Catalyst, method for preparation thereof, and a method of isomerization of n-butane using this catalyst

FIELD: petrochemical process catalysts.

SUBSTANCE: invention relates to catalytic methods of isomerizing n-butane into isobutane and provides catalyst constituted by catalytic complex of general formula MexOy*aAn-*bCnXmH2n+2-m, where Me represents group III and IV metal, x=1-2, y=2-3, An- oxygen-containing acid anion, a=0.01-0.2, b=0.01-0.1; CnXmH2n+2-m is polyhalogenated hydrocarbon wherein X is halogen selected from a series including F, Cl, Br, I, or any combination thereof, n=1-10, m=1-22, dispersed on porous carrier with average pore radius at least 500 nm and containing hydrogenation component. Method of preparing this catalyst is also disclosed wherein above-indicated catalytic complex is synthesized from polyhalogenated hydrocarbon CnXmH2n+2-m wherein X, n, and m are defined above, group III and IV metal oxide, and oxygen-containing acid anion, and dispersed on porous carrier with average pore radius at least 500 nm, hydrogenation component being introduced either preliminarily into carrier or together with catalytic complex. Process of isomerizing n-butane into isobutane utilizing above-defined catalyst is also described.

EFFECT: lowered butane isomerization process temperature and pressure and increased productivity of catalyst.

13 cl, 1 tbl, 24 ex

 

The invention relates to the field of petrochemicals, namely catalytic method for the isomerization of n-butane to isobutane.

The isomerization of normal paraffins contained in the various hydrocarbon fractions petrochemical industries, is one of the most important processes that improve the quality of motor fuels in the energy and environmental performance.

In the isomerization reactions is the conversion of normal paraffins C4-C8with generally low octane index, ISO-paraffins with a significant increase octane index.

The isomerization of n-butane provides increased resource refineries in isobutane - raw materials for the production of alkylate and methyl tertiary butyl ether - environmentally friendly high-octane additives.

The process is carried out in the presence of different types of acid catalysts: aluminium chloride, chlorinated alumina, zeolites, sulfated metal oxides.

The stability of catalyst performance and process provide an introduction to the hydrogenating catalyst additives, usually metal of group VIII, and holding process in the presence of hydrogen.

The isomerization of n-paraffins may be accompanied by disclosure or contraction cycle naphthenic whom is onenow, as well as the hydrogenation of aromatic hydrocarbons that may be present in the feedstock.

It is known that the octane value of the index associated with the structure of the hydrocarbon skeleton of the hydrocarbon molecules. So, the value of the octane index for n-octane is equal to 0, and 2,2,4-trimethylpentane (isooctane) is 100.

Thermodynamic parameters of the process of isomerization of paraffins determine the predominant formation of the most branched paraffins at low temperatures, the most thermodynamically favorable temperature range of the isomerization process is in the range 0-200°C. Therefore, the main research aimed at finding catalysts for isomerization of n-paraffins, which have high activity and selectivity for the branched isomers in the specified temperature range.

A known process for the isomerization of paraffins in the presence of chlorinated alumina (U.S. Pat. U.S. No. 4004859, F 01 D 25/00, 25.01.1977; U.S. Pat. U.S. No. 4149993, C 07 C 5/30, 12.09.1978; U.S. Pat. U.S. No. 6133496, C 07 C 5/22, 17.10.2000). In the presence of chlorinated alumina achieve high conversion of n-paraffins With4-C6in the temperature range of the process 100-160°C. the Conversion of n-butane at 142°C, a pressure of 31 MPa, the ratio of N2/S4equal to 0.05, the speed of feeding n-butane 4 g/gcat·h, the concentration of x is ordersusage promoter 170 million weighted shares in the calculation of raw materials is 59-62% with a selectivity to isobutane 99%, in similar conditions the conversion of pentane and hexane is 75 and 88%, respectively. Selectivity to isopentane is 98.5%isohexane - 98%. The total content of the most branched isomers of hexane-dimethylbutanol in the reaction products 42-43 wt.%.

The disadvantages of this method of isomerization of n-paraffins in the presence of a catalyst based on chlorinated alumina is the sensitivity of the catalyst to sulfur, fluorine, alkali compounds, and water, which irreversibly inactivate the catalyst. As a result, there are increased requirements to the content of trace contaminants in raw materials relative concentrations of water, sulfur, fluorine and alkali compounds, which should be 2-5 million weighted shares.

The known method using zeolite catalysts for the isomerization of pentane-hexane hydrocarbon fractions (U.S. Pat. U.S. No. 5639933, C 07 C 5/22, 17.06.1997).

As catalysts usually used crednerite and broad porous zeolites of the following structural types: ZSM-5, mordenite, and Beta, which modify 0.3 to 0.5 wt.% platinum or palladium. The optimal temperature in the region of the isomerization process in the presence of mordenite or zeolite Beta is 200-270°zeolite ZSM-5 - 320-380°C. the isomerization Process is carried out in the presence of 0.5-1 mol H2/mol si the article. When carrying out the isomerization of pentane-hexane fraction on the mordenite is achieved by conversion of n-pentane 72%, the conversion of n-hexane 83%. Selectivity to isopentane is 97%isohexane - 96%. The total content of the most branched isomers of hexane - dimethylbutanol in the reaction products 39-40 wt.%. The catalyst is not sensitive to high concentrations of sulfur and water in raw materials.

The disadvantage of these methods isomerization of n-paraffins in the presence of catalysts based on zeolites is the need to work in a high-temperature region, which is not thermodynamically favorable in relation to education of the most branched isomers with high octane values of the index.

There are also known processes for the isomerization of hydrocarbon fractions in the presence of catalysts based on sulfated metal oxides, mainly on the basis of sulfated Zirconia, modified with platinum, palladium, Nickel, iron or manganese.

According to the method described in U.S. Pat. U.S. No. 5382731, C 07 C 1/00, 17.01.1995, know the use of halogen-containing promoters, in particular of carbon tetrachloride for the process of isomerization of hydrocarbon mixtures containing cycloparaffin, with the aim of increasing the activity of the catalyst in the reaction disclosure cycle using catalytics what their systems on the basis of zirconium oxide, modified oxide of tungsten or molybdenum.

In accordance with this method the preparation of the catalyst involves the following stages:

the precipitation of zirconium hydroxide from a solution of zirconium oxychloride 10 N solution of ammonia, followed by washing and drying the hydroxide at 140°C;

- deposition of tungsten oxide from a solution of metavolume ammonium on the moisture content of 11 wt.% followed by calcining the sample at 800°C;

- deposition of platinum from a solution chloroplatinic acid capacity, followed by drying and calcining at 300°C.

The catalyst used for the conversion of raw materials consisting of, in wt.%: 50 - hexane, 14,5 - Methylcyclopentane, and 31.7 - cyclohexane, 3,9 - benzene at 260°C, a pressure of 30 atmospheres, a weight load of hydrocarbons on the catalyst 0.6 g/gcat·h, the ratio of N2/raw=2. In the patent it is shown that the introduction into the reaction mixture 700 weight ppm of carbon tetrachloride results in increased activity of the catalyst in the reaction disclosure ring cycloparaffins 10% from 38 to 48 wt.%.

The closest in technical essence and the achieved effect is a method of obtaining and using a solid acid catalyst, disclosed in U.S. Pat. U.S. No. 4918041, 01 J 27/02; 17.04.1990.

In accordance with the method proposed sentence is Olenye catalyst consists of several stages:

- preparation of a solution of zirconium oxychloride containing 0.5 wt.% Mn, 1.5 wt.% Fe in relation to the content of zirconium in solution;

the coprecipitation of the hydroxides of zirconium, iron, and manganese in an aqueous solution of ammonia;

- washing and drying the hydrogel zirconium oxide modified with iron and manganese at room temperature;

- sulfation of the resulting material 1 M solution of ammonium sulfate;

- calcination of the obtained sample at 600°C.

In accordance with this method, the isomerization catalyst contains, wt%: 6,8 - sulfate ion, 1,5 - iron oxide, 0.5 to manganese oxide and 91.2 - Zirconia.

In accordance with this method, during the process of isomerization of n-butane at a temperature of 70°With a total weight of paraffins on the catalyst 0.15 g/gcat·h in the absence of hydrogen is achieved by the conversion of butane to isobutane 55%.

The disadvantage of this method is the low activity and the performance of the catalyst.

The present invention solves the problem of creating improved method of isomerization of n-butane by reducing the temperature and pressure of the process, increasing the productivity of the catalyst prepared on the basis of sulfated metal oxides.

Improved in comparison with the prototype performance is achieved due to:

- selection of the optimization of the carrier;

- optimization of the composition and distribution of the active component grains of the media;

- optimization of the nature and distribution of the hydrogenating component grains of the media;

- increase the activity of the catalyst due to the synthesis catalytic complex of the active component and POLYHALOGENATED on the catalyst surface.

A number of studies on the isomerization of n-paraffins (Adv. In Catalysis, 1969, V.23 supported, 1969 R-372) States that the activity of the isomerization catalysts based on chlorinated alumina has a significant influence of the porous structure of the carrier, the preferred average radius of the pores of the support shall be not less than 150 nm. In the chlorination of alumina decreases the average radius and the total volume of pores, which leads to reduction of the proportion of active grain volume of catalyst. Apparently, as a result of applying the active component on the carrier in the case of dispersed sulfated metal oxides observed a similar effect of reducing the average radius and the total pore volume. So, after sulfation of zirconium oxide is observed decline in the share of wide pores of the zirconium oxide and the formation of mesopores with an average radius of less than 100 nm. This phenomenon is associated with the reconstitution of the oxide in sulfuric acid and the formation of massive sulfate on the surface of the hydroxy is and.

In the present invention as the best media to use the oxides of metals of the III-IV groups, having an extensive system of transport pores with an average diameter of about 500 nm, obtained by granulation resulting amorphous oxide with an average particle diameter of 50-150 microns. The use of biporous oxides of metals of the III-IV groups with wide pores as a carrier or catalyst component allows you to increase the share of active grain volume of the catalyst and, hence, increase its activity.

Typically, the distribution of sulfate ion on the catalyst grain when sulfation corresponds to the radial distribution of sulfate in the catalyst grain with decreasing sulfate concentrations to the center of the grain. This leads to a suboptimal composition of the active component in the catalyst grain and affects its activity.

In the present invention, a method of uniform application of the active component on the grain aluminium oxide due to competitive sorption of sulfate from sulfuric acid media, pre-processed components, sorption capacity (SOY) which is lower than the SOY sulfate ion, and a method of producing a catalyst by mixing and subsequent granulation of the active component and microspherical alumina, ensure iwaisako formation as required porous structure of the catalyst, and uniform distribution of the active component of the catalyst grain.

Uniform distribution of the hydrogenating component of the catalyst ensures the stability of the active component in the whole grain volume of catalyst. To ensure homogeneous distribution of the hydrogenating component method was used competitive sorption of palladium and platinum on a carrier with the subsequent synthesis of sulfated oxide component on its surface.

The increase in the activity proposed in the present invention the catalyst is a consequence of the formation of the catalytic complex comprising sulfated metal oxide and POLYHALOGENATED, which can be halogenated compounds, preferably carbon tetrachloride, perchloroethylene, chloroform. The formation of the complex occurs at low temperatures 0-160°therefore, an increase in catalyst activity as a result of his handling of 0.1-3 wt.% kalogeropoulou cannot be explained by processes of chlorination, proceeding according to the literature data in the temperature region above 200°C. the Activity of the obtained catalyst complex is comparable with the activity of the aluminum chloride, sublimated on chlorinated alumina.

Thus, the task d is correspondingly proposed composition of the catalyst for isomerization of n-butane to isobutane. The catalyst is a catalytic complex of the General formula: IUxAbouty*aAn-*bnXmH2n+2-mwhere Me is the metal III-IV groups, x=1-2, y=2-3, An-anion oxygen-containing acid selected from the range of: sulfur, phosphorus, molybdenum, tungsten, or a mixture in any combination, and=from 0.01 to 0.2, b=0,01-0,1; CnXmH2n+2-m- polyhalogen hydrocarbon, where X is a halogen selected from the range of: F, Cl, Br, I, or any combination thereof, and n=1-10; m=2-22, dispersed on a porous carrier with an average radius of pores of not less than 500 nanometers and containing a hydrogenating component.

The porous carrier is an oxide of the element III-IV groups, preferably Al; Si; Zr, taken in the amount of 50-95 wt.% with respect to the catalytic complex.

The catalyst as the hydrogenating component may contain not more than 3.0 wt.% metal of group VIII, preferably palladium or platinum, or any combination thereof.

The task is also solved by a method of preparation of the catalyst of the isomerization of n-butane to isobutane at which the catalytic complex of the General formula: MexOy*aAn-*bnXmH2n+2-mwhere Me is the metal III-IV groups, x=1-2, y=2-3, An-anion oxygen-containing acid selected from the range of: sulfur, phosphorus, molybdenum, tungsten or their mixture in any to the combination, a=0.01-0.2, b=0.01-0.1, the CnXmH2n+2-m- polyhalogen hydrocarbon, where X is a halogen selected from the range of: F, Cl, Br, I, or any combination thereof, and n=1-10; m=2-22, synthesize oxide or acidic, basic or neutral metal salt of III-IV groups and oxygen-containing acid selected from the range of: sulfur, phosphorus, molybdenum, tungsten or a mixture in any combination, by impregnation or adsorption or mixture or combinations thereof with a porous carrier with an average radius of pores of not less than 500 nanometers in conjunction with a hydrogenation component, or hydrogenating component is injected previously in the media, carry out the heat treatment of the thus obtained carrier at a temperature not exceeding 800°With the subsequent restoration of the hydrogenating component and the introduction of polyhalogen hydrocarbon at a temperature of not more than 200°C.

Heat treatment of the carrier is carried out for not more than 15 p.m.

Use a porous carrier having a particle size of not more than 200 microns.

The catalytic complex contains not more than 10 wt.% polyhalogen hydrocarbon synthesized by adsorption at a temperature of not more than 200°C for no more than 5 hours

Acidic, basic or neutral metal salt of III-IV groups and oxygen-containing acid selected from the range of: sulfur, phosphorus, molybdenum, tungsten or the mixture in any combination, injected into the porous media in the amount of 2-30 wt.% with respect to the catalytic complex.

Use porous media representing the oxide of the element III-IV groups, preferably Al; Si; Zr, taken in the amount of 50-95 wt.% with respect to the catalytic complex.

As a hydrogenating component use a metal of group VIII, preferably palladium or platinum, or any combination thereof in an amount of not more than 3.0 wt.%.

The task is also solved by a method for processing balanzategui oil fractions in isobutane at a temperature of 20 to 200°mass loadings original mix 0.1-0 kg/kgcat·h, a pressure of 1-50 atmospheres, in the presence of 0.2-10 wt.% hydrogen and 0.0005-0.005 wt.% halogenated promoter, and a catalyst for use described above, prepared as described above.

There are two variants of the method of preparation of the catalyst.

In the first embodiment as a starting material for the preparation of the catalyst of the proposed method using oxide, an acidic, basic or neutral metal salt of III-IV groups that are dispersed on a porous carrier by impregnation. Next, the source material thermoablative at temperatures of 300-800°C. To the resulting material is injected anions of acid - sulfate, phosphate, tungstate or molybdate or a mixture by PR the tiles with a solution, containing the appropriate acid or salt. Hydrogenating component (palladium or platinum) is administered either beforehand on a porous carrier, or after heat treatment of the catalyst.

According to the second variant of the solution containing the metal III-IV groups, hydrogenating component (platinum or palladium), anion oxygen-containing acid, homogenized with a porous carrier having a particle size of 50-150 microns, and subjected to granulation. The catalyst thermoablative at a temperature of 450-800°C.

Thus prepared catalyst is placed in a flow reactor, rinsed or nitrogen, or hydrogen, or inert gas, and then served galgenwaard at a temperature of 0-200°at the rate of 10-1000 µl/gcat·h in a stream of hydrogen, nitrogen or inert gas with a speed of 50-1000 h-1. Then served hydrogen, promoter and hydrocarbons at a cost of 0.1-10 h-1, a molar ratio hydrogen/hydrocarbons 0.1 to 10; a temperature of 20-200°C, pressure of 50 ATM.

The invention is illustrated by the following examples.

Example 1. The catalyst is prepared by the first option.

A. Deposition of palladium on alumina.

100 g of aluminum oxide (gamma-form surface by adsorption of nitrogen 205 m2/g, average pore 320 nanometers, the content of oxides of alkali metals is not more than 0.05 mA is.%) placed in a beaker with a capacity of 2 l, poured 500 ml of distilled water and with stirring, add 1 ml of glacial acetic acid. A solution of palladium chloride, obtained by dissolving 0,643 g of palladium chloride containing metal 59 wt.% in 3 ml of concentrated hydrochloric acid, dilute to volume 18 ml of distilled water and added dropwise with stirring is added to a suspension of aluminum oxide for 1 h To complete the adsorption of palladium from a solution sample is stirred for 1 hour

After adsorption, the sample is decanted and dried for 3 hours at a temperature of 130°C.

Calcined in air flow at a temperature of 750°C for 2 hours Obtain 98 g of aluminum oxide containing 0.39 wt.% Pd.

B. Sulfation of aluminum oxide modified with palladium.

To 89 g of the sample obtained by p.a. is added with stirring to 70 ml of a solution containing 19.5 g of 96% sulfuric acid in distilled water. The wet granules are dried in air to friable state, then at 200°C for 1 h

Calcined in air flow at 500°C for 2 hours

Obtain 102 g of the sample with the sulfate content of 18.7 wt.%.

The composition of the synthesized catalyst and catalytic complex are shown in table 1.

3.2 g of catalyst was loaded into an isothermal microreactor, carry out the restoration of palladium in hydrogen flow 375 h-1PR is the temperature 145° C and a pressure of 1 ATM for 1 h Synthesis catalytic complex on the surface of the catalyst is carried out by feeding 100 microlitres of carbon tetrachloride into the reactor in a stream of hydrogen 375 h-1at a temperature of 145°and a pressure of 1 ATM for 15 min, and then fed into the reactor a mixture of butane containing 30 ppm of carbon tetrachloride, and hydrogen, taken in a molar ratio of 0.02 to hexane with a massive load on the catalyst 4 h-1the hexane at a temperature of 145°and a pressure of 15 ATM.

Analysis of the reaction products is performed gas chromatography on a capillary column Gas-Pro length 30 m, internal diameter of 0.25 mm

From gas chromatographic data analysis calculate the conversion of n-butane selectivity of the formation of isobutane. Get the following indicators of activity and selectivity of the catalyst.

Conversion of n-butane56,0%.
The selectivity of the formation of isobutane96,4%.

The results show that isomerization of n-butane in the presence of a catalytic complex, composed of sulfated alumina and carbon tetrachloride leads to increased activity of sulfated alumina to the level of activity of the sulfated oxide CID is one, demonstrated in the prototype.

Example 2.

of 6.9 g of the catalyst obtained in example 1, is loaded into an isothermal microreactor, carry out the restoration of palladium in hydrogen flow 375 h-1at a temperature of 145°and a pressure of 1 ATM for 1 h, and then fed into the reactor a mixture of n-butane, which does not contain carbon tetrachloride, and hydrogen, taken in a molar ratio of 0.07 mass load on the catalyst 1 h-1the hexane at a temperature of 145°and a pressure of 15 ATM.

Get the following indicators of activity and selectivity of the catalyst.

Conversion of n-butane3,0%.
The selectivity of the formation of isobutane99,9%.

The results show that in the absence of surface catalytic complex of carbon tetrachloride catalyst is practically not active in the isomerization process.

Example 3.

A. Deposition of palladium on alumina.

100 g of aluminum oxide (gamma-form surface by adsorption of nitrogen 205 m2/g, average pore 320 nanometers, the content of oxides of alkali metals is not more than 0.05 wt.%) placed in a beaker with a capacity of 2 l, poured 500 ml of distilled water and with stirring, add 1 ml of glacial acetic acid. A solution of palladium chloride, receive the config dissolution 0,643 g of palladium chloride containing metal 59 wt.% in 3 ml of concentrated hydrochloric acid, dilute to volume 18 ml of distilled water and added dropwise with stirring is added to a suspension of aluminum oxide for 1 h To complete the adsorption of palladium from a solution sample is stirred for 1 hour

After adsorption, the sample is decanted and dried for 3 hours at a temperature of 130°C.

Calcined in air flow at a temperature of 750°C for 2 hours Obtain 98 g of aluminum oxide containing 0.39 wt.% Pd.

B. Application of zirconium oxide on alumina. A solution of 45.5 g of oxynitride zirconium in 70 ml of distilled water is put on capacity 89 g of the sample obtained by the PA, the sample is dried at 120°C for 2 h and calcined at 600°C for 5 hours Get of 100.2 g of the sample with the content of zirconium oxide and 11.2 wt.%.

C. Sulfation of zirconium oxide deposited on alumina modified with palladium. To 89 g of the sample obtained by Pb, is added with stirring to 70 ml of a solution containing 22 g of 96% sulfuric acid in distilled water. The wet granules are dried in air to friable state, then at 200°C for 1 h

Calcined in air flow at 500°C for 2 hours

Obtain 119 g of the sample containing sulfate 15.9 wt.%. The composition of the synthesized catalyst and catalytic complex are shown in table 1.

2.7 g of the catalyst load of thermal microreactor, spend synthesis catalytic complex and the isomerization of n-butane, as in example 1, with the mass load on the catalyst 4,3 h-1for n-butane at a temperature of 139°and pressure of 17 ATM.

Get the following indicators of activity and selectivity of the catalyst.

Conversion of n-butane65,0%.
The selectivity of the formation of isobutane98,3%.

The results show that isomerization of n-butane in the presence of a catalytic complex, synthesized from sulfated zirconium oxide dispersed on the alumina and carbon tetrachloride, increases the performance of the isomerization process in comparison with the prototype.

Example 4. The catalyst prepared according to the second option.

A. preparation of a solution of the active component. 31.7 g of zirconium sulfate, 4.9 g of concentrated sulfuric acid dissolved in 32 g of distilled water at room temperature for 5 h, after complete dissolution of the components added to 0.22 g of palladium chloride.

B. Preparation of isomerization catalyst. Received the item And the solution is homogenized with 66,9 g of amorphous alumina, representing the resulting granules with a mean diameter of 10 microns, average radius of the pores 510 nm, surface adsorption of nitrogen 270 m2/g in the presence of 7.0 ml of concentrated nitric acid and granularit by extrusion into pellets with a diameter of 2 mm, the Granular catalyst is dried at 120°C for 4 h, and calcined at 550°C for 2 hours

The resulting catalyst contains, wt%: 11,0 - zirconium oxide, 21.3 - sulfate ion, 0.15 - palladium, the rest is aluminum oxide. The composition of the synthesized catalyst and catalytic complex are shown in table 1.

3.6 g of catalyst was loaded into an isothermal microreactor, conduct synthesis catalytic complex and the isomerization process as in example 1 except that the baking temperature of the catalytic complex is 80°C process temperature 95°C load n-butane 3 h-1.

Get the following indicators of activity and selectivity of the catalyst.

Conversion of n-butane71,0%.
The selectivity of the formation of isobutaneof 99.5%.

Example 5.

The preparation of the catalyst were carried out as in example 4, except that instead of sulfuric acid in the preparation of a solution of the active component used to 4.23 g of zirconium oxychloride. The resulting catalyst contains, the AC.%: 11,0 - zirconium oxide, 18.3 - sulfate ion, 0.15 - palladium, the rest is aluminum oxide.

The isomerization process is conducted as in example 4.

Get the following indicators of activity and selectivity of the catalyst.

Conversion of n-butane73,0%.
The selectivity of the formation of isobutane99,3%.

Example 6.

The preparation of the catalyst were carried out as in example 4, except that instead of the aluminum oxide using silicon oxide.

The isomerization process is conducted as in example 4.

Get the following indicators of activity and selectivity of the catalyst.

Conversion of n-butane67,0%.
The selectivity of the formation of isobutane99.7 per cent.

Example 7.

The isomerization process is conducted as in example 4, except that the process temperature is 70°C.

Get the following indicators of activity and selectivity of the catalyst.

Conversion of n-butane59,0%.
The selectivity of the formation of isobutane99,8%.

Example 8.

The isomerization process is conducted as in example 4, except that the process temperature is 120° C.

Get the following indicators of activity and selectivity of the catalyst.

Conversion of n-butane76,0%.
The selectivity of the formation of isobutaneof 91.3%.

Example 9.

The isomerization process is conducted as in example 4, except that the mass loading on the catalyst for n-butane is 6,1 h-1.

Get the following indicators of activity and selectivity of the catalyst.

Conversion of n-butane62,0%.
The selectivity of the formation of isobutane99,9%.

Example 10.

The isomerization process is conducted as in example 4, except that the mass loading on the catalyst for n-butane is 0.8 h-1.

Get the following indicators of activity and selectivity of the catalyst.

Conversion of n-butane90,0%.
The selectivity of the formation of isobutane71,4%.

Example 11.

The isomerization process is conducted as in example 4, except that the molar ratio of hydrogen/ butane is 3.

Get the following indicators of activity and selectivity of the catalyst.

Conversion of n-butane63,0%.
The selectivity of the formation of isobutane99,9%.

Example 12.

The isomerization process is conducted as in example 4, except that the molar ratio of hydrogen/ butane equal to 0.005.

Get the following indicators of activity and selectivity of the catalyst.

Conversion of n-butane79,0%.
The selectivity of the formation of isobutaneof 89.1%.

Example 13.

The preparation of the catalyst were carried out as in example 4, except that instead of sulfuric acid in the preparation of a solution of the active component used 14,23 g of zirconium oxychloride. The resulting catalyst contains, wt%: 11.0 zirconium oxide, 5.3 sulfate ion, 0.15 palladium, the rest is aluminum oxide. The composition of the synthesized catalyst and catalytic complex are shown in table 1.

The isomerization process is conducted as in example 4.

Get the following indicators of activity and selectivity of the catalyst.

Conversion of n-butane48,0%
The selectivity of the formation of isobutaneof 99.1%.

Example 14.

The isomerization process is conducted as in example 4, except that, what to prepare catalytic complex used tetrachlorethylene. The composition of the catalytic complex are shown in table 1.

Get the following indicators of activity and selectivity of the catalyst.

Conversion of n-butane75,0%
The selectivity of the formation of isobutane99,4%.

Example 15.

The isomerization process is conducted as in example 4, except that for the preparation of the catalytic complex used chloroform. The composition of the catalytic complex are shown in table 1.

Get the following indicators of activity and selectivity of the catalyst.

Conversion of n-butane66,0%
The selectivity of the formation of isobutane99,9%.

Example 16.

The isomerization process is conducted as in example 4, except that for the preparation of the catalytic complex used trichlorpropane. The composition of the catalytic complex are shown in table 1.

Get the following indicators of activity and selectivity of the catalyst.

Conversion of n-butane51,0%
The selectivity of the formation of isobutane/td> 99,9%.

Example 17.

The isomerization process is conducted as in example 4, except that for the preparation of the catalytic complex used tetrabromophenol. The composition of the catalytic complex are shown in table 1.

Get the following indicators of activity and selectivity of the catalyst.

Conversion of n-butane56,0%
The selectivity of the formation of isobutaneof 99.1%.

Example 18.

The preparation of the catalyst are as in example 4, except that instead of sulfuric acid using a solution of 14.3 g of metavolume of ammonia in 120 ml of water. The composition of the synthesized catalyst and catalytic complex are shown in table 1.

Isomerization of n-butane are in the conditions of example 4.

Get the following indicators of activity and selectivity of the catalyst.

Conversion of n-butane4,2%
The selectivity of the formation of isobutane99,9%.

Example 19.

The preparation of the catalyst are as in example 4, except that instead of sulfuric acid using a solution of 17.0 g of metavolume of ammonia in 120 ml of water. The composition of the synthesized catalyst and kataliticheskikh are shown in table 1.

Isomerization of n-butane are in the conditions of example 4.

Get the following indicators of activity and selectivity of the catalyst.

Conversion of n-butane3,7%
The selectivity of the formation of isobutane99,9%.

Example 20.

The preparation of the catalyst are as in example 4, except that instead of palladium chloride used solution hexachloroplatinic acid. The composition of the synthesized catalyst and catalytic complex are shown in table 1.

Isomerization of n-butane are in the conditions of example 4.

Get the following indicators of activity and selectivity of the catalyst.

Conversion of n-butane69,0%
The selectivity of the formation of isobutane99,3%.

Example 21.

The preparation of the catalyst are as in example 4, except that instead of palladium chloride, a mixture solution hexachloroplatinate and tetrachloropalladate acid. The composition of the synthesized catalyst and catalytic complex are shown in table 1.

Isomerization of n-butane are in the conditions of example 4.

Get the following indicators of activity and selectivity of the catalyst.

Conversion of n-butane68,0%
The selectivity of the formation of isobutane99,6%.

Example 22.

The preparation of the catalyst are as in example 4, except that for the preparation of the catalytic complex use 150 ál of tetrachloride carbon. The composition of the catalytic complex are shown in table 1.

Isomerization of n-butane are in the conditions of example 4.

Get the following indicators of activity and selectivity of the catalyst.

Conversion of n-butane73,0%
The selectivity of the formation of isobutane89.4 per cent.

Example 23.

The preparation of the catalyst are as in example 4, except that for the preparation of the catalytic complex using 70 μl of tetrachloride carbon. The composition of the catalytic complex are shown in table 1.

Isomerization of n-butane are in the conditions of example 4.

Get the following indicators of activity and selectivity of the catalyst.

Conversion of n-butane63,0%
The selectivity of the formation of isobutane99,8%.

Example 24.

The preparation of the catalyst are for example 3, except that the instead of oxynitride use of zirconium chloride of tin. The composition of the synthesized catalyst and catalytic complex are shown in table 1.

Isomerization of n-butane are in the conditions of example 4.

Get the following indicators of activity and selectivity of the catalyst.

Conversion of n-butane49,0%
The selectivity of the formation of isobutane99,9%.

Thus, as seen from the above examples, the present invention allows to create an improved method for the isomerization of n-butane by reducing the temperature and pressure of the process, increasing the productivity of the catalyst prepared on the basis of sulfated metal oxides.

td align="center"> 0.2*SO4
Table 1
The composition of catalysts and catalytic complexes of the isomerization of n-butane
No. when

measure
The composition of the catalytic complex, molCatalyti-

ical complex, wt.%
Media, wt.%The metal of group VII, wt.%
IUxAboutyAn-CnXmH2n+2-m,
1Al2O30,05*CCl424,61Pd-0.39Al2O3-75
2Al2O30.2*SO4024,61Pd-0.39Al2O3-75
3ZrO20.16*SO40,05*CCl426,61Pd-0.31Al2O3-73
4ZrO20.19*SO40,05*CCl434,85Pd-0.15Al2O3-65
5ZrO20.12*SO40,05*CCl421,85Pd-0.15Al2O3-78
6ZrO20.19*SO40,05*CCl434,85Pd-0.15Al2O3-65
7ZrO20.19*SO40,05*CCl434,85Pd-0.15Al2O3-65
8ZrO20.19*SO40,05*CCl434,85Pd-0.15Al2O3-65
9ZrO20.19*SO 40,05*CCl434,85Pd-0.15Al2O3-65
10ZrO20.19*SO40,05*CCl434,85Pd-0.15Al2O3-65
11ZrO20.19*8O40,05*CCl434,85Pd-0.15Al2O3-65
12ZrO20.19*SO40,05*CCl434,85Pd-0.15Al2O3-65
13ZrO20.05*SO40,05*C2Cl424,85Pd-0.15Al2O3-75
14ZrO20.05*WO40,05*CHCl324,85Pd-0.15Al2O3-75
15ZrO20.05*WO40,05*CCl428,85Pd-0.15Al2O3-71
16ZrO20.08*WO40,05*CCl431,85Pd-0.15Al2O3-68
17ZrO2 0.19*SO40,05*CCl434,85Pt-0.15Al2O3-65
18ZrO20.19*SO40,08*CCl434,85Pd-0.15Al2O3-65
19ZrO20.19*SO40,01*CCl434,85Pd-0.15Al2O3-65
20ZrO20.19*SO40,01*CCl434,85Pd-0.15Al2O3-65
21ZrO20.19*SO40,01*CCl434,85Pd-0.15Al2O3-65
22ZrO20.19*SO40,01*CCl434,85Pd-0.15Al2O3-65
23ZrO20.19*SO40,01*CCl434,85Pd-0.15Al2O3-65
24SnO20.16*SO40,05*CCl434,85Pd-0.31Al2O3-73

1. The catalyst for the process isomers is of n-butane to isobutane, incorporating the metal oxide III-IV groups, anion oxygen-containing acid, characterized in that it is a catalytic complex of the General formula MexOy*aAn-*b CnXmH2n+2-mwhere Me is the metal III-IV groups, x=1-2, y=2,3, An-anion oxygen-containing acid selected from the range of: sulfur, phosphorus, molybdenum, tungsten or a mixture in any combination, and=from 0.01 to 0.2, b=0,01-0,1; CnXmH2n+2-m- polyhalogen hydrocarbon, where X is a halogen selected from the range of: F, Cl, Br, I or any combination thereof, and n=1-10; m=2-22, dispersed on a porous carrier with an average radius of pores of not less than 500 nm, and containing a hydrogenating component.

2. The catalyst of claim 1, wherein the porous carrier is an oxide of the element III-IV groups, preferably Al; Si; Zr, taken in the amount of 50-95 wt.% with respect to the catalytic complex.

3. The catalyst according to claim 1, characterized in that the catalyst as the hydrogenating component may contain not more than 3.0 wt.% metal of group VIII, preferably palladium or platinum, or any combination of them.

4. The method of preparation of the catalyst of the isomerization of n-butane to isobutane, incorporating a metal oxide III-IV groups, anion oxygen-containing acid, characterized in that the catalytic complex of the General formula: the e xAbouty*aAn-*bnXmH2n+2-mwhere Me is the metal III-IV groups, x=1-2, y=2-3, An-anion oxygen-containing acid selected from the range of: sulfur, phosphorus, molybdenum, tungsten or a mixture in any combination, and=from 0.01 to 0.2, b=0.01 and 0.1, WithnXmH2n+2-m- polyhalogen hydrocarbon, where X is a halogen selected from the range of: F, Cl, Br, I or any combination thereof, and n=1-10; m=2-22, synthesize oxide or acidic, basic or neutral metal salt of III-IV groups and oxygen-containing acid selected from the range of: sulfur, phosphorus, molybdenum, tungsten or a mixture in any combination, by impregnation or adsorption, or mixing, or combinations thereof with a porous carrier with an average radius of pores of not less than 500 nm in conjunction with a hydrogenation component, or hydrogenating component previously administered in the media, carry out the heat treatment of the thus obtained carrier at a temperature not exceeding 800°With subsequent recovery of the hydrogenating component and the introduction of polyhalogen hydrocarbon at a temperature of not more than 200°C.

5. The method according to claim 4, characterized in that the heat carrier is carried out for not more than 15 p.m.

6. The method according to claim 4, characterized in that the use of a porous carrier having a particle size of less than 200 microns.

7. The method according to claim 4, characterized in that calificaci complex contains not more than 10 wt.% polyhalogen hydrocarbon, synthesized by adsorption at a temperature of not more than 200°C for no more than 5 hours

8. The method according to claim 4, characterized in that an acidic, basic or neutral metal salt of III-IV groups and oxygen-containing acid selected from the range of: sulfur, phosphorus, molybdenum, tungsten or a mixture in any combination, injected into the porous media in the amount of 2-30 wt.% with respect to the catalytic complex.

9. The method according to claim 4, characterized in that use porous media representing the oxide of the element III-IV groups, preferably Al; Si; Zr, taken in the amount of 50-95 wt.% with respect to the catalytic complex.

10. The method according to claim 4, characterized in that the catalyst is introduced as hydrogenating component is not more than 3.0 wt.% metal of group VIII, preferably palladium or platinum, or any combination of them.

11. Way catalytic isomerization of n-butane to isobutane, characterized in that the catalyst used catalyst according to any one of claims 1 to 10.

12. The method according to claim 11, characterized in that the catalytic isomerization of n-butane is carried out at a temperature of not more than 200°mass loadings initial mixture is not more than 10 kg/kgcat·h, pressure of 50 atmospheres, in the presence of not more than 10 mol.% of hydrogen.

13. The method according to claim 11, characterized in that the hydrocarbon feedstock for the process some is Itachi use the fraction of n-butane, containing not more than 0.01 wt.% water or oxygen-containing compounds, not more than 0.15 wt.% compounds of sulphur, not more of 0.0005 wt.% nitrogen compounds or compounds of alkali metals.



 

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