RU2457902C2 - Catalyst, synthesis method thereof (versions) and method for liquid-phase alkylation of isobutane with c2-c4 olefins in presence said catalyst - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to petrochemistry, particularly to production of a zeolite-based catalyst for alkylation of isobutane with olefins and can be used in oil refining industry. Described is a zeolite-based catalyst for alkylation of isobutane with olefins which contains aluminium oxide and silicon dioxide with molar ratio of silicon dioxide to aluminium oxide equal to 2.8-7.0, sodium and rare-earth element oxides and active metal oxides in form of platinum oxide and/or palladium oxide and/or rhenium oxide and/or rhodium oxide and/or halogen - chlorine or fluorine, with the following ratio of components in wt %: sodium oxide 0.26-0.8, calcium oxide 0.8-4.2, rare-earth element oxide 12.1-20.0, platinum oxide and/or palladium oxide and/or rhenium oxide and/or rhodium oxide 0.02-2.0, and/or chlorine 0.05-0.8 and/or chlorine 0.005-0.5, a zeolite with ratio SiO₂/Al₂O₃ equal to 2.8-7.0 being the balance. Disclosed also are two versions of the method of producing a zeolite-based catalyst for alkylation of isobutane with C₂-C₄ olefins, involving treatment thereof with aqueous solutions of salts of calcium, a rare-earth element and ammonium at high temperature and pressure of saturated vapour for a period of time necessary to convert the zeolite into a rare-earth calcium zeolite, and depositing active metal oxides onto it by saturation with aqueous solutions containing active metals, followed by washing, drying and calcination, where at the beginning, the obtained rare-earth calcium zeolite is saturated with unipolar water until the release of air from zeolite pores stops, and then depositing active metal oxides: platinum oxide and/or palladium oxide and/or rhenium oxide and/or rhodium oxide and/or halogen - chlorine or fluorine, taken in amounts which ensure said content of the oxide of the corresponding metal and halogen in the ready product, or deposition of active metal oxides - platinum oxide and/or palladium oxide and/or rhenium oxide and/or rhodium oxide and/or halogen - chlorine or fluorine - onto the rare-earth calcium zeolite is carried out from solutions containing the corresponding metals or halogen in unipolar water, taken in amounts which ensure said content of oxide of the oxide of the corresponding metal in the ready catalyst, wherein in both versions, deposition of active metals and halogen is carried out in two steps: at the first step via cold saturation at temperature not higher than 30°C for 1 hour, at the second step - at temperature not lower than 70°C for 1 hour, after which treatment with an organic acid is carried out in the presence of 30% aqueous hydrogen peroxide solution, followed by drying, tableting and calcination. Described is a method for liquid-phase alkylation of isobutane with olefins in the presence of the catalyst described above.

EFFECT: longer stable operation of the catalyst with activity thereof up to almost 100 wt % and isooctane selectivity of up to 75,7 wt %.

20 cl, 10 ex, 2 tbl

Description

The invention relates to the field of petrochemistry, in particular to the preparation of a catalyst based on zeolites and a method for the alkylation of isobutane with C ₂ ÷ C ₄ olefins in its presence, and can be used in the oil refining industry.

Due to increased demands on the quality of gasoline (limiting the content of aromatic hydrocarbons), interest in the process of alkylation of isobutane with olefins has sharply increased. The product of the process, alkylbenzine, consists almost entirely of isoparaffin hydrocarbons, mainly isooctanes (Σiso-C ₈ ). Alkylbenzene does not contain aromatic hydrocarbons, but has a high octane rating. The development of a technology suitable for implementation in industry primarily depends on the creation of a catalytic system that exhibits high activity, selectivity in obtaining target products and stability. Currently, for the industrial-scale alkylation process, mineral acids — sulfuric and hydrofluoric — are used as catalysts. However, their use causes a number of problems associated with their high toxicity and corrosion activity. As an alternative, a wide range of catalysts of various qualitative and quantitative composition is proposed, however, the most promising catalysts are based on zeolites, in which various modifiers are introduced to increase activity and selectivity.

The closest in technical essence and the achieved result is a catalyst based on a faujasite type zeolite for the alkylation of isobutane with C ₂ ÷ C ₄ olefins, described in SU 1309383, B01J 29/12, C07B 37/00, 10/20/1996. According to the well-known technical solution, the catalyst has the following composition,% wt .: sodium oxide 0.26 ÷ 0.8; rare earth oxide 12.0 ÷ 20.0; calcium oxide 0.8 ÷ 4.2; platinum or palladium oxide 0.02 ÷ 1.2; aluminum oxide and silicon dioxide - the rest. The test of CC during the alkylation of isobutane with ethylene at 90 ° C, a feed rate of 1.3 h ^-1 and a duration of 7 h shows an alkylate yield of 190 ÷ 210% wt.

The disadvantage of the catalyst is the low selectivity for the target product Σiso-C ₈ (total isooctanes) - 67.4% wt. when alkylating isobutane with ethylene and butenes, and when alkylating isobutane with propylene at 20 ° C and a duration of 3 hours, it shows a low yield of alkylate - 100 wt.%, while the selectivity for the target product Σiso-C ₈ (total isooctanes) is 26.8% wt.

The objective of the proposed technical solution is to develop a catalyst that shows high stability in the process of alkylation of isobutane with olefins C ₂ ÷ C ₄ and exhibits high activity and selectivity for the target product Σiso-C ₈ , as well as in the development of a method for producing such a catalyst.

The problem is solved by the fact that the proposed catalyst for the alkylation of isobutane with olefins C ₂ ÷ C ₄ based on zeolite containing aluminum oxide and silicon dioxide in a molar ratio of silicon dioxide: aluminum oxide equal to 2.8 ÷ 7.0, sodium, calcium, rare earth oxides element and oxides of active metals, which as oxides of active metals contains oxides of platinum, and / or palladium, and / or rhenium, and / or rhodium, as well as halogen - chlorine or fluorine in the following ratio, wt.%:

sodium oxide 0.26 ÷ 0.8 calcium oxide 0.8 ÷ 4.2 rare earth oxide 12.0 ÷ 20.0 platinum oxide and / or palladium oxide, and / or rhenium oxide, and / or rhodium oxide 0.02 ÷ 2.0 and / or chlorine 0.05 ÷ 0.8 and / or fluorine 0.005 ÷ 0.5 zeolite with a ratio SiO ₂ / Al ₂ O ₃ equal to 2.8 ÷ 7.0 rest

The proposed catalyst may additionally contain a binder, preferably aluminum hydroxide boehmite structure in an amount of 10 ÷ 50% wt. in relation to the finished catalyst, and as a zeolite, it contains a faujasite type zeolite with a molar ratio of SiO ₂ / Al ₂ O ₃ equal to 2.8-7.0.

The problem is also solved by the fact that the proposed method for producing an isobutane alkylation catalyst with C ₂ -C ₄ olefins based on zeolite, including its treatment with aqueous solutions of calcium salts, rare earth element and ammonium at elevated temperature and saturated vapor pressure for the time required to transfer the zeolite into rare-earth calcium zeolite and the deposition of active metal oxides on it by impregnation with aqueous solutions containing active metals, then washing and drying, in which before application using active metals, first, the resulting rare-earth calcium zeolite is treated with unipolar water until the air ceases to leave the pores of the zeolite, then the application of oxides of active metals: platinum and / or palladium and / or rhenium and / or rhodium together with halogen - chlorine or fluorine, taken in an amount providing the specified oxide content of the corresponding metal and halogen in the finished catalyst, and the deposition of active metals and halogen is carried out in two stages: in the first stage by cold impregnation at mperature not more than 30 ° C, the second - at a temperature not less than 70 ° C, after which the processing is carried out with an organic acid in the presence of 30% aqueous hydrogen peroxide solution, followed by drying, calcination and tableting.

A particular case of the method, when the zeolite is mixed with a binder — preferably aluminum hydroxide of boehmite structure and a solution of mineral or organic acid, preferably nitric, at a pH of 2 ÷ 4, the mixture is evaporated, formed by extrusion, the extrudates are dried, dried and calcined .

As a zeolite, a faujasite type zeolite is used with a molar ratio of SiO ₂ / Al ₂ O ₃ equal to 2.8-7.0.

Processing zeolite with aqueous solutions of calcium salts, rare earth element and ammonium to obtain rare earth calcium zeolite is carried out at a temperature of 140 ÷ 220 ° C.

As aqueous solutions of active metals, platinum chloride, or rhenium, or rhodium acid, or palladium tetraammonia is used.

Cold impregnation is carried out for at least 1 hour, and hot for 0.5-2 hours, preferably 0.75-1.0 hours.

The application of halogen is carried out from an aqueous solution of hydrochloric or hydrofluoric acid.

As an organic acid, an aqueous solution of oxalic, formic, acetic or citric acid or a mixture thereof is used.

The problem is solved in that a second embodiment of a method for producing an isobutane alkylation catalyst with C ₂ ÷ C ₄ olefins based on a zeolite is proposed, including its treatment with aqueous solutions of calcium salts, a rare earth element and ammonium at an elevated temperature and saturated vapor pressure for the time required for converting zeolite to rare-earth calcium zeolite, and applying active metal oxides to it by impregnation with aqueous solutions containing active metals, then washing and drying, in which the deposition on rare earth calcium zeolite of oxides of active metals - platinum, and / or palladium, and / or rhenium, and / or rhodium and halogen - chlorine or fluorine is carried out from solutions containing the corresponding metals or halogen in unipolar water, taken in quantities, providing the specified oxide content of the corresponding metal or halogen in the finished catalyst, and the application of active metals and halogen is carried out in two stages: in the first stage by cold impregnation at a temperature of not more than 30 ° C, in the second - at a rate at least 70 ° C, after which they are treated with an organic acid in the presence of a 30% aqueous solution of hydrogen peroxide, and then dried, tableted and calcined.

The zeolite impregnated with oxides of active metals is mixed in a particular case with a binder — preferably aluminum hydroxide of boehmite structure and a solution of mineral or organic acid, preferably nitric, at a pH in the range of 2–4, the mixture is evaporated, formed by extrusion, the extrudates are dried, dried and ignite.

As a zeolite, a faujasite type zeolite with a molar ratio of SiO ₂ / Al ₂ O ₃ equal to 2.8 ÷ 7.0 is used.

Processing zeolite with aqueous solutions of calcium salts, rare earth element and ammonium to obtain rare earth calcium zeolite is carried out at a temperature of 140 ÷ 220 ° C.

As aqueous solutions of active metals, platinum chloride, or rhenium, or rhodium acid, or palladium tetraammonia is used.

Cold impregnation is carried out for at least 1 hour, and hot for 0.5-2 hours, preferably 0.75-1.0 hours.

The application of halogen is carried out from an aqueous solution of hydrochloric or hydrofluoric acid.

As an organic acid, an aqueous solution of oxalic, formic, acetic or citric acid or a mixture thereof is used.

The problem is also solved by the fact that the proposed method of liquid-phase alkylation of isobutane with olefins C ₂ ÷ C ₄ at elevated pressure and temperature, in which the process is carried out in the presence of the described catalyst obtained by any of these methods.

The prior art patent RU No. 2289475, B01J 2/256, publ. December 20, 2006, which describes a catalyst containing chlorine and fluorine, along with other active components. The catalyst is used for catalytic cracking in order to obtain gasoline fractions.

However, the catalyst for carrying out the alkylation process of isobutane with C ₂ -C ₄ olefins containing halogen — chlorine or fluorine — is not known in the art.

The technical result that can be obtained from the invention is as follows:

- in increasing the stable activity of the catalyst;

- increasing the activity of the catalyst for the conversion of olefins, up to almost 100% wt .;

- increasing the selectivity of the catalyst in the process of liquid-phase alkylation of isobutane with C ₂ ÷ C ₄ olefins in the target product - isooctanes (iso-C ₈ ) up to 75.7% wt .;

- increasing the yield of the target product (alkylbenzene) by 10 ÷ 15% wt.

The following examples illustrate the proposed technical solution, but in no way limit it.

Obtaining catalysts and carrying out a liquid phase alkylation reaction in their presence.

Example 1

Rare-earth calcium zeolite is obtained according to the procedure described in patent SU 936991, B01J 37/30, 06/23/1982. To this end, 40 g of powdered faujasite type zeolite with a molar ratio of SiO ₂ / Al ₂ O ₃ equal to 4.0 are loaded into autoclave and pour in a solution of calcium chloride (concentration of 60 g / l, the amount of 260 ml). The autoclave is heated to 160 ° C and held for 3 hours. At the end of the treatment, the autoclave is cooled, the spent solution is poured, a solution of an industrial mixture of rare earth nitrates is poured (concentration 30 g / l, quantity 210 ml) and reheated to 160 ° C, kept for 3 hours and cool.

After cooling and separation of the mother liquor, the zeolite is washed with demineralized water (condensate). The zeolite cake is dried, pressed into tablets and calcined.

Then, the rare-earth calcium zeolite thus obtained is first treated with unipolar water, which is obtained in the REH-1 electrochemical reactor (STEL-type plants) (the method is described in Bakhir V.M. Modern technical electrochemical systems for disinfection, purification and activation of water. - M .: VNIIIMT, 1999 .-- 84 s; - ill.). Unipolar water is supplied for the purpose of chemically modifying the surface by chemisorption of hydrogen ions (H ⁺ ), intensification and uniformity of the process of its further impregnation with active components, removal of air zeolite from the pores, as well as for gentle moistening of the zeolite, which prevents cracking of the catalyst, and for washing from dust and crumbs.

Next, a sample of rare-earth-calcium zeolite is poured with a mixture of solutions of active metals. In this example, a solution of ammonium nitrate, palladium tetraammonia and rhodium chloride (concentration of 0.05 g / l for palladium and 7.35 g / l for rhodium), in an amount that provides full coverage of the granules.

The application of active metals to rare-earth calcium zeolite is carried out in two stages: in the first stage, cold impregnation is carried out with stirring for 1 hour at a temperature of 25 ° C. After cold impregnation in the second stage, the impregnation solution is heated to a temperature of 75 ° C and the rare-earth calcium zeolite is impregnated for another 1 hour. Then, 0.02 g of oxalic acid (calculated on anhydrous salt) is added to the impregnation solution in the form of an aqueous solution with a concentration of 50 g / dm ³ and 0.02 g of hydrogen peroxide in the form of a 30% aqueous solution. Processing is continued for 0.25 hours with stirring, then the solution is drained, the catalyst is dried and calcined.

Then the solution, practically free of palladium, is drained, the tablets are washed with condensate, dried and calcined.

Get the catalyst of the following chemical composition,% wt .:

Na ₂ O - 0.5; La ₂ O ₃ - 20.0; CaO - 1.4; PdO - 0.01; RhO - 1.5; Al ₂ O ₃ + SiO ₂ - the rest (SiO ₂ / Al ₂ O ₃ = 4.0).

The catalyst is tested in the reaction of liquid-phase alkylation of isobutane (isobutane fraction with an isobutane content of 99.5% by weight, the rest is n-butane) with ethylene with a concentration of 99.5% by weight of the basic substance, at a ratio of ISO-C ₄ : C ₂ "= 17: 1, a temperature of 90 ° C, a volumetric feed rate of 1.3 h ^-1 and a catalyst run time of 7 hours in a laboratory flow unit.

The catalyst is loaded into the reactor in such a way that crushed quartz is found above and below its layer (the particle size fraction is an order of magnitude higher than the catalyst fraction), which serves as a device to prevent the removal of the catalyst with the stream. The upper quartz layer also contributes to a uniform distribution of the feed stream on the catalyst surface, and the alkylation installation is checked for tightness with nitrogen at P = 1.5 ÷ 2.0 MPa.

After checking for leaks, the catalyst is tested in the process of isobutane alkylation with C ₂ ÷ C ₄ olefins.

The contact of only the alkylating component, ethylene, with the catalyst leads to its oligomerization on the surface of the catalyst and rapid deactivation of the latter. To avoid oligomerization, a reactor with a ready-to-use catalyst is pre-filled with isobutane.

At the end of filling the system with isobutane, close the valve on the isobutane tank and, with the help of the pump, feed the mixture into the reactor from the feed tank. As a result of the interaction of the alkylated and alkylating components in the presence of a catalyst, liquid reaction products and unreacted excess isobutane are formed, which are collected at the outlet of the reactor into a cooled trap.

The liquid product, the alkylate, is stabilized and then analyzed on a Kristallux-4000M chromatograph using gas adsorption chromatography on a SE-30 column. In the work, the NetChrom program was used, intended for automation of the Crystallux-4000M chromatograph. This program provides chromatographic signal processing.

The complete composition of the alkylate is determined - it is a mixture of isomers of paraffinic hydrocarbons C ₅ ÷ C ₉ , as well as its calculated octane number.

The resulting gaseous stabilization products — mainly unreacted excess isobutane — are also analyzed by gas adsorption chromatography: on an alumina column.

The yield of reaction products - alkylate is calculated according to the following reaction equation:

2 Ethylene + Isobutane → 2,2,4-Trimethylpentane

(100 octane research method - OCH)

The olefin conversion characterizes the completeness of the use of raw materials in this process and is the ratio of the amount of converted olefin (OL) to the taken, expressed in%, and is calculated by the formula:

X (OL) - OL conversion,% wt .;

C (OL) raw materials - the concentration of OL in raw materials,% wt .;

m (raw materials) - mass of raw materials, g;

C (OL) prod. - concentration of OL in the product,% wt .;

m (product) - mass of product, g.

The yield of alkylbenzene to olefins in the feed (the yield of AB in the taken OL), expressed in%, is determined by the formula:

η (AB) - The output of AB,% wt .;

m (product) is the mass of the product, g;

C (OL) raw materials - the concentration of OL in raw materials,% wt .;

m (raw materials) - mass of raw materials, g.

The selectivity of the process is evaluated by the content of the isoactane fraction in the mixture of the obtained products - alkylbenzene, as the most valuable component of gasoline obtained by mixing high-octane gasoline by catalytic cracking of vacuum gas oil and reforming low-octane gasoline.

The selectivity of the reaction is the relative concentration of the isooctane fraction on the reaction products is calculated by the formula:

δ (AB) is the selectivity of the reaction,% wt .;

C (ΣC ₈ ) is the concentration of the isooctane fraction in the product,% wt .;

C (cont.) - the total concentration of reaction products,% wt.

Stable activity of the catalyst — the change in the yield of alkylbenzene to olefins in the feed during operation is calculated by the formula

A _n is the degree of decrease in the stable activity of the catalyst,% relates .;

n is the duration of the feed, h;

η ₁ (AB) is the yield of alkylbenzene on olefins in the feed for the first hour from the feed,% wt .;

η _n (AB) is the yield of alkylbenzene on olefins in the feed for the n-th hour from the feed,% wt .;

In accordance with the presented calculations, the degree of decrease in the stable activity of the catalyst for 7 hours from the supply of raw materials is 2% (compared with 14% in the prototype).

The selectivity of the process is 68.5% wt.

The test results are shown in table 2.

Example 2

The catalyst is prepared according to example 1, only with the aim of varying the composition, a mixture of rare-earth elements and ammonium nitrates is treated for 4 hours at 200 ° C, the concentration of the mixture of solutions of palladium tetraammonium and ammonium nitrate is 0.68 g / l for palladium, and into this mixture a solution of hydrochloric acid and rhodium chloride with a concentration of 0.25 g / l rhodium and containing 0.04 g Cl in the form of hydrochloric acid is introduced.

The catalyst has the following chemical composition,% wt .:

Na ₂ O - 0.26; La ₂ O ₃ - 17.4; CaO - 0.8; PdO - 0.11; RhO 0.05; Cl is 0.1; Al ₂ O ₃ + SiO ₂ - the rest (SiO ₂ / Al ₂ O ₃ = 4.0).

The catalyst is tested in the reaction of liquid-phase alkylation of isobutane with butylenes at a ratio of iso-C ₄ : C ₄ ″ = 27: 1, a temperature of 90 ° C., a space velocity of 1.2 h ⁻¹ , a catalyst run time of 7 hours according to the procedure described in example 1, but the butane-butylene fraction obtained from the + catalytic cracking unit (BBP), the hydrocarbon composition, which was determined by gas adsorption chromatography (a Crystallux-4000M chromatograph with a flame ionization detector), is used as the alkylating component, and is presented in Table 1.

Table 1 Characterization of butane-butylene fraction Hydrocarbons Concentration,% wt. Isobutane 30,280 n-butane 8,076 trans butylene 18,228 Butylene 13,003 Isobutylene 15,283 cis-butylene 13,876 Isopentane 1,316

The yield of the reaction product, alkylate, is calculated according to the reaction equations presented below:

Alkylation with butene-2

Butene-2 + Isobutane → 2,2,4-Trimethylpentane

(100 GPI)

Alkylation with butene-1

Butene-1 + Isobutane → 2,3-Dimethylhexane

(71.3 OCHI)

Butene-1 + Isobutane → 2,3,4-Trimethylpentane

(102.7 GPI)

Isobutene Alkylation

Isobutene + Isobutane → 2,2,4-Trimethylpentane

(100 GPI)

The yield of alkylbenzene to olefins and the selectivity of the process are calculated as shown in Example 1.

The results are presented in table 2.

Example 3

40 g of powdered zeolite type U with a molar ratio of SiO ₂ / Al ₂ O ₃ equal to 5 is subjected to all the operations of Example 1, only 180 ml of a mixture of rare earth nitrate and ammonium nitrates are taken for processing, and the concentration of the mixture of solutions of palladium tetraammiacate and ammonium nitrate is 5.04 g / l for palladium, and a solution of hydrofluoric and rhenium acids with a concentration of 0.043 g / l of rhenium and containing 0.32 g F in the form of hydrofluoric acid is introduced into this mixture.

The catalyst has the following chemical composition,% wt .:

Na ₂ O - 0.48; La ₂ O ₃ - 18.1; CaO - 1.4; PdO - 1.2; Re ₂ O ₇ - 0.01; F is 0.05; Al ₂ O ₃ + SiO ₂ - the rest (SiO ₂ / Al ₂ O ₃ = 5.0).

The catalyst was tested under the conditions of example 1.

The yield of alkylbenzene to olefins and the selectivity of the process are calculated as shown in Example 1.

The results are presented in table 2.

Example 4

100 g of granular zeolite type X with a molar ratio of SiO ₂ / Al ₂ O ₃ equal to 2.8, is loaded into the autoclave and poured with a solution of calcium chloride (concentration of 40 g / l, the amount of solution is 1020 ml). The autoclave is heated to 150 ° C, incubated for 3 hours and cooled. The waste solution is drained and the operation is repeated, processing a weighed portion of 450 ml of a mixture of solutions of rare-earth elements and ammonium nitrate (concentration of 15 g / l according to La ₂ O ₃ ). Then the zeolite is washed with demineralized water and filtered to obtain a wet cake.

To implement the second version of the catalyst preparation method, a sample (10 g dry) of pellets of rare-earth-calcium zeolite is poured with 20 ml of a solution of ammonium chloroplatinate (concentration of 0.25 g / l by Pt), hydrochloric acid containing 0.005 g of Cl and unipolar water until completely covered masses.

The application of active metals to rare-earth calcium zeolite is carried out in two stages: in the first stage, cold impregnation is carried out with stirring for 1 hour at a temperature of 25 ° C. After carrying out cold impregnation in the second stage, the impregnating solution is heated to a temperature of 75 ° C and the rare-earth calcium zeolite is impregnated for another 1 hour. In the second stage, after 0.75 hours, 0.005 g of oxalic acid in the form of an aqueous solution with a concentration of 50 g / dm ³ and 0.025 g of hydrogen peroxide in the form of a 30% aqueous solution are added to the impregnation solution, and the treatment is continued for 0.25 hours with stirring.

Then the mass is filtered off, washed, dried, tabletted and calcined.

The catalyst has the following chemical composition,% wt .: Na ₂ O - 0.8; La ₂ O ₃ - 15.5; CaO - 2.4; PtO - 0.06; Cl 0.05; Al ₂ O ₃ + SiO ₂ - the rest (SiO ₂ / Al ₂ O ₃ = 2.8). The catalyst was tested under the conditions of example 1.

The yield of alkylbenzene to olefins, stable activity and selectivity of the process are calculated as shown in example 1. The test results are shown in table 2.

Example 5

The rare-earth calcium zeolite is prepared according to example 4, only a sample (10 g per dry) of the cake of rare-earth-calcium zeolite is mixed with a binder - aluminum hydroxide of boehmite structure and a solution of nitric acid, at a pH of 2-4, the mixture is evaporated, formed by the method extrusion, extrudates are dried, dried and calcined. Then, the rare-earth calcium zeolite thus obtained is treated with unipolar water, impregnated with a mixture of a solution of ammonium nitrate, platinum tetraammonia and rhodium chloride (with a concentration of 2.4 g / l in Pt and 0.10 g / l in Rh).

The application of active metals to rare-earth calcium zeolite is carried out in two stages: in the first stage, cold impregnation is carried out with stirring for 1 hour at a temperature of 25 ° C. After carrying out cold impregnation in the second stage, the impregnating solution is heated to a temperature of 75 ° C and the rare-earth calcium zeolite is impregnated for another 1 hour. In the second stage, after 0.75 hours, 0.003 g of oxalic acid in the form of an aqueous solution with a concentration of 50 g / dm ³ and 0.025 g of hydrogen peroxide in the form of a 30% aqueous solution are added to the impregnation solution, and processing is continued for 0.25 hours with stirring.

Extrudates are dried, dried and calcined.

The catalyst has the following chemical composition,% wt .:

Na ₂ O - 0.6; La ₂ O ₃ - 15.1; CaO - 2.0; PtO - 0.55; RhO 0.02; Al ₂ O ₃ + SiO ₂ - the rest (SiO ₂ / Al ₂ O ₃ = 2.8).

The catalyst was tested in a liquid phase alkylation reaction under the conditions of Example 2.

The test results are shown in table 2.

Example 6

40 g of powdered zeolite type U with a molar ratio of SiO ₂ / Al ₂ O ₃ equal to 5, is loaded into the autoclave and poured with a solution of calcium chloride (concentration of 60 g / l, amount of 3320 ml). The autoclave is heated to 160 ° C and incubated for 3 hours. At the end of the treatment, the autoclave is cooled, the spent solution is poured, a solution of an industrial mixture of rare earth nitrates is poured (concentration 30 g / l, quantity 190 ml) and reheated to 160 ° C, incubated for 3 hours and cool.

After cooling and separation of the mother liquor, the zeolite is washed with demineralized water (condensate) and filtered to obtain a wet cake. Further, as described in Example 4, active metals are applied in two stages by treatment with a solution of hydrochloric, rhenium and platinum chloride acids with a concentration of 7.2 g / l for platinum, 0.26 g / l for Re and containing 0.32 g Cl in the form of hydrochloric acid.

Then, the obtained rare-earth calcium zeolite with active metals is mixed with a binder - aluminum hydroxide of boehmite structure and a solution of nitric acid, at a pH in the range of 2-4, the resulting mixture is evaporated, formed by extrusion, the extrudates are dried, dried and calcined.

The catalyst has the following chemical composition,% wt .:

Na ₂ O - 0.5; La ₂ O ₃ - 14.8; CaO - 1.2; PtO - 1.5; Re ₂ O ₇ - 0.06; Cl - 0.8; Al ₂ O ₃ + SiO ₂ - the rest (SiO ₂ / Al ₂ O ₃ = 5.0).

The catalyst was tested in a liquid phase alkylation reaction under the conditions of Example 1.

The results are shown in table 2.

Example 7

The catalyst is prepared according to example 1, but with a doubled number of treatments with a solution of calcium chloride and for processing take 140 ml of a mixture of nitrates of rare earth elements and ammonium. Next, a sample of the obtained rare-earth-calcium zeolite is treated in two stages, as described in example 4, with a solution of ammonium nitrate, rhenium chloride and hydrochloric acid (with a concentration of 7.37 g / l according to Re and 0.12 g Cl in the form of hydrochloric acid). The catalyst has the following chemical composition,% wt .:

Na ₂ O - 0.6; La ₂ O ₃ - 12.1; CaO - 3.0; Re ₂ O ₇ - 1.7; Cl - 0.3; Al ₂ O ₃ + SiO ₂ - the rest (SiO ₂ / Al ₂ O ₃ = 4.0).

The catalyst is tested in a liquid phase alkylation reaction of isobutane with propylene at a concentration of 99.5% by weight. on the basic substance, with a ratio of ISO-C ₄ : C ₃ "= 8: 1, a temperature of 20 ° C and a catalyst run time of 3 hours

The yield of the reaction product, alkylate, is calculated according to the reaction equations presented below:

Propylene + Isobutane → 2,3-Dimethylpentane

(84 OCHI)

The calculation of the yield of reaction products and the selectivity of the process, as shown in example 1.

The results are shown in table 2.

Example 8

The dealumination of the sodium form of type U zeolite with a molar ratio of SiO ₂ / Al ₂ O ₃ equal to 5.1 is carried out by treatment with a mixture of solutions of hydrochloric acid and trilon B at 95 ° C to a molar ratio of SiO ₂ / Al ₂ O ₃ = 7.0 . Then the rare-earth-calcium form of the catalyst is prepared according to example 1, only treatment with a mixture of nitrates of rare-earth elements and ammonium is carried out for 3 hours at 140 ° C. Further processing of the weighed sample is carried out according to example 4 in two stages with a mixture of solutions of ammonium nitrate, hydrofluoric acid and platinum tetraammonium (with a concentration of 0.076 g / l Pt and 0.002 g F in the form of hydrofluoric acid).

The catalyst has the following chemical composition,% wt .:

Na ₂ O - 0.5; La ₂ O ₃ - 15.4; CaO - 0.8; PtO - 0.015; F is 0.005; Al ₂ O ₃ + SiO ₂ - the rest (SiO ₂ / Al ₂ O ₃ = 7.0).

The catalyst was tested in a liquid phase alkylation reaction under the conditions of Example 1.

The results are shown in table 2.

Example 9

The catalyst is prepared according to example 1, only treatment with a mixture of rare earth nitrates and ammonium nitrates is carried out for 3 hours at 150 ° C, and the resulting rare-earth-calcium zeolite is treated in two stages with a mixture of solutions of ammonium nitrate, hydrofluoric acid, rhodium chloride and ammonium perrenate (with a concentration of g / l at 5.2 Re, 0.05 g / l at Rh and 0.2 g F in the form of hydrofluoric acid).

The catalyst has the following chemical composition,% wt .:

Na ₂ O - 0.5; La ₂ O ₃ - 16.0; CaO - 0.4; Re ₂ O ₇ - 1.2; RhO - 0.01; F is 0.5; Al ₂ O ₃ + SiO ₂ - the rest (SiO ₂ / Al ₂ O ₃ = 4).

The catalyst was tested in a liquid phase alkylation reaction under the conditions of Example 1.

The results are shown in table 2.

Example 10

The catalyst is prepared according to example 7, only treatment with a solution of calcium chloride is carried out at 200 ° C, and the obtained rare-earth-calcium zeolite is treated in example 4 in two stages with a mixture of solutions of ammonium nitrate, hydrofluoric acid, palladium tetraammonia, platinum tetraammonia, rhodium chloride, ammonium perrenate ( with a concentration of 0.05 g / l for palladium, 0.05 g / l for platinum, 0.43 g / l for Re, 0.44 g / l for Rh and 0.04 g F in the form of hydrofluoric acid) and unipolar water.

The catalyst has the following chemical composition,% wt .:

Na ₂ O - 0.7; La ₂ O ₃ - 10.1; CaO - 6.0; PtO - 0.01; PdO - 0.01; Re ₂ O ₇ - 0.1; RhO - 0.1; F is 0.1; Al ₂ O ₃ + SiO ₂ - the rest (SiO ₂ / Al ₂ O ₃ = 2.8).

The catalyst was tested in a liquid phase alkylation reaction under the conditions of Example 1.

The results are shown in table 2.

Thus, the proposed technical solution allows to increase the activity on the conversion of olefins to almost 100% by weight, the yield of product (alkylbenzene) by 10-15% by weight, the selectivity of the alkylation of isobutane with olefins C ₂ ÷ C ₄ according to the target product - isooctanes (iso - C ₈ ) to 75.9% wt., And the degree of decrease in the stable activity of the catalyst for 7 hours from the supply of raw materials is a maximum of 3% (compared with 7 ÷ 25% in the prototype).

table 2 Test results of catalysts in a liquid phase alkylation reaction Indicators Examples one 2 3 four 5 6 7 8 9 10 Na ₂ O 0.5 0.26 0.48 0.8 0.6 0.5 0.6 0.5 0.5 0.7 REE 20,0 17.4 18.1 15,5 15.1 14.8 12.1 15.4 16,0 10.1 CaO 1.4 0.8 1.4 2,4 2.0 1,2 3.0 0.8 0.4 6.0 Pto - - - 0.06 0.55 1,5 - 0.015 - 0.01 Pdo 0.01 0.11 1,2 - - - - - - 0.01 Re ₂ O ₇ - - 0.01 - - 0.06 1.7 - 1,2 0.1 Rho 1,5 0.05 - - 0.02 - - - 0.01 0.1 Chlorine - 0.1 - 0.05 - 0.8 0.3 - - - Fluorine - - 0.05 - - - - 0.005 0.5 0.1 The number of hours of operation of the catalyst N 7 7 7 7 7 7 3 7 7 7 The conversion of olefins,% wt. X _n (OL) 95 one hundred one hundred 95 one hundred one hundred one hundred one hundred one hundred one hundred The output of alkylbenzene in the 1st hour, η ₁ (AB) 190 204 204 185 204 204 197 200 203 204 The output of alkylbenzene in the n-th hour, η _n (AB) 186 200 200 180 200 200 195 198 200 201 The degree of decrease in stability, A _n 2 2 2 3 2 2 one one 1,5 1,5 Selectivity,% wt., Δ (AB) 70.5 74.5 71.2 69.8 75.9 69,4 66.7 68.5 65.6 73,2

Claims (20)

1. The isobutane alkylation catalyst of zeolite-based C ₂ -C ₄ olefins, containing alumina and silica at a molar ratio of silica: alumina of 2.8-7.0, sodium, calcium, rare earth oxides and active metal oxides , characterized in that as the oxides of active metals it contains oxides of platinum and / or palladium and / or rhenium and / or rhodium and / or halogen - chlorine or fluorine in the following ratio of components, wt.%:
sodium oxide 0.26 ÷ 0.8 calcium oxide 0.8 ÷ 4.2 rare earth oxide 12.0 ÷ 20.0 platinum oxide and / or palladium oxide and / or rhenium oxide and / or rhodium oxide 0.02 ÷ 2.0 and / or chlorine 0.05 ÷ 0.8 and / or fluorine 0.005 ÷ 0.5 zeolite with a ratio SiO ₂ / Al ₂ O ₃ equal to 2.8 ÷ 7.0 rest 2. The catalyst according to claim 1, characterized in that it further comprises a binder preferably aluminum hydroxide boehmite structure in an amount of 10 ÷ 50 wt.% In relation to the finished catalyst. 3. The catalyst according to claim 1, characterized in that as a zeolite it contains a faujasite type zeolite with a molar ratio of SiO ₂ / Al ₂ O ₃ equal to 2.8 ÷ 7.0. 4. The method of producing a catalyst according to claim 1, comprising treating the zeolite with aqueous solutions of calcium salts, rare earth elements and ammonium at elevated temperature and saturated vapor pressure for the time required to convert the zeolite to rare earth calcium zeolite and applying active metal oxides to it by impregnation aqueous solutions containing active metals - platinum or palladium, then washing and drying, characterized in that before applying the active metals, the obtained rare-earth calcium zeolite with unipolar water until the air ceases to escape from the pores of the zeolite, then the deposition of oxides of active metals: platinum and / or palladium and / or rhenium and / or rhodium and / or halogen-chlorine or fluorine, taken in amounts that provide the oxide content of the corresponding metal and halogen in the finished catalyst, and the application of active metals and halogen is carried out in two stages: in the first stage by cold impregnation at a temperature of not more than 30 ° C, in the second - at a temperature of not less than 70 ° C, after which They are treated with organic acid in the presence of a 30% aqueous solution of hydrogen peroxide, and then dried, tableted, and calcined. 5. The method according to claim 4, characterized in that the zeolite is mixed with a binder — preferably aluminum hydroxide of boehmite structure and a solution of mineral or organic acid, preferably nitric, at a pH in the range of 2–4, the resulting mixture is evaporated, formed by extrusion, the extrudates are dried , dried and calcined. 6. The method according to claim 4, characterized in that as a zeolite, a faujasite type zeolite is used with a molar ratio of SiO ₂ / Al ₂ O ₃ equal to 2.8 ÷ 7.0. 7. The method according to claim 4, characterized in that the processing of zeolite with aqueous solutions of calcium salts, rare earth elements and ammonium is carried out at a temperature of 140 ÷ 220 ° C. 8. The method according to claim 4, characterized in that platinum chloride, or rhenium, or rhodium acid, or ammonium perrenate or ammonium chloroplatinate, or rhodium chloride or palladium tetraammonium are used as aqueous solutions of active metals. 9. The method according to claim 4, characterized in that the cold impregnation is carried out for at least 1 hour, and hot for 0.5 ÷ 2 hours, preferably 0.75 ÷ 1.0 hours 10. The method according to claim 4, characterized in that the application of the halogen is carried out from an aqueous solution of hydrochloric or hydrofluoric acid. 11. The method according to claim 4, characterized in that the treatment with an organic acid is carried out from an aqueous solution of oxalic, acetic, formic or citric acid (or a mixture thereof), preferably within 0.25 ÷ 1.0 hours 12. The method of producing a catalyst according to claim 1, comprising treating the zeolite with aqueous solutions of calcium salts, a rare earth element and ammonium at elevated temperature and saturated vapor pressure for the time required to convert the zeolite to rare earth calcium zeolite and applying active metal oxides to it by impregnation aqueous solutions containing active metals, then washing and drying, characterized in that the deposition of rare earth calcium zeolite oxides of active metals - platinum, and / or palladium, and / and and rhenium, and / or rhodium and / or halogen-chlorine or fluorine, is carried out from solutions containing the corresponding metals or halogen in unipolar water, taken in amounts that provide the specified oxide content of the corresponding metal in the finished catalyst, and the deposition of active metals and halogen is carried out in two stages: in the first stage by cold impregnation at a temperature of not more than 30 ° C, in the second - at a temperature of not less than 70 ° C, after which they are treated with organic acid in the presence of a 30% aqueous solution B hydrogen, followed by drying, calcination and tableting. 13. The method according to p. 12, characterized in that the zeolite impregnated with oxides of active metals is mixed with a binder — preferably aluminum hydroxide of boehmite structure and a solution of mineral or organic acid, preferably nitric, at a pH in the range of 2–4, the resulting mixture is evaporated, formed by extrusion, the extrudates are dried, dried and calcined. 14. The method according to p. 12, characterized in that as a zeolite using a faujasite type zeolite with a molar ratio of SiO ₂ / Al ₂ O ₃ equal to 2.8 ÷ 7.0. 15. The method according to p. 12, characterized in that the processing of zeolite with aqueous solutions of calcium salts, rare earth elements and ammonium is carried out at a temperature of 140 ÷ 220 ° C. 16. The method according to p. 12, characterized in that platinum chloride, or rhenium, or rhodium acid, or ammonium perrenate or ammonium chloroplatinate, or rhodium chloride or palladium tetraammonium are used as aqueous solutions of active metals. 17. The method according to p. 12, characterized in that the cold impregnation is carried out for at least 1 hour, and hot for 0.5 ÷ 2 hours, preferably 0.75 ÷ 1.0 hours 18. The method according to p. 12, characterized in that the application of the halogen is carried out from an aqueous solution of hydrochloric or hydrofluoric acid. 19. The method according to p. 12, characterized in that the treatment with an organic acid is carried out from an aqueous solution of oxalic, acetic, citric acid or formic (or a mixture thereof), preferably within 0.25 ÷ 1.0 hours 20. The method of liquid-phase alkylation of isobutane with C ₂ -C ₄ olefins at elevated pressure and temperature in the presence of a zeolite catalyst, characterized in that the process is carried out in the presence of a catalyst according to any one of claims 1 to 3.