RU2603774C1 - Catalyst for oxidative aromatisation of lower alkanes - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to catalysts of process of producing aromatic hydrocarbons from hydrocarbon material. Catalyst for oxidative aromatisation of lower alkanes contains, wt%: zinc oxide (with respect to metal) 3.00-7.00, gallium (III) oxide (with respect to metal) 0.5-3.00, germanium (IV) oxide (with respect to metal) 0.01-0.10; γ-aluminium oxide - 10.00-30.00, a pentasil-type zeolite in hydrogen form - balance up to 100.

EFFECT: technical result consists in improvement of catalyst activity in relation to output desired aromatic hydrocarbons, its selectivity, conversion.

1 cl, 1 ex

Description

The invention relates to catalysts for the production of aromatic hydrocarbons from hydrocarbons, in particular to catalysts for aromatization of lower alkanes in the presence of oxygen.

Aromatic hydrocarbons are one of the main basic products of petrochemicals. Considering the growing role in the industry of the processes of deep processing of oil raw materials, including gas, the development of catalysts for the process of aromatization of lower alkanes becomes especially urgent.

Aromatization catalysts for alkanes containing from one to four carbon atoms are known by contacting with catalysts containing zeolites and various metals, for example platinum on ZSM-5 (WO 2005/065393, 2005), cerium or cerium oxide, as well as a group VIII metal or its oxide, for example platinum or platinum oxide on zeolite (RU 2377230, 2009; US 7186871, 2007), zinc, cerium, lanthanum, magnesium, iron, calcium (RU 2165293, 2001).

The process of this catalytic aromatization has a number of disadvantages, which are as follows:

- thermodynamic features of the process determine the aromatization at high temperatures, while the temperature limit is limited by the thermal stability of the raw materials and reaction products;

- significant endothermicity makes it difficult to maintain a given temperature and requires the use of inter-reactor heating in the industry to maintain the required temperature of the reaction mixture;

- in the process of aromatization, the catalysts are carbonized and lose activity, as a result of which there is a need for periodic regeneration. To do this, the process is carried out periodically, switching the reactors from the aromatization process to oxidative regeneration.

Moreover, the conversion of the feedstock and the yield of aromatic hydrocarbons are not high enough.

The process of aromatization in the presence of oxygen allows to reduce the coking of the catalyst, which allows, among other things, to improve these indicators.

Closer to the invention is a catalyst for the process of oxidative aromatization of lower alkanes to produce aromatic hydrocarbons by oxidation of lower alkanes, in particular ethane, ethane-containing gases (RU 2523801, 2014).

The specified catalyst is a two-layer composition in the form of a mixed oxide Mo _1.0 V _0.37 Te _0.17 Nb _0.12 O ₃ component located in the flow reactor at the inlet of the gas feedstock and HZSM-5 zeolite located downstream of the feedstock, while the catalyst components are taken in volume ratio of 20-30 and 70-80, respectively.

The method is carried out in the presence of oxygen taken in a volume ratio of ethane: oxygen of 60-70% vol. and 30-40% vol., respectively. The mixture of feedstock and oxygen is subjected to contact with a catalyst heated to 400-450 ° C, and the aromatization process is carried out at atmospheric pressure and a gas feed rate of 1000-2000 h ^-1 .

The disadvantage of this catalyst is its insufficiently high activity. So, the yield of target aromatic hydrocarbons does not exceed 22.2% of the mass., The conversion is 75.9% of the mass. In addition, the known catalyst loses its activity, not reaching the day of work.

Thus, the specified catalyst is not effective enough.

The objective of the invention is to increase the efficiency of the catalyst for oxidative aromatization of lower alkanes.

The task is achieved by creating a catalyst for the oxidative aromatization of lower alkanes containing zinc oxide, gallium oxide, germanium oxide, γ-alumina and high silica zeolite type pentasil in hydrogen form in the following ratio of components,% mass:

zinc oxide (in terms of metal) 3.00-7.00 gallium oxide (in terms of on metal) 0.5-3.00 germanium oxide (in terms of metal) 0.01-0.10 γ-alumina 10.00-30.00 zeolite the rest is up to 100

The technical result achieved is to increase the activity of the catalyst with respect to the yield of target aromatic hydrocarbons, its selectivity, conversion, and also to increase the time of activity of the catalyst.

The described catalyst is prepared as follows.

An aqueous solution of 0.05-0.2 N hydrochloric acid is poured into a wide-necked glass flask and the required amount of germanium oxide, gallium nitrate and zinc nitrate are carefully transferred into the flask alternately. The mixture is stirred with a glass rod or by rotation of the flask until completely dissolved. Then zeolite is poured. If the solution does not completely cover the zeolite, add the required amount of an aqueous solution of hydrochloric acid. After stirring for 5-30 minutes, the flask is placed on a tile and evaporated. With constant stirring with a stick or a specialized electrically conductive stirrer, the contents of the flask are evaporated to dryness. In the event of “stains” on the walls of the flask, an additional infusion of the amount of an aqueous solution of hydrochloric acid and its subsequent evaporation are carried out.

After evaporation, the flask is placed in a drying oven, where it is heated to the decomposition temperature of nitrates at a rate of not more than 100 ° C / h and kept at a final temperature of 20-60 minutes.

After calcining the prepared zeolite, the flask is cooled in air. After cooling, alumina and a solution of carboxymethyl cellulose (CMC) are placed in a flask with zeolite. After thorough mixing, chemically purified water is poured into the flask to a state suitable for extrusion.

The prepared mass is placed in an extruder to obtain extrudates with a diameter of 2.0 ± 0.2 mm After extrusion, the mass is divided into extrudates with a length of 8 ± 2 mm.

The final calcination of the mass is carried out at a temperature of 500-600 ° C for 30 minutes in a muffle furnace (heating to 200 ° C is carried out at a speed of 100 ° C / h, after 200 ° C, heating is carried out at a speed of not more than 50 ° C / h).

Before the experiment, the catalyst is activated.

The purpose of activation is to achieve the minimum size of the dispersed metal or its compound, as well as inhibiting the increase in the size of the active grain to prevent cracking and premature loss of catalyst activity.

Activation is carried out as follows.

When loaded into the reactor, the catalyst is calcined; therefore, up to 500 ° C, heating at a rate of up to 250 ° C / h in a stream of air with a flow velocity of at least 10 m / min is allowed. At a temperature of 500-550 ° C, the air is switched to nitrogen (oxygen content not more than 0.5% vol.) And the catalyst is heated to a temperature of 550-570 ° C at a speed of not more than 100 ° C / h, followed by at least 10 minutes.

After keeping the catalyst in a neutral atmosphere, nitrogen gradually begins to be replaced with the original hydrocarbon feed without adding oxygen, heating it to a temperature below the working one by 10-20 ° C. After heating and holding for 20-50 minutes for 10-30 minutes, the oxygen (or air) additive is slowly adjusted to the required amount with constant temperature control. The amount of oxygen used is 10-250 liters per 100 liters of hydrocarbon material in a gaseous state. With a sharp increase in temperature above 20 ° C, the oxygen supply is stopped and resumed when the temperature of the catalyst decreases by an additional 10-20 ° C. After complete supply of oxygen, the temperature is raised to the working one and after 10 minutes the experiment is started.

The aromatization process is carried out at a temperature of 550-625 ° C, a pressure of 5.0-15.0 atm, a volumetric feed rate of 500-2000 h ^-1 .

Lower alkanes are used as a feedstock in the process of oxidative aromatization.

The term "lower alkanes" in the framework of this invention means individual hydrocarbons, such as ethane, propane, butane, C ₂ -C ₄ hydrocarbon gases, propane-butane fractions, light low-octane hydrocarbon fractions, in particular a wide fraction of light hydrocarbons (NGL), gases thermal and catalytic cracking, natural gas, degassing gases of gas condensates and straight-run gasolines, other hydrocarbon fractions and mixtures of these hydrocarbons.

After the aromatization process, regeneration is carried out - a rational burning out of coke deposits formed during the operation of the catalyst, without the risk of overheating and changes in both the activity and selectivity of the catalytic system.

After the experiment, the catalyst is cooled in a reactor in a neutral environment or when the feed is supplied to a temperature of not more than 200 ° C to prevent “flare-up” of the catalyst when the oxidizing medium is fed.

After cooling to a temperature of 180-220 ° C, the reactor is purged with nitrogen for at least 20 minutes. After the purge is completed, the amount of oxidizing agent, oxygen, is slowly increased by replacing nitrogen with air. If the temperature rises spontaneously by more than 10 ° С, the air supply is stopped and renewed after no less than 5 minutes.

After switching to air supply, the catalyst is kept at a temperature of 180-250 ° C for at least 30 minutes and then at a speed of no more than 100 ° C / h the temperature is increased to 550-600 ° C. Raising the temperature of more than 600 ° C is prohibited due to a decrease in the dispersion of active metals. Regeneration is carried out for at least 2 hours.

After regeneration, aromatization of raw materials is allowed without cooling the unit after a 20-40 minute purge with nitrogen.

The following is an example illustrating the invention, but not limiting it.

Example.

Get the catalyst for oxidative aromatization of the following composition,% mass: zinc oxide (in terms of metal) 5.00; gallium oxide (in terms of metal) 1.00; germanium oxide (in terms of metal) 0.05; γ-alumina 20.00, zeolite CVN (30) - the rest, up to 100.

The following components are used to prepare 5 kg of catalyst:

- 4-aqueous zinc nitrate (803 g) or 6-aqueous zinc nitrate (913 g);

- gallium nitrate water (157 g) or gallium nitrate 8-water (229 g);

- germanium oxide (2.9 g);

- γ-alumina (1.0 kg);

- CMC to obtain the consistency necessary for pressing or extruding, technical 10 g;

- TsVN zeolite (30) in hydrogen form - the rest, up to 5 kg.

The catalyst is prepared as follows.

500 ml of 0.05 N are poured into a 2-liter wide-necked glass flask. a solution of hydrochloric acid and alternately carefully transfer germanium oxide, gallium nitrate and zinc nitrate. The mixture is stirred with a glass rod or by rotation of the flask until completely dissolved. Then zeolite is poured. If the solution does not completely cover the zeolite, add the required amount of 0.05 N. hydrochloric acid solution. After stirring for 10 minutes, the flask is placed on a tile with a temperature of not more than 95 ° C. With constant stirring with a stick or a specialized electrically conductive stirrer, the contents of the flask are evaporated to dryness. In the case of the appearance of "stains" on the walls of the flask, an additional infusion of 0.05 N hydrochloric acid solution and its subsequent evaporation.

After evaporation, the flask is placed in a drying oven, where it is heated to 260 ° С (nitrate decomposition temperature) at a rate of not more than 100 ° С / h and maintained at a final temperature of 30 minutes.

After calcining the prepared zeolite, the flask is cooled in air. After cooling, alumina and CMC solution are placed in a flask with zeolite. After thorough mixing, chemically purified water is poured into the flask to a state suitable for extrusion.

The prepared mass is placed in an extruder to obtain extrudates with a diameter of 2.0 ± 0.2 mm After extrusion, the mass is divided into extrudates with a length of 8 ± 2 mm.

The final calcination of the mass is carried out at a temperature of 530 ° C for 30 minutes in a muffle furnace (heating to 200 ° C is carried out at a speed of 100 ° C / h, after 200 ° C heating is carried out at a speed of not more than 50 ° C / h).

As a raw material for the aromatization process, a propane-butane fraction ((PBF) produced by Moscow Gas Processing Plant OJSC) is used. The composition of the propane-butane fraction,% vol .: methane 4,5; ethane 11.5; propane 59.4; i-butane 8.4; n-butane 15.7; C ₅₊ 0.5.

The aromatization process is carried out according to the above scheme at a temperature of 575 ° C, a pressure of 8 atm, a volumetric feed rate of 1250 h ^-1 , adding oxygen in an amount of 0.6 liters of oxygen per liter of propane-butane fraction.

The following results were obtained: conversion of 97.5% by mass, selectivity of 83.5% by mass, yield of aromatic hydrocarbons (ArU) 81.4% by mass, yield of CH ₄ - 7.9% by mass. The composition of the gases obtained,% vol .: H ₂ - 19.3; CH ₄ - 69.8; C ₂ H ₆ - 9.3; C ₂ H ₄ - 0.5; CO ₂ 0.4; ∑С ₄ - from .; CO ₂ 0.7; O ₂ - out. The composition of the catalate,% wt .: C ₆ H ₆ - 40.4; C ₇ H ₈ - 34.8; 8C ₈ H ₁₀ - 13.4; 9C ₉ N ₁₂ - 1.0; C ₁₀ H ₈ - 6.3; C ₁₁₊ - 4, l.

In order to intensify the process, an experiment is conducted with the recycling of unconverted raw materials. The following results are obtained: conversion of 97.3% by mass, selectivity of 83.5% by mass, yield of ArU - 81.2% by mass, yield of CH ₄ 8.1% by mass. The composition of the gases obtained,% vol .: H ₂ - 18.2; CH ₄ - 70.5; C ₂ H ₆ - 9.5; C ₂ H ₄ 0.6; C ₃ H ₈ - 0.4; ∑С ₄ - from .; CO ₂ 0.8; O ₂ - out. The composition of the catalate,% wt .: C ₆ H ₆ - 39.9; C ₇ H ₈ - 35.1; 8C ₈ H ₁₀ - 13.4; ∑C ₉ H ₁₂ - 1.0; C ₁₀ H ₈ - 6.4; C ₁₁₊ - 4.2.

The catalyst having a composition determined by the above-mentioned interval values of the concentrations of the components, other than those described in the example, but included in the indicated intervals, exhibits similar properties. The use of transcendental interval values of the concentrations of the components in the catalyst does not lead to the desired results.

To clarify the time of the inter-regeneration run of the catalyst, it is conducted lengthy tests. From the data obtained it follows that the life of the catalyst exceeds 25 days.

Thus, the described catalyst has an increased activity, since it allows to increase the yield of aromatic hydrocarbons by more than 3.5 times, the conversion of more than 1.2 times, has a high selectivity (above 83%). In this case, the catalyst is characterized by a significantly increased inter-regeneration run time (the operating time of the known catalyst, during which a 50% decrease in the yield of aromatic hydrocarbons is 28-32 hours, the cycle of operation of the described catalyst exceeds 25 days).

Thus, the described catalyst allows to increase the yield of aromatic hydrocarbons by more than two times, significantly increase the inter-regeneration run time (the operating time of the known catalyst, during which a 50% decrease in the yield of aromatic hydrocarbons is 28-32 hours, the cycle of the described catalyst exceeds 25 days) .

Claims (1)

The catalyst for oxidative aromatization of lower alkanes containing zinc oxide, gallium oxide, germanium oxide, γ-alumina and high-silica pentasil type zeolite in hydrogen form in the following ratio of components, wt.%:
zinc oxide (in terms of metal) 3.00-7.00 gallium oxide (III) (in terms of on metal) 0.5-3.00 germanium (IV) oxide (in terms of metal) 0.01-0.10 γ-alumina 10.00-30.00 zeolite the rest is up to 100