Method of reactor loading

FIELD: process engineering.

SUBSTANCE: invention can be used for filling the reactor with poly element oxide catalyst. Catalyst particles are prepared that contain substance liquid at 20°C and 1 atm, substance content varying from 0.05 to 10% by weight. Reactor is filled with catalyst particles fed through hole made in reactor top section, said particles being lowered inside the reactor by gravity.

EFFECT: efficient loading of catalyst into reactor with small-diametre tubes for catalysed vapor-phase reactions, ruling out of catalyst attrition.

1 tbl, 4 ex, 28 cl

 

The present invention relates to a method of filling of the reactor multi-element oxide catalyst filled by this method reactors and their use for the implementation of catalytic vapor-phase reactions.

Filled with catalysts reactors are used for various catalytic vapor-phase reactions. The catalyst particles comprise a catalytically active mass, which the extrusion, pelletizing or other means, if necessary, requires the use of a suitable binder, transformed into a molded body (so-called solid catalysts), or contain at least one catalytically active mass is applied in the form of the shell, usually an inert carrier (so-called shell catalysts). On an industrial scale is similar to the catalytic vapor-phase reaction, usually carried out in a reactor with a fixed bed of catalyst, that is, the reaction gas mixture is passed through in a stationary state of the catalyst, and the chemical transformation of the reactants takes place during the time of their stay in such a reactor. Depending on the nature of catalyzed reactions require either the exercise of external heating of the reactor or the heat dissipation through intended for heat is BMENA environment, such as molten salt. In this regard, the catalytic vapor-phase reaction, it is often advisable to carry out filled with catalyst tubes, usually made in the form of a tubular reactors (reactors with a large number of contact tubes). The length of the tubes of such reactors is usually several meters (typical length of the contact tube is about 2 to 4 m), and their inner diameter is a few centimeters. Used catalysts may have the form of beads, rings, cylinders, cubes, rectangular parallelepipeds or configuration of other bodies, and the length of the catalyst particles in the longitudinal direction commensurate with the inner diameter of cantatrix tubes of the reactor and typically amounts to a few millimeters.

When loading catalyst particles into the reactor, especially in a vertical tube under the action of mechanical stress may lead to the destruction or partial exfoliation of the catalytically active mass of the medium, which depends on the resistance to lateral pressure and resistance to the destruction of the used catalysts. The resulting fragments, respectively, the products of abrasion of the catalyst, cause compaction and increase in pressure loss during subsequent operation of the tubular reactor.

The production of the catalyst is in the form of particles and their use in catalysis vapor reactions many publications, however, they are not given due attention to the problems of filling of the reactor.

Oxidative chemical transformations carried out in the vapor phase using solid catalysts based on the catalytically active oxides, many publications. For example, in applications U.S. patent US-A 4438217 and US-A 4522671 for vapor-phase catalytic oxidative synthesis of acrolein, respectively methacrolein, it is recommended to use a solid catalyst in the form of rings. In the application of the U.S. patent US-A 4537874 for vapor-phase catalytic oxidative synthesis of aldehydes with α,β-position of olefinic bonds is also recommended to use solid catalysts in the form of rings based on molybdenum as a main component contained in polymetallic oxides.

In the German patent application DE-A 2025430 described a method of manufacturing a spherical shell catalysts on the basis of a catalytically active oxide of the masses and their use for the implementation of catalytic vapor-phase oxidation, for example, to turn Indiana in the anthraquinone. German patent application DE-A 1642921 relates to the manufacture of spherical oxide shell catalysts by spraying a liquid with dissolved or suspended therein oxide active mass over the hot speeches is their particle carrier and application are received by the specified image catalysts for the catalytic vapor-phase oxidation of aromatic and unsaturated hydrocarbons to carboxylic acids or anhydrides of carboxylic acids. The concept of the German patent applications DE-A 2510994 and DE-A 1642921 are basically the same except for the fact that in the first of these publications are also encouraged to use the annular carrier. From German patent application DE-A 2106796 known about the manufacture of shell catalysts for the catalytic vapor-phase oxidation, in accordance with which the aqueous suspension of the catalytically active oxide material applied by spraying in the floating particles of the medium. With the purpose of increasing the adhesion strength of the catalytically active oxide shell with the surface of the carrier particles in accordance with German patent application DE-A 2626887 in the sprayed aqueous suspension, it is recommended to enter inorganic basic salts. The concept of the German patent applications DE-A 2909670 and DE-A 2626887 largely the same. At the same time as suspendida environment, you can also use a mixture of water and alcohol. In the German patent application DE-A 2909671 described a method of manufacturing a shell catalyst, in accordance with which the spherical particles of the medium periodically pass under two dosing devices, sequentially arranged at a certain distance from each other.

The UK patent GB-1331423, and European patent application EP-A 286448 and EP-A 37492 relate to the method of manufacturing sphere the definition of the oxide shell catalysts. In European patent application EP-293859 a method of manufacturing a spherical shell catalysts with a device for coating with a centrifugal flow. At the same time as the binder, along with ammonium nitrate, graphite and starch, use water, alcohol and acetone.

From German patent application DE-A 2526238, U.S. patent US-3956377 and German patent application DE-A 235151 known method of manufacturing spherical oxide shell catalysts, in accordance with which the medium is in the form of balls first, moisturize is used as a binder with water or other liquids, such as petroleum ether. Then hydrated binder media put a catalytically active oxide mixture with a running-wet material media in powdered catalytically active oxide mass.

In the German patent applications DE-A-10360057 and DE-A-10360058 described a method of manufacturing a catalytically active multi-element oxide mass heat treatment of the corresponding initial mass in a rotating tube furnace.

In the international application WO 98/37967 described a method of manufacturing a shell catalyst, whereby to form shells carry out the application of the solution or suspension containing the source connection for the catalytically active mass, is the l catalyst and then equipped with a membrane carrier is subjected to heat treatment.

From German patent application DE-A-19824532 known method of producing shell catalysts by spraying aqueous suspensions of the active mass containing a binder above is heated to a temperature of from 50 to 450°C material media. When this binder is a mixture of a polymer containing units anhydrides of acids or dibasic acids with ethylene unsaturation, at least one alkanolamine. Spray suspensions of the active mass on the preheated carrier accompanied by a curing contained in the active mass of the binder.

In European patent application EP-A 714700 described a method of manufacturing a shell catalyst, in accordance with which the first particles of the medium moisturize liquid binder on the wetted surfaces of the particles of the carrier capture layer of the catalyst by contact of the particles with dry finely dispersed active oxide mass, and then remove the liquid binder.

Device for filling tubular reactors with catalysts known from German patent applications DE-A-2511411 and DE-A-2849664, European patent application EP-IN-041144, as well as from German patent applications DE-A-19934324 and DE-A-10250022. Problems when loading catalyst particles into the reactor and due to exposure to N. the mechanical load, in these documents will not be considered.

In addition, it is known that for filling the reactor with catalyst use assistive devices, for example, lowering the rate of fall of the loaded catalyst particles. For example, in European patent application EP-A 548999 a method of filling tubes of the reactor, whereby particles of the loaded catalyst is moved along the cord, provided with spaced at a certain distance from each other transverse fibers.

Another way of loading catalyst particles into the tube described in U.S. patent US 3608751. We offer this document as an auxiliary means is a flexible body, such as hemp rope with attached inclined blades.

In the German patent application DE-A-10337998 described method of filling a vertical tube with catalyst particles, whereby in the vertical tube of the injected used as accessories flexible elongated body, and then carry out the loading of catalyst particles.

However, the use of assistive devices is always accompanied by additional complication of the process load of the catalyst. In addition, if the tubes have a small diameter, many assistive devices cause them quickly is the clogging or the adhesion of the catalyst particles. However, it is not always possible to the extent necessary to avoid destruction, respectively catalyst attrition.

With regard to the foregoing, the present invention was based on the task to offer a way of loading the catalyst into the reactor, primarily in the reactor tubes of small diameter, used for carrying out catalyzed vapor-phase reactions, in order to avoid destruction, respectively catalyst attrition.

This problem is solved, by way of filling the reactor with catalyst particles, at least the surface of which is provided with a catalytically active multi-element oxide by weight, whereby carry out the preparation of catalyst particles containing liquid at a temperature of 20°C and a pressure of 1 ATM substance, and download the prepared catalyst particles in the reactor.

It was found that by filling the reactor containing the liquid substance particles of catalyst loaded catalyst has the preferred properties. So, for example, containing such liquid catalyst particles have a higher mechanical stability compared to not containing the catalyst particles. The reactor filled with the catalyst according to the invention method, contain m is nisee the number of destroyed catalyst particles and/or products of abrasion, formed due to mechanical load acting on the catalyst during the boot process. Therefore, when filling the reactor is formed of loose granular mass of catalyst with a low packing density and low bulk weight. This makes it possible at least to reduce the pressure drops along the loaded catalyst that occur during operation of the reactor. The combination of uniformity passed through the reactor flow of reagents and exceptions excessively large values of partial pressure of the reactants are preferred when carrying out catalytic vapor-phase reactions of any type. So, for example, by reducing pressure losses in the operation of the reactor can save the energy needed to compress the incoming gas into the reactor, since in this case the gas should be compressed to the lower pressure. In addition, the temperature maximum (the so-called hot spot), commonly encountered in containing the catalyst tube along the direction of gas flow and the characteristic, for example, for reactions exothermic catalytic vapor-phase oxidation, has a smaller amplitude. This circumstance has a positive effect on the durability (lifetime) used active mass. Furthermore, the reduction in pressure loss when assests the Institute catalyzed reactions can have a positive impact on the yield of the target product in terms of per unit of reaction volume per unit of time. These benefits are especially common in the case of filling a tubular reactor containing typically at least 5000 contact tubes. When filling in the individual tubes of the reactor is much easier to avoid the destruction of the catalyst particles and/or abrasion, for example, due to slower loading of the catalyst or the use of appropriate assistive devices. However, loading a fresh catalyst in industrial tubular reactors associated with prolonged cessation of the production process, and therefore the loading should be done as quickly as possible. In addition, due to a lower total pressure loss during operation of the tubular reactor with a large number of tubes possible a much more significant savings required to compress the reaction gas energy than in the case of a reactor with a single tube. Along with this, in particular for reactors with a large number of tubes required the most uniform implementation of the reactions are also used in each tube. However, such uniformity can only be achieved due to uniform flow of the reaction gas supplied to each of the tubes, which involves mostly uniform and perfect filling of all of the tubes of the reactor catalyst particles.

Use the m according to the invention, the liquid substance may be any liquid under normal conditions (at a temperature of 20°C and 1 ATM pressure) of the substance. Such substances include individual liquid compounds and mixtures of two or more liquid compounds. The liquid substance may optionally contain dissolved substances, which in the most General case refers to an individual dissolved compounds or a mixture of two or more dissolved compounds.

In a preferred embodiment of the invention, the catalyst particles are combined with a liquid substance which is chosen so that used to fill the reactor, the particles of this substance remained chemically unchanged state. It is that although you can change the quantitative composition of a mixture of substances or physical interaction of matter with particles of catalyst, however, the chemical composition of the liquid substance when it is contact with the catalytically active oxide mass must remain constant. If (as considered in more detail below) of the catalyst particles is combined with the composition, for example, as a binder, which, along with a liquid substance that contains the components that were used to populate the particles contain a similar composition as a whole in a chemically unchanged form. First of all, the catalyst particles do not combine with liquid substance or composition containing one of these substances, which include to mponent with interoperability, additional functional groups. Upon completion of the filling process the chemical composition of the liquid substance, obviously, may vary, for example, as a result, if necessary, carried out at elevated temperatures, drying operations.

Suitable liquid substance selected from the group comprising inorganic and organic liquids, and mixtures thereof. Suitable liquids include water, anhydrous inorganic solvents, such as HClO4, nitric acid, sulfuric acid and so forth; organic solvents, such as monohydroxy alcohols (e.g. methanol, ethanol, n-propanol, isopropanol, butanol, pentanol, cyclohexanol), polyhydric alcohols (e.g. ethylene glycol, glycerin), ethers, and simple glycol ethers (e.g. diethyl ether, disutility ether, anisole, dioxane, tetrahydrofuran, ethers, mono-, di-, tri - or polyalkyleneglycols), ketones (e.g. acetone, butanone, cyclohexanone), esters (e.g. ethyl acetate complex of glycolic esters), acids (e.g. acetic acid), amines, aminoalcohols, amides and other nitrogen-containing compounds (for example, ethanolamine, diethanolamine, dimethylformamide, pyridine, N-organic, acetonitrile), sulfur-containing compounds (for example, carbon disulfide, dimethylsulfoxide, sulfolan), nitro compounds (e.g., nitrobenzene), halogen-containing Ugledar the water (for example, dichloromethane, chloroform, carbon tetrachloride, dichloroethane), hydrocarbons (such as gasoline, petroleum ether, naphtha, pentane, hexane, heptane, cyclohexane, methylcyclohexane, decalin, aromatic hydrocarbons such as benzene, toluene and xylenes), and also mixtures of these solvents.

The liquid substance is preferably chosen from the group comprising water and organic solvents, the boiling point of which at normal pressure (1 atmosphere) is more than 100°C. In a particular embodiment of the invention a liquid substance selected from the group comprising water, miscible with water and organic compounds, the boiling point of which at normal pressure (1 atmosphere) is more than 100°C., and mixtures thereof.

If used in accordance with the proposed invention by way of a liquid substance contains dissolved inorganic or organic substances, at normal pressure (1 atmosphere) they have a boiling point or temperature of sublimation, in excess of 100°C. Suitable dissolved inorganic substances are, for example, halides of alkali metals, such as sodium chloride and potassium chloride, halides of alkaline earth metals such as calcium chloride and magnesium chloride, sulfates of alkali and alkaline earth metals such as sodium sulfate and self is tons of calcium, hydroxides of alkali and alkaline earth metals such as sodium hydroxide, potassium hydroxide and calcium hydroxide, and other substances. Suitable dissolved organic substances are, for example, fatty acids such as capric, undecanoate, lauric, tridecanoate, myristic, pentadecanoic, palmitic, margaric, stearic, nonadecanoic, arachnid, Bekenova, Ognianova, palmitoleic, oleic, linoleic, linolenic or aleocharinae acid and other acids. Also suitable are monosaccharides and oligosaccharides.

In a preferred embodiment of the invention used according to the invention, the liquid substance is identical to the substance which is usually used for the manufacture intended to fill the reactor catalyst particles. The latter may be, for example, used for the manufacture of a catalyst binder, or one of the components of this binder. In this case, if the binding was not separated from the catalyst, as a rule, to refuse to sell the contact of the catalyst particles with a liquid substance before filling of the reactor. For carrying out the invention method, the contact of the catalyst in accordance with the conditions of its manufacture does not contain liquid substances which do contain a small amount of these substances, with the liquid substance, obviously, can be implemented by conventional methods, such as irrigation, water immersion, and so forth.

As the liquid substance is preferably used at least one liquid under normal conditions (at 20°C and a pressure of 1 ATM) water-soluble organic compound having a boiling point or temperature of sublimation of which at normal pressure (1 atmosphere) is more than 100°C. it is also preferable to use a liquid substance in the form of a composition containing at least one liquid under normal conditions (20°C and pressure 1 ATM) connection and one water-soluble organic compound having a boiling point or temperature of sublimation of which at normal pressure (1 atmosphere) exceeds 100°C. such mixtures include:

- a mixture of at least one liquid under normal conditions, water-soluble organic compounds with at least one dissolved solid organic compound,

- a mixture of water with at least one (solid or liquid) water-soluble organic compound.

Organic component used according to the invention, the liquid compositions preferably selected from polimernyh components, excluding the oligosaccharides, the use of which is valid.

Preferred liquid HDMI what Nations are the solutions used according to the European patent application EP-A 714700 as liquid binders which contain from 20 to 90 wt.%, water and from 10 to 80 wt.%, dissolved organic compounds. In this case, the content of organic component in the underlying liquid composition is preferably from 10 to 50 wt.%, first of all, from 20 to 30 wt.%.

Suitable organic components such liquid compositions, especially, are monatomic and polyatomic organic alcohols, such as ethylene glycol, 1,4-butanediol, 1,6-hexanediol or glycerol, monobasic or polybasic organic carboxylic acids, such as propionic, oxalic, malonic, glutaric, or maleic acid, aminoalcohols, such as ethanolamine or diethanolamine, organic monosubstituted amides or amides with a higher degree of substitution, such as formamide, or monosaccharides and oligosaccharides such as glucose, fructose, sucrose or lactose.

Organic components contained in the liquid compositions as liquid substances and components of such liquid substances, preferred are such compounds, the boiling point or temperature of sublimation of which at normal pressure is greater than the firing temperature used in forming the catalytically active m the ssy. Preferred are organic components, destruction with formation of gaseous components in the presence of oxygen in the catalytically active oxide mass is at a temperature lower than the firing temperature. As further explained below, an important feature of the proposed invention the method is that used to fill the reactor catalyst particles contain catalytically active mass and as such do not contain the original material for the catalytically active mass. Order to obtain a catalytically active mass similar to the original mass is usually subjected to heat treatment (so-called firing), providing its transformation into a catalytically active oxide mass. The firing temperature is usually less than 500°C., often less than 400°C. and usually less than 300°C. the firing Temperature of the source of the oxide mass, as a rule, is at least 150°C., preferably at least 200°C. and especially at least 250°C. According to the invention particularly preferred are liquid substances, the boiling point of which at normal pressure is above 100°C., preferably higher than 150°C.

Examples of preferably used liquids are glycerin and a mixture of glycerol and water.

Content is the liquid substance in prepared to fill the reactor the catalyst particles is preferably from 0.05 to 10 wt.%, particularly preferably from 0.1 to 5 wt.%, first of all, from 0.5 to 2 wt.%, in terms of the total weight of the catalyst particles.

The content of the liquid substance in reasonably good approximation can be determined by the weight loss of containing liquid catalyst particles occurring under heating up to 300°C for one hour in an atmosphere of air. If in contact with the liquid substance enters the finished catalyst (i.e. a catalyst with a fully formed during firing phases) before loading into the reactor, the content of liquid substances can also easily determine the difference in mass of the sample catalyst. Upon contact of the catalyst particles with a liquid substance, carried out directly in the process of their preparation, the content of the liquid substance can be determined on the basis of the total mass balance of the manufacturing process of the catalyst.

In a special embodiment of the invention is prepared to fill the reactor catalyst particles contain a liquid substance in the associated form. In accordance with the present invention under an associated liquid substance is meant a liquid environment, which catalyst contains due to physical interactions, such as adsorption. In the General case it is not located on the surface of the catalyst in the liquid phase, to whom I can be detected visually, that is, not exceeding the maximum degree of saturation of the catalyst particles.

According to the invention is used to fill the reactor catalyst particles contain only the catalytically active oxide mass and they are completely missing the original oxide mass. However, in accordance with the invention under a catalytically active multi-element oxide weight mean catalytically active mass, which contains the metals (and, if necessary, contained any other elements different from oxygen) mainly in oxide form (not in the form of basic metals). The maximum molar content of non-metals in the total number of all dierent from oxygen elements catalytically active multi-element oxide mass is preferably 10 mol.%, particularly preferably 5 mol.%. In a special embodiment of the invention it is a purely polymetallic oxide masses.

Used according to the invention the catalyst particles contain a catalytically active oxide mass, which is characterized in that when heated to commonly used when the firing temperature weight loss is mostly absent. The maximum weight loss of catalytically active mass contained in used according to the image is the shadow of the catalyst particles together with the material of the carrier (if present), when heated for one hour at 300°C in air is preferably 2.5 wt.%, especially preferably 2 wt.%, first of all, preferably 1.5 wt.%, in terms of the total weight of the catalytically active mass and the carrier (if present).

Multi-element oxide masses and methods of their manufacture in principle known and proposed in the invention method is not limited to using only certain polymetallic oxide masses. In the manufacture of a catalytically active mass usually come from well-known suitable sources of catalytically active mass, forming the most thoroughly mixed, preferably finely dispersed dry mixture, which is then subjected to firing and, if necessary, grinding to fine condition. For example, in the preparation of the active oxide masses originate from the oxides or of compounds which, when heated, if necessary, carried out in the presence of oxygen, can be converted into oxides. Suitable parent compounds are, for example, halides, nitrate, formate, oxalates, acetates, carbonates, hydroxides, and so forth. Thorough mixing of the starting compounds may be implemented in dry and wet form. In the case of mixing in a dry form of the parent compound, it is advisable to use the ü in the form of a fine powder, and after mixing and, if necessary, we perform preliminary pressing, to be fired. However, thorough mixing of the starting compounds is preferably carried out in a wet form. This is usually mixed with each other starting compound, in aqueous solution or suspension. Then the water mass is dried, and after drying, is subjected to firing. The drying process is preferably implemented in the form of spray drying. The obtained powder often has too high variance for direct further processing. In such cases, it can mix with the addition of water. The resulting kneaded mass is subjected to firing and subsequent grinding in a finely dispersed oxide active mass. Experts know the conditions of firing various possible oxide active mass. In this case, the firing can represent both the exothermic and endothermic process.

Below are examples of some preferred stechiometry multi-element oxide masses, designed to implement a separate vapor-phase reactions. Particularly suitable multi-element active mass of the catalysts for heterogeneously catalyzed partial vapor oxidation acrolein in acrylic acid, methacrolein in methacrylic acid, propylene to acrolein, and tre is-butanol, isobutane, isobutene or tert-butyl methyl ether in methacrolein along with other elements such as niobium (Nb) and/or tungsten (W), and molybdenum (Mo), vanadium (V) and copper (Cu) may additionally contain, for example, tantalum (TA), chromium (Cr), cerium (CE), Nickel (Ni), cobalt (Co), iron (Fe), manganese (Mn), zinc (Zn), antimony (Sb), bismuth (Bi), alkali metals such as lithium (Li), sodium (Na), potassium (K), rubidium (Rb) and cesium (Cs), hydrogen (H), alkaline earth metals such as magnesium (Mg), calcium (CA), strontium (Sr) and barium (BA), silicon (Si), aluminum (Al), titanium (Ti) and zirconium (Zr). Used according to the invention the multi-element active oxide weight along with oxygen, obviously, may also contain only niobium (Nb) and/or tungsten (W), and molybdenum (Mo), vanadium (V) and copper (Cu).

Catalytically active multi-element oxide mass, particularly suitable catalysts for vapor-phase oxidation of acrolein in acrylic acid, methacrolein in methacrylic acid and propylene to acrolein, have a total stoichiometry I:

in which

X1means tungsten, niobium, tantalum, chromium and/or cerium,

X2means copper, Nickel, cobalt, iron, manganese and/or zinc,

X3means antimony and/or bismuth,

X4means one or more alkali metal and/or hydrogen

X5means Odie is or more alkaline earth metals (Mg, Ca, Sr, Ba)

X6means silicon, aluminum, titanium and/or zirconium,

a represents a number from 1 to 6,

b denotes a number from 0.2 to 4,

by means of a number from 0.5 to 18,

d is a number from 0 to 40,

E. means a number from 0 to 2,

f denotes a number from 0 to 4,

g denotes a number from 0 to 40 and

n means the number determined by the valency and frequency different from the oxygen elements in I.

Manufacture of active polymetallic oxides I, including in terms of their firing, as described, for example, in German patent application DE-A 4335973. In this application the preferred variants of such active polymetallic oxides. For example, in the first preferred polymetallic oxides

X1means tungsten, niobium and/or chromium,

X2means copper, Nickel, cobalt and/or iron,

X3means antimony,

X4mean sodium and/or potassium,

X5mean calcium, strontium and/or barium,

X6means silicon, aluminum and/or titanium,

a represents a number from 2.5 to 5,

b denotes a number from 0.5 to 2,

by means of a number from 0.5 to 3,

d is a number from 0 to 2,

E. means a number from 0 to 0.2,

f denotes a number from 0 to 1,

g denotes a number from 0 to 15 and

n means the number determined by the valency and frequency different from the oxygen elements in I.

Predpochtitel the parameters are the following multi-element active oxide mass II:

in which

X1means tungsten and/or niobium,

X2mean copper and/or Nickel,

X5mean cobalt and/or strontium,

X6means silicon and/or aluminum,

a represents a number from 3 to 4.5,

b denotes a number from 1 to 1.5,

by means of a number from 0.75 to 2.5,

f denotes a number from 0 to 0.5,

g denotes a number from 0 to 8 and

n means the number determined by the valency and frequency different from the oxygen elements in II.

In addition, it is preferable to use multi-element oxide mass General formula III:

in which

X1mean Nickel and/or cobalt,

X2means thallium, an alkali metal and/or alkaline earth metal,

X3mean phosphorus, arsenic, boron, antimony, tin, cerium, lead, niobium and/or tungsten,

X4means silicon, aluminum, titanium and/or zirconium,

a represents a number from 0.5 to 5,

b denotes a number from 0.01 to 3,

with a mean number of 3 to 10,

d is a number from 0.02 to 2,

E. means a number from 0 to 5,

f denotes a number from 0 to 10 and

n means the number determined by the valency and frequency different from the oxygen elements in III.

Preparation of active polymetallic oxides III, including conditions of firing, is described in German application p is the awning DE-A 4023239. Shell catalysts manufactured using active polymetallic oxides III, above all, suitable for vapor-phase catalytic oxidative synthesis of acrolein from propylene. General reaction conditions for vapor-phase catalytic oxidation of propylene to acrolein are also given in the German patent applications DE-A 4023239 and DE-A 4431957. However, these shell catalysts with active polymetallic oxides of the formula III suitable for vapor-phase catalytic oxidative synthesis of methacrolein of tert-butanol, isobutane, isobutylene or tert-butyl methyl ether. General reaction conditions for the above reactions the catalytic vapor-phase oxidation is shown, for example, in German patent applications DE-A 4023239 and DE-A 4335172.

Proposed in the invention method is in principle suitable for filling the catalyst reactor of any structural type. Preferred properties proposed in the invention method are manifested primarily in the case of filling the reactor with a large length (for example, starting with 500 mm), which carried out from the top side through the use of gravity of the catalyst. This also applies to reactors with the aim of filling the catalyst is installed in such a way that their longitudinal side was situated PR is vertically property, however, exploiting such reactors in another, for example, a predominantly horizontal position. Reactors, fill proposed in the invention method is preferably characterized by the ratio of the average length in the vertical direction to the average length in the horizontal direction, comprising at least 1:1, especially at least 2:1 and particularly preferably at least 5:1. Preferred reactors are elongated hollow body having a cross-section, preferably round in shape.

Proposed in the invention method is preferably used to fill the reactor comprising at least one tube. The length of the tube reactor is preferably from about 500 to 20000 mm, particularly preferably from about 1000 to 10000 mm, an Inner diameter of the tube reactor is preferably from 5 to 100 mm, particularly preferably about 10 to 50 mm length of the tube reactor to its diameter is preferably from about 2 to 10,000, particularly preferably from about 5 to 7000.

The method is particularly preferably suitable for the filling of the reactors with design shell-and-tube reactor (tubular reactor with a large number of contact tubes). Reactors such constructive type usually with coat from the reservoir, generally cylindrical shape, in which is placed a large number (beam) tubes, usually located in a vertical position. Each of these tubes (contact tubes) filled with catalytically active mass intended for the catalytic vapor-phase reactions, or the original product for this active mass. The ends of the contact tubes are usually tightly fixed in intended for fastening the bottoms of the tubes, and the internal volume of the tubes pass into the inner space connected to the reactor covers (top, bottom cover respectively). Through these covers can be input, respectively output, passed through the contact tube gases, such as used for drying and/or firing oxygen-containing gas or reactive gas mixture. Through surrounding the contact tube space, you can skip the means for heat exchange, which allows heating of the contact tubes, respectively, to dissipate the reaction heat. In a suitable embodiment, tubular reactors contain at least 5000, preferably at least 10,000 tubes. In the usual design of the reactor, the number of contact tubes is, for example, from 15,000 to 30,000. As a means for heat exchange is suitable gaseous and liquid baths is stateroom environment, such as superheated steam and salt melts.

Average (largest) diameter of the catalyst particles in the range of from 1 to 40 mm, preferably from 2 to 30 mm, especially 3 to 20 mm Suitable solid catalysts consist of a catalytically active mass, which, if necessary, using a suitable binder, is formed into the extrusion, pelletizing, extrusion or other means, receiving molded articles, such as press articles, tablets or similar products. However, the catalytically active mass, you can add the usual tools, e.g. tools to improve slip, such as graphite or fatty acids (such as stearic acid), and/or tools to facilitate the forming and reinforcing agents such as fibers of glass, asbestos, silicon carbide or potassium titanate. In addition, as described above, before or after molding to the catalytically active mass can be added to a liquid substance or composition containing a liquid substance.

Proposed in the invention method is preferably suitable for filling of the reactor shell catalysts. Shell catalysts contain catalytic mass, supported on a carrier in the form of a shell. Such catalysts may have the form of beads, rings, cylinders, is Ubicom, rectangular parallelepipeds or bodies other geometric shape.

The materials of the carrier are preferably chemically inert substances, i.e., they mostly do not participate in the flow of vapor catalyzed reaction used shell catalysts. Suitable material particles of the medium (pH media) is aluminum oxide, silicon dioxide, silicates such as clay, kaolin, steatite, pumice, aluminum silicate, magnesium silicate, silicon carbide, oxide of zinc and thorium dioxide. Suitable commercially available media is steatite (Steatit With 220 CeramTec).

The surface pH of the media has mainly roughness, because the increased surface roughness, as a rule, leads to a stronger adhesion of the deposited layer from the oxide active mass with the body of the carrier. The surface roughness Rzthe pH of the medium is preferably from 30, 40 respectively, to 200 microns, preferably from 30, 40, and 100 ám (roughness determined according to DIN 4768, sheet 1, with the device "Hommel Tester" by Hommelwerke, intended for the measurement of surfaces according to DIN-ISO). These values of surface roughness, above all, preferred for use as a media product Steatit the 220 CeramTec. The material of the carrier may be a porous or non-porous. Preferred is a porous material medium (total pore volume in terms of the volume of the bodies of the carrier is less than 1 vol.%).

In principle proposed in the invention method is suitable body of the carrier of any geometrical shape. Their length usually ranges from 1 to 10 mm, However, it is preferable to use as a phone carrier beads or cylinders, first and foremost, hollow cylinders.

In the case of use as a phone carrier beads have diameters in the range of from 1 to 10 mm, especially 3 to 8 mm

In the case of use as a phone carrier cylinder length is preferably from 2 to 10 mm and the outer diameter is preferably from 4 to 10 mm In the case of rings for these parameters should be added wall thickness, which is usually from 1 to 4 mm, Especially preferred are the annular body of the carrier, the length of which is 3 to 6 mm, outer diameter 4 to 8 mm and wall thickness from 1 to 2 mm, Even more preferred are rings with dimensions of 7 mm × 3 mm × 4 mm (external diameter × length × inner diameter).

Suitable thickness is deposited on the body of the carrier shell of catalytically active mass or the corresponding initial mass usually is from 10 to 1000 μm. The preferred thickness, especially in the case of annular bodies of media that corresponds to the interval from 10 to 500 μm, particularly preferably from 100 to 500 μm and more preferably from 200 to 300 microns.

The body of the catalyst can be manufactured by known methods. While it is preferable to use a binder containing the above liquid substance, and non-drying, leading to complete or mostly complete removal of liquid substances. Partial drying can be carried out, for example, by heating to a temperature component is not more than 150°C., preferably not more than 120°C. the Drying may be accompanied by additional passing the gas stream through the particle. Drying time preferably does not exceed 60 minutes and particularly preferably does not exceed 30 minutes.

Catalyst particles containing the above liquid substance, for example, in associated form, have a high stability under the influence of mechanical loads. In the General case, their mechanical stability exceeds the stability of the catalyst particles produced in a similar method, but subjected to additional drying aimed mostly complete removal of liquid substances.

Mechanical stability of the prepared particles was pushing the congestion estimate due to the next test. A portion of the catalyst mass of 20 g is lowered into the tube with a length of 3.5 m (material RST 37.8), the diameter of which clearance is 25 mm, the Catalyst falls in a porcelain Cup, tightly attached to the lower end of the tube, and in case of three tests it is separated from the formed during the blow dust and again lowered into the tube. Measure the resistance of the catalyst to abrasion is the total loss of mass of the catalyst after a single, correspondingly multiple tests fall.

The maximum weight loss of the prepared catalyst particles when tested in the fall of preferably 0.8 wt.%, particularly preferably 0.7 wt.%, first of all, 0.6 wt.%. When a single drop test weight loss used according to the invention the catalyst compared to a catalyst of similar composition but not containing liquid, less preferably at least 0.9 wt.%, especially preferably, at least 5 wt.%, first of all, at least 10 wt.%. Despite a threefold repetition of the test in the fall of the same prepared according to the invention the catalyst particles, the maximum loss of mass is preferably 3 wt.%, particularly preferably 2.5 wt.%, first of all, 2 wt.%. Weight loss is used according to the invention catalyst than catalyst similarly, what about the composition, but not containing fluid defined at three times the repetition of the test in the fall, can be reduced preferably at least 3 wt.%, especially preferably, at least 15 wt.%, first of all, at least 30 wt.%.

Loose weight loaded proposed in the invention by way catalysts in the dried state is characterized by a less dense and more loose packing (lower bulk weight). The pressure loss in the completed proposed in the invention method reactors is less than the pressure loss in the reactor filled with dry catalyst particles.

Regardless of the type and composition of the catalytically active material of the particle shell catalyst, in principle, can be prepared through the implementation of a contact carrier with a liquid binding agent and a catalytically active mass, and the media put a layer of active mass, and then, if necessary, carry out partial removal of the binder. For the preparation of catalyst particles of catalytically active material is applied in its ready catalytically active form, for example in the form of already subjected to calcination of the mixed oxide. For the preparation of catalyst particles in a technical scale, it is recommended to use, for example, proposed in the German patent application Pat on the HT DE-A-2909671 technique, optionally, instead of using water more of the above liquid binder. The preferred implementation of such technology is described in European patent application EP-A 714700. Under this option the media moisturize first liquid binder, then hold the contact carrier with dry finely dispersed active mass of the catalyst, securing the layer of pulp on the wetted surfaces of the particles of the medium, and then, if necessary, remove a portion of the liquid binder. In a special embodiment of the invention the operation of the humidifying media, its contact with the active mass of the catalyst and removal of the liquid binder is performed once or repeatedly until the deposited layer will not reach the required shell catalyst thickness. When this liquid binder can be completely removed before making the last of the repeated operations of the application.

In a preferred embodiment of the invention intended for the application of the active weight of the carrier preferably loaded into an inclined rotary vessel (for example, rotating a disk device or the drageeing tank), the slope of which typically ranges from 30 to 90°. Rotating the tank moves the bodies of the media, especially, spherical or cylindricus the th forms (primarily hollow cylinders) under two located at a certain distance from each other dosing devices. In a suitable embodiment, the first such device is a nozzle through which irrigation and controlled hydration rolling in the rotating disk device of the bodies of the media to be used in accordance with the invention a liquid binder. The second metering device is located outside the cone of the spray of liquid binder and intended for the introduction of finely dispersed active mass (for example, by tilting tray or feed auger). Controlled moist body media absorb supplied to the tank powdered active mass, which by rolling a cylindrical or spherical bodies media is sealed at their outer surface, forming the associated shell. (In the inner contour of the hollow cylindrical carrier particles such sealing movement is absent, and therefore the inner surface of such particles remains largely uncovered. However, this disadvantage can be eliminated, for example, by applying the method of squeezing the application, for example, using ultrastructure coating company Aeromatic Fielder, SN).

During subsequent rotation of the inclined cutting the upstream reservoir provided with a base coating of the body of the carrier, if necessary, again passed through the atomizer, exposing them to controlled wetting, so that during further movement they can absorb the additional layer of finely dispersed active mass, and so forth (intermediate drying is generally not required). A particular advantage of the above variant of the invention consists in the fact that the implementation of a single process operations used to produce catalysts, membranes which consist of two or more layers of active mass of different types.

The advantage of the considered variant of the preparation to be loaded into the reactor catalyst particles is controlled wetting the coated surface of the bodies of the media and get the shell catalysts. When this moisture is advisable to be implemented so that the liquid binder, although adsorbirovannoi on the surface of the bodies of the media, however, it, respectively, on the surface of the deposited layers, there was no visually detectable liquid phase. The application of the described variant allows to obtain catalyst particles containing exactly the specified amount of liquid associated binder. The maximum amount of liquid corresponding to the maximum degree of saturation of its catalyst particles. Ka is indicated above, in accordance with the proposed invention by way of contact with the liquid substance, obviously, you can also expose the catalyst particles obtained by any method, and then use the prepared catalyst to fill the reactor.

The maximum temperature of the reactor and catalyst particles during filling of the reactor is preferably 50°C., particularly preferably 40°C. and, above all, 30°C. In a preferred embodiment, the reactor is filled with catalyst at ambient temperature. Filling the reactor with catalyst particles in the General case is downloading via the upper side of the reactor hole and subsequent lowering under the action of gravity. The filling of the reactor with catalyst particles preferably carried out mainly at a constant speed, first of all, using a suitable filling device. For filling the tubular reactor is preferably used for filling the device, allowing time to fill a catalyst for multiple handsets. Such devices, for example, provided with a feeding hopper with multiple compartments, the catalyst particles of which extend in an oblique swinging chute. Due to vibration cazaudehore gutters catalyst particles uniformly slip on it and pad the Ute through the corresponding slots in below the tube. Suitable devices for loading catalyst particles into the tubular reactor described in the German patent applications DE-A-2511411, DE-A-2849664, European patent application EP-A-041144 and German patent applications DE-A-19934324, DE-A-10250022. These documents are used in the present description as a reference. Especially preferred is the use described in the German patent application DE-A-19934324 device for loading bulk materials into tubes, which are equipped with a certain number of collections of granular material and located underneath the transport chute, in which the bulk material is fed under the action of vibration and comes to a place out, and it is possible to batch fed into the transport chute of loose material. In addition, it is possible to achieve advantages through the use proposed in the German patent application DE-A-10250022 device for filling, which consists of many startup items, and therefore, especially suitable for filling tubular reactors with a large number of contact tubes.

Proposed in the invention, the method preferably allows to refuse from the use of assistive devices for filling of the reactor, which causes a decrease in the rate of fall of the particles of the catalyst.

According to a preferred variant domestic the invention before use filled with a catalyst reactor for the implementation of catalytic vapor-phase reactions to first perform the processing of the catalyst, the purpose of which is to remove at least part of the liquid substance and, if necessary, other volatile components present, such as other components of the binder. Such processing may be performed, for example, by heating the reactor to elevated temperature (usually part of from 50 to 220°C) and/or passing through it, the gas stream. In the most simple embodiment, the liquid substance, and, optionally, other components present are removed, due to the effect of suitably temperature of hot gases. As such gas in the General case, use of oxygen-containing gas, primarily oxygen. The temperature of the reactor, as a rule, should not be higher than the firing temperature, which is carried out during manufacture of the oxide of the active mass. As a rule, it is sufficient heating of the reactor to a temperature below the firing temperature, since water and most organic solvents, as well as numerous organic components of the binder to be used as the oxide catalyst masses and in the presence of oxygen into gaseous components, such as formic acid, acetic acid, water vapor, carbon dioxide or carbon monoxide. Thus, as a rule, has what I can this heat treatment, carried out in order to remove liquid substances, and, if necessary, other components, which resulted in the stream leaving the reactor gas can be discharged into the atmosphere without additional processing.

In a typical embodiment of the invention the filled reactors proposed in the invention method, used in the production of the plant designed, for example, a vapor-phase catalytic oxidation of acrolein in acrylic acid. Such production units typically consist of one or more connected in parallel production lines. Each production line, in turn, may consist of one or more series-connected reactors. The products of the catalytic vapor-phase reaction of each of the reaction lines can be subjected to individual or joint processing, such as separation or purification usual methods known in the art. For efficient operation intended for processing plants, for example, commonly used distillation columns containing the reaction product streams from two or more production lines are often sent for joint processing. Proposed in the invention method is particularly preferably suitable for effective ek is operating production units, includes two, three or more parallel connected production line, and to replace the catalyst after a certain period of his service disables only one corresponding individual line, continuing the synthesis of the product on other lines. Due to the possibility of ongoing proposed in the invention by way of, nevertheless, the uniform filling of the reactor with the catalyst without the destruction and/or abrasion of the production loss can be reduced to a minimum level.

In a suitable embodiment of the invention filled with fresh catalyst to the reactor, respectively connected in series in the production line reactors, in order to remove liquid substances and, if necessary, present the other binder components, is heated by passing through the reactor hot gas, usually air, with simultaneous removal from the reactor volatile components. The flow passed through each tube of gas is, for example, from about 0.8 to 1.2 Nm3/H. As noted above, emerging from the reactor exhaust air can be discharged to the atmosphere. Thermal processing reactor is preferably carried out with a temperature gradient that allows you to avoid impacts on the reactor and loaded catalyst if the com big load due to the strong short-term heating. The heating rate is preferably not more than 10°C per hour. For example, the first reactor can be heated air, the temperature of which is less than 100°C and is, for example, in the range from 50 to 90°C. the temperature Difference at the inlet to the reactor and the exit from it (measured respectively at the inlet and outlet gas flow), as a rule, should not exceed 120°C, preferably 90°C. is Used to heat the reactor gases can be heated using conventional devices, such as a gas compressor or heated water vapor heat exchanger. Upon reaching a sufficiently high temperature reactor further heating may be accomplished through the normally surrounding the contact tube means for heat exchange, such as molten salt. The heating of such tools can be implemented using electricity, for example, through placed in the medium for heat exchange of electric heaters. For further heating of the reactor instead of air through it, you can also skip another gas, preferably oxygen-enriched air. For complete removal of liquid substances and, if necessary, other components connecting the reactor is heated to a sufficiently high temperature of approximately 160 do220°C, over a long enough period of time, approximately 12 to 72 hours. After the exit of the reactor will be the predominant absence of liquid substances, the binder components or products of their degradation, reactor, respectively production line, you can reconnect to the reaction path, be heated to the required initial temperature and to start feeding the source gas.

Another object of the present invention is a reactor that can be filled with catalyst particles using the above method.

In connection with the above preferred features download catalyst such reactors are perfectly suitable for the implementation of catalytic vapor-phase reactions.

The object of the present invention is also the application of the proposed invention is a reactor for the implementation of catalytic vapor-phase reactions, first of all, to obtain an unsaturated aliphatic carboxylic acids or aldehydes vapor-phase oxidation of aldehydes, alkanes or alkenes, to obtain NITRILES by ammoxidation of Alamanov or alkenes, for the preparation of aromatic carboxylic acids or the corresponding anhydrides vapor-phase oxidation of aromatic hydrocarbons, as well as for reactions E. the oxidation and hydrogenation.

In a preferred embodiment of the invention proposed in the invention reactors after filling in the appropriate catalyst is used to produce acrylic acid catalyzed vapor-phase oxidation of acrolein. In this synthesis, at least partially, especially completely carried out in the above reactor. Polymetallic oxides suitable for vapor-phase catalytic oxidative synthesis of acrylic acid from acrolein discussed above and are well-known catalysts. The reaction conditions for vapor-phase catalytic oxidation of acrolein in acrylic acid is described, for example, in German patent application DE-A-4335973. Used according to the invention catalysts are also suitable for obtaining acrylic acid in a stationary catalyst bed loaded in the reactor with a large number of contact tubes, the space around which circulates the medium for heat exchange (similar to the reactor described in the German patent application DE-A-4431949).

For the synthesis of acrylic acid vapor-phase catalytic oxidation of acrolein you can use acrolein, in turn, synthesized by catalytic vapor-phase partial oxidation of propylene. For the oxidation of propylene can also be used filled according to the invention the reactor Containing the acrolein reaction gases, obtained by the oxidation of propylene, can be used to obtain acrylic acid, as a rule, without intermediate purification. In this case, between the corresponding reaction stages, if necessary, you can perform the cooling of the reaction gases.

As the oxidizing agent for the oxidation of acrolein in acrylic acid and propylene to acrolein) preferably use oxygen, in an expedient embodiment, diluted with inert gases, such as oxygen in air or preferably in the form of so-called thin air (air with low oxygen content). Suitable oxidizing agents are also gases containing oxygen in the bound form, such as the N2O. Suitable dilution gases are, for example, nitrogen, carbon dioxide, hydrocarbons, recycled spent reaction gases of the process of synthesis of acrylic acid or acrolein and/or water vapor. In a suitable embodiment, the partial oxidation of acrolein in acrylic acid volume ratio of acrolein:oxygen:steam:inert gas is set in the range of 1:(1-3):(0-20):(3-30), preferably 1:(1-3):(0.5 to 10):(7-18). The reaction pressure in the range of about 1 to 3 bar, the total flow of the reaction gas is preferably from 1000 to 4000 Nl/l/h the Reaction temperature is usually in the range from about 230 to 330°C. In a suitable embodiment of the invention acrylic acid synthesize a vapor-phase catalytic oxidation of acrolein carried out as described above, at the production plant consisting of one or more production lines. In this case, the filled reactors proposed in the invention method and heated by the hot air stream may be again subjected to exploitation as part of the production installation. For this purpose, if necessary, it is possible for a short time to stop the synthesis of the product on other production lines. Svezhezavarennogo production line from the outlet side of the reaction gases is again connected to a device for the separation of the last set required for the synthesis of acrylic acid, the ratio of oxygen to inert gas, regulating the flow of used air, and then fed to the reactor gas stream is injected acrolein.

Downloadable proposed in the invention by way catalysts, primarily suitable for vapor-phase catalytic oxidative synthesis of acrolein from propylene. General reaction conditions for vapor-phase catalytic oxidation of propylene to acrolein is shown, for example, in German patent applications DE-A-4023239 and DE-A-4431957 used in the present description as a reference.

The loaded is proposed by the invention by way catalysts suitable for vapor-phase catalytic oxidative synthesis of methacrolein of tert-butanol, Isobutanol, isobutylene or tert-butyl methyl ether. The General reaction conditions of the above processes, a vapor-phase catalytic oxidation is shown, for example, in German patent applications DE-A-4023239 and DE-A-4335172.

In addition, downloadable proposed in the invention method suitable catalysts for partial oxidation of aromatic hydrocarbons to carboxylic acids and/or anhydrides of carboxylic acids. Used as educt aromatic hydrocarbons are, for example, benzene, toluene, isomers of xylene, naphthalene, and so forth. In this case, receive, for example, benzoic acid, maleic anhydride, phthalic anhydride, isophthalic acid, terephthalic acid or the anhydride pyromellitic acid. As for the industrial synthesis, it is of particular importance vapor-phase partial oxidation of o-xylene into phthalic anhydride.

For vapor-phase oxidation of aromatic hydrocarbons to carboxylic acids and/or anhydrides of carboxylic acids preferably used catalysts, the catalytically active material which contains titanium dioxide (preferably anatase modification), oxide derivatives of vanadium, first of all, vanadium pentoxide, niobium (V2O5), and, if necessary, the oxide promoters, for example, on the basis of alkali metals, alkaline earth metals, thallium (Tl), aluminum (Al), zirconium (Zr), iron (Fe), Nickel (Ni), cobalt (Co), manganese (Mn), tin (Sn), silver (Ag), copper (Cu), chromium (Cr), molybdenum (Mo), tungsten (W), iridium (Ir), tantalum (TA), Nickel (Ni), arsenic (As), cerium (CE) and/or phosphorus (P). For vapor-phase oxidation of aromatic hydrocarbons are preferably used shell catalysts. Suitable catalytic compositions and methods for their manufacture are described, for example, in German patent application DE-A-2546268, European patent application EP-A-286448, German patent application DE-A-2547624, European patent application EP-A-163231, German patent application DE-A-2830765 and international application WO 98/37967.

For vapor-phase oxidation of use containing molecular oxygen in the reaction gas. The reaction gases, along with oxygen, can also contain suitable reaction retarders and/or diluents, such as water vapor, carbon dioxide and/or nitrogen. In the General case, the reaction gas preferably contains from 1 to 100 mol.%, particularly preferably from 2 to 50 mol.%, first of all, 10 to 30 mol.% the oxygen. The reaction gas may further contain up to 30 mol.%, preferably up to 10 mol.% water vapor, and from 0 to 50 mol.%, preferably from 0 to 1 mol.% of carbon dioxide. The reaction gas may be added to 100 mol.% the nitrogen. Directed into the reactor, the reaction gas contains, for example, from 5 to 120 who/Nm 3preferably from 60 to 120 g/Nm3and especially from 80 to 115 g/Nm3subject to the oxidation of aromatic hydrocarbons.

The reaction temperature in the range of from 300 to 450°C., preferably from 320 to 420°C and, above all, from 340 to 400°C. the Reaction is usually carried out at a pressure in the General case, comprising from 0.1 to 2.5 bar, preferably from 0.3 to 1.5 bar. Space velocity in the range of from 750 to 5000 h-1.

Vapor-phase oxidation can be performed with a single standard reaction temperature or separated at a temperature zone of the reactor. When two or more zones in the reaction tube of a catalyst thermostatic at different reaction temperatures. Suitable for this, for example, reactors with separate salt baths, as described, for example, in German patent applications DE-A-2201528 and DE-A-2830765. When carrying out the synthesis in two reaction zones (e.g., as described in the German patent application DE-A-4013051) adjacent to the entrance of the reaction gas reaction zone, which in General contains from 30 to 80 vol.% from the total amount of catalyst, in the General case thermostatic at a temperature which is higher than the reaction temperature of the reaction zone adjacent to the outlet of the reaction gas from the reactor, the amount of 1 to 20°C, pre is respectfully from 1 to 10°C and first of all, from 2 to 8°C. Such an operating mode referred to as a two-band or multi-band structuring of the reactor.

Similar technology can be used for the oxidation of toluene to benzoic acid, initially formed mixture consisting of neprevyshenie toluene, benzoic acid and benzaldehyde. In another embodiment, if necessary, you can also select benzaldehyde as a by-product.

Catalyst loading proposed in the invention method, especially suitable for replacement of the catalyst is carried out in accordance with the international application WO 2004009525 A1. After partial replacement of the catalyst to carry out the removal of liquids and, if necessary, present a different binder in accordance with the above proposed in the invention, without prejudicing the quality is not superseded layer the rest of the catalyst present in the reactor to replace.

Below the invention is explained in more detail by examples, not limiting the scope of the invention.

Examples

I. Manufacture of shell catalysts

Example 1 (comparative)

The original mass, intended for forming the active multi-element oxide mass with the stoichiometric composition Mo12V3W1,2Cu2,4Ox, the floor is Ali in accordance with example A) of German patent application DE-A-10360057 and was subjected to heat treatment in a rotary tubular furnace, carried out as described in example C) said application, receiving the catalytically active mass. Received the catalytically active mass was crushed in dual mill BQ 500 company Hosokawa-Alpine Augsburg in fine powder, 50% of the particles which passed through the sieve mesh size from 1 to 10 μm, and the content of particles with a longitudinal size larger than 50 μm in this fraction was less than 1%.

28 kg annular phone carrier of steatite (external diameter 7 mm, length 3 mm, inner diameter 4 mm) with surface roughness (Rz), part 45 μm, and a pore volume in terms of the volume of the phone carrier, constituting less than 1% vol. (manufacturer company Hoechst Ceramtec, Germany)were loaded into the drageeing tank Hicoater (firm Lödige, Germany) with an angle of 90° and the inner volume of 200 liters. Then the drageeing tank was brought into rotation with a frequency of 16 rpm Body media within 25 minutes by Schlick nozzle type (0.5 mm, 90°) watered 2000 g of a solution consisting of 75 wt.%, water and 25 wt.%, glycerol. At the same time within a specified period of time through the swinging chute located on the outside of the nozzle spray nozzle, continuously they dosaged 10,35 kg catalytically active material. In the process of applying entered in the drageeing tank powder of the active material is completely settled on the surface the surface pH of the medium, moreover, the agglomeration of finely dispersed oxide active mass was absent. Upon completion of the feed powder and a binder during the rotation of the drageeing tank with a speed of 2 rpm it within 20 minutes blew heated to 110°With air. Then the catalyst in the form of a stationary granular mass was subjected carried out within two hours drying in lattice furnace in air atmosphere at a temperature of 250°C.

Example 2 (according to the invention)

Repeating example 1, but excluded the two-hour drying of the catalyst in the lattice oven at 250°C.

Example 3 (comparative)

The original mass, intended for forming multi-element oxide mass with the stoichiometric composition (Mo12Vof 3.46W1,39)0,87(CuMo0,5W0,5O4)for 0.4(CuSb2O6)for 0.4received in accordance with example 5 of German patent application DE-A-10360058 and was subjected to heat treatment in a rotary tubular furnace, receiving the catalytically active mass. Received the catalytically active mass was crushed in dual mill BQ 500 company Hosokawa-Alpine Augsburg in fine powder, 50% of the particles which passed through the sieve mesh size from 1 to 10 μm, and the content of particles with a longitudinal size larger than 50 μm in this fraction was less than 1%. Shell catalyst obtained from Catalytica the key active mass was formed, as described in comparative example 1.

Example 4 (according to the invention)

Repeating example 3, however, ruled out a two-hour drying of the catalyst in the lattice oven at 250°C.

II. Production and technical characteristics of the catalysts

a) drop Test

20 g of the catalyst was lowered into the tube is 3.5 m in length with a diameter lumen, comprising 25 mm Catalyst, falling directly under the tube Cup, was separated from formed in the fall of dust and again lowered into the tube. Total weight loss is achieved due from one to three times of trials served as a measure of the strength of the catalyst attrition. The results are given in table 1.

Table 1
The number of repeat fallsMass loss of active mass [wt.%]
Example 1 (comparative)Example 2 (according to the invention)Example 3 (comparative)Example 4 (according to the invention)
10,930,560,900,59
22,991,332,441,19
34,351,993,291,89

1. The way of filling the reactor with catalyst particles, at least the surface of which is provided with a catalytically active multi-element oxide by weight, whereby carry out the preparation of catalyst particles containing liquid at a temperature of 20°C and a pressure of 1 ATM substance and content of the liquid substance is from 0.05 to 10 wt.%, and download the prepared catalyst particles in the reactor.

2. The method according to claim 1, whereby the catalyst particles are selected from the group comprising a molded body containing at least one catalytically active multi-element oxide mass, and particles containing at least one catalytically active multi-element oxide mass supported on a carrier in the form of a shell.

3. The method according to claim 1, and a liquid substance selected from the group comprising water and organic compounds with a boiling point at a pressure of 1 ATM 100°C.

4. The method according to claim 1, the reactor comprises at least one tube.

5. The method according to claim 4, the length of the tube reactor is from 00 to 20000 mm, preferably from 1000 to 10000 mm

6. The method according to claim 4, with the inner diameter of the tube reactor is from 5 to 100 mm, preferably from 10 to 50 mm

7. The method according to claim 4, and the ratio of the length of the tube reactor to its diameter is in the range from 2 to 10,000, preferably from 5 to 7000.

8. The method according to claim 4, wherein the reactor is a tubular reactor (a reactor with a large number of contact tubes).

9. The method of claim 8, whereby the tubular reactor contains at least 5000 tubes.

10. The method according to claim 1, whereby the liquid content of the substance prepared in the catalyst particles is from 0.1 to 5 wt.% in terms of the total weight of the catalyst particles.

11. The method according to claim 1, and a maximum reduction of weight of the prepared catalyst particles when they drop tests (dropping 20 g of the catalyst particles in a tube with an inner diameter of 25 mm and a length of 3500 mm) 0.8 wt.%, preferably 0.7 wt.%.

12. The method according to claim 1 and a maximum weight loss of the same binder containing catalyst particles with three replications tested in the fall is 3 wt.%, preferably 2.5 wt.%.

13. The method according to claim 1, with an average outer diameter of the binder containing catalyst particles is from 1 to 40 mm, preferably from 2 to 30 mm, especially 3 to 20 mm.

14. The method according to claim 1, and preparation, is the catalyst particles is carried out, exposing the contact carrier with a binder containing liquid at 20°C and a pressure of 1 ATM substance or consisting of this substance, and then, if necessary, removing the part of the binder.

15. The method according to 14, according to which the first media hydrate containing liquid binder, then on the wetted surfaces of the bodies of the media clip layer in the active mass of the catalyst, subjecting the body contact carrier with dry finely dispersed active mass of the catalyst, and then, if necessary, remove a portion of the liquid binder.

16. The method according to clause 15, in accordance with which the manufacturing operation, including hydration carrier, his contact with the active mass of the catalyst and removal of the liquid binder, carry from one to several times, with the last repetition of the specified operation of the liquid binder can be removed completely.

17. The method according to claim 2, in accordance with which the use of the body of the carrier with a surface roughness Rzfrom 40 to 100 microns.

18. The method according to claim 2, in accordance with which the use of the body of the carrier with the maximum total pore volume comprising 1% of the volume of the bodies of the media.

19. The method according to claim 1 and a maximum reactor temperature and catalyst particles during filling of the reactor is 50°C, preferably 40°C, first of all, 30°C.

20. SPO is about according to claim 1, in accordance with which the reactor is filled by the introduction of catalyst particles located in the upper part of the reactor hole and the subsequent lowering of the catalyst particles in the reactor under the action of gravity.

21. The method according to claim 20, and in the reactor there is no auxiliary device for filling, lowering the speed of lowering of the catalyst particles.

22. The method according to claim 1, whereby the filled reactor is subjected to processing to remove liquid substance.

23. The method according to one of claims 1 to 22, in accordance with which the filled reactor used for vapor-phase catalytic oxidative synthesis of acrylic acid from acrolein.

24. The method according to one of claims 1 to 22, in accordance with which the filled reactor used for vapor-phase catalytic oxidative synthesis of methacrylic acid from methacrolein.

25. The method according to one of claims 1 to 22, in accordance with which the filled reactor used for vapor-phase catalytic oxidative synthesis of acrolein from propylene.

26. The method according to one of claims 1 to 22, in accordance with which filled the reactor used for the synthesis of carboxylic acids and/or anhydrides of carboxylic acids by vapor-phase catalytic oxidation of aromatic hydrocarbons.

27. The method of synthesis of acrylic acid vapor is analiticheskii oxidation acrolein, moreover, at least part of the synthesis is carried out in a reactor filled with catalyst particles by the method according to claims 1 to 22.

28. The use of a reactor filled with catalyst particles by the method according to claims 1 to 22, for the implementation of catalytic vapor-phase reactions, especially for the synthesis of unsaturated aliphatic carboxylic acids or aldehydes vapor-phase oxidation of aldehydes, alkanes or alkenes, synthesis of NITRILES by ammoxidation of alkanes or alkenes, synthesis of aromatic carboxylic acids or anhydrides of aromatic carboxylic acids by vapor-phase oxidation of aromatic hydrocarbons, as well as for the implementation of the epoxidation reactions or hydrogenation.



 

Same patents:

FIELD: process engineering.

SUBSTANCE: invention relates to rectification separation of fluid containing acrylic acid whereat said fluid is fed through loading point to rectification column and mass flow is discharged there through at discharge point arranged above said loading point. Content of acrylic acid in said mass flow in terms of mass flow weight makes ≥90 % by weight and exceeds acrylic acid content in fluid in rectification column zone located at least two theoretical separation stages above said loading point. Content of di-acrylic acid in reflux in terms of reflux weight in at least partial zones, makes ≥550 ppm by weight. Note here that said content of di-acrylic acid in reflux is defined from the presence of Bronsted acid with pKa ≤ 16 in fluid containing acrylic acid, or at least one Bronsted base with pKb ≤ 10, and/or adding to reflux of at least one compound from the group comprising aforesaid Bronsted acid with pKa ≤ 16, Bronsted base with pKa ≤ 10, di-acrylic acid and acrylic acid that contains acrylic acid. That is, mass flow enriched with acrylic acid is discharged from rectification column at the point above loading point while radial polymerisation is inhibited by di-acrylic acid at rectification column top.

EFFECT: efficient separation of fluids.

23 cl, 3 ex

FIELD: chemistry.

SUBSTANCE: invention relates to an improved method of continuous, heterogeneous, catalytic, partial gas-phase oxidation of at least one organic compound selected from a group comprising propene, acrolein, isobutene, methacrolein, isobutene and propane, in an oxidation reactor loaded with a gas mixture which, along with at least one compound to undergo partial oxidation and molecular oxygen as an oxidation agent, includes at least one diluent gas which is essentially inert in conditions of heterogeneous, catalytic, gas-phase partial oxidation, where the source of oxygen and inert gas for the loaded gas mixture is air which is compressed in a compressor beforehand from a low initial pressure value to a high final pressure value, where before entering the compressor, the air undergoes at least one mechanical separation procedure through which particles of solid substance dispersed in the air can be separated.

EFFECT: method prevents negative effect of solid particles on the air compression stage, undesirable increase in pressure loss and reduction of activity or selectivity of the catalyst.

21 cl, 2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method for prolonged heterogeneously catalysed partial oxidation of propene to acrylic acid in gaseous phase, in which the initial gaseous reaction mixture 1, containing propene, molecular oxygen and at least one inert gas, where molecular oxygen and propene are in molar ratio O2:C3H6≥1, is first passed through a fixed catalyst bed 1 at high temperature at the first stage of the reaction, where the active mass of the catalysts is at least one multimetal oxide, containing molybdenum and/or tungsten, as well as at least one element from a group consisting of bismuth, tellurium, antimony, tin and copper, so that, conversion of propene in a single passage is ≥93 mol % and associated selectivity of formation of acrolein, as well as formation of acrylic acid by-product together is ≥90 mol %, temperature of the product gaseous mixture 1 leaving the first reaction stage is reduced if necessary through direct and/or indirect cooling, and if necessary, molecular oxygen and/or inert gas is added to the product gaseous mixture 1, and after that, the product gaseous mixture 1, acting as initial reaction mixture 2, which contains acrolein, molecular oxygen and at least one inert gas, where molecular oxygen and acrolein are in molar ratio O2:C3H4O≥0.5, is passed through a second fixed catalyst bed 2 at high temperature at the second reaction stage, where the active mass of the catalysts is at least one multimetal oxide, containing molybdenum and vanadium so that, conversion of acrolein in a single passage is ≥90 mol % and selectivity of the resultant formation of acrylic acid at both stages is ≥80 mol % in terms of converted propene, and temperature of each fixed catalyst bed is increased independently of each other. Partial oxidation in gaseous phase is interrupted at least once and at temperature of fixed catalyst bed 1 ranging from 250 to 550°C and temperature of fixed catalyst bed 2 ranging from 200 to 450°C, gaseous mixture G, which consists of molecular oxygen, inert gas and water vapour if necessary, is first passed through fixed catalyst bed 1, and then, if necessary, through an intermediate cooler and then finally through fixed catalyst bed 2, in which at least a single interruption takes place before temperature of the fixed catalyst bed 2 increases by 8°C or 10°C, wherein prolonged increase of temperature by 8°C or 10°C, is possible when virtual passage of temperature of the fixed catalyst bed in the period of time on the leveling curve running through the measuring point using the Legendre-Gauss method of the least sum of squares of errors, temperature increase of 7°C or 10°C is achieved.

EFFECT: method increases service life of catalyst.

24 cl, 1 ex, 3 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to improved method of carrying out heterogenous catalytic partial oxidation in gas phase of acrolein into acrylic acid, during which reaction gas mixture, containing acrolein, molecular oxygen and at least one inert gas-thinner, is passed through having higher temperature catalytic still layer, whose catalysts are made in such way that their active mass contains at least one oxide of multimetal, containing elements Mo and V, and in which during time, temperature of catalytic still layer is increased, partial oxidation in gas phase being interrupted at least once and at temperature of catalytic still layer from 200 to 450°C acrolein-free, containing molecular oxygen, inert gas and, if necessary, water vapour, as well as, if necessary, CO, gas mixture of G oxidative action is passed through it, at least one interruption being performed before increase of catalytic still layer temperature constitutes 2°C or 4°C or 8°C or 10°C during a long period of time, temperature increase constituting 2°C or 4°C or 8°C or 10°C over a long period of time occurring when in plotting factual course of temperature of catalytic still layer during time on laid through measurement points equation curve according to elaborated by Legendre and Gauss method of the least sum of error squares 2°C or 4°C or 8°C or 10°C temperature increase is achieved.

EFFECT: ensuring spread of hot point with time which is less than in previous methods.

21 cl, 3 dwg, 1 ex

FIELD: chemistry.

SUBSTANCE: method of (meth)acrolein or (meth)acrylic acid production is implemented by of catalytic phase oxidation reaction of propane, propylene, isobutylene or (meth)acrolein with oxygen-containing gas. Non-organic salt is used as heat carrier for reaction temperature adjustment. Pipeline for heat carrier feeding has adjustment valve adjusting heat carrier feed and circulation rate and rotating freedom of rotation axis. Rotation axis adjoins case with capability of sliding against each other. Gasket filling material sealing the case of adjustment valve is based on mica.

EFFECT: high-precision temperature adjustment ensuring stable process of gas phase catalytic oxidation.

5 cl, 5 dwg, 2 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to an improved method for synthesis of acrolein or acrylic acid or their mixture. Method involves at step (A) propane is subjected for partial heterogenous catalyzed dehydrogenation in gaseous phase to form a gaseous mixture A of product comprising molecular hydrogen, propylene, unconverted propane and components distinct from propane and propene, and then from a gaseous mixture of product from step (A) distinct from propane and propylene at least partial amount of molecular hydrogen is isolated and a mixture obtained after this isolation is used as a gaseous mixture A' at the second step (B) for loading at least into one oxidation reactor and in at least one oxidation reaction propylene is subjected for selective heterogenous catalyzed gas-phase partial oxidation with molecular oxygen to yield as the end product of gaseous mixture B containing acrolein or acrylic acid, or their mixture, and the third (C) wherein in limits of partial oxidation of propylene at step (B) of gaseous mixture B acrolein or acrylic acid or their mixtures as the end product are separated and at least unconverted propane containing in gaseous mixture at step (B) is recovered to the dehydrogenation step (A) wherein in limits of partial oxidation of propylene at step (B) molecular nitrogen is used as additional diluting gas. Method provides significant decreasing of by-side products.

EFFECT: improved method of synthesis.

39 cl, 11 ex

FIELD: industrial production of methacrylic acids at reduced amount of industrial wastes.

SUBSTANCE: proposed method is performed by catalytic oxidation of propane, propylene or isobutylene in vapor phase at separation of final product and forming of high-boiling mixture as by-product which contains (according to Michaels addition) water, alcohol or methacrylic acid added to methacrylic group. By-product is decomposed in thermal decomposition reactor at simultaneous distillation of decomposition products in distilling column from which methacrylic acid is taken in form of distillate. Flow of liquid decomposition residue is forced for peripheral direction by means of mixing blades before withdrawal from reactor. Peripheral direction is obtained with the aid of liquid fed from the outside of decomposition reactor; to this end use is made of initial high-boiling material or flow of liquid discharged from decomposition reactor. If necessary, etherification stage is performed through interaction with alcohol for obtaining methecrylic ester. Decomposition of by-product formed at obtaining methacrylic acid by oxidation of propylene or isobutylene or at obtaining methacrylic acid by interaction of acid with alcohol by alcohol through introduction of by-product into thermal decomposition reactor provided with distilling column which has plates made in form of disks and toroids for simultaneous decomposition and distillation. Plant proposed for realization of this method includes thermal decomposition reactor and distilling column, level meters and lines for discharge of liquid containing easily polymerized compounds. Level indicator mounted at area of accumulation of liquid shows pressure differential. Line for detecting the side of high pressure of this level meter is connected with accumulated liquid discharge line.

EFFECT: updated technology; increased yield of target products.

38 cl, 14 dwg, 2 tbl, ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for synthesis of acrolein and/or acrylic acid from propane and/or propene. Method involves the following steps: (a) isolating propane and/or propene from gaseous mixture A containing propane and/or propene by their absorption with adsorbent; (b) isolating propane and/or propene from adsorbent to form gas B containing propane and/or propene, and (c) using gas B obtained in stage (b) for oxidation of propane and/or propene to acrolein and/or acrylic acid wherein the heterogeneous catalytic dehydrogenation of propane without feeding oxygen is not carried out. Method shows economy and maximal exploitation period of used catalyst without its regeneration.

EFFECT: improved method of synthesis.

12 cl, 7 dwg, 1 ex

The invention relates to an improved method for the removal of formaldehyde or its adducts of organic liquid mixtures obtained in the production of methyl methacrylate containing at least a carboxylic acid or an ester of carboxylic acid and formaldehyde or its adducts, which forms a two-phase mixture of water, comprising at least one extraction liquid organic mixture in the system liquid-liquid using water as the extractant with getting the flow of the organic phase and flow of the aqueous phase, and the flow of the organic phase contains significantly reduced the concentration of formaldehyde or its adducts compared with the liquid organic mixture

The invention relates to an improved process for the preparation of methyl methacrylate, comprising the stages of (i) interaction propionic acid or its ester with formaldehyde or its predecessor in the condensation reaction with the formation of the stream of gaseous products containing methyl methacrylate, residual reactants, methanol and by-products, (ii) processing at least one portion of the stream of gaseous products with the formation of a stream of liquid products containing almost all of the methyl methacrylate and at least one impurity, which melts at a temperature above the melting temperature of pure methyl methacrylate, run over the flow of the liquid product at least one operation fractional crystallization, which contains the stage (iii) cooling the specified flow of liquid product to a temperature between about -45oAnd about -95oSo that the flow of liquid product forms solid crystals of methyl methacrylate and uterine fluid, and these crystals have a higher content of methyl methacrylate than the specified stream of liquid products or uterine fluid, (iv) the separation of these crystals of solid methyl methacrylate from the specified match Azania impurity in a lower concentration, than the specified stream of liquid products

FIELD: chemistry.

SUBSTANCE: group of inventions relates to control of reactions during transitions from an initial reaction to a target reaction with respect to reduction of the amount of off-grade product. The method of determining transition parametres in a polymerisation reactor from an initial reaction for production of a product whose properties satisfy a set of initial requirements to a target reaction for production of a product whose properties satisfy a set of target requirements involves the following steps: identification of a primary property by obtaining data which indicate instantaneous and average values for each of at least two different product properties before, during and after the transition, where each of the said different properties corresponds to the set of initial requirements at the beginning of the transition, and identification as a primary property, based on the said data, of one product property which can be a reason for production of a large amount of off-grade product during the transition compared to any other property; determination of initial conditions for transition, including the initial value of the primary property, which considerably reduce the amount of off-grade product produced during the transition; and determination of variable process control parametres for the transition which begins with the said initial conditions. Disclosed also is a method of identifying the primary property of the product produced in a polymerisation reactor with properties which satisfy the set of initial requirements.

EFFECT: more reliable control.

14 cl, 10 dwg

FIELD: process engineering.

SUBSTANCE: this invention covers acoustic device (and method) facilitating interaction between solid body and gas that envelopes that body or at least staying in contact with said body surface. Acoustic device facilitating interaction between solid body (100) and gas (500) that envelopes that body or at least staying in contact with said body surface (204), comprises sound or high-intensity ultrasound source (301) to act on surface (204), outer part (305) and inner part (306) that defines passage (303), hole (302), chamber (304) arranged inner part (306). Note here that said acoustic source (301) serves to receive compressed gas and force it into hole (302), wherefrom said gas is forced into nozzle towards chamber (304). Note here that sound or high-intensity ultrasound is applied directly to gas (500) to propagate said sound or ultrasound to surface (204) of body (100), to reduce and/or minimise laminar sublayer (203) on surface (204) of body (100). Note that sound or ultrasound intensity makes 140 dB or higher.

EFFECT: decrease in laminar sublayer causes increase in efficiency of heat exchange and/or rate of said catalytic process and/or that of gas exchange.

15 cl, 12 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing vinyl chloride, involving feeding chlorine gas and ethane into an ethane chlorination reaction area lying in the bottom part of a pyrolysis reactor in which there are solid particles; chlorination of ethane when chlorine gas and ethane come into contact with the solid particles such that, the ethane chlorination reaction product and the solid particles rise to the top part of the pyrolysis reactor at the same time and the formed coke settles on the solid particles; the ethane chlorination reaction takes place at 400-800°C and pressure of 1-25 atm, with molar ratio of ethane to chlorine gas equal to 0.5-5 and time of 0.5-30 seconds; the pyrolysis reaction takes place in the pyrolysis reaction area lying in the top part of the pyrolysis reactor when the ethane chlorination reaction product comes into contact with the solid particles such that, the ethane chlorination reaction product and solid particles rise at the same time and the formed coke settles on the solid particles; the pyrolysis reaction takes place at temperature of 300-800°C, pressure 1-50 atm and time ranging from 0.05 to 20 seconds; separation of solid particles obtained from the pyrolysis reaction and the pyrolysis reaction product in a separator; moving the separated solid particles to the regeneration reactor with subsequent burning of the coke settled on the solid particles for regeneration of the solid particles; and feeding the regenerated solid particles into the pyrolysis reactor. The invention also relates to a device for producing vinyl chloride, which includes a pyrolysis reactor having an ethane chlorination reaction area in the bottom part and a pyrolysis reaction area in the top part; a separator which separates the pyrolysis reaction product and solid particles; a regeneration reactor which regenerates separate solid particles through burning and at least one module through which solid particles move.

EFFECT: high product output and reduced formation of coke.

14 cl, 4 tbl, 2 ex, 3 dwg

FIELD: process engineering.

SUBSTANCE: invention relates to production of acrolein. Proposed method consists in filling separate contact tubes uniformly section-by-section, from bottom to top, by different-composition catalyst formed products. Note that, to produce at least one section, first, uniform quantitative portions of said products are formed to be wrapped by packing means to produce packages filled by catalyst formed products. Then equal integer number of packages are voided into every separate contact tube provided that composition of catalyst formed products consists of two or more different-type catalyst formed products differing in geometry, active mass composition, physical properties of their active mass and/or in weight fraction of active mass applied onto inert diluting formed product, or representing a mix of catalyst formed products and diluting formed products.

EFFECT: high rate and degree of filling contact tubes by catalyst formed products.

13 cl, 2 ex

FIELD: process engineering.

SUBSTANCE: invention can be used for production of carbonyl compounds of metals. Circular partition is arranged inside cylindrical tight casing to make first and second sections. Said casing can revolve with respect to inclined lengthwise axis. Material transfer device circulates material in closed circuit and represents a drum fitted aligned in said reactor and furnished with outer and inner rings that make a chamber there between covered by face circular elements. First multi-start auger is arranged on drum outer ring inner surface. Drum inner ring end sections have loose material inlet and outlet openings. Loose material mixer is mounted along the edges of drum inner ring coupled with heat exchanger. Tube plate with ceramet filter elements is arranged inside second sections to form dust and end chambers. Saud dust chamber accommodates second multi-start auger arranged on reactor casing inner surface. One end of second auger is coupled with circular partition to force dust filtered from reaction product into first section. Guide element turns direction is opposite the direction of reactor casing direction in the reaction of synthesis.

EFFECT: higher efficiency and expanded operating performances.

9 cl, 8 dwg

FIELD: process engineering.

SUBSTANCE: invention relates to methods of conducting gas-fluid reactions in reactors with monolithic catalyst and can be used in chemical and other industries, as well as in analytical chemistry. Proposed method comprises gas dispersion in fluid with the help of disperser, feeding of gas-fluid mix into capillary channels and additional gas feed between layers. Amount N of gas bubbles formed continuously at disperser outlet during measurement time T is continuously measured. Fluid and gas flow rates are set to make gas bubble formation frequency being at least not less than maximum designed frequency. If not, control signals are generated to either reduce fluid flow rate, or increase gas flow rate, or to improve dispersion degree.

EFFECT: higher efficiency of mass exchange and reaction processes, reduced costs of equipment and power consumption.

3 dwg, 5 ex

FIELD: power engineering.

SUBSTANCE: invention relates to set of prefabricated units of shell-and-tube reactors made with the possibility of assembly on construction site to form shell-and-tube reactor in order to perform catalytic reactions in gas and/or liquid phase. Reactor comprises a bundle of vertical reactor tubes filled with catalyst, ends of which are tightly fixed in upper and lower tube plates. Tubes are surrounded by reactor shell, which is tightly connected to tube plates. Reactor body together with tube plates forms pressurised reservoir, in which liquid coolant washes reactor tubes under pressure. Tube plates are covered with reactor covers, which are joined to reactor body and with which reactor pipes communicate. In reactor there are supply pipes for supply of coolant that washes reactor tubes under pressure and drain pipes to drain coolant that washes reactor tubes under pressure. Supply and/or drain pipes pass through tube plate in axial direction.

EFFECT: such design provides for the possibility of easy transportation and assembly.

35 cl, 27 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to processing different starting material through catalytic cracking with a fluidised catalyst bed. The invention pertains to a method for catalytic cracking with a fluidised catalyst bed designed for increasing output of C3 and C4 hydrocarbons, involving: (a) feeding main starting material which contains hydrocarbons, characterised by boiling point in the range from 400°F (204°C) to 1150°F (621°C), into a catalytic cracking reactor with an ascending fluidised catalyst bed through a set of injectors for the main starting material which has a section inclined to downwards and a vertical section downstream the said inclined section; (b) feeding light starting material containing hydrocarbons, characterised by boiling point which does not exceed approximately 440°F (227°C), into the said apparatus for catalytic cracking with a fluidised catalyst bed through a first injector for light starting material lying in the bottom part of the reactor and through a second injector for light material lying on the inclined section of the reactor above the first injector for light material. The first and second light material injectors are near points where the catalyst stream changes direction and is not uniform.

EFFECT: higher output of C3 and C4 hydrocarbons.

24 cl, 3 ex, 4 tbl, 8 dwg

FIELD: power industry.

SUBSTANCE: invention refers to reactors with air-fluidised bed. One of the versions discloses the procedure facilitating operation of a two-phase reactor with fluidised bed, which consists in low-level supply of at least one gaseous reagent into vertical directed air-fluidised mass of solid particles. Also air-fluidised mass is present in at least two vertically arranged neighbour columns located inside a common shell of the reactor. Each column is divided into a multitude of vertically running channels. At least part of the channels is inter-communicated with flow of air-fluidised mass. Notably, air fluidised mass is present in at least some of the channels. At least some of the columns and/or channels are limited with surfaces of heat exchange. Further, the procedure consists in creating conditions for reaction of the gaseous reagent, when it rises through air-fluidised mass present in at least some of the channels of the columns. Thus, there is produced a gaseous product. Successively, the procedure consists in creating conditions for extracting the gaseous product and/or not-reacted gaseous reagent from air-fluidised mass in head free space above air-fluidised mass, and in removing the gaseous product and not-reacted gaseous reagent, if present, from head free space. The disclosed designs of the reactors have large areas of heat transfer surfaces and limit degree of undesirable reverse mixing, owing to which there is potentially possible to obtain optimal combination of desired characteristics of plug flow (facilitating high efficiency and good selectivity) and characteristics of good mixing (required for wanted distribution of solid particles and for uniform temperature profiles).

EFFECT: invention essentially reduces risk of zooming at conversion of prototype to industrial installation.

25 cl, 4 dwg

FIELD: process engineering.

SUBSTANCE: invention relates to physico-chemical processes treatment in the presence of gas, fluid and finely-dispersed catalyst and can be used, in particular for synthesis of hydroxylamine sulphate. Reactor housing accommodates mixer with drive and loose catalyst in the form of finely-dispersed graphite particles with platinum chemically applied thereon. Mixer drive is arranged on said housing and rated to mixer maximum rpm that provided for uniform distribution of finely-dispersed catalyst in liquid phase. To add to dispersion, the union intended for introducing liquid phase into reactor housing bottom section represents multi-stage swirling mixer. Liquid phase inlet union is connected to one of the multi-stage swirling mixer tangential inlets.

EFFECT: reduced power consumption, higher safety.

5 cl, 3 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to an improved method for synthesis of an ester through reaction of 1-olefin with a monobasic carboxylic acid and water in vapour phase in the presence of a heteropolyacid catalyst on silica gel, in which the silica gel support is in from of granules treated with water vapour at temperature between 100 and 300°C for a period of time between 0.1 to 200 hours, before or simultaneously with application of the heteropolyacid onto the support. The invention also relates to a heteropolyacid catalyst deposited on silica gel and to a method of preparing the catalyst, where the support is obtained by treating silica gel granules with water vapour at temperature between 100 and 300°C for a period of time between 0.1 and 200 hours, before or simultaneously with application of the heteropolyacid onto the support.

EFFECT: use of the said catalyst in the ester synthesis method through reaction of 1-olefin with a monobasic carboxylic acid and water in vapour phase enables to reduce content of methyl ethyl ketone in products.

43 cl, 1 ex

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