Method for making catalyst to produce methacrylic acid

FIELD: chemistry.

SUBSTANCE: object of the present invention is to develop method for making catalyst to produce methacrylic acid by gaseous catalytic oxidation of metacrolein, isobutyl aldehyde or isobutyric acid. There is disclosed method for making catalyst to produce methacrylic acid by gaseous catalytic oxidation of metacrolein, isobutyl aldehyde or isobutyric acid, involving as follows: (a) the stage of mixing water and compounds, each containing any Mo, V, P, Cu, Cs or NH4, to prepare aqueous solution or dispersed compounds (further, both mentioned as a suspension); (b) the stage of drying suspension produced at the stage (a), to make dry suspension; (c) the stage of burning dry suspension produced at the stage (b), to make burnt substance; (d) the stage of filtrating mixed burnt substance produced at the stage (c) and water to separate aqueous solution and water-insoluble substance; and (e) the stage of drying water-insoluble substance produced at the stage (d) to make dry water-insoluble substance; and (f) the stage of coating the carrier with dry water-insoluble substance produced at the stage (e), with using a binding agent to make coated mould product, and (g) the stage of burning coated mould product produced at the stage (f) in inert gas atmosphere, in the air or with reducing agent added.

EFFECT: making catalyst with long life, high activity and selectivity.

8 cl, 9 tbl, 9 ex

 

The technical field to which the invention relates.

The present invention relates to a method for producing a catalyst for producing methacrylic acid gas-phase oxidation of methacrolein, isobutyl aldehyde or somaclonal acid having a long service life, high activity and high selectivity.

The level of technology

It was proposed that a large number of catalysts for the production of methacrylic acid gas-phase catalytic oxidation of methacrolein, isobutyl aldehyde or somaclonal acid. Most of these catalysts, mainly composed of molybdenum and phosphorus and have patterns of heteropolyacids or their salts. However, the catalysts used in the reaction, have low reactivity, low selectivity for the product and a short lifespan compared to catalysts based on molybdenum and vanadium proposed for the production of acrylic acid gas-phase catalytic oxidation of acrolein, which is known as a reaction similar to gas-phase catalytic oxidation of methacrolein, isobutyl aldehyde and somaclonal acid. Therefore, an improvement of the operating characteristics of the catalysts, although some of them are used in industry.

These inventors first tortured the ü to improve low activity, low selectivity and short service life of the conventional catalysts for gas-phase catalytic oxidation of methacrolein and found that the catalysts for gas-phase catalytic oxidation of methacrolein prepared by adding various elements to Mo, V and P are patterns of heteropolyacids (salts) and have a high activity, high selectivity and virtually stable over the lifetime. The inventors have proposed the catalysts described in Japanese Patent Publication No. 58-11416, Japanese Patent Publication No. 59-24140, Japanese Patent Publication No. 62-14535, Japanese Patent Publication No. 62-30177.

Recently, due to the high concentration of raw material gas and the operating conditions under which the oxidation reaction is carried out at elevated temperatures, the necessary catalysts, which show higher activity, selectivity and lifetime. Proposed various methods for producing catalysts, which would satisfy these requirements. For example, Japanese Patent Laid-open No. 5-31368 and Japanese Patent Laid-open No. 8-196908 offer ways to obtain a molded catalyst, which include the use of NH4in addition to the components of Mo, V and P, and use of aqueous ammonia as a source of ammonium. In addition, Japanese Patent Laid-open No. 11-226411 describes the method of preparation of the molded catalyst which contains purified using the rajmala, when the active component of the catalyst granularit that improves pore volume of the catalyst during the burnout of starch at the stage of calcination.

In addition, when the catalyst loaded into the reactor with a porous layer as an industrial catalyst, it is required that the catalyst was molded to a constant size in order to reduce the pressure loss of the reaction gas before and after the catalyst bed. For this purpose, the known methods include usually forming catalytic powder in a cylindrical material, granules, the annular material, stereopony material and similar forms, and the impregnation or coating of inert carrier active catalytic material.

Advantages of supported catalysts with an inert carrier as the core, include (i) the ability to better factor in the effective use of active catalyst components, (ii) the expected improvement in selectivity due to the uniform distribution of contact time of the reaction material in the catalyst, and (iii) facilitating removal of heat of reaction by improving thermal conductivity of the catalyst or effect of dilution with an inert carrier. As a result, there are many examples of the use of selective oxidation with great heat.

On the other hand, technical flaws in prigot is no supported catalysts include (i) peeling of the coating layer and the difficulties in obtaining mechanically solid catalyst, as the catalyst is subjected to cracking, (ii) difficulties in coating media a large number of active catalytic material, and (iii) difficulties in obtaining highly active catalyst due to the inclusion of inert materials.

Ways to overcome these disadvantages associated with the properties of the catalytically active substances, and in this situation it is necessary to study the catalysts individually, as there is no General methods.

Disclosure of inventions

The purpose of the present invention is a method of producing a catalyst for producing methacrylic acid with high yield and high selectivity gas-phase catalytic oxidation of methacrolein, isobutyl aldehyde or somaclonal acid.

The present inventors tried to improve the low activity, low selectivity and short service life of the conventional catalysts for gas-phase catalytic oxidation of methacrolein as a way to solve the above problems and found that the preparation of the catalyst containing the essential components, Mo, V, P, Cu, Cs and NH4can be obtained industrial catalyst having high activity, high selectivity and high stability during the term of service, if will be executed a specific stage of filtration. On this base the ve present invention comes to an end.

We can say that the present invention applies to:

(1) preparation method of catalyst for production of methacrylic acid gas-phase catalytic oxidation of methacrolein, isobutyl aldehyde or somaclonal acid, the method includes:

(a) the stage of mixing with water connections, each of which contains any one of Mo, V, P, Cu, Cs or NH4and , if necessary, the compound containing the metal element other than the above, for the preparation of an aqueous solution or dispersion of the compounds (hereinafter both referred to as a suspension);

(b) a stage of drying the suspension obtained in stage (a), to obtain a dry mist;

(C) stage calcination dry suspension obtained in stage (b), to obtain a calcined substance;

(d) stage filtration of the mixture obtained by mixing the calcined substance, obtained in stage (C)with water to separate the aqueous and water-insoluble substance and

(e) stage of drying water-insoluble matter obtained in stage (d), to obtain a dry water-insoluble substances,

(2) preparation method of catalyst for production of methacrylic acid gas-phase catalytic oxidation of methacrolein, isobutyl aldehyde or somaclonal acid, the method includes:

(a) the stage of mixing with water connections, each of which contains any of Mo, V, P, Cu, Cs or NH4and, if necessary, the compound containing the metal element other than the above, provided that Cu is excluded, for the preparation of an aqueous solution or dispersion of the compounds (hereinafter, both are referred to as suspended);

(b') a stage of drying the suspension obtained in stage (a), to obtain a dry mist, followed, if necessary, by dry mixing the suspension with a compound containing Cu, in the presence of a solvent and further, if necessary, drying the mixture and obtaining, thus, dry matter;

(C) stage calcination of dry matter obtained in stage (b'), to obtain a calcined substance;

(d) stage filtration of the mixture, obtained by mixing calcined substances obtained in stage (C), with water, to separate the aqueous and water-insoluble substance and

(e) stage of drying water-insoluble matter obtained in stage (d), to obtain a dry water-insoluble substances,

(3) method of obtaining the deposited catalyst for production of methacrylic acid gas-phase catalytic oxidation of methacrolein, isobutyl aldehyde or somaclonal acid, the method includes:

(a) the stage of mixing with water connections, each of which contains any one of Mo, V, P, Cu, Cs or NH4and, if necessary, connect the out, containing a metal element other than the above, for the preparation of an aqueous solution or dispersion of the compounds (hereinafter both referred to as a suspension);

(b) a stage of drying the suspension obtained in stage (a), to obtain a dry mist;

(C) stage calcination dry suspension obtained in stage (b), to obtain a calcined substance;

(d) stage filtration of the mixture obtained by mixing the calcined substance, obtained in stage (C)with water to separate the aqueous and water-insoluble substance;

(e) stage of drying water-insoluble matter obtained in stage (d), to obtain a dry water-insoluble substances, and

(f) the stage of coating medium dry water-insoluble substance obtained in stage (e) using the binder to produce a coated molded product,

(4) the method of obtaining the deposited catalyst for production of methacrylic acid gas-phase catalytic oxidation of methacrolein, isobutyl aldehyde or somaclonal acid, the method includes:

(a) the stage of mixing with water connections, each of which contains any one of Mo, V, P, Cs or NH4and, if necessary, the compound containing the metal element other than the above, provided that Cu is excluded, for the preparation of an aqueous solution or di is Persia compounds (hereinafter both referred to as slurry);

(b') a stage of drying the suspension obtained in stage (a), to obtain a dry mist, followed, if necessary, by dry mixing the suspension with a compound containing Cu, in the presence of a solvent and further, if necessary, drying the mixture and obtaining, thus, dry matter;

(C) stage calcination dry suspension obtained in stage (b'), to obtain a calcined substance;

(d) stage filtration of the mixture, obtained by mixing calcined substances obtained in stage (C)with water to separate the aqueous and water-insoluble substance;

(e) stage of drying water-insoluble matter obtained in stage (d), to obtain a dry water-insoluble substance and

(f) the stage of coating medium dry water-insoluble substance obtained in stage (e) using the binder to produce a coated molded product,

(5) the method according to p.(3) or (4)containing phase from (a) to (f), and

(g) stage of annealing the coated molded product obtained in stage (f), in the atmosphere of inert gas, in the air or in the presence of a reducing agent,

(6) the method according to p.(5), in which stage (g) is a stage of annealing the coated molded product obtained in stage (f), in the atmosphere of inert gas,

(7) the method according to any who. from (1) to (6), in which the compound containing Cu represents a copper acetate or copper oxide,

(8) the method according to any PP of (1) to (7), in which the compound containing Cs, is a cesium salt and a weak acid or cesium hydroxide, the compound containing the NH4represents ammonium acetate or ammonium hydroxide,

(9) the method according to any PP of (1) to (8), in which the connection used as a possible component on the stage (a)is a compound containing one or more elements selected from the group consisting of Sb, As, Ag, Mg, Zn, Al, B, Ge, Sn, Pb, Ti, Zr, Cr, Re, Bi, W, Fe, Co, Ni, Ce, Th, K and Rb,

(10) the method according to any PP of (1) to (9), in which the suspension contains no arsenic compounds, and

(11) the method according to any PP of (3) to (8), in which the binder is a binder containing ethanol.

Best mode for carrying out the invention

The method of preparation according to the invention comprises the stages of drying and calcination of aqueous solutions containing compounds comprising active ingredients of the catalyst or water dispersion (hereinafter both referred to as a suspension), followed by mixing the resulting calcined substance with water, followed by filtering and drying the filter cake.

The first preferred variant implementation of the method of obtaining this image is meniu comprises dissolving and/or dispersing a variety of compounds, each of which contains one or more of Mo, V, P, Cu, Cs and NH4and, if necessary, the elements other than the above (hereinafter, in some cases, these compounds containing these components will be referred to as "the compound containing the active ingredient"), in water to prepare a suspension (stage (a)), drying (stage (b)) and calcination (stage (C)suspension, mixing the resulting calcined substance with water and filtration (stage (d), drying the filtered precipitate (stage (e)) and use it as a catalytically active component.

In the invention, the compound containing the active ingredient used for preparation of the suspension, is preferably a compound which forms heteroalicyclic or its salt due to drying (stage (b)) or annealing (stage (C)). These compounds can be chlorides, sulfates, nitrates, oxides or acetates of the elements of the active component. The most typical examples of preferred compounds include nitrates such as potassium nitrate or cobalt nitrate; oxides such as molybdenum oxide, vanadium pentoxide, antimony trioxide, cerium oxide, zinc oxide or the oxide of Germany, and such acids as phosphoric acid, phosphoric acid, boric acid, aluminum phosphate or 12-wolframalpha acid (Il is their salts). In addition, when the compounds of copper using copper acetate (acetate of monovalent and divalent copper, primary copper acetate or oxide of divalent copper, preferably copper acetate or copper oxide (oxide of monovalent copper, divalent oxide of copper) in some cases, there may be obtained a positive effect. And, in addition, as of caesium, preferably using cesium acetate, cesium hydroxide, a salt of a weak acid and cesium, and ammonium compounds are preferably used, and ammonium acetate, and ammonium hydroxide. Compounds comprising active components can be used individually or in combination of two or three of them. For cesium salt and a weak acid because it is a salt of cesium and well-known weak acid, there are practically no restrictions. For example, can be used cesium bicarbonate, cesium carbonate, and cesium acetate, and among them cesium acetate is preferred. Among them, as cesium acetate, commercially available acetate can be used as it is; however, adding acetic acid, more than the equivalent by weight, aqueous solution of water-soluble salts, such as cesium hydroxide or cesium carbonate, these solutions can be added as an aqueous solution of cesium acetate. Alternative water Rast is the PR of cesium hydroxide may be added, as he has.

In the invention as the active components other than Mo, V, P, Cu, Cs and NH4,can be included one or more components selected from the group consisting of As, Sb, Ag, Mg, Zn, Al, B, Ge, Sn, Pb, Ti, Zr, Cr, Re, Bi, W, Fe, Co, Ni, Ce, Th, K and Rb. Among them, preferred elements, other than As.

The invention uses the following ratios of compounds containing an active component, the atomic ratio of in relation to 10 atoms of molybdenum: normally, 0.1 or more and 6 or less of vanadium, preferably 0.3 or more and 2.0 or less; normal, 0.5 or more and 6 or less of phosphorus, preferably 0.7 or more and 2.0 or less, normal, more than 0, and 3 or less for copper, preferably 0.01 or more and 1 or less; normal, 0.01 or more and 4.0 or less for cesium, preferably 0.1 to or more and 2.0 or less, and normally, 0.1 or more and 4.0 or less for ammonium, preferably 0.5 or more and 3.0 or less. The types and ratios of other active ingredients that are used when necessary, respectively determined so that could be obtained consistent with the terms of use of the catalyst, which shows optimal performance.

The method of receiving according to the invention is carried out according to the method mentioned below.

First, get a mixture of compounds containing active ingredient (stage (a)). TOD is camping can be obtained by homogeneous mixing of the respective compounds, containing the active ingredient, and water. The suspension preferably contains all compounds containing the active ingredient, in their required quantities as a catalyst. There are no particular restrictions on the order of addition of compounds containing an active component in the preparation of the suspension. However, it is preferable first to make compounds containing Mo, V, P and other elements that are metals, and then adding in the suspension, if necessary, compounds containing cesium, compounds containing ammonia, and compounds containing copper.

Upon receipt of the suspension no particular restrictions on the temperature while it is in the range of not hindering the receipt. However, adding compounds containing cesium, compounds containing ammonia, and compounds containing copper, when the temperature normally ranges from 0 to 35°C, preferably in the range from 10 to 30°C, in some cases, the catalyst may have increased activity. This trend becomes more apparent when the copper acetate is used as the compound of copper, the production method of the suspension becomes more effective when you choose the preferred way to add.

In the invention it is preferable that the suspension was an aqueous solution. There are no particular restrictions on the quantity and the use of water in suspension, until the specified number is able to completely dissolve the total amount of the compounds or can uniformly mix them. However, it is suitably determined in consideration of the drying method and drying conditions mentioned below. Generally, the amount of water used is, in essence, from 200 to 2000 parts by mass relative to 100 parts by weight of the total weight of the compounds for the preparation of suspensions. The amount of water may be larger than necessary, however, when water is in excess, such disadvantages as the cost of energy during drying, increase, and in some cases incomplete drying can be caused by this reason. That is, because of the advantages in less than disadvantages, preferably corresponding amount of water.

Next, a suspension, obtained above, is dried and, thus, receive a dry suspension (stage (b)). There is no specific limitation on the method of drying, if the suspension is dried completely. Examples of the drying method include drum drying, freeze drying, spray drying and evaporation to dryness. Among these methods, in the invention, it is preferable to use spray drying, which can dry on a state of suspension until the powder or granulated powder in a short time, or evaporation to dryness, which can directly suspension was evaporated and which is simple, evaporation to dryness is especially preferred.

Drying temperature when using spray drying varies depending on suspended sediment concentration and feed rate of the suspension. Usually, however, the exit temperature of the drying machine is in the range from 70 to 150°C. in Addition, it is preferable to dry so that the diameter of the particles obtained dry mist could be in the range from 30 to 700 μm. In the case of evaporation to dryness, in particular, dry slurry may be obtained in the form of a lump or coarse particles. Therefore, it is preferable to appropriately grind, it is preferable to use was 700 μm or less. Thus, according to the invention the crushed particles are also contained in the dry mist.

Then dry the suspension obtained in this way, calcined, preferably in air and thus receive the calcined substance (stage (C)). In this case, usually calcined at a temperature in the range from 100 to 420°C., preferably in the range from 250 to 400°C. the Preferred time of calcination is from 1 to 20 hours. Thus, the calcined substance is preferably manufactured in the form of powder.

Next, the calcined substance is mixed with an appropriate amount of water, preferably 2 to 5 times greater by weight than the calcined substance, and, therefore, delete the Ute water-soluble components. It is assumed that the water-insoluble components are compounds having the structure of heteropolyacids. As salts of heteropolyacids, representing the purpose of the invention, do not dissolve in water, separated by filtration (stage d)) and dried (stage (e)). Thus obtained dry material is preferably a powder, and can be used as it is as a catalyst for gas-phase catalytic oxidation.

Next will be described a second preferred implementation of the invention.

A second preferred implementation of the invention involves the blending of a variety of compounds, and each contains one or more of Mo, V, P, Cs and NH4and , if necessary, the elements other than the above items, provided that Cu is excluded, with water to obtain a suspension (stage(I)), drying the mixture, mixing the resulting dry mist with Cu-containing compound in the presence of a solvent, if necessary, drying the obtained, if necessary to obtain dry matter (stage(b')), followed by calcination (stage (C)), mixing the resulting calcined substance with water and filtering the received (stage(d), drying the filtered precipitate (stage e)) and using this as the catalytically active component is. Thus obtained dry matter can be used as it is as a catalyst for gas-phase catalytic oxidation.

In the second embodiment according to the invention the step of obtaining a catalytically active component, except that the compound containing copper, are mixed separately from the dry mist other compounds containing a catalytically active component, can be carried out similarly to the first variant implementation of the type of compounds containing an active component used ratios and other conditions. Dry suspension and Cu-containing compound can be mixed in powder, alternative Cu-containing compound may be mixed with a solvent, preferably water, to form a suspension. In this case, the amount of water used may be comparable to the amount used in the first embodiment. A mixture of dry suspension and Cu-containing compounds in the case of water use in the cooking process, respectively dried to obtain dry matter. Next, the dry matter calcined similar to the first variant of implementation, followed by mixing with water, drying and filtering the precipitate, and, thus, may be obtained of the target catalyst. In the second embodiment, added later connection honey is after the stage of drying and calcination) does not exist as a loose connection.

Below will be explained a third preferred variant implementation of the invention.

Thus obtained dry water-insoluble substance which is a catalytically active component, in order to reduce the pressure loss of the reaction gas is preferably used after molding into the cylinders, pellets, rings or spheres. Including, if you expect improvement in selectivity and removal of the reaction heat, it is most preferable to cover the inactive carrier dry, insoluble in water substance for the formation of molded material, covered by a catalyst.

At the stage of coating (stage (f)) can be preferably used a method of granulating rolling, described later. In this way, the device having a flat or uneven disk, for example, at the lower part of the fixed vessel, the disc rotates at high speed, and thus, the media in the vessel intensively shaken for repeated autorotation and spin. When a binder and dry, water-insoluble substance, and, if necessary, other components, such as a mixture that helps shaping and improving strength, add in the vessel during the rotation, the mixture is applied to the carrier. As a method of adding a binder can be made arbitrarily adding the total quantity is STV, (i) a method of mixing a binder and mixture in advance, (ii) a method of adding a binder in a fixed vessel simultaneously with the mixture, (iii) a method of adding a binder after the mixture was added in a fixed vessel, (iv) a method of adding a binder before the mixture was added in a fixed vessel, and (v) the method of separation of mixtures and binders separately and the corresponding combining methods from (ii) to (iv). Among these methods, in the case of the method (v), it is preferable to control the speed of adding, using the automatic feeding mechanism and the like, so that a predetermined number may be printed on media such as, without sticking of the mixture to the fixed wall of the vessel and coagulation of the mixture.

There are no particular restrictions on the binder, when at least one kind selected from the group consisting of water and organic compounds having a boiling point at atmospheric pressure of 150°C. or lower. However, when considering drying after coating, the organic compounds having a boiling point of 100°C. or lower are preferred. Specific examples of the binder other than water include alcohols such as methanol, ethanol, propanol and butanol, preferably alcohols having from 1 to 4 carbon atoms; simple is Fira, such as ethyl ether, butyl ether or dioxane, esters, such as ethyl acetate or butyl acetate; ketones, such as acetone or methyl ethyl ketone, and their aqueous solutions. Among them, ethanol is particularly preferred. When ethanol is used as a binder, ethanol/water are in the range of from 10/0 to 1/9 (by mass ratio), preferably in the range of from 10/0 to 7/3 (by mass ratio). When a mixture of ethanol and water, should be considered the limit of ignition depending on drying conditions. In this case, the concentration of ethanol is preferably in the range from 15 to 40 wt.%. The number of these binder used is normally in the range from 2 to 60 parts by weight relative to 100 parts by weight of a dry, water-insoluble substances, preferably in the range from 5 to 25 parts by weight.

Typical examples of the carrier used in the invention include spherical carriers made of silicon carbide, aluminum oxide, alumosilicate, mullite and alund cuota and having a diameter in the range from 1 to 15 mm, preferably in the range from 2.5 to 10 mm In the normal case as media use media having a pore volume from 10 to 70%. The ratio of the carrier and a dry, water-insoluble substance used for coating, is, normally, in which intervale from 10 to 75 wt.% in terms of dry water-insoluble substance(dry, water-insoluble substance + media), preferably in the range from 15 to 60 wt.%.

When the ratio of dry, water-insoluble substance used for coating, more activity deposited catalyst becomes larger, on the one hand, but on the other hand, tends to decrease in mechanical strength (the ability to wear tends to increase). Conversely, when the ratio of the applied dry, water-insoluble substance is small, the mechanical strength becomes larger (the ability to wear becomes smaller), on the one hand, but on the other hand, the activity tends to become smaller.

In the invention, in the case of coating medium dry, water-insoluble substance, if necessary, to dry, water-insoluble substance may be added substances promoting the formation, such as silica gel, diatomaceous earth, alumina powder. The number of added substances that promote the formation is usually from 5 to 60 parts by weight relative to 100 parts by weight of a dry, water-insoluble substances.

In addition, to improve the mechanical strength of the catalyst is useful to add to a component of the catalyst is an inorganic fiber such as ceramic fiber, initi, not active component of the catalyst, but improving strength. However, such fibers, as the fibers of potassium titanate and the threads of the basic magnesium carbonate, which can interact with a component of the catalyst, are not suitable. The number of these added fibers is typically in the range from 1 to 30 parts by mass relative to 100 parts by weight of a dry, water-insoluble substances.

Additional agents, such as contributing to the formation and improves strength, add usually at the stage of coating granulator together with the carrier, dry, water-insoluble substance and a binder and is used to cover the media.

In this way the media cover the dry, water-insoluble substance, and the diameter of the coated material obtained by this method is typically in the range of from about 3 to 15 mm

Caused the catalyst obtained in this way can be used in gas-phase catalytic oxidation as a catalyst unchanged. However, it is preferably calcined (stage(g)), because in some cases, the catalytic activity is improved by annealing. In this case, the temperature of calcination is typically in the range from 100 to 450°C., preferably from 250 to 420°C. the Time of annealing is preferably in the range from 1 to 20 hours.

Also what about the, the calcination is usually carried out in air. However, it may be conducted in an atmosphere of inert gas, such as nitrogen, and after the annealing in the atmosphere of inert gas annealed in air may be carried out additionally, if circumstances require. In addition, preferably, the annealing in the atmosphere of inert gas, more preferably in the presence of a reducing agent, as in some cases it may be obtained more active catalyst. There are no specific limitations to the reducing agent, preferably when he becomes a gas at the temperature of calcination. Examples of reducing agents include, alcohols, aldehydes, ketones and organic acids having from 2 to 5 carbon atoms, and ethanol is particularly preferred.

The catalyst obtained in the way described above (hereinafter referred to as catalyst according to the invention), is used to produce methacrylic acid gas-phase catalytic oxidation of methacrolein, isobutyl aldehyde and somaclonal acid. When the phrase "the catalyst according to the invention is used without specific notes, it is used to denote like a dry, water-insoluble substance obtained in stages (a) through (e), and deposited catalyst obtained by an additional stage (f), (prés is also respectfully stage (g)).

Gas-phase catalytic oxidation using methacrolein, which is the most suitable raw material for the use of the catalyst according to the invention will be disclosed below.

In the gas-phase catalytic oxidation using molecular oxygen or a gas containing molecular oxygen. The ratio used molecular oxygen and methacrolein is in the range from 0.5 to 20 at a relative molar ratio, particularly preferably in the range from 1 to 10. For a relaxing flow of the reaction process, it is preferable to add water to gas feedstock with a molecular ratio of about methacrolein in the range from 1 to 20.

Gas raw materials may contain in addition to oxygen and, optionally, water (in normal cases, the water is contained in the form of vapor), gases inert to the reaction such as nitrogen, carbon dioxide and saturated hydrocarbons.

In addition, as methacrolein, gases, obtained by the oxidation of isobutylene, tert-butanol and methyl tert-butyl ether, may be submitted without modification.

The reaction temperature during the gas-phase catalytic oxidation is usually in the range from 200 to 400°C., preferably in the range of from 260 to 360°C. the amount of gas feedstock is, in terms of flow rate (OS), usually in the range from 100 to 6000 cha is -1, preferably in the range from 400 to 3000 h-1.

In the case of using the catalyst according to the invention there is large variation in the results, even when the OS increases. Accordingly, it is possible to conduct the reaction at a high volume rate.

In addition, although it is possible to carry out gas-phase catalytic oxidation under pressure and under reduced pressure, in General, a pressure of about atmospheric is appropriate.

Examples

Below the present invention will be more specifically disclosed in the examples.

The degree of conversion, selectivity and yield in these examples are defined as follows.

- Conversion rate = (number of moles reacted methacrolein/the number of moles of submitted methacrolein) × 100.

- Selectivity = (number of moles of the obtained methacrylic acid/number of moles reacted methacrolein) × 100.

Output = (number of moles of the obtained methacrylic acid/number of moles of submitted methacrolein) × 100.

Example 1

1) preparation of catalyst

In 2100 ml of purified water was added 300 g of molybdenum trioxide, 13,26 g of vanadium pentoxide and 27,62 g of 85 wt.% phosphoric acid followed by heating under reflux in the temperature range from 90 to 100°C for 5 hours, thus received brownish clear solution. Then it dobavlyali,15 g of antimony trioxide, and then further heated under reflux at a temperature in the range of from 90 to 100°C for 2 hours and thus was given a dark blue solution, in which was dissolved antimony trioxide. Then the solution was cooled to a temperature of 15-20°C, followed by gradual addition with stirring, 20 g of cesium acetate, dissolved in 150 ml of purified water, together with 24,09 g of ammonium acetate dissolved in 150 ml of purified water, followed by additional curing at a temperature of from 15 to 20°C for 1 hour, and got so rusty suspension containing cesium salt predecessor of heteroalicyclic and ammonium salt.

Then 16,64 g of the monohydrate of bivalent copper acetate dissolved in 240 ml of purified water, was added to the suspension followed by additional aging at a temperature of from 15 to 20°C for 15 minutes

Then the suspension was dried by evaporation to dryness with hot water, followed by crushing in a mortar and with additional follow-dropouts to 700 μm or less, and following the primary annealing at 310°C in a stream of air for 5 hours, thus obtaining calcined granular powder. The composition is calcined granulated powder in units of the ratio of the reacting substances was expressed as

Mo10V0,7P1,15Cufor 0.4Sbfor 0.4Cs0,5(NH4)1,5.

Next, 300 g of the obtained calcined granulated powder was dispersible in 1000 ml of purified water with subsequent paramashiva is receiving at 40°C for 1 hour. Then the dispersion liquid was filtered and the filtered greenish-white, water-insoluble substance (precipitate after filtering) and the brown filtrate were separately evaporated to dryness with hot water and then crushed from 300 to 700 μm and an additional subsequent dropout, received thus granulated catalyst (A) from the precipitate after filtration and filtrate was obtained solidified product for comparison (A).

In this case the degree distribution between the precipitate after filtration and the filtrate was 86.8 wt.% the precipitate after filtration and 13.2 wt.% the filtrate. Was found using fluorescent x-ray analysis that the atomic ratio of the elements of the metals in the resulting granular catalyst (A) was equal to

Mo10V1,53Pa 1.8Cu0,32Sb0,41Cs0,46,

x-ray diffraction analysis showed that the granular catalyst was a salt heteroalicyclic, and the nitrogen content (i.e. NH4and so on) were determined by CHN analysis.

In addition, it was found by the fluorescent x-ray analysis that the atomic ratio of the elements metals in the obtained cured substance for comparison (A) was expressed as

Mo10V1,53P2,46Cu1,14Sb0,13,

the hardened substance represented predestiny is, which was not heteroalicyclic by x-ray diffraction analysis, and nitrogen was not detected by the method CHN analysis.

Then 176,8 g of sample, which was obtained by grinding and sifting the obtained granulated catalyst (a), 300 μm or less, and 25.9 g of improving the strength of the material (ceramic fiber) were uniformly mixed, followed by the application and molding on 173,7 g of spherical porous carrier of aluminum oxide (particle diameter 3.5 mm) when used as a binder 90 wt.% an aqueous solution of ethanol. Then, the resulting molded particles were subjected to a secondary annealing at 310°C for 5 hours in a stream of air, thus obtaining the applied catalyst, designated as (A).

2) Catalytic oxidation of methacrolein

The tube reactor of stainless steel with internal diameter of 18.4 mm, was filled with 10.3 ml of the obtained deposited catalyst (A). Catalytic oxidation of methacrolein conducted under the conditions of the composition of the gas (in molar ratio) methacrolein : oxygen : water vapor : nitrogen = 1:2:4:18,6, flow rate (OS), 1200 h-1and the temperature of the reaction bath is equal to 310°C. the Reaction is first maintained at a temperature of the reaction bath, equal to 310°C. for 3 hours, then the temperature of the reaction bath was raised to 350°C and under arrival this temperature for 15 hours. Then the temperature of the reaction bath was lowered to 310°C and evaluated the outcome of the reaction. The results are presented in table 1. Next, 4.0 g of granulated catalyst (A) and the same number of hardened substances for comparison (A) was mixed separately with 8 g of quartz sand from 300 to 700 μm and used in the oxidation reaction under the same reaction conditions as mentioned above. The results are together shown in table 1.

Table 1
Maximum temperature (°C)The degree of conversion (%)Selectivity (%)Output (%)
The applied catalyst (A)32588,582,773,1
The granular catalyst (A)-87,686,775,9
The hardened substance for comparison (A)-40,683,133,7

Compare the capacity example 1

1) preparation of catalyst

In 2100 ml of purified water was added 300 g of molybdenum trioxide, 13,26 g of vanadium pentoxide and 27,62 g of 85 wt.% phosphoric acid followed by heating under reflux in the temperature range from 90 to 100°C for 5 h and was thus given a brownish clear solution. Then thereto was added 12,15 g of antimony trioxide, and then further heated under reflux at a temperature in the range of from 90 to 100°C for 2 hours and got so dark blue solution, which was dissolved antimony trioxide. Then the solution was cooled to a temperature of from 15 to 20°C, followed by gradual addition with stirring, 20 g of cesium acetate, dissolved in 150 ml of purified water, together with 24,09 g of ammonium acetate dissolved in 150 ml of purified water, followed by additional curing at a temperature of from 15 to 20°C for 1 hour, and got so rusty suspension containing cesium salt predecessor of heteroalicyclic and ammonium salt.

Then 16,64 g of the monohydrate of bivalent copper acetate dissolved in 240 ml of purified water, was added to the suspension, followed by additional curing for 1 hour.

Then the suspension was dried by evaporation to dryness using hot water and then crushed and additional follow what they dropouts from 300 μm to 700 μm, thus receiving the hardened substance for comparison (B).

The composition of the hardened substance for comparison (C) in units of the ratio of reactive substances in this case was expressed as

Mo10V0,7P1,15Cufor 0.4Sbfor 0.4Cs0,5(NH4)1,5.

Then the obtained solidified product for comparison (In) were crushed and were selected to 300 μm or less and 365,4 g of the specified substance is homogeneously mixed with of 52.1 g of substance that improves the strength (ceramic fiber) and then applying and molding on 349,8 g of spherical porous carrier of aluminum oxide (particle diameter 3.5 mm) when used as a binder 90 wt.% an aqueous solution of ethanol. Then, the resulting molded particles were subjected to calcination at a temperature of 310°C for 5 hours in a stream of air, thus obtaining the applied catalyst for comparison ().

2) Catalytic oxidation of methacrolein

Received caused the catalyst for comparison (In) used for catalytic oxidation of methacrolein analogously to example 1, and the results of the reaction were evaluated as in example 1. The results are presented in table 2. In addition, mixing 4.0 g of hardened substance for comparison (C) and 8.0 g of quartz sand from 300 to 700 μm and used in the oxidation reaction under the same conditions as above. Rez is ltati presented together in table 2.

Table 2
Maximum temperature (°C)The degree of conversion (%)Selectivity (%)Output (%)
The applied catalyst (In)32282,783,168,7
The hardened substance for comparison (In)-74,189,4to 66.3

Example 2

1) preparation of catalyst

In 2100 ml of purified water was added 300 g of molybdenum trioxide, 13,26 g of vanadium pentoxide and 27,62 g of 85 wt.% phosphoric acid followed by heating under reflux in the temperature range from 90 to 100°C for 5 h and was thus given a brownish clear solution. Then thereto was added 12,15 g of antimony trioxide, and then further heated under reflux at a temperature in the range of from 90 to 100°C for 2 hours and thus was given a dark blue solution, which was dissolved antimony trioxide. Then the solution was cooled to a temperature of 15-20 is With subsequent gradual addition with stirring, 20 g of cesium acetate, dissolved in 150 ml of purified water, together with 24,09 g of ammonium acetate dissolved in 150 ml of purified water, followed by additional curing at a temperature of from 15 to 20°C for 1 hour and got so rusty suspension containing cesium salt predecessor of heteroalicyclic and ammonium salt.

Then the suspension was dried by evaporation to dryness using hot water and then crushed in a mortar and subsequent additional screening to 700 μm or less, thus obtaining the powdered substance. The composition of the crushed substance in units of the ratio of reactive substances in this case was expressed as

Mo10V0,7P1,15Cufor 0.4Sbfor 0.4Cs0,5(NH4)1,5.

Then the crushed substance was added 16,64 g of the acetate monohydrate divalent copper in the form of a powder, followed by adding 100 g of 90 wt.% an aqueous solution of ethanol, followed by stirring and then the following one by evaporation to dryness with hot water, then crushed in a mortar to 700 microns or less and then the following primary calcination in a stream of air at 310°C for 5 hours, thus obtaining calcined granules (C). The granulated composition of matter in units of the ratio of reactive substances in this case was expressed as

Mo10V,7 P1,15Cufor 0.4Sbfor 0.4Cs0,5(NH4)1,5.

In addition, it was shown by x-ray diffraction analysis that added copper was not allocated in the form of copper acetate or copper oxide.

Next, 356 g of the obtained calcined granules (C) was dispersible in 1317 ml of purified water, followed by stirring at 40°C for 1 hour. Then the dispersion liquid was filtered and the filtered greenish-white, water-insoluble substance (precipitate after filtering), and the brown filtrate were separately evaporated to dryness with hot water and then crushed from 300 to 700 μm and the subsequent dropping out and got so granular catalyst (C) from the precipitate after filtration and hardened substance for comparison (C) from the filtrate.

In this case the degree distribution between the precipitate after filtration and the filtrate amounted to 88.4 wt.% the precipitate after filtration and 11.6 wt.% the filtrate.

Then 324,4 g of sample, which was obtained by grinding and sifting the obtained granulated catalyst (C) to 300 μm or less, and 47.4 g of improving the strength of the material (ceramic fiber) were uniformly mixed, followed by the application and molding on 318,2 g of spherical porous carrier of aluminum oxide (particle diameter 3.5 mm) when used as a binder 90 wt.% an aqueous solution of this is Nola. Then, the resulting molded product was subjected to secondary calcination in an air stream at a temperature of 310°C for 5 hours and got so deposited catalyst, designated as (C).

2) Catalytic oxidation of methacrolein

Received caused the catalyst (C) used for the catalytic oxidation of methacrolein analogously to example 1 and the results of the reaction were evaluated as in example 1. The results are presented in table 3. In addition, 4.0 g of calcined granules (S), granulated catalyst (C) and the hardened substance for comparison (C), each mixed with 8 g of quartz sand from 300 to 700 μm and used in the oxidation reaction in the same conditions as above. The results are presented together in table 3.

Table 3
Maximum temperature (°C)The degree of conversion (%)Selectivity (%)Output (%)
The applied catalyst (C)32892,282,375,9
The calcined granules (C) -88,287,577,2
The granular catalyst (C)-93,786,481,0
The hardened substance for comparison with (C)-35,882,829,6

Comparative example 2

1) preparation of catalyst

In 2100 ml of purified water was added 300 g of molybdenum trioxide, 13,26 g of vanadium pentoxide and 27,62 g of 85 wt.% phosphoric acid followed by heating under reflux in the temperature range from 90 to 100°C for 5 h and was thus given a brownish clear solution. Then thereto was added 12,15 g of antimony trioxide, and then further heated under reflux at a temperature in the range of from 90 to 100°C for 2 hours and thus was given a dark blue solution, which was dissolved antimony trioxide. Then the solution was cooled to a temperature of from 15 to 20°C, followed by gradual addition with stirring, 20 g of cesium acetate, dissolved in 150 ml of purified water, together with 24,09 g of ammonium acetate dissolved in 150 ml of purified water, follow the additional curing at a temperature of from 15 to 20°C for 1 hour and got so rusty suspension, containing cesium salt predecessor of heteroalicyclic and ammonium salt.

Next, the suspension was dried by evaporation to dryness with hot water and then crushed in a mortar and subsequent drop-out rates of up to 300 μm or less and got so crushed substance. The composition of the crushed substance in units of the ratio of reactive substances in this case was expressed as

Mo10V0,7P1,15Cufor 0.4Sbfor 0.4Cs0,5(NH4)1,5.

Then 16,64 g of the acetate monohydrate divalent copper in powder form was added to the crushed substance, followed by stirring, and thus obtained mixture.

Then 381,5 g of crushed substances and 53.8 g of improving the strength of the material (ceramic fiber) were uniformly mixed, followed by the application and molding on 358,4 g of spherical porous carrier of aluminum oxide (particle diameter 3.5 mm) when used as a binder 90 wt.% an aqueous solution of ethanol. Then, the resulting molded product was progulivali in the air stream at a temperature of 310°C for 5 hours and got so deposited catalyst for comparison (D).

The composition of the catalytically active component after calcinations (ground substance) in units of the ratio of the reacting substances was expressed as Mo10V0,7P1,15Cufor 0.4Sb Cs0,5(NH4)1,5.

In addition, it was shown by x-ray diffraction analysis that added copper was not allocated in the form of copper acetate or copper oxide.

2) Catalytic oxidation of methacrolein

The applied catalyst (D) used for the catalytic oxidation of methacrolein analogously to example 1, and the results of the reaction were evaluated as in example 1. The results are presented in table 4.

Table 4
Maximum temperature (°C)The degree of conversion (%)Selectivity (%)Output (%)
The applied Catalyst (D)32688,582,573,0

Example 3

1) preparation of catalyst

In 2100 ml of purified water was added 300 g of molybdenum trioxide, 15,16 g of vanadium pentoxide and 27,62 g of 85 wt.% phosphoric acid followed by heating under reflux in the temperature range from 90 to 100°C for 5 h and was thus given a brownish clear solution. Then the solution was cooled to a temperature of from 15 to 20°C With p the following gradual addition with stirring 17,49 g of the monohydrate of cesium hydroxide, dissolved in 100 ml of purified water, along with to 20.88 g of ammonium acetate dissolved in 100 ml of purified water, followed by additional curing at a temperature of from 15 to 20°C for 15 min and got so yellowish-white suspension containing cesium salt predecessor of heteroalicyclic and ammonium salt.

Then 16,64 g monohydrate copper acetate dissolved in 200 ml of purified water, was added to the suspension, followed by additional curing at a temperature of from 15 to 20°C for 1 hour.

Then the suspension was dried by evaporation to dryness using hot water and then crushed in a mortar and subsequently dropping to 700 μm or less, and the primary calcination in a stream of air at a temperature of 310°C for 5 hours, thus obtaining calcined granules. The composition of the calcined granules (E) in units of the ratio of the reacting substances was expressed as Mo10V0,8P1,15Cufor 0.4Cs0,5(NH4)1,3.

Next 351,5 g obtained calcined pellets were dispersible in 1300 ml of purified water, followed by stirring at 40°C for 1 hour. Then the dispersion liquid was filtered, the filtered yellowish-white, water-insoluble substance (precipitate after filtering) and the brown filtrate were separately evaporated to dryness with hot water and then crushed from 30 to 700 μm and an additional subsequent dropout and got so granular catalyst (E) from the precipitate after filtration, and from the filtrate were obtained solidified product for comparison (E).

In this case the degree distribution between the precipitate after filtration and the filtrate amounted to 78.9% wt.% the precipitate after filtration and 21.1 wt.% the filtrate.

Then 245,0 g of sample, which was obtained by grinding and sifting the obtained granulated catalyst (E), 300 μm or less, and 36.2 g of improving the strength of the material (ceramic fiber) were uniformly mixed, followed by the application and molding on 243,4 g of spherical porous carrier of aluminum oxide (particle diameter 3.5 mm) when used as a binder 90 wt.% an aqueous solution of ethanol. Then, the resulting molded product was divided into two equal parts, (i) one has progulivali (secondary annealing) in camera-type channel furnace for calcination in a stream of nitrogen (5 l/min) in the presence of ethanol (20 g/hour) as a reducing agent at 380°C for 10 hours and got so target caused the catalyst (E-1), and (ii) the second part again progulivali in camera-type channel furnace for calcination in a stream of air at 380°C for 10 hours and got so target applied the catalyst (E-2).

2) Catalytic oxidation of methacrolein

Received caused catalysts (E-1) and (E-2) was used for the catalytic oxidation of methacrolein similarly, when the ERU 1, and the results of the reaction were evaluated as in example 1. The results are presented in table 5. In addition, mixed in 4.0 g of granulated catalyst (E) and the hardened substance for comparison (E) and 8.0 g of quartz sand from 300 to 700 μm, and each mixture was used in the oxidation reaction under the same reaction conditions as in example 1. The results are presented together in table 5.

Table 5
Maximum temperature (°C)The degree of conversion (%)Selectivity (%)Output (%)
The applied catalyst (E-1)32178,087,768,4
The applied catalyst (E-2)32076,987,467,2
The granular catalyst (E)-78,2to 89.970,3
The hardened substance for comparison (E) -46,284,839,2

Comparative example 3

1) preparation of catalyst

In 2100 ml of purified water was added 300 g of molybdenum trioxide, 15,16 g of vanadium pentoxide and 27,62 g of 85 wt.% phosphoric acid followed by heating under reflux in the temperature range from 90 to 100°C for 5 h and was thus given a brownish clear solution. Then the solution was cooled to a temperature of from 15 to 20°C, followed by gradual addition with stirring 17,49 g of the monohydrate of cesium hydroxide dissolved in 100 ml of purified water, along with to 20.88 g of ammonium acetate dissolved in 100 ml of purified water, followed by additional curing at a temperature of from 15 to 20°C for 15 min, and got so yellowish-white suspension containing cesium salt predecessor of heteroalicyclic and ammonium salt.

Then 16,64 g of the monohydrate of bivalent copper acetate dissolved in 200 ml of purified water, was added to the suspension, followed by additional curing for 1 hour.

Then the suspension was dried by evaporation to dryness using hot water and then crushed in a mortar and subsequent drop-out rates from 300 to 700 μm, and thus gained the crushed substance (F). The composition of the crushed prophetic the STV (F) in units of the ratio of the reacting substances was expressed as

Mo10V0,8P1,15Cufor 0.4Cs0,5(NH4)1,3.

Then the crushed substance was crushed to 300 μm or less and were selected, 334,0 g disqualified substances and 48.6 g of improving the strength of the material (ceramic fiber) were uniformly mixed, followed by the application and molding on 326,6 g of spherical porous carrier of aluminum oxide (particle diameter 3.5 mm) when used as a binder 90 wt.% an aqueous solution of ethanol. Then, the resulting molded product was divided into two equal parts, (i) one has progulivali (secondary annealing) in camera-type channel furnace for calcination in a stream of nitrogen (5 l/min) in the presence of ethanol (20 g/hour) as a reducing agent at 380°C for 10 hours and got so target caused the catalyst (F-1), and (ii) the second part again progulivali in camera-type channel furnaces for annealing the hot air in a stream of air at 380°C for 10 hours and got so target caused the catalyst (F-2).

2) Catalytic oxidation of methacrolein

Received caused the catalysts (F-1) and (F-2) was used for the catalytic oxidation of methacrolein analogously to example 1, and the results of the reaction were evaluated as in example 1. The results are presented in table 6. In addition, 4.0 g of the crushed substance (F) spesialis 8.0 g of quartz sand from 300 to 700 μm, the mixture used in the oxidation reaction under the same reaction conditions as in example 1. The results are presented together in table 6.

Table 6
Maximum temperature (°C)The degree of conversion
(%)
Selectivity (%)Output (%)
The applied catalyst (F-1)31753,985,646,1
The applied catalyst (F-2)31861,285,952,6
The crushed substance(F)-69,288,561,3

Example 4

1) preparation of catalyst

In 2100 ml of purified water was added 300 g of molybdenum trioxide, 15,16 g of vanadium pentoxide and 27,62 g of 85 wt.% phosphoric acid followed by heating under reflux in the temperature range from 90 to 100°C for 5 h and was thus given a brownish transparent process is. Then it was added 1.52 g of antimony trioxide, and then further heated under reflux in the temperature range from 90 to 100°C for 2 hours, thus obtaining a greenish-brown solution, which was dissolved antimony trioxide. Then the solution was cooled to a temperature of from 15 to 20°C, followed by gradual addition with stirring 17,49 g of the monohydrate of cesium hydroxide dissolved in 100 ml of purified water, along with to 20.88 g of ammonium acetate dissolved in 100 ml of purified water, followed by additional curing at a temperature of from 15 to 20°C for 1 hour, and got so brownish-yellow suspension containing cesium salt predecessor of heteroalicyclic and ammonium salt.

Then the suspension was dried by evaporation to dryness using hot water and then crushed in a mortar and subsequently dropping to 700 μm or less, and thus gained the powdered substance. The composition of the crushed substance in units of the ratio of the reacting substances was expressed as

Mo10V0,8P1,15Sb0,05Cs0,5(NH4)1,3.

Then the crushed substance was added 16,64 g of the acetate monohydrate divalent copper in the form of a powder, followed by adding 100 g of 90 wt.% an aqueous solution of ethanol with subsequent additional paramasivan who eat then again evaporated to dryness with hot water, then crushed in a mortar to 700 μm or less, followed by the primary calcination in an air stream at a temperature of 310°C for 5 hours and got the thus calcined granules (G). The composition of the calcined granules (G) in units of the ratio of reactive substances in this case was expressed as

Mo10V0,8P1,15Sb0,05Cs0,5(NH4)1,3.

Next 366,4 g obtained calcined granules (G) was dispersible in 1360 ml of purified water, followed by stirring at 40°C for 1 hour. Then the dispersion liquid was filtered, and the filtered, pale-yellow, water-insoluble substance (precipitate after filtering) and the brown filtrate were separately evaporated to dryness with hot water and then crushed from 300 to 700 μm and an additional subsequent dropout and got so granular catalyst (G) from the precipitate after filtration, and the filtrate was obtained solidified product for comparison (G).

In this case the degree distribution between the precipitate after filtration and the filtrate was $ 81.8 wt.% the precipitate after filtration and 18.2 wt.% the filtrate.

Then 259,2 g of the substance obtained by grinding and sifting the obtained granulated catalyst (G), 300 μm or less and of 38.4 g of improving the strength of the material (ceramic is Alekno) were uniformly mixed, followed by the application and molding on 318,2 g of spherical porous carrier of aluminum oxide (particle diameter 3.5 mm) when used as a binder 90 wt.% an aqueous solution of ethanol. Then, the resulting molded product was divided into two equal parts, (i) one has progulivali (secondary annealing) in camera-type channel furnace for calcination in a stream of nitrogen (5 l/min) in the presence of ethanol (20 g/hour) as a reducing agent at 380°C for 10 hours and got so target deposited catalyst (G-1), and (ii) the second part again progulivali in camera-type channel furnace for calcination in a stream of air at 380°C for 10 hours and got so target applied catalyst (G-2).

2) Catalytic oxidation of methacrolein

Received caused catalysts (G-1) and (G-2) used for catalytic oxidation of methacrolein analogously to example 1, and the results of the reaction were evaluated as in example 1. The results are presented in table 7. In addition, 4.0 g of calcined granules (G) and the hardened substance for comparison (G) were each mixed with 8.0 g of quartz sand from 300 to 700 μm and used in the oxidation reaction under the same reaction conditions as above. The results are presented together in table 7.

Table 7
Maximum temperature (°C)The degree of conversion (%)Selectives the ü (%) Output (%)
The applied catalyst (G-1)32176,686,766,4
The applied catalyst (G-2)32171,4of 87.062,1
The granular catalyst (G)-68,589,661,1
The hardened substance for comparison (G)-42,185,135,9

Comparative example 4

1) preparation of catalyst

In 2100 ml of purified water was added 300 g of molybdenum trioxide, 15,16 g of vanadium pentoxide and 27,62 g of 85 wt.% phosphoric acid followed by heating under reflux in the temperature range from 90 to 100°C for 5 h and was thus given a brownish clear solution. Then it was added 1.52 g of antimony trioxide, and then further heated under reflux in the temperature range from 90 to 100°C for 2 hours, thus obtaining a greenish-measles is Navy solution in which was dissolved antimony trioxide. Then the solution was cooled to a temperature of from 15 to 20°C, followed by gradual addition with stirring 17,49 g of the monohydrate of cesium hydroxide dissolved in 100 ml of purified water, along with to 20.88 g of ammonium acetate dissolved in 100 ml of purified water, followed by additional aging at a temperature of from 15 to 20°C for 1 hour and got so rusty suspension containing cesium salt predecessor of heteroalicyclic and ammonium salt.

Then the suspension was dried by evaporation to dryness using hot water and then crushed in a mortar and subsequent drop-out rates of up to 300 μm or less and thus gained the powdered substance. The composition of the crushed substance in units of the ratio of the reacting substances was expressed as

Mo10V0,8P1,15Sb0,05Cs0,5(NH4)1,3.

Then the crushed substance was added 16,64 g of the acetate monohydrate divalent copper powder thus obtained granules for formation of a catalyst containing copper. Composition of matter in units of the ratio of the reacting substances was expressed as

Mo10V0,8P1,15Cufor 0.4Sb0,05Cs0,5(NH4)1,3.

Then 361,0 g of crushed substances and 51.2 g of improving the strength of the material (ceramic in the fiber) was uniformly mixed with the subsequent drawing and forming at 344,0 g of spherical porous carrier of aluminum oxide (particle diameter 3.5 mm) when used as a binder 90 wt.% an aqueous solution of ethanol. Then, the resulting molded product was divided into two equal parts, (i) one has progulivali (secondary annealing) in camera-type channel furnace for calcination in a stream of nitrogen (5 l/min) in the presence of ethanol (20 g/hour) as a reducing agent at 380°C for 10 hours and got so target caused the catalyst (H-1), and (ii) the second part again progulivali in camera-type channel furnace for calcination in a stream of air at 380°C for 10 hours and got so target applied the catalyst (H-2).

2) Catalytic oxidation of methacrolein

Received caused catalysts (H-1) and (H-2) used for catalytic oxidation of methacrolein analogously to example 1, and the results of the reaction were evaluated as in example 1. The results are presented in table 8.

Table 8
Maximum temperature (°C)The degree of conversion (%)Selectivity (%)Output (%)
The applied catalyst (H-1)31859,785,150,8
Caused the initial catalyst (G-2) 31756,9to 83.547,5

Example 5

1) preparation of catalyst

In 2450 ml of purified water was added 350 g of molybdenum trioxide, 17,69 g of vanadium pentoxide and 32,23 g of 85 wt.% phosphoric acid followed by heating under reflux in the temperature range from 90 to 100°C for 5 h and was thus given a brownish clear solution. Then the solution was cooled to a temperature of from 15 to 20°C, followed by gradual addition with stirring 20,41 g of the monohydrate of cesium hydroxide dissolved in 115 ml of purified water, together with 39,35 g of ammonium acetate dissolved in 175 ml of purified water, followed by additional curing at a temperature of from 15 to 20°C for 1 hour, and got so yellowish-white suspension containing cesium salt predecessor of heteroalicyclic and ammonium salt.

Then 19,41 g of the monohydrate of bivalent copper acetate dissolved in 240 ml of purified water, was added to the suspension, followed by additional curing at a temperature of from 15 to 20°C for 15 minutes

Then the suspension was dried by evaporation to dryness using hot water and then crushed in a mortar and subsequently dropping to 700 μm or less, and with the subsequent primary proKLIMA is receiving in a stream of air at 310°C for 5 hours and got the thus calcined granules. The composition of the calcined granules in units of the ratio of the reacting substances was expressed as

Mo10V0,8P1,15Cufor 0.4Cs0,5(NH4)2,1.

Next 421,9 g obtained calcined pellets were dispersible in 2220 ml of purified water, followed by stirring at 70°C for 3 hours. Then the dispersion liquid was filtered, and the filtered, pale-yellow, water-insoluble substance (precipitate after filtering) and the brown filtrate were separately evaporated to dryness with hot water and then crushed from 300 to 700 μm and an additional subsequent dropout and got so granular catalyst (I) from the precipitate after filtration, and the filtrate was obtained solidified product for comparison (I).

In this case the degree distribution between the precipitate after filtration and the filtrate amounted to 82.6 wt.% the precipitate after filtration and 17.4 wt.% the filtrate.

Then 345,0 g of the substance obtained by grinding and sifting the obtained granulated catalyst (I), 300 μm or less, and 48,8 g improves the strength of the material (ceramic fiber) were uniformly mixed, followed by the application and molding on 327.8 g of spherical porous carrier of aluminum oxide (particle diameter 3.5 mm) when used as a binder 90 wt.% an aqueous solution of ethanol. Then the obtained spormann the e substance was divided into two equal parts, (i) one pre-progulivali in a stream of air at 273°C for 3 hours, followed by annealing in nitrogen as a secondary calcination in a stream of nitrogen at 410°C for 7 h, followed by calcination in a stream of air at 370°C for 3 hours and got so target caused the catalyst (I-1), and (ii) another part again progulivali in a stream of air at 383°C for 5 hours and got so target caused the catalyst (I-2).

2) Catalytic oxidation of methacrolein

Received caused catalysts (I-1) and (I-2) used for catalytic oxidation of methacrolein analogously to example 1, and the results of the reaction were evaluated as in example 1. The results are presented in table 9. In addition, 4.0 g of calcined pellets (I) and the hardened substance for comparison (I) were each mixed with 8.0 g of quartz sand from 300 to 700 μm, each mixture was used in the oxidation reaction under the same reaction conditions as above. The results are presented together in table 9.

Table 9
Maximum temperature (°C)The degree of conversion (%)Selectivity (%)Output (%)
The applied catalyst (I-1)32283,986,872,8
The applied catalyst (I-2)32380,186,769,4
The granular catalyst (I)-70,087,761,4
The hardened substance for comparison (I)-12,273,79,0

Advantages of the invention

Catalyst, method for producing according to the invention gives the possibility of obtaining methacrylic acid with high yield and high selectivity from methacrolein, isobutyl aldehyde or somaclonal acid. In addition, it can be used in the reaction under conditions of high load, and thus has a very high industrial value.

1. The way to obtain a catalyst for production of methacrylic acid gas-phase catalytic oxidation of methacrolein, isobutyl aldehyde or somaclonal acid, the method comprises:
(a) phase mixing in with the water connections, each of which contains any one of Mo, V, P, Cu, Cs or NKt, and, if necessary, the compound containing the metal element other than the above, selected from the group of Sb, As or Bi to preparation of an aqueous solution or dispersion of the compounds (hereinafter, both are referred to as suspended);
(b) stage of drying the suspension obtained in stage (a), to obtain a dry mist;
(c) stage calcination dry suspension obtained in stage (b), to obtain a calcined substance;
(d) stage filtration of the mixture obtained by mixing the calcined substance, obtained in stage (C), with water, to separate the aqueous and water-insoluble substance; and
(e) stage of drying water-insoluble matter obtained in stage (d), to obtain a dry water-insoluble substances.

2. The way to obtain a catalyst for production of methacrylic acid gas-phase catalytic oxidation of methacrolein, isobutyl aldehyde or somaclonal acid, the method comprises:
(a) the stage of mixing with water connections, each of which contains any one of Mo, V, P, Cu, Cs or NH4and, if necessary, the compound containing the metal element other than the above, selected from the group of Sb, As or Bi, to prepare an aqueous solution or dispersion of the compounds (hereinafter, both are referred to as suspended);
(') the stage of drying the suspension, obtained in stage (a), to obtain a dry mist, followed by dry mixing the suspension with a compound containing Cu, if necessary, in the presence of a solvent, followed, if necessary, drying the mixture and obtaining, thus, dry matter;
(c) stage calcination of dry matter obtained in stage (b'), to obtain a calcined substance;
(d) stage filtration of the mixture, obtained by mixing calcined substances obtained in stage (C), with water, to separate the aqueous and water-insoluble substance; and
(e) stage of drying water-insoluble matter obtained at the stage
(d)to obtain a dry water-insoluble substances.

3. The method of obtaining the deposited catalyst for production of methacrylic acid gas-phase catalytic oxidation of methacrolein, isobutyl aldehyde or somaclonal acid, the method comprises:
(a) the stage of mixing with water connections, each of which contains any one of Mo, V, P, Cu, Cs or NH4and, if necessary, the compound containing the metal element other than the above, selected from the group of Sb, As or Bi, to prepare an aqueous solution or dispersion of the compounds (hereinafter, both are referred to as suspended);
(b) a stage of drying the suspension obtained in stage (a), to obtain a dry mist; (c) stage calcination dry suspension obtained in stage (b), to obtain a calcined substance;
(d) stage filtration of the mixture obtained by mixing the calcined substance, obtained in stage (C), with water, to separate the aqueous and water-insoluble substance;
(e) stage of drying water-insoluble matter obtained in stage (d), to obtain a dry water-insoluble substances, and
(f) the stage of coating medium dry water-insoluble substance obtained in stage (e), using a binder to obtain a coated molded product, and
(g) stage of annealing, coated molded product obtained in stage (f), in the atmosphere of inert gas, in the air or in the presence of a reducing agent.

4. The method of obtaining the deposited catalyst for production of methacrylic acid gas-phase catalytic oxidation of methacrolein, isobutyl aldehyde or somaclonal acid, the method comprises:
(a) the stage of mixing with water connections, each of which contains any one of Mo, V, P, Cs or NH4and, if necessary, the compound containing the metal element other than the above, selected from the group of Sb, As or Bi, to prepare an aqueous solution or dispersion of the compounds (hereinafter, both are referred to as suspended);
(b') stage of drying is zvezi, obtained in stage (a), to obtain a dry mist, followed by dry mixing the suspension with a compound containing Cu, if necessary in the presence of a solvent, followed, if necessary, drying the mixture and obtaining, thus, dry matter;
(C) stage calcination of dry matter obtained in stage (b'), to obtain a calcined substance;
(d) stage filtration of the mixture, obtained by mixing calcined substances obtained in stage (C), with water, to separate the aqueous and water-insoluble substance;
(e) stage of drying water-insoluble matter obtained in stage (d), to obtain a dry water-insoluble substance; and
(f) the stage of coating medium dry water-insoluble substance obtained in stage (e), using a binder to obtain a coated molded product and
(g) stage of annealing the coated molded product obtained in stage (f), in the atmosphere of inert gas, in the air or in the presence of a reducing agent.

5. The method according to any one of claims 1 to 3 or 4, in which the compound containing Cu represents a copper acetate or copper oxide.

6. The method according to any one of claims 1 to 3 or 4, in which the compound containing Cs, is a cesium salt and a weak acid or cesium hydroxide, connection, content is the future of NH 4represents ammonium acetate or ammonium hydroxide.

7. The method according to any one of claims 1 to 3 or 4, in which the suspension contains no arsenic compounds.

8. The method according to any one PP or 4, in which the binder is a binder that contains ethanol.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: present invention pertains to improvement of the method of producing (met)acrylic acid and complex (met)acrylic esters, involving the following stages: (A) reacting propane, propylene or isobutylene and/or (met)acrolein with molecular oxygen or with a gas, containing molecular oxygen through gas-phase catalytic oxidation, obtaining crude (met)acrylic acid; (B) purification of the obtained crude (met)acrylic acid, obtaining a (met)acrylic acid product; and (C) reacting raw (met)acrylic acid with alcohol, obtaining complex (met)acrylic esters, in the event that the installation used in any of the stages (B) and (C), taking place concurrently, stops. The obtained excess crude (met)acrylic acid is temporarily stored in a tank. After restoring operation of the stopped installation, the crude (met)acrylic acid, stored in the tank, is fed into the installation, used in stage (B), and/or into the installation used in stage (C). (Met)acrylic acid output of the installation used in stage (A) should be less than total consumption of (met)acrylic acid by installations used in stages (B) and (C).

EFFECT: the method allows for processing (met)acrylic acid, temporarily stored in a tank, when stage (B) or (C) stops, without considerable change in workload in stage (A).

2 ex

FIELD: chemistry.

SUBSTANCE: present invention pertains to improvement of the method of producing (met)acrylic acid or (met)acrolein using a multi-pipe reactor with a fixed bed. The reactor has several pipes, with at least one catalyst bed in the direction of the axis of the pipe. A heat carrier can regulate temperature outside the flow of the reaction pipe. In the reaction pipes, there is gas-phase catalytic oxidation of at least one type of oxidisable substance, propylene, propane, isobutylene and (met)acrolein by molecular oxygen or a gas, containing molecular oxygen. At the beginning of the process, the difference between the coolant temperature and the peak temperature of the catalyst is set in the interval 20-80°C, and during the process, peak temperature T(°C) of the catalyst in the direction of the axis of the pipe satisfies equation 1, given below: (equation 1), where L, T0, X and X0 stand for length of the reaction pipe, peak temperature of the catalyst in the direction of the axis of the pipe at the beginning of the process, the length up to the position which gives the peak temperature T at the input of the reaction pipe, and the length to the position which gives the peak temperature T0 at the input of the reaction pipe, respectively.

EFFECT: method allows for stable output of the target product, with high output for a long period of time, without reduction of catalyst activity.

3 dwg, 2 ex

FIELD: chemistry.

SUBSTANCE: present invention pertains to improvement of the method of producing (met)acrylic acid or (met)acrolein using a multi-pipe reactor with a fixed bed. The reactor has several pipes, with at least one catalyst bed in the direction of the axis of the pipe. A heat carrier can regulate temperature outside the flow of the reaction pipe. In the reaction pipes, there is gas-phase catalytic oxidation of at least one type of oxidisable substance, propylene, propane, isobutylene and (met)acrolein by molecular oxygen or a gas, containing molecular oxygen. At the beginning of the process, the difference between the coolant temperature and the peak temperature of the catalyst is set in the interval 20-80°C, and during the process, peak temperature T(°C) of the catalyst in the direction of the axis of the pipe satisfies equation 1, given below: (equation 1), where L, T0, X and X0 stand for length of the reaction pipe, peak temperature of the catalyst in the direction of the axis of the pipe at the beginning of the process, the length up to the position which gives the peak temperature T at the input of the reaction pipe, and the length to the position which gives the peak temperature T0 at the input of the reaction pipe, respectively.

EFFECT: method allows for stable output of the target product, with high output for a long period of time, without reduction of catalyst activity.

3 dwg, 2 ex

FIELD: chemistry.

SUBSTANCE: present invention pertains to perfection of the method of obtaining at least, one product of partial oxidation and/or ammoxidising of propylene, chosen from a group, comprising propylene oxide, acrolein, acrylic acid and acrylonitrile. The starting material is raw propane. a) At the first stage, raw propane, in the presence and/or absence of oxygen, is subjected to homogenous and/or heterogeneous catalysed dehydrogenation and/or oxydehydrogenation. Gas mixture 1, containing propane and propylene is obtained. b) If necessary, a certain quantity of the other components in gas mixture 1, obtained in the first stage, besides propane and propylene, such as hydrogen and carbon monoxide is separated and/or converted to other compounds, such as water and carbon dioxide. From gas mixture 1, gas mixture 1' is obtained, containing propane and propylene, as well as other compounds, besides oxygen, propane and propylene. c) At the third stage, gas mixture 1 and/or gas mixture 1' as a component, containing molecular oxygen, of gas mixture 2, is subjected to heterogeneous catalysed partial gas-phase oxidation and/or propylene, contained in gas mixture 1 and/or gas mixture 1', undergoes partial gas-phase ammoxidising. Content of butane-1 in gas mixture 2 is ≤1 vol.%. The method increases output of desired products and efficiency of the process.

EFFECT: increased output of desired products and efficiency of the process.

72 cl, 10 ex

FIELD: heating.

SUBSTANCE: invention concerns improved method of catalytic oxidation in vapour phase which supplies effective removing of reactionary heat, excludes hot spot formation, and supplies effective receipt of base product. Method of catalytic oxidation is disclosed in the vapour phase (a) of propylene, propane or isobutene by the instrumentality of molecular oxygen for receiving (meth)acrolein, and/or oxidation (b) of (meth)acrolein by molecular oxygen for receiving (meth)acryl acid, by the instrumentality of multiple-tubular reactor, contained: cylindrical reactor vessel, outfitted by initial material supply inlet hole and discharge hole for product, variety of reactor coolant pipes, located around the cylindrical reactor vessel and used for insertion the heat carrier into cylindrical reactor vessel or for removing the heat carrier from it, circulator for connection of variety loop pipeline to each other, variety of reaction tube, mounted by the instrumentality of tube reactor lattices, with catalyst. Also multiple-tubular reactor contains: variety of partitions, located lengthways of reaction tubes and used for changing heat carrier direction, inserted into reactor vessel. According to this heat carrier coolant flow is analysed and there are defined zones in reactor which have heat-transfer coefficient of heat carrier less than 1000 W/(m2·K); also reaction of catalytic oxidation is averted in the vapour phase in mentioned zones of reactor and reaction of catalytic oxidation is implemented in the vapour phase in reactor.

EFFECT: receiving of improved method catalytic oxidation in vapour phase which supplies effective removing of reactionary heat, excludes hot spot formation, and supplies effective receipt of base product.

3 cl, 6 dwg, 2 ex

FIELD: industrial organic synthesis.

SUBSTANCE: invention relates to improved process to produce acrylic acid via heterogeneously catalyzed gas-phase partial oxidation of propane wherein starting reactive gas mixture containing propane, molecular oxygen, and at least one gas diluent is passed at elevated temperature over a multimetal oxide bulk depicted by total stoichiometry as Mo1VbM1сM2вOn (I), in which M1 = Te and/or Sb and M2 is at least one element from group comprising Nb, Ta, W, Ti, Al, Zr, Cr, Mn, Ga, Fe, Ru, Co, Rh, Ni, Pd, Pt, La, Bi, B, Ce, Zn, Si, and In; b = 0.01 to 1, c = >0 to 1, d = >0 to 1, and n = number, which is determined by valence and number of non-oxygen elements in (I). Propane is partially oxidized to produce acrylic acid in a process wherein composition of starting reaction mixture is at least two times varied in the course of process such that molar percentage of gas diluent (water steam) in starting reaction gas mixture decreases relative to molar percentage of propane contained in starting gas mixture.

EFFECT: reduced amount of water steam in gas mixture without loss in selectivity and activity of catalyst regarding target product.

5 cl, 1 dwg, 10 ex

FIELD: improved method for production of (meth)acrolein and (meth)acrylic acid.

SUBSTANCE: claimed method includes feeding of raw gas mixture through pipeline from raw material mixer into oxidation reactor and catalytic oxidation of raw mixture in vapor phase to produce (meth)acrolein or (meth)acrylic acid. Said pipeline is heated and/or maintained in heated state and temperature of gas mixture fed into oxidation reactor is by 5-250C higher then condensation temperature of raw gas mixture.

EFFECT: stable and effective method for production of (meth)acrolein and (meth)acrylic acid without alteration of raw mixture composition, abrupt temperature elevation and reducing of catalyst activity and durability.

5 cl, 1 dwg, 2 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to the improved method for preparing acrylic acid and selective oxidation of propylene to acrolein. Method involves carrying out reaction of propylene with oxygen in the first zone reaction with the first catalyst corresponding to the following formula: AaBbCcCadFeeBifMo12Ox wherein A means Li, Na, K, Rb and Cs and their mixtures also; B means Mg, Sr, Mn, Ni, Co and Zn and their mixtures also; C means Ce, Cr, Al, Sb, P, Ge, Sn, Cu, V and W and their mixtures also wherein a = 0.01-1.0; b and e = 1.0-10; c = 0-5.0 but preferably 0.05-5.0; d and f = 0.05-5.0; x represents a number determined by valence of other presenting elements. Reaction is carried out at enhanced temperature providing preparing acrylic acid and acrolein and the following addition of acrolein from the first reaction zone to the second reaction zone containing the second catalyst used for conversion of acrolein to acrylic acid. Method provides high conversion of propylene to acrylic acid and acrolein.

EFFECT: improved preparing method.

7 cl, 1 tbl, 5 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to the improved method for preparing acrylic acid and selective oxidation of propylene to acrolein. Method involves carrying out reaction of propylene with oxygen in the first zone reaction with the first catalyst corresponding to the following formula: AaBbCcCadFeeBifMo12Ox wherein A means Li, Na, K, Rb and Cs and their mixtures also; B means Mg, Sr, Mn, Ni, Co and Zn and their mixtures also; C means Ce, Cr, Al, Sb, P, Ge, Sn, Cu, V and W and their mixtures also wherein a = 0.01-1.0; b and e = 1.0-10; c = 0-5.0 but preferably 0.05-5.0; d and f = 0.05-5.0; x represents a number determined by valence of other presenting elements. Reaction is carried out at enhanced temperature providing preparing acrylic acid and acrolein and the following addition of acrolein from the first reaction zone to the second reaction zone containing the second catalyst used for conversion of acrolein to acrylic acid. Method provides high conversion of propylene to acrylic acid and acrolein.

EFFECT: improved preparing method.

7 cl, 1 tbl, 5 ex

FIELD: chemistry.

SUBSTANCE: present invention pertains to improvement of the method of producing (met)acrylic acid and complex (met)acrylic esters, involving the following stages: (A) reacting propane, propylene or isobutylene and/or (met)acrolein with molecular oxygen or with a gas, containing molecular oxygen through gas-phase catalytic oxidation, obtaining crude (met)acrylic acid; (B) purification of the obtained crude (met)acrylic acid, obtaining a (met)acrylic acid product; and (C) reacting raw (met)acrylic acid with alcohol, obtaining complex (met)acrylic esters, in the event that the installation used in any of the stages (B) and (C), taking place concurrently, stops. The obtained excess crude (met)acrylic acid is temporarily stored in a tank. After restoring operation of the stopped installation, the crude (met)acrylic acid, stored in the tank, is fed into the installation, used in stage (B), and/or into the installation used in stage (C). (Met)acrylic acid output of the installation used in stage (A) should be less than total consumption of (met)acrylic acid by installations used in stages (B) and (C).

EFFECT: the method allows for processing (met)acrylic acid, temporarily stored in a tank, when stage (B) or (C) stops, without considerable change in workload in stage (A).

2 ex

FIELD: chemistry.

SUBSTANCE: present invention pertains to improvement of the method of producing (met)acrylic acid or (met)acrolein using a multi-pipe reactor with a fixed bed. The reactor has several pipes, with at least one catalyst bed in the direction of the axis of the pipe. A heat carrier can regulate temperature outside the flow of the reaction pipe. In the reaction pipes, there is gas-phase catalytic oxidation of at least one type of oxidisable substance, propylene, propane, isobutylene and (met)acrolein by molecular oxygen or a gas, containing molecular oxygen. At the beginning of the process, the difference between the coolant temperature and the peak temperature of the catalyst is set in the interval 20-80°C, and during the process, peak temperature T(°C) of the catalyst in the direction of the axis of the pipe satisfies equation 1, given below: (equation 1), where L, T0, X and X0 stand for length of the reaction pipe, peak temperature of the catalyst in the direction of the axis of the pipe at the beginning of the process, the length up to the position which gives the peak temperature T at the input of the reaction pipe, and the length to the position which gives the peak temperature T0 at the input of the reaction pipe, respectively.

EFFECT: method allows for stable output of the target product, with high output for a long period of time, without reduction of catalyst activity.

3 dwg, 2 ex

FIELD: chemistry.

SUBSTANCE: invention concerns improved method of obtaining at least one product of partial propylene oxidation and/or ammoxidation, propylene selected out of group including propyleneoxide, acrolein, acrylic acid and acrylnitryl, where source substance is propane. Method involves a) at the first stage, homogeneous and/or heterogeneous catalysed dehydration and/or oxydehydration of raw propane in the presence and/or in the absence of oxygen, to obtain gas mix containing propane and propylene; and b) if required, separation of part gas mix 1 obtained at the first stage and its components other than propane and propylene, such as hydrogen, carbon monoxide, or transformation of this part in the other compounds, such as water, carbon dioxide, so that gas mix 1' containing propane and propylene and compounds other than oxygen, propane and propylene is obtained from gas mix 1; and at least one more stage c) heterogeneous catalysed ammoxidation and/or partial gas phase ammoxidation of propylene containing in gas mix 1 and/or gas mix 1' in gas mix 1 or gas mix 1' containing molecular oxygen of gas mix 2, where total C4-hydrocarbon content in gas mix 2 is < 3 volume %.

EFFECT: reduced process performance due to reduced output of target product and enhanced selectivity of carbon oxide generation at the second process stage.

50 cl, 10 ex

FIELD: chemistry.

SUBSTANCE: invention concerns organic synthesis field, particularly method of obtaining benzoic acid (C6H5COOH, benzenecarboxylic acid) by catalytic oxidation of benzyl alcohol in hydrogen peroxide solution, as well as catalysts for method implementation, and method of obtaining catalysts. Catalysts of benzoic acid production is nanostructurised bifunctional metallocomplex catalyst acting as oxidation and interphase transport catalyst. It is a complex compound of the general formula Q3{PO4[W(O)(O2)2]4}, where: Q is quadruple ammonium cation [(R1)3N R2]+, where: R1 and R2 contain 8 to 24 carbon atoms. The invention concerns method of obtaining catalyst for benzoic acid production by dissolution of compounds containing phosphor and tungsten in hydrogen peroxide solution with added interphase transport catalyst compound, with phosphor-tungsten heteropolyacids of Keggin or Dawson structure are used as compounds containing phosphor and tungsten, dissolution is performed at the following mol ratio: hydrogen peroxide to tungsten [H2O2]/[W]=15-50, with further addition of quadruple ammonium cation - [(R1)3N R2]+ as interphase transport catalyst, where: R1 and R2 contain 8 to 24 carbon atoms. The invention also concerns method of obtaining benzoic acid by substrate oxidation in hydrogen peroxide in the presence of the catalyst described above.

EFFECT: increased efficiency of benzoic acid production process.

8 cl, 21 ex, 2 tbl, 1 dwg

FIELD: heating.

SUBSTANCE: invention concerns improved method of catalytic oxidation in vapour phase which supplies effective removing of reactionary heat, excludes hot spot formation, and supplies effective receipt of base product. Method of catalytic oxidation is disclosed in the vapour phase (a) of propylene, propane or isobutene by the instrumentality of molecular oxygen for receiving (meth)acrolein, and/or oxidation (b) of (meth)acrolein by molecular oxygen for receiving (meth)acryl acid, by the instrumentality of multiple-tubular reactor, contained: cylindrical reactor vessel, outfitted by initial material supply inlet hole and discharge hole for product, variety of reactor coolant pipes, located around the cylindrical reactor vessel and used for insertion the heat carrier into cylindrical reactor vessel or for removing the heat carrier from it, circulator for connection of variety loop pipeline to each other, variety of reaction tube, mounted by the instrumentality of tube reactor lattices, with catalyst. Also multiple-tubular reactor contains: variety of partitions, located lengthways of reaction tubes and used for changing heat carrier direction, inserted into reactor vessel. According to this heat carrier coolant flow is analysed and there are defined zones in reactor which have heat-transfer coefficient of heat carrier less than 1000 W/(m2·K); also reaction of catalytic oxidation is averted in the vapour phase in mentioned zones of reactor and reaction of catalytic oxidation is implemented in the vapour phase in reactor.

EFFECT: receiving of improved method catalytic oxidation in vapour phase which supplies effective removing of reactionary heat, excludes hot spot formation, and supplies effective receipt of base product.

3 cl, 6 dwg, 2 ex

FIELD: industrial organic synthesis.

SUBSTANCE: invention provides improved process for production of isobutyric acid suitable for use in production of higher carboxylic acid esters and drying oils. Process comprises oxidation of isobutyric aldehyde with air oxygen on heating in column-type reactor filled with zeolite of types CaX, CaA, NaX, or NaA with packing diameter-to-packing width ratio 1:(7.2-8), at volumetric air supply velocity 684.0-874.0 h-1, butyric acid-to oxygen molar ratio 1:(0.7-1.0), and temperature 62-66°C.

EFFECT: increased yield of desired product and intensified process.

3 tbl, 4 ex

FIELD: organic synthesis.

SUBSTANCE: synthesis involves oxidation of substrate with chlorine dioxide in organic solvent at 40-50°C, said selected from myrtenal or myrtenol and said organic solvent from acetone, benzene, and alcohol at molar ratio of myrtenal or myrtenol to chlorine dioxide 1:(0.5-3.5). Thus formed myrtenic acid is isolated in the form of its water-soluble salt and, when alcohol is used as solvent, in the form of ester.

EFFECT: increased yield of product to 66%, reduced expenses, and shortened reaction time.

3 cl, 1 tbl, 2 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for preparing 2-ethylhexanoic acid. Method involves catalytic hydrogenation of fraction isolating from the manufacturing waste in the presence of hydrogen by rectification method followed by oxidation of prepared hydrogenation product with air oxygen at temperature 30-80°C and under pressure 0.1-1.0 MPa. Vat residue from rectification of butyl alcohols in oxo-synthesis is used as raw for the process. Fraction with the total content of unsaturated and saturated C8-alcohols 65-95 wt.-% is isolated from vat residue by rectification and in residual pressure on column top 100-300 mm of mercury column. This fraction is subjected for hydrogenation in vapor phase under atmosphere pressure, temperature 220-270°C, volume rate of raw feeding 0.5 h-1, volume ratio raw : hydrogen = 1:1 on copper-containing catalyst and the following isolation 2-ethylhexanal from catalyzate by rectification on two columns working at residual pressure on top of the first column 60-100 mm of mercury column and on top of the second column 20-80 mm of mercury column, and 2-ethylhexanal is oxidized with air oxygen. The end 2-ethylhexanoic acid is isolated from the prepared oxidized product by rectification on two columns working at residual pressure on top of column 20-70 and 10-60 mm of mercury column, respectively. Method provides enhancing the yield of 2-ethylhexanoic acid.

EFFECT: improved method for preparing.

2 cl, 16 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to the improved method for preparing 2-keto-L-gulonic acid. This compound is an intermediate substance in synthesis of vitamin C. Method involves oxidation of L-sorbose in the presence of platinum-containing polymeric catalyst applied on Al2O3 in medium with the equimolar content of NaHCO3 under atmosphere pressure, at the rate stirring 870-1 000 rev/min and bubbling pure oxygen as an oxidizing agent. Reaction is carried out in medium water : ethyl alcohol 7-10 vol. %, in the concentration of L-sorbose 0.29-0.6 mole/l, on spherical microparticles of catalyst in the amount 20-40 g/l with ultra-thin layer of polydiallyldimethylammonium chloride as cationic polyelectrolyte with platinum nanoparticles formed on it. The content of platinum in catalyst is 1-2%. The feeding rate of oxidizing agent is 400-450 ml/min. The end product is obtained with high yield 97-99%.

EFFECT: improved preparing method, enhanced yield of product.

7 cl, 1 tbl, 1 sch, 7 ex

The invention relates to chemical technology, in particular to an improved method for producing a saturated monocarboxylic acids WITH4-C8by oxidation of the corresponding aldehydes with oxygen, aldehydes impose additional isopropanol at a volume ratio of isopropanol to the aldehyde, equal 0,0007-0,0038, and the reaction is carried out at a temperature of 50-700With

FIELD: chemistry.

SUBSTANCE: present invention pertains to the method of prolonged heterogeneous catalysed partial oxidation of propene to acrolein in gaseous phase. The initial reaction gaseous mixture, containing propene, molecular oxygen and at least one inert gas-diluting agent, is passed through a fixed catalyst bed at high temperature. The catalysts are such that, their active mass contains at least, one multi-metal oxide, which contains molybdenum and/or tungsten, as well as at least, one of the elements bismuth, tellurium, antimony, tin, and copper. The temperature of the catalyst bed is increased for a period of time. Partial oxidation in gaseous phase is interrupted at least, once in a calendar year, and at 250-550°C temperature of the fixed catalyst bed a gas mixture, containing molecular oxygen, inert gas and, if necessary, water vapour, is passed through the fixed catalyst bed.

EFFECT: proposed method increases the lifespan of the catalyst.

28 cl, 2 ex

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