RU2664124C1 - Catalyst for dehydration of alkylaromatic, alkylpyridine and olefin hydrocarbons - Google Patents

Abstract

FIELD: technological processes.SUBSTANCE: invention relates to production of catalysts, namely, to production of catalysts for dehydrogenation of alkylaromatic, alkylpyridine and olefinic hydrocarbons. Catalyst of the following composition is described, in wt.%: potassium compounds (in terms of potassium oxide) 10.0–25.0; magnesium compound and/or a calcium compound (in terms of magnesium oxide and/or calcium oxide) 0.2–5.0; cerium oxide 1.0–15.0; molybdenum oxide 0.5–5.0; cement 0.5–14.0; barium and/or silicon compounds (in terms of barium oxide and/or silicon oxide) 0.1–6.0 and iron oxide – the rest. In addition, the catalyst may contain at least one component selected from the group of compounds of lanthanum, neodymium, rubidium, cesium, zirconium, aluminum, titanium, tungsten in an amount of 0.01–3.0 wt.%.EFFECT: technical result consists in preparation of a catalyst having increased activity, selectivity and mechanical strength.6 cl, 8 ex, 2 dwg

Description

The present invention relates to the production of catalysts, namely, the production of catalysts for the dehydrogenation processes of alkyl aromatic, alkyl pyridine and olefinic hydrocarbons.

A known catalyst for the dehydrogenation of olefinic hydrocarbons of the following composition, mass. %: potassium compounds (in terms of potassium oxide) 10.0-25.0; chromium oxide 0.5-7.0; molybdenum oxide 0.7-7.0; cerium oxide 1.0-15.0; Portland cement 0.5-13.0; iron oxide - the rest (RF patent No. 2361667, 03/05/2008, published July 20, 2009, bull. No. 20).

Also known is a catalyst for the dehydrogenation of alkyl aromatic hydrocarbons, containing, by weight. %: potassium compounds 8-22; compounds of magnesium and / or calcium 0.5-10; molybdenum oxide 0.5-5; cerium oxide 1-8; Portland cement 2-12; strontium oxide and / or ferrite 0.5-10; lanthanum and / or neodymium oxide 0.01-1; iron oxide - the rest. Additionally, the catalyst may contain oxide and / or ferrite of rubidium and / or cesium in an amount of 0.05-5.0 mass% (RF patent 2187364, 13.112000, published on 08.20.2002, bull. No. 23).

Closest to the proposed is a catalyst for the dehydrogenation of alkylaromatic hydrocarbons containing, by weight. %: potassium compounds (in terms of potassium oxide) 8.0-25.0; magnesium compounds and / or calcium compounds (in terms of magnesium oxide and / or calcium oxide) 0.2-7.0; molybdenum oxide 0.7-7.0; cerium oxide 1.0-15.0; Portland cement 0.5-12.0; lanthanum oxide and / or neodymium oxide 0.01 to 7.0; iron oxide - the rest. Additionally, the catalyst may contain zirconium oxide, tin oxide and tungsten oxide in an amount of 0.01-1.0 mass% each (RF patent 2285560, April 15, 2005, published October 20, 2006, bull. No. 29).

The disadvantages of these catalysts are their relatively low activity, selectivity and mechanical strength.

The problem solved by the present invention is to increase the activity, selectivity and mechanical strength of the catalyst.

A catalyst for the dehydrogenation of alkylaromatic, alkylpyridine and olefinic hydrocarbons of the following composition, mass. %: potassium compounds (in terms of potassium oxide) 10.0-25.0; magnesium compounds and / or calcium compounds (in terms of magnesium oxide and / or calcium oxide) 0.2-5.0; cerium oxide 1.0-15.0; molybdenum oxide 0.5-5.0; cement 0.5-14.0; compounds of barium and / or silicon (in terms of barium oxide and / or silicon oxide) 0.1-6.0 and iron oxide - the rest.

As potassium compounds, the catalyst may contain ferrites and / or potassium polyferrites.

As the barium compound, the catalyst may comprise barium ferrite.

Additionally, the catalyst may contain at least one component selected from the group of compounds of lanthanum, neodymium, rubidium, cesium, zirconium, aluminum, titanium, tungsten in an amount of 0.01-3.0% of the mass.

As compounds of rubidium and / or cesium, the catalyst may contain ferrites and / or polyferrites of rubidium and / or cesium.

Preferably, the catalyst is molded in the form of cylindrical, or three-petalled, or five-petal granules (Fig. 1 and Fig. 2).

The difference between the proposed catalyst from the prototype is the additional content of barium and / or silicon compounds and a new ratio of components (qualitative and quantitative).

Additional differences from the prototype are:

- the content as potassium compounds of ferrites and / or potassium polyferrites;

- the content as a barium compound of barium ferrite;

- additional content of at least one component selected from the group of compounds of lanthanum, neodymium, rubidium, cesium, zirconium, aluminum, titanium, tungsten in an amount of 0.01-3.0% of the mass.

- the content of rubidium and / or cesium ferrites and / or polyferrites of rubidium and / or cesium as compounds;

- molding the catalyst in the form of cylindrical, three-petalled or five-petal granules.

In the proposed catalyst, a new combination of all components allows to increase its activity, selectivity and mechanical strength. The shape of the catalyst improves its performance.

As silicon compounds, the catalyst may contain silicon dioxide or potassium silicate.

The following oxides can be used as iron compounds: α-Fe ₂ O ₃ (hematite), Fe ₃ O ₄ (magnetite); metahydroxide (FeOOH) or mixtures thereof.

As cement can be used cement grades M-400 ÷ M-700 (gray and / or white).

The proposed catalyst is prepared by mixing in a predetermined ratio of finely ground oxides or compounds of iron, molybdenum, magnesium and / or calcium, cerium, barium and / or silicon, potassium, which are easily decomposed to oxides. At the same stage, at least one component selected from the group of compounds of lanthanum, neodymium, rubidium, cesium, zirconium, aluminum, titanium and tungsten can be introduced.

The silicon compound is introduced in the form of dioxide and / or in the form of an aqueous solution of potassium silicate.

Barium compounds may be introduced as ferrite.

Barium ferrite is obtained by mixing finely ground powders of barium oxides and iron (III) oxides, followed by calcining at 1000-1400 ° C or by calcining a catalyst containing the claimed components at a temperature of 1000 ° C.

Potassium compounds are introduced in the form of ferrites and / or polyferrites, or an aqueous solution of carbonate and / or potassium hydroxide.

Potassium ferrites and / or polyferrites are prepared by one of the known methods:

mixing in a predetermined ratio of oxide or iron compound easily decomposed to oxide with an aqueous solution of carbonate and / or potassium hydroxide for 0.5-3.5 hours, molding the resulting paste into granules with a diameter of 2.0-6.0 mm, drying at a temperature 100-150 ° C and calcination at a temperature of 650-1000 ° C; before introduction into the catalyst, the polyferrites are crushed.

- calcination of the catalyst containing the inventive components at a temperature of 800-1000 ° C.

Rubidium and cesium ferrites and / or polyferrites are prepared similarly to potassium ferrites and / or potassium polyferrites.

Cement is found in the mixing stage of the dry catalyst components.

The catalyst mass is stirred for 1.0-5.0 hours to obtain a homogeneous mass, then molded by extrusion into cylindrical or three to five petal granules, dried first at room temperature for 8-16 hours, then at a temperature of 100-200 ° C. for 8-16 hours and calcined at a temperature of 550-1000 ° C.

The invention is illustrated by the following examples.

Example 1

The estimated amount of dry catalyst components: iron oxide (α-Fe ₂ O ₃ ), molybdenum oxide, cerium oxide, magnesium oxide, calcium oxide, cement (gray, M-500), barium ferrite and lanthanum oxide are mixed for 1.5 hours . An aqueous solution containing potassium carbonate and potassium silicate is added. The catalyst mass is stirred for 2 hours until a homogeneous mass is obtained, then it is extruded into cylindrical granules with a diameter of 3.0 mm, dried at room temperature for 16 hours, then at a temperature of 120 ° C for 8 hours and calcined at a temperature of 670 ° C for 4 hours .

Get the catalyst composition, mass%: Fe ₂ O ₃ - 56.58; K ₂ O - 13.62; MgO - 3.0; CaO - 0.2; MoO ₃ - 1.5; CeO ₂ - 8.0; La ₂ O ₃ - 3.0; barium ferrite (in terms of BaO) - 1.0; SiO ₂ - 0.1; cement - 10.0

Tests of catalytic activity are carried out in the reaction of dehydrogenation of ethylbenzene to styrene at a temperature of 620 ± 10 ° C, a feed rate of liquid ethylbenzene of 0.5-1.5 l / l of catalyst per hour and mass dilution of the feed with water vapor 1: 2-3. The catalyst provides the following activity indicators: ethylbenzene conversion 84.4%; selectivity for styrene 95.5%.

The mechanical abrasion resistance was determined in a ball mill, into which a catalyst with a volume of 60 cm ³ and 10 metal balls with a diameter of 8 mm was loaded. The result was the ratio of the mass of the catalyst after abrasion to the mass of the catalyst taken for testing in percent. The tests were carried out for 20 minutes. The mechanical strength measured in this way was 99.2%. The mechanical strength of the prototype was 98.5-98.9%.

Example 2

The catalyst is prepared analogously to example 1, but instead of calcium oxide, lanthanum oxide and potassium silicate, the calculated amount of cesium carbonate and tungsten oxide is used. Cesium carbonate is introduced as an aqueous solution. Tungsten oxide is introduced at the stage of mixing the dry components. Instead of barium ferrite, barium oxide is used. Cement is used grade M-600 (white). Change the ratio of components and get a catalyst composition, mass. %: Fe ₂ O ₃ - 60.4; K ₂ O - 10.0; MgO - 5.0; MoO ₃ - 0.5; CeO ₂ - 1.0; BaO - 6.0; Cs ₂ O - 2.0; WO ₃ - 1.0; cement - 14.0.

The catalyst mass was stirred for 1 hour. Form in 3 petal granules with a diameter of 5 mm. At room temperature, the catalyst was dried for 8 hours and at 200 ° C for 8 hours. Calcined at 550 ° C for 6 hours.

Tests of catalytic activity are carried out in the dehydrogenation reaction of 2-methyl-5-ethylpyridine to 2-methyl-5-vinylpyridine at a temperature of 620 ± 10 ° C, the flow rate of liquid 2-methyl-5-ethylpyridine is 0.5-1.5 l / l catalyst per hour and mass dilution of raw materials with water vapor 1: 5-7. The catalyst provides the following activity indicators: conversion of 2-methyl-5-ethylpyridine 71.1%; selectivity for 2-methyl-5-vinylpyridine 91.1%.

The mechanical strength was 99.4%.

Example 3

The catalyst is prepared analogously to example 1, but instead of magnesium oxide, lanthanum oxide and potassium silicate, the calculated amount of silicon oxide is used. Instead of barium ferrite, barium oxide is used. Cement is used grade M-700 (white). 20% of the total amount of potassium carbonate is introduced in dry form at the stage of mixing the dry components, the remaining 80% of the total amount of potassium carbonate is introduced in the form of an aqueous solution. Lanthanum oxide, neodymium oxide, zirconium oxide and silicon oxide are introduced at the stage of mixing the dry components. Change the ratio of components and get a catalyst composition, mass. %: Fe ₂ O ₃ - 52.9; K ₂ O - 25.0; CaO - 5.0; MoO ₃ - 5.0; CeO ₂ 6.5; BaO - 0.1; SiO ₂ - 0.5; cement - 5.

At room temperature, the catalyst was dried for 12 hours and at a temperature of 150 ° C for 6 hours. Calcined at 900 ° C for 0.5 hours.

Tests of catalytic activity are carried out in the reaction of dehydrogenation of n-butylene to butadiene at a temperature of 620 ± 10 ° C, a feed rate of 500 l / l of catalyst per hour for gas and a 1: 15-17 molar dilution of the feed with water vapor. The catalyst provides the following activity indicators: butylene conversion of 41.8%; butadiene selectivity 88.1%.

Mechanical strength 99.1%.

Example 4

The catalyst is prepared analogously to Example 1 but metahydroxide (FeOOH) is used instead of lanthanum oxide and barium ferrite as compounds of iron - 80% of the total content of iron compounds, based on Fe ₂ O3, and magnetite Fe ₃ O ₄ - 20% of the total content of the compounds iron, counting on Fe ₂ O ₃ . Cement is used grade M-700 (white). 30% of the total amount of potassium carbonate is introduced in dry form at the stage of mixing the dry components, the remaining 70% of the total amount of potassium carbonate is introduced in the form of an aqueous solution. Change the ratio of components and get a catalyst composition, mass. %: Fe ₂ O ₃ - 57.0; K ₂ O - 15.0; MgO - 3.0; CaO - 1.5; MoO ₃ - 1.0; CeO ₂ - 16.0; SiO ₂ - 6.0; cement - 0.5.

The catalyst mass is molded into cylinders with a diameter of 2 mm. The catalyst was dried at room temperature for 16 hours and at a temperature of 100 ° C for 16 hours. Calcined at 670 ° C for 5 hours.

Tests of catalytic activity are carried out in the reaction of isopropylbenzene dehydrogenation to a-methylstyrene at a temperature of 570 ± 10 ° C, a flow rate of liquid isopropylbenzene of 0.5-1.5 l / l of catalyst per hour and mass dilution of the feed with 1: 3 steam. The catalyst provides the following activity indicators: isopropylbenzene conversion 79.6%; selectivity for a-methylstyrene 96.6%.

Mechanical strength 98.9%.

Example 5

The catalyst is prepared analogously to example 1, but instead of calcium oxide, the calculated amount of neodymium oxide, rubidium polyferrite, cesium polyferrite, aluminum hydroxide and zirconium oxide are used. Instead of potassium silicate, silica is used. 20% of the total amount of potassium oxide is introduced in the form of potassium polyferrite in dry form at the stage of mixing the dry components, the remaining 80% of the total amount of potassium oxide is introduced in the form of an aqueous solution of potassium carbonate. Neodymium oxide, rubidium polyferrite, cesium polyferrite, aluminum hydroxide and zirconium oxide are introduced at the stage of mixing the dry components. Cement is used grade M-400 (gray). Change the ratio of components and get a catalyst composition, mass. %: Fe ₂ O ₃ - 53.22; potassium polyferrite (in terms of K ₂ O) - 3.41; potassium carbonate (in terms of K ₂ O) - 13.63; MgO - 0.2; MoO ₃ - 1.0; CeO ₂ - 9.5; La ₂ O ₃ - 0.03; Nd ₂ O ₃ - 0.01; barium ferrite (in terms of BaO) - 3.5; rubidium polyferrite (in terms of Rb ₂ O - 0.01; cesium polyferrite (in terms of CsO ₂ ) - 0.01; SiO ₂ - 0.5; ZrO ₂ - 2.18; Al ₂ O ₃ - 0.8 ; cement - 12.

The catalyst was dried at room temperature for 16 hours and at a temperature of 150 ° C for 12 hours. Calcined at 600 ° C for 10 hours.

Tests of catalytic activity are carried out in the reaction of dehydrogenation of isoamylenes to isoprene at a temperature of 620 ± 10 ° C, a feed rate of liquid isoamylenes of 0.5-1.5 l / l of catalyst per hour and mass dilution of the feedstock with steam 1: 4-6. The catalyst provides the following activity indicators: isoamylene conversion 56.9%; selectivity for isoprene 91.9%.

Mechanical strength 99.3%.

Example 6

The catalyst is prepared analogously to example 1, but instead of magnesium oxide and potassium silicate, the calculated amount of rubidium ferrite, zirconium oxide, titanium oxide and tungsten oxide is used. Instead of barium ferrite, barium oxide is used. 20% of the total amount of potassium oxide is introduced in the form of dry potassium ferrite at the stage of mixing the dry components, the remaining 80% of the total amount of potassium oxide is introduced in the form of an aqueous solution of potassium carbonate. Rubidium ferrite, zirconium oxide, titanium oxide and tungsten oxide are introduced at the stage of mixing the dry components. Cement is used grade M-600 (white). Change the ratio of components and get a catalyst composition, mass. %: Fe ₂ O ₃ - 59.5; potassium ferrite (in terms of K ₂ O) - 3.3; potassium carbonate (in terms of K ₂ O) - 13.2; CaO -1.5; MoO ₃ - 0.5; CeO ₂ 8.5; La ₂ O ₃ - 0.01; BaO - 2.5; rubidium ferrite (in terms of Rb ₂ O - 1.97; ZrO ₂ - 0.01; TiO ₂ - 0.01 WO ₃ - 1.0; cement - 8.

The catalyst mass is formed into 5 petal granules with a diameter of 6 mm The catalyst was dried at room temperature for 16 hours and at a temperature of 170 ° C for 16 hours. Calcined at 650 ° C for 6 hours.

Tests of catalytic activity are carried out in the reaction of dehydrogenation of ethylbenzene to styrene at a temperature of 620 ± 10 ° C, a feed rate of liquid ethylbenzene of 0.5-1.5 l / l of catalyst per hour and mass dilution of the feed with water vapor 1: 2-3. The catalyst provides the following activity indicators: ethylbenzene conversion 84.5%; selectivity for styrene 95.7%.

Mechanical strength 99.2%.

Example 7

The catalyst is prepared analogously to example 1, but additionally use the estimated number of compounds of rubidium and cesium, zirconium oxide, titanium oxide and tungsten oxide. The rubidium and cesium compounds are administered as an aqueous solution of rubidium and cesium hydroxides. Zirconia, titanium oxide and tungsten oxide are introduced at the stage of mixing the dry components. Cement is used grade M-600 (white). Change the ratio of components and get a catalyst composition, mass. %: Fe ₂ O ₃ - 56.48; K ₂ O - 14.31; MgO - 2.5; CaO - 0.5; MoO ₃ - 0.7; CeO ₂ - 7.5; La ₂ O ₃ - 0.01; barium ferrite (in terms of BaO) - 5.0; Rb ₂ O - 0.5; CsO ₂ - 1.6; SiO ₂ - 1.0; ZrO ₂ - 0.1; TiO ₂ 0.2; WO ₃ - 0.5; cement - 9.1.

The catalyst was dried at room temperature for 8 hours and at a temperature of 150 ° C for 10 hours. Calcined at 590 ° C for 10 hours.

Tests of catalytic activity are carried out in the dehydrogenation reaction of 2-methyl-5-ethylpyridine to 2-methyl-5-vinylpyridine at a temperature of 620 ± 10 ° C, the flow rate of liquid 2-methyl-5-ethylpyridine is 0.5-1.5 l / l catalyst per hour and mass dilution of raw materials with water vapor 1: 5-7. The catalyst provides the following activity indicators: conversion of 2-methyl-5-ethylpyridine 71.5%; selectivity for 2-methyl-5-vinylpyridine 91.0%.

Mechanical strength was 99.2%.

Example 8

The catalyst is prepared analogously to example 1, but additionally use the estimated number of compounds of rubidium and cesium, titanium oxide. Instead of barium ferrite, barium oxide is introduced. Instead of potassium silicate, silica is introduced. The rubidium and cesium compounds are introduced as an aqueous solution of rubidium and cesium carbonates. Titanium oxide is introduced at the stage of mixing the dry components. Cement is used grade M-700 (white) in the amount of 95% of the mass of the total cement content and gray grade M-400 in the amount of 5% of the mass of the total cement. Change the ratio of components and get a catalyst composition, mass. %: Fe ₂ O ₃ - 55.85; K ₂ O - 12.95; MgO - 4.5; CaO - 0.5; MoO ₃ - 1.5; CeO ₂ - 7.0; La ₂ O ₃ - 0.1; BaO - 1.5; SiO ₂ - 3.5; Rb ₂ O - 0.1; CsO ₂ - 0.5; TiO ₂ - 2.0; cement - 10.0.

The catalyst was dried at room temperature for 12 hours and at a temperature of 170 ° C for 8 hours. Calcined at 680 ° C for 5 hours.

Tests of catalytic activity are carried out in the reaction of dehydrogenation of ethylbenzene to styrene at a temperature of 620 ± 10 ° C, a feed rate of liquid ethylbenzene of 0.5-1.5 l / l of catalyst per hour and mass dilution of the feed with water vapor 1: 2-3. The catalyst provides the following activity indicators: ethylbenzene conversion 84.6%; selectivity for styrene 95.6%.

Mechanical strength 99.3%.

Claims (7)

1. A catalyst for the dehydrogenation of alkyl aromatic, alkyl pyridine and olefinic hydrocarbons, including iron oxide, potassium compounds, magnesium compounds and / or calcium compounds, molybdenum oxide, cerium oxide, cement, characterized in that it further comprises barium and / or silicon compounds in the following the ratio of components, wt.%: Potassium compounds (in terms of potassium oxide) 8.0-25.0 Magnesium compounds and / or calcium compounds (in terms of oxides) 0.2-5.0 Molybdenum oxide 0.5-5.0 Cerium oxide 1.0-16.0 Cement 0.5-14.0 Compounds of barium and / or silicon (in terms of oxides) 0.1-6.0 Iron oxide rest 2. The catalyst according to claim 1, characterized in that as potassium compounds it contains ferrites and / or potassium polyferrites. 3. The catalyst according to claim 1, 2, characterized in that it contains barium ferrite as a barium compound. 4. The catalyst according to claims. 1-3, characterized in that it additionally contains at least one component selected from the group of compounds of lanthanum, neodymium, rubidium, cesium, zirconium, aluminum, titanium, tungsten in an amount of 0.01-3.0 wt.%. 5. The catalyst according to paragraphs. 1-4, characterized in that as the compounds of rubidium and / or cesium, it contains ferrites and / or polyferrites of rubidium and / or cesium. 6. The catalyst according to paragraphs. 1-5, characterized in that it is molded in the form of cylindrical or triple-petal, or five-petal granules.

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