Zeolite-containing catalyst, method for obtaining same and method of transformation of c2-c12 aliphatic hydrocarbon into aromatic hydrocarbons or high-octane gasoline component

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

 

The invention relates to the field of oil refining and petrochemical industries and is dedicated to the creation of the catalysts used in the processing of aliphatic hydrocarbon, C2-C12in a mixture of aromatic hydrocarbons or high-octane component of gasoline.

Known zeolite-containing catalyst and the method for its use of high-octane gasoline and aromatic hydrocarbons (RF patent No. 2087191, 1997). The catalyst includes zeolite group Pancasila, oxide of zinc, oxide of rare earth element (REE), a binder component and further comprises an oxide of boron and fluorine, and as a rare earth element or two or more oxides selected from the group of lanthanides: lanthanum oxide, cerium oxide, neodymium oxide, praseodymium oxide, and has the following content, wt.%: zeolite 20-70, zinc oxide, 1.0 to 4.0, the REE oxides of 0.1-2.0, boron oxide of 0.1-3.0, fluoride of 0.1 to 3.0, the binder component is rest. The method of transformation of aliphatic hydrocarbon, C2-C12in high-octane gasoline and aromatic hydrocarbons by contact of them with the catalyst at 280-550°C, a pressure of 0.5 to 3.0 MPa and space velocity of the raw material of 0.5 to 3.0 HR-1.

Known zeolite-containing catalyst for the conversion of aliphatic hydrocarbons, C2-C12in high-octane gasoline, obocaman the second aromatic hydrocarbons (RF patent No. 2092240, 1997). The catalyst contains a zeolite group pentasil with silicate module SiO2/Al2About3=20-80 mol/mol and a residual content of Na2About 0.1 to 0.4 wt.%, a binder component, zinc and a mixture of oxides of rare earth elements in the following ratio, wt.%: zeolite 25,0-50,0, zinc 1,0-3,0, total REE oxides of 0.1-2.0, representing a mixture of the following composition, wt.%: SEO240,0-55,0, the amount of La2O3Pr2O3Nd2O360,0-45,0, the binder component is rest. The method of transformation of aliphatic hydrocarbon, C2-C12in a high-octane component of motor gasoline with an octane rating of at least 76 points or concentrate of aromatic hydrocarbons is carried out by contact of the catalyst with the feedstock at a temperature 280-550°C, a pressure of 0.2 to 2.0 MPa and space velocity of the raw material of 0.5 to 5.0 h-1.

Known zeolite-containing catalyst for the conversion of aliphatic hydrocarbons, C2-C12in a high-octane component of gasoline with an octane rating of at least 76 points or in a concentrate of aromatic hydrocarbons (RF patent No. 2100075, 1997). The catalyst contains a zeolite group pentasil with silicate module SiO2/Al2About3=20-80 mol/mol and a residual content of Na2O not more than 0.2 wt.%, a binder component, the oxides of zinc and rare earth elements in which the quality of the promoters, and characterized in that it further contains patikis phosphorus when used as REE oxides of two or more of the following: CeO2La2O3Nd2O3Pr2O3etc. at the following content, wt.%: zeolite 50-75, ZnO 0,5-3,0, sum (REE)2O30,5-3,0, P2O50.5 to 2.0, the binder component is rest. The method of transformation of aliphatic hydrocarbon, C2-C12in a high-octane component of motor gasoline with an octane rating of at least 76 points or concentrate of aromatic hydrocarbons at this zeolite catalyst is carried out by contact of the catalyst with the feedstock at a temperature 280-550°C, a pressure of 0.2 to 2.0 MPa and space velocity of the raw material of 0.5 to 5.0 h-1.

Known methods for producing motor fuels from gas condensate (RF patents №№2008323, 1994 and 2030446, 1995). Straight-run gasoline fraction in contact with 300-480°and 0.2-4.0 MPa with a zeolite-containing catalyst. The products obtained fractionary with gaseous and liquid fraction, the liquid fraction rectificatum emitting high-octane and residual fractions. Straight-run residual fraction or its mixture with gaseous products of the probe is subjected to pyrolysis. The products obtained fractionary with the release of pyrolysis condensate fraction and pyrogas with the settlement of edusim mixing of pyrogas with straight-run gasoline fraction and their joint contact with the catalyst. The pyrolysis condensate fraction compounding with liquid products contact and expose their joint rectification with a target allocation of gasoline and residual fractions. As the catalyst systems prepared on the basis of zeolites with structures of ZSM-5 or ZSM-11, including modified items I, II, III, V, VI and VIII groups of the periodic system of elements.

The disadvantages of the above methods of obtaining zeolite catalysts are their complex composition and the presence of harmful effluents in the process of their production, as well as the necessity of application in the synthesis of fluorine (RF patent No. 2087191, 1997), high residual content of sodium oxide and low mass fraction of the active portion of the catalyst (patent RF №2092240, 1997), which significantly reduces its performance on the target product, the high cost of catalysts containing expensive oxides of rare earth elements. In addition, a significant drawback of most zeolite catalysts is the lack of implementation of a method of conversion of gaseous aliphatic hydrocarbon composition With2-C4in the condensed liquid phase aromatic hydrocarbons.

Closest to the claimed catalyst is a zeolite-containing catalyst, method of its production and the way prevremeni the aliphatic hydrocarbons in the concentrate of aromatic hydrocarbons or high-octane component of gasoline (patent of the Russian Federation, 2221643, 2004). Zeolite-containing catalyst contains zeolite group pentasil with silicate module SiO2/Al2O3=55-102 mol/mol and a residual content of sodium oxide of 0.02-0.07 wt.%, the oxides of zinc, tin and lanthanum as elements of the structure of the zeolite, and as a promoter oxide of chromium at the following content, wt.%: zeolite 65,0-80,0; ZnO 0,0-4,0; SnO20,0-2,5; La2O30,0-0,8; Cr2O30,0-5,0; Na2O 0,02-0,07, the binder component is rest. Describes how transformations of aliphatic hydrocarbons in the concentrate of aromatic hydrocarbons or high-octane component of gasoline (options) by passing a gaseous mixture of low molecular weight saturated hydrocarbons or vapors straight-run gasoline fractions of oil through a bed of the zeolite catalyst, respectively, at a temperature of 500-600°and 300-380°C, the load of the catalyst raw materials 100-400 h-1and 2 h-1. The yield of the target product in the processing of gaseous hydrocarbons and straight-run gasoline fractions of oil, respectively 49,0-60.2% and not less than 67%.

The main disadvantages of this zeolite-containing catalyst are its complex composition, the use of expensive rare earth element oxide (lanthanum oxide) and a large number of stages of preparation. This price is listeriosis catalyst, method thereof and method of use is selected as a prototype. Output, octane number and group composition of gasolines obtained by the method-prototype of straight-run gasoline fractions of oil, as well as the conversion of a mixture of alkanes With2-C4the yield and selectivity of the formation of aromatic hydrocarbons on the catalyst are shown in tables 2 and 8.

The proposed zeolite-containing catalyst, process for its production and method of conversion of aliphatic hydrocarbons With2-C12in a mixture of aromatic hydrocarbons or high-octane component of gasoline with its use eliminates these drawbacks.

The objective of the invention is the reduction of the catalyst, the simplification of the method of its production, increasing the degree of conversion of raw material, quality and yield of the target products.

The technical result of the invention is to reduce the number of components and stages of the synthesis of the zeolite catalyst, increasing the degree of conversion of raw material, quality and yield of the target product for the claimed catalyst.

The technical result concerning the method of obtaining a zeolite-containing catalyst is achieved in that the zeolite catalyst contains zeolite group pentasil with silicate module SiO2/Al2About3=60-80 mol/mol and the oxides of zirconium and Nickel as elements article shall ucture zeolite, and as a promoter of zinc oxide in the following ratio, wt.%: zeolite 65,00-80,00; ZrO20-4,00; NiO 0-1,00; ZnO 0-5,00; Na2O 0,02-0,05; a binder component - the rest.

The technical result regarding methods based on the use of the proposed zeolite-containing catalyst for the conversion of aliphatic hydrocarbons, C2-C12in a high-octane component of gasoline, is achieved by passing vapors of straight-run gasoline fractions of crude oil (raw material) through a stationary catalyst bed heated to a temperature of 300-420°s, when the load of the catalyst raw materials 2 h-1and with the yield of the target product is not less than 53%.

The technical result in relation to the method based on the proposed use of the zeolite catalyst to obtain a mixture of aromatic hydrocarbons is achieved by passing vapors of a gaseous mixture of saturated hydrocarbons With2-C4(raw materials) through a stationary catalyst bed heated to a temperature of 550-600°s, when the load of the catalyst raw materials 100-200 h-1with the conversion of raw materials 99-100% and the yield of aromatic hydrocarbons 42,0-61,1%.

The advantages offered by the zeolite-containing catalyst include the use of cheaper and more available connections for its synthesis in the absence of expensive oaks is Yes rare earth element - lanthanum, and in reducing the number of components and stages of the synthesis catalyst.

Further, the invention is illustrated with specific examples of its implementation.

Example 1. To obtain a zeolite-containing catalyst of a given composition containing as the active component of the zeolite group Pancasila in the protonated form (65-80 wt.%) and the media in the form γ-Al2About3(15-30 wt.%), first hydrothermal synthesis get the Na-form of the zeolite, modified at the stage of synthesis of zirconium and Nickel. To do this, in the intermediate tanks prepare aqueous solutions of aluminum nitrate, Nickel nitrate and hydroxide of sodium. In the capacity of a volume of 3.5 liters, made of stainless steel and equipped with a mechanical stirrer vane type, enter or 28.7 g of zirconium sulfate 4-water mark "h" (the content of the basic substance in the reagent 99.5%pure), 400,0 g of silicic acid water mark "analytical grade" (mass loss on ignition PP400=15,56%) and 1430 ml of water. Include the stirrer and under vigorous stirring successively added to the mixture 133,9 ml of an aqueous solution of aluminum nitrate with a concentration of aluminum of 28.2 g/l, 637,6 ml solution of hydrate of sodium oxide with a concentration of sodium hydroxide 128,4 g/l 12.0 g seed crystals of zeolite in Na or H-form and 123,0 ml of n-butanol. After stirring the mixture at t the value of 5 min turn off the mixer and pour the mixture in the autoclave with a volume of 5.0 l, equipped with a mechanical stirrer with blades. The released capacity rinsed 2-3 reception 714 ml water, which was poured into the autoclave. Include a stirrer autoclave and cooked the reaction mixture was kept in an autoclave at 160-190°C for 10-20 hours After completion of the hydrothermal synthesis slurry Na-form of the zeolite is filtered, the precipitate washed with water drinking to achieve in the washing filtrate-the mother liquor pH of 8.5-7.0 (ratio of the liquid and solid phases when washing is 22:1). The washed precipitate Na-forms are sent to the conducting salt ion exchange.

In a volume of 3.5 liters, made of stainless steel and equipped with a mechanical stirrer, Rasulova sediment Na-form of the zeolite in 1.8 l of a 25%aqueous solution of ammonium chloride. The resulting slurry is maintained at a temperature of 90-100°and With constant stirring for 4-6 hours

Obtained after salt ion exchange slurry was filtered, washed with water drinking at the ratio of liquid and solid phases W:T=18:1 and then washed with demineralized water at a ratio of liquid and solid phases W:T=2:1.

The washed precipitate ammonium form of the zeolite is dried in a drying Cabinet at a temperature of 100-110°C for 6-8 h and is directed to the operation of preparation of a catalyst mass.

Washed and you Osenniy precipitate ammonium form of the zeolite is mixed with 125 ml of demineralized water, to the resulting mixture add 176,6 g of active aluminum hydroxide in the form of a wet paste (with a residual mass fraction of moisture 26.7%) and 80 ml of nitric acid with the concentration of nitric acid to 76.7 g/l

The resulting mixture is stirred until a homogeneous plastic catalyst mass suitable for extrusion and granulation of the catalyst (a mixture optionally kept in a vacuum oven to obtain a consistency suitable for extrusion and molding pellets of the catalyst).

Obtained after extrusion and granulation wet granules of the catalyst is dried in a vacuum drying Cabinet at a temperature of 100-110°C for 4-6 h and calcined in a muffle furnace at a temperature of 550-650°C for 1 h

The calcined catalyst pellet is subjected to sieving classification. The fraction of the finished catalyst is separated and the fraction of granules <2.5 mm sent for grinding in a ball mill to obtain a homogeneous powder, which is subsequently used as a component of the charge on the operation of preparation of a catalyst mass.

Example 2. Straight-run gasoline fraction oil (25,44 wt.% n-paraffins, 39,24 wt.% i-paraffins, 29,34 wt.% naphthenes, 5,98 wt.% aromatic hydrocarbons, octane number 51 and 44, according to the research and motor methods meet the but) is subjected to contacting with a zeolite-containing catalyst, placed in a reactor with a volume of 5 cm3at a temperature of 300-420°C, space velocity of the liquid raw material 2 h-1and atmospheric pressure. The catalyst consists of 80,38 wt.% the zeolite of the structure type ZSM-5, containing in its structure to 1.59 wt.% zirconium, and 19,62 wt.% γ-Al2About3used as a binder.

Zeolite-containing catalyst was prepared according to the method described in example 1, except that as the silicon-containing component used crushed silica gel (brand XCG, fraction of less than 50 microns). Qualitative and quantitative composition of the obtained catalyst are shown in table 1. Output group composition and octane number of the gasoline obtained are given in table 2.

Example 3. Similar to example 1, except that as the zeolite component of the zeolite catalyst is zeolite structure of ZSM-5, containing in its structure 1.99 wt.% zirconium and obtained with the use of crushed silica gel (brand XCG, fraction of less than 50 microns).

Qualitative and quantitative composition of the zeolite catalyst are presented in table 1. Output group composition and octane number of the gasoline obtained are given in table 3.

Example 4. Similar to example 1, except that as the zeolite component of the zeolite catalyst is zeolite structure ZSM5, containing in its structure to 2.42 wt.% Zirconia.

Qualitative and quantitative composition of the zeolite catalyst are presented in table 1. Output group composition and octane number of the gasoline obtained are given in table 3.

Example 5. Similar to example 1, except that as the zeolite component of the zeolite catalyst is zeolite structure of ZSM-5, containing in its structure is 3.21 wt.% Zirconia.

Qualitative and quantitative composition of the zeolite catalyst are presented in table 1. Output group composition and octane number of the gasoline obtained are given in table 4.

Example 6. Similar to example 4, only as the zeolite component of the zeolite catalyst is zeolite structure of ZSM-5, promoted by zinc.

Qualitative and quantitative composition of the zeolite catalyst are presented in table 1. Output group composition and octane number of the gasoline obtained are given in table 4.

Example 7. Analogously to example 4, only as the zeolite component of the zeolite catalyst is zeolite structure of ZSM-5 with different silicate module.

Qualitative and quantitative composition of the zeolite catalyst are presented in table 1. Output group composition and octane number of the gasoline obtained result is I in table 5.

Example 8. Similar to example 7, only as the zeolite component of the zeolite catalyst is zeolite structure of ZSM-5, promoted by zinc.

Qualitative and quantitative composition of the zeolite catalyst are presented in table 1. Output group composition and octane number of the gasoline obtained are given in table 5.

Example 9. Similar to example 7, only as the zeolite component of the zeolite catalyst is zeolite structure of ZSM-5, containing in its structure to 0.08 wt.% Nickel.

Qualitative and quantitative composition of the zeolite catalyst are presented in table 1. Output group composition and octane number of the gasoline obtained are given in table 6.

Example 10. Similar to example 7, only as the zeolite component of the zeolite catalyst is zeolite structure of ZSM-5, containing in its structure to 0.39 wt.% Nickel.

Qualitative and quantitative composition of the zeolite catalyst are presented in table 1. Output group composition and octane number of the gasoline obtained are given in table 6.

Example 11. Samples of zeolite-containing catalyst was prepared according to the method described in example 1. In result, they have received eight samples of the zeolite catalyst, characterized by the number in the article is ucture zirconium, silicate module zeolite component and the presence of zinc as a promoter. All samples were tested in the process of conversion of a mixture of saturated hydrocarbons With2-C4in a mixture of aromatic hydrocarbons in equal conditions: the raw material of the following composition, wt.%: 2.2 ethane, 73.7 propane, 24,1 i - and n-butane were subjected to contacting with samples of the zeolite catalyst at a temperature of 600°C, flow rate 100 h-1and atmospheric pressure. After the end of the process analyzed the degree of transformation of raw materials into a final product (X, %), the selectivity of the formation of aromatic hydrocarbons (Sap, wt.%) and the mass content of aromatic hydrocarbons in the final product (ωar, wt.%). The results are presented in table 7.

As shown in table 7 data high catalytic activity (X, %) and selectivity (Sap, wt.%) the zeolite catalyst is characteristic for the samples containing 2,42 wt.% zirconium-promoted zinc. The increase in silicate module from 60 to 80 mol/mol leads to higher mass content of aromatic hydrocarbons in the final product (ωap, wt.%).

Example 12. A sample of zeolite-containing catalyst was prepared according to the method described in example 1. Content components can produce the RA was wt.%: SiO275,76; Al2About31,60; ZrO22,39; ZnO 1,00; Na2O 0,05; a binder component 19,20. To compare the activity of the prepared zeolite catalyst shows the activity of the zeolite catalyst of the prototype. The samples were tested in the process of conversion of a mixture of saturated hydrocarbons With2-C4in a mixture of aromatic hydrocarbons in equal conditions: the raw material of the following composition, wt.%: 2.2 ethane, 73.7 propane, 24,1 i - and n-butane were subjected to contacting with samples of the zeolite catalyst at a temperature of 600°C, flow rate 100 and 200 h-1and atmospheric pressure. After the end of the process analyzed the degree of transformation of raw materials into a final product (X, %), the selectivity of the formation of aromatic hydrocarbons (Sap, wt.%) and the mass content of aromatic hydrocarbons in the final product (ωar, wt.%). The results are presented in table 8.

Presented in table 8, the data shows that the activity (X, %), outωap, wt.%) and selectivity (Sap, wt.%) education aromatic hydrocarbons claimed zeolite-containing catalyst is not inferior to the performance of the prototype. At different volumetric flow rates of the raw materials the conversion rates compared to zeolite catalysts was 100%. Mass sod is neigh aromatic hydrocarbons in the final product after conversion of raw materials in the presence of the inventive zeolite catalyst at space velocities of 100 and 200 h -1changed from 61,1 to 57.1%. Mass content of aromatic hydrocarbons in the final product when using another zeolite-containing catalyst at flow rate of 100-200 h-1changed from 60,2 to 56.3%, slightly lower compared with the values obtained for the inventive zeolite catalyst.

1,99
Table 1
Qualitative and quantitative composition of the zeolite catalysts
ExampleStructural type zeoliteContent, wt.%
The structure elementsThe promoter ZnOBinder γ-Al2O3
SiO2Al2O3ZrO2NiONa2O
2ZSM-576,622,151,59-0,02-19,62
3ZSM-575,442,15-0,02-20,40
4ZSM-576,731,612,42-0,04-19,20
5ZSM-575,071,843,21-0,03-19,85
6ZSM-575,841,502,42-0,041,0019,20
7ZSM-576,491,612,40-0,05-19,45
8ZSM-575,761,602,39-0,051,0019,20
9ZSM-574,831,66 to 2.290,080,04-21,10
10ZSM-574,411,651,960,390,04-21,55
Table 2
Exit and group composition of the liquid products of the reaction*
ExamplePrototype2
Temperature, °300340360380300340380420
The output of gasoline8875736791827570
Output products:
Alkanes With3-C49,68,66,96,19,44,44,03,7
Alkenes With3-C40,60,80,80,60,40,30,40,6
n-Alkanes With5+8,96,76,0the 5.79,58,17,58,1
i-Alkanes With5+36,534,933,333,2of 37.841,337,234,7
Alkenes With5+3,02,82,82,82,43,13,03,0
Naphthenes With5+8,08,27,47,79,28,18,4the 9.7
Arenathe 33.438,042,843,931,334,739,540,2
Octane number8183848477818384
* the values are expressed in wt.%.
Table 3
Exit and group composition of the liquid products of the reaction*
Example34
Temperature, °300340380420300340380420
The output of gasoline8980716585706560
Output products:
Alkanes With3-C48,56,24,43,11,71,71,10,6
Alkenes With3-C40,3 0,40,40,50,30,40,20,1
n-Alkanes With5+7,76,8the 5.76,711,43,4of 5.44,5
i-Alkanes With5+37,738,236,6to 33.838,728,526,225,1
Alkenes With5+2,62,22,12,62,02,50,60,6
Naphthenes With5+9,37,36,67,512,15,65,05,0
Arena33,938,944,245,8to 33.857,961,564,1
Octane number7883 868778909293
* the values are expressed in wt.%.

6,2td align="center"> 6,0
Table 4
Exit and group composition of the liquid products of the reaction*
Example56
Temperature, °300340380420300340380420
The output of gasoline9180706585665960
Output products:
Alkanes With3-C47,95,05,63,02,51,10,50,7
Alkenes With3-C40,30,30,50,50,10,10,10,1
n-Alkanes With5+8,67,56,911,44,63,53,3
i-Alkanes With5+37,636,235,033,635,420,518,219,5
Alkenes With5+2,72,82,02,20,10,40,30,3
Naphthenes With5+the 9.77,07,36,811,87,7of 5.47,4
Arena33,241,242,747,738,765,672,068,7
Octane number7784858782929695
* the values are expressed in wt.%.
Table 5
Exit and group composition of the liquid products of the reaction*
Example78
Temperature, °300340380 420300340380420
The output of gasoline7567605868635553
Output products:
Alkanes With3-C42,80,70,80,90,80,20,20,2
Alkenes With3-C40,20,10,3-----
n-Alkanes With5+5,64,23,12,34,53,63,73,2
i-Alkanes With5+27,722,022,1of 21.922,020,418,517,7
Alkenes With5+1,30,70,80,70,20,20,50,6
Naphthenes With5+6,7a 4.95,15,13,13,43,6
Arena55,767,467,868,267,472,573,774,7
Octane number8994959693969797
* the values are expressed in wt.%.
Table 6
Exit and group composition of the liquid products of the reaction*
Example910
Temperature, °300340380420300340380420
The output of gasoline7365575470645553
Output products:
Alkanes With3-C49,8 6,94.22,11,20,91,01,3
Alkenes With3-C40,20,10,20,20,10,10,10,2
n-Alkanes With5+6,66,76,2a 4.96,04,64,8the 4.7
i-Alkanes With5+32,635,128,728,226,220,618,720,3
Alkenes With5+2,42,41,41,41,60,80,91,5
Naphthenes With5+7,16,15,15,64,52,93,03,7
Arena41,342,754,257,660,470,171,568,3
Octane number838489908995 9694
* the values are expressed in wt.%

Table 7
The dependence of the activity of the zeolite catalyst from the silicate module zeolite component and content in its structure of zirconium
No. sample12345678
Silicate module SiO2/Al2O3, mol/mol6060606060608080
The Zr concentration, wt.%1,591,992,423,212,422,402,39
The concentration of Zn, wt.%1,01,0
X, % 97991009510099100
Sap, wt.%27,327,028,930,832,943,050,761,1
ωap, wt.%26,226,228,630,831,243,050,261,1
Table 8
The activity of zeolite catalysts with different volumetric feed rate of the raw material
Zeolite-containing catalystObtained by the method described in example 1Prototype
The volumetric feed rate, h-1100200100200
X, %100100100100
Sap, wt.%61,157,160,256,3
ωar, wt.%61,157,160,256,3

1. Zeolite-containing catalyst for the conversion of aliphatic hydrocarbons, C2-C12in a mixture of aromatic hydrocarbons or high-octane component of gasoline containing zeolite ZSM-5 with silicate module SiO2/Al2O3=60-80 mol/mol and a residual content of sodium oxide to 0.02-0.05 wt.%, the element structure of the zeolite, a promoter and a binder component, wherein as part of the structure of the zeolite catalyst contains zirconium oxide or oxides of zirconium and Nickel as a promoter of zinc oxide in the following content, wt.%:

zeolite65,00-80,00
ZrO21,59-4,00
NiO0-1,00
ZnO0-5,00
Na2O0,02-0,05
a binder componentrest

2. A method of obtaining a zeolite-containing catalyst according to claim 1, including op the radio mixing of reagents, hydrothermal synthesis, washing, drying and calcination of the precipitate, wherein the reaction mixture obtained by mixing aqueous solutions of salts of aluminum, zirconium, Nickel, sodium hydroxide, silica and/or silicic acid water, seed crystals of zeolite with structure of ZSM-5, Na - or H-form of amendment, for example n-butanol, loaded into an autoclave in which carry out hydrothermal synthesis at a temperature of 160-190°C for 10-20 h with constant stirring, after hydrothermal synthesis slurry Na-form of the zeolite was filtered, the obtained the precipitate was washed with drinking water and direct the conduct of salt ion exchange by treatment with an aqueous solution of ammonium chloride by heating and stirring the slurry obtained after the salt ion exchange slurry was filtered, washed with drinking water and then washed with demineralized water to a residual content of sodium oxide to 0.02-0.05 wt.% in terms of the dried and calcined product, the washed precipitate ammonium form of the zeolite is directed to the operation of promoter - zinc and preparation of a catalyst mass by mixing ammonium form of the zeolite modified with zinc, with active aluminum hydroxide obtained catalyst mass is extruded and the grain is the key, the granules are dried at a temperature of 100-110°and calcined at 550-650°C, calcined granules of zeolite-containing catalyst classify, separate faction ready zeolite-containing catalyst, and the fraction of granules <2.5 mm milled until a homogeneous powder and return to the operation preparation of a catalyst mass.

3. The method of conversion of aliphatic hydrocarbons to high octane component of gasoline using a zeolite-containing catalyst, comprising heating and passing the raw material through the zeolite catalyst, characterized in that is used as raw material of the pair of straight-run gasoline fraction of oil that is passed through the stationary layer of zeolite-containing catalyst according to claim 1, heated to a temperature of 300-420°s, when the load of the catalyst raw materials 2 h-1.

4. The method of conversion of aliphatic hydrocarbons in a mixture of aromatic hydrocarbons using a zeolite-containing catalyst, comprising heating and passing the raw material through the zeolite catalyst, characterized in that is used as raw material gaseous mixture of saturated hydrocarbons With2-C4, which is passed through the stationary layer of zeolite-containing catalyst according to claim 1, heated to a temperature of 550-600°s, when the load of the zeolite catalyst with the ryu 100-200 h -1.



 

Same patents:

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: 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: 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.

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: 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.

3 cl, 1 tbl, 13 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: 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

FIELD: chemistry.

SUBSTANCE: method involves hydrocarbon transformation in a reactor in the presence of modified catalyst containing, mass %: 53.0-60.0 of ZSM-5 high-silica zeolite with the ratio of SiO2/Al2O3=39, 34.0-38.0 of Al2O3, 2.0-5.0 of B2O3, 1.0-5.0 of Zn, 0.0-5.0 of W, 0.0-3.0 of La, 0.0-3.0 of Ti at 300÷700°C, including separation of liquid and solid transformation products, followed by burning oxidation of gaseous products and addition of the obtained mix of carbon dioxide and water vapour to the source hydrocarbons at the rate of 2.0÷20.0 mass %. Before the raw material intake the reaction system is flushed by an inert gas (nitrogen), starting from 300°C and to the transformation temperature. Hydrocarbons used are alkanes, olefins or alkane olefin mixes C2-C15 without preliminary separation into fractions. Gaseous transformation products undergo burning and complete oxidation in the presence of an oxidation catalyst of vanadium/molybdenum contact piece, V2O5/MoO3. To sustain continuous process two identical reactors are used, where the catalyst is transformed and recovered in turns.

EFFECT: longer working transformation cycle due to the continuous process scheme; higher yearly output of aromatic hydrocarbons; reduced energy capacity and improved ecology of the process.

2 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: organic synthesis catalysts.

SUBSTANCE: invention relates to catalyst for aromatization of alkanes, to a method of preparation thereof, and to aromatization of alkanes having from two to six carbon atoms in the molecule. Hydrocarbon aromatization method consists in that (a) C2-C6-alkane is brought into contact with at least one catalyst containing platinum supported by aluminum/silicon/germanium zeolite; and (b) aromatization product is isolated. Synthesis of above catalyst comprises following steps: (a) providing aluminum/silicon/germanium zeolite; (b) depositing platinum onto zeolite; (c) calcining zeolite. Hydrocarbon aromatization catalyst contains microporous aluminum/silicon/germanium zeolite and platinum deposited thereon. Invention further describes a method for preliminary treatment of hydrocarbon aromatization catalyst comprising following steps: (a) providing aluminum/silicon/germanium zeolite whereon platinum is deposited; (b) treating zeolite with hydrogen; (c) treating zeolite with sulfur compound; and (d) retreating zeolite with hydrogen.

EFFECT: increased and stabilized catalyst activity.

26 cl, 1 dwg, 5 tbl, 4 cl

FIELD: petrochemical processes.

SUBSTANCE: simultaneous dehydrogenation of mixture containing alkyl and alkylaromatic hydrocarbons is followed by separating thus obtained dehydrogenated alkyl hydrocarbon and recycling it to alkylation unit. Dehydrogenation reactor-regenerator employs C2-C5-alkyl hydrocarbon as catalyst-transportation carrying medium.

EFFECT: increased process flexibility and extended choice of catalysts.

36 cl

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 catalytic composition for the alkylation and/or parallelomania aromatic compounds, in which the use of beta zeolite as such or modified isomorphous substitution of aluminum by boron, iron or gallium, or modified by the introduction of alkali and/or alkaline earth metals by ion exchange, and the said catalytic composition has extramarital porosity, i.e. the porosity obtained by summing the fractional meso and macro porosity present in the composition, and which is such that the proportion of at least 25% consists of pores with a radius greater thanmoreover, the full amount of extracolonic pores of the catalyst is greater than or equal to 0.8 ml/g; a method for producing the catalytic composition; the method of alkylation of aromatic hydrocarbons, the way they parallelomania, as well as the method of obtaining monoalkylated aromatic hydrocarbons using the above catalytic composition

The invention relates to methods for producing aromatic hydrocarbons and can be used in the refining and petrochemical industry

The invention relates to a method for conversion of heavy aromatic hydrocarbons to lighter aromatic compounds such as benzene, by contacting the fraction WITH9+ aromatic hydrocarbons and toluene above the first catalyst containing a zeolite having an index of permeability of 0.5 - 3, and a hydrogenation component and a second catalyst composition comprising a zeolite with an average size of pores having an index of permeability 3 - 12, the ratio of silica to alumina of at least 5, this reduces the number or preventing the formation of jointly boiling compounds

FIELD: chemistry.

SUBSTANCE: catalyst of aromatic hydrocarbon obtaining process is a complex catalyst with acidic properties and pore size over 5 E, containing an oxide component with dehydrating properties, where the oxide component is mixed zinc-aluminum oxide material with spinel structure and specific surface area of not less than 50 m2/g, branched system of transport pores of average diametre of not less than 2.0 nm and pore volume of not less than 0.2 cm3/g. The invention describes a method of catalyst preparation by mixing micropore component and mixed zinc-aluminum oxide material with spinel structure and properties described above, and application of obtained catalyst to obtaining aromatic hydrocarbons from aliphatic hydrocarbons C2-C6 at the temperature not lower than 400°C, pressure of not over 10 MPa and C2-C6 hydrocarbon volume flow of not over 10000 h-1.

EFFECT: increased activity of aliphatic hydrocarbons transformation and selectivity in aromatic hydrocarbon formation, improved catalyst effect stability.

14 cl, 2 tbl, 14 ex

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