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

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

 

The invention relates to the field of petrochemicals, in particular the production of a catalyst based on zeolite and method of alkylation of isobutane by olefins C2÷C4in his presence, and can be used in the oil industry.

Due to the increased requirements to the quality of gasoline (limit of polynuclear aromatic hydrocarbons) has dramatically increased interest in the process of alkylation of isobutane by olefins. The product of the process - alkylbenzene consists almost completely of isoparaffin hydrocarbons, mainly isooctanol (Σ-C8). Alkilbenzin does not contain aromatic hydrocarbons, however, has a high octane number. The development of technology suitable for implementation in industry, primarily depends on the development of catalytic systems having a high activity, selectivity in obtaining the desired products and stability. In the present alkylation process on an industrial scale as catalysts are mineral acids - sulfuric, and hydrofluoric. However, their use raises a number of problems associated with their high toxicity and corrosion activity. As an alternative wide range of catalysts of different qualitative and quantitative composition, however, the prospects for the s catalysts based on zeolites, in which to increase activity and selectivity impose various modifiers.

The closest in technical essence and the achieved result is a catalyst based on zeolite type pajazit for alkylation of isobutane With olefins2÷4described in SU 1309383, B01J 29/12, SW 37/00, 20.10.1996, According to known technical solution, the catalyst has the following composition, % wt.: the sodium oxide 0,26÷0.8; oxide of rare earth element to 12.0÷20,0; calcium oxide 0,8÷4,2; platinum oxide or palladium 0,02÷1,2; aluminium oxide and silicon dioxide - the rest. Test CC in the alkylation of isobutane with ethylene at 90°C, the speed of feed of 1.3 h-1and duration 7 h shows the yield of alkylate 190÷210% wt.

The disadvantage of the catalyst is low selectivity for the target product Σ-C8(total isooctane) - 67,4% wt. when the alkylation of isobutane with ethylene and butenes, and in the alkylation of isobutane with propylene at 20°C and a duration of 3 h shows a low yield of alkylate - 100% wt., while the selectivity for the target product Σ-C8(total isooctane) and do is by 26.8% wt.

The objective of the proposed technical solution is the development of a catalyst having a high stability in carrying out the alkylation of isobutane With olefins2÷4and rawsumer high activity and selectivity for the target product Σ-C 8and also in the development of a method of producing such a catalyst.

The problem is solved in that the proposed catalyst for the alkylation of isobutane With olefins2÷4on the basis of a zeolite containing aluminum oxide and silicon dioxide in a molar ratio of silica : alumina, equal to 2.8÷7,0, oxides of sodium, calcium, rare earth element and the oxides of active metals, as oxides of active metals contains oxides of platinum and/or palladium, and/or rhenium, and/or rhodium, and the halogen is chlorine or fluorine in the following ratio of components, wt.%:

the sodium oxide0,26÷0,8
calcium oxide0,8÷4,2
the oxide of rare earth element12,0÷20,0
the oxide of platinum,
and/or palladium oxide,
and/or rhenium oxide,
and/or rhodium oxide0,02÷2,0
and/or chlorine0,05÷0,8
and/or fluorine 0,005÷0,5
zeolite with a ratio
SiO2/Al2O3equal to 2,8÷7,0rest

The proposed catalyst may optionally contain a binder, preferably aluminum hydroxide bemani patterns in number 10÷50% wt. with respect to the finished catalyst, and as it contains zeolite zeolite type pajazit a molar ratio of SiO2/Al2O3equal to a 2.8-7,0.

The problem is solved also by the fact that the method of preparation of the catalyst of the alkylation of isobutane With olefins2-C4based on zeolite, including his handling of aqueous solutions of salts of calcium, rare earth element and ammonia at elevated temperature and pressure saturated vapor for a time sufficient to convert the zeolite in rare-earth calcium zeolite and the application to it of the oxides of active metals by impregnation with aqueous solutions containing the active metals, then rinsing and drying, in which before application of the active metals first handle obtained rare-earth calcium zeolite unipolar water to stop coming out of the air from the pores of the zeolite, then the application of the oxides of active metals: platinum, and/or palla is Oia, and/or rhenium, and/or rhodium together with the halogen is chlorine or fluorine, taken in an amount to provide the specified content of the oxide 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 soaking at a temperature not exceeding 30°C, the second at a temperature of not less than 70°C, followed by treatment with an organic acid in the presence of 30% aqueous hydrogen peroxide solution, and then drying, pelleting and calcining.

A special case of the method, when the zeolite is mixed with a binder, preferably aluminum hydroxide bemani structure and solution of a mineral or organic acid, preferably nitrogen, at a pH in the range of 2÷4, the resulting mixture was evaporated, formed by extrusion, the extrudates provalivajut, dried and calcined.

As the zeolite used zeolite type pajazit a molar ratio of SiO2/Al2O3equal to a 2.8-7,0.

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

As the aqueous solutions of the active metals used hexachloroplatinic, or rhenium or rhodium acid or Tetra is miecat palladium.

Cold impregnation spend at least 1 hour, and hot for 0.5-2 hours, preferably 0.75 to 1.0 hour.

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

As organic acids using an aqueous solution of oxalic, formic, acetic or citric acid, or mixtures thereof.

The problem is solved in that the proposed second variant implementation of the method of producing catalyst for the alkylation of isobutane With olefins2÷4based on zeolite, including his handling of aqueous solutions of salts of calcium, rare earth element and ammonia at elevated temperature and pressure saturated vapor for a time sufficient to convert the zeolite in rare-earth calcium zeolite, and the application to it of the oxides of active metals by impregnation with aqueous solutions containing the active metals, then rinsing and drying, in which the application of rare earth calcium zeolite oxides of active metals - platinum and/or palladium, and/or rhenium, and/or rhodium and halogen is chlorine or fluorine carried out from solutions containing the appropriate metal or halogen in unipolar water, taken in an amount to provide the specified content of the oxide of the corresponding metal or halogen in the finished catalyst, and the application of active IU allow and halogen is carried out in two stages: in the first stage by cold soaking at a temperature not exceeding 30°C, on the second at a temperature of not less than 70°C, followed by treatment with an organic acid in the presence of 30% aqueous hydrogen peroxide solution, and then drying, pelleting and calcining.

Impregnated with oxides of active metals zeolite in the particular case mixed with a binder, preferably aluminum hydroxide bemani structure and solution of a mineral or organic acid, preferably nitrogen, at a pH in the range of 2÷4, the resulting mixture was evaporated, formed by extrusion, the extrudates provalivajut, dried and calcined.

As the zeolite used zeolite type pajazit a molar ratio of SiO2/Al2O3equal to 2,8÷7,0.

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

As the aqueous solutions of the active metals used hexachloroplatinic, or rhenium or rhodium acid, or tetraamine palladium.

Cold impregnation spend at least 1 hour, and hot for 0.5-2 hours, preferably of 0.75 to 1.0 hours.

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

As organic acids using an aqueous solution of oxalic, formic, uksosn the th or citric acid, or mixtures thereof.

The problem is solved also by the fact that the method of liquid-phase alkylation of isobutane With olefins2÷4at high pressure and temperature, in which the process is conducted in the presence of the described catalyst obtained in any of these ways.

The prior art patent RU No. 2289475, B01J 2/256, publ. 20.12.2006, which describes a catalyst containing chlorine and fluoride, along with other active components. The catalyst used for catalytic cracking with the aim of obtaining gasoline fractions.

However, the catalyst for the alkylation of isobutane With olefins2-C4containing in its composition, the halogen is chlorine or fluorine, in the prior art is not known.

The technical result, which can be obtained from the present invention is as follows:

- to increase the stable activity of the catalyst;

- increase the activity of the catalyst for the conversion of olefins to almost 100% wt.;

- increase the selectivity of the catalyst in the process of liquid-phase alkylation of isobutane With olefins2÷4on target product - isooctane (ISO-C8) up to 75.7% wt.;

- to increase the yield of the target product (alkylbenzene) 10÷15% wt.

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

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

Example 1

Rare earth calcium zeolite receive according to the method described in patent SU 936991, B01J 37/30, 23.06.1982, With this purpose, 40 g of powdered zeolite type pajazit a molar ratio of SiO2/Al2O3equal to 4.0, loaded into an autoclave and pour a solution of calcium chloride (concentration of 60 g/l, the amount of 260 ml). The autoclave is heated up to 160°C and incubated for 3 hours At the end of processing, the autoclave is cooled, pour the used solution, pour the solution of an industrial mixture of nitrates of rare-earth elements (concentration 30 g/l, the amount of 210 ml) and again heated to 160°C, incubated for 3 hours and cooled.

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

Then thus obtained rare-earth calcium zeolite is treated first unipolar water, which is obtained in an electrochemical reactor RAG-1 (units of type STEL) (method described in Bahir V.M. Modern technical electrochemical systems for disinfection, purification and activation of water. - M.: VNIIIMT, 1999. - 84; - Il.). Unipolar water served with the aim of chemical modi is mcirowave surface by chemisorption of hydrogen ions (H +), the intensification and the uniformity of the process it further impregnation of the active components, removal from the pores of the zeolite air, and the soft wetness of zeolite, which prevents the cracking catalyst, and for cleaning of dust and crumbs.

Next, a portion of the rare-earth-calcium zeolite pour mixture solutions of the active metals. In this example, a solution of ammonium nitrate, terramicina palladium and rhodium chloride (concentration 0.05 g/l palladium and 7.35 g/l for rhodium), in an amount to provide full coverage of the granules.

The application of active metals in the rare earth calcium zeolite is carried out in two stages: the first stage carrying cold impregnation with stirring for 1 hour at 25°C. After holding the cold impregnation in the second stage impregnating solution is heated to a temperature of 75°C and are impregnated rare earth calcium zeolite a further 1 hour. Then in the impregnating solution was added 0.02 g of oxalic acid (calculated on the anhydrous salt) in aqueous solution with a concentration of 50 g/DM3and 0.02 g of hydrogen peroxide in the form of a 30% aqueous solution. Processing continues 0.25 hours under stirring, then the solution is drained, the catalyst is dried and calcined.

Then the solution containing no palladium, drained, tablets washed with condensate, dried and calcined.

Get catalyst the following chemical composition, wt.%:

Na2O - 0,5; La2O3- 20,0; CaO - 1,4; PdO Is 0.01; RhO - 1,5; Al2O3+SiO2- the rest (SiO2/Al2O3=4,0).

The catalyst was tested in the reaction of liquid-phase alkylation of isobutane (isobutane fraction containing isobutane - to 99.5 wt.%, the rest n-butane) an ethylene concentration of 99.5 wt.% primary substance at a ratio of ISO-C4:C2"=17:1, a temperature of 90°C, flow rate of feed of 1.3 h-1and duration of the catalyst 7 h in laboratory flow-through installation.

The catalyst loaded into the reactor in such a way that over and under it layer is crushed quartz (fraction of particle sizes substantially higher fraction of catalyst)serving as a device for preventing removal of the catalyst stream. The top layer of quartz also promotes uniform distribution of the flow of raw materials on the catalyst surface, and tests the alkylation unit for leaks with nitrogen at P=1,5÷2,0 MPa.

After checking the leak tightness test of the catalyst in the alkylation of isobutane With olefins2÷4.

The only contact alkylating component ethylene with a catalyst leads to the flow of its oligomerization on the surface of the catalyst and fast is th decontamination last. To avoid oligomerization reactor with ready-to-use catalyst pre-filled with isobutane.

After filling the system with isobutane close the valve on isobutane tank and use the pump to start the flow in the reactor, the raw material mixture of raw capacity. As a result of interaction alkilirutego and alkylating components in the presence of a catalyst to form a liquid reaction products and unreacted excess isobutane, which is taken at the outlet of the reactor in a cooled trap.

Liquid product alkylate is subjected to stabilize, and then analyze the chromatograph "Crystallux-4000M using getaccountinfo chromatography on a column of SE-30. The work was used the program "NetChrom intended for automation chromatograph "Crystallux-4000M". This program provides treatment of the chromatographic signals.

Determine the full composition of the alkylate - it is a mixture of isomers paraffin hydrocarbon, C5÷C9and its estimated octane number.

The resulting gaseous products of stabilization is mainly unreacted excess isobutane, also analyzed by gas adsorption chromatography: column of alumina.

The output of the reaction products - alkylate count on to depict alanamu following reaction equation:

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

(100 octane number research method - EYES)

Conversion of olefin characterizes the completeness of the use of raw materials in this process and is the ratio of the number of converted olefins (OL) taken, expressed in %, and is calculated by the formula:

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

(OL)raw concentration OL in raw materials, wt.%;

m(raw) - the mass of the raw material, g;

(OL)cont. the concentration of AL in the product, wt.%;

m(product - weight of the product,

The output of alkylbenzene on the olefins in the feedstock (exit AB taken on OL), expressed in percent, is determined by the formula:

η(AB) - Output AB, % wt.;

m(product) - product mass, g;

(OL)raw concentration OL in raw materials, wt.%;

m(raw) - weight raw materials,

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

The selectivity of the reaction is the relative concentration of isooctanol fraction of the reaction products are calculated according to the formula:

δ(AB) - the reaction selectivity, wt.;

C(ΣC8- concentration isooctanol fraction in product, wt.%;

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

Stable activity of the catalyst to change output alkylbenzene on the olefins in the feedstock during operation calculated by the formula:

Anthe degree of reduction of the stable activity of the catalyst, % refers.;

n is the duration of the supply of raw materials, h;

η1(AB) - output alkylbenzene on the olefins in the feedstock in the first hour from the feed, wt.%;

ηn(AB) - output alkylbenzene on the olefins in the feedstock for the n-th hour from feed, wt.%;

In accordance with the submitted calculations of the reduction of the stable activity of the catalyst 7 hours from the raw material supply is 2% (compared with 14% in the prototype).

The selectivity of the process is and 68.5% wt.

The results are given in table 2.

Example 2.

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

A catalyst which has the following chemical composition, % wt.:

Na2O - 0,26; La2O3- 17,4; CaO - 0,8; PdO - 0,11; RhO - 0,05; Cl - 0.1; Al2O3+SiO2- the rest (SiO2/Al2O3=4,0).

The catalyst was tested in the reaction of liquid-phase alkylation of isobutane with butylenes in the ratio of ISO-C4:C4"=27:1, a temperature of 90°C, flow rate of 1.2 h-1, the duration of the catalyst 7 h according to the method described in example 1, but as the alkylating component use a butane-butylene fraction, obtained by + installing catalytic cracking (BBF), hydrocarbon composition, which is determined by the method getaccountinfo chromatography (GC "Crystallux-4000M with a flame ionization detector) and are presented in table 1.

Table 1
Characteristics of the butane-butylene fraction
HydrocarbonsConcentration, % wt.
Isobutane30,280
n-butane8,076
TRANS-Butylene18,228
Butylene13,003
From the scrap 15,283
CIS-Butylene13,876
Isopentane1,316

The reaction product yield of alkylate are calculated according to the following reaction equations:

Alkylation of the butene-2

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

(100 EYES)

Alkylation of the butene-1

Butene-1 + Isobutane → 2,3-Dimethylhexane

(71.3 EYES)

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

(102.7 EYES)

Alkylation of isobutene

Isobutene + Isobutane → 2,2,4-Trimethylpentane

(100 EYES)

The output of alkylbenzene on the olefin selectivity calculated, as shown in example 1.

The results are presented in table 2.

Example 3.

40 g of powder-type zeolite with a molar ratio of SiO2/Al2O3equal to 5, is subjected to all the operations of example 1, only the processing take 180 ml of a mixture of nitrates of rare-earth elements and ammonium, and the concentration of the mixture of solutions terramicina palladium and ammonium nitrate is 5,04 g/l palladium, and the mixture injected a solution of hydrofluoric and rhenium acid concentration 0,043 g/l for rhenium and provided the 0.32 g F in the form of hydrofluoric acid.

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

Na2O - 0,48; La2O3- 18,1; CaO - 1,4; PdO - 1,2; Re2O7- 0,01; F - 0,05; Al2O3+SiO2- the rest (SiO2/Al2O3=5,0).

The catalyst was tested under the conditions of example 1.

The output of alkylbenzene on the olefin selectivity calculated, as shown in example 1.

The results are presented in table 2.

Example 4.

100 g of granulated zeolite of type X with a molar ratio of SiO2/Al2O3equal to 2.8, loaded into an autoclave and pour a solution of calcium chloride (concentration 40 g/l, the amount of solution 1020 ml). The autoclave is heated to 150°C, incubated 3 h and cooled. The spent solution is drained and operation repeat, processing the sample to 450 ml of a mixture of solutions of nitrate of rare earth elements and ammonium (concentration 15 g/l in La2O3). Then, the zeolite is washed with demineralized water and filtered to obtain a wet cake.

For the implementation of the second variant of the method of preparation of the catalyst sample (10 g dry) pellet rare earth-calcium zeolite pour 20 ml of chloroplatinate ammonium (concentration of 0.25 g/l for Pt), hydrochloric acid, containing 0.005 g Cl and unipolar with water to cover the mixture.

The application of active metals in the rare earth calcium zeolite Khujand who are in two stages: the first stage carrying cold impregnation with stirring for 1 hour at 25°C. After conducting cold impregnation in the second stage impregnating solution is heated to a temperature of 75°C and are impregnated rare earth calcium zeolite a further 1 hour. In the second stage in the impregnating solution in 0.75 hour add 0.005 g of oxalic acid in aqueous solution with a concentration of 50 g/DM3and 0.025 g of hydrogen peroxide in the form of a 30% aqueous solution and processing continues 0.25 hours under stirring.

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

The catalyst has the following chemical composition, wt.%: Na2O - 0,8; La2O3- 15,5; CaO - 2,4; PtO - 0,06; Cl - 0,05; Al2O3+SiO2- the rest (SiO2/Al2O3=2,8). The catalyst was tested under the conditions of example 1.

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

Example 5.

Rare earth calcium zeolite prepared as in example 4, only a portion (10 g dry) pellet rare earth-calcium zeolite is mixed with a binder is aluminum hydroxide bemani structure and solution of nitric acid, at a pH in the range equal to 2-4, the mixture was evaporated, formed by extrusion, the extrudates provalivajut, dried and calcined. Then thus obtained rare-earth calcium is the first zeolite is treated unipolar water, impregnated with a mixture solution of ammonium nitrate, terramicina platinum and rhodium chloride (with a concentration of 2.4 g/l for Pt and 0.10 g/l for Rh).

The application of active metals in the rare earth calcium zeolite is carried out in two stages: the first stage carrying cold impregnation with stirring for 1 hour at 25°C. After holding the cold impregnation in the second stage impregnating solution is heated to a temperature of 75°C and are impregnated rare earth calcium zeolite a further 1 hour. In the second stage in the impregnating solution in 0.75 hour add 0.003 g of oxalic acid in aqueous solution with a concentration of 50 g/DM3and 0.025 g of hydrogen peroxide in the form of a 30% aqueous solution and processing continues 0.25 hours under stirring.

The extrudates provalivajut, dried and calcined.

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

Na2O - 0,6; La2O3- 15,1; CaO - 2,0; PtO - 0,55; RhO - 0,02; Al2O3+SiO2- the rest (SiO2/Al2O3=2,8).

The catalyst was tested in the reaction liquid phase alkylation in the conditions of example 2.

The results are given in table 2.

Example 6.

40 g of powder-type zeolite with a molar ratio of SiO2/Al2O3equal to 5, is loaded into the autoclave and pour a solution of calcium chloride (concentration of 60 g/l, the number 3320 ml). Auto is love is heated up to 160°C and incubated for 3 hours When processing is completed, the autoclave is cooled, pour the used solution, pour the solution of an industrial mixture of nitrates of rare-earth elements (concentration 30 g/l, number 190 ml) and again heated to 160°C, incubated for 3 hours and cooled.

After cooling and separation of the mother liquor zeolite is washed with demineralized water (condensate) and filtered to obtain a wet cake. Further, as described in example 4 is applied in two stages active metals by treatment with hydrochloric, rhenium and hexachloroplatinic acid 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 are mixed with a binder is aluminum hydroxide bemani structure and solution of nitric acid, at a pH in the range equal to 2-4, the mixture was evaporated, formed by extrusion, the extrudates provalivajut, dried and calcined.

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

Na2O - 0,5; La2O3- 14,8; CaO - 1,2; PtO - 1,5; Re2O7- 0,06; Cl - 0,8; Al2O3+SiO2- the rest (SiO2/Al2O3=5,0).

The catalyst was tested in the reaction liquid phase alkylation in the conditions of example 1.

The results are shown in table 2.

Example 7.

The catalyst is prepared is about example 1, but with double the number of treatments with a solution of calcium chloride and processing take 140 ml of a mixture of nitrates of rare-earth elements and ammonium. Next, a portion of the obtained rare earth-calcium zeolite is treated in two stages, as described in example 4, a solution of ammonium nitrate, rhenium chloride and hydrochloric acid (concentration 7,37 g/l on Re and 0.12 g Cl in the form of hydrochloric acid). The catalyst has the following chemical composition, wt.%:

Na2O - 0,6; La2O3- 12,1; CaO - 3,0; Re2O7- 1,7; Cl - 0,3; Al2O3+SiO2- the rest (SiO2/Al2O3=4,0).

The catalyst was tested in the reaction of liquid-phase alkylation of isobutane with propylene, with the concentration of 99.5% by weight. primary substance at a ratio of ISO-C4:C3"=8:1, 20°C and the duration of operation of the catalyst 3 o'clock

The reaction product yield of alkylate are calculated according to the following reaction equations:

Propylene + Isobutane → 2,3-Dimethylpentan

(84 EYES)

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

The results are shown in table 2.

Example 8.

Dealumination sodium form of type zeolite with a molar ratio of SiO2/Al2O3equal to 5.1, is carried out by treatment with a mixture of hydrochloric acid solutions and trylon B at 95°C is about molar ratio of SiO 2/Al2O3=7,0. Then rare earth-calcium form of the catalyst prepared according to example 1, except that the treatment with a mixture of nitrates of rare-earth elements and ammonium are for 3 h at 140°C. Further processing of the received sample lead by example 4 in two stages with a mixture of solutions of ammonium nitrate, hydrofluoric acid and terramicina platinum (with a concentration 0,076 g/l for Pt and 0.002 g F in the form of hydrofluoric acid).

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

Na2O - 0,5; La2O3- 15,4; CaO - 0,8; PtO - 0,015; F - 0,005; Al2O3+SiO2- the rest (SiO2/Al2O3=7,0).

The catalyst was tested in the reaction liquid phase alkylation in the conditions of example 1.

The results are shown in table 2.

Example 9.

The catalyst prepared according to example 1, except that the treatment with a mixture of nitrates of rare-earth elements and ammonium are for 3 h at 150°C, and the resulting rare earth-calcium zeolite is treated according to example 4 in two stages with a mixture of solutions of ammonium nitrate, hydrofluoric acid, rhodium chloride and ammonium perrhenate (with concentration g/l by 5.2 Re, 0.05 g/l for Rh and 0.2 g of F in the form of hydrofluoric acid).

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

Na2O - 0.5; La2O3- 16,0; CaO - 0,4; Re2O7- 1,2; RhO - 0,01; F - 0,5; Al2O3+SiO2 - the rest (SiO2/Al2O3=4).

The catalyst was tested in the reaction liquid phase alkylation in the conditions of example 1.

The results are shown in table 2.

Example 10.

The catalyst prepared according to example 7, only the processing solution of calcium chloride is carried out at 200°C, and the resulting rare earth-calcium zeolite is treated according to example 4 in two stages with a mixture of solutions of ammonium nitrate, hydrofluoric acid, terramicina palladium, terramicina platinum, rhodium chloride, ammonium perrhenate (with a concentration of 0.05 g/l palladium, 0.05 g/l for platinum, 0,43 g/l by Re, of 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.%:

Na2O - 0,7; La2O3- 10,1; Cao - 6,0; PtO - 0,01; PdO - 0,01; Re2O7- 0,1; RhO - 0,1; F - 0,1; Al2O3+SiO2- the rest (SiO2/Al2O3=2,8).

The catalyst was tested in the reaction liquid phase alkylation in the conditions of example 1.

The results are shown in table 2.

Thus, the proposed solution allows to increase the activity for the conversion of olefins to almost 100% wt., the product yield (alkylbenzene) 10÷15% wt., the selectivity of the alkylation of isobutane With olefins2÷4on target product - isooctane (ISO - C8) to 75.9% wt., and with Epen reduce the stable activity of the catalyst 7 hours from the raw material supply is a maximum of 3% (compared to 7÷25% in the prototype).

Table 2
The results of the tests of the catalysts in the reaction of liquid-phase alkylation
IndicatorsExamples
12345678910
Na2O0,50,260,480,80,60,50,60,50,50,7
REE20,017,418,115,515,114,812,115,416,0the 10.1
CaO 1,40,81,42,42,01,23,00,80,46,0
PtO---0,060,551,5-0,015-0,01
PdO0,010,111,2------0,01
Re2O7--0,01--0,061,7-1,20,1
RhO1,5--0,02---0,010,1
Chlorine-0,1-0,05-0,80,3---
Fluoride--0,05----0,0050,50,1
The number of hours the catalyst N7777773777
Conversion of olefins, wt.%. Xn(OL) 9510010095100100100100100100
The output of alkylbenzene for the 1st hour, η1(AB)190204204185204204197200203204
The output of alkylbenzene for the n-th hour, ηn(AB)186200200180200200195198200201
The degree of decreasing stability, An22232211,5 1,5
Selectivity, wt.%, δ (AB)70,574,571,269,875,969,466,768,565,673,2

1. The catalyst for the alkylation of isobutane With olefins2-C4on the basis of a zeolite containing aluminum oxide and silicon dioxide in a molar ratio of silica: alumina, equal to 2.8÷7,0, oxides of sodium, calcium, rare earth element and the oxides of active metals, 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 the halogen is chlorine or fluorine in the following ratio, wt.%:

the sodium oxide0,26÷0,8
calcium oxide0,8÷4,2
the oxide of rare earth element12,0÷20,0
the platinum oxide
and/or palladium oxide
and/or rhenium oxide
and/or rhodium oxide0,02÷2,0
and/or chlorine0,05÷0,8
and/or fluorine0,005÷0,5
zeolite with a ratio
SiO2/Al2O3equal to 2,8÷7,0rest

2. The catalyst according to claim 1, characterized in that it further comprises a binder, preferably aluminum hydroxide bemani patterns in number 10÷50 wt.% with respect to the finished catalyst.

3. The catalyst according to claim 1, characterized in that it contains zeolite zeolite type pajazit a molar ratio of SiO2/Al2O3equal to 2,8÷7,0.

4. The method of preparation of the catalyst according to claim 1, comprising processing a zeolite with aqueous solutions of salts of calcium, rare earth elements and ammonia at elevated temperature and pressure saturated vapor for a time sufficient to convert the zeolite in rare-earth calcium zeolite and the application to it of the oxides of active metals by impregnation with aqueous solutions containing the active metal is platinum or palladium, then washing the at and drying, characterized in that before applying the active metals first handle obtained rare-earth calcium zeolite unipolar water to stop coming out of the air from the pores of the zeolite, then the application of the oxides of active metals: platinum and/or palladium, and/or rhenium, and/or rhodium and/or the halogen is chlorine or fluorine, taken in an amount to provide the specified content of the oxide 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 soaking at a temperature not exceeding 30°C, the second at a temperature of not less than 70°C, followed by treatment with an organic acid in the presence of 30%aqueous hydrogen peroxide solution, and then drying, pelleting and calcining.

5. The method according to claim 4 characterized in that the zeolite is mixed with a binder, preferably aluminum hydroxide bemani structure and solution of a mineral or organic acid, preferably nitrogen, at a pH in the range equal to 2÷4, the resulting mixture was evaporated, formed by extrusion, the extrudates provalivajut, dried and calcined.

6. The method according to claim 4, characterized in that the zeolite used zeolite type pajazit a molar ratio of SiO2/Al2O3equal to 2,8÷7,0.

7. The method according to claim 4, Otley is audica fact, what is the treatment of the zeolite with aqueous solutions of salts of calcium, rare earth elements and ammonia is carried out at a temperature of 140÷220°C.

8. The method according to claim 4, characterized in that the aqueous solutions of the active metals used hexachloroplatinic, or rhenium or rhodium acid, or ammonium perrhenate or chloroplatinate ammonium chloride or rhodium or tetraamine palladium.

9. The method according to claim 4, characterized in that the cold impregnation is conducted for at least 1 h, and hot for 0.5÷2 h, preferably of 0.75÷1.0 hours

10. The method according to claim 4, characterized in that the application of halogen is carried out on an aqueous solution of hydrochloric or hydrofluoric acid.

11. The method according to claim 4, characterized in that the processing of organic acid is carried out on an aqueous solution of oxalic, acetic, formic or citric acid (or mixtures thereof), preferably within 0,25÷1.0 hours

12. The method of preparation of the catalyst according to claim 1, comprising processing a zeolite with aqueous solutions of salts of calcium, rare earth element and ammonia at elevated temperature and pressure saturated vapor for a time sufficient to convert the zeolite in rare-earth calcium zeolite and the application to it of the oxides of active metals by impregnation with aqueous solutions containing the active metals, then rinsing and drying, characterized those who, the application of rare earth calcium zeolite oxides of active metals - platinum and/or palladium, and/or rhenium, and/or rhodium and/or halogen is chlorine or fluorine, carried out from solutions containing the appropriate metal or halogen in unipolar water, taken in an amount to provide the specified content of the oxide of the corresponding metal in the finished catalyst, and the application of active metals and halogen is carried out in two stages: in the first stage by cold soaking at a temperature not exceeding 30°C, the second at a temperature of not less than 70°C, after which process organic acid in the presence of 30%aqueous hydrogen peroxide solution, and then drying, pelleting and calcining.

13. The method according to item 12, characterized in that the impregnated oxides of the active metals zeolite is mixed with a binder, preferably aluminum hydroxide bemani structure and solution of a mineral or organic acid, preferably nitrogen, at a pH in the range equal to 2÷4, the resulting mixture was evaporated, formed by extrusion, the extrudates provalivajut, dried and calcined.

14. The method according to item 12, characterized in that the zeolite used zeolite type pajazit a molar ratio of SiO2/Al2O3equal to 2,8÷7,0.

15. The method according to item 12, wherein the processing of the zeolite in the governmental solutions of calcium salts, rare earth elements and ammonia is carried out at a temperature of 140÷220°C.

16. The method according to item 12, characterized in that the aqueous solutions of the active metals used hexachloroplatinic, or rhenium or rhodium acid, or ammonium perrhenate or chloroplatinate ammonium chloride or rhodium or tetraamine palladium.

17. The method according to item 12, wherein the cold impregnation is conducted for at least 1 h, and hot for 0.5÷2 h, preferably of 0.75÷1.0 hours

18. The method according to item 12, wherein the application of the halogen is carried out on an aqueous solution of hydrochloric or hydrofluoric acid.

19. The method according to item 12, wherein the processing of the organic acid is carried out on an aqueous solution of oxalic, acetic, citric acid or formic (or mixtures thereof), preferably within 0,25÷1.0 hours

20. The method of liquid-phase alkylation of isobutane With olefins2-C4at high pressure and temperature in the presence of a zeolite catalyst, wherein the process is conducted in the presence of a catalyst according to any one of claims 1÷3.



 

Same patents:

FIELD: process engineering.

SUBSTANCE: invention relates to petrochemistry, particularly, to production of zeolite-based catalyst for alkylation of isobutane by olefins and may be used in oil processing. Invention covers catalyst of alkylation of isobutane by zeolite-based olefins that contains aluminium oxide and silicon dioxide at silicon dioxide-to-aluminium oxide molar ratio equal to 2.8-7.0, sodium oxide, rare-earth element, oxides of active metals, which contains oxides of platinum and/or palladium and/or rhenium and/or ruthenium at the following ratio of components, in wt %: sodium oxide - 0.26-0.8, calcium oxide - 0.8-4.2, rare earth element oxide - 12.0-20.0, oxides of platinum and/or palladium and/or rhenium and/or ruthenium - 0.02-2.0, zeolite with SiO2/Al2O3 equal to 2.8-7.0, making the rest. It covers also two versions of the method of catalyst production comprising zeolite treatment by water solutions of salts of calcium, rare earth element and ammonium at increased temperature and pressure of saturated vapors for time period required for conversion of zeolite into rare-earth calcium zeolite, its washing, drying and calcinating. In compliance with this method, first, rare-earth calcium zeolite is impregnated with unipolar water unless air escapes from zeolite pores and, then, processing is performed by impregnation with water solutions of salts of oxides of active metals, which contains oxides of platinum and/or palladium and/or rhenium and/or ruthenium taken in amount that ensures said content of metal oxide in finished catalyst. It comprises also drying, calcinating, or applying on rare-earth metal calcium zeolite of water solutions of salts of oxides of active metals, which contains oxides of platinum and/or palladium and/or rhenium and/or ruthenium in unipolar water taken in amount that ensures aforesaid content of metal oxide in finished catalyst, drying, tabletting and calcinating.

EFFECT: increase in catalyst activity to 100 wt %, in isooctane selectivity to 75,7 wt % and in yield of target alkyl benzene by 10-15 wt %.

14 cl, 10 ex, 2 tbl

FIELD: process engineering.

SUBSTANCE: invention relates to petrochemistry, particularly, to production of zeolite-based catalyst for alkylation of isobutane by olefins and may be used in oil processing. Invention covers catalyst of alkylation of isobutane by zeolite-based olefins that contains aluminium oxide and silicon dioxide at silicon dioxide-to-aluminium oxide molar ratio equal to 2.8-7.0, sodium oxide, rare-earth element, oxides of active metals, which contains oxides of platinum and/or palladium and/or rhenium and/or ruthenium at the following ratio of components, in wt %: sodium oxide - 0.26-0.8, calcium oxide - 0.8-4.2, rare earth element oxide - 12.0-20.0,oxides of platinum and/or or palladium and/or molybdenum and/or nickel and/or cobalt - 0.02-2.0, zeolite with SiO2/Al2O3 equal to 2.8-7.0, making the rest. It covers also two versions of the method of catalyst production comprising zeolite treatment by water solutions of salts of calcium, rare earth element and ammonium at increased temperature and pressure of saturated vapors for time period required for conversion of zeolite into rare-earth calcium zeolite, its washing, drying and calcinating. In compliance with this method, first, rare-earth calcium zeolite is impregnated with unipolar water unless air escapes from zeolite pores and, then, processing is performed by impregnation with water solutions of salts of oxides of active metals, which contains oxides of platinum and/or palladium and/or molybdenum and/or nickel and/ or cobalt taken in amount that ensures said content of metal oxide in finished catalyst. It comprises also drying, calcinating, or applying on rare-earth metal calcium zeolite of water solutions of salts of oxides of active metals, which contains oxides of platinum and/or palladium and/or molybdenum and/or nickel and/or cobalt. The process includes two stages: first, cold impregnation at not over 30°C, and, second, at, at least, 70°C, and finally drying, tabletting and calcinating.

EFFECT: increase in catalyst activity approximating to 100 wt %, isotope selectivity approximating to 73.5 wt %, yield of target alkyl benzene by 10-15 wt %.

16 cl, 10 ex, 2 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to a method of isomerising vitamin D analogues such as compounds used in synthesis of calcipotriol using a flow-type photoreactor or a photoreactor with continuous flow for preparing said vitamin D analogues. The invention also relates to use of intermediates produced using said method to produce calcipotriol or monohydrate of calcipotrol or its pharmaceutical medicinal forms.

EFFECT: improved properties of compounds.

21 cl, 4 ex, 1 tbl

FIELD: organic synthesis and catalysts.

SUBSTANCE: invention relates to improved method of telomerization of diene with conjugated double bonds, wherein said diene interacts with a compound having active hydrogen atom and selected from group, consisting of alkanols, hydroxyaromatic compounds, carboxylic acids, and water, in presence of telomerization catalyst based on VIII group metal source and bidentate ligand. The latter is depicted by general formula (I): R1R2M1-R-M2R3R4, wherein M1 and M2 independently represent P; R1, R2, R3, and R4 independently represent monovalent aliphatic group or R1, R2, and M1 jointly and/or R3, R4, and M2 jointly independently represent cycloaliphatic group with 5-12 carbon atoms in cycle, wherefrom one atom is M1 or M2; and R represents (i) bivalent organic bridge group, which is unsubstituted alkylene group or alkylene group substituted by lower alkyl groups optionally incorporating oxygen as heteroatom, or (ii) group containing two benzene rings bound to each other or to alkylene groups, which in turn are linked to M1 and M2. Invention also relates to novel bidentate ligands, which can be utilized in the method of invention and having following general formulas: R1R2M1-V-M2R3R4 (II) and Q1Q2M1-Q5-Ar1-Q6-M2Q3Q4 (III). Invention further relates to improved method for production of 1-octene involving 1,3-butadiene telomerization step to form 1-substituted 2,7-octadiene.

EFFECT: expanded synthetic possibilities in conjugated dienes area.

10 cl, 1 dwg, 1 tbl, 10 ex

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

FIELD: heterogeneous catalysts.

SUBSTANCE: catalyst contains porous carrier, buffer layer, interphase layer, and catalytically active layer on the surface wherein carrier has average pore size from 1 to 1000 μm and is selected from foam, felt, and combination thereof. Buffer layer is located between carrier and interphase layer and the latter between catalytically active layer and buffer layer. Catalyst preparation process comprises precipitation of buffer layer from vapor phase onto porous carrier and precipitation of interphase layer onto buffer layer. Catalytic processes involving the catalyst and relevant apparatus are also described.

EFFECT: improved heat expansion coefficients, resistance to temperature variation, and reduced side reactions such as coking.

55 cl, 4 dwg

The invention relates to new phosphorus ylides F.-ly (I)

< / BR>
in which R1, R2and R3represent the amino group R R N, where R' and R" are C1-C6alkyl; R4- H, Me; R5polymer media polystyrene type f crystals of (S)

< / BR>
where n, n' and m are integers greater than or equal to 1

FIELD: chemistry.

SUBSTANCE: present invention relates to a catalyst for decomposing N2O, a method of preparing said catalyst and use thereof to decompose laughing gas in exhaust or process gases. Described is a catalyst for decomposing N2O to nitrogen and oxygen in gas phase with a porous support made from polycrystalline or glass-like inorganic material, consisting of magnesium oxide or ceramic mixed oxides containing at least 50 wt % magnesium oxide on which a functional layer of cerium oxide is deposited and on which a layer of material containing cobalt oxide is deposited. Described is a method of preparing the catalyst which involves preparing said porous support, impregnation thereof with a solution containing a cerium salt, drying and/or calcination, and subsequent impregnation with a cobalt salt solution, drying and/or calcination. The catalysts can particularly be used in apparatus for producing nitric acid as secondary or tertiary catalysts.

EFFECT: high activity and selectivity of the catalyst.

22 cl, 1 tbl, 7 ex

FIELD: chemistry.

SUBSTANCE: invention relates to methods of producing catalysts for cleaning diesel engine emissions. Described is a method of producing a catalyst for diesel soot after-burning, involving mixing a copper extract in n-caprylic acid and a molybdenum extract in isoamyl alcohol in a ratio which ensures content of metals in the obtained mixture which corresponds to the composition CuMoO4, subsequent removal of the solvent from the obtained mixture and pyrolysis thereof on air, wherein the obtained mixture of extracts is brought to total concentration of metals of 1.5-2.0 wt % using isoamyl alcohol; the diluted mixture is deposited on a substrate made from titanium or alloy thereof, which is treated by plasma-electrolytic oxidation in an aqueous electrolyte; the solvent is removed by heating the titanium substrate with the deposited mixture of extracts to 150°C for not less than 1 hour; subsequent pyrolysis is carried out at temperature 540-550°C for not less than 1 hour.

EFFECT: simple method of producing a catalyst on a metal substrate and high efficiency thereof while simultaneously improving quality and efficiency of the obtained catalyst.

2 cl, 3 dwg, 3 ex

FIELD: chemistry.

SUBSTANCE: invention relates to catalysts for vapour conversion of synthetic fuel. Described is a catalyst for producing synthetic gas via vapour conversion of synthetic hydrocarbon fuel, preferably methanol, characterised by that the catalyst is a catalytic structured block with a gas distribution system consisting of alternating corrugated and flat catalytically active bands which form channels; the catalyst contains copper, zinc, chromium and aluminium compounds as active components, said compounds being in the following amounts, wt %: copper oxide 5-15, chromium oxide 0.4-2.6, zinc oxide 3-16 and aluminium oxide 2-8, reinforced metal porous support - the balance up to 100. Described is a method of preparing said catalyst by depositing active components onto the support by impregnating a heat-resistant reinforced metal porous support with a solution of copper, chromium, zinc and aluminium salts, drying and calcining at 400-450°C, followed by cutting catalytically active bands from the obtained reinforced catalyst and forming the catalyst, which is a catalytic structured block with a gas distribution system consisting of alternating corrugated and flat catalytically active bands which form channels. Described is a method of producing synthetic gas through vapour conversion of methanol using the catalyst described above.

EFFECT: high efficiency of the process of producing synthetic gas.

7 cl, 1 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: invention relates to making sorbents and supports for supported catalysts and can be used in preparing catalysts for different catalytic processes. Described is a method of making supports for catalysts based on fibreglass, involving treatment by single- or multiple incipient wetness impregnation with aqueous solutions of modifying precursors in form of silica sol, aluminium hydroxide sol, aluminium oxynitrate, or single- or multiple immersion in an alcohol solution of tetraethoxy silane with hydrolysis in water vapour at 70-80°C for 3 hours, followed by drying at 120°C for 1 hour and calcination at 550°C for 4 hours. Described also is a catalyst support based on fibreglass obtained using the disclosed method and containing up to 30 wt % deposited catalyst from the mass of fibreglass or up to 20 wt % deposited Al2O3 from the mass of glassfibre, having specific surface area of up to 60 m2/g, and mean pore diameter of 50-60 Ǻ.

EFFECT: linear increase of specific surface area of the support from the amount of the deposited additive.

2 cl, 2 tbl, 27 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a novel catalyst for use in synthesis of aliphatic carboxylic acid containing (n+1) carbon atoms, where n denotes an integer of up to 6, and/or an ether derivative thereof by bringing an aliphatic alcohol containing n carbon atoms, and/or reactive derivative thereof, selected from dialkyl ether, ester of alcohol and alkyl halide, into contact with carbon monoxide, where said catalyst is prepared via ion exchange or saturation of the ammonium or hydrogen form of mordenite with silver, drying the saturated/ion exchange-treated mordenite and subsequent calcination of the dried silver-containing mordenite at temperature from 500 to 600°C. The invention also relates to a method of producing aliphatic carboxylic acid containing (n+1) carbon atoms, where n denotes an integer of up to 6, and/or an ether derivative thereof, which involves bringing the aliphatic alcohol containing n carbon atoms and/or reactive derivative thereof, selected from dialkyl ether, ester of alcohol and alkyl halide, into contact with carbon monoxide in the presence of said catalyst.

EFFECT: improved selectivity with respect to carbonylation products.

22 cl, 2 tbl, 16 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a catalyst for selective hydrogenation of acetylene and diene hydrocarbons to C2-C5+ hydrocarbon fractions. The catalyst is an alumina support on which there is an active palladium component and a promoter, said promoter being in attached in oxide form and palladium particles being in zero oxidation state in the electron stat of valence orbitals of their atoms. The catalyst is characterised by an absorption band of a carbon monoxide and palladium complex with wave number 2060-2100 cm-1 in the infrared spectrum of the adsorbed carbon monoxide, wherein the catalyst has the following composition, wt %: palladium 0.005-1, promoter 0.005-5, aluminium oxide being the balance.

EFFECT: high activity and selectivity of the catalyst for selective hydrogenation of alkyne and diene hydrocarbons to C2-C5+ hydrocarbon fractions owing to high dispersity and change in electron density and geometric characteristics of particles of the active component with more complete interaction with the promoter.

3 cl, 4 tbl, 18 ex

FIELD: process engineering.

SUBSTANCE: invention relates to vanadium-free catalyst for reduction of aluminium oxides by ammonium or compound decomposing thereto. It relates also to activation of homogeneous mixed cerium and zirconium oxides for nitrogen oxide reduction. Proposed catalyst comprises catalytically active coat applied on inner carries body. Note here that said coat consists, partially or completely, of homogeneous mixed cerium and zirconium oxides with cerium amount varying from 10 wt % to 90 wt % per total weight of said mix, activated for reduction by introducing transition metal. Transition metal is selected from the group including chromium, molybdenum and mixes of said transition metals or combinations thereof.

EFFECT: high-activity, vanadium-free, cheap and effective reduction catalyst.

19 cl, 9 dwg, 1 tbl, 13 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing a hydrotreatment catalyst. Described is a method of producing a hydrotreatment catalyst which involves the following steps: a) at least one step for saturating a dried and/or annealed catalyst precursor containing at least one group VIII element and/or at least one group VIB element and an amorphous support using an impregnating solution consisting of at least one phosphorus-containing compound dissolved in at least one polar solvent with relative permittivity higher than 20; b) a step for maturation of said saturated catalyst precursor obtained at step a); wherein said maturation step is carried out at atmospheric pressure, at temperature ranging from ambient temperature to 60°C for maturation period of 12 to 340 hours; c) a step for drying without a subsequent step for annealing said catalyst precursor obtained at step b), wherein the drying step c) is carried out in a drying oven at atmospheric or low pressure and at temperature 50-200°C. Described is use of the catalyst obtained using the described method to carry out hydrofining and hydroconversion of hydrocarbon material.

EFFECT: high catalyst activity.

14 cl, 8 tbl, 17 ex

FIELD: chemistry.

SUBSTANCE: invention relates to catalysts, particularly, to those intended for hydration of vegetable oil and fat and may be used in food, chemical and petrochemical industries. Proposed method comprises preparing granulated catalysts for liquid-phase hydration of vegetable oils and distilled fat acids by hydrogen that represent metallic palladium applied in amount of 0.5-2.0 wt % on carbon carrier of 0.5-6.0 mm-fraction with specific surface of 100-450 m2/g and volume of pores of 0.2-0.6 cm3/g. Hydration is conducted on catalyst stationary bed at 140-210°C, hydrogen pressure of 2 to 12 atm and raw stock consumption of 100 to 1500 g/(kgkt·h).

EFFECT: high hydration rate and stability of technical brands.

4 cl, 1 dwg, 3 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to catalysts for dehydrogenation of paraffin hydrocarbons and methods of producing said catalysts, as well as methods of producing olefin hydrocarbons via catalytic dehydrogenation of corresponding C3-C5 paraffin hydrocarbons and can be used in chemical and petrochemical industry. Described is a catalyst for dehydrogenation of C3-C5 paraffin hydrocarbons, which contains chromium and potassium oxides and optionally zirconium dioxide, deposited on a solid solution of formula ZnxAl2O(3+x) where x=0.025-0.25, with a defective spinel structure. Described is a method of producing the catalyst by hydrating a precursor of the solid solution, saturating with a mixture of solutions of chromic acid, potassium chromate and a zinc salt and optionally zirconyl nitrate, followed by drying and calcination in air, wherein hydration is carried out during the saturation process. A method of dehydrogenating paraffin hydrocarbons in the presence of said catalyst is also described.

EFFECT: high catalytic activity, selectivity and stability with low coke formation.

14 cl, 2 tbl, 12 ex

FIELD: process engineering.

SUBSTANCE: invention relates to petrochemistry, particularly, to production of zeolite-based catalyst for alkylation of isobutane by olefins and may be used in oil processing. Invention covers catalyst of alkylation of isobutane by zeolite-based olefins that contains aluminium oxide and silicon dioxide at silicon dioxide-to-aluminium oxide molar ratio equal to 2.8-7.0, sodium oxide, rare-earth element, oxides of active metals, which contains oxides of platinum and/or palladium and/or rhenium and/or ruthenium at the following ratio of components, in wt %: sodium oxide - 0.26-0.8, calcium oxide - 0.8-4.2, rare earth element oxide - 12.0-20.0, oxides of platinum and/or palladium and/or rhenium and/or ruthenium - 0.02-2.0, zeolite with SiO2/Al2O3 equal to 2.8-7.0, making the rest. It covers also two versions of the method of catalyst production comprising zeolite treatment by water solutions of salts of calcium, rare earth element and ammonium at increased temperature and pressure of saturated vapors for time period required for conversion of zeolite into rare-earth calcium zeolite, its washing, drying and calcinating. In compliance with this method, first, rare-earth calcium zeolite is impregnated with unipolar water unless air escapes from zeolite pores and, then, processing is performed by impregnation with water solutions of salts of oxides of active metals, which contains oxides of platinum and/or palladium and/or rhenium and/or ruthenium taken in amount that ensures said content of metal oxide in finished catalyst. It comprises also drying, calcinating, or applying on rare-earth metal calcium zeolite of water solutions of salts of oxides of active metals, which contains oxides of platinum and/or palladium and/or rhenium and/or ruthenium in unipolar water taken in amount that ensures aforesaid content of metal oxide in finished catalyst, drying, tabletting and calcinating.

EFFECT: increase in catalyst activity to 100 wt %, in isooctane selectivity to 75,7 wt % and in yield of target alkyl benzene by 10-15 wt %.

14 cl, 10 ex, 2 tbl

FIELD: process engineering.

SUBSTANCE: invention relates to petrochemistry, particularly, to production of zeolite-based catalyst for alkylation of isobutane by olefins and may be used in oil processing. Invention covers catalyst of alkylation of isobutane by zeolite-based olefins that contains aluminium oxide and silicon dioxide at silicon dioxide-to-aluminium oxide molar ratio equal to 2.8-7.0, sodium oxide, rare-earth element, oxides of active metals, which contains oxides of platinum and/or palladium and/or rhenium and/or ruthenium at the following ratio of components, in wt %: sodium oxide - 0.26-0.8, calcium oxide - 0.8-4.2, rare earth element oxide - 12.0-20.0,oxides of platinum and/or or palladium and/or molybdenum and/or nickel and/or cobalt - 0.02-2.0, zeolite with SiO2/Al2O3 equal to 2.8-7.0, making the rest. It covers also two versions of the method of catalyst production comprising zeolite treatment by water solutions of salts of calcium, rare earth element and ammonium at increased temperature and pressure of saturated vapors for time period required for conversion of zeolite into rare-earth calcium zeolite, its washing, drying and calcinating. In compliance with this method, first, rare-earth calcium zeolite is impregnated with unipolar water unless air escapes from zeolite pores and, then, processing is performed by impregnation with water solutions of salts of oxides of active metals, which contains oxides of platinum and/or palladium and/or molybdenum and/or nickel and/ or cobalt taken in amount that ensures said content of metal oxide in finished catalyst. It comprises also drying, calcinating, or applying on rare-earth metal calcium zeolite of water solutions of salts of oxides of active metals, which contains oxides of platinum and/or palladium and/or molybdenum and/or nickel and/or cobalt. The process includes two stages: first, cold impregnation at not over 30°C, and, second, at, at least, 70°C, and finally drying, tabletting and calcinating.

EFFECT: increase in catalyst activity approximating to 100 wt %, isotope selectivity approximating to 73.5 wt %, yield of target alkyl benzene by 10-15 wt %.

16 cl, 10 ex, 2 tbl

Up!