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

FIELD: petrochemical process catalysts.

SUBSTANCE: invention relates to catalytic methods of isomerizing n-paraffins 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-paraffins utilizing above-defined catalyst is also described.

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

17 cl, 3 tbl, 25 ex

 

The invention relates to the field of petrochemicals, namely catalytic methods isomerization of normal paraffins structure.

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 With4-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 narrowing of cycle n is fanovich components, 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 C4-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*hour, the concentration of chlorine is terasawa 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 with the earth with the total amount. 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 Catalytica is of such 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 (U.S. Pat. U.S. No. 6448198, B 01 J 27/053, 10.09.2002).

The preparation of the catalyst used in this method consists of the escolca stages:

two - time application of zirconium oxychloride on alumina from an aqueous solution of zirconium oxychloride with an intermediate calcining at 500°C;

- calcination of the obtained sample at 800°C;

- sulfation of the resulting material with a solution of 5N sulfuric acid;

- calcining the resulting material at 500°C;

- modification of 0.3 wt.% platinum by impregnation of the sample solution hexachloroplatinate acids;

- the calcination of the material obtained at 500°C.

Indicators of activity of the catalyst is determined in the isomerization of n-hexane at 145°C, a pressure of 30 ATM, the weight load on the catalyst in hexane 4 g/gcat*h & H2/hexane=3. The catalyst is judged by the content of 2.2 Dimethylbutane in the reaction products, which is in these terms 27-28 wt.%. In the patent concludes approximate correspondence of the activity of the catalyst industrial designs of isomerization catalysts based on chlorinated alumina.

Information about the conversion of hexane and the selectivity of the process in the patent is not given.

The disadvantage of the proposed method is the difficulty of preparation of the catalyst, and high consumption of hydrogen in the conversion of hydrocarbons.

The present invention solves the problem of creating improved method p is ocess isomerization of n-paraffins in the isoparaffin fraction 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:

- optimization of the porous structure of the media;

- 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 oxide zirconiabased 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 oxide.

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, especially in the isomerization of hydrocarbons with the number of carbon atoms greater than 5.

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, sorbl the fair exchange capacity (SOY) which is lower than SOY sulfate ion, and a method of producing a catalyst by mixing and subsequent granulation of the active component and microspherical alumina, providing the formation as required porous structure of the catalyst and a homogeneous 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, the current flowing through the literature dealing with the major 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 problem is solved by the proposed composition of the catalyst for isomerization of n-paraffins in the isoparaffin fraction. 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, which catalitic the ski complex of the General formula: Me xOy·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=0.01-0.2, b=0.01-0.1, thenXmH2n+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 nanometers in conjunction with the hydrogenating 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 subsequent recovery 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 hours 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 what adsorbsia 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 a 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.

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.

The problem is solved by a method for processing wax oil fractions in the isoparaffin fraction with an octane rating no lower than 84 by the motor method and an end boiling point not higher than 200°consisting in the conversion of paraffins With5-C8normal structure at a temperature of 30-200°mass load initial mixture of 0.1-10 kg/kgcat*hour, a pressure of 1-50 atmospheres, in the presence of 0.2-10 wt.%. hydrogen and not more than 0.1 wt.% halogenated promoter, and a catalyst using the above catalyst prepared by the above method.

The main distinguishing feature of the proposed method is that the isomerization of n-paraf the new C 5-C8carried out in the presence of a catalyst comprising a complex of polyhalogen hydrocarbon with the General formula CnXmH2n+2-m, acidic, basic or neutral metal salt of III-IV groups, oxygen-containing acid selected from the range of: sulfur, phosphorus, molybdenum, tungsten, which previously termoobrabotannyj at a temperature of 450-800°C for 0.5 to 15 hours, and the metal of group VIII.

The technical effect of the proposed method is that when the conversion of n-paraffins C5-C8normal structure at a temperature of 30-200°mass load initial mixture of 0.1-10 kg/kgcat*hour, a pressure of 1-50 atmospheres, in the presence of 0.02 to 80 wt %. hydrogen and optionally halogen-containing promoter in an amount of not more than 0.1 wt.% and in the presence of the specified catalyst formed isoparaffin fraction with an octane rating no lower than 84 by the motor method and an end boiling point not higher than 180°C.

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 raw material ThermoBrite shall indicate at a temperature of 450-800° C. To the resulting material is injected anions of acid - sulfate, phosphate, tungstate or molybdate or a mixture by impregnation with a solution containing the appropriate acid or salt. Hydrogenating component (palladium or platinum, or a mixture thereof) is administered either beforehand on a porous carrier, or after heat treatment of the catalyst.

According to the second variant of the method, the solution containing the metal III-IV groups, hydrogenation component is platinum or palladium, or their mixture, the oxygen-containing anion of the 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.

Prepared according to any of the options for the 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*hours 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 to 10.0 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. Preparation of the catalyst according to the first option.

A. Deposition of palladium on aluminum oxide is tion. 100 g of aluminum oxide (gamma-form, the average radius of the pores 320 nanometers, the surface adsorption of nitrogen 205 m2/g, 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, obtained by dissolving 0,643 g of palladium chloride containing metal 59 wt.% in 3 ml of concentrated hydrochloric acid diluted to a volume of 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.%.

3.2 g of the catalyst load of thermal microreactor, carry out the restoration of palladium in hydrogen flow 375 h-1at a temperature of 145°C, a pressure of 1 ATM for 1 h Synthesis catalytic complex on the surface of the catalyst is carried out by feeding 10 microlitres of carbon tetrachloride into the reactor in a stream of hydrogen 375 h-1at a temperature of 145°C, a pressure of 1 ATM for 15 min, and then fed into the reactor a mixture of hexane containing 10 ppm of carbon tetrachloride, and hydrogen, taken in a molar ratio of 0.07 to hexane with a massive load on the catalyst 4 h-1in hexane, at a temperature of 145°C, a pressure of 15 ATM.

Analysis of the reaction products is performed gas chromatography on a capillary column DB1. From gas chromatographic data analysis calculate the conversion of hexane, the selectivity of the formation of dimethylbutanol and methylpentanol.

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

Conversion of n-hexane, %88,0
The selectivity of the formation of C6 isomers, %of 99.1
The content of dimethylbutanol in the reaction products, wt.%.41,3
The content of 2.2-Dimethylbutane, wt.%29,3.

The results show that isomerization of n-hexane in the presence of triticosecale complex, composed of sulfated alumina and carbon tetrachloride leads to increased activity of sulfated alumina to the level of activity of sulfated Zirconia, demonstrated in the prototype.

Example 2.

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

Conversion of n-hexane, %13,0
The selectivity of the formation of C6 isomers, %99,9
The content of dimethylbutanol in the reaction products, wt.%2,3
The content of 2.2-Dimethylbutane, wt.%1,1.

The results show that in the absence of surface catalytic complex of carbon tetrachloride activity of the catalyst, expressed in the conversion of n-hexane, below 7 times.

Example 3.

A. Application of ballad is I on alumina. 100 g of aluminum oxide (gamma-form, the average radius of the pores 320 nanometers, the surface adsorption of nitrogen 205 m2/g, 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, 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 h After completion of 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 B, 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.%.

2.1 g of catalyst was loaded into an isothermal microreactor, conduct synthesis catalytic complex and process for the isomerization of hexane as in example 1, with the mass load on the catalyst 6 h-1in hexane, at a temperature of 135°C, a pressure of 12 ATM. Get the following indicators of activity and selectivity of the catalyst.

Conversion of n-hexane, %89,0
The selectivity of the formation of C6 isomers, %99,0
The content of dimethylbutanol in the reaction products, wt.%42,3
The content of 2.2-Dimethylbutane, wt.%33,3.

The results show that isomerization of n-hexane in the presence of catalytic complex containing sulfated zirconium oxide, dispersed aluminum oxide, and carbon tetrachloride, increases the performance of the isomerization process and content of 2.2-Dimethylbutane compared to p what otation.

Example 4.

2.1 g of catalyst according to example 3 is loaded into an isothermal microreactor, conduct synthesis catalytic complex and the process of isomerisation of heptane as in example 1, with the mass load on the catalyst 6 h-1for heptane, at a temperature of 110°C, a pressure of 12 ATM, the molar ratio hydrogen/heptane equal to 0.5. Get the following indicators of activity and selectivity of the catalyst.

Conversion of n-heptane, %97,0
The selectivity of the formation of isomers of C7, %81,0.

Example 5.

2.1 g of catalyst according to example 3 is loaded into an isothermal microreactor, conduct synthesis catalytic complex and the isomerization process of octane as in example 1, with the mass load on the catalyst 6 h-1in octane at a temperature of 90°C, a pressure of 12 ATM, the molar ratio hydrogen/heptane equal to 0.5. Get the following indicators of activity and selectivity of the catalyst.

Conversion of n-octane %97,0
The selectivity of the formation of C8 isomers, %71,3.

Example 6.

2.1 g of catalyst according to example 3 is loaded into an isothermal microreactor, conduct synthesis catalytic complex and the process isomers the tion of hexadecane, as in example 1, with the mass load on the catalyst 6 h-1on hexadecane, at a temperature of 90°C, a pressure of 12 ATM, the molar ratio hydrogen/hexadecan equal to 2. Get the following indicators of activity and selectivity of the catalyst.

Conversion of n-hexadecane, %98,0
The selectivity of the formation of isomers From 16 %12,3.

Example 7.

2.1 g of catalyst according to example 3 is loaded into an isothermal microreactor, conduct synthesis catalytic complex and process for the isomerization of cyclohexane, as in example 1, with the mass load on the catalyst 6 h-1in cyclohexane, at a temperature of 100°C, a pressure of 12 bar and a molar ratio hydrogen/cyclohexane equal to 0.05. Get the following indicators of activity and selectivity of the catalyst.

The conversion of cyclohexane, %48,0
The selectivity of the formation of isomers From 16 %99,7.

Example 8.

The preparation of the catalyst is conducted according to example 3, except that the intermediate sample, prepared in part B of example 3 is treated with 300 ml of a solution containing 2.5 wt.% hydrochloric acid for 3 hrs, dried at 120°C. the result is 121 g of which were acquired with the sulfate content of 18.1 wt.%.

2.0 g of catalyst was loaded into an isothermal microreactor, conduct synthesis catalytic complex and process for the isomerization of hexane as in example 1, with the mass load on the catalyst 6,1 h-1in hexane, at a temperature of 120°C, a pressure of 10 ATM. Get the following indicators of activity and selectivity of the catalyst.

Conversion of n-hexane, %88,0
The selectivity of the formation of C6 isomers, %99,6
The content of dimethylbutanol in the reaction products, wt.%45,3
The content of 2.2-Dimethylbutane, wt.%34,6.

The results show that the use of competitive sorption of sulfate in the preparation of the catalyst significantly increases its activity.

Example 9.

2.0 g of the catalyst obtained in example 8, loaded into an isothermal microreactor, conduct synthesis catalytic complex and the isomerization process as in example 8, except that for the process using n-hexane containing 0,008 wt.% water, and 0.15 wt.% thiophene sulfur. The process should be performed within 72 h after the fall of the activity of the reactor temperature was raised to 160°and rinsed with hydrogen at a speed of 400 h-1within 2 h, and then ve is ut the isomerization process in the conditions of example 8.

Indicators of activity and selectivity of the catalyst are shown in table 1

Table 1
Time, mileage, hour10527210
The number of submitted materials, g/g cat63
H2Oh, g/g-catalyst0,0050,026being 0.0360,005
Conversion of n-hexane, %89867388
The isomerization selectivity, %99,899,999,999,7
The content of dimethylbutanol in the reaction products, wt.%44,842,326,144,1
The content of 2.2-Dimethylbutane in the reaction products, wt.%33,930,714,232,1

The results show that the catalytic complex is resistant to sulfur-containing impurities and water impurities in raw materials, the catalytic activity of the complex is recovered after heating the reactor at a temperature of 150-170°C.

Example 10. The catalyst prepared according to the second option.

A. you need a kitchen the other 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 120 microns, an average pore 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 of 11.0 wt.% zirconium oxide, 21.3 wt.% the sulfate ion, 0.15 wt.% palladium, the rest is aluminum oxide.

2.9 g of catalyst was loaded into an isothermal microreactor, conduct synthesis catalytic complex and the isomerization process as in example 8, except that the temperature of the catalytic complex is 50°With, the process temperature is 70°With, the burden of hexane is 4 h-1. Get the following indicators of activity and selectivity of the catalyst.

To the version of n-hexane, %90,0
The selectivity of the formation of C6 isomers, %99,8
The content of dimethylbutanol in the reaction products, wt.%52,1
The content of 2.2-Dimethylbutane, wt.%37,6.

Example 11.

The preparation of the catalyst were carried out as in example 10, 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 of 11.0 wt.% zirconium oxide, 18.3 wt.% the sulfate ion, 0.15 wt.% palladium, the rest is aluminum oxide.

The isomerization process is conducted as in example 10. Get the following indicators of activity and selectivity of the catalyst.

Conversion of n-hexane, %93,0
The selectivity of the formation of C6 isomers, %99,3
The content of dimethylbutanol in the reaction products, wt.%54,2
The content of 2.2-Dimethylbutane, wt.%39,6

Example 12.

The isomerization process is conducted according to example 11, except that the temperature of the process 120°C. Receive the following indicators of activity and selectivity of the catalyst.

The type field is ia n-hexane, %96,0
The selectivity of the formation of C6 isomers, %69,3
The content of dimethylbutanol in the reaction products, wt.%34,2
The content of 2.2-Dimethylbutane, wt.%9,6.

Example 13.

The isomerization process is conducted according to example 11, except that the temperature of the process 42°C. Receive the following indicators of activity and selectivity of the catalyst.

Conversion of n-hexane, %82,0
The selectivity of the formation of C6 isomers, %99,9
The content of dimethylbutanol in the reaction products, wt.%39,1
The content of 2.2-Dimethylbutane, wt.%28,3.

Example 14.

The isomerization process is conducted according to example 11, except that the mass loading on the catalyst in hexane 6,3 h-1. Get the following indicators of activity and selectivity of the catalyst.

Conversion of n-hexane, %89,0
The selectivity of the formation of C6 isomers, %99,7
The content of dimethylbutanol in the reaction products, wt.%42,7
The content of 2.2-Dimethylbutane wt.% 31,4.

Example 15.

The isomerization process is conducted according to example 11, except that the mass loading on the catalyst in hexane and 1.0 h-1. Get the following indicators of activity and selectivity of the catalyst.

Conversion of n-hexane, %97,0
The selectivity of the formation of C6 isomers, %of 89.1
The content of dimethylbutanol in the reaction products, wt.%49,1
The content of 2.2-Dimethylbutane, wt.%29,6.

Example 16.

The isomerization process is conducted according to example 11, except that the molar ratio of hydrogen/hexane equal to 4. Get the following indicators of activity and selectivity of the catalyst.

Conversion of n-hexane, %81,0
The selectivity of the formation of C6 isomers, %99,9
The content of dimethylbutanol in the reaction products, wt.%49,1
The content of 2.2-Dimethylbutane, wt.%32,7.

Example 17.

The isomerization process is conducted according to example 11, except that the molar ratio of hydrogen/hexane equal to 0.01 Poluchaut the following activity indicators and selection the activity of the catalyst.

Conversion of n-hexane, %97,0
The selectivity of the formation of C6 isomers, %65,9
The content of dimethylbutanol in the reaction products, wt.%33,1.
The content of 2.2-Dimethylbutane, wt.%16,7.

Example 18.

The preparation of the catalyst is conducted according to example 11, 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 of 11.0 wt.% zirconium oxide, 5.3 wt.% the sulfate ion, 0.15 wt.% palladium, the rest is aluminum oxide.

The isomerization process is conducted according to example 10. Get the following indicators of activity and selectivity of the catalyst.

Conversion of n-hexane, %74,0
The selectivity of the formation of C6 isomers, %99,9
The content of dimethylbutanol in the reaction products, wt.%17,9
The content of 2.2-Dimethylbutane, wt.%7,0.

Example 19.

The isomerization process is conducted according to example 10, except that for the preparation of the catalytic complex used tetrachlorethylene. Get the following dormancy is the result of the activity and selectivity of the catalyst.

Conversion of n-hexane, %91,0
The selectivity of the formation of C6 isomers, %99,5
The content of dimethylbutanol in the reaction products, wt.%53,9
The content of 2.2-Dimethylbutane, wt.%38,1.

Example 20.

The isomerization process is conducted according to example 10, except that for the preparation of the catalytic complex used chloroform. Get the following indicators of activity and selectivity of the catalyst.

Conversion of n-hexane, %,88,0
The selectivity of the formation of C6 isomers,%99,8
The content of dimethylbutanol in the reaction products, wt.%41,3
The content of 2.2-Dimethylbutane, wt.%31,6.

Example 21.

The isomerization process is conducted according to example 10, except that the raw material used n-pentane, and the process temperature 80°C. Receive the following indicators of activity and selectivity of the catalyst.

Conversion of n-pentane, %83,0
The selectivity of the formation of isopentane, %99,5.

Example 22.

The isomerization process is conducted according to example 12, except that the raw material used fraction of hydrocarbons NC 21°-QC 70°C.

The results are shown in table 2.

Table 2
Raw materials, wt %The product, wt %
C1-C45.76,2
Pentane22.3632,69
Isopentane22.8012,32
2.2-Dimethylbutan1.436,93
2.3-Dimethylbutan2.123,01
2-Methylpentan8.1412,09
3-Methylpentan4.448,29
Hexane10.646,63
C7+22,3714,85

Example 23.

The preparation of the catalyst are for example 3, except that instead of sulfuric acid using a solution of 14.3 g of orthophosphoric acid in 70 ml of water.

Isomerization of n-hexane lead in the conditions of example 3. Get the following indicators of activity and selectivity of the catalyst.

The con is version n-hexane, %22,0
The selectivity of the formation of C6 isomers, %99,9
The content of dimethylbutanol in the reaction products, wt.%a 3.9
The content of 2.2-Dimethylbutane, wt.%1,3.

Example 24.

The preparation of the catalyst are for example 3, except that instead of sulfuric acid using a solution of 14.3 g of metavolume of ammonia in 120 ml of water.

Isomerization of n-hexane lead in the conditions of example 3. Get the following indicators of activity and selectivity of the catalyst.

Conversion of n-hexane, %41,0
The selectivity of the formation of C6 isomers, %99,9
The content of dimethylbutanol in the reaction products, wt.%12,4
The content of 2.2-Dimethylbutane, wt.%5,4.

Example 25.

The preparation of the catalyst are for example 3, except that instead of sulfuric acid using a solution of 17.0 g of metavolume of ammonia in 120 ml of water.

Isomerization of n-hexane lead in the conditions of example 3. Get the following indicators of activity and selectivity of the catalyst.

Conversion of n-hexane, %38,0
The selectivity of the formation of C6 isomers,%99,9
The content of dimethylbutanol in the reaction products, wt.%10,7
The content of 2.2-Dimethylbutane, wt.%3,1.

Thus, as seen from the above examples, the present invention allows to create an improved method for the isomerization of n-paraffins by reducing the temperature and pressure of the process, increasing the productivity of the catalyst.

Table 3
The composition of catalysts and catalytic complexes of the isomerization process
No. when

measure
The composition of the catalytic complex, molCatalytics

cue the complex, wt.%
Media, wt.%The metal of group VII, wt.%
IUxAboutyAn-CnXmH2n+2m,
1Al2O30.2*SO40,05*CCl424,61Pd-0.39Al2O3-75
2Al2O30.2*SO4024,61Pd-0.39 Al2O3-75
3ZrO20.16*SO40,05*CCl426,61Pd-0.31Al2O3-73
4ZrO20.16*SO40,05*CCl426,61Pd-0.31Al2O3-73
5ZrO20.16*SO40,05*CCl426,61Pd-0.31Al2O3-73
6ZrO20.16*SO40,05*CCl426,61Pd-0.31Al2O3-73
7ZrO20.16*SO40,05*CCl426,61Pd-0.31Al2O3-73
8ZrO20.19*SO40.05*CCl434,85Pd-0.15Al2O3-65
9ZrO20.18*SO40,05*CCl435,85Pd-0.15Al2O3-65
10ZrO20.19*SO40,05*CCl434,85Pd-0.15Al 2O3-65
11ZrO20.12*SO40,05*CCl421,85Pd-0.15Al2O3-78
12ZrO20.12*SO40,05*CCl421,85Pd-0.15Al2O3-78
13ZrO20.12*SO40,05*CCl421,85Pd-0.15Al2O3-78
14ZrO20.12*SO40,05*CCl421,85Pd-0.15Al2O3-78
15ZrO20.12*SO40,05*CCl421,85Pd-0.15Al2O3-78
16ZrO20.12*SO40,05*CCl421,85Pd-0.15Al2O3-78
17ZrO20.12*SO40,05*CCl421,85Pd-0.15Al2O3-78
18ZrO20.05*SO40,05*CCl424,85Pd-0.15l 2O3-75
19ZrO20.19*SO40,05*C2Cl434,85Pd-0.15Al2O3-65
20ZrO20.19*SO40,05*CHCl334,85Pd-0.15Al2O3-65
21ZrO20.19*SO40,05*CCl434,85Pd-0.15Al2O3-65
22ZrO20.12*SO40,05*CCl421,85Pd-0.15Al2O3-78
23ZrO20.16*PO40,05*CCl426,61Pd-0.31Al2O3-73
24ZrO20.05*WO40,05*CCl428,85Pd-0.15Al2O3-71
25ZrO20.08*WO40,05*CCl431,85Pd-0.15Al2O3-68

1. The catalyst for the isomerization of n-butane to isobutane, incorporating a metal oxide III-IV groups, anion key is oradatabase acid, characterized in that it is a catalytic complex with a total formore MexOy*aAn-*b CnXmH2n+2mwhere 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 for isomerization of n-paraffins in the isoparaffin fraction, consisting of a metal oxide III-IV groups, anion oxygen-containing acid, characterized in that the catalytic complex of the General formula MexOy*aAn-*b CnXmH2n+2-m, where the IU - 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, 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 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 the catalytic complex contains not more than 10 wt.% polyhalogen the seal 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. Method of isomerization of n-paraffins in the isoparaffin fraction by contacting the hydrocarbon feedstock with a catalyst, wherein the catalyst used catalyst according to any one of claims 1 to 10.

12. The method according to claim 11, characterized in that the hydrocarbon raw material is introduced optionally halogen-containing promoter in an amount of not more than 0.1 wt.%.

13. The method according to any of § § 11 and 12, characterized in that hydrocarbons are used fraction of the paraffin and/or cycloprop the new hydrocarbons with carbon atoms of not less than 5, the isomerization process is carried out at a temperature of not more than 200°mass load initial mixture is not more than 10 kg/kgcat·h, pressure of 50 atmospheres, in the presence of not more than 80 mol.% of hydrogen.

14. The method according to any of § § 11 and 12, characterized in that the hydrocarbon raw material for isomerization process using a fraction of the paraffin and/or cycloparaffinic hydrocarbons with carbon atoms of not less than 5, 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 alkaline compounds.

15. The method according to any of § § 11 and 12, characterized in that the hydrocarbon raw material for isomerization process using pentane at a temperature not exceeding 170°mass load initial mixture is not more than 10 kg/kgcat·h, pressure up to 35 MPa, in the presence of not more than 5 mol.% of hydrogen.

16. The method according to any of § § 11 and 12, characterized in that the hydrocarbon raw material for isomerization process using hexane at a temperature not exceeding 150°mass load initial mixture is not more than 10 kg/kgcat·h, pressure up to 35 MPa, in the presence of not more than 5 mol.% of hydrogen.

17. The method according to any of § § 11 and 12, characterized in that the hydrocarbon raw material for isomerization process using the cycle is hexane at a temperature not exceeding 150° With mass load initial mixture is not more than 10 kg/kgcat·h, pressure up to 35 MPa, in the presence of not more than 5 mol.% of hydrogen.



 

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31 cl, 2 tbl, 13 ex

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12 cl, 3 dwg, 1 tbl, 2 ex

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10 cl, 3 tbl, 15 ex

FIELD: petrochemical process catalysts.

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

13 cl, 1 tbl, 24 ex

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