High-octane gasoline production process

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

 

The invention relates to the field of organic chemistry and catalysis, particularly to a method of joint processing of low-octane hydrocarbon fractions and various oxygen-containing organic compounds (alcohols C1-C4and/or DME) with a one-stage high-octane motor fuels.

Due to the strict requirements of the benzene content in automotive fuels important task is the search for new ways method catalytic sweetening straight-run gasoline.

Currently, catalytic reforming of gasoline is the most important process of modern refining and petrochemicals as a method of catalytic sweetening straight-run gasoline. It serves simultaneously for basic component of high-octane gasoline, aromatic hydrocarbons, raw material for petrochemical synthesis - and hydrogen-containing gas.

There is a method of transformation of aliphatic hydrocarbon, C2-C12in a high-octane component of motor gasoline with an octane rating of at least 76 points by the motor method or in a concentrate of aromatic hydrocarbons by contacting them with a catalyst containing a group zeolite with silica module SiO2/Al2About3=20-80 and residual contents of Na2O not bol is e 0.2 wt.%, a binder component, the oxides of zinc and rare earth metals as promoters, characterized in that the catalyst additionally contains P2O5and as the oxide of rare earth metal is used, two or more oxides of rare earth elements (CeO2La2O3Nd2About3Pr2O3etc. at the following content, wt.%:

Zeolite50-75
ZnO0,5-3,0
Sum(REE)2O30,5-3,0
P2O50,5-2,0
A binder componentRest

The method is carried out at a temperature 280-550°C, a pressure of 0.2 to 2.0 MPa, the space velocity of the raw material of 0.5-5.0 h-1(RF application No. 96103318).

From the patent of the Russian Federation No. 2181750 a method of refining petroleum distillates to gasoline fraction with an end boiling point not higher than 195°C and octane rating below 80 by the motor method. The method consists in converting hydrocarbons in the presence of porous catalyst at a temperature of 250-500°C, a pressure of not more than 2 MPa, the mass expense of a mixture of hydrocarbons of not more than 10 h-1. As raw materials use of petroleum distillates with end boiling point 200-400°C, and as the catalyst is used or zeolite aluminosilicate composition with a molar ratio of SiO 2/Al2O3not more than 450 selected from a number of ZSM-5, ZSM-11, ZSM-35, ZSM-38, ZSM-48, BETA, or gallosilikata, haloaluminate, gelatoria, telesolutions, prosilica, chromalusion with the structure of ZSM-5, ZSM-11, ZSM-35, ZSM-38, ZSM-48, BETA, or lumotast structure type ARO-5, ARO-11, ARO-31, ARO-41, ARO-36, ARO-37, ARO-40 entered in the structure at the stage of synthesis of element selected from a number of: magnesium, zinc, gallium, manganese, iron, silicon, cobalt, cadmium. The technical result is a simplification of the technology and increase the yield of target products.

A significant drawback of the above methods is the high content of benzene (5-10%) in the composition of gasolines produced.

From the application of the Russian Federation No. 99124152 a method of obtaining high-octane additive component of gasoline at acidic heterogeneous catalyst from registereda gasoline fractions by etherification methanol, wherein the process is conducted in a single or a twin node at a temperature of 60-120°C, a pressure of 0.05-1.0 MPa, the space velocity of the mixture of methanol and gasoline 0.5 to 10 h-1the mass ratio of methanol: source gas 1:12-1:40 on the trail catalysts of type KU-PPP, KU-23 or KU-2-8 emergency or similar trail catalysts in N-form with the degree of etherification not less than 70% with the addition in the final product anticyclic is I not more than 0.2 wt.%. As raw materials for etherification is a gasoline fraction following hydrocarbon composition, wt.%: olefins, C4+- 28-64, aromatic C6+- 5-35, naphthenes, C5+- 9-21, paraffins C5+- 5-26.

The disadvantage of this method is complicated instrumentation process and that the final product has an octane number of only 2-5 points higher than the original gasoline fraction.

Known methods for producing gasoline directly from methanol. Thus, in the patent of Russian Federation №1153501 the conversion of methanol is carried out in a reactor at 410-430°C, the pressure 0.6-0.8mpa on containing zeolite ZSM catalyst with a binder - gamma-Al2About3. In the method provided by the cooling of products, condensation and separation of their emitting gas reforming of methanol, water and target products and recycling the cooled gases conversion of methanol into the reactor. The process is carried out in a reactor having 2-14 sequentially increased by 10-20% by volume of the reaction zone, alternating with zones filled with an inert material, which serves circulating gas in amounts increasing from zone to zone by 10-20%, with decreasing space velocity of the raw materials and reaction products from zone to zone by 10-30%.

In U.S. patent No. 5191142 and No. 5602289 described process technology MTG (methanol to gasoline), embedded technology Mobil n the plant in New Zealand. Processed mixture of methanol and olefins C2-C3. The presence of methanol in the reaction mixture can increase the activity and selectivity in the reaction of formation of gasoline and olefins to C12and the service life of the catalyst. Increased activity in the presence of methanol allows the use of process catalysts based on zeolites Y and amorphous aluminosilicates.

Disadvantages of the process is that MTG catalysts are very sensitive to the presence of water in methanol and the reaction temperature (at low temperatures have low activity at high temperatures is their decontamination). High capital and operational costs due to problems associated with heat balances at the facility.

Known methods for producing high-octane gasoline fractions by catalytic conversion of low-octane fractions in the mixture of oxygenated organic compounds (alcohols, ethers).

Thus, in particular, from the patent of the Russian Federation 2078792 a method of obtaining high-octane gasoline, which consists in the fact that straight-run gasoline fraction NC-160°C is subjected to Hydrotreating and then fractionation to obtain fractions NK-85°C and MK-85°C-QC fraction MK-85°C is subjected to isomerization with the formation of the isomerized product, and the fraction of NC-85°C-CC ACC is Laut catalytic reforming, then 10-40% gasoline catalytic reforming is subjected to fractionation to obtain a fraction of gasoline catalytic reforming, wikipeida in the range of 110°C-QC, and the target product is obtained by mixing fractions of gasoline catalytic reforming 110°C-QC, catalytic reforming of gasoline, alkylate and the isomerized product in the ratio, wt.%: 15-40, 15-40, 5-15, respectively. Moreover, the Hydrotreating straight-run gasoline fraction NK°C is carried out at a temperature of 330-380°C, the pressure of 3.3 to 3.7 MPa in the presence of nitelivebingo catalyst. Isomerization fraction MK-85°C is carried out at a temperature of 250-280°C, a pressure of 2.5-2.8 MPa in the presence of aluminium oxide-platinum catalyst. Also offered in some cases to a target product to be 1-15% wt.% ethers of alcohols C1-C5or mixtures thereof with lower alcohols C1-4. The data of the known method are the high-octane gasoline a-95 and a-98, however, this method is quite complicated technologically.

Known another way of producing high octane gasoline fractions and/or aromatic hydrocarbons by processing low-octane hydrocarbon fractions, wikipaedia in the temperature range 35-200°C. increasing the yield of high octane gasoline fractions and the reduction of energy consumption is achieved by the catalytic processing of the bottom of octanoic hydrocarbon fractions in mixtures with olefins, and/or alcohols and/or ethers, components of 5-20 wt.% from the amount fed to the catalyst of low-octane hydrocarbon fractions by the way Zeoforming, namely zeolite (elementobject) catalysts at temperatures 340-480°C, a pressure of 0.1-2.0 MPa and space velocity of the raw material 0,5-4,0 h-1(RF patent 2103322).

Also known is a method of obtaining high-octane gasoline fractions and/or aromatic hydrocarbons, C6-C10from a hydrocarbon feedstock by contacting the stream of feedstock at elevated temperature and pressure with a catalyst;

The catalyst containing the silicate composition (0,02-0,32)Na2O Al2About3(0,003-2,4) ΣenAboutm(28-212)SiO2where ΣenAboutm- one or two oxide elements II, III, V, VI, VIII groups of the periodic system, or zeolite type pentasil with the structure of ZSM-5 or ZSM-11 having the composition described by the General empirical formula (0,02-0,32) Na2O e2O3(28-212) SiO2kH2Oh, where e is at least one element of a number of Al, Ga, In, Fe, a k is the corresponding coefficient of moisture content, use of hydrocarbon raw material containing the arena, and/or naphthenes, and/or olefins and/or paraffins, wikipaedia up to 250°C and/or oxygen-containing organic compounds, the stage contacting of the feedstock with the catalyst is carried out sequentially on m is Nisha least two reaction zones in a single reactor device or at least two reactors, with a supply or dissipation intermediate reaction flow between zones, and the temperature of the flow at the entrance to each subsequent downstream feed reaction zone at 5-50°C lower than the reaction temperature in each of the preceding reaction zone, cooling, condensation, separation and distillation products contact in the respective process apparatuses emitting fractions of hydrocarbon gases, fractions, wikipeida above 185-215°C, gasoline fractions and/or aromatic hydrocarbons, at this stage of the oxidative regeneration of the catalyst is carried out at elevated temperature initially regenerating gas with low oxygen content, and then with a higher concentration of oxygen. When this process is carried out at a temperature 300-480°C, a pressure of 0.1 to 6.0 MPa and a mass flow rate of feed of 0.3-10 h-1and regeneration of the catalyst is carried out at a temperature of 350-550°C and a pressure of 0.1 to 6.0 MPa initially regenerating gas with an oxygen content of 0.1 to 5.0 vol.%, and then with oxygen 10-21% vol. (RF application 2001124533).

This known method is technologically complex.

The closest analogue of the proposed method of obtaining high-octane gasoline is patent RF №2163623. Low-octane gasoline fraction is subjected to reforming in prisutstvie - or diatomic alcohols, taken in an amount of 0.2-5.0 wt.%. The catalyst of the process is a mechanical mixture of two catalysts, the zeolite catalyst C-10 and allocable(Nickel)-molybdenum oxide catalyst. You can use alumapro(tungsten)new catalysts modified with fenilalanina. The process is carried out at 460-510°C and flow rate of feed of 0.3-0.9 h-1. Adding alcohols to the low-octane gasoline is achieved by increasing the yield of the target product, the octane number and reduce gassing.

The disadvantage of this method is the high process temperature and low volumetric feed rate. In addition, there is a high sensitivity oxide catalyst to sulfur-containing impurities (sulfur content is limited to 27 ppm). The process for sulfur-containing raw materials is possible only in the presence of hydrogen, while its content in the raw material mixture must not exceed 0.1 mol.%.

In addition, a disadvantage of this known method is that the raw material for his serve narrow gasoline fraction, wikipaedia within 85-180°C. Processing of light hydrocarbons (pentane-hexane and Nicholas -85°C fractions) leads to intensive gas. The higher end of the boil helps coxworthy and therefore undesirable.

the technical task, solved by the present invention is to develop a new method of joint processing of hydrocarbon fractions and oxygen-containing organic compounds with the aim of obtaining high-octane gasoline in one stage, and the production of motor fuels with an octane rating of at 15-25 points higher than in the initial hydrocarbon fraction, in comparison with known methods is achieved by reducing the number of produced dry gas, and benzene content in the resulting gasoline does not exceed 1.5 wt.%.

The goal of the project is achieved in that in a method of producing high-octane gasoline by contacting a hydrocarbon feedstock comprising a hydrocarbon fraction and an oxygen-containing organic compounds with zeolite-containing catalyst at elevated temperature and pressure and subsequent separation (separation) of the reaction products (gasoline), as a carbon-containing raw material using narrow and wide hydrocarbon fraction, wikipaedia within NC to 205°C, and C1-C4- alcohol and/or dimethyl ether, which are mixed in the mixer at a separate submission (two pumps) and a volume ratio 20-90:80-10, as the zeolite-containing catalyst is a catalyst comprising the zeolite of type pentasil with silicate module SiO2/Al2O 3=25-100 in the number of 65-70 wt.% with a residual amount of sodium ions, equivalent to a content of 0.05-0.1 wt.% sodium oxide, modifiers - zinc oxide 0.5 to 3.0 wt.%, the oxides of rare earth elements is 0.1 to 5.0 wt.%, oxides of cobalt, 0.05 to 2.5 wt.% or chromite copper, 0.1 to 0.3 wt.%, the rest binder is alumina, the process of contacting is carried out at 380-420°C, a pressure of 0.2 to 5.0 MPa and space velocity of the liquid raw material is 0.5 to 2.0 h-1.

The present invention using a modified zeolite catalyst allows a high output to process different types of gasoline low-octane fuels (gas condensates, straight-run gasoline, pentane-hexane fraction) together with oxygen-containing organic compounds can be achieved increasing the octane number of fuels 15-25 points, when the content of benzene in gasoline is not higher than 1.5%.

A distinctive feature of the proposed method is that the raw material may be a mixture of hydrocarbon fractions (NK - 65°C, 65-85°C, 85-240°C or other limits boiling) and alcohols C1-C4or DME in a wide range of concentrations from 0 to 100%vol.

In the claimed method according to this invention is used, the catalyst used for the processing of DME in a high-octane component of motor fuels. It has the following composition, m is S.%: crystalline aluminosilicate, type pentasil with SiO2/Al2O3=25-100 in the number of 65-70%, with a residual amount of sodium ions, equivalent to a content of 0.05-0.1 wt.% sodium oxide; zinc oxide - 0,5-3,0%; oxides REE - 0.1 to 5.0%; oxide of cobalt, 0.05 to 2.5% and the rest binder is aluminum oxide or silicon oxide. Another variant of the catalyst instead of cobalt oxide contains chromite copper in an amount of 0.1-0.3 wt.%.

To achieve the specified result, it is proposed to use the following way to obtain high-octane gasoline. The hydrocarbon fraction is fed into the reaction zone in a mixture with oxygen-containing organic compounds (alcohols C1-C4or DME). The process is carried out in the presence of an aluminosilicate zeolite catalyst (type pentasil)simultaneously possessing activity in the reaction of aromatization and alkylation of benzene with olefins C2-C4formed in suti) during the conversion of alcohols.

As oxygen-containing organic compounds used alcohols are methanol, ethanol, propanol, butanol, DME, and mixtures thereof. A distinctive feature of the method is that the mixture of the hydrocarbon fraction with oxygen-containing organic compounds is carried out in a mixer with separate feeding of reagents two pumps; contacting the prepared emulsion with catalyst implementation is given at a volume ratio of hydrocarbon fraction/oxygenates, 0.2-30/1, and separation of the reaction products formed from the reaction of water is carried out in the separator. You can use the injector mixer with a rate of injection of 3.3 and 5.2. These differences help to improve the quality of alkylbenzene containing up to 45 wt.% aromatic hydrocarbons (benzene content up to 1.5%) and to increase the octane number of the original hydrocarbon fraction by 30-40 points.

The process is carried out at a temperature of 380-420°C, a pressure of 5-20 MPa and space velocity of the reaction mixture is 0.5 - 2 h-1.

It should be noted that in the case of mixtures with a volume ratio of hydrocarbon fraction/oxygenates = 20-90/80-10 there is no need for the mixer and the flow of the mixture in the reactor can be accomplished by a single pump, as is necessary mixing of the components.

Joint processing of low-octane gasoline hydrocarbons with alcohols simplifies the technology of processing of hydrocarbons, as in this case facilitates supply of heat to the endothermic process of refining hydrocarbon fractions due to the exothermic conversion of alcohols to olefins (or immediately in the gasoline), which reduces the energy consumption, leads to simplification of the reactor site and increases the yield of high octane gasoline by 3-5%. Exothermic heat effect of reaction 420-50 kcal/kg converted oxygen-containing compounds. The endothermic effect of the conversion of gas condensate feedstock 50-60 kcal/kg converted raw materials.

When using the proposed method increases the time mezhregionalnogo run with 240-320 hours to 400-500 hours compared to the reforming process. Produced gasoline for the same value of the octane number and a total content of aromatic compounds have a lower benzene content of 1.5 wt.%).

Using the proposed method of addition of alcohols prevents leakage of unwanted processes, such as poisoning of the catalyst containing sulfur compounds (hydrogen sulfide), and on the other hand helps to remove from the final product (high octane gasoline) parts of benzene during the reaction it is formed from alkylation of alcohols light olefins. In addition, in the process, there is a decrease in coke formation. In the proposed method, the conversion of oxygen-containing compounds for 1 pass is not less than 99,8%.

The invention is illustrated by the following examples without limiting it.

Examples 1-6. The catalyst comprising the zeolite of type pentasil with silicate module SiO2/Al2O3=55 in the amount of 68 wt.%, the sodium oxide of 0.1 wt.%, zinc oxide 2.0 wt.%, the oxides of rare earth elements to 1.0 wt.%, the cobalt oxide 1.5 wt.%, the rest binder is alumina, preparation, the config according to the patent of Russian Federation №2160161, experienced in the way of joint processing of hydrocarbon fractions and oxygen-containing organic compounds. The process was carried out by running the install with catalyst loading of 12 cm3at a temperature of 380-420°C, a pressure of 8 to 20 ATM and a space velocity of the mixture for 0.5-2 h-1. The raw material used mixtures of different hydrocarbon fractions (NK - 105°C OC=48,9; gas condensate with OC=60,0; straight-run gasoline with OC=49,6) and oxygenated compounds (methanol, DME, propanol and mixtures thereof). The composition of raw materials and final product are shown in table 1. Obtained in the course of the reaction gas to accumulate within 6 hours, and then chromatographic determine its composition.

Table 1 presents specific information on the conversion of various types of low-octane feedstock in the presence of certain oxygen-containing compounds and specific process conditions

Below to compare and justify that the technical results obtained at the expense of the totality of differences proposed in the present invention method of producing high-octane gasoline, examples 7-9.

Examples 7-9. The catalyst according to examples 1-6 were tested in the processing of hydrocarbon fractions. The process was carried out by running the install with catalyst loading of 12 cm3 at a temperature of 380-420°C, a pressure of 8 to 20 ATM and a space velocity of the mixture for 0.5-2 h-1. The raw material used the same hydrocarbon fractions, as in examples 1-6. The composition of raw materials and final product are shown in table 2.

Table 2 presents data on direct conversion of different types of the same low-octane hydrocarbons in the absence of additives oxygen-containing compounds.

Table 2
Example No.
789
Reaction conditions:

T°C


380


400


420
Pressure, MPa0,81,20,8
The volumetric rate of,0,51,02,0
h-1
Taken, vol.%:

FR-I NK - 105°C
100,0
The condensate100,0
Straight-run gasoline100,0
Total %100,0100,0100,0
The selectivity of the formation of liquid hydrocarbons, %71,567,263,6
The composition of the gasolineComposition, wt.%
Alkanes55,155,555,7
Alkenes0,90,20,3
Naphthenes15,0the 15.617,1
Aromatic-in,27,724,9
including29,03,33,2
benzenea 3.9
Total, %:100100100
The octane number on IM79,178,776,3

From the comparison of tables 1 and 2 shows (compare examples 2 and 7; 3, 4 and 8; No. 6 and 9 in tables 1 and 2, respectively), h is about during the process of the proposed method supplements the various oxygen-containing compounds to low-octane hydrocarbon feedstock under other equal process conditions (temperature, the pressure and volumetric feed rate) lead to increase the octane characteristics of the resulting gasoline, when the observed General increase in the concentration of aromatic hydrocarbons is significantly reduced benzene content in gasoline (from 3-4% to 0.5 to 1.5%).

In addition, in all cases, the addition of oxygen-containing compounds increases the selectivity of the formation of liquid hydrocarbons by reducing gassing during the recycling method proposed in the present invention. Eventually supplements oxygen-containing compounds increases the yield of high octane gasoline by 3-5%. It should also be noted that in the presence of oxygen-containing additives increases the stability of the catalyst used in this invention, apparently, the result of the interaction of water formed in the course of the proceeding reactions with the active centers of the catalyst. For example, when using the proposed method (example No. 3) time mezhregionalnogo mileage (in the mode of temperature rise of 10°C after 72 hours) is 400-410 hours, while during the processing of gas condensate (sample No. 8) - 240-260 hours. Simultaneously, a decrease of coke formation.

Thus, the comparison of the conversion of various feedstocks suggests that in the presence of saradapitha compounds (alcohols, DME) significantly improved performance of low-octane reforming process of hydrocarbons. Produced gasoline is more adapted to environmental requirements due to the significantly lower content of benzene that meets modern international standards. In some cases produced gasoline do not require compounding.

References

1. RF application No. 96103318: ZEOLITE-containing CATALYST AND METHOD for the CONVERSION of ALIPHATIC HYDROCARBONS, C2-C12IN A HIGH-OCTANE COMPONENT OF GASOLINE OR A CONCENTRATE OF AROMATIC HYDROCARBONS. Publication date: 10.01.1998. Registration application number: 96103318/04.

2. RF patent №2181750: a METHOD of PROCESSING PETROLEUM DISTILLATES (OPTIONS) publication date: 27.04.2002.

3. RF application No. 99124152: a method of OBTAINING a high-OCTANE ADDITIVE COMPONENT of MOTOR FUEL. Publication date: 10.09.2001. Registration application number: 99124152/04.

4. RF patent №1153501: METHOD for producing GASOLINE FROM METHANOL. Publication date: 27.09.1996. Registration application number: 3611414/04.

5. U.S. patent No. 5191142: Process for converting methanol to olefins or gasoline. Date of publication: March 2, 1993.

6. U.S. patent No. 5602289: Conversion of methanol to gasoline. Publication date: February 11, 1997.

7. RF patent №2078792: METHOD of producing high-OCTANE GASOLINE. Date of publication: 10.05.1997. Registration application number: 95112127/04.

8. RF patent №2103322: a METHOD of OBTAINING GASOLINE FRACTIONS AND AROMATIC HYDROCARBONS. Publication date: 27.01.1998.

Registration application number: 95117314/04.

9. RF application No. 2001124533: Method of producing high octane gasoline fractions and aromatic hydrocarbons (options). Publication date: 20.12.2003. Registration application number: 2001124533/04.

10. RF patent №2163623: a METHOD of PROCESSING low-octane GASOLINE FRACTIONS. Publication date: 27.02.2001. Registration application number: 2000116778/04.

Method of producing high octane gasoline by contacting a hydrocarbon feedstock comprising a hydrocarbon fraction and an oxygen-containing organic compounds with zeolite-containing catalyst at elevated temperature and pressure followed by the separation of the reaction products, characterized in that hydrocarbons using narrow and wide hydrocarbon fraction, wikipaedia within NC to 205°C, and C1-C4- alcohol and/or dimethyl ether, which are mixed in a system with separate feeding them (two pumps) and a volume ratio of their 20-90:80-10, as the zeolite catalyst using a catalyst comprising the zeolite of type pentasil with silicate module SiO2/Al2O3=25-100 in the number of 65-70 wt.% with a residual amount of sodium ions equivalent to the detention therein of 0.05-0.1 wt.% sodium oxide, modifiers - zinc oxide 0.5 to 3.0 wt.%, the oxides of rare earth elements, 0.1 to 3.0 wt.%, the cobalt oxide of 0.05-2.5 wt.% or chromite copper, 0.1 to 0.3 wt.%, the rest binder is aluminum oxide or silicon oxide, the process of contacting is carried out at 380-420°C, a pressure of 0.2 to 5.0 MPa and space velocity of the liquid raw material is 0.5 to 2.0 h-1.



 

Same patents:

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: 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.

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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.

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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

The invention relates to the technology of organic synthesis, namely, catalytic methods of processing of hydrocarbon raw materials to produce products, which can be used either directly as motor fuel or as a component of a fuel or as raw material for separation of aromatic hydrocarbons and a catalyst for the implementation of these methods

The invention relates to the refining and petrochemical industries, in particular to methods of producing catalysts for the conversion of aliphatic hydrocarbons2-C12in high-octane gasoline and/or aromatic hydrocarbons

The invention relates to the production of motor fuels to the one-step catalytic process for the production of high-octane gasoline and diesel fuels with low sulfur content of various hydrocarbon materials with a high content of chemically stable sulfur compounds

The invention relates to the refining and petrochemical industries, in particular to methods of producing catalysts for the conversion of aliphatic hydrocarbons WITH2-C12in high-octane gasoline and/or aromatic hydrocarbons

The invention relates to the refining and petrochemical industries and is dedicated to the creation of the catalysts used in the processing of aliphatic hydrocarbons in the concentrate of aromatic hydrocarbons or high-octane component of gasoline

The invention relates to a technology for environmentally friendly high-octane gasoline and can be used in the refining and petrochemical industry to improve low-octane hydrocarbons in the presence of contact of the composition consisting of zeolite catalysts

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

The invention relates to the refining and petrochemical industries, in particular to methods of producing catalysts for the conversion of aliphatic hydrocarbons2-C12in high-octane gasoline and/or aromatic hydrocarbons

The invention relates to the refining and petrochemical industries, in particular to methods of producing catalysts for the conversion of aliphatic hydrocarbons WITH2-C12in high-octane gasoline and/or aromatic hydrocarbons

The invention relates to methods of producing unleaded high-octane gasoline fractions with reduced benzene content and/or aromatic hydrocarbons WITH6-C10of hydrocarbons and/or oxygen-containing organic compounds

The invention relates to methods of producing unleaded high-octane gasoline fractions and/or aromatic hydrocarbons from hydrocarbon and/or oxygen-containing organic compounds

The invention relates to the production of motor fuels and can be used in refining and petrochemical industries

The invention relates to the field of oil refining and petrochemistry, namely the composition of the zeolite catalyst conversion on it, aliphatic hydrocarbons2- C12contained in the low-octane straight-run petroleum or gas condensate gasoline fractions, wide fraction of light hydrocarbons, petroleum or waste refinery paraffin and registergui gases, high-octane component of motor gasoline with an octane rating of at least 76 points by the motor method or in a concentrate of aromatic hydrocarbons in stationary or moving layer of granulated or pelletized catalyst

The invention relates to a catalyst and method for the conversion of hydrocarbons of aliphatic C2-C12in high-octane gasoline or concentrate of aromatic hydrocarbons

The invention relates to a hydrodewaxing catalysts straight-run petroleum or gas condensate fractions and how to use it

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

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