socialization protected from the hydrogenation steps of the above-mentioned catalyst, and is usually able to maintain its activity for a longer time, compared to using no catalyst for hydrogenation.

If socialization consists of zeolites, they are appropriately distributed in the reaction medium, may be contained in socializaton: these zeolites are preferably selected from the group comprising zeolites with intermediate or large pore sizes, for example, beta-zeolite, zeolite Y, MCM-22, ZSM-12 and ZSM-5, ERS-10, ZSM-23; more preferred beta-zeolite, zeolite Y and MCM-22.

Specified socialization may also contain oxides or sulfides of Mo.

If socialization consists of oxides, or sulfides, or predecessors of sulfides of Ni, Co, W and Mo, it can be applied to solid particles having characteristics suitable for their effective distribution in the reaction with the food, i.e. preferably low density, micron or submicron dimensions, low abrasive capacity; such particles are preferably selected from aluminum oxide, silicon dioxide, aluminum silicate, talc and mica.

The mass ratio of the catalyst to acetalization is preferably from 100:1 to 1:20, more preferably from 75:1 to 1:10.

The catalyst and socialization can be applied to the same particle formed of a catalytic system, i.e. all catalytic system comprising a catalyst and socializaton, may be applied to the same particle media.

Another aspect of the present invention relates to a method for hydroperiod heavy oils for the purpose of denitrification and desulphurization, which includes the supply of heavy oil to the stage of hydrobromide in suspension, characterized in that it includes the use of the catalytic system described above.

In accordance with the method according to the invention after a stage of hydrobromide preferably perform the separation of departing from specified phase flow, in which the heavier separated liquid fraction containing the dispersed catalyst and socialization, direct recycle to the stage of hydrobromide.

Heavy oil processing preferably chosen from crude oil, heavy is Efti, bitumen from tar Sands, residues after distillation, heavy fractions of distillation, deasphalting residue after distillation of vegetable oils, oils from coal and bituminous shale, oils, obtained by thermal decomposition of waste plastics, biomass, distillates, such as vacuum gas oil or heavy gas oil.

The concentration of the hydrogenation catalyst, distributed in raw materials, including recycled stream directed on stage hydrobromide determined on the basis of the concentration in the catalyst metal or metals, is preferably from 100 to 30,000 parts per million.

Stage hydrobromide preferably performed at a temperature of from 350 to 480°C and a pressure of from 8 to 22 MPa (80 to 220 bar).

The method involves the conversion of raw materials into the reaction section of the suspension reactor (reactors), separation of liquid products (naphtha, atmospheric gas oil (AGO), vacuum gas oil (VGO)and gaseous products (fuel gas and LPG (liquid petroleum gas)in section separation, and fractionation and, finally, recycling unreacted fraction in the reactor.

Catalysts are not constantly in the reactor and transferred to the heavy flow of fluids through the system in the form of dispersed solids. Thus, as a catalyst, and socializaton post is up recycle to the reactor with unreacted stream.

To stabilize changes in the content of metals and organic solids in the installation, you can perform the purging of the reaction cycle. To maintain a constant concentration of both catalytic materials provide the addition of fresh catalyst materials.

System catalyst-socialization can also be applied to improve the quality of distillates such as gas oil and vacuum gas oil.

For a better understanding of the invention below, the following non-limiting examples.

Example 1

Improving the quality of the residue by vacuum distillation, Ural oil mikroavtobus with stirring

The test, which should be considered as a comparative example was carried out using as catalyst Mo (input in the form of oil-soluble precursor together with the raw material).

The raw material used the residue of vacuum distillation of the Urals oil, the main characteristics of which are presented in the following Table I.

9,4
Table I. Basic properties of the vacuum residue Ural oil used as raw material
Density at 15°C (g/cm3)1,0043
°API
Viscosity 100°C (JV)1277
Coking ability to Chandranshu (% wt.)18,9
C (% mass)86,0
N (% mass)10,2
N/s (mol/mol)1,4
N (% mass)0,57
S (% wt.)2,60
Ni (ppm)84
V (parts per million)262
Fe (ppm)48
Mo (ppm)No
ASFS(%)16,0
The initial boiling point of 170°C (%)0
170-350°C (%)0
350-500°C (%)6,5
500 - Final boiling point (%)93,5

The operating conditions used the e to improve quality, were as follows:

Processed raw materials10 g
The concentration of the Mo6000 parts by weight per million
Pressure16 MPa (160 bar)
The reaction temperature420°C
Duration of response4 h

The yields of products, conversion and characteristics of hydrodenitrification (GAM) and hydrodesulfurization (SDS) are presented below:

H2SGas C1-C4NaphthaAGOGEDBeastality C5 500+ASF. C5CONV. ASF. C5CONV. 500+GAMSDS
wt. -%wt. -%wt. -%wt. -%wt. -%wt. -%wt. -%
0,82,46,625,427,630,64,373623372

Example 2

Improving the quality of the residue by vacuum distillation, Ural oil mikroavtobus with stirring

The test was performed under the operating conditions of example 1, using as raw material the residue of vacuum distillation of the Urals oil, Mo as a catalyst (the input in the form of oil-soluble precursor together with the raw material) and beta zeolite as socializaton (subjected to preliminary calcination at 500°C and injected in powder form together with Mo). The average particle size of the beta zeolite was 10 μm.

Processed raw materials10 g
The concentration of the Mo6000 parts by weight per million
The concentration of socializaton4% of the mass.
Pressure 16 MPa (160 bar)
The reaction temperature420°C
Duration of response4 h

The yields of products, conversion and specifications hydrodenitrification (GAM) and hydrodesulfurization SDS below:

the 3.8
H2SGas1-C4NaphthaAGOGEDBeastality C5 500+ASF. C5CONV ERT. C5CONV. 500+GAMSDS
wt. -%wt. -%wt. -%wt. -%wt. -%wt. -%wt. -%
1,03,46,326,526,930,176634272

Observed improved performance of hydrodenitrification and increase the degree of conversion of asphaltenes.

Example 3

Improving the quality of the residue of vacuum distillation of the Urals in mikroavtobus periodic action with stirring

The test was performed using the residue of vacuum distillation of Urals oil in the working conditions of example 1, using as socializaton MCM-22 zeolite. The average particle size of MCM-22 zeolite was 10 μm.

The yields of products, conversion and specifications hydrodenitrification (GAM) and hydrodesulfurization SDS below:

H2SGas C1-C4NaphthaAGOGEDBeastality C5 500+ASF. C5CONV ERT. C5CONV. 500+GAMSDS
wt. -%wt. -%wt. -%wt. -% wt. -%wt. -%wt. -%
1,U3,36,925,226,730,93,777634372

The results show that in all cases have the same distribution of products and similar activity in hydrodesulfurization, while for activity in hydrodenitrification and conversion of asphaltenes observed improved performance when tested in the presence of socializaton.

Example 4

Improving the quality of tar visbreaking using the experimental setup

The test was performed in a pilot plant, equipped with a suspension reactor continuous operation, operating in accordance with the conventional scheme with recycle of unreacted heavy fraction containing the catalyst, using Mo (input in the form of oil-soluble precursor together with the raw material) and as socializaton beta zeolite (subject will prefix Inoi calcined at 500°C and the input in the form of a dispersion in a suitable hydrocarbon matrix). The average particle size of the beta zeolite was 10 μm.

The raw material used tar visbreaking (slight cracking), the main characteristics of which are given in the following Table II.

Table II. The basic properties of tar visbreaking used as raw materials
Density at 15°C (g/cm3)1,056
Viscosity 140°C (JV)146,1
Coking ability to Chandranshu (% wt.)32,5
C (% mass)85,4
N (% mass)8,8
N/s (mol/mol)1,24
N (% mass)0,5
S (% wt.)5,8
Mi (parts per million)77,7
V (parts per million)209
Fe (ppm)31
Mo (ppm)11,5
ASF. C5 (%)20
THFi (%)0,2
The initial boiling temperature of -170°C (%)-
170-350°C(%)-
350-500°C (%)9,8
500 - Final boiling point (%)70,0

Operating conditions used for testing were as follows:

Processed raw materials2500 g/h
The concentration of the Mo6000 parts by weight per million
The concentration of socializaton4% of the mass.
Pressure14.4 Psi (144 bar)
The reaction temperature420°C

The assessment of the technical characteristics of the installation in stationary conditions in the presence of socializaton performed during the working period of 10 hours, comparing the quality and distribution of outputs derived synthetic crude oil (CLO) with the data obtained in comparable is x working conditions.

MoBeta zeoliteH2SGas C1-C4NaphthaAGOGEDDEAS felicitate C5 500+ASF. C5CONV 500+CONV ERT. C5GAMSDS
Parts by weight per millionwt. -%%%%%
300004,5the 10.15,331,336,36,10,192,399,57932
1000 05,810,25,235,735,73,50,195,799,59051
460045,89,26,839,133,22,90,196,599,89164

The product distribution was observed a tendency to increase the number of light fractions with increasing content of atmospheric gas oil by reducing the number of heavier fractions. The quality of the product also increased due to a significant decrease in the content of S and N, which is comparable with the results obtained when working with high concentrations of Mo (12000 parts by weight per million).

Example 5

Improving the quality of the residue by vacuum distillation, Ural oil mikroavtobus periodic action with stirring using a catalyst based on Ni/Mo

And the test was performed under the operating conditions of example 1, using as raw material the residue of vacuum distillation of the Urals oil, as a catalyst Mo (input in the form of oil-soluble precursor together with the raw material) and as socializaton - catalyst hydroperiod based on Ni-Mo (15% of the mass. Mo and 5% of the mass. Ni)supported on alumina. The average particle size of socializaton was 30 μm. Applied operating conditions were as follows:

Processed raw materialsSouth
The concentration of the Mo6000 parts by weight per million
The concentration of socializaton4% of the mass.
Pressure16 MPa (160 bar)
The reaction temperature420°C
Duration of response4 h

The yields of products, conversion and specifications hydrodenitrification/hydrodesulfurization presented below:

H2SGas C1-C4NaphthaAGO GEDBeastality C5 500+ASF. C5CONV ERT. C5CONV. 500+GAMSDS
wt. -%wt. -%wt. -%wt. -%wt. -%wt. -%wt. -%
0,82,46,326,327,230,53,578644081

The results show that the distribution of products and the conversion of heavy fractions are similar to the values of comparative example (example 1), while the characteristics of hydrodenitrification and hydrodesulfurization improves and increases the conversion of heavy 500°C.+ fraction.

1. The catalytic system used for hydroperiod heavy oils, characterized in that it is includes:
a) a catalyst having the function of a hydrogenation catalyst and chosen from:
- catalyst consisting of MoS2or WS2or mixtures thereof in the form of plates, or oil-soluble precursor;
- catalyst consisting of MoS2or WS2or mixtures thereof in the form of plates, or oil-soluble precursor and sulphides V, Ni and Fe;
- catalyst consisting of MoS2distributed in the carbon-containing matrix comprising crystalline domains sulphides V, Ni and Fe;
b) socialization comprising particles of nano-or micron size selected from catalysts cracking and/or denitrification, where the specified socialization consists of zeolites and/or deposited oxides, or sulfides, or predecessors of sulfides of Ni and/or Co in a mixture with Mo and/or W.

2. The catalytic system according to claim 1, in which the catalyst consists of MoS2or WS2or mixtures thereof in the form of plates, or oil-soluble precursor, and socialization consists of zeolites.

3. The catalytic system according to claim 1, in which the catalyst consists of MoS2or WS2or mixtures thereof in the form of plates, or oil-soluble precursor, and socialization consists of deposited oxides or sulfides, or predecessors of sulfides of Ni and/or Co in a mixture with Mo and/or W.

4. The catalytic system according to claim 2, in which toroi zeolites selected from the group including zeolites with intermediate or large pore sizes.

5. The catalytic system according to claim 4, in which the zeolite with an intermediate or large pore sizes selected from beta-zeolite, zeolite Y and MCM-22.

6. The catalytic system according to claim 3, in which socialization deposited on the solid particles of micron or submicron dimensions.

7. The catalytic system according to claim 6, in which solid particles, which caused socialization selected from aluminum oxide, silicon dioxide, silicates, talc and mica.

8. The catalytic system according to claim 1, in which the mass ratio of the catalyst to acetalization is from 100:1 to 1:70.

9. The catalytic system of claim 8, wherein the mass ratio of the catalyst to acetalization is from 75:1 to 1:50.

10. How hydroperiod heavy oils extracted from crude oil, heavy oil, bitumen from tar Sands, residues after distillation, heavy fractions of distillation, deasphalting residue after distillation of vegetable oils, oils from coal and bituminous shale, oils, obtained by thermal decomposition of waste plastics, biomass, distillates, such as vacuum gas oil or heavy gas oil, which includes the supply of heavy oil to the stage of hydrobromide in suspension, characterized in that it comprises the application of kata is eticheskoi system according to claims 1-9.

11. The method according to claim 10, in which, after the stage of hydrobromide perform the separation of departing from specified phase flow, in which the heavier separated liquid fraction containing the dispersed catalyst and socialization, direct recycle to the stage of hydrobromide.

12. The method according to claim 10, in which the concentration of the hydrogenation catalyst dispersed in raw materials, including recycled stream directed on stage hydrobromide determined on the basis of the concentration in the catalyst metal or metals is from 100 to 30,000 parts per million.

13. The method according to claim 10, in which hydrobromide performed at a temperature of from 350 to 480°C and a pressure of from 8 to 22 MPa (80 to 220 bar).



 

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14 cl, 1 ex

FIELD: petrochemical processes.

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

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

12 cl, 3 tbl, 22 ex

FIELD: oil and gas industry.

SUBSTANCE: invention describes method of fine desulfurisation of oxygen-containing compounds, hydrocarbon material and sulphur-containing organic compounds by sulphur trapping from bulk containing ferric or zinc oxides in quantity of 20% by weight, zinc ferrite; at that the above method is implemented in presence of hydrogen at temperature within range of 200°C - 400°C.

EFFECT: increasing process efficiency.

10 cl, 2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to catalysis field. Is described catalyst for oil fractions and raffinates of selective purification hydrotreating, which is characterised by the following component ratio, wt %: molybdenum oxide (MoO3)-12.0-20.0, tungsten oxide (WO3)-1.0-6.0, nickel oxide or cobalt oxide (NiO or CoO)-4.0-6.0, phosphorus oxide (P2O5) - 0.5-0.9, zinc oxide (ZnO)-0.2-6.0, aluminium oxide- 61.1-82.3. Method of claimed catalyst obtaining is described.

EFFECT: increase of catalyst activity.

4 cl, 1 tbl, 6 ex

FIELD: oil and gas industry.

SUBSTANCE: method includes the following: supply of a flow of olefin naphtha (16), containing olefin and sulphur; hydraulic treatment of a flow of olefin naphtha in the first zone of desulphurisation (12) under the temperature of the first reaction efficient for conversion of a part of sulphur content into hydrogen sulfide to produce effluent that comes out from the first zone of desulphurisation (24); hydraulic treatment of effluent coming out without removal of hydrogen sulfide from the first zone of desulphurisation (24), in the second zone of desulphurisation (14) at the second higher temperature of reaction compared to the first stage of hydraulic treatment using a selective layerwise catalyst, efficient for desulphurisation of the effluent produced in the second zone of desulphurisation (32). At the same time the catalyst of the second zone of hydrodesulphurisation includes an inner nucleus and an active thin outer layer with thickness of 5-100 microns, surrounding the inner nucleus, besides, the tin outer layer contains active materials for desulphurisation.

EFFECT: using this invention makes it possible to reduce saturation of olegins and recombination of sulphur to mercaptans to the minimum.

11 cl, 1 ex, 3 tbl, 1 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a method of initiating a hydrotreatment process on a bulk metallic catalyst, involving the following steps: i) providing a stream of hydrocarbon material containing less than 100 ppm of nitrogen-containing compounds; ii) adding the nitrogen-containing compound to said stream of hydrocarbon material; and iii) contacting the obtained stream of material with said bulk metallic catalyst in the presence of hydrogen and sulphur-containing compounds, where the bulk metallic catalyst is a composition of general formula (I): (X)b(M)c(Z)d(Y)e, where X represents at least one group VIII metal, M represents a group VIb metal, Y represents one or more elements selected from oxygen and sulphur, Z, together with an oxygen component in form of element Y, forms a refractory inorganic oxide, and b, c, d and e represent relative values of molar content. The invention also relates to another method for hydrotreating hydrocarbon material.

EFFECT: preventing formation of nickel sulphide on the catalyst and loss of product output.

7 cl, 1 dwg, 4 tbl, 11 ex

FIELD: oil and gas industry.

SUBSTANCE: invention comprises contact of hydrocarbon raw material with one or several catalysts to obtain total product that contains crude product representing a liquid mixture at the temperature of 25°C and the pressure of 0.101 MPa; besides, hydrocarbon raw material has the residue content at least of 0.1 grams per 1 gram of hydrocarbon raw material; and at least one of the hydrocarbons can be obtained by mixing of the following components: small particles of mineral oxide, which have the size in the range of 0.2 to 500 micrometres, one or several metals of Group 6 of the Periodic Table and/or one or several compounds of one or several metals of Group 6 of the Periodic Table, and a carrier; and preparation of the catalyst having the pore distribution as per sizes with average pore diameter of at least 80 A, and in which 1% to 10% pores have the size of 1000 to 5000 Angstrom. Pore size is measured as per ASTM standard, method D4284; and control of contact conditions at partial hydrogen pressure at least of 3 MPa and temperature of at least 200°C so that crude product can be obtained. Crude product has the residue content of not more than 90% of the hydrocarbon raw material residue content, where the residue content is determined as per ASTM standard, method D5307. The invention is also related to the other method for obtaining crude product and catalyst for processing of hydrocarbon raw material.

EFFECT: improved product characteristics.

11 cl, 12 dwg, 9 ex

FIELD: chemistry.

SUBSTANCE: described is method of obtaining catalyst composition for hydroprocessing of hydrocarbons, which contains from 0.5% wt to 20% wt of metal component, selected from group consisting of cobalt and nickel, and from 0.5% wt to 50% wt of metal component, selected from group, consisting of molybdenum and tungsten, where said method includes: introduction of metal-containing solution into carrier to obtain carrier material with introduced in it metal; introduction of hydrocarbon oil into said carrier with introduced in it metal to obtain oil-impregnated composition; processing of said carrier material with introduced in it metal and said hydrocarbon oil with hydrogen; and contact of said carrier material with introduced in it metal and said hydrocarbon oil, further processed with hydrogen, with sulphur-containing compound. Described is catalyst composition, obtained by method described above. Described is method of hydrodesulphurisation, which includes: contact of initial hydrocarbon raw material with said composition at reaction temperature in the range from 200°C to 420°C and pressure within the range from 689.5 kPa (100 lbs/square inch) to 13879 kPa (2000 lbs/square inch).

EFFECT: claimed method makes it possible to obtain catalyst compositions for hydroprocessing, which possess high catalytic activity.

9 cl, 1 tbl, 1 dwg, 2 ex

FIELD: oil and gas industry.

SUBSTANCE: invention refers to crude product obtaining method involving contact of hydrocarbon raw material, where hydrocarbon raw material has viscosity at least of 500 cSt at 37.8°C, with hydrogen in presence of one or several catalysts so that total product can be obtained, which includes crude product, where crude product represents liquid mixture at 25°C and pressure of 0.101 MPa. At that, crude product has viscosity of not more than 50% of viscosity of hydrocarbon raw material at 37.8°C; and where P-factor of hydrocarbon raw material/total product mixture is at least 1.0. At that, viscosity is determined as per ASTM, method D445, and P-factor is determined as per ASTM, method D7060; where at least one catalyst includes metal (metals) of 6-10 groups in combination with carrier and has pore distribution as per sizes with average pore diameter in the range of 50 to 180 A; at that, catalyst includes at least 0.01 gram of aluminium silicate per 1 gram of catalyst; and where contact conditions are controlled at temperature of 370 to 450°C, partial hydrogen pressure of not more than 7 MPa and volume rate of liquid supply of at least 0.1 h-1. Invention also refers to catalyst for obtaining crude product.

EFFECT: crude product with residue content of not more than 90 percent of residue content in hydrocarbon raw material or reduced viscosity value which represents not more than the half in relation to residue content or viscosity value in hydrocarbon raw material.

14 cl, 27 dwg, 34 ex

FIELD: oil-and-gas production.

SUBSTANCE: invention relates to processing of sulphuric gas condensate boiler oils by non-catalytic hydrovisbreaking in hydrogen-containing gas for production of hydrogenator to be subjected to separation to obtain hydrovisbreaking residue as a liquid phase and, as vapor phase, the mix of hydrogen-containing gas and fraction boiling away at below 450°C and intended for catalytic hydraulic desulfurisation on two layers of low-activity catalysts. Note here that, first layer comprises catalyst in the form of Rushig rings containing nickel and cobalt oxides in amount of 0.8-1.5 wt %, molybdenum oxide - 3.5-4.5 wt %, and aluminium oxide making the rests. Note also that second layer comprises catalyst in the form of extrudates containing nickel oxide in amount of 1.5-2.5 wt %, molybdenum oxide - 6-7 wt %, and aluminium oxide making the rest. Mind that volume ratio of the first and second catalyst layers varies from 1.0:0.6 to 1.0:1.2 to produce hydraulic desulfurization catalyst accompanied by its condensation and cooling, separation of hydrogen-containing and hydrocarbon gases and stabilisation together with hydrovisbreaking residue resulting in fraction boiling away at below 350°C and stabilised fraction boiling away at above 350°C to be used as oiler or marine fuel.

EFFECT: deeper desulfurisation of sulphuric gas condensate boiler oils, higher processe efficiency.

4 ex, 1 tbl

FIELD: oil and gas production.

SUBSTANCE: invention refers to procedure for production of semi-finished product. The procedure consists in contacting oil stock with one or more catalyst at presence of a source of gaseous hydrogen for production of a common product containing a semi-product and gas and in separation of common product into semi-product and gas. The semi-finished product here corresponds to liquid mixture at 25°C and 0.101 MPa and has contents of micro-carbon residue (MCR) as high, as 90% of MCR contents in oil stock wherein contents of MCR amounts to at least 0.0001 gram per gram of oil stock. Also, content of MCR is determined by the method of ASTM D4530. At least one catalyst is the catalyst on base of metal of group 6 of periodic table with average diameter of pores at least 90 Å. Volume of pores with diameter at least 350 Å amounts to as much, as 15% of volume of pores of carrier, wherein diameter of pores and volume of pores is determined by the method of ASTM D4282. Contact is performed at temperature 50-500°C, pressure 0.1-20 MPa, hour volume rate of flow of oil stock 0.05-30 hour-1 and ratio of gaseous hydrogen in source of gaseous hydrogen to flow of oil stock 0.1-100000 nm3/m3. The invention also refers to catalyst for production of semi-finished product and to procedure of production of catalyst for output of semi-finished product.

EFFECT: production of semi-finished product with characteristics more improved, than characteristics of source oil stock.

24 cl, 6 ex, 4 tbl, 8 dwg

FIELD: process engineering.

SUBSTANCE: invention relates to catalyst of hydraulic treatment and/or conversion of heavy hydrocarbon beds. Proposed catalyst comprises aluminium oxide-based carrier, at least, one catalytic metal or compound of catalytic metal of group VIB and/or VIII with porous structure consisting of multiple, contact agglomerates, each formed by multiple needle-like plates. Note here that plates of every agglomerate are oriented radially relative to each other and to agglomerate center. Note that aforesaid agglomerate features irregular and non-spherical shape, exists in the form of fragments produced by crushing aluminium oxide balls and is obtained in the following stages: a) granulation of the powder of active aluminium oxide that feature poorly crystallised and/or amorphous structure to produce ball-shaped agglomerates; b) curing in humid atmosphere at 60°C to 100°C. Then, balls are dried; c) screening to recover fractions of aforesaid balls; d) crushing of aforesaid fraction; e) calcination of, at least, a part of said fraction at 250°C to 900°C; f) impregnation by acid and hydrothermal treatment at 80°C to 250°C; g) drying followed by calcination at 500°C to 1100°C. Invention covers also the method of hydraulic treatment and/or conversion of heavy hydrocarbons containing metals incorporating above described catalyst.

EFFECT: improved process performances in hydraulic conversion and/or treatment of heavy hydrocarbons beds.

28 cl, 8 tbl, 11 ex

FIELD: medicine, pharmaceutics.

SUBSTANCE: invention refers to medicine and pharmaceutics, namely to a drug substance and a biologically active substance carrier for treating and diagnosing representing a nanoparticle having a ferric oxide coated zirconium dioxide nucleus having a nearly spherical shape and a size of 15-100 nm, and to a method for preparing the carrier wherein to a solution containing iron II, iron III and zirconium IV cations, having pH=7.5; an ammonium mixture is added to pH=8-9 at a rate providing preparing t nanoparticles of a pre-set size of 15-100 nm; the product is recovered by centrifugation, washed and lyophilised.

EFFECT: invention provides creating the new drug substance and the biologically active substance carrier.

4 cl, 2 ex, 1 tbl, 3 dwg

FIELD: nanotechnology.

SUBSTANCE: inventions can be used in the field of nanotechnologies and inorganic chemistry. The method of production of boride nanofilm or nanowire comprises depositing on the alumina nanowire or on fiberglass of low-melting glass in vacuum the multiple alternating layers of titanium and boron, after which the resulting composition is gradually heated to a temperature of 1500°C. In another embodiment, the method of production of boride nanofilm comprises depositing of titanium boride layer of nanothickness on alumina nanofilm of the gas phase comprising titanium halogenide and boron.

EFFECT: inventions enable to obtain boride nanostructures.

4 cl, 2 ex

FIELD: chemistry.

SUBSTANCE: coating is based on titanium carbonitride with addition of additional elements which provide the required set of mechanical and tribological properties, as well as biologically active and antibacterial properties. Overall concentrations of basic and additional elements are in the following ratio: 1,2<XiYj<20, where Xi is the overall concentration of basic elements Ti, C, N in the coating, Yj is the overall concentration of additional elements Ag, Ca, Zr, Si, O, P, K, Mn in the coating.

EFFECT: coating has high hardness, low modulus of elasticity, high value of elastic recovery, low coefficient of friction and rate of wear in different physiological media.

1 tbl, 2 ex

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