Catalyst and isobutane alkylation process

FIELD: petrochemical processes and catalysts.

SUBSTANCE: invention concerns catalytic process for obtaining isooctane fractions via alkylation of isobutane with butylene fractions. Process involves catalytic complex having following composition: MexOy*aAn-*bCnClmH2n+2-m, wherein Me represents group III-IV metal, x=1-2, y=2-3, and An- anion of oxygen-containing acid selected from sulfuric, phosphoric, molybdenic, and tungstenic acid, or mixture thereof in any proportions; a=0.01-0,2, b=0.01-0.1; bCnClmH2n+2-m is polychlorine-substituted hydrocarbon with n=1-10 and m=1-22, dispersed on porous support and containing hydrogenation component. Alkylation process is carried out at temperature not exceeding 150°C, mass flow rate of starting mixture not higher than 3 g/g cat*h, pressure not higher than 40 atm, and in presence of 10 mol % hydrogen.

EFFECT: increased catalyst stability and selectivity.

5 cl, 3 tbl, 20 ex

 

The invention relates to the field of petrochemicals, namely, catalytic method of obtaining isooctanol fractions by alkylation of isobutane-butylene fractions.

The alkylation of isobutane olefinic fractions petrochemical industry is one of the most important processes that improve the quality of motor fuels in the energy and environmental performance.

In the alkylation reaction is a joint conversion of isobutane and butylenes with the formation of gasoline fractions containing mainly isooctane with high octane number (PTS).

The process of alkylation of isobutane provides increased performance oil refineries on high-octane components of motor fuels that meet modern environmental requirements, with low sulphur content, the absence of aromatic hydrocarbons.

The product of alkylation of isobutane - alkylate has a low vapor pressure and high octane characteristics (PTS of trimethylpentane have values of 100 and above, PTS WITH5-C7isoalkanes,9+-hydrocarbons and DMG mostly lie in the range from 70 to 93).

The process of alkylation of isobutane is catalytic. Traditionally, as catalysts are highly concentrated behold the Naya and hydrofluoric acid, however, as a result of strengthening economic and environmental requirements for industrial processes are currently under intensive development of new types of environmentally friendly catalysts for the alkylation of isobutane.

Promising catalysts for the alkylation are solid acid catalysts, such as zeolites, halides of metals in combination with inorganic salts, as well as Lisovskii or pentecosta acid deposited on inorganic and organic carriers, which also include sulfated metal oxides and perfluorinated polymers.

The alkylate obtained by the use of solid acids, the quality is not inferior to alkylate obtained in conventional processes. However, the problem of low stability tverdookisnyh catalysts are still not resolved.

Research in the field of heterogeneous catalysts for the alkylation aimed at finding systems operating in the temperature range 20-120°that does not contain toxic components, the stability of which would be comparable to traditional liquid catalysts.

The activity of catalysts for the alkylation is characterized by the conversion of butylene wt.%, the weight yield of alkylate submitted in response butylene, gC5+/gbutylenes.

The selectivity of the catalyst alkyl is characterized by content trimethylpentane hydrocarbons (SST) in the alkylate, wt.%.

The stability of the catalyst is characterized by a weight amount of butylene, processed by the unit mass of the catalyst during the run, gbutylenes/gcatalyst.

Known alkylation process using Lewis sites of acid - halides of metals 3-group applied to the oxide of the element 3-or 4-And group-modified Nickel (1-5 wt.%) or a metal of subgroups of platinum (0.1-1 wt.%), additions of alkali (alkaline earth) metal in the amount of 1-10 wt.% (US 3318820, B 01 J 27/06, 09.05.1967; US 5849977, B 01 J 23/02, 15.12.1998; US 6103947, C 07 C 2/60, 15.08.2000). It is shown that adding in the original reaction mixture of chlorinated hydrocarbons increases the stability and selectivity of the catalyst. In the patent US 6103947 declared the use of aluminium chloride are caused by the sublimation of the aluminum oxide in the reaction of alkylation of isobutane with butylenes.

When the load on the butylenes 0.16 g/gcatalyst·h, temperature 30°With a molar ratio of isobutane/butylene, equal to 25, the content of chlorinated - secondary butyl chloride, equal to 1000 ppmw, a pressure of 27 atmospheres and time of the process 4-5 h the catalyst has the following characteristics of activity, selectivity and stability:

Conversion of butylene, %80-97
The yield of alkylate, g /gbutylenes1.8 to 2.3
Selectivity for TDM, %To 69
Stability, gbutylenes/gcatalyst0,8

The disadvantage of this method is the low lifetime of the catalyst, and the high content promoting additive, causing the necessity of cleaning products from hydrogen chloride and neprivrednih of chlorinated paraffin wax.

A method of low-temperature regeneration of a catalyst comprising hydrogenation of carbon deposits hydrogen at 130°With subsequent supply of isobutane containing alkylchloride.

Know the use of broad porous zeolites, modified Lisovskii acids (BF3, SbF5, AlCl3) (US 4384161, B 01 J 27/06, 17.05.83). The introduction of the Lewis sites of zeolites acids can increase the activity of the zeolites and the selectivity for C8to reduce the ratio of isobutane/olefin to values of 3 to 20, and increase the feed rate of butylenes to values of 2.5-5 g/gcat·h For sample HZSM-4 modified BF3the selectivity for TDM was 90%. Mainegenealogy mileage according to the patent is difficult to assess

The known process developed by Haldor Topsoe, using liquid Pentecostal supercolony and polar media (US 5220095, B 01 J 31/02, 15.06.93; US 525100, B 01 J 31/02, 14.09.93; US 5675053, C 07 C 2/62, 07.10.97). The mobile reaction zone, created by the periodic change in the direction of flow in the reaction zone, allows for increased stability of the alkylation process.

The disadvantages of these methods of alkylation in the presence of applied pentecosta acids is the use of low temperature (-40 to +20° (C)partial ablation of the acid component, causing the need for separation from the alkylate and disposal or regeneration of the acid.

To the same class of catalysts for the alkylation are fixed on an inert carrier perfluorinated polymers, liquid impregnated kislotnym component (US 6593505, B 01 J 31/02, 03.07.2003; US 6531640, B 01 J 31/02, 26.09.2002).

Known methods of alkylation (US 6583330, B 01 J 21/06, 24.06.2003), where the catalysts are used heteroalicyclic printed on the media with a developed surface area and larger pore volume.

As the alkylation catalyst is a known system including phosphormolybdenum or fosforilamido acid deposited on the zirconium oxide, silicates or aluminosilicates modified metal subgroups of platinum. At temperatures up to 200°C, flow rates butylene 0.02 to 2 g/gcat·h and relationships isobutane/olefin of 3 to 50 during the same mileage was received is 15.7 g alkylate/gcatat the final conversion of olefins at least 99.8%. After 95 h process alkylate contained 80-90% fraction C8with the concentration of TMP at least 80%.

Lack of catalysts based on applied code of civil procedure, in addition to their high cost and complexity of manufacture, is the difficulty of regeneration. The CCP structure is destroyed by prolonged high-temperature heating, it is shown that the most active catalysts with intact structure of the CCP.

As catalysts for the alkylation typically use broad porous high-modulus zeolite beta, ZSM, MCM, USY (US 4384161, B 01 J 27/06, 17.05.83; US 6844479, B 01 D 53/02, 15.01.2004).

There is a method of alkylation, using broad porous zeolites (fogasa, ZSM-3, 4, 18, 20, mordenite, MSM-22, 36, 49, 56), treated with compounds of rare-earth elements (La, CE) and modified perekhodnymi metals (Cr, Mo, W, Cu, Zn, Ga, Sn, Pb) or 8 group metals with hydrogenating function (US 5705729, C 07 C 2/58, 06.01.1998). The process is conducted at a temperature of 100°With high regard isobutane/olefin (above 500), and dosing of raw materials alkylation of hydrogen in amount of 0.2/1 in relation to the olefin, which helped to achieve stability work more than 30 hours at a feed rate of the butylenes 0,06 h-1, conversion of butylene about 100% and target selectivity for C8about 65%. 1.8 g/gcat.

<> The disadvantages of zeolite alkylation catalysts in addition to the low stability is the higher temperature of the process and the need to use higher relations isobutane/olefin.

The closest in technical essence is a method of obtaining a solid acid catalyst (US 5310868, B 01 J 23/00, 10.05.94), in which the sulfated oxide of the element 4 And the group is modified with three additives: element metal or a metal ion 6 (8) groups (Mo or other), metal or metal ion 5A (V, Nb, TA), 6B (Ge, Sn, Pb), 6A (Cr, Mo, V), 1V (Cu, Ag, Au), 2B (Zn, Cd, Hg)3A (Sc, Y), 3B (IN, Al, Ga, In, Tl) or 4B (Ge, Sn, Pb) groups, the third metal is selected from a subgroup of lanthanum. As the carrier, in addition to the oxide of the element 4A group, used his mixture of oxides 3A and b and 4A and In groups. The process is conducted at a feed rate of butylenes 0,074 g/gcat·h Mainegenealogy mileage according to the patent is difficult to assess. It is noted that the composition of the alkylate after 4 hours the catalyst based on sulfated zirconium oxide, modified W, Mo, CE, corresponds to the selectivity for C878% and more than 99 RON, outselling characteristic of the process using sulphuric acid.

The disadvantage of the proposed method is a multi-component catalyst composition and the related difficulty when it is otopleniya, and low feed rate butylenes.

The invention solves the problem of creating an effective process for alkylation using a solid acid catalyst consisting of a metal oxide III-IV groups and oxygen-containing anion of the acid.

To solve this problem it is proposed to apply as a catalyst for the alkylation of isobutane with butylenes catalytic complex of the General formula: IUxAbouty·aAn)-·b CnClmH2n+2-mwhere: IU - 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 mixtures thereof in any combination, and=from 0.01 to 0.2, b=0,01-0,1; CnClmH2n+2-m- polichlorpylene hydrocarbon, where n=1-10; m=1-22, dispersed on a porous carrier, and containing a hydrogenating component (RU 2264256, B01J 23/40, 20.11.2005).

The porous carrier is an oxide of the element III-IV groups, preferably Al, 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 of them.

The catalytic complex of the General formula: IUxAbouty·aAn-·bnXmH where: IU - 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, the CnClmH2n+2-m- polichlorpylene hydrocarbon, where n=1-10; m=1-22, synthesize (EN 2264256, B01J 23/40, 20.11.2005) 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 mixtures thereof in any combination, by impregnation or adsorption, or mixing, or combinations thereof with a porous carrier together with the hydrogenating 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 polichlorpylene 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.

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

Acidic, basic or neutral metal salt of III-IV groups and oxygen-containing acid selected from the range of sulfur, phosphorus, molybdenum, tungsten or their smesi 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, 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 task is also solved by a method of catalytic alkylation of isobutane, in which the catalyst used is described catalyst.

Catalytic alkylation of isobutane is carried out at a temperature not exceeding 150°mass loadings initial mixture is not more than 3 g/gcat·h, pressure of not more than 40 MPa, in the presence of not more than 10 mol.%. of hydrogen.

As the hydrocarbon feedstock for the alkylation use isobutane-butylene raw materials containing not more than 20 wt.% butylenes.

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

- the introduction of the catalyst, hydrogenating component;

- conduct process in the presence of hydrogen;

- selection and optimization of 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 of the grain of the media.

Improved in comparison with the prototype process indicators (increased activity, selectivity and stability) is achieved by using as a main component aluminum oxide, as well as modification of the catalyst surface chlorinated hydrocarbons.

Own the acidity of the aluminum oxide is much lower than the acidity of the zirconium oxide, which allows to obtain a higher selectivity on TDM when using aluminum oxide, modifying the surface of the anion of sulfuric acid in various concentrations, as well as additives of various metal ions. Thus, using as a catalyst sulfated alumina allows you to increase the selectivity of the alkylation compared with the processes of smalcinasanai and cracking, leakage which occurs on the catalysts with excess acidity (sulfated oxides of group IV).

Sulfated alumina, modified additives of various metal ions with low activity during the alkylation, in the presence of chlorinated hydrocarbons allows the reaction with performance, superior activity similar patterns of sulfated Zirconia.

Improved stability of the proposed catalysis the Torah is ensured by the presence of a hydrogenating catalyst component and a process in the presence of hydrogen. When this occurs, the hydrogenation and removal from the surface of the catalyst alkylation highly unsaturated oligomers, blocking the activity of the catalyst. Due to changes in the concentration, dispersion and distribution of the hydrogenating component of the catalyst grain can minimize side hydrogenation process butylenes reaction raw material and provide a high yield of alkylation products submitted in response butylene.

Increase stability and selectivity of catalyst performance is also due to the presence of a catalytic complex on the surface of sulfated oxide, formed with the participation of the chlorinated hydrocarbon, entered before submitting materials. It is assumed that an activated molecule of chlorinated hydrocarbons contributes to the intensification of the hydride transfer at the initiation stage of the reaction and is not accompanied by processes of chlorination of the media.

The technical result of the proposed method lies in the fact that in the alkylation of isobutane with butylene at a temperature of 40-100°S, feed rate butylenes not less than 0.17 g/gcat·h, pressure 8-25 ATM, in the presence of no more than about 10. % hydrogen and content on the catalyst surface is not more than 10% of the halogenated promoter is formed alkylate with selectivity for TDM up to 90%.

<> The finished catalyst is placed in a static reactor, inert purge gas, restored in an atmosphere of hydrogen at 1-16 ATM, then enter the promoter in an amount of not more than 10% by weight of catalyst, fill in the static reactor isobutane fraction containing isobutane at least 98 wt.% and served raw with a ratio of isobutane/butylene 5-20 and a temperature of 40-100°C.

The invention is illustrated by the following examples.

Example 1.

A. Deposition of palladium on alumina. For the application of 1.1 wt.% palladium on gamma alumina (surface adsorption of nitrogen 205 m2/g, the content of alkali metals is not more than 0.05 wt.%, fraction 0.5-0.8 mm) using a palladium nitrate solution containing 14.4 wt.% palladium and 18.8 wt.% nitric acid. 30 g of aluminum oxide is placed on the filter SCHOTT with 250 ml of distilled water, are added dropwise 2,743 g of palladium nitrate solution, diluted with distilled water to 8 ml Stirring is carried out by the current of air entering through the side outlet of the flask Bunsen. After adsorption of the palladium sample is filtered, dried at room temperature for 12 h and calcined at a temperature of 550°C for 2 h in a stream of air. The result of 29.9 g of alumina-modified palladium.

B. Sulfation and heat treatment of aluminum oxide, m is definerowana palladium. of 29.9 g of the sample obtained at the point a, is placed in a tank with 130 ml of distilled water containing 8.2 g 91.2% of sulfuric acid. Then evaporated and dried at 140°C for 12 h and calcined at 550°C for 2 hours

Gain of 35.2 g of the sample the following composition, wt.%:

1.1% Pd

15,3% (SO4)2-

83,6% Al2O3

The catalytic test is carried out in a static reactor with stirring at a temperature of 50°C. In a static reactor load 2.1 g of catalyst, rinsed with argon, restore under atmospheric pressure hydrogen for one hour. Then the supply of hydrogen is stopped and for modification of the catalyst surface Microlitre syringe injected 0,063 g of carbon tetrachloride, which is 3% by weight of the catalyst.

Static fill the reactor isobutane fraction in the amount of 26.8 g containing isobutane at least 98%, then at a temperature of 50°and a pressure of 10 ATM begin feeding raw speed of 3.96 g/h and the content of butylene total of 8.74%.

The compositions of isobutane and butylene fractions are shown in table 1.

Table 1
ComponentBiophysics Institute, wt.%BBF, wt.%
Propane0,910,54
Isobutane 88,4
Butene-102,6
N.-butane0,660,65
TRANS-Butene-20to 3.67
CIS-Butene-202,47
N.-Pentane01,67

Analysis of the reaction products perform chromatography on a capillary column DB1. According to chromatographic analysis to calculate the conversion of butylene, the selectivity of the formation of isomers C8the output in the calculation of the transformed butylene and get the following averages when the total load on the butylenes 1.8 g/gcatalyst:

Conversion of butylene, %97,7
Output converted butylene, g/gbutylenes1,7
Selectivity for TDM, %72,0

The conversion of butylene calculated by the formula:

X=100%-(C4=)shox·C(stand)raw materials/((C4=)raw materials)·C(stand)shox), where:

X - conversion of butylene,

C4=)shoxthe concentration of butylenes in the products,

C(stand)raw materialsthe concentration of standard raw materials

C4=)si is d the concentration of butylenes in the raw materials

C(stand)shoxthe concentration of the standard in the products.

Output converted butylene calculated by the formula:

Y(C5+)=100·C5+)·C(stand)raw materials/(C(C4=)raw material·X·C(stand)shox), where:

Y(C5+- the output is turned on butylene,

C5+- the concentration of products.

Selectivity for trimethylpentane (TDM) calculated by the formula:

Sel(TMP)=(TMP)shox/C5+), where

With(TMP)shoxthe concentration of TMP in the products.

Example 2.

A. Deposition of palladium on alumina. For the application of a 0.9 wt.% palladium (based on the final catalyst) on gamma alumina (surface adsorption of nitrogen 205 m2/g, the content of alkali metals is not more than 0.05 wt.%) use a solution of palladium chloride containing 0,648 g of palladium/ml To 49 g of aluminum oxide, is placed in a vessel with 350 ml of distilled water, with stirring, added dropwise 0,86 ml of a solution of palladium chloride, diluted with distilled water to 15 ml After the adsorption of the palladium sample is filtered and dried at room temperature for 12 hours and Then sieved fraction more 0,315 mesh, which is calcined at a temperature of 550°C for 2 h in a stream of air to obtain 46 g of alumina-modified palladium.

B. With lefterova and heat treatment of aluminum oxide, modified palladium. Carried out, as in Pb of example 1, get a sample of the following composition, wt.%:

0,9% Pd

19,7% (SO4)2-

79,4% Al2About3

The alkylation process is conducted as in example 1. According to chromatographic analysis of the products have got the following average values for the total load on the butylenes 1.0 g/gcat:

Conversion of butylene, %99,7
Output converted butylene, g/gbutylenes1,8
Selectivity for TDM, %33,0

Example 3.

A. Deposition of platinum on alumina. As in example 2 except that for the application of 1 wt.% platinum (based on the final catalyst) use a solution hexachloroplatinic acid with a concentration of 0.09 g of platinum/ml.

B. Sulfation and heat treatment of aluminium oxide modified platinum. Carried out as in example 1. Get a sample of the following composition, wt.%:

1% Pt

19,2%(SO4)2-

79,8% Al2O3

The alkylation process is conducted as in example 1. According to chromatographic analysis of the products have got the following average values for the total load on the butylenes 1.1 g/gcat:

Conversion of butylene, %99,9
Output converted butylene, g/gbutylenes1,7
Selectivity for TDM, %38,0

Example 4.

A. Deposition of palladium on alumina. As in example 2 except that for the application of 2 wt.% palladium (based on the final catalyst) use a solution of palladium chloride, obtained by dissolving 1,684 g of palladium chloride with the concentration of palladium 59,4% 1.89 g of hydrochloric acid.

B. Sulfation and heat treatment of aluminum oxide modified with palladium. Carried out as in example 1. Get a sample of the following composition, wt.%:

2% Pd

20,6% (SO4)2-

77,4% Al2O3

The alkylation process is conducted as in example 1. According to chromatographic analysis of the products have got the following average values for the total load on the butylenes 0.9 g/gcat:

Conversion of butylene, %99,9
Output converted butylene, g/gbutylenes1,64
Selectivity for TDM, %50,0

Example 5.

A. Deposition of palladium on alumina is carried out, as in example 2, except that for the application of 2 wt.% ballad is I (based on the final catalyst) use a solution of palladium nitrate, containing 25.7% of palladium and 13.2% of nitric acid.

B. Sulfation and heat treated aluminum oxide, modified palladium carried out as in example 1. Get a sample of the following composition, wt.:

2%Pd

21% (SO4)2-

77% Al2O3

The alkylation process is conducted as in example 1. According to chromatographic analysis of the products have got the following average values for the total load on the butylene 1,2 g/gcat:

Conversion of butylene, %99,9
Output converted butylene, g/gbutylenes2,25
Selectivity for TDM, %26,0

Example 6.

A. Deposition of palladium on alumina is carried out, as in example 3, except that for the application of 0.4 wt.% palladium (based on the final catalyst) using a palladium nitrate solution containing 14.4% of palladium and 18.8% of nitric acid.

B. Sulfation and heat treated aluminum oxide, modified palladium carried out as in example 1. Get a sample of the following composition, wt.%:

0,4% Pd

20,3% (SO4)2-

79,3% Al2About3

The alkylation process is conducted as in example 1. According to chromatographic analysis of the products have got the following the e average when the total load on the butylenes 0.9 g/g cat:

Conversion of butylene, %99,8
Output converted butylene, g/gbutylenes1,7
Selectivity for TDM, %36,0

Example 7.

A. Deposition of palladium on alumina carried out as in example 1.

B. Sulfation and heat treatment of aluminum oxide modified with palladium. The sulfation is carried out, as in example 1, after which the sample for 2 h and calcined at a temperature of 500°C. Receive a sample of the following composition, wt.%:

1,1% Pd

18,9%(SO4)2-

80% of Al2About3

The alkylation process is conducted as in example 1. According to chromatographic analysis of the products have got the following average values for the total load butylene, 1,5 g/gcat:

Conversion of butylene, %99,3
Output converted butylene, g/gbutylenes1,68
Selectivity for TDM, %54,0

Example 8.

A. Deposition of palladium on alumina carried out as in example 1.

B. Sulfation and heat treatment of aluminum oxide modified with palladium. The sulfation is carried out, as the example 1, then the sample for 2 h and calcined at a temperature of 600°C. Receive a sample of the following composition, wt.%:

1,1% Pd

13,4%(SO4)2-

85.5% of Al2About3

The alkylation process is conducted as in example 1. According to chromatographic analysis of the products have got the following average values for the total load butylene, 1,5 g/gcat:

Conversion of butylene, %99,6
Output converted butylene, g/gbutylenes1,67
Selectivity for TDM, %76,0

Example 9.

A. Deposition of palladium on alumina carried out as in example 1.

B. Sulfation and heat treatment of aluminum oxide modified with palladium. The sulfation is carried out, as in example 1, after which the sample for 2 h and calcined at a temperature of 700°C. Receive a sample of the following composition, wt.%:

1,1% Pd

10,5% (So4)2-

88.4% of Al2O3

The alkylation process is conducted as in example 1. According to chromatographic analysis of the products have got the following average values for the total load on the butylenes 1.1 g/gcat:

Conversion of butylene, %97,2
Output converted butylene, g/gbutylenes1,6
Selectivity for TDM, %82,0

Example 10.

In a static reactor load of 2.1 g of the catalyst obtained in example 1. The alkylation process is conducted as in example 1 except that the raw materials is served with rate of 1.95 g/h According to the chromatographic analysis of the products have got the following average values for the total load on the butylenes 2.5 g/gcat:

Conversion of butylene, %of 98.2
Output converted butylene, g/gbutylenes1,67
Selectivity for TDM, %74,0

Example 11.

In a static reactor load of 2.1 g of the catalyst obtained in example 1. The alkylation process is conducted as in example 1 except that the temperature of the process 80°C. According to the chromatographic analysis of the products have got the following average values for the total load on the butylene 1,3 g/gcat:

Conversion of butylene, %of 98.2
Output converted butylene, g/gbutylenes1,64
Selectivity for TDM, % 65,0

Example 12.

In a static reactor load of 2.1 g of the catalyst obtained in example 1. The alkylation process is conducted as in example 1 except that the raw material used BBF with a lower content of butylenes.

The composition of the BBF are shown in table 2.

Table 2
ComponentBBF, wt.%
Propane0,66
Isobutane91,68
Butene-11,23
N.-butane0,92
TRANS-Butene-22,02
CIS-Butene-21,69
N.-Pentane1,8

According to chromatographic analysis of the products have got the following average values for the total load on the butylene-2,3 g/gcat:

Conversion of butylene, %98,5
Output converted butylene, g/gbutylenes1,67
Selectivity for TDM, %76,0

Example 13.

In a static reactor load of 2.1 g of the catalyst obtained in example 1. The alkylation process is conducted as in example 1, except that the article is Diya recovery of the catalyst is absent. According to chromatographic analysis of the products have got the following average values for the total load on the butylenes 0.6 g/gcat:

Conversion of butylene, %97,7
Output converted butylene, g/gbutylenes1,4
Selectivity for TDM, %66,0

Example 14.

The catalyst prepared in example 1, except that there is no stage of deposition of palladium. The alkylation process is conducted as in example 1, except that there is no stage of recovery of palladium, and at the stage of activation is not administered carbon tetrachloride. According to chromatographic analysis of the products have got the following average values for the total load on the butylene 0.07 g/gcat:

Conversion of butylene, %71,0
Output converted butylene, g/gbutylenes0,45
Selectivity for TDM, %90,0

Example 15.

In a static reactor load of 2.1 g of the catalyst obtained in example 1. The alkylation process is conducted as in example 1, except that instead of carbon tetrachloride to obtain catalytic the use of the complex tetrachlorethylene. According to chromatographic analysis of the products have got the following average values for the total load on the butylenes 0.8 g/gcat:

Conversion of butylene, %the 98.9
Output converted butylene, g/gbutylenes1,5
Selectivity for TDM, %81,0

Example 16.

In a static reactor load of 2.1 g of the catalyst obtained in example 1. The alkylation process is conducted as in example 1, except that instead of carbon tetrachloride to obtain catalytic complex used trichlormethane. According to chromatographic analysis of the products have got the following average values for the total load on the butylenes 0.5 g/gcat:

Conversion of butylene, %96,1
Output converted butylene, g/gbutylenes1,2
Selectivity for TDM, %68,0

Example 17.

200 g of the solution of ammonium complex gidroksicarbonata zirconium content ZrO20,093 g/g of the solution with vigorous stirring, added dropwise 2,72 g of the solution of 93 wt.% H2SO4and 4.26 g of the solution of palladium chloride with the content of what W palladium 0,050 g/g solution. The resulting solution was heated to 90°C and maintained at this temperature under stirring for 0.5 h Sol Obtained is dried for 2 h at 180°C, calcined in air flow at 620°C. Receive a sample of the following composition, wt.%:

1% Pd

12% (SO4)2-

87% ZrO2

The alkylation process is conducted as in example 1.

According to chromatographic analysis of the products have got the following average values for the total load on the butylenes 0,98 g/gcatalyst:

Conversion of butylene, %99,7
Output converted butylene, g/gbutylenes1,8
Selectivity for TDM, %80,0

Example 18.

200 g of the solution of ammonium complex gidroksicarbonata zirconium content ZrO20.093 g/g of the solution with vigorous stirring, added dropwise to 3.16 g (NH4)2SO4, 1.86 g of the solution of palladium chloride containing palladium 0,050 g/g of the solution and to 20.52 g of aluminum isopropylate. The resulting solution was heated to 90°C and maintained at this temperature under stirring for 0.5 h Sol Obtained is dried for 2 h at 180°C, calcined in air flow at 720°C. Receive a sample of the following composition, wt.%:

1% P

12% (SO4)2-

30% Al2About3

57% ZrO2

The alkylation process is conducted as in example 1. According to chromatographic analysis of the products have got the following indicators when the total load on the butylene 1,2 g/gcatalyst:

Conversion of butylene, %99,9
Output converted butylene, g/gbutylenes1,7
Selectivity for TDM, %70,0

Example 19.

The preparation of the catalyst were carried out as in example 16, except that instead of sulfuric acid use of 2.72 g of tungsten oxide. The catalyst was calcined in air flow at 800°C. Receive a sample of the following composition, wt.%:

1% Pd

12% WO3

87% ZrO2

The alkylation process is conducted as in example 1.

According to chromatographic analysis of the products have got the following average values for the total load on the butylenes 0.8 g/gcatalyst:

Conversion of butylene, %91,0
Output converted butylene, g/gbutylenes1,1
Selectivity for TDM, %68,0

Example 20.

The preparation of the catalyst PR the lead, as in example 16, except that instead of sulfuric acid use of 2.72 g of molybdenum oxide. The catalyst was calcined in air flow at 800°C. Receive a sample of the following composition, wt.%:

1% Pd

12% of Moo3

87% ZrO2

The alkylation process is conducted as in example 1.

According to chromatographic analysis of the products have got the following average values for the total load on the butylenes 0.8 g/gcatalyst:

Conversion of butylene, %88,0
Output converted butylene, g/gbutylenes0,9
Selectivity for TDM, %61,0

Table 3 shows the compositions of the catalytic complexes for each example

Table 3
# exampleThe composition of the catalytic complexThe catalytic complex, wt.%The metal of group VIII, wt.%Media, wt.%
IUxAboutyAn-CnXmH2n+2-m
1Al2About30,15·SO40,03·CCl4 18,3Pd-1,1Al2About3-81
2Al2About30,2·SO40,03·CCl422,7Pd-0,9Al2O3-76
3Al2About30,19·SO40,03·CCl422,2Pt-1,0Al2O3-74
4Al2About30,21·SO40,03·CCl423,6Pd-2,0Al2O3-74
5Al2About30,21·SO40,03·CCl424,0Pd-2,0Al2O3-74
6Al2About30,2·SO40,03·CCl423,3Pd-0,4Al2O3-76
7Al2About30,19·SO40,03·CCl4of 21.9Pd-1,1Al2O3-77
8Al2About30,13·SO40,03·CCl416,4Pd-1,1Al2O3-83
9Al2About30,11·SO40,03·CCl413,5Pd-1,1Al2O3-85
10Al2About30,15·SO40,03·CCl418,3Pd-1,1Al2O3-81
11Al2About30,15·SO40,03·CCl418,3Pd-1,1Al2O3-81
12Al2About30,15·SO40,03·CCl418,3Pd-1,1Al2O3-81
13Al2About30,15·SO40,03·CCl418,3Pd-1,1Al2O3-81
14Al2About30,16·SO4-16,0-Al2About3-84
15Al2About30,15·SO40,03·C2Cl418,3Pd-1,1Al2O3-81
16Al2About3 0,15·SO40,03·CHCl318,3Pd-1,1Al2O3-81
17ZrO20,12·SO40,03·CCl415,0Pd-1,0ZrO2-84
18ZrO20,12·SO40,03·CCl415,0Pd-1,0Al2About3-30
19ZrO20,12·WO40,03·CCl415,0Pd-1,0ZrO2-84
20ZrO20,12·NGO30,03·CCl415,0Pd-1,0ZrO2-84

1. The catalytic complex of the General formula IUxAbouty·aAn)-·b CnClmH2n+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 mixtures thereof in any combination, and=0,01-0,2; b=0,01-0,1; CnClmH2n+2-m- polichlorpylene hydrocarbon, where n=1-10; m=1-22, dispersed on a porous carrier containing hydrogenating component, as a catalyst for alkyl process is the formation of isobutane with butylenes.

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

3. The use 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. Way catalytic alkylation of isobutane with butylenes, wherein the process is carried out at a temperature not exceeding 150°at mass loadings initial mixture is not more than 3 g/gcat×h, pressure of not more than 40 atmospheres in the presence of not more than 10 mol. %. hydrogen as a catalyst using the catalyst according to any one of claims 1 to 3.

5. The method according to claim 4, characterized in that the hydrocarbon feedstock for the alkylation use isobutane-butylene raw materials containing not more than 20 wt.% butylenes.



 

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