Combined method of catalytic cracking in catalyst fluidised bed for producing high-quality hydrocarbon mixtures as fuel

FIELD: oil and gas industry.

SUBSTANCE: invention is related to a combined method of conversion of oil-derived hydrocarbon fractions into high-quality hydrocarbon mixtures as fuel, which includes catalytic cracking of hydrocarbon fraction in catalyst fluidised bed with catalyst containing ERS-10 zeolite, where the specified catalyst contains at least two components, where the specified components represent: (a) a component containing one or more catalytic cracking catalysts in fluidised, and (b) a component containing ERS-10 zeolite for obtaining Light Cycle Gas Oil (LCGO), hydrotreatment of light cycle gas oil, interaction of hydrotreated light cycle gas oil obtained at the previous stage of hydrotreatment in presence of hydrogen with catalytic system. The invention also touches the method of catalytic cracking and a stage of catalytic cracking in fluidised bed.

EFFECT: production of high-quality hydrocarbons, conversion increase.

21 cl, 3 tbl, 1 ex

 

The present invention relates to the United way catalytic cracking in a fluidized bed of a catalyst (PAC), which allows to obtain high-quality hydrocarbon mixture as fuel. Specifically, the invention relates to a combined process comprising a stage of catalytic cracking in a fluidized bed of catalyst, which converts hydrocarbon fractions of petroleum origin in the presence of a catalyst at least two components containing ERS-10, in a mixture with a high content of light cycle gas oil (LRG)with high quality in terms of density and nature of the contained aromatic compounds, which, after phase separation and phase Hydrotreating expose stage quality improvement by treatment with hydrogen with a catalyst containing one or more metals selected from Pt, Pd, Ir, Ru, Rh and Re, and acidic aluminosilicate.

In WO 2006/124175 describe how the conversion of hydrocarbon fractions to obtain olefins, aromatic compounds and diesel fuel with low sulfur content, which includes a step of catalytic cracking in a fluidized bed to obtain olefins and, in smaller numbers, LRG, phase transformation fraction of high-boiling olefins ethylene and propylene and the stage of hydrocracking is a, which faction LRG mainly converted into aromatic compounds and, to a lesser parts, diesel fuel with low sulfur content.

In WO 2007/006473 describe how to improve the quality blends of hydrotreated hydrocarbons, used as fuel, which comprises bringing into contact of these compounds with hydrogen in the presence of a catalytic system containing one or more metals selected from Pt, Pd, Ir, Ru, Rh and Re, and acidic aluminosilicate.

In MI 2007A001610 describe the combined process comprising a stage of catalytic cracking in a fluidized bed of a catalyst, in which the hydrocarbon fraction of oil origin is converted into a mixture with a high content of LRH that after stage separation stage and is subjected to Hydrotreating stage quality improvement by treatment with hydrogen, with a catalyst containing one or more metals selected from Pt, Pd, Ir, Ru, Rh and Re, and acidic aluminosilicate.

In MI 2008A001036 describe the way in which the zeolite ERS-10 is used as an additive in the method of cracking hydrocarbon mixtures.

Found United way of obtaining high-quality hydrocarbon mixtures as fuel, which includes a step of catalytic cracking in a fluidized bed of a catalyst (PAC), performed in the presence of a catalyst of at least two components is nami, containing zeolite ERS-10, to obtain fractions LRG, stage Hydrotreating specified fraction LRG stage and improve the quality of the resulting hydrotreated LRG by reaction with hydrogen in the presence of a catalytic system containing one or more metals selected from Pt, Pd, Ir, Ru, Rh and Re, and acidic aluminosilicate.

Stage catalytic cracking process in the fluidized bed catalyst according to the method of the present invention not only provides a higher conversion compared to the results that can be achieved with traditional catalytic systems, but also provides optimal performance by conversion of the heavier fraction (residues after cracking), expressed as the ratio LRG and TWG (heavy cycle gas oil)with reduced receive TWG even up to 50% compared to the known methods.

Stage quality improvement according to the method according to the present invention includes the enrichment of the resulting mixture of alkylbenzene compounds, at least partially derived from the conversion of naphtha and aromatic structures contained in the faction LRG formed during the stage of the CCP, as well as during the stage hydrotreatment. United way of the present invention leads to mixtures of hydrocarbons with additionally improved cetane index and low PLO the activities the latter is comparable with the density obtained through the full dearomatization, but with much less consumption of hydrogen.

Particularly preferred aspect the present invention consists in the implementation stage of catalytic cracking in a fluidized bed of a catalyst (PAC) under such conditions to obtain high yield fraction high quality LG in terms of the density and nature of the contained aromatic compounds. In particular, in this case, the fraction LRG is characterized not only by high quality in terms of density, but also extremely preferred composition in terms of aromatic compounds, which makes it particularly suitable for processing in subsequent stages of the combined method according to the invention.

The content of polyaromatic compounds is actually lower in relation to fractions LRG obtained under normal conditions the CCP, whereas the content benzonitrile compounds is higher. This is a preliminary enrichment benzonitrile connections simplifies subsequent stage Hydrotreating and quality improvement, providing as fuel mixes with optimum performance at a lower total consumption of hydrogen compared with that described in prior art.

Also, the stage of catalytic cracking in a fluidized bed of catalyst in the presence containing ERS-10 catalyst, increase the conversion of heavier fractions, adding further to the total output LRG.

The purpose of the present invention, therefore, is associated with the United way of conversion of hydrocarbon fractions of petroleum origin in the high-quality mixture of hydrocarbons as fuel, which includes the following stages:

catalytic cracking of hydrocarbon fractions in a fluidized bed of a catalyst (PAC) in the presence containing zeolite ERS-10 catalyst, where the specified catalyst contains at least two components, to obtain a light cycle gas oil (LRG),

- Hydrotreating of light cycle gas oil,

interaction hydrotreated light cycle gas oil obtained in the previous stage Hydrotreating, with hydrogen in the presence of a catalytic system containing:

A1) one or more metals selected from Pt, Pd, Ir, Ru, Rh and Re,

B1) acidic aluminosilicate selected from a zeolite belonging to the MTW family, and a fully amorphous micrometeorite aluminosilicate having a molar is th ratio SiO 2/Al2O3from 30 to 500, a surface area of more than 500 m2/g, pore volume from 0.3 to 1.3 ml/g and average pore diameter of less than 40 Å.

According to a particularly preferred aspect of the method according to the present invention is implemented by the following steps:

(1) catalytic cracking of hydrocarbon fractions of petroleum origin in the fluidized bed of catalyst (PAC) in the presence containing zeolite ERS-10 catalyst, where the specified catalyst contains at least two components, to obtain a mixture containing LRG,

(2) separating the mixture obtained in the previous phase catalytic cracking in a fluidized bed of a catalyst, so as to divide at least a fraction LRG and the fraction of the TWG,

(3) re-submission, if necessary, to the stage of catalytic cracking in a fluidized bed of a catalyst (PAC) at least part of the fraction TWG obtained at stage (2),

(4) Hydrotreating faction LRG obtained at stage (2),

(5) the interaction of the product obtained in the previous phase, with hydrogen in the presence of a catalytic system containing:

A1) one or more metals selected from Pt, Pd, Ir, Ru, Rh and Re,

B1) acidic aluminosilicate selected from a zeolite belonging to the MTW family, and a fully amorphous micrometeorite aluminosilicate having a molar Rel is the solution of SiO 2/Al2About3from 30 to 500, a surface area of more than 500 m2/g, pore volume from 0.3 to 1.3 ml/g and average pore diameter of less than 40 Å.

Used in the first stage, the catalyst contains at least two distinct components: (a) a component containing one or more cracking catalysts, preferably the catalyst in the fluidized bed, and (b) a component containing zeolite ERS-10.

In line with this, in the first stage of the combined method can be used catalytic composition of the present invention, containing:

a) a first component containing one or more catalysts selected from zeolites, amorphous cracking catalysts based on inorganic oxides and neoreality crystalline cracking catalysts based on inorganic oxides,

b) a second component containing zeolite ERS-10.

This catalyst component (a)containing one or more of the catalyst, preferably a catalytic cracking process in the fluidized bed of catalyst, together with a component (b), which is additive.

Examples of amorphous materials that can suitably be used in the component (a), as described in EP 1011291 are, for example, clay, aluminosilicate, miniserial, zirconosilicate, titanosilicate, agriolimacidae, zirconosilicate, zirconiumsilicat.

Crystalline aluminosilicate described, for example, in US 4309279, can be used as Nicolaasga crystalline material in the component (a).

A preferred aspect of the present invention is the use of zeolite as a component (a), even more preferably zeolites with large pores.

Zeolites that can be used for these purposes, are zeolite Y (US 3130007), zeolite L (US 3126789), zeolite omega (Cryst. Struct. Comm., 3, 339-344, 1974), zeolite Beta (US 3308069) and mordenite (Z. Kristallogr., 115, 439-450, 1961). It is preferable to use zeolite Y. the same zeolite ERS-10 can be used in component (a) as a cracking catalyst in a mixture of at least one other catalyst cracking.

Suitable for use with Y zeolites are zeolite subjected to ion exchange with hydrogen and/or rare earth metal, or zeolites, which was subjected to heat treatment through technology, well known to specialists in this field.

Examples of zeolites which can usually be used as catalyst components, describe:

Paul C. Venuto, E. Thomas Habib, Jr., "Fluid Catalytic Cracking with Zeolite Catalysts", vol. 1, M. Dekker, Inc.,

Julius Scherzer, "Octane-Enhancing Zeolitic FCC Catalysts", M. Dekker, Inc.

Zeolites are selected as component (a), can be used in bound form sovetujusj, selected, for example, from silicon dioxide, aluminum oxide, aluminum silicate, clay, zirconosilicate, minielite, aluminum phosphate, or mixtures thereof. Cooking bound form of the zeolite is carried out according to technologies known to specialists in this field.

Component (b) of the catalytic composition of the present invention contains zeolite ERS-10, and the specified zeolite acts as a Supplement.

This zeolite was first described in EP 796821, well-described in:

- S.Zanardi, G, Cruciani, L.G.Carluccio, G.Bellussi, C.Perego, R.Millini, "the Framework topology of ERS-10 zeolite", Angew. Chem. Int. Ed., 41(21), 2002, 4109-4112.

- Creedo, M.Margotti, L.G.Carluccio, L.Zanibelli, G.Bellussi, "The catalytic performances of zeolite ERS-10", Stud. Surf. Sci. Catal., 135, 2001, 29 On 01.

- S.Zanardi, G, Cruciani, L.G.Carluccio, G.Bellussi, C.Perego, R.Millini, "Synthesis and framework topology of the new disordered ERS-10 zeolite", J.Porous Mater., 14, 2007, 315-323.

Preparation of zeolite ERS-10 is well described in EP 796821. The synthesis is preferably carried out by heating the reaction mixture containing the hydroxide 6-azonia-Spiro-[5,5]-undecane (Q) as organic additives, tetraethylorthosilicate (TEOS) and isopropoxy aluminum (IPA) as sources of silicon dioxide and aluminum, respectively, the sodium hydroxide (NaOH) and water, preferably in the following molar relationship:

SiO2/Al2O3from 50/1 to be the limbs
Na+/SiO2from 0.05/1 to 0.15/1
Q/SiO2from 0.2/1 to 0.3/1
H2O/ SiO2from 40/1 to 50/1
HE-/SiO2from 0.25/1 to 0.45/1

in the temperature range from 150 to 180°C., preferably from 155 to 170°C for 7-28 days, preferably within 7-14 days at autogenous pressure in an autoclave of stainless steel.

The resulting crystalline material is dried at a maximum temperature of 170°C, preferably at a temperature of from 90 to 120°C. and calcined at a temperature of from 500 to 700°C., preferably from 550 to 650°C, during the period from 4 to 20 hours, preferably from 6 to 15 hours.

From a structural point of view, it is experimentally shown that the aluminosilicate lattice ERS-10 is disordered and can be described as the germination of three structurally interrelated zeolites: nenasala (NON, type zeolite clathrasil, characterized by the presence of only frames that are not connected with the outside of the crystal), EU-1 (EUO zeolite with pores of average size, which is characterized by one dimensional system of channels with holes containing 10 tetrahedra (10-corresponding member of the TES ring) with large side pockets) and Nu-87 (NES, zeolite with pores of average size, which is characterized by one dimensional system of channels with holes containing 10 tetrahedra (10-membered ring)). In more detail the structure of the ERS-10 can be constructed using two periodic block (known as periodic building blocks, PSB). A random combination of these periodic blocks leads to the formation within a single zeolite crystal regions, with characteristics of all three of the above zeolites (NON, EUO and NES), in addition to the presence of additional structures, which are characterized by the presence of pores with openings containing 14 tetrahedra (14-membered ring). Therefore, characteristics, typical for zeolites with pores of average size (10-membered ring), and zeolites with pores of very large size (14-membered ring), co-exist in the same structure.

Zeolite ERS-10 crystallized in pure form from a mixture of compounds with a molar ratio of SiO2/Al2O3(OKA) in the range from 80 to 160, which is therefore preferred.

Crystalline products are subjected to enrichment of Al to values of an EYE in the range from 60 to 80: through the use of reaction mixtures having a magnitude of an EYE<80, you can get a joint crystallization of mordenite (MOR).

When the values OKA>160 can be formed zeolite ZSM-12 (MTW).

As the zeolite ERS-10 is predstavljaet a result of germination of different zeolite phases, this implies variability relative, or, from a technical point of view, the likelihood of laying in a pile of periodic blocks. This leads to the possibility of obtaining products having different characteristics in terms of the relative content areas corresponding to the three structures NON, EDO and NES and channels with holes formed 14-membered rings.

When using zeolite ERS-10 as a component of a new catalytic composition for cracking hydrocarbon mixtures, in particular of the PAC, the fact that it is the result of germination of different phases with variable composition, does not affect its catalytic properties, as they are not even affected by the presence of small amounts of mordenite or ZSM-12, possibly formed during the synthesis of zeolite ERS-10, preferably in an amount of not more than 30 mass. % relative to the weight of zeolite ERS-10. The possible formation of additional phases of NON zeolites, EUO and NES in small amounts, preferably not higher than 30 mass. % relative to the weight of zeolite ERS-10, no significant effect on the characteristics of the catalyst.

When used as an additive for the CCP according to the combined method according to the present invention ERS-10 can be used in various related forms, prepared in accordance with technology what technologies, well-known experts in this field, such as granules or, preferably, the microspheres. Microspheres containing zeolite in bound form, can be prepared by spray drying, using known techniques. As the binder is preferably possible to use silicon dioxide, amorphous aluminosilicate, aluminum oxide or mixtures thereof.

In the component (b) zeolite bound using a binder form is preferably from 5 to 90 mass. % relative to the total weight of the specified component.

In the composition of the present invention the zeolite ERS-10 preferably is present in an amount of from 1 to 10 mass. % relative to the weight of the catalyst contained in the component (a).

The catalytic composition used at the stage of catalytic cracking in a fluidized bed of catalyst, it is possible to prepare:

by mechanical mixing of the component (a) and (b) according to technologies known to specialists in this field, and in this case, the zeolite ERS-10 is a component of the catalytic particles, physically distinct from the particles containing the catalyst component (a)

by simultaneous binding according to known technologies zeolite ERS-10 and the catalyst contained in the component (a), and in this case, the zeolite ERS-10 and the catalyst contained in the ne and the same catalytic particle composition,

- in situ by adding the component (b) in component (a), already present in the way of cracking at any point of this method.

The use of zeolite ERS-10 as an additive for cracking, preferably for catalytic cracking in a fluidized bed of catalyst provides a higher conversion of raw materials CCP and, in particular, high cracking of the lower fractions with the predominant formation of the faction LNG and diesel fuel in relation to the formation of the faction of the TWG.

Hydrocarbon mixtures suitable for processing according to the method of the present invention are, for example, gas oils, petroleum fractions containing VGO (vacuum gas oil)having a boiling point of between 350 and 550°C, atmospheric residues, neasfaltirovanyj oil, the products of thermal cracking and hydrocracking residues. The products obtained from the United way catalytic cracking in the movable layer of the catalyst of the present invention, are listed below: fuel gas (H2, C1-C2), LPG (liquefied petroleum gas; C3-C4), gasoline (C5-221°C), LRG (221-350°C), TWG (350+°C).

Stage PAC can be performed under conditions known to specialists in this field and are described, for example, in Fluid Catalytic Cracking Handbook, 2ndedition, Reza Sadeghbeigi, ed. Gulf Professional Publishing, 2000.

Method for catalytic cracking in a fluidized bed catalysis the Torah generally divided into two stages: cracking, carried out in the separation column, and recovery of the catalyst is performed in the regenerator, both stage is carried out with the catalyst in pseudovirions phase.

The cracking reaction is substantially endothermic, it is supported by physical heat captured by the flow of the recovered catalyst, and it proceeds by bringing into contact of hydrocarbons with hot recovered catalyst.

Reaction conditions for catalytic cracking in a fluidized bed of the catalyst include a temperature in the range from 400 to 650°C., preferably from 450 to 650°C. the pressure in the reaction zone is from 100 to 500 kPa (1 to 5 bar), preferably from 130 to 450 kPa (from 1.3 to 4.5 bar). The ratio of catalyst/oil is from 1 to 10 kg/kg, the residence time of the vapors in the area of the reaction is from 0.5 to 10 seconds, preferably from 1 to 5 seconds.

Restore the depleted catalyst cracking occurs by combustion in oxygen of coke deposited on the catalyst, at a temperature of from 600 to 815°C and pressure of the regenerator from 130 to 450 kPa (from 1.3 to 4.5 kg/cm2), preferably from 240 to 400 kPa (from 2.4 to 4.0 bar).

Stage catalytic cracking process in the fluidized bed of catalyst may operate continuously or periodic manner, with a fixed bed, moving bed or sevdigini layer. The flow of the hydrocarbon mixture can be served either on the thread or in countercurrent with respect to the catalyst stream.

According to a particularly preferred aspect of the present invention, the stage of catalytic cracking in a fluidized bed of the catalyst is performed under such conditions that allow to obtain a fraction LRG with extra high quality from the point of view of density, and is characterized by particularly preferred composition in terms of aromatic compounds. Essentially, the content of polyaromatic compounds lower compared with factions LRG obtained under normal conditions the CCP, thus increase the content benzonitrile connections.

This characteristic of the composition facilitates the subsequent stage Hydrotreating and improve quality, allowing you to get the mixture as fuel with optimal performance and use less hydrogen compared to that described in prior art. According to this preferred aspect of the present patent application, the high outputs LRG obtained at the stage of the CCP, reached by selecting special and specific conditions of temperature and/or by selection of a particular temperature pre-heating of raw materials. The choice of these special conditions for the implementation stage of catalytic cracking in a fluidized bed of the white catalyst also allows you to direct the cracking reaction towards greater education TWG as a by-product of the reaction, which you can direct recycle to the stage of the PAC, helping to achieve a higher total output LRG.

Special and selected temperature conditions that allow you to maximize the education LRG range from 490 to 530°C.

Special preheating temperature materials that allow you to maximize the output LRG range from 240 to 350°C.

In both cases, it is preferable to operate at a pressure of from 200 to 350 kPa (2.0 to 3.5 bar).

As for the remaining parameters of the method, you can choose terms that are frequently used by specialists in this field.

Implementing stage of the CCP to satisfy at least one of the preceding conditions for temperature and preheating temperature, increasing the output LRG at least 50%, and addition to 100% consists of:

fuel gas (H2, C1, C2)

- LPG (C3-C4)

-gasoline (C5-210°C)

TRG (370+ °C)

- coke.

With regard to stage (a), carried out in the presence containing zeolite ERS-10 catalyst, the above conditions of the method associated with temperature and/or temperature of pre-heating of raw materials, which allow you to maximize the education LRG and get faction LRG with high quality in relation to density and the content of aromatic compounds are new and are from the battle an additional aspect of the present invention.

The mixture obtained in the first stage of the joint method according to the present invention, separated, preferably by distillation.

Obtained by dividing the fraction of the TWG preferably direct recycle to the stage of the PAC, for example, in a mixture with the raw materials.

Obtained by dividing fraction LRG characterized by composition, rich benzonitrile compounds in terms of the content of aromatic compounds, is subjected to hydrotreatment in order to reduce the content of nitrogen and sulfur and to change the composition of the fractions, further enriching its benzonitrile connections.

The fraction Hydrotreating LRG perform in one or more reactors with a fixed layer, and the catalyst layers may contain the same or different catalysts. Usually choose the catalysts based on compounds of metals of Group VI and/or Group VIII on a carrier, preferably an amorphous medium such as, for example, alumina or aluminosilicate. Metals that can suitably be used are, for example, Nickel, cobalt, molybdenum and tungsten. Examples of catalysts that can be selected, and their preparation is described in "Hydrocracking Science and Technology", J. Scherzer and A.J. Gruia, Marcel Dekker, 1996. Hydrotreating is described, for example, in "Catalysis Science and Technology", ed. by R. Anderson and M. Boudart, vol. 11, Springer Verlag, 1996. Catalysts gidroksistearinovoj in solifidians form. Sulfatirovnie can be obtained, for example, by sending a catalyst suitable raw materials containing sulfur compounds such as dimethyl disulfide (DMDS), dimethylsulfoxide (DMSO) or other compounds which, by decomposition, causing the formation of H2S.

The hydrotreatment is preferably performed at a temperature of from 200 to 400°C., even more preferably at a temperature of from 330 to 380°C. Typically, the pressure is 2 MPa to 10 MPa (20 to 100 bar), preferably from 4 MPa to 8 MPa (40 to 80 bar). The volumetric rate CASE is preferably from 0.3 to 3 h-1. The relation of H2/raw material is preferably from 200 to 2000 standards. l/L. for Hydrotreating raw LRG undergoes reaction saturation of aromatic rings with reduced content of aromatic carbon and enrichment naturopaticheskie connections.

The next stage of quality improvement is carried out in accordance with WO 2007/006473 in the presence of the bifunctional catalytic system containing one or more metals selected from Pt, Pd, Ir, Ru, Rh and Re, and acidic aluminosilicate selected from micrometeorite aluminosilicate having a suitable composition, and a zeolite belonging to the MTW family.

This stage of the method leads to a significant improvement of the characteristics of hydrotreated LRG, in particular, in terms of cetane is indexa (number), density and distillation curve, which are equivalent to the characteristics obtained by simple hydrogenation of aromatic structures. At this stage, find a small formation of products with a low molecular weight and requires lower the cost of hydrogen compared to known methods.

This stage is performed in the presence of hydrogen with a catalytic system containing:

A1) one or more metals selected from Pt, Pd, Ir, Ru, Rh and Re,

b1) acidic aluminosilicate selected from a zeolite belonging to the MTW family, and a fully amorphous micrometeorite aluminosilicate having a molar ratio of SiO2/Al2O3from 30 to 500, a surface area of more than 500 m2/g, pore volume from 0.3 to 1.3 ml/g and average pore diameter of less than 40 A.

This stage of the method allows to significantly increase the cetane index (number) together with a decrease in density and T hydrotreated mixture LRG. Thus obtained mixture LRG is, among other things, additionally enriched alkylbenzene compounds, which, at least partially, derived from partially hydrogenated polycyclic aromatic compounds benzenetriol type, either already present in the faction LRG obtained from special stage PCC of the present United way, or arose them during Hydrotreating.

Used at this stage of the method, the catalyst promotes the formation of alkylbenzene structures through gidrodistillyacii naphthenic rings naphthalenesulfonic or inftantly structures, thus getting the best possible compromise between the consumption of hydrogen and the improvement of the performance of the product, at the same time limit as the reaction is complete hydrogenation of aromatic rings, and the cracking reaction for the formation of light products.

Used catalysts described in the patent application WO 2007/006473. Acid component (B1) of the catalytic composition used in the present invention can be selected from zeolites of type MTW: family MTW described in Atlas of zeolite structure types, W.W. Meier and D.H.Olson, 1987, Butterworths. Zeolite MTW structural type, which is suitable for use in the present invention is a silicate with a molar ratio of SiO2/Al2O3above or equal to 20. This zeolite and its preparation is described in A.Katovic and G. Giordano, Chem. Ind. (Dekker), Synthesis of Porous Materials, 1997, 69, 127-137. According to a preferred aspect of the use of zeolite ZSM-12 is described in US 3832449 and Ernst et al., Zeolites, 1987, vol. 7, September.

In the preparation of the catalytic composition, the zeolite is used in its acid form.

If the acid component (B1) is an aluminosilicate, in a preferred aspect, the molar ratio of SiO2/Al O3ranges from 50 to 300. According to another preferred aspect, the porosity of the aluminosilicate is from 0.4 to 0.5 ml/year

Fully amorphous micrometeorite the silicates that can be used at the stage of improving the quality of the present invention, referred to as MSA, and their preparation are described in US 5049536, EP 659478, EP 812804. Their range of powder x-ray diffraction analysis does not correspond to the crystal structure and does not show any peak.

Catalytic compositions which can be used at the stage of improving the quality of the present invention, in which the acidic component is an aluminosilicate of type MSA, described in EP 582347.

The silicates that can be used at the stage of improving the quality of the method according to the present invention can be prepared according to EP 659478 based on of tetraalkylammonium hydroxide, aluminum compounds, hydrolyzable in Al2About3and silicon compound, a hydrolyzable in SiO2where specified of tetraalkylammonium hydroxide is a hydroxide, Tetra(C2-C6)alkylamine specified hydrolyzable compound of aluminum is three(C2-C4)alkoxide and specified the hydrolyzable silicon compound is a Tetra(C1-C5)alkylethoxylates: these reagents are subjected to hydrolysis and gelification, Actua at a temperature equal to or above the boiling point, at atmospheric pressure, of any alcohol which is produced as a by-product of the specified hydrolysis reaction, without deleting or without substantial removal of these alcohols from the surrounding reaction environment.

The resulting gel is dried and calcined, preferably in an oxidizing atmosphere at a temperature of from 500 to 700°C for 6-10 hours.

This procedure includes the preparation of an aqueous solution of tetraalkylammonium hydroxide and tralkoxydim aluminum, and tetrachlorosilane add to this aqueous solution, operating at a temperature below the temperature of hydrolysis, with quantities of reagents, which are such to provide a molar ratio of SiO2/Al2O3from 30/1 to 500/1, of tetraalkylammonium hydroxide/SiO2from 0.05/1 to 0.2/1 and H2O/SiO2from 5/1 to 40/1, and the hydrolysis and gelification start by heating to a temperature of from about 65 to about 110°C, acting in an autoclave at autogenous pressure of the system or at atmospheric pressure in a reactor equipped with a condenser.

As the metal component of the catalyst compositions used in the stage of improving the quality of the present invention, are selected from Pt, Pd, Ir, Ru, Rh, Re and mixtures thereof. According to a particularly preferred aspect of the present invention IU is all is platinum, iridium or mixtures thereof.

The amount of metal or mixture of metals is preferably from 0.1 to 5 mass. % relative to the total weight of the catalytic composition, and preferably ranges from 0.3 to 1.5 mass. %.

The mass percentage of the metal or metals refers to the metal content, expressed in the form of the content of elemental metal in the final catalyst, after calcination, the specified metal is in the form of oxide.

Before using on stage quality improvement activate the catalyst by known technologies, for example through restorative treatment, preferably by drying and subsequent recovery. Drying is carried out in an inert atmosphere at temperatures from 25 to 100°C, while rebuilding receive through heat treatment of the catalyst in a reducing atmosphere (N2) at a temperature of from 300 to 450°C and a pressure of preferably from 100 kPa to 5 MPa (from 1 to 50 ATM.).

Acid component (B1) of the catalyst, which is used at the stage of improving the quality of the method according to the present invention may be extruded in the form of a conventional binder, such as alumina, boehmite or pseudoboehmite. Extruded product can be prepared according to techniques well known to specialists in this field. only component (B1) and a binder can be pre-mixed in the mass ratios from 30:70 to 90:10, preferably from 50:50 to 70:30. At the end of mixing the resulting product is compacted into the final desired shape, for example in the form of extruded granules or tablets. Alternatively, if the component (B1) is an aluminosilicate catalyst in extruded form, prepared as described in EP 665055, can be used as an extruded component (B1).

As the metal phase (A1) catalyst under quality improvement, it can be entered by impregnation or ion exchange. According to the above technology, the acid component (B1), also in extruded form, hydrate aqueous solution of metal joining, acting, for example, at room temperature and pH from 1 to 4. The resulting product is dried, preferably in air, at room temperature, and calcined in an oxidizing atmosphere at a temperature of from 200 to 600°C.

In the case of impregnation with alcohol acid component (B1) is suspended in containing metal ethanol solution. After impregnation, the solid is dried and calcined.

According to the technology of ion exchange acidic component (B1) is suspended in an aqueous solution of a metal complex or metal salt, operating at room temperature and pH from 6 to 10. After ion exchange, the solid is separated, washed with water, dried and finally thermally obrabecim the Ute in an inert or oxidizing atmosphere. Temperature, which can be used for this purpose range from 200 to 600°C.

Metal compounds which can be used in the above-described methods of preparation, are H2PtCl6, PT(NH3)4(OH)2Pt(NH3)4Cl2, PD(NH3)4(OH)2, PdCl2H2IrCl6, RuCl3, RhCl3.

Stage improve the quality of the method according to the present invention is preferably performed at a temperature of from 240 to 380°C., at a pressure of from 1 to 10 MPa (10 to 100 ATM.), MCOS from 0.5 to 5 h-1and with the ratio of hydrogen to the raw material (N2/NS) from 400 to 2000 NORML/kg (Nlt/kg). It is preferable to operate at pressures above 2 MPa (20 ATM.) and less than or equal to 8 MPa (80 bar), then as the temperature is preferably from 250 to 330°C. when the acid component (61) is an MTW-type zeolite, and preferably ranges from 300 to 380°C. when the acid component (61) is aluminum silicate.

Example

Tests were carried out using micro-reactor with a fixed layer, which is a quartz reactor placed in a furnace. The reactor was loaded with different number of commercially available catalyst that belongs to a class of zeolitic systems and containing, in particular, zeolite Y as the active phase, while maintaining balance (according to the ratio of catalyst/not the required load, specified as Cat/Oil), diluted with quartz microspheres and pre-heated in a stream of nitrogen. Download, the characteristics of which are given below in table 1, was filed with adjustable speed.

Table 1
Density at 15°C, kg/l0,9003
The refractive index at 75°C1,4810
Sulfur, %0,45
ASTM D 6352 [°C]
TNK/5%218/305
10%/30%341/410
50%/70%454/507
90%/TAC602/713
Nitrogen, %0,14

Operating conditions are listed in the following table.

The reaction temperature, °C560
Download (Oil), g1,5
Injection time, 12

Characteristics of the ERS-10 as an additive were evaluated by mixing of 3.0% of the mass. ERS-10 catalysts while maintaining balance and compare with the catalyst as such.

- Base case: a commercially available catalyst based on zeolite Y and load according to table 1.

- The example of ERS-10: base case +3,0% ERS-10.

The table below shows the results, expressed in terms of conversion, comparing the base case with the case, which was added ERS-10, when operating with a ratio of cat./oil (2,0) and (T, component 560°C:

The basic caseThe example of ERS-10
Cat./Oil22
Conversion60,871,2
Fuel gas2,22,4
CIS17,419,1
Gasoline37,145,2
LRG (370-)21,618,3
TWG (370+)of 17.510,4
Cox4,04,4
Remains after cracking1,21,8

As can be seen from the table, the addition of ERS-10 as an additive contributes to a noticeable increase in conversion rates and a significant increase in balances after cracking, i.e. the relationship between LRG and the TWG. Specified a greater number LRG then used at a later stage of quality improvement.

1. United way of conversion of hydrocarbon fractions of petroleum origin in the high-quality mixture of hydrocarbons as fuel, which includes the following stages:
catalytic cracking of hydrocarbon fractions in a fluidized bed of a catalyst (PAC) at a temperature of from 400 to 650°C and at a pressure of from 100 to 500 kPa (1 to 5 bar) in the presence containing zeolite ERS-10 catalyst, where the specified catalyst contains at least two components, where these components are:
(a) a component containing one or more of the catalyst in the fluidized bed, and
(b) a component containing zeolite ERS-10,
to obtain a light cycle gas oil (LRG),
the Hydrotreating formed the CSOs recycle gas oil,
- interaction hydrotreated light cycle gas oil obtained in the previous stage Hydrotreating, with hydrogen in the presence of a catalytic system containing:
a1) one or more metals selected from Pt, Pd, Ir, Ru, Rh and Re,
B1) acidic aluminosilicate selected from a zeolite belonging to the MTW family, and a fully amorphous micrometeorite aluminosilicate having a molar ratio of SiO2/Al2O3from 30 to 500, a surface area of more than 500 m2/g, pore volume from 0.3 to 1.3 ml/g and average pore diameter of less than 40 Å.

2. The method according to claim 1, comprising the following stages:
(1) catalytic cracking of hydrocarbon fractions of petroleum origin in the fluidized bed of catalyst (PAC) in the presence containing zeolite ERS-10 catalyst, where the specified catalyst contains at least two components, to obtain a mixture containing LRG,
(2) separation of the mixture obtained at the previous stage of catalytic cracking in a fluidized bed of a catalyst, so as to divide at least a fraction LRG and the fraction of the TWG,
(3) if necessary, reapply at least part of the fraction TWG obtained at stage (2), stage (1) catalytic cracking in a fluidized bed of catalyst,
(4) the fraction Hydrotreating LRG obtained at stage (2),
(5) the interaction of product, poluchasa the Osia on the previous stage, with hydrogen in the presence of a catalytic system containing:
A1) one or more metals selected from Pt, Pd, Ir, Ru, Rh and Re,
B1) acidic aluminosilicate selected from a zeolite belonging to the MTW family, and a fully amorphous micrometeorite aluminosilicate having a molar ratio of SiO2/Al2O3from 30 to 500, a surface area of more than 500 m2/g, pore volume from 0.3 to 1.3 ml/g and average pore diameter of less than 40 Å.

3. The method according to claim 2, in which is used in the first stage, the catalyst includes:
a) a first component containing one or more catalysts selected from zeolites, amorphous cracking catalysts based on inorganic oxides and neoreality crystalline cracking catalysts based on inorganic oxides,
b) a second component containing zeolite ERS-10.

4. The method according to claim 3, in which component (a) zeolites are zeolites with large pores.

5. The method according to claim 4, in which component (a) zeolite is zeolite Y.

6. The method according to claims 1 or 2, in which the first stage zeolite ERS-10 crystallized together with mordenite or ZSM-12.

7. The method according to claims 1 or 2, in which the first stage zeolite ERS-10 contains auxiliary phase NON zeolites, EUO and NES.

8. The method according to claims 1 or 2, in which the first stage zeolite ERS-10 used in bound form.

9. The method according to claim 1, in which the component (b) zeolite ERS-10 is present in an amount of from 1 to 10% relative to the weight of the catalyst, contained in the component (a).

10. The method according to claims 1 or 2, in which the first stage catalytic cracking in a fluidized bed of a catalyst of a catalytic composition prepared by a method chosen from:
mechanical mixing component (a) and (b) according to the technology, well-known specialist in the prior art, and in this case, the zeolite ERS-10 is a component of the catalytic particles, physically distinct from the particles containing the catalyst component (a),
- performed simultaneously binding the zeolite ERS-10 and the catalyst contained in the component (a),
- mixing in situ performed by adding the component (b) in component (a), already present in the method for catalytic cracking in a fluidized bed of a catalyst, at any point in the method.

11. The method according to claims 1 or 2, in which the first stage catalytic cracking process in the fluidized bed of the catalyst is performed at a temperature of from 400 to 650°C.

12. The method according to claims 1 or 2, in which the first stage catalytic cracking process in the fluidized bed of the catalyst is performed at a pressure of from 100 to 500 kPa (1 to 5 bar).

13. The method according to claims 1 or 2, in which the mixture of hydrocarbons to be processed in the first stage, are gas oils, petroleum fractions, consisting of VGO (vacuum gas oil)with temperature to the singing from 350 to 550°C, atmospheric residue, neasfaltirovanyj oil, the products of thermal cracking and hydrocracking residues.

14. The method according to claims 1 or 2, in which the temperature at which carry out the first stage is from 490 to 530°C.

15. The method according to claims 1 or 2, in which the first stage using the temperature of pre-heating the loaded substances from 240 to 350°C.

16. The method according to claims 1 or 2, in which stage Hydrotreating is performed at a temperature of from 200 to 400°C and a pressure of from 2 to 10 MPa (20 to 100 bar).

17. The method according to claims 1 or 2, in which at the stage of improving the quality of the metal component (A1) are selected from platinum, iridium or mixtures thereof.

18. The method according to claims 1 or 2, in which the stage of quality improvement performed at a temperature of from 240 to 380°C and a pressure of from 1 to 10 MPa (10 to 100 ATM.), MCOS from 0.5 to 5 h-1and with the ratio of hydrogen to the raw material (H2/HC) of from 400 to 2000 standards. l/kg

19. Method for catalytic cracking in a fluidized bed of a catalyst for the conversion of hydrocarbon fractions of petroleum origin in a mixture containing LRG performed at a temperature of from 490 to 530°C in the presence of a catalyst containing zeolite ERS-10, with the specified catalyst contains at least two components.

20. Stage catalytic cracking in a fluidized bed of a catalyst for the conversion of hydrocarbon fractions of petroleum origin which ia in the mixture, containing LRG performed in the presence of a catalyst containing zeolite ERS-10, with the specified catalyst contains at least two components, where the temperature of pre-heating the loaded substances ranges from 240 to 350°C.

21. The method according to PP and 20 performed in the presence of a catalyst containing zeolite ERS-10, with the specified catalyst contains at least two components and the specified method is performed at a temperature of from 490 to 530°C with temperature pre-heating of the loaded substances from 240 to 350°C.



 

Same patents:

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SUBSTANCE: method of integrated waste management for oily wastes with random composition with production wide range of energy sources include low-temperature pyrolysis with heating source, before pyrolysis oily wastes with random composition are sorted during accumulation, mixed mechanically in the preset ratio and homogenised thermally with moisture evaporation by flue gases at temperature of 100-130°C, in process pyrolysis gas is sent to condensation unit in order to separate light hydrocarbon fractions from heavy ones. Light fractions are directed to rectification tower with production of benzene, kerosene and diesel fuel, heave fractions with residual oil from condensation unit are delivered to pre-activation unit where oxidation cracking takes place within temperature range of 250-350°C with air purging with ratio of 1:(300-500); after oxidation cracking activated heave fractions are delivered to catalytic cracking for additional production of benzene, kerosene and diesel fuel and fuel oil, bitumen and tar oil; after pyrolysis solid pyrolysate is transferred and water-gas generator, flue combustion gases from condensation column are delivered to water-gas generator, at that flue combustion gases are enriched by superheated steam and in solid pyrolysate they are converted to gaseous energy carrier - water gas. Additionally one proposes a plant for the method implementation.

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2 cl, 1 dwg, 1 tbl

FIELD: oil and gas industry.

SUBSTANCE: invention is related to process of hydrocarbon oil catalytic conversion. Invention is referred to conversion of law-grade raw feedstock which is input to the first reaction zone in catalytic conversion reactor and subjected to catalytic reactions of cracking by means of raw feedstock contacting with catalyst of catalytic conversion. Vapours and used catalyst are mixed at random basis with light raw feedstock and/or cooling medium and are introduced into the second reaction zone in catalytic conversion reactor for the purpose of further cracking, hydrogen transfer and isomerisation reactor. Products of the reaction are separated from used catalyst by separation into gaseous and solid phases and introduced into separation system in order to obtain dry gas, LPG, petrol and diesel fuel and catalytic gas oil with c suspended catalyst (FGO). Used catalyst is desorbed, regenerated and then hot regenerated catalyst is returned to the reactor. FGO is introduced into hydrofining plant and/or plant for aromatic hydrocarbons separation in order to receive hydrofined FGO and/or FGO raffinate. Hydrofined FGO and/or FGO raffinate is transferred to the first reaction zone of catalytic conversion reactor and/or to other FCC plants for further reactions in order to receive the target oil fuel as a high-quality product.

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21 cl, 4 dwg, 10 tbl, 16 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a compound method of converting hydrocarbon fractions originating from oil into mixtures of hydrocarbons having high fuel quality, involving the following steps: 1) conducting fluid catalytic cracking (FCC) of the hydrocarbon fraction to obtain a mixture which contains light cycle gas oil (LCG); 2) separating the mixture obtained at the last FCC step in order to extract at least one LCG fraction and a heavy cycle gas oil (HCG) fraction; 3) re-feeding at least a portion of the HCG fraction to the FCC step; 4) conducting hydrifining of the LCG fraction; 5) reacting the product obtained at step (4) with hydrogen in the presence of a catalyst system comprising: a) one or more metals selected from Pt, Pd, Ir, Ru, Rh and Re; b) acidic aluminosilicate selected from a MTW zeolite, and completely amorphous micro-mesoporous aluminosilicate, having molar ratio SiO2/Al2O3 from 30 to 500, surface area greater than 500 m2/g, pore volume from 0.3 to 1.3 ml/g, average pore diameter less than 40 E, wherein the FCC step is carried out at temperature ranging from 490 to 530°C; and at the FCC step preheating temperature of the feed stream ranges from 240 to 350°C. The invention also relates to a FCC method.

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22 cl, 3 tbl, 2 ex

FIELD: oil and gas production.

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4 cl, 3 ex

Composition of fuel // 2414502

FIELD: gas-and-oil producing industry.

SUBSTANCE: here is disclosed composition of fuel with flash point 45°C or more containing synthetic oil Fisher-Tropsh and hydrocarbon mixture A on base of oil with following properties from (1) to (5) at amount from 10 to 30 percents by volume on base of total weight of composition: (1) density at 15°C: 800 kg/cm3 or more and 900 kg/m3 or less; (2) temperature of distillation of 10 vol. % (T10): 150°C or more and 200°C or less; (3) temperature of distillation of 97 vol. % (T97): 270°C or less; (4) contents of aromatic compounds: 40 percents by volume or more and 70 percents by volume or less; and (5) contents of sulphur: 30 shares per million by weight or less.

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2 cl, 5 ex, 2 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to the technology of cracking hydrocarbon material. The invention pertains to a method of processing hydrocarbon material containing a vacuum distillate fraction or deasphalted oil or a mixture of these two fractions, in which crude oil undergoes distillation at atmospheric pressure to extract a gasoil cut and a distillation residue at atmospheric pressure; said distillation residue at atmospheric pressure undergoes vacuum distillation to extract a vacuum distillate which is taken for mild hydrocracking, and a vacuum distillation residue; deasphalted oil and asphalt are obtained through additional deasphalting of at least a portion of the vacuum distillation residue; said vacuum distillate and/or deasphalted oil, called the main raw material, undergo mild hydrocracking in the presence of hydrogen and a catalyst, as well as a lighter hydrocarbon fraction which is called secondary raw material; effluent formed from mild hydrocracking is separated in order to tap a fraction having initial boiling point higher than 320°C, which contains less than 0.25 wt % sulphur, and a fraction whose distillation interval lies between 130 and 390°C, having the following characteristics: D15/4: 0.845-0.855, sulphur content: 5-200 parts per million, by weight, cetane number: 48-52; said fraction which has initial boiling point higher than 320°C is fed into the catalytic cracking zone to obtain catalytic cracking light gasoil and heavy gasoil. The invention also relates to apparatus for realising this method.

EFFECT: obtaining gasoil with low content of sulphur, having higher cetane number.

23 cl, 3 ex, 5 tbl, 4 dwg

FIELD: explosives.

SUBSTANCE: one of methods includes the following stages: a. steam-phase cracking of ethane or mainly ethane initial raw materials, containing 70% or more of ethane, with production of, thereby, cracking product, containing ethylene, hydrogen, ethane, methane, acetylene and C3 and heavier carbohydrates; b. processing of mentioned cracking product in extraction section of ethylene plant, also removal of mentioned hydrogen, methane and C3 and heavier carbohydrates from it and conversion of mentioned acetylene available in it mainly into ethylene with production of, thereby, cracking product exposed to processing, containing mainly ethylene and ethane, and also fractioning of specified cracking product that has been processed into C2 fractioning column and production of ethylene fraction, consisting of chemical ethylene and characterized with level of ethylene content below 99% (vol.), and ethane fraction in the form of distillation residue; c. sending of specified ethane fraction in the form of distillation fraction for recycle to specified steam-phase cracking; d. performance of reaction by mechanism of dimerisation in dimerisation section for the first part of specified ethylene fraction with thereby production of butene-enriched flow; e. performance of reaction by metathesis mechanism in metathesis section between butene in specified flow enriched with butene, and the second part of specified ethylene fraction with thereby production of flow enriched with propylene, ethylene and ethane; f. separation of propylene from specified ethylene and ethane in specified flow enriched with propylene and g. sending of at least part of specified ethylene and ethane from specified flow enriched with propylene for recycle into mentioned C2 fractioning plant. Besides invention is related to method for production of propylene from carbohydrate raw materials.

EFFECT: application of proposed methods makes it possible to improve and make process of propylene production from carbohydrate initial raw materials more profitable.

39 cl, 6 dwg

FIELD: chemistry.

SUBSTANCE: proposal is given of a method of obtaining high-octane engine fuels through cracking heavy oil stock in the presence of zeolite containing catalysts. The cracking process is carried out under the condition that, the oil stock undergoes hydroprocessing, with obtaining three fractions: initial boiling-180°C, 180-360°C, over 360°C, where over 360°C fractions are taken for cracking, obtaining three fractions after cracking: initial boiling-180°C, 180-360°C, over 360°C. The initial boiling-180°C and 180-360°C fractions, obtained after hydroprocessing and cracking are combined, obtaining components of end products. Not less than 10% of the heaviest cracking fraction is added to the hydroprocessing raw materials. A zeolite containing catalyst is used in the cracking process, chosen from a group comprising Y type zeolite, zeolite Y modified with rare-earth elements, either zeolite Y and ZSM-5 in ratio ranging from 2:1 to 10:1, or a system of catalysts containing Y type zeolite and ZSM-5 type zeolite in cation-decationated form, in ratio ranging from 2:1 to 10:1 in terms of zeolite, under the condition of differentiation of catalysts by strength and packed density of not more than 10%.

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2 cl, 5 ex, 5 tbl

FIELD: petroleum processing.

SUBSTANCE: invention is directed to process petroleum stock resulting in production of diesel fuels meeting existing quality level (Euro-4 and Euro-5). Proposed processing method involves stages of hydrogenation refining of petroleum stock and catalytic cracking of residue obtained from hydrogenation refining products. Diesel distillate from hydrogenation refining stage is combined with diesel distillate from catalytic cracking stage in proportion between 15:85 and 60:40, whereupon resulting blend is subjected to common hydrofining.

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5 cl, 3 ex

The invention relates to the refining industry, in particular to a method for producing motor fuels

FIELD: machine building.

SUBSTANCE: invention relates to the hydroconversion method for raw hydrocarbons in the mix with the circulating part of the hydroconversion vacuum residue by a high-aromatic modifier, dispersion of a catalyst precursor and hydrogen-containing gas which is supplied in the amount of maximum 800 nm3 per 1 m3 of raw material in terms of hydrogen and of minimum the value of chemical hydrogen demand. The above is carried out in a reactor with an internal circular baffle plate which adjoins the reactor top in a pressure tight way and forms axial and circular cavities, and with separation space at the top of the circular cavity. Hydroconversion gas is removed from the separation space, liquid hydroconversion product is removed from the top of the axial cavity, circulating reaction mass is removed from the bottom of the reactor's circular cavity, cooled and delivered for mixing with heated raw liquid-vapour mixture, the temperature of the liquid hydroconversion product is kept close to the upper limit of the hydroconversion temperature range, the temperature of the heated raw mixture and the temperature of the circulating reaction mass are kept close to the lower limit of the hydroconversion temperature range. Hydroconversion products are separated and rectified to isolate light fractions, heavy gas oil and vacuum residue, part of the latter is recirculated, and the balance part is recovered to produce regenerated catalyst precursor.

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1 dwg, 1 ex

FIELD: engines and pumps.

SUBSTANCE: invention relates to production of fuel for jet engines from kerosene stock. Proposed method comprises hydrofining of kerosene stock with freezing point interval of 163-302°C (325-575°F) over hydrofining catalyst under conditions of hydrofining. This allows getting hydrofined kerosene stock. Besides, it includes dewaxing of, in fact, all hydrofined kerosene stock over catalyst including 1-D molecular sieve with ten rings under conditions of dewaxing to get water-dewaxed kerosene stock. Also, it includes fractionating of water-dewaxed kerosene stock to get fuel for jet engines.

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10 cl, 1 dwg, 2 tbl, 1 ex

FIELD: chemistry.

SUBSTANCE: initial hydrocarbon raw material is initially separated and first part of initial raw material is introduced into first zone of dehydration reaction, which functions without oxidation re-heating, and obtained as a result output flow is introduced into second zone of dehydration reaction, which functions without oxidation re-heating. Obtained as a result output flow from second zone of dehydration reaction, together with second part of initial raw material is introduced into third zone of dehydration reaction, which functions with oxidation re-heating.

EFFECT: increased method productivity.

10 cl, 1 dwg

FIELD: oil and gas industry.

SUBSTANCE: invention is referred to method of production of high-octane petrol and includes fractionation of hydrotreated naphtha into light and heave fractions; light naphtha isomerisation and heavy naphtha reforming in presence of platinum-containing catalyst with delivery of excessive hydrogen from reforming to isomerisation. Isomerisation is carried out with sulfate-zirconia catalyst with subsequent separation of isomerisate into three fractions: low-boiling fraction, medium fraction containing n-hexane and methylpenthanes and high-boiling fraction; medium fraction is recirculated to isomerisation raw material. By rectification from reformate light and heavy reforming fractions are obtained; heavy fraction is mixed with low- and high-boiling fractions of isomerisate with production of the target product while light fraction of reforming boiling away up to 85-95°C is subjected to hydroisomerisation at 250-300°C in presence of platinum-containing catalyst and obtained hydroisomerisate is delivered to be mixed with isomerisate.

EFFECT: reduction of benzole and aromatic hydrocarbons content in compliance with requirements to modern types of petrol with preservation of integration for reforming and isomerisation processes.

2 cl, 1 tbl, 7 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method for hydrocracking a hydrocarbon stream involving the following operations: providing hydrocarbon starting material (12); feeding the hydrocarbon starting material (12) into a hydrofining zone (14) to obtain an output stream (30) of the hydrofining zone; feeding the output stream (30) of the hydrofining zone into a separation zone (16) in order to separate one or more streams of hydrocarbons with a lower boiling point (34, 58, 62, 66) from a stream of liquid hydrocarbons with a higher boiling point (68); inlet of at least a portion of the stream of liquid hydrocarbons with a higher boiling point as material (68) for hydrotreatment without using a considerable amount of hydrocarbons coming from the hydrotreatment zone with an essentially continuous liquid phase; adding hydrogen (70) to the material (68) for hydrotreatment in an amount which is sufficient to maintain essentially liquid-phase conditions; feeding the material (68), mixed with hydrogen, for hydrotreatment into the hydrocracking zone (24) with an essentially continuous liquid phase; and carrying out a reaction for hydrocracking the material (68) for hydrotreatment in the hydrocracking zone (24) with an essentially continuous liquid phase with a hyrocracking catalyst in hydrocracking conditions to obtain an output stream (72) of the hydrocracking zone having a lower boiling point compared to the stream (68) of liquid hydrocarbons with a higher boiling point. The invention also relates to another method for hydrocracking a hydrocarbon stream.

EFFECT: improved characteristics of products, higher conversion.

16 cl, 5 dwg, 4 tbl, 1 ex

FIELD: power engineering.

SUBSTANCE: method is described to produce hydrocarbon fractions, which may be used as diesel fuel or as components of diesel fuel, based on a mixture of biological origin, containing ethers of fatty acids, possibly, with a certain amount of free fatty acids, which includes the following stages: 1) hydrodesoxygenation of a mixture of organic origin; 2) hydroisomerisation of a mixture produced at the stage (1), after possible treatment for cleaning; besides, the specified stage of hydroisomerisation is carried out in presence of a catalytic system, which contains the following: a) a carrier of acid nature, including a fully amorphous micro-mesoporous silicon-aluminium oxide, having a mole ratio SiO2/Al2O3 in the range from 30 to 500, the surface area of more than 500 m2/g, volume of pores in the range from 0.3 to 1.3 ml/g, the average diameter of pores below 40 Ǻ, b) a metal component containing one or more metals of group VIII, possibly mixed with one or more metals of the group VIII.

EFFECT: production of a hydrocarbon fraction, which may be applied as diesel fuel or as a component of diesel fuel.

55 cl, 4 tbl, 3 dwg, 2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing jet fuel for supersonic aircraft via hydrogenation and subsequent hydrodewaxing of secondary petroleum material in the presence of a hydrogen-containing gas and catalysts, at high temperature and pressure in two hydrogenation reactors and in a hydrodewaxing reactor. The secondary material used is a mixture of gas oils from catalytic cracking and delayed coking in ratio from 90%-10% to 70%-30% and straight-run gas oil is further added in amount of not more than 30 wt % based on the total load of the material, wherein the straight-run gas oil is fed into the top part of the first or second hydrogenation reactor or in different fractions into the top part of the first and second hydrogenation reactors, wherein the hydrogenation reactors are loaded with nickel sulphide - tungsten catalyst, and the hydrodewaxing reactor is 70% loaded with a molybdenum catalyst on a zeolite support, and 30% by a nickel sulphide - tungsten catalyst.

EFFECT: wider range of raw material resources for producing scarce jet fuel for supersonic aircraft, improved technological effectiveness of the process owing to a simple temperature control scheme in the reaction zone and high output of the end jet fuel.

3 cl, 3 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method for synthesis of branched olefins, said method involving dehydrogenation of an isoparaffin composition containing 0.5% or less quaternary aliphatic carbon atoms on a suitable catalyst. Said isoparaffin composition is obtained via hydroisomerisation a paraffin composition and contains paraffin containing 7-18 carbon atoms. Said paraffins, at least some of their molecules, are branched, where content of branched paraffins in the isoparaffin composition is equal to at least 50% of the weight of the isoparaffin composition. The average number of branches per paraffin molecule is between 0.5 and 2.5 and the branches include methyl and optional ethyl branches. Said branched olefins contain 0.5% or less quaternary aliphatic carbon atoms. Said paraffin composition is obtained using Fischer-Tropsch method. The invention also relates to methods of producing a branched alkyl aromatic hydrocarbon and branched alkylaryl sulphonates including the method described above.

EFFECT: high versatility and cost effectiveness of the method.

7 cl, 19 ex

FIELD: oil and gas production.

SUBSTANCE: procedure consists in following stages: (a) there is performed hydrocarbon raw stock hydraulic processing by means of gas enriched with hydrogen for production of hydraulically treated output flow containing mixture of fluid and vapour; mixture of fluid and vapour is separated into liquid phase and vapour phase; (b) liquid phase is separated to controlled liquid part and excessive liquid part; (c) vapour phase is connected with excessive liquid part for production of vapour-liquid part; (d) there is extracted fraction containing raw stock for FCC from controlled liquid part and simultaneously there is performed hydro-cracking of vapour-liquid part for production of diesel-containing fraction or there is performed hydro-cracking of controlled liquid part for production of diesel containing fraction and simultaneously there is extracted fraction containing raw stock for FCC from vapour-liquid part. The invention also refers to the device for implementation of the procedure of hydraulic cracking with partial conversion.

EFFECT: production of diesel fuel with ultra-low content of sulphur and substantially better combustibility.

9 cl, 3 ex, 4 tbl, 4 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a method for isomerisation of light gasoline fractions containing C7-C8 paraffin hydrocarbons by extracting the C7-C8 fraction from wide gasoline fractions and bringing said C7-C8 fraction into contact with a catalyst containing a hydrogenating-dehydrogenating component on an oxide support in a hydrogen medium at high temperature and pressure in two reactors, fractionation to obtain a product fraction and a fraction of n-paraffins, monomethyl-substituted paraffins and methylcyclohexane which is recirculated into the gas-raw material mixture. The C7-C8 fraction (raw material) is extracted such that its content of C5-C6 hydrocarbons is equal to 0.1-15 wt %, while that of C8 hydrocarbons is equal to 0.1-20 wt %, by mixing the extracted C7-C8 fraction with hydrogen in molar ratio hydrogen: raw material equal to 0.5-4, with formation of a gas-raw material mixture and feeding said mixture into the first of two series-connected isomerisation reactors at temperature 160-250°C, pressure 1.0-4.0 MPa, and bulk speed for feeding material equal to 1-5 h-1. Quenched hydrogen at 40-60°C is fed into the second reactor, with molar ratio hydrogen: raw material equal to (0.1-1.0):1, and the oxide support is a composition of metal oxides: aAI2O3·bZrO2·cWO3·dTiO2·eMnO2, where weight ratios of the oxides are as follows: a=0.04-0.30; b=0.60-0.90; c=0.05-0.15; d=0.001-0.10; e=0.001-0.01.

EFFECT: obtaining isomerisate with high octane number.

2 cl, 3 tbl, 17 ex

FIELD: process engineering.

SUBSTANCE: invention relates to mixing of recovered catalyst with carbonised catalyst. Besides, it relates to the device designed to bring recovered catalyst in contact with hydrocarbon stock. This device comprises riser reactor wherein hydrocarbon stock contacts with catalyst particles for catalytic cracking of hydrocarbons in said hydrocarbon stock. This results in light-end product composed of lighter hydrocarbons and carbonised catalyst. Besides it includes stock distributor, reactor vessel, recovery vessel, recovered catalyst pipeline, recovered catalyst baffle and carbonised catalyst pipeline. Besides, it relates to the device designed to bring recovered catalyst in contact with hydrocarbon stock.

EFFECT: higher quality of hydrocarbon product.

9 cl, 3 dwg, 1 ex

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