Catalyst for lowering content of benzene and unsaturated hydrocarbons in gasoline fractions, method for preparation thereof, and a method for lowering content of benzene and unsaturated hydrocarbons in gasoline fractions

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 a method for producing catalysts for the isomerization of paraffins and alkylation of unsaturated and aromatic hydrocarbons and a method of catalytic isomerization of paraffins and alkylation of unsaturated and aromatic hydrocarbons to obtain a gasoline fraction with reduced benzene content and unsaturated hydrocarbons.

The main industrial process of producing high octane gasoline and aromatic hydrocarbons is catalytic reforming of straight-run gasoline fractions, which is held at a temperature of 450-550°C, a pressure of 0.1 to 3.5 MPa and a hydrogen-containing gas.

The disadvantages of catalytic reforming process are the use of expensive platinum source of catalyst, the hydrogen-containing gas and a high content of benzene in the liquid products.

In connection with the tightening of requirements for environmental protection trademark high-octane gasoline should not contain antiknock additives based on tetraethyl lead and benzene content should be no more than 5-6 wt.%.

In an industrial process thermal pyrolysis of hydrocarbons along with lower olefins produce large quantities of liquid pyrolysis products, cha is in the surrounding area, the pyrolysis condensate fraction. Light pyrolysis condensate fraction in its fractional composition corresponds to the fractional composition of the gasoline fractions, however, the hydrocarbon composition of light pyrolysis condensate fraction contains a large number of olefins (15-20 wt.%), benzene (up to 30-35 wt.%) and alkenylamine hydrocarbons. To reduce the content of olefins, cycloolefins and alkenylamine hydrocarbon pyrolysis condensate fraction is subjected to hydrogenation on aluminium oxide-platinum or alumapalooza catalysts, however, the resulting gidrostabilizirovannoy gasoline fraction of liquid products of pyrolysis (railway checkpoint), wikipaedia in the interval 35-230°contain large amounts of benzene (up to 28-30 wt.%) and olefins (up to 10-15 wt.%), which hampers their use as a trademark high-octane gasoline. In this regard, a need for new catalysts and processes that reduce benzene content and unsaturated hydrocarbons in gidrostabilizirovannoy railway checkpoint and other similar fuel hydrocarbon fractions with a high content of benzene and unsaturated hydrocarbons.

Known catalyst for the reduction of benzene content in gasoline fractions (U.S. Pat. EN N2129464, 01 J 23/40, 1994). The catalyst consists of a carrier based on alumina, consisting 88-92 wt.% from this-alumina and 10 wt.% gamma-alumina, which caused 0.05 to 1.0 wt.% IU the Alla of group VIII, 4-15 wt.% the halogen chlorine.

This catalyst is used to reduce the benzene content in gasoline fractions by isomerization of hydrocarbons.

The disadvantages of this catalyst are the complexity of the preparation of the catalyst, the use of expensive Pt-modifier.

Known catalyst and method of its production on the basis of high zeolites ZSM-5, adopted for the prototype (U.S. Pat. EN N1527154, 01 33/28, 1987). High zeolites of type ZSM-5 with silicate module SiO2/Al2O3=30-200 get the hydrothermal crystallization of a reaction mixture at 120-180°C for 1-6 days, containing sources of silicon oxide, aluminum oxide, alkali metal oxide, hexamethylenediamine were, and water. The degree of crystallinity of the obtained product 85-100%.

The disadvantage of this catalyst is not a high yield of high octane gasoline from a hydrocarbon mixture consisting of railway checkpoint.

There is a method of reducing the content of benzene in gasoline fractions, which carried out the hydrogenation of the load, consisting of 40 to 80% of paraffins, 0.5 to 7.0 percent of cyclic hydrocarbons and 6 : 45 a.m.% aromatics and having a maximum distillation temperature between 70 and 90°With, then carry out the isomerization hydrogenation products when mixed with a specified load and/or effluent fraction5-C6 (EP-A-552070).

European patent application EP-A-552069 describes a method of isomerization of load, such as a light reformate and/or fraction C5-C6in the presence of isomerization catalyst, which preferably contains at least one metal of group VIII and mordenite with a ratio Si/Al between 5 and 50.

The closest to the essence of the technical solution is the way to reduce the benzene content in gasoline fractions, using a catalyst based on alumina, consisting 88-92 wt.% from ataxia aluminum and 10 wt.% gamma-alumina, which caused 0.05 to 1.0 wt.% metal of group VIII, 4-15 wt.% halogen-free chlorine (U.S. Pat. EN N2129464, 01 J 23/40, C 07 C 5/22, 10 G 35/08, 1994; U.S. Pat. EN N2130962, With 10 G 65/08, 1994).

This method is used to reduce the benzene content in gasoline fractions by isomerization of hydrocarbons, consisting of the boot that contains 40-80 wt.% paraffins, 0.5 to 7 wt.% cyclic hydrocarbons and 6 : 45 a.m wt.% aromatic hydrocarbons and having a maximum temperature distillation 70-90°and of the fraction5-C6with a paraffin content greater than 90 wt.%, cyclic hydrocarbons below 10 wt.% and benzene below 1.5 wt.%. The isomerization process of the mixture of hydrocarbons (benzene content in the mixture of 11.1 wt.%, the octane number of the mixture of 72.9) aluminium oxide-platinum catalyst provoditsya a temperature of 100-300° C, flow rate of feed of 0.2-10 h-1, pressure 1-70 bar and in the presence of raw materials chlorine compounds in the number of 50-5000 million-1and the hydrogen-containing gas. In the resulting liquid product after isomerization of the mixture of hydrocarbons benzene content slightly, octane liquid products due to the reaction of isomerization is 75-80.

The disadvantages of this method of reducing the content of benzene in gasoline fractions are the use of expensive aluminium oxide-platinum catalyst, corrosive chlorine-containing compounds, high-pressure, hydrogen-containing gas and a low octane gasoline fractions obtained, no more than 75-81.

The objective of the invention is the obtaining of an active and selective catalyst and the development of a method of reducing the content of benzene and unsaturated hydrocarbons in gasoline and other hydrocarbon fractions (fuel) mixtures.

The technical result is achieved by the fact that the proposed catalyst for reducing the amount of benzene and unsaturated hydrocarbons in the gasoline fractions contains: telesolutions with the structure of high zeolite ZSM-5 with silicate module SiO2/Al2O3=20-160, SiO2/Fe2O3=30-550, as modifying component contains at least one oxide selected from oppy metals: copper, zinc, gallium, lanthanum, cerium, rhenium, Nickel in an amount of 0.1-10.0 wt.%, as a hardening additive is 0.1 to 5.0 wt.% oxide of boron, phosphorus, or their mixture, the binder is alumina.

The cooking process of the proposed catalyst comprises the following steps: crystallization of the reaction mixture under hydrothermal conditions, decationization, impregnation decationizing of zhelezohromovye salts of metals modifier, the dry mixture with a compound of boron, phosphorus, or mixtures thereof as a hardening additive and the binder is a compound of aluminum, followed by mechanochemical processing of the catalyst mass, shaping, drying and calcining at a high temperature.

Telesolutions (JAS) with the structure of high zeolite ZSM-5 get the hydrothermal crystallization at 120-180°C for 0.5 to 6 days the reaction mixture containing a source of cations of alkali metal, silicon oxide, aluminum oxide, iron oxide, hexamethylenediamine were and water in the ratio of SiO2/Al2O3=20-160, SiO2/Fe2O3=30-550; H2O/SiO2=20-80; R/SiO2=0,03-1,0; HE-/SiO2=0,076-0,6; Na+/SiO2=0.2 to 1.0.

After crystallization of the zeolite is washed with distilled water, dried at 110°From 2-12 h and calcined at 550-600°C for 4 to 12 hours

In the IR spectra obtained JAS OBS is given absorption band at 445, 550, 810 cm-1and a broad band in the region of 1000-1300 cm-1characteristic of high zeolite ZSM. According to IR-spectroscopy and x-ray analysis of the obtained JAS identical to the zeolite ZSM-5, the degree of crystallinity obtained JAS is 85-100%.

For translation in H-shape JAS decationized processing 25% solution of NH4Cl (10 ml per 1 g of zeolite) at 90°2 h, then washed with water, dried at 110°4-12 h and calcined at 550-600°4-12 hours

Next, JAS H-shape with silicate module SiO2/Al2O3=20-160, SiO2/Fe2O3=30-550 with the structure of zeolite ZSM-5, impregnated with the modifying component - one compound from the group of metals: copper, zinc, gallium, lanthanum, molybdenum, rhenium in an amount of 0.1-10.0 wt.%, dried at 110°C for 4-6 hours Processed and dried N-JAS mixed with a calculated amount of the binder is a compound of aluminum: aluminum hydroxide or aluminum oxide and a hardening additive in an amount of 0.1-5.0 wt.% connection of boron, phosphorus, or mixtures thereof. The resulting mixture is subjected to mechanochemical treatment in a vibrating mill for 0.1 to 72 hours, the catalyst mass is molded, dried at 25-30°C for 3-4 h, then at 110°C for 8 h and calcined at a temperature of 550-600°C for 0.1 to 24 hours

The invention is illustrated by following the examples.

Example 1 (prototype). To 200 g of water glass (29 wt.% SiO2, 9 wt.% Na2O, 62 wt.% H2O) with stirring, add 11 g of the diamine in 100 ml of N2O, 1 g high zeolite as a "seed", 24,15 g of Al(NO3)3·N2O in 160 ml of N2O and poured a 0.1 n solution of HNO3. The resulting mixture was loaded into a stainless steel autoclave, heated to 175-180°C and maintained at this temperature and stirring for 6 days, then cooled to room temperature. The synthesized product is washed with distilled water, dried at 110°With 6-8 hours and calcined at 550-600°C for 8 hours To transfer in the H-form high-silica zeolite decationized processing 25 wt.% aqueous solution of NH4Cl (10 ml per 1 g of zeolite) at 90°C for 2 h, then washed with distilled water, dried at 110°With 4-6 h and calcined at 550°8 o'clock Get high-silica type zeolite H-ZSM-5 with silicate module SiO2/Al2O3=30.

Then 25 g of zeolite H-ZSM-5 with silicate module SiO2/Al2O3=30 mix from 12.6 g of boehmite AlO(OH) and subjected to mechanochemical treatment in a vibrating mill for 8 hours the resulting powder was molded, dried 2 h at 20-30°With, then at 100-110°C for 3-4 h and calcined in air for 8 h at 550-600°C.

The obtained zeolite was pushing the congestion has the composition wt.%:

H-ZSM-570,0
Al2O330,0

Example 2. JAS with the structure of zeolite ZSM-5 receive the same as in example 1, but instead 24,15 g of Al(NO3)3·9H2O take 12,07 g of Al(NO3)3·9H2O and 12,08 g Fe(NO3)3·N2O. Get telesolutions with silicate module SiO2/Al2O3=60, SiO2/Fe2O3=65.

Then 25 g decationizing JAS mixed with 12,18 g of boehmite AlO(OH) and 0,633 g H3BO3and subjected to mechanochemical treatment in a vibrating mill for 12 hours the resulting powder was molded, dried for 8 h at 20-30°With, then at 100-110°C for 8 h and calcined in air for 12 h at 550-600°C.

The obtained zeolite catalyst has a composition, wt.%:

N-JAS70,0
In2O31.0
Al2O329,0

Example 3. JAS receive the same as in example 1, but instead 24,15 g of Al(NO3)3·9H2O take 13,027 g of Al(NO3)3·9H2O and 1,447 g Fe(NO3)3·N2O. Get JAS with silicate module SiO2/Al2O3=55, SiO2/Fe2O3=540. Then 25 g of de is tonirovannogo JAS mixed with 12,18 g of boehmite AlO(OH) and 0.49 g of N 3PO4and subjected to mechanochemical treatment in a vibrating mill for 48 hours the resulting powder was molded, dried for 1-2 h at 20-30°With, then at 100-110°C for 8 h and calcined in air for 24 h at 550-600°C.

The obtained zeolite catalyst has a composition, wt.%:

N-JAS70.0
P2O51,0
Al2O329,0

Example 4. 25 g decationizing JAS with silicate module SiO2/Al2O3=55, SiO2/Fe2O3=540, obtained according to example 3, by impregnation put capacity of the zeolite under stirring for 3-4 h 2.17 g of Cu(NO3)2·3H2O, after which the zeolite is dried at 110°With 4-6 hours Then dried and processed JAS mix from 11.34 g of boehmite AlO(OH), 0,633 g H3BO3and subjected to mechanochemical treatment in a vibrating mill for 24 hours the resulting powder was molded, dried for 3-4 h at 25-30°With, then at 100-110°C for 8 h and calcined in air for 24 h at 550-600°C.

The obtained zeolite catalyst has a composition, wt.%:

N-JAS70,0
CuO2,0
In2O31,0
Al2O327,0

Example 5. On 22,86 g decationizing JAS with silicate module SiO2/Al2O3=55, SiO2/Fe2O3=540, obtained according to example 3, by impregnation put capacity of the zeolite with stirring for 3-4 hours 5,44 g of Cu(NO3)2·3H2O, after which the zeolite is dried at 110°With 4-6 hours Then dried and processed JAS mixed with 12,61 g of boehmite AlO(OH), 0,633 g H3PO4and subjected to mechanochemical treatment in a vibrating mill for 72 hours the resulting powder was molded, dried for 6-8 h at 25-30°With, then at 100-110°C for 12 h and calcined in air for 24 h at 550-600°C.

The obtained zeolite catalyst has a composition, wt.%:

N-JAS64,0
CuO5,0
In2O31,0
Al2O330,0

Example 6. Zeolite-containing catalyst was prepared as in example 4, but instead of 2.17 g of Cu(NO3)2·3H2O take 2,61 g Zn(NO3)2·6N2O.

The obtained zeolite catalyst has a composition, wt.%:

N-JAS70,0
ZnO2,0
Br2O31,0
Al2O327,0

Example 7. Zeolite-containing catalyst was prepared as in example 4, but instead of 2.17 g of Cu(NO3)2·3H2O take 3,05 g Ga(NO3)2·8H2O.

The obtained zeolite catalyst has a composition, wt.%:

N-JAS70,0
Ga2O32,0
In2O31,0
Al2O327,0

Example 8. 25 g decationizing JAS with silicate module SiO2/Al2O3=55, SiO2/Fe2O3=540, obtained according to example 3, by impregnation put capacity of the zeolite with stirring for 3-4 hours at 3.69 g of La(NO3)·N2O, after which the zeolite is dried at 110°With 4-6 hours Then dried and processed JAS mixed with 19,608 g of boehmite AlO(OH), 0,737 g H3PO4and subjected to mechanochemical treatment in a vibrating mill for 48 hours the resulting powder was molded, dried for 3-4 h at 25-30°With, then at 100-110°C for 12 h and calcined in air for 24 h at 550-600°C.

The obtained zeolite catalyst has a composition, wt.%:

60,0
Ga2O32,0
In2O31,0
Al2O337,0

Example 9. Zeolite-containing catalyst was prepared as in example 4, but instead of 2.17 g of Cu(NO3)2·3H2O, 0,633 g H3BO3and 11,34 g AlO(OH) take 0.95 g La(NO3)3·6H2O, 11,76 g AlO(OH) and 0.49 g of H3PO4.

The obtained zeolite catalyst has a composition, wt.%:

N-JAS70,0
La2O31,0
P2O51,0
Al2O328,0

Example 10. Zeolite-containing catalyst was prepared as in example 9, but instead of 0.95 g of La(NO3)3·6H2O take 0,94 g Ce(NO3)3·6H2O.

The obtained zeolite catalyst has a composition, wt.%:

N-JAS70,0
CE2O31,0
P2O51,0
Al2O328,0

Example 11. Zeolite-containing catalyst was prepared as in example 4. but instead of 2.17 g of Cu(NO3 )2·3H2O and 11,34 g AlO(OH) take of 4.17 g of Ni(NO3)2·6H2O and 10.92 g AlO(OH).

The obtained zeolite catalyst has a composition, wt.%:

N-JAS70,0
NiO3,0
In2O31,0
Al2O326,0

Example 12. Zeolite-containing catalyst was prepared as in example 5. but instead 5,44 g of Cu(NO3)2·3H2O take 6,97 grams Ni(NO3)2·6H2O.

The obtained zeolite catalyst has a composition, wt.%:

telesolutions64,0
NiO5,0
B2O31,0
Al2O330,0

Example 13. 25 g decationizing JAS with silicate module SiO2/Al2O3=55, SiO2/Fe2O3=540, obtained according to example 3, by impregnation put capacity of the zeolite with stirring for 3-4 hours 16,221 grams Ni(NO3)2·6N2O, after which the zeolite is dried at 110°With 4-6 hours Then dried and processed JAS mixed with 14,215 g of boehmite AlO(OH), 0,739 g H3BO3and subjected to mechanochemical treatments the ke in a vibrating mill for 48 hours The resulting powder was molded, dried for 3-4 h at 25-30°With, then at 100-110°C for 8 h and calcined in air for 24 h at 550-600°C.

The obtained zeolite catalyst has a composition, wt.%:

N-JAS60,0
NiO10,0
In2O31,0
Al2O329,0

The resulting catalysts are experiencing in the process of turning girostabilizirovannoi railway checkpoint faction 35-230°With (benzene content of 27.6 wt.%, olefins With5+of 13.9 wt.%, the estimated octane number on IM 90) in the presence of an alkylating agent is methanol on the installation of flow-type fixed bed of the catalyst at a temperature of 350-550°C, flow rate of feed of 0.5-4 h-1, a pressure of 0.1 to 1.5 MPa, and a mass ratio of railway checkpoint : methanol=1:0.1 to 0.3.

In the process of turning girostabilizirovannoi railway checkpoint in the presence of an alkylating agent is methanol with increasing reaction temperature from 350 to 500°on zhelezohromovyh with the structure of high zeolite ZSM-5 reactions proceed cracking, dehydrogenation, isomerization, dehydrocyclization and alkylation of unsaturated and aromatic hydrocarbons with the formation of predominantly isoparaffin and alkylaromatics is their hydrocarbons. Introduction to telesolutions modifying additives from the group of metals: copper, zinc, Nickel, gallium, lanthanum, cerium and rhenium in an amount of 0.1-10.0 wt.% allows to considerably increase the output of high-octane gasoline and the selectivity of the formation of alkylaromatic hydrocarbons from girostabilizirovannoi railway checkpoint.

The table below shows examples clarify the invention without limiting it.

As can be seen from examples 1-13 table, the catalysts 2-13 higher output (73-83%) of liquid products of the reaction is high - octane gasoline from railway checkpoint than the catalyst of the prototype 72-81% (example 1).

Thus, the proposed catalyst for reducing the amount of benzene and unsaturated hydrocarbons in the gasoline fractions contains: telesolutions with the structure of high zeolite ZSM-5 with silicate module SiO2/Al2O3=20-160, SiO2/Fe2O3=30-550; as modifying component, at least one oxide from the group of metals: copper, zinc, Nickel, lanthanum, cerium, rhenium in an amount of 0.1-10.0 wt.%; as a hardening additive is 0.1 to 5.0 wt.% oxide of boron, phosphorus, or a mixture thereof; the binder is alumina.

The decrease in the content of benzene and olefins in gasoline fractions is achieved through the use of zhelezohromovye with the structure of high zeolite ZSM-5. The l is a comparative introduction to telesolutions metals modifiers in an amount of 0.1-10.0 wt.% increases the activity and selectivity of the catalyst in the reactions of isomerization and alkylation of benzene and unsaturated hydrocarbons and reducing the concentration of benzene and unsaturated hydrocarbons, to increase the selectivity of the formation of alkylaromatic hydrocarbons and the octane number of the resulting gasoline fractions from the railway checkpoint. The result is a gasoline fraction with low benzene content (not more than 5-6 wt.%), olefins (not more than 0.6-2.5 wt.%), with a high content of alkylaromatic hydrocarbons7-C9and having a high octane number.

Table
The transformation of the gasoline fraction with a high content of benzene and unsaturated hydrocarbons over zeolite catalysts
Example catalystT °CV,

h-1
P, MPaThe ratio of railway checkpoint/CH3OHContent

in raw material

alkenes,

wt.%
Content

in raw material

arenes,

wt.%
The yield of reaction products, wt.%Settlement

octane

number

IM
the gas phasethe liquid phasealkenesbenzenearena
140020,110013,927,623,776,31,517,155,094
(prototype)45020,110013,927,628,072,01,716,057,195
40020,190/1012,524,8of 21.278,81,716,760,7100
45030,590/1012.524,822,677,41,616,061,3100
40020,580/2011,122,120,579,51,315,161,8101
45041,080/2011,122,121,378,71,115,063,1102
40020,570/30the 9.719,320,279,81,312,1of 60.5100
45030,570/30the 9.719,321,678,41,3to 12.065,6102
240020,270/30the 9.719,320,779,31,211,961,3100
45030,570/30the 9.719,322,677,60,911,064,5103
340020,270/30the 9.719,322,877,21.413,562,3101
450/td> 30,570/30the 9.719,323,073,01,5the 13.462,9102
440020,570/30the 9.719,326,273,80,610,554,0100
45030,570/30the 9.719,326,873,20,89,155,5100
47530,570/30the 9.719,325,674,40,88,857,8101
540020,570/30the 9.719,324,575,50,66,157,4101
45030,570/30the 9.719,325,174,90,7the 5.757,9102
64502 0,570/30the 9.719,324,975,10,77,854,299
47531,070/30the 9.719,325,674,40,65,9of 54.899
740020.570/30the 9.719,323,376,70,8the 9.752,398
45021,070/30the 9.719,325,774,30,97,155,6100
740020,570/30the 9.719,321,878,20,910,251,897
45021.070/30the 9.719,323,576,51,17,854,999
940020,570/30 the 9.719,320,979,11,2the 10.162,4102
50041,070/30the 9.719,317,882,21,77,265,9103
1040020,570/30the 9.719,321,378,71,011,859,8101
45041,070/30the 9.719,320,779,31,18,760,1102
1140020,570/30the 9.719,322,777,32,17,653,298
47541,070/30the 9.719,321,378,71,85,0of 54.8100
1240020,570/30the 9.719,3 19,380,72,56,052,398
45041.070/30the 9.719,3the 17.382,72,15,153,799
1340020.570/30the 9.719,318,781,30,55,250,196
45041.070/30the 9.719,318,181,90,9a 4.951,597
14 (prototype17023,011,180,3
Pat. EN
N 2129464

1. Catalyst for reducing the amount of benzene and unsaturated hydrocarbons in the gasoline fractions in the isomerization and alkylation of hydrocarbons in the presence of methanol on the basis of high zeolite ZSM-5, characterized in that it contains telesolutions with the structure of zeolite ZSM-5 with silicate module SiO2/Al2About3=20÷160, SiO2/Fe2About3=30÷550; modifying component selected from at least one oxide of the metals: copper, zinc, Nickel, gallium, lanthanum, cerium, rhenium; as a hardening additive is an oxide of boron, phosphorus, or a mixture thereof; the binder is alumina; catalyst formed during the heat treatment and has the following composition, wt.% in terms of the oxide:

N - Telesolutions60,0÷80,0
The oxide modifier component0,1÷10,0
The oxide of boron, phosphorus, or a mixture0,5÷5,0
Aluminium oxideRest

2. The method of preparation of the catalyst according to claim 1, characterized in that Glazounov the ikat with silicate module SiO 2/Al2About3=20÷160, SiO2/Se2O3=30÷550 receive the hydrothermal crystallization of a reaction mixture at 120÷180°C for 1-6 days., containing sources of silicon oxide, aluminum oxide, iron oxide, oxide of alkali metal, and hexamethylenediamine were water; transfer received JAS N-JAS further impregnation of zhelezohromovye compound modifier metal, followed by drying at 110°C for 2÷12 h, the mixture with the addition of hardening, with a binder, followed by mechanochemical processing in a vibrating mill for 4÷72 h, forming the catalyst mass, drying at a temperature of 100÷110° (C) for 0.1÷24 h and calcining at a temperature of 550÷600° (C) for 0.1÷24 hours

3. The method of reducing the content of benzene and unsaturated hydrocarbons in the gasoline fractions in the presence of a catalyst comprising isomerization of hydrocarbons, characterized in that the use of the catalyst according to claim 1 and a process of isomerization and alkylation of hydrocarbons is carried out at 300÷500°C, space velocity of the raw material 2÷4 h-1the mass ratio of hydrocarbon raw materials:methanol = 1:0,1÷0,3; a pressure of 0.1÷1.5 MPa, and as hydrocarbons used gidrostabilizirovannoy liquid products of pyrolysis fractions 35÷230°C.



 

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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: 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
The invention relates to the production of motor fuel, namely a catalytic process for the production of a variety of hydrocarbons of high octane gasoline and vysokochetkogo diesel fuel with a low freezing point

FIELD: petrochemical process catalysts.

SUBSTANCE: preparation of crusted metallic catalyst comprises: (i) applying suspension containing diluent, catalytically active metal selected from cobalt and ruthenium groups, and optionally first refractory element (atomic number at least 20) oxide onto surface of carrier particles to form wet coating and (ii) removing at least part of diluent from wet coating, said suspension containing at least 5% by weight of catalytically active metal based on the weight of calcination residue, which would result after drying and calcination of suspension. Crusted metallic catalyst itself and hydrocarbon production process are also described.

EFFECT: simplified catalyst preparation technology, improved physicochemical properties of catalyst as well as selectivity thereof, and increased productivity of hydrocarbon production process.

10 cl, 1 tbl, 3 ex

FIELD: industrial organic synthesis.

SUBSTANCE: invention is dealing with catalysts showing high catalytic stability in production of chloroform from carbon tetrachloride via catalytic dehydrochlorination reaction. Catalyst containing γ-alumina-supported platinum is characterized by that platinum in the form of particles 1 to 12 nm in size is distributed throughout the bulk of microspheric γ-alumina particles having median diameter 30 to 70 μm and pore volume 0.3 -0.6 cm3/g. Preparation of catalyst involves impregnation step accomplished via spraying γ-alumina with aqueous platinum compound solution used in amount equal to or less than alumina pore volume followed by platinum compound reduction step, wherein this compound is deposited onto γ-alumina with aqueous solution of formic acid or alkali metal formate.

EFFECT: achieved retention of high catalyst activity and selectivity over a long time period without being preliminarily activated.

9 cl, 2 tbl, 4 cl

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