Method of producing high octane gasoline fractions

 

(57) Abstract:

Usage: in the petrochemical industry, in particular in the methods of processing of hydrocarbon raw materials. The inventive method provides for the rectification of hydrocarbons with obtaining and/or hexane and/or heptane, and/or octane, and/or nonanol, and/or heavy gasoline fractions which are in contact with a catalyst based on zeolite ZSM, including ZSM-5, including the modified elements of the second, sixth, and eighth groups of the Periodic system. Products contact is separated into gaseous and liquid. The latter is mixed with the remaining fraction of raw. When rectification allocate these fractions, wikipaedia not less than about 50. in the intervals of temperatures: 65 75, 95 105, 120 130, 145 150°With, and a heavy gasoline fraction, wikipaedia not less than 70% when the temperature is above or 95 or 120 or 145°C. the Contacting is carried out at 300 to 480°C., a pressure of 0.2 to 0.4 MPa, it is possible in the environment of the water-containing gas. 5 C. p. F.-ly, 5 PL.

The invention relates to methods of producing unleaded high-octane gasoline fractions from hydrocarbon material, wikipaedia in the temperature range of boiling gasoline. Raw material process can be straight-run be the condensates associated gases, etc.

High-octane unleaded gasoline produced by compounding the base gasoline (straight-run gasoline, gasoline catalytic cracking and so on) with high-octane components (reformate, alkylates, and so on ), i.e., by mixing the components obtained by various refining processes [1] the Technology of getting each of them is quite complicated, so recently intensively develop ways to obtain high octane gasoline one catalytic process. Currently, for these purposes, develop catalysts based on zeolites with structure of ZSM-5, -11, allowing for processing of different raw material.

Known methods for the conversion of hydrocarbons WITH2-C12in high-octane gasoline or high-octane components in the environment of the hydrogen-containing gas. According to these methods, the processing of hydrocarbons is carried out in the temperature range of reactions 100-700aboutWith pressure of 0.1 to 11 MPa for the catalysts prepared on the basis of zeolites of type ZSM, including ZSM-5, -11 and including modified items I-VIII groups or fluorides of various elements. A common disadvantage of these methods and their analogs processing unit of weight of raw material, and in some cases low yields and low octane number gasolines produced.

There are hydrogen-free methods of processing hydrocarbon fractions, wikipaedia in the temperature range of the boiling point of the gasoline, high octane gasoline and its components. According to these methods is the transformation of raw materials on the catalyst is generally carried out in the temperature range of reactions 200-815aboutC and pressures of 0.1 to 7 MPa. The catalysts are prepared on the basis of zeolites of type ZSM, including ZSM-5, -11, and, in addition, they can be modified by items I-VIII groups or contain zeolites of type X and Y. the Common disadvantage of these methods is the large amount of catalyst required for processing a unit mass of the raw material, and in some cases:

the relatively low outputs gasoline fractions;

a slight increase octane numbers of gasoline;

the use of high temperature reactions;

the complexity of the preparation of the catalyst;

obtaining high-octane component of gasoline, not gasoline.

To improve yield and octane number of gasoline use a combination of methods of processing of hydrocarbon raw materials, combining several stages: as catalytic and stages of fractionation. For example, the Tropsch fractionary emitting fractions WITH5-C6and C7+. Fraction WITH7+in one reaction zone is subjected to hydrogenation at Al-Co-Mo catalyst, and the fraction WITH5-C6turn in the other reaction zone at a temperature 165-260aboutC and a pressure of from 4.2 to 4.9 MPa catalyst containing zeolites of type ZSM-5, -11, -12, -21, -35, -38. Liquid products contact both reaction zones are mixed and fractionary emitting gasoline FR. WITH5- 205aboutAnd residual fractions > 205aboutC. as a result of implementation of the described method it is possible to increase the octane number of gasoline from 84 to 91.5 MM. The main disadvantages of this method are the use of two fundamentally different types of catalysts and a large specific need in the catalyst.

The closest in technical essence and the achieved effect is a method of improving the octane number of gasoline catalytic cracking [3] in Accordance with the selected prototype feedstock fractionary emitting fractions WITH6-and C7+. Fraction WITH7+(having an octane number lower than for the original raw material) is subjected to contacting at a temperature 204-426aboutC and pressure up to 7 MPa with a catalyst based on zeolite ZSM-5 or ZSM-8, the hydrogen gas WITH1-C3and fraction4+that compounding with a fraction WITH the6-(having an octane number higher than for feedstock). The main disadvantages of the prototype are:

small (0.9-1.7 points) increase in the octane number of gasoline;

relatively high specific need in the catalyst, i.e. a larger amount of catalyst required for processing a unit mass of raw materials;

for some types of hydrocarbon raw materials this method is not workable because there are hydrocarbon fractions (e.g., reformate), in which the easy part (FR. < 82about(C) has a lower octane number than the heavy component (i.e. FR. > 82aboutC).

The aim of the invention is the reduction necessary for processing a unit mass of the raw material quantity of catalyst, characterized by the mass ratio of the catalyst to the weight of the processed per unit of time of the raw materials, as well as an increase in the yield and octane number of gasoline fractions obtained.

This goal is achieved as follows. Hydrocarbons, wikipaedia in the temperature range of the boiling point of gasoline is subjected to rectification emitting from it and/or hexane, and/or galanopoulos combination with each other) and are contacting at elevated temperature and pressure with a zeolite-containing catalyst. Possible the implementation stage contacting of the feedstock with the catalyst in the environment of the hydrogen-containing gas. Products contact share with the release of hydrocarbon gases and liquid gasoline fraction. The gasoline fraction is mixed with a fraction of the raw material remaining after separation of these fractions, to obtain the target high-octane gasoline fraction.

Allocated fractionation of the raw material hexane, heptane, octane, novanova fraction boils away not less than 50% in the following temperature ranges: hexane 65-75aboutWith, heptane 95-105aboutWith, 120-130 octaneaboutWith novanova 145-155aboutWith a heavy gasoline fraction boils not less than 70% at temperatures above or 95aboutWith, or 120aboutWith, or 145aboutC. however, in the case of the selection of the raw material heavy gasoline fraction > 95aboutWith, allocate hexane fraction; if the allocation of the heavy gasoline fraction > 120aboutFrom raw materials emit and/or hexane and/or heptane fractions; in the allocation of the heavy gasoline fraction > 145aboutFrom raw materials emit and/or hexane and/or heptane, and/or octane fractions. The choice available for contact with the catalyst fractions is determined based on the fractions with the catalyst is carried out in the temperature range of the reaction 300-480about(Better 320-460aboutC) and pressure range 0,2-4 MPa (preferably 0.5 to 4 MPa). In the process used catalysts based on zeolites with structure of ZSM-5 or ZSM-11, including modified items I, II, III, IV, V, VI and VIII groups of the periodic system of elements. The catalysts are prepared by known methods.

Distinctive features of the invention are:

fractionation of raw material selection and/or hexane and/or heptane, and/or octane, and/or nonanalog fractions, and/or heavy gasoline fractions and their subsequent mixing and contacting with the catalyst;

the use of zeolites with structure of ZSM-11;

the possibility of conducting the process in an environment of hydrogen containing gas.

The main advantages of the proposed method are:

a smaller amount of catalyst required for processing a unit mass of raw materials;

large outputs and large octane gasoline fractions;

the possibility of processing of hydrocarbon raw materials of different types.

The materiality of the proposed method and the achieved effect is confirmed by the given examples.

P R I m e R 1 prototype. The catalytic cracking gasoline with oktay 82aboutAnd with 97 PTS THEM and 68.1 wt. (63.) fractions WITH7+with initial boiling point 82aboutWith PTS 90,7 THEM. Fraction WITH7+put communication at the reaction temperature of 373aboutC, a pressure of 3.5 MPa and space velocity of the liquid raw material 1,3 h-1with the catalyst of the zeolite H-ZSM-5. In the contact is formed (wt. on FR. WITH7+): 0,9% of hydrocarbon gases WITH1-C3and 98.8% of the liquid fraction WITH4+(i.e., including liquefied butane) with PTS 93,2 THEM, which is mixed with a fraction WITH the6-to obtain the desired gasoline fraction with PTS 93,3 THEM and with access to the raw materials of 99.1 about.

P R I m e R s 2-5. Similar to example 1. Model hydrocarbon fraction 36-170aboutC containing 60 wt. n-paraffins (C55, P615, P820, WITH920), 20% isoparaffins (isooctane), 20% aromatic (C715, P95) and with the estimated octane number OCp34 MM, share with the allocation of 20 wt. fractions WITH6-(FR. 36-72aboutWith PTSp35 MM) and 80% fraction 72-170aboutC. Fraction 72-170aboutTo put communication at the reaction temperature Tp, the pressure P and the mass feed rate of the raw material g with a catalyst containing 70 wt. the zeolite with structure of ZSM-5 composition of 0.03 Na2O Al26-isolated from raw material to obtain the target product. Necessary for the digestion process unit weight of raw material quantity of catalyst (W) is 0.4 kg of catalyst/kg of raw material. The process conditions, the yields of products contact (raw contact), and outputs OCHptarget gasoline fractions are given in table.1.

Examples 6-21 illustrate the proposed method.

P R I m e R s 6-7. Model hydrocarbon fraction 36-170aboutC containing 60 wt. n-paraffins (C55; C615; C820; C9-20), 20% isoparaffins (isooctane), 20% aromatic (C715, P95) and with the estimated octane number OCp34 MM, is subjected to rectification with the allocation of 20 wt. octane and 20% of nonanalog fractions. The remaining fraction of the raw material (60 wt.) boils within 36-170aboutWith has a PTSp79 MM and contains 34 wt. n-paraffins, 33% isoparaffins and 33% aromatic hydrocarbons; octane fraction 95% boils in the range of 120-130aboutWith; 95% of nonanalog fraction boils in the range of 145-155aboutC. Octane and nonnovel faction smeshivayut g catalyst. Products contact share with the release of hydrocarbon gases and gasoline fraction (the composition of the liquid products and their estimated octane number given in the table. 2). The liquid fraction is mixed with the remaining fraction of the raw material to obtain the target product. The process conditions, the yields of products contact (raw contact), and outputs the estimated octane number of the target gasoline fractions are given in table.1. Used catalyst contains 70 wt. the zeolite with structure of ZSM-5, the composition of 0.03 Na2O Al2O30,3 Fe2O x 86SiO230% of Al2O3and modified 3% La3+. The amount of catalyst (W) required to support processing unit weight of raw material is W0,2 kg of catalyst/kg of raw material.

P R I m e R s 8,9. Similar to example 6. Model hydrocarbon fraction of the composition and properties shown in example 6, is subjected to rectification with allocation of 15 wt. hexane, 20% octane and 20% of nonanalog fractions. The remaining fraction of the raw material (45 wt.) boils within 36-170aboutWith has a PTSp97 MM and contains 12 wt. n-paraffins, 44% isoparaffins and 44% aromatic hydrocarbons; hexane fraction 95% boils in the range of 65-75aboutC; 95% octane fraction WoW and nonnovel fractions are mixed and subjected to contacting with the reaction temperature Tp, the pressure P and the mass feed rate of the raw material g with the catalyst of example 6. The reaction products separated with the separation of hydrocarbon gases and liquid gasoline fraction, which is mixed with the remaining raw material fraction to obtain the target gas. The process conditions, the yields of products contact (raw contact), and outputs the estimated octane number of the target gasoline fractions are given in table.1, the compositions and OCHpliquid products contact are given in table. 2. The amount of catalyst W required for the refining process unit weight of raw material is W 0,23 kg catalyst/kg of raw material.

P R I m e R s 10, 11. As raw materials use of model hydrocarbon fraction 36-115aboutC containing 60 wt. n-paraffins (C510;620; C730), 30% isoparaffins (2,2-dimethylpentan), 10% aromatic (toluene) and with the estimated octane number OCp50 MM. In example 10 the feedstock is subjected to rectification with the allocation of 20 wt. hexane fraction, 90% wikipeida in the range of 65-75aboutWith; the remaining fraction of the raw material (80 wt.) boils within 36-115aboutWith and has a PTSp55 MM. In example 11 the feedstock is subjected to rectification with fidelipac within 36-115aboutWith and has a PTSp71 MM. Isolated from raw material fraction is subjected to contacting with Tp380aboutS, the pressure P Of 1.5 MPa and mass feed rate of the raw material g 2 h-1with the catalyst in the presence of hydrogen, the molar ratio of H2/CH 10. The reaction products separated with the separation of hydrocarbon gases and liquid gasoline fraction. The obtained gasoline fraction is mixed with the remaining fraction of the raw material to obtain the target product. The used catalyst contains 40 wt. Al2O3and 60% of ZSM-5 composition of 0.02 Na2O Al2O30,3 Ga2O30,1 Fe2O388SiO2. The process conditions, the yields of products of probe and target products, the estimated octane number of gasoline fractions are given in table.1. The composition of liquid products contact their VERYpare given in table.3. The amount of catalyst required for processing the unit weight of raw material is 0.1 and 0.15 kg of catalyst/kg of raw material, respectively, in examples 10 and 11.

P R I m e R s 12-14. Model hydrocarbon fraction of the composition and properties shown in example 10, is subjected to rectification with the allocation of 20 wt. hexane fraction and 30% heptane fractions. The remaining practicable 65-75aboutC; heptane fraction at 90% boils in the range of 95-105aboutC. Hexane and heptane fractions are mixed and subjected to contacting with the reaction temperature Tp, the pressure P and the mass feed rate of the raw material g with a catalyst in the presence of hydrogen molar ratio of H2/CH 10. The reaction products separated with the separation of hydrocarbon gases and liquid gasoline fraction. Selected products from contacting the gasoline fraction is mixed with the remaining raw material fraction to obtain the target product of high-octane gasoline fraction. The conditions of the process, the number of used catalysts, the yields of products of probe and target products, the estimated octane number of gasoline fractions are given in table. 1, the compositions of the catalysts in table.2. The composition of liquid products contact and Ipare given in table.3. The amount of catalyst required to process a unit mass of feedstock, catalyst is 0.25/kg of raw material.

P R I m e R s 15, 16. Model hydrocarbon fraction 36-170aboutWith containing 65 wt. n-paraffins (C55; C615; C710;820; C915), 15% isoparaffins (isooctane), 20% aromatic (C7p62 MM and boils in the range 36-145aboutC; hexane fraction at 90% boils in the range of 65-75aboutC; octane fraction 90% boils in the range of 120-130aboutWith; heavy gasoline fraction boils in the range of 135-170aboutWith 90% fraction boils above 145aboutC. Hexane, octane and heavy gasoline fractions are mixed and subjected to contacting with the reaction temperature Tp, the pressure P and the mass feed rate of the raw material g with a catalyst in the presence of hydrogen, the molar ratio of H2/CH10. Products contact share with the release of hydrocarbon gases and gasoline fractions. The gasoline fraction is mixed with the remaining fraction of raw materials to produce the target product of high-octane gasoline fraction. The process conditions are given in table.1, the compositions of the catalysts in table.2, the composition of liquid products in the table.3.

P R I m e R s 17, 18. Model hydrocarbon fraction 36-170aboutC containing 60 wt. n-paraffins (C55; C615; C820; C920), 20% isoparaffins (isooctane), 20% aromatic (C715, P95) and with the estimated octane number OCRaboutWith has a PTSp96 MM and contains 13 wt. n-paraffins, 50% isoparaffins and 37% aromatic hydrocarbons; hexane fraction at 90% boils in the range of 65-75aboutWith; heavy gasoline fraction boils in the range of 120-170aboutWith 95% fraction boils above 120aboutC. Hexane and heavy gasoline fractions are mixed and subjected to contacting with the catalyst at the reaction temperature Tp, the pressure P and the mass feed rate of the raw material g. Products contact share with the release of hydrocarbon gases and gasoline fraction (the composition of the liquid products and their estimated octane number given in the table. 3). The liquid fraction is mixed with the remaining fraction of the raw material to obtain the target product. The process conditions, the compositions of the catalysts, the yields of products contact (raw contact), and outputs the estimated octane number of the target gasoline fractions are given in table.1.

P R I m e R 19. Similar to example 6. The raffinate process of reforming hydrocarbon fraction 35-150aboutWith PTSp63 MM, composition is shown in table.4, is subjected to rectification with the release of 19.7 wt. hexane fraction and 13.8% heptane fractions. The remaining fraction of the raw material to 66.5 wt.) has estimated octane is no within 60-85aboutWith 50% fraction boils in the range of 65-75aboutC; heptane fraction is OCHp31 MM and boils in the range 90-115aboutWith 50% fraction boils in the range of 95-105aboutWith; the fractions are given in table.4. Hexane and heptane fractions are mixed and subjected to contacting with Tp420aboutC, P 1 MPa and g 3,0 h-1with catalyst. The reaction products separated with the separation of hydrocarbon gases and liquid gasoline fraction (56,8% and 43.2% respectively for raw materials contact). The liquid fraction having OCHp86 MM, mixed with the remaining fraction of raw materials and production of 80.9% (the raw material) of the target product gasoline-OCHp76 MM. Used catalyst contains 70 wt. the zeolite with structure of ZSM-11, composition of 0.3 Na2O Al2O3x x120SiO230% Al2O3and modified with 0.1% Pdo. The compositions provided, and the obtained fractions are given in table.4.

P R I m e R s 20-21. Analogous to example 17. The raffinate process of reforming hydrocarbon fraction 35-150aboutWith PTSp63 MM, composition is shown in table.5, is subjected to rectification with the release of 19.7 wt. hexane fraction and 25.7% of the heavy gasoline fraction. The remaining fraction of the raw material (54,6%) PTSaboutWith; heavy gasoline fraction is OCHp54 MM and boils in the range 85-150aboutWith 70% fraction boils above 95aboutWith; the fractions are given in table.5. Hexane and heavy gasoline fractions are mixed and subjected to contacting with the reaction temperature Tp, the pressure P and the mass feed rate g catalyst. The reaction products separated with the separation of hydrocarbon gases and liquid gasoline fraction. The liquid fraction is mixed with the remaining fraction of raw materials to produce the target product of high-octane gasoline fraction. The process conditions, catalysts, outputs, products, contact, and outputs the estimated octane number of the target gasoline fractions are given in table.1, the compositions of the catalysts in table.2. The compositions of the obtained fractions and target products are shown in table.5.

Thus from the above examples and data tables, it follows that in case of realization of the proposed method may receive gasoline fractions (for the same output compared to the prototype) with large octane numbers (3-5 points) than the prototype (see examples 2 and 6; 3 and 7; 4 and 8; 5 and 9). When receiving gasoline fractions with the same octane numbers of the enemy, necessary for processing a unit mass of feedstock, 1.7-2 times or more lower than in the case of the implementation process similar to the prototype (see examples 2-5 and 6-9). An additional advantage of the proposed method is that when receiving gasoline fractions with the same octane numbers offered by way possible the implementation process at lower reaction temperatures than similar prototype (see examples 5 and 8).

1. METHOD of producing high OCTANE GASOLINE FRACTIONS from wikipaedia in the temperature range of the gasoline boiling hydrocarbons by distillation with the release of factions, contact the latter at elevated temperature and pressure with a catalyst based on zeolite ZSM, including ZSM=5, including modified elements II, VI and VIII groups, with subsequent separation of the products of the contacting gas and liquid, mixing the liquid ingredients with the remaining fraction of the raw material, characterized in that during the distillation of the feedstock is isolated and/or hexane and/or heptane, and/or octane, and/or nonanoyl, and/or heavy gasoline fraction with subsequent mixing of the selected fractions and direction for contacting hexane, heptane, octane and nonnovel faction, wikipaedia not less than about 50. accordingly, in the intervals of temperatures 65-75, 95-105, 120-130, 145-150oWith a heavy gasoline fraction, wikipaedia not less than about 75. at temperatures above or 95 or 120 or 145oC.

3. The method according to p. 1, characterized in that the use of catalyst based on zeolite ZSM=11.

4. The method according to p. 1, wherein the used catalyst modified with elements I, III, IV and V groups.

5. The method according to p. 1, characterized in that the contacting is carried out at a temperature of 300-480oC and a pressure of 0.2 to 4.0 MPa.

6. The method according to p. 1, characterized in that the contacting is carried out in an environment of hydrogen containing gas.

 

Same patents:

The invention relates to catalytic reforming, in particular the elevation of gasoline over zeolite catalysts, and can be used in refining and petrochemical industries

The invention relates to methods for preparing catalysts for reforming of gasoline fractions and can be used at the enterprises of chemical, oil-refining and petrochemical industry

The invention relates to the refining industry, namely the technology of catalytic reforming

The invention relates to a catalytic process for the production of unleaded high-octane gasoline fractions of hydrocarbons in the environment of the hydrogen-containing gas

The invention relates to methods of producing unleaded high-octane gasoline fractions and aromatic hydrocarbons from hydrocarbon feedstock, wikipaedia in the temperature range of boiling gasoline

The invention relates to methods of producing unleaded high-octane gasoline fractions from hydrocarbon material, wikipaedia in the temperature range of boiling gasoline

The invention relates to a catalyst for reforming of gasoline fractions and can be used at the enterprises of oil refining and petrochemical industries

FIELD: petrochemical processes.

SUBSTANCE: high-octane fuels and propane-butane fraction are obtained via conversion of hydrocarbon feedstock on contact with hot catalyst placed in reactor, into which diluting gas is supplied at elevated pressure. Catalyst is Pentasil-type zeolite with general formula xM2/nO,xAl2O3,ySiO2,zMe2/mO wherein M represents hydrogen and/or metal cation, Me group II or VII metal, n is M cation valence, m is Me metal valence, x, y, z are numbers of moles of Al2O3, SiO2, and Me2/mO, respectively, and y/x and y/z ratios lie within a range of 5 to 1000. Metal oxide Me2/mO is formed during calcination, in presence of oxygen, of Me-containing insoluble compound obtained in zeolite reaction mixture.

EFFECT: increased octane number of gasoline fractions with propane-butane fraction as chief component of gas products, and prolonged inter-regeneration time of catalyst.

11 cl, 4 dwg, 3 tbl, 16 ex

FIELD: petroleum processing and petrochemistry.

SUBSTANCE: hydrocarbon feed is converted in presence of porous catalyst at 250-500°C and pressure not higher than 2.5 MPa, feed uptake being not higher than 10 h-1. Hydrocarbon feed utilized are various-origin hydrocarbon distillates with dry point not higher than 400°C. Catalyst is selected from various aluminosilicate-type zeolites, gallosilicates, galloaluminosilicate, ferrosilicates, ferroaluminosilicates, chromosilicates, and chromoaluminosilicates with different elements incorporated into structure in synthesis stage. Resulting C1-C5-hydrocarbons are separated from gasoline and diesel fuel in separator and passed to second reactor filled with porous catalyst, wherein C1-C5-hydrocarbons are converted into concentrate of aromatic hydrocarbons with summary content of aromatics at least 95 wt %. In other embodiments of invention, products leaving second reactor are separated into gas and high-octane fraction. The latter is combined with straight-run gasoline fraction distilled from initial hydrocarbon feedstock.

EFFECT: increased average production of liquid products.

18 cl, 3 dwg, 9 ex

FIELD: petroleum processing and petrochemistry.

SUBSTANCE: invention relates to catalysts for isomerization of paraffins and alkylation of unsaturated and aromatic hydrocarbons contained in hydrocarbon stock. Catalyst of invention is characterized by that it lowers content of benzene and unsaturated hydrocarbons in gasoline fractions in above isomerization and alkylation process executed in presence of methanol and catalyst based on high-silica ZSM-5-type zeolite containing: 60.0-80.0% of iron-alumino-silicate with ZSM-5-type structure and silica ratio SiO2/Al2O3 = 20-160 and ratio SiO2/Fe2O3 = 30-550; 0.1-10.0% of modifying component selected from at least one of following metal oxides: copper, zinc, nickel, gallium, lanthanum, cerium, and rhenium; 0.5-5.0% of reinforcing additive: boron oxide, phosphorus oxide, or mixture thereof; the rest being alumina. Preparation of catalyst includes following steps: hydrothermal crystallization of reaction mixture at 120-180°C during 1 to 6 days, said reaction mixture being composed of precursors of silica, alumina, iron oxide, alkali metal oxide, hexamethylenediamine, and water; conversion of thus obtained iron-alumino-silicate into H-iron-alumino-silicate; further impregnation of iron-alumino-silicate with modifying metal compound followed by drying operation for 2 to 12 h at 110°C; mixing of dried material with reinforcing additive, with binder; mechanochemical treatment on vibrating mill for 4 to 72 h; molding catalyst paste; drying it for 0.1 to 24 h at 100-110°C; and calcination at 550-600°C for 0.1 to 24 h. Lowering of content of benzene and unsaturated hydrocarbons in gasoline fractions in presence of above catalyst is achieved during isomerization and alkylation of hydrocarbon feedstock carried out at 300-500°C, volumetric feedstock supply rate 2-4 h-1, weight ratio of hydrocarbon feedstock to methanol 1:(0.1-0.3), and pressure 0.1 to 1.5 MPa. In particular, hydrocarbon feedstock utilized is fraction 35-230°C of hydrostabilized liquid products of pyrolysis.

EFFECT: facilitated reduction of benzene and unsaturated hydrocarbons in gasoline fractions and other hydrocarbon fuel mixtures.

3 cl, 1 tbl, 13 ex

FIELD: petrochemical processes.

SUBSTANCE: feedstock is brought into contact with catalyst based on Pentasil family zeolite in at least two zones differing from each other in conditions of conversion of aliphatic hydrocarbons into aromatic hydrocarbons, first in low-temperature conversion zone to covert more active feedstock components to produce aromatic hydrocarbons containing product followed by recovering C5+-hydrocarbons therefrom and, then, contacting the rest of hydrocarbons produced in low-temperature conversion zone with catalyst in high-temperature conversion zone, wherein less active component(s) is converted into aromatic hydrocarbons containing product followed by recovering C5+-hydrocarbons therefrom.

EFFECT: enabled production of aromatic hydrocarbons under optimal conditions from feedstock containing aliphatic C1-C4-hydrocarbons with no necessity of separating the latter.

4 cl, 1 dwg, 1 tbl

FIELD: petrochemical processes.

SUBSTANCE: hydrocarbon feedstock, containing narrow and wide hydrocarbon fractions boiling within a range from boiling point to 205°C and C1-C4-alcohols and/or dimethyl ether, which are blended in a system, to which they are supplied separately (by two pumps) at volume ratio (20.0-90.0):(10-80), respectively, is brought into contact with zeolite-containing catalyst at 380-420°C, pressure 0.2-5.0 MPa, and liquid feedstock volume flow rate 0.5-2.0·h-1, whereupon reaction products are liberated from water produced in the reaction. Above-mentioned zeolite-containing catalyst is comprised of (i) Pentasil-type zeolite with silica ratio (SiO2/Al2O3) 25-100 in amount 65-70% including residual amount of sodium ions equivalent to 0.05-0.1% sodium oxide, (ii) modifiers: zinc oxide (0.5-3.0%), rare-earth element oxides (0.1-3.0%), cobalt oxide (0.05-2.5%) or copper chromite (0.1-0.3%), and (iii) binder: alumina or silica in balancing amount.

EFFECT: increased octane number of gasoline.

2 tbl, 9 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: petrochemical processes and catalysts.

SUBSTANCE: invention provides isodewaxing catalyst for petroleum fractions containing supported platinum and modifiers wherein supporting carrier is fine powdered high-purity alumina mixed with zeolite ZSM 5 in H form having SiO2/Al2O3 molar ratio 25-80 or with zeolite BETA in H form having SiO2/Al2O3 molar ratio 25-40 at following proportions of components, wt %: platinum 0.15-0.60, alumina 58.61-89.43, zeolite 5-40, tungsten oxide (modifier) 1-4, and indium oxide (modifier) 0.24-0.97. Preparation of catalyst comprises preparing carrier using method of competitive impregnation from common solution of platinum-hydrochloric, acetic, and hydrochloric acids followed by drying and calcinations, wherein carrier is prepared by gelation of fine powdered high-purity alumina with the aid of 3-15% nitric acid solution followed by consecutive addition of silicotungstenic acid solution and indium chloride solution, and then zeolite ZSM 5 in H form having SiO2/Al2O3 molar ratio 25-80 or with zeolite BETA in H form having SiO2/Al2O3 molar ratio 25-40.

EFFECT: increased yield of isoparaffin hydrocarbons.

7 cl, 2 tbl, 7 ex

FIELD: CHEMISTRY.

SUBSTANCE: zeolite catalyst for process of conversion of straight-run gasoline to high-octane number component is described. The said catalyst contains high-silica zeolite with SiO2/Al2O3=60 and residual content of Na2О of 0.02 wt.% maximum, metal-modified, Pt, Ni, Zn or Fe metals being in nanopowder form. Content of the said metals in the catalyst is 1.5 wt.% maximum. Method to manufacture zeolite catalyst for conversion of straight-run gasoline to high-octane number component is described. The said method implies metal modification of zeolite, Pt, Ni, Zn or Fe metals being added to zeolite as nanopowders, produced by electric explosion of metal wire in argon, by dry pebble mixing in air at room temperature. Method to convert straight-run gasoline using the said catalyst is also described.

EFFECT: increase in catalyst activity and gasoline octane number, accompanied by increase in yield.

4 cl, 3 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: invention describes zeolite-containing catalyst for transformation of aliphatic hydrocarbons C2-C12 to a mix of aromatic hydrocarbons or high-octane gasoline component containing zeolite ZSM-5 with silicate module SiO2/Al2O3=60-80 mol/mol and 0.02-0.05 wt % of residual sodium oxide content, zeolite structural element, promoter and binding component, with zirconium or zirconium and nickel oxides as zeolite structural component, and zinc oxide as promoter, at the following component ratio (wt %): zeolite 65.00-80.00; ZrO2 1.59-4.00; NiO 0-1.00; ZnO 0-5.00; Na2O 0.02-0.05, the rest being binding component. Also, a method for obtaining zeolite-containing catalyst is described, which involves mixing reagents, hydrothermal synthesis, flushing, drying and calcinations of sediment. The reaction mix of water solutions of aluminum, zirconium and nickel salts, sodium hydroxide, silicagel and/or aqueous silicate acid, inoculating zeolite crystals with ZSM-5 structure in Na or H-form, and structure-former, such as n-butanol, is placed in an autoclave, where hydrothermal synthesis is performed at 160-190°C for 10-20 hours with continuous stirring; the hydrothermal synthesis over, Na-form pulp of the zeolite is filtered; the obtained sediment is flushed with domestic water and transferred to salt ion exchange by processing by water ammonium chloride solution with heating and stirring of the pulp; the pulp obtained from salt ion exchange is filtered and flushed with demineralised water with residual sodium oxide content of 0.02-0.05 wt % on the basis of dried and calcinated product; flushed sediment of ammonium zeolite form proceeds to zinc promoter introduction and preparation of catalyst mass by mixing of ammonium zeolite form modified by zinc and active aluminum hydroxide; obtained catalyst mass is extruded and granulated; the granules are dried at 100-110°C and calcinated at 550-650°C; calcinated granules of zeolite-containing catalyst are sorted, ready fraction of zeolite-containing catalyst is separated, while the granule fraction under 2.5 mm is milled into homogenous powder and returned to the stage of catalyst mass preparation. The invention also describes method of transformation of aliphatic hydrocarbons to high-octane gasoline component or a mix of aromatic hydrocarbons (variants), involving heating and passing raw material (gasoline oil fraction direct sublimation vapours or gas mix of saturated C2-C4 hydrocarbons) through stationary layer of the aforesaid catalyst.

EFFECT: reduced number of components and synthesis stages of zeolite-containing catalyst; increased transformation degree of raw material; improved quality and yield of target products with the said catalyst.

4 cl, 8 tbl, 12 ex

FIELD: chemistry.

SUBSTANCE: invention refers to production method of high-octane gasoline fractions and/or aromatic hydrocarbons C6-C10 as follows, hydrocarbon materials is heated, evaporated and overheated to process temperature, thereafter providing its contact at temperature 320-480°C and excess pressure with periodically recyclable catalyst containing zeolite of composition ZSM-5 or ZSM-11. Then it is cooled. Contact products are partially condensed, separated into gaseous and liquid fractions by separation. Liquid products of separation are supplied as power primarily to the first distillation column for separation of hydrocarbon gases and liquid stable fraction. The latter is supplied to the second distillation column for separation of high-octane gasoline fraction, or aromatic hydrocarbon fraction, and heavy charge fraction. Gaseous fraction resulted from separation of contact products is supplied to the first distillation column, specifically to intermediate section between infeed and external reflux inlet. External reflux is liquid distillate of the first distillation column.

EFFECT: reduction of power inputs, i.e. quantities of heat and cooling agent, required for reaction products separation.

5 cl, 2 ex

Up!