Catalytic composition for selectivity of transformation alkanes into unsaturated carbonic acids, method of obtaining composition and method of composition application

FIELD: chemistry.

SUBSTANCE: catalytic composition contains compounds of formula: Mo1VaSbbNbcMdOx, in which Mo represents molybdenum, V stands for vanadium, Sb stands for antimony, Nb stands for niobium, M represents gallium, a constitutes from 0.01 to 1, b constitutes from 0.01 to 1, c constitutes from 0.01 to 1, d constitutes from 0.01 to 1, and x is determined by requirements of valency of other present elements.

EFFECT: increase of alkane conversion degree, increase of selectivity of catalytic composition in one stage process of alkane transformation into unsaturated carbonic acid.

9 cl, 1 tbl, 12 ex

 

The technical field to which the invention relates.

This invention relates to a method for producing unsaturated carboxylic acids from alkanes. In particular, this invention relates to a method for producing acrylic acid from propane using a one-step process of oxidation in the vapor phase.

The level of technology

Obtaining unsaturated carboxylic acids such as acrylic acid or methacrylic acid, traditionally carried out by catalytic interaction of olefins, such as propylene or isobutylene with oxygen with the formation of alkanolamides, such as acrolein or methacrolein, which is then catalytically oxidized by oxygen. Alkanes, such as propane, have advantages in the cost and availability compared with olefins. In addition, one-step method will have advantages compared to the existing industrial process.

Well-known examples of obtaining acrylic acid and other unsaturated carboxylic acid from propane and other alkanes in single-stage catalytic oxidation in the vapor phase. In U.S. patent No. 5380933 describes how to obtain an unsaturated carboxylic acid such as acrylic acid, in the presence of a mixed metal oxide catalyst containing molybdenum, vanadium, tellurium and at least one of niobium, tantalum, tungsten, titanium, aluminum, zirconium, chromium, manganese, iron, ruthenium, cobalt, rhodium, Nickel, palladium, platinum, antimony, bismuth, boron, indium and cerium. As a component of the catalyst were mentioned neither GA nor silver, nor gold. In the patent there is no assumption about the choice of antimony as a possible component of the catalyst. Tellurium is a necessary component of this catalyst according to the prior art.

In published patent application Japan N10-57813 uncovered metal oxide catalyst containing molybdenum, vanadium, tellurium and/or antimony and the element that is selected from niobium, tantalum, tungsten, titanium, aluminum, zirconium, chromium, manganese, iron, ruthenium, cobalt, rhodium, Nickel, palladium, platinum, bismuth, boron, indium, phosphorus, rare earth elements, alkali metals, alkaline-earth metals. As a component of the catalyst were not described or gallium, nor silver, nor gold. There is no assumption about the choice of bismuth as a possible component of the catalyst.

In published patent application Japan N10-45664 described catalyst of oxides of molybdenum, vanadium, antimony and which element selected from niobium, tantalum, tungsten, titanium, zirconium, chromium, iron, manganese, ruthenium, cobalt, rhodium, Nickel, palladium, platinum, boron, indium, alkali metals, alkaline-earth is yellow, and rare earth elements. Either gallium or bismuth, nor silver, nor gold is not described as a component of the catalyst.

In published application EP 0962253 described catalyst containing oxides of molybdenum, tungsten, iron, niobium, tantalum, zirconium, ruthenium and mixtures thereof; vanadium, cerium, chromium and mixtures thereof; tellurium, bismuth, antimony, selenium, and mixtures thereof; and niobium, tantalum, tungsten, titanium, aluminum, zirconium, chromium, manganese, iron, ruthenium, cobalt, rhenium, Nickel, palladium, platinum, antimony, bismuth, boron, indium, cerium, and mixtures thereof. Neither GA nor silver, nor gold is not disclosed as a component of the catalyst. There is no assumption about the choice of antimony or bismuth as a possible component of the catalyst.

In the published Japan patent No. 10-120617 described inflicted catalyst containing oxides of molybdenum, vanadium, antimony, one of the oxides of niobium, tantalum, tin, tungsten, titanium, Nickel, iron, chromium or cobalt and at least one of the oxides of sodium, potassium, rubidium, cesium, phosphorus and arsenic. Either gallium or bismuth, nor silver, nor gold have not been mentioned as a component of the catalyst.

In published patent application Japan N6-218286 disclosed heterophilically the catalyst having the oxides of phosphorus, molybdenum, vanadium, at least one of the oxides of arsenic and antimony, and at least one of the oxides of tin is, lead, cerium, cobalt, iron, zirconium, thorium, tungsten, germanium, Nickel, rhenium, bismuth, chromium, boron, magnesium, calcium, barium, strontium, selenium, tellurium, silver, aluminum, zinc, copper, titanium, potassium, rubidium, cesium and thallium. Neither GA nor gold, nor niobium were not disclosed as a component of the catalyst. There is no assumption about the choice of antimony and silver as a possible catalyst components.

In U.S. patent No. 6160162 and 6114278 disclosed calcined catalyst containing molybdenum, vanadium, gallium, palladium, niobium and at least one of lanthanum, tellurium, germanium, zinc, silicon, indium and tungsten. No antimony or bismuth, neither gold nor silver are disclosed as a component of the catalyst.

In U.S. patent No. 5994580 and 6060422 disclosed is a method of obtaining acrylic acid from propane and oxygen in the mixed metal oxide catalyst containing molybdenum, vanadium, antimony and at least one of niobium, tantalum, tin, tungsten, titanium, Nickel, iron, chromium and cobalt. Either gallium or bismuth, nor silver, nor gold is not disclosed as a component of the catalyst.

In Japan patent No. 11114418 describes a catalyst containing the oxides of niobium, molybdenum, antimony, at least one of the oxides of phosphorus, arsenic, boron, silicon and germanium and at least one of the oxides of potassium, cesium, rubidium, calcium, m is fester, tellurium, chromium, manganese, iron, cobalt, Nickel, copper, silver, lead, bismuth, aluminum, gallium, indium, tin, zinc, lanthanum, cerium, yttrium, tungsten, tantalum, ruthenium, rhodium, palladium, platinum, iridium, osmium, rhenium and hafnium. Neither gold, nor vanadium is not described as a component of the catalyst. There is no assumption about the choice of gallium, bismuth or silver as a possible component of the catalyst.

In the patent application China 1159960 described catalysts based on bismuth vanadium, niobium or tantalum, chromium, molybdenum or tungsten, with optional lithium, sodium, potassium, copper, silver or gold. No antimony or gallium is not described as a component of the catalyst. There is no assumption about the choice of gold or silver as a possible component of the catalyst.

In U.S. patent No. 4339355 disclosed a catalyst containing molybdenum, vanadium and niobium, chromium, copper, manganese, or yttrium. No antimony or gallium, neither gold nor silver are disclosed as a component of the catalyst.

In U.S. patent No. 6252122 described catalyst containing molybdenum, bismuth and phosphorus to vanadium, niobium, tantalum, chromium, tungsten, gallium, cerium or lanthanum; lithium, sodium, potassium, rubidium, cesium, copper, silver, gold, palladium or platinum; tin, lead, antimony, bismuth, tellurium, iron, cobal the volume or Nickel; and silicon, aluminium, titanium or zirconium. There is no assumption about the choice of gallium or gold as a possible component of the catalyst.

In U.S. patent No. 5807531 disclosed a catalyst containing molybdenum and vanadium-tungsten, niobium, titanium, zirconium, hafnium, tantalum, chromium, silicon or germanium. No antimony or gallium or bismuth, nor silver, nor gold is not disclosed as a component of the catalyst.

In the patent application of Japan No. 246108 (2000) describes a catalyst containing molybdenum, vanadium and antimony with niobium or tantalum, silver, zinc, tin, lead, arsenic, copper, thallium or selenium. Either gallium or bismuth or gold is not described as a component of the catalyst. There is no assumption about the choice of silver as a possible component of the catalyst.

In U.S. patent No. 6114278 and 6160162 described catalyst for obtaining acrylic acid by catalytic vapor-phase partial oxidation of propane in one stage. This catalyst contains molybdenum, vanadium, gallium, palladium, niobium and at least one of lanthanum, tellurium, germanium, zinc, silicon, indium or tungsten. There is no description antimony, bismuth, silver or gold as a catalyst component.

In document PCT/EP 01/06821 (WO 01/98246) disclosed is a method of obtaining acrylic acid using the catalyst, the content of asego molybdenum, vanadium and tellurium or antimony and at least one of niobium, tantalum, tungsten, titanium, aluminum, zirconium, chromium, manganese, iron, ruthenium, cobalt, rhodium, Nickel, palladium, gallium, platinum, bismuth, boron and cerium. Neither silver nor gold is not described as a component of the catalyst of this invention. There is no assumption about the choice of gallium and antimony as a possible component. There are no experimental examples for the catalyst containing antimony or gallium.

In U.S. patent No. 6383978 described catalyst for oxidation in the vapor phase alkane to an unsaturated carboxylic acid and for the vapor Ammonite alkane to an unsaturated nitrile. This catalyst contains molybdenum, vanadium, at least one of tellurium, antimony, tin, germanium or bismuth, at least one of niobium, tantalum, titanium, aluminum, zirconium, chromium, manganese, iron, ruthenium, cobalt, rhodium, Nickel, platinum, boron, indium, arsenic, lithium, sodium, potassium, rubidium, cesium, France, beryllium, magnesium, calcium, strontium, barium, hafnium, lead, phosphorus, promethium, europium, gadolinium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, lanthanum, scandium, gold, silver, palladium, gallium, praseodymium, rhenium, iridium, neodymium, yttrium, samarium, terbium, tungsten, cerium, copper or zinc and at least one of selenium, or bismuth. No is there an assumption about the choice of gallium, gold, silver and antimony as a possible component. The catalyst of this invention must contain selenium or bismuth.

In U.S. patent No. 6407280 described catalyst for oxidation of propane or isobutane to acrylic acid or methacrylic acid. This catalyst contains molybdenum or tungsten; vanadium or cerium; tellurium, antimony or selenium; optionally, at least one of niobium, tantalum, titanium, aluminum, zirconium, chromium, manganese, iron, ruthenium, cobalt, rhodium, Nickel, platinum, antimony, bismuth, boron, indium, arsenic, germanium, tin, lithium, sodium, potassium, rubidium, cesium, France, beryllium, magnesium, calcium, strontium, barium, radium, hafnium, lead, phosphorus, promethium, europium, gadolinium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium; and at least one of Nickel, palladium, copper, silver or gold. Gallium was not disclosed as a component of the catalyst of this invention. There is no assumption about the choice of antimony as a possible component. There is no experimental example for a catalyst containing antimony or gallium.

In U.S. patent No. 6403525 disclosed catalyst for oxidation or amoicillin alkanes. This catalyst contains molybdenum, vanadium, at least one of tellurium, antimony, tin, germanium or bismuth, at least one of niobium, tantalum, titanium, al the MINIA, zirconium, chromium, manganese, iron, ruthenium, cobalt, rhodium, Nickel, platinum, boron, arsenic, lithium, sodium, potassium, rubidium, cesium, France, beryllium, magnesium, calcium, strontium, barium, hafnium, lead, phosphorus, promethium, europium, gadolinium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, lanthanum, scandium, gold, silver, palladium, gallium, praseodymium, rhenium, iridium, neodymium, yttrium, samarium, thorium, tungsten, cerium, copper or zinc and at least one of indium or rhenium. There is no assumption about the choice of gallium, bismuth, silver or gold and antimony as a possible component. The catalyst of this invention must contain indium or rhenium.

The catalysts of similar composition were used in other processes, different from obtaining acrylic acid and other unsaturated carboxylic acid from propane and other alkanes in single-stage catalytic oxidation in the vapor phase.

In U.S. patent No. 4250346 disclosed a catalyst for catalytic oxidative dehydrogenation of ethane to ethylene, with the specified catalyst contains molybdenum, chromium, manganese, niobium, tantalum, titanium, vanadium or tungsten, or bismuth, cerium, cobalt, copper, iron, potassium, magnesium, Nickel, phosphorus, lead, antimony, silicon, tin, thallium or uranium. Neither GA nor silver, nor gold not p is hidden as a component of the catalyst. There is no assumption about the choice of vanadium, niobium and antimony as a possible component of the catalyst.

In the patent application of Japan No. 10-310539 described catalyst to obtain propylene from propane, and the catalyst contains molybdenum, vanadium and niobium. Either gallium or bismuth, nor silver, nor gold is not disclosed as a component of the catalyst.

In U.S. patent No. 6043185 disclosed catalyst to obtain Acrylonitrile or Methacrylonitrile through catalytic interaction of propane or isobutane with oxygen and ammonia in the vapor phase. This catalyst contains molybdenum, vanadium, antimony, gallium and at least one of arsenic, tellurium, selenium, niobium, tantalum, tungsten, titanium, zirconium, chromium, manganese, iron, ruthenium, cobalt, rhodium, Nickel, palladium, platinum, boron, indium, cerium, rhenium, iridium, germanium, tin, bismuth, yttrium, praseodymium, alkali metals and alkaline-earth metals, and means 1; b is from 0.0 to 0.99; C is from 0.01 to 0.9; d is equal to 0.01-0,5; e is 0.0 to 1.0; and x is determined by the oxidation state cations present, and preferably the catalyst does not contain tellurium (less than 0.01). For raw materials containing propane, ammonia, oxygen, nitrogen and water, in the comparative example catalyst without gallium obtained values of selectivity for Acrylonitrile 50.7% and acrylic acid 1.5%, and in the examples on which I catalyst, promoted gallium obtained values of selectivity for Acrylonitrile 45,8-60.3% and acrylic acid from 0.4 to 3.4%. Neither silver nor gold is not disclosed as a component of the catalyst. There is no assumption about the choice of bismuth as a possible component of the catalyst.

In U.S. patent No. 6036880 described the oxidation of propane on the catalyst containing molybdenum, vanadium, niobium and tellurium and/or antimony, in which the niobium is dissolved in a specific amount of dicarboxylic acid. Gallium, bismuth, silver and gold were not disclosed as catalyst components.

In U.S. patent No. 5973186 and 6080882 disclosed catalyst to obtain unsaturated nitrile from an alkane by the reaction of Ammonite, which contains molybdenum, vanadium, niobium, or tellurium, or antimony, and, optionally, tantalum, tungsten, titanium, zirconium, hafnium, iron, chromium, manganese, rhenium, ruthenium, cobalt, rhodium, Nickel, palladium, osmium, iridium, platinum, copper, silver, zinc, cadmium, boron, aluminum, gallium, indium, thallium, germanium, tin, lead, phosphorus, bismuth, selenium, scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, gadolinium, alkali metals and alkaline earth metals. There is no assumption about the choice of gallium, bismuth or silver as a possible component. Gold is not described as a component of the catalyst.

In U.S. patent No. 603728 disclosed catalyst amoicillin to obtain Acrylonitrile or Methacrylonitrile. This catalyst contains molybdenum, vanadium, niobium and tellurium or antimony and at least one of tantalum, tungsten, chromium, titanium, zirconium, bismuth, tin, hafnium, manganese, rhenium, iron, ruthenium, cobalt, rhodium, Nickel, palladium, platinum, silver, zinc, boron, aluminum, gallium, indium, germanium, lead, phosphorus, rare earth elements and alkaline-earth metals. There is no assumption about the choice of gallium, silver and antimony as a possible component. There is no description of gold as a catalyst component.

In U.S. patent No. 6395936 disclosed a catalyst containing the oxides of bismuth, tellurium, antimony, tin and/or copper and molybdenum and/or tungsten and oxides of alkali metal, thallium and/or samarium; alkaline-earth metals, Nickel, cobalt, copper, manganese, zinc, tin, cadmium and/or mercury, iron, chromium, cerium and/or vanadium, phosphorus, arsenic, boron and/or antimony; rare-earth metals, titanium, zirconium, niobium, tantalum, rhenium, ruthenium, rhodium, silver, gold, aluminum, gallium, indium, silicon, germanium, lead, thorium and/or uranium and molybdenum and/or tungsten. There is no assumption about the choice of vanadium, silver, gold, gallium, niobium and antimony as a possible component.

Disclosure of inventions

This invention relates to a catalyst used in the one-step method of obtaining easymenu carboxylic acid, such as acrylic acid or methacrylic acid, from alkanes, such as propane or isobutane, to a method for producing the catalyst and a method for producing unsaturated carboxylic acids such as acrylic acid or methacrylic acid, from alkanes, such as propane or isobutane. The catalyst is a composition of General formula:

Mo1VaSbbNbcMdOx

in which M represents one or more elements of gallium, bismuth, silver or gold and is from 0.01 to 1, preferably from 0.01 to 0.75, most preferably from 0.1 to 0.5; b is from 0.01 to 1, preferably from 0.01 to 0.5, most preferably from 0.1 to 0.5; C is from 0.01 to 1, preferably from 0.01 to 0.5, most preferably from 0.01 to 0.1; d is from 0.01 to 1, preferably from 0.01 to 0.5, most preferably 0.01 to 0.1, and x is determined the valence requirements of the other components. The catalytic composition may be represented by the formula:

Mo1VaSbbNbcMdM'eOx

in which M' represents one or more elements of tantalum, titanium, aluminum, zirconium, chromium, manganese, iron, ruthenium, cobalt, rhodium, Nickel, platinum, boron, arsenic, lithium, sodium, potassium, rubidium, calcium, beryllium, magnesium, cerium, strontium, hafnium, phosphorus, Heb is Pius, gadolinium, dysprosium, holmium, erbium, thulium, terbium, ytterbium, lutetium, lanthanum, scandium, palladium, praseodymium, neodymium, yttrium, thorium, tungsten, cesium, zinc, tin, germanium, silicon, lead, barium and thallium, and s ranges from 0.0 to 1, preferably from 0.0 to 0.5, most preferably from 0.0 to 0.1.

This catalyst was prepared by co-precipitation of compounds of molybdenum, vanadium, antimony, niobium, gallium, bismuth, silver or gold, and, optionally, other elements with the formation of the mixed metal oxide catalyst. This catalyst can be used for selective conversion of alkanes to unsaturated carboxylic acids in a one-step process.

This invention generally relates to a mixed metal oxide catalyst and, more specifically, molybdenate the catalyst. The catalyst of the present invention is a mixture of oxides of molybdenum, vanadium, antimony, niobium and either gallium, bismuth, silver, or gold General formula:

Mo1VaSbbNbcMdOx

in which M represents one or more elements of gallium, bismuth, silver or gold and is from 0.01 to 1, preferably from 0.01 to 0.75, most preferably from 0.1 to 0.5; b is from 0.01 to 1, preferably from 0.01 to 0.5, most preferably from 0.1 to 0.5; C is from 0.01 up to 1, preferably from 0.01 to 0.5, most preferably from 0.01 to 0.1; d is from 0.01 to 1, preferably from 0.01 to 0.5, most preferably from 0.01 to 0.1, and x is determined by the valence requirements of the other components. Preferably M represents gallium.

The catalyst of the present invention may have the structure described by the following formula:

Mo1VaSbbNbcMdM'eOx

in which optional element M' may be one or more elements selected from tantalum, titanium, aluminum, zirconium, chromium, manganese, iron, ruthenium, cobalt, rhodium, Nickel, platinum, boron, arsenic, lithium, sodium, potassium, rubidium, calcium, beryllium, magnesium, cerium, strontium, hafnium, phosphorus, europium, gadolinium, dysprosium, holmium, erbium, thulium, terbium, ytterbium, lutetium, lanthanum, scandium, palladium, praseodymium, neodymium, yttrium, thorium, tungsten, cesium, zinc, tin, germanium, silicon, lead, barium and thallium, and s ranges from 0.0 to 1, preferably from 0.0 to 0.5, most preferably 0.0 to 0.1.

Specific examples of the catalyst of the present invention are

Mo1Vfor 0.3Sbof 0.15Nb0,05Ga0,03Ox; Mo1Vfor 0.3Sb0,08Nb0,05Ga0,03Ox; Mo1Vfor 0.3Nb0,05Sbof 0.15Bi0,03Ox;

Mo1Vfor 0.3Sbof 0.15Nb005 Ag0,06Ox; Mo1Vfor 0.3Sbof 0.15Nb0,05Au0,015Oxand Mo1Vfor 0.3Nb0,05Sbof 0.15Ga0,03W0,012Ox.

This catalyst can be used in single-stage production method of unsaturated carboxylic acids such as acrylic acid or methacrylic acid, from alkanes, such as propane or isobutane. Preferably alkane has from three to eight carbon atoms, and most preferred are propane or isobutane. Preferably the method is carried out in the vapor phase, in which the catalyst is brought into contact with alkanol and oxygen. Preferably the molar ratio of alkane:oxygen is in the range from 0.01:1 to 10:1. Preferably the contact time of the reactants is in the range from 0.1 to 10 seconds, preferably from 0.1 to 5 seconds. In the reaction gas mixture may be added water vapor. If steam is used the molar ratio of alkane:water vapor is in the range from 0.05:1 to 10:1. In addition, there may be used an inert gas, such as nitrogen, argon or helium as a carrier. If you are using a gaseous medium, preferably the molar ratio of alkane:the carrier is preferably in the range from 0.01:1 to 10:1.

The reaction temperature in the method according to the present invention is 320-450&x000B0; With, preferably 350-400°C. the Reaction pressure is from 0 to 100 psi (0-689,48 kPa), preferably from 5 to 50 pounds per square inch (34,47-344,74 kPa).

In addition to the unsaturated carboxylic acid, in the method according to the present invention can be formed by-products, including olefins. For example, when the alkane is a propane, can be formed by-products: carbon monoxide, carbon dioxide, acetic acid and propylene. Olefin, such as propylene, can be separated from other by-products and recycling in raw stream. The catalyst in the method of the present invention can convert the olefins to unsaturated carboxylic acids, such as propylene to acrylic acid. Alternatively, the olefins can be separated from other by-products and converted into unsaturated carboxylic acid in a different process using known catalysts for the conversion of olefins to unsaturated carboxylic acids or used in other processes for other products.

The catalyst of the present invention can be used as neozhidanny catalyst or supported catalyst. In the case of deposited catalyst media is an inert solid substance having reactivity with respect to any of the active to mponent catalyst, and preferred carrier is silica, alumina, niobium oxide, titanium oxide, zirconium oxide or mixtures thereof. The catalyst may be secured to the carrier by methods known from the prior art, which include the impregnation of water capacity, reaction in a slurry and spray drying. The shape, size or distribution of the catalyst particles is not limited, and, depending on the situation, the catalyst can be obtained in the reaction vessel in the process. Examples are powders, granules, spheres, cylinders, air bags and other

Preferably the catalyst is prepared from a solution of the water-soluble compounds of each of the component metals. If compounds are not soluble in water, there can be obtained a suspension or slurry and thoroughly dispersed or mixed. Alternatively, there may be used a solvent different from water, such as acid or alkali. To facilitate dissolution of the solvent can be heated. Usually dissolves a mixture of compounds of elements such as salts or complexes, in approximately the desired molar ratio, with the formation of a solution. This solution can be heated to facilitate interaction of the compounds, and to form the desired phase. To apply elevated temperature and pressure in the solution, could the t to be used are known from the prior art hydrothermal methods. The liquid solvent is removed, and the resulting catalytic composition is dried and then calcined.

Suitable precursor compounds of molybdenum are salts of molybdenum, such as paramolybdate ammonia, oxides of molybdenum, molybdenum acid or chlorides of molybdenum. Suitable precursor compounds of vanadium are salts of vanadium, such as ammonium metavanadate, vanadium oxides, vanadium oxalate or sulphate vanadium.

Suitable precursor compounds of antimony are the oxides of antimony, chlorides of antimony sulphate antimony tartrate of antimony and antimony acetate.

Suitable precursor compounds of niobium are niobium oxalate, oxalate ammonium niobium, niobium oxide, hydrated oxide of niobium or niobium acid. Oxalic acid and niobic acid can be dissolved with water to obtain a solution. With regard to the obtained solution, it is preferable that the molar ratio of oxalic acid to niobium is in the range of from 1:1 to 12:1, preferably from 3:1 to 6:1. For the formation of the solution can be used dicarboxylic acid different from oxalic acid, such as malonic acid, succinic acid, glutaric acid and adipic acid, or tricarboxylic acids such as citric acid, with Niobe the howling acid or without it.

Suitable precursor compounds of gallium represent gallium oxide, gallium nitrate, gallium chloride, gallium acetylacetonate and gallium sulfate.

Suitable precursor compounds of silver are silver oxide, silver acetate, silver carbonate, silver nitrate or silver halides such as silver chloride.

Suitable precursor compounds of bismuth are bismuth acetate, bismuth hydroxide, bismuth nitrate, hydrate nitrate bismuth nitrate oxide of bismuth(III)oxide, bismuth(III), bismuth citrate, bismuth fluoride, bismuth chloride, bromide, bismuth iodide, bismuth, oxychloride of bismuth(III), xinitrc bismuth(III), phosphate, bismuth(III), subcarbonate bismuth, subnitrate bismuth, monohydrate subnitrate bismuth subsalicylate bismuth and bismuth sulfide(III).

Suitable precursor compounds of gold are gold bromide, gold chloride, hydroxide, gold iodide, gold or soloconsolidation acid.

Suitable precursor compounds of other metals, such as tantalum, titanium, aluminum, zirconium, chromium, manganese, iron, ruthenium, cobalt, rhodium, Nickel, platinum, boron, arsenic, lithium, sodium, potassium, rubidium, calcium, beryllium, magnesium, cerium, strontium, hafnium, phosphorus, europium, gadolinium, dysprosium, holmium, erbium, thulium, terbium, ytterbium, Lutece is, lanthanum, scandium, palladium, praseodymium, neodymium, yttrium, thorium, tungsten, cesium, zinc, tin, germanium, silicon, lead, barium and thallium, are salts such as oxalates, tartratami, citrates, nitrates, halides, carbonates, bicarbonates, hydroxides, oxides and the like, and nitrates and oxalates are preferred and available. For phosphorus and arsenic suitable connections precursor may include ammonium phosphate, ammonium phosphate, phosphorus pentoxide, phosphoric acid, phosphorous acid, arsenic acid and oxide of arsenic.

The liquid solvent may be removed by filtration, evaporation or centrifugation. If you remove the liquid using heat, preferably the temperature is in the range from 40 to 100°C. the Catalytic composition is dried using known from the prior art methods. Spray drying can be used as a means to remove the liquid solvent and drying of the catalyst in a single operation. Typical temperature at the outlet of the spray drying of the catalyst of this invention is 90-105°C. After drying, the catalyst composition preferably it is subjected to heat treatment in air at a temperature in the range of 250-350°C for 1 to 10 hours. Preferably the calcination kata is eticheskoi composition is carried out in an inert gas, such as argon or nitrogen, at a temperature in the range of 550-650°C for 1 to 10 hours.

In addition, the solid catalyst may be prepared using high-energy ball mill planetary moving balls or low-energy means of grinding or crushing, in order to obtain the desired crystallite size, particle size, particle shape and/or distribution of particles by size.

There are two factors which help evaluate the effectiveness of the catalyst for oxidation of alkanes to unsaturated carboxylic acids. The first factor represents the degree of conversion of alkane (conversion, %). The second factor represents the degree to obtain the desired product (selectivity, %). The product of these two factors, in turn, determines the total yield of unsaturated carboxylic acids by the catalytic oxidation of alkane. The catalyst of the present invention can provide a degree of conversion of propane 50% and the selectivity for acrylic acid 56.2 per cent, that is, the total yield of 28.2%.

The implementation of the invention

After a General description of the invention, the following examples showing specific variants of embodiment of the invention and its practical implementation and benefits. Of course, these examples are for illustrative purposes and are not intended for having such a restriction of the description or the claims.

Comparative example 1

Preparing a mixed metal oxide composition of the following composition:

Mo1Vfor 0.3Nb0,05Sbof 0.15Ox.

Solution A. ammonium Vanadate (of 7.95 g) was dissolved in 165 ml of water at 90°C. Add the oxide of antimony (III) (4,92 g)and the mixture is blown with nitrogen and heated at 92°With approximately 4,5 hours stop Heating, and the mixture is cooled overnight in a nitrogen atmosphere. Water (105 ml) is removed using a rotary evaporator. Add paramolybdate ammonium (40,0 g), and the mixture is stirred under nitrogen atmosphere for 4.5 hours

The solution Century. Monoaxial niobium oxalate (7,12 g) is stirred in 40 ml of water within 5 hours the Solution is added to the solution, and the resulting mixture is subjected to spray drying to obtain the precursor of the solid catalyst. The catalyst precursor is heated in air at 120°C for 1 h, and then carry out the decomposition at 300°C for 5 h, and then calcined in argon at 600°C for 2 h the Resulting powder is crushed by crushing and sieved 18/35 mesh. This catalyst (1 g) tested in the oxidation of propane with raw materials, with the ratio of propane/About2/N2/water equal to 1/1,6/14,4/15. These results are shown in the table.

Comparative example 2

Mixed metal oxide catalyst (1 g)obtained in CPA is a comparative example 1, tested in the oxidation of propane with raw materials, with the ratio of propane/O2/N2/water equal to 1/1,6/14,4/15. These results are shown in the table.

Comparative example 3

Mixed metal oxide catalyst (1 g)obtained in comparative example 1 is tested in the oxidation of propane with raw materials, with the ratio of propane/About2/N2/water equal to 1/1,6/14,4/15. These results are shown in the table.

Example 1

Preparing a mixed metal oxide composition with a nominal composition of Mo1Vfor 0.3Nb0,05Sbof 0.15Ga0,03Oxas follows.

Solution A. ammonium Vanadate (of 7.95 g) was dissolved in 165 ml of water at 90°C. Add the oxide of antimony (III) (4,92 g), and the mixture is heated at 98°With approximately 5 hours

The heating is stopped, and the mixture is cooled. Remove part of the water using a rotary evaporator. Add paramolybdate ammonium (40,0 g), and the mixture is stirred over night. The solution Century. Monoaxial niobium oxalate (7,12 g) is stirred in 40 ml of water during the night. Solution C. gallium Oxide (to 0.645 g) is stirred in 20 ml of water during the night. To the solution add solution and then the solution, and after 20 minutes the resulting mixture is subjected to spray drying to obtain a solid catalyst precursor. This catalyst precursor is heated in air at 120°With those who tell 1 h, then decompose at 300°C for 5 h, and then calcined in argon at 600°C for 2 h the Resulting powder is crushed by crushing and sieved 18/35 mesh. This catalyst (1 g) tested in the oxidation of propane with raw materials, with the ratio of propane/O2/N2/water equal to 1/1,6/14,4/15. These results are shown in the table.

Example 2

Mixed metal oxide catalyst (1 g)obtained in example 1 is tested in the oxidation of propane with raw materials, with the ratio of propane/O2/N2/water equal to 1/1,6/14,4/15. These results are shown in the table.

Example 3

Preparing a mixed metal oxide composition with a nominal composition of Mo1Vfor 0.3Nb0,05Sb0,08Ga0,03Oxas follows.

Solution A. ammonium Vanadate (of 7.95 g) was dissolved in 165 ml of water by heating. Add oxide of antimony (III) (2.64 g)and the mixture heated at 92°With approximately 7 hours Heating ceased, the mixture is blown with nitrogen and cooled during the night. Part water (153 g) is removed using a rotary evaporator (20 ml water). Add paramolybdate ammonium (40,0 g), and the mixture is stirred for 3.5 hours, the Solution Century. Monoaxial niobium oxalate (7,12 g) is stirred in 40 ml of water during the night. Solution C. gallium Oxide (to 0.645 g) is stirred in 20 ml of water during the night. The solution is added to dissolve the And, then add the solution, and after 5 minutes the resulting mixture is subjected to spray drying to obtain the precursor of the solid catalyst. The catalyst precursor is heated in air at 120°C for 1 h, and then decompose at 300°C for 5 h, and calcined in argon at 600°C for 2 h the Resulting powder is crushed by crushing and sieved 18/35 mesh. This catalyst (1 g) tested in the oxidation of propane with raw materials, with the ratio of propane/About2/N2/water equal to 1/1,6/14,4/15. These results are shown in the table.

Example 4

Preparing a mixed metal oxide composition with a nominal composition of Mo1Vfor 0.3Nb0,05Sbof 0.15Ca0,03W0,012Oxas follows.

Solution A. ammonium Vanadate (of 7.95 g) was dissolved in 170 ml of water while heating, Add the oxide of antimony (III) (4,92 g), and the mixture is heated under 96-100°With approximately 4 hours in a stream of nitrogen. The heating is stopped, and the mixture is cooled overnight in a nitrogen atmosphere. Add paramolybdate ammonium (40,0). Part water (100 g) is removed using a rotary evaporator. The mixture is stirred only for 1.5 hours the Solution Century. Monoaxial niobium oxalate (7,12 g) is stirred in 40 ml of water during the night. Solution C. gallium Oxide (0,654 g) is stirred in 20 ml of water during the night. The solution is To add auth to the solution, then add the solution, and after 20 minutes the resulting mixture is subjected to spray drying to obtain the precursor of the solid catalyst. The catalyst precursor is heated in air at 120°C for 1 h, and then decompose at 300°C for 5 hours the mixture (9,23 g) after decomposition impregnate 0.156 g of ammonium tungstate in 5 ml of water. The solid is dried at 50°With, then at 300°C for 30 minutes and then calcined in argon at 600°C for 2 h the Resulting powder is crushed by crushing and sieved 18/35 mesh. This catalyst (1 g) tested in the oxidation of propane with raw materials, with the ratio of propane/About2/N2/water equal to 1/1,6/14,4/15. These results are shown in the table.

Example 5

Mixed metal oxide catalyst (1 g)obtained in example 4 is tested in the oxidation of propane with raw materials, with the ratio of propane/O2/N2/water equal to 1/3,0/27/14. These results are shown in the table.

Example 6

Preparing a mixed metal oxide composition with a nominal composition of Mo1Vfor 0.3Nb0,05Sbof 0.15Ag0,06Oxin the following way. Solution A. ammonium Vanadate (of 7.95 g) was dissolved in 165 ml of water by heating. Add oxide of antimony (III) (4,92 g)and the mixture is blown with nitrogen and heated at 95°With approximately 5 h Heating stop, and the mixture is cooled overnight in a nitrogen atmosphere. Part water (130 ml) is removed using a rotary evaporator. Add paramolybdate ammonium (40,0 g)and the mixture stirred for 4 h under nitrogen atmosphere. The solution Century. Monoaxial niobium oxalate (7,12 g) is stirred in 40 ml of water during the night. Solution C. silver Nitrate (2,31 g) was dissolved in 20 ml of water. The solution is added to the solution, then add the solution, and the resulting mixture was kept under nitrogen atmosphere for 20 minutes, then subjected to spray drying to obtain the precursor of the solid catalyst. The catalyst precursor is heated in air at 120°C for 1 h, and then decompose at 300°C for 5 h, and then calcined in argon at 600°C for 2 h the Resulting powder is crushed by crushing and sieved 18/35 mesh. This catalyst (2.6 g) is tested in the oxidation of propane with raw materials, with the ratio of propane/O2/N2/water equal to 1/1,6/14,4/15. These results are shown in the table.

Example 7

Mixed metal oxide catalyst (1.8 g)obtained in example 6, are tested in the oxidation of propane with raw materials, with the ratio of propane/O2/N2/water equal to 1/0,5/4,5/1,3. These results are shown in the table.

Example 8

Preparing a mixed metal oxide composition nominal composition is and Mo 1Vfor 0.3Nb0,05Sbof 0.15Au0,015Oxin the following way. Solution A. ammonium Vanadate (of 7.95 g) was dissolved in 165 ml of water by heating. Add oxide of antimony (III) (4,92 g), and the mixture is heated at 94°With approximately 4,5 hours stop Heating, and the mixture is cooled during the night. Part water (105 ml) is removed using a rotary evaporator. Add paramolybdate ammonium (40,0 g), and the mixture is stirred for 2.5 h under nitrogen atmosphere. The solution Century. Monoacetate of niobium oxalate (7,12 g) is stirred in 40 ml of water during the night. The solution C. the Hydroxide of gold (0,843 g) is suspended in 60 ml of water. The solution is added to the solution, then add the solution, the resulting mixture is stirred for 15 minutes, and then subjected to spray drying to obtain the precursor of the solid catalyst. The catalyst precursor is heated in air at 120°C for 1 h, and then decompose at 300°C for 5 h, and then calcined in argon at 600°C for 2 h the Resulting powder is crushed by crushing and sieved 18/35 mesh. This catalyst (2.7 g) is tested in the oxidation of propane with raw materials, with the ratio of propane/O2/N2/water equal to 1/1,6/14,4/15. These results are shown in the table.

Example 9

Mixed metal oxide catalyst (2.7 g)obtained in Primera, tested in the oxidation of propane with raw materials, with the ratio of propane/O2/N2/water equal to 1/3,0/27/14. These results are shown in the table.

Example 10

Mixed metal oxide catalyst (2.7 g)obtained in example 8, is tested in the oxidation of propane with raw materials, with the ratio of propane/O2/N2/water equal to 1/1,6/14,4/15. These results are shown in the table.

Example 11

Preparing a mixed metal oxide composition with a nominal composition of Mo1Vfor 0.3Nb0,05Sbof 0.15Bi0,03Oxin the following way. Solution A. ammonium Vanadate (of 7.95 g) was dissolved in 165 ml of water by heating. Debavalya oxide antimony (III) (4,92 g), and the mixture is heated at 95°C for 4 hours

The heating is stopped, and the mixture is cooled in nitrogen atmosphere overnight. Water (109 g) is removed using a rotary evaporator. Add solid paramolybdate ammonium (40,0 g)and the mixture stirred for 4 h the Solution Century. Monoaxial niobium oxalate (7,12 g) is stirred in 40 ml of water for 4 hours the Solution C. the nitrate Pentahydrate bismuth (3,298 g) is suspended in 60 ml of water for 4 hours the Solution is added to the solution, then add the solution, and after 5 minutes the resulting mixture is subjected to spray drying to obtain the precursor of the solid catalyst. The catalyst precursor is heated in air at 120� C for 1 h, and then decompose at 300°C for 5 h, and then calcined in argon at 600°C for 2 h the Resulting powder is crushed by crushing and sieved 18/35 mesh. This catalyst (2.65 g) tested in the oxidation of propane with raw materials, with the ratio of propane/O2/N2/water equal to 1/3,0/27/14. These results are shown in the table.

Example 12

Mixed metal oxide catalyst (1 g)obtained in example 11, is tested in the oxidation of propane with raw materials, with the ratio of propane/O2/N2/water equal to 1/3,0/27/14. These results are shown in the table.

For each of the catalysts of the examples above the specified weight of the catalyst is mixed with a sufficient quantity of silica fume to get the layer of catalyst 5.0 ml reactor with supply of raw materials from the top down. The reactor is heated to the temperature indicated in each example. A mixture of propane, oxygen, nitrogen and water vapor having a composition and flow rate specified in the table, served in the reactor.

The reaction is carried out under pressure specified in the table, at least for three hours. The calculated value of the degree of conversion (%)selectivity (%) acrylic acid (AA) and productivity (kg AK/(m3catch) - kg of acrylic acid per cubic meter of catalyst per hour) is shown in the face.

Table
Examples No.The temperature in the catalyst bed (°)The pressure at the inlet to the reactor pound/square inch (kPa)The contact time of the reactant (s)The gas flow (l/l(cat)h)Conversion of propane, %Selectivity for AK, %The output AK, %Capacity, kg AK/m3(cat)h
Srvnet40020 (137,9)0,3697034040,016,2169,7
Srvnet40020 (137,9)0,221536330of 45.713,8216,6
Srvnet40020 (137,9)0,27127853341,413,8190,4
140032 (241,32)0,27169344753,3to 25.3435,3
240020 (137,9)0,31110685148,825,0281,5
340020 (137,9) 0,30116663739,114.4V177,0
440032 (241,32)0,33141413139,512,3180
538032 (241,32)0,7167604529,913,667
640032 (241,32)1,1939115056,228,2118
736020 (137,9)0,4482661357,17,6280
840010 (68,9)0,5346143240,713,259,8
940032 (241,32)1,0444575839,222,674,1
1040032 (241,32)1,0146024839,519,086,0
1138020 (137,9)0,8143725644,525,18,0

The above examples demonstrate the effectiveness of the mixed metal oxide molybdenate catalyst containing antimony, niobium and one of the elements gallium, silver or gold, for the conversion of the alkane to an unsaturated carboxylic acid in a one-step process. Moreover, the use of such a catalyst which contains gallium, as shown by the above data, provides the following benefits: improves the conversion of propane, the selectivity for acrylic acid, the yield of acrylic acid and performance acrylic acid. Under the given conditions, there are advantages to using such a catalyst which contains silver or gold, or gallium, and tungsten.

Obviously, in light of the above recommendations, there are numerous modifications and variations of the present invention. Therefore, it should be understood that within the scope of the accompanying claims, the invention may be practically carried out differently than specified in the description.

Catalyst and method of the present invention is applicable to other reaction systems, such as reactors, fixed bed, moving bed and fluidized layer. For the desired reaction systems the particle size of the catalyst and process conditions can be changed.

Cat is a lyst of the present invention should be applicable to other processes, such as amoicillin alkanes and olefins, for example, of Acrylonitrile from propane, oxygen and ammonia or getting Methacrylonitrile of isobutane, oxygen, and ammonia.

1. Catalytic composition for obtaining unsaturated carboxylic acid from an alkane containing compound of the formula:

Mo1VaSbbNbcMdOx,

in which Mo represents molybdenum, V means vanadium, Sb means antimony, Nb is niobium, M represents gallium, and ranges from 0.01 to 1, b is from 0.01 to 1, C is from 0.01 to 1, d is from 0.01 to 1 and x is determined by the valence requirements of the other elements present.

2. The catalytic composition according to claim 1, which additionally contains M' number e, where M' represents tantalum, titanium, aluminum, zirconium, chromium, manganese, iron, ruthenium, cobalt, rhodium, Nickel, platinum, boron, arsenic, lithium, sodium, potassium, rubidium, calcium, beryllium, magnesium, cerium, strontium, hafnium, phosphorus, europium, gadolinium, dysprosium, holmium, erbium, thulium, terbium, ytterbium, lutetium, lanthanum, scandium, palladium, praseodymium, neodymium, yttrium, thorium, tungsten, cesium, zinc, tin, germanium, silicon, lead, barium and thallium, and s ranges from 0.0 to 1.

3. The catalytic composition according to claim 1, in which as is 0.3.

4. The catalytic composition according to claim 1, inwhich b is equal to 0.15.

5. The catalytic composition according to claim 1, in which a is equal to 0.05.

6. The catalytic composition according to claim 1 or 2 which is selected from the group consisting of Mo1Vfor 0.3Sbof 0.15Nb0,05Ga0,03Ox; Mo1Vfor 0.3Sb0,08Nb0,05Ga0,03Ox; and Mo1Vfor 0.3Nb0,05Sbof 0.15Ga0,03W0,012Ox.

7. The catalytic composition according to claim 1, in which the catalytic composition is deposited on an inert carrier.

8. The catalytic composition according to claim 7, in which the inert carrier is a silicon dioxide, aluminum oxide, niobium oxide, titanium oxide, zirconium oxide or mixtures thereof.

9. The catalytic composition according to claim 1, in which the catalytic composition is formed into the form of a powder, granules, spheres, cylinders or pillows.



 

Same patents:

FIELD: organic chemistry, medicine, dermatology.

SUBSTANCE: invention relates to zinc and aliphatic halogen-carboxylic acid salts that can be used in treatment of benign neoplasms of skin and visible mucosa tissues. Invention proposes the following formula of zinc and aliphatic halogen-carboxylic acid salts: (1): wherein R means -CHal3, -CHHal2, -CH2Hal and (2): wherein R' means Alk, hydrogen atom (H); R'' means Hal; R' means Alk; R'' means H, Alk wherein in these formulae halogen atom can be represented by fluorine atom (F), chlorine atom (Cl), bromine atom (Br) or iodine atom (J). Invention provides the development of original preparation used in treatment of benign neoplasms of skin and visible mucosa tissues with low toxicity, rapid effect, expressed therapeutic effect and eliciting good tolerance, absence of complications in treatment, healing without formation of scar tissue. The development of the preparation provides expanding assortment of agents used in treatment of such diseases.

EFFECT: enhanced and valuable properties of agents.

13 ex

The invention relates to a method for production of propionic acid by hydroxycarbonylmethyl ethylene carbon monoxide in the environment of water and organic Karabanovo acid2-C4

FIELD: chemistry.

SUBSTANCE: reaction of alkene with molecular oxygen is carried out in reactor with pseudoliquefied layer in presence of catalytically active pseudoliquefied layer of solid particles, which lies in the following: gas, containing molecular oxygen, concentration of oxygen in which exceeds its concentration in air, is introduced into pseudoliquefied layer simultaneously supporting turbulent mode in pseudoliquefied layer. Invention also relates to method of obtaining vinylacetate by reaction of ethylene and acetic acid with molecular oxygen in reactor with pseudoliquefied layer in presence of catalytically active pseudoliquefied layer of solid particles, which have diameter in range from 20 to 300 mcm, distribution according to particle diameter constitutes at least 20 mcm; at to method of carrying out reaction of molecular oxygen with ethane, ethylene or their mixture obtaining acetic acid and optionally ethylene in reactor with pseudoliquefied layer in presence of catalytically active pseudoliquefied layer of solid particles.

EFFECT: elaboration of safer method of carrying out reaction.

45 cl, 2 tbl, 3 ex,4 dwg

FIELD: chemistry.

SUBSTANCE: invention concerns improved method for obtaining (meth)acrylic acid involving steam phase catalytic oxidation of propylene, propane or isobutylene for production of reaction mix, absorption of oxidised reaction product in water to obtain water solution containing (meth)acrylic acid, concentration of water solution in the presence of azeotropic agent and distillation of obtained (meth)acrylic acid in distillation column to obtaining purified (meth)acrylic acid. During operation of distillation column, including operation interruption and resumption, the column is washed with water, and afterwards azeotropic distillation is performed in the presence of azeotropic agent.

EFFECT: efficient and fast cleaning of distillation column with extraction of valuable substance.

5 cl, 5 dwg, 3 ex

FIELD: heating.

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

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

3 cl, 6 dwg, 2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to method of oxidising alkane from C2 to C4 with the obtaining of corresponding alkene and carboxylic acids. The method includes the following stages: (a) contact in the oxidation reaction zone of the alkane, which contains molecular oxygen gas, not necessarily corresponding to the alkene and not necessarily water in the presence of at least one catalyst, effective with the oxidation of the alkane to the corresponding alkene and carboxylic acid, alkane, oxygen and water; (b) separation in the first separating agent at least part of the first stream of products in a gaseous stream, which includes alkene, alkane and oxygen, and a liquid stream, which includes carboxylic acid; (c) contact of the mentioned gaseous stream with the solution of a salt of metal, capable of selectively chemically absorbing alkene, with the formation of a liquid stream rich in chemically absorbed alkene; (d) isolation from the flow of the solution of salt of the metal. The invention also relates to combined methods of obtaining alkyl-carboxylate or alkenyl-carboxylate (for example vinyl acetate), moreover these methods include oxidising of alkane from C2 to C4 with the obtaining of corresponding alkene and carboxylic acid, isolation of alkene from the mixture of alkene, alkane and oxygen by absorption using the solution of the salt of metal and extraction of the stream rich in alkene from the solution of the salt from metal for using when obtaining alkyl-carboxylate and alkenyl-carboxylate.

EFFECT: improved method of oxidising alkane from C2 to C4 with the obtaining of corresponding alkene and carboxylic acids.

46 cl, 1 dwg

FIELD: industrial organic synthesis.

SUBSTANCE: invention relates to a process for production of C2-C4-alkane into alkene and carboxylic acid and immediately using them in ester synthesis stage. According to invention, to produce alkyl carboxylate, in particular ethyl acetate, or alkenyl carboxylate, in particular vinyl acetate, stage wherein alkane is oxidized to corresponding alkene and carboxylic acid is combined with alkenyl carboxylate or alkyl carboxylate production stage. Process comprises contacting of alkane- and alkene-containing gas raw material with molecular oxygen and catalyst in the first oxidation reaction zone, catalyst being efficient in oxidation of alkane into corresponding alkene and carboxylic acid. In the second reaction zone, part of streams isolated in separation stage and enriched with alkene and carboxylic acid is brought into contact with at least one catalyst efficient to produce either alkyl carboxylate or alkenyl carboxylate in presence of oxygen-containing gas. For example, first product stream consists of ethylene and acetic acid with water admixture. In the second reaction zone, stream enriched with alkene and carboxylic acid comes into contact with oxygen, optionally in presence of additional amount of ethylene and/or acetic acid from the first product stream. As a result, second product stream comprising vinyl acetate, water, acetic acid, and optionally small amounts of carbon oxides is obtained. Second product stream is separated into fractions containing vinyl acetate and acetic acid, which are subjected to further purification. In a cycle wherein acetic acid from main fraction is regenerated, the latter is recycled to vinyl acetate stage in the second reaction zone.

EFFECT: improved economical efficiency of process.

36 cl, 1 dwg

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: chemistry of halogenated hydrocarbon, chemical technology.

SUBSTANCE: invention relates to an improved method for synthesis of higher saturated chlorinated acids of the general formula: R(CHCl)nCOOH wherein R means aliphatic hydrocarbon radical comprising 9-22 carbon atoms; n = 1-4. Method involves oxidation of chloroparaffins in the presence of catalyst that is mixed with chloroparaffins in the presence of air oxygen at temperature 120-1250C, and oxidation is carried out with air oxygen at temperature 105-1100C under atmosphere pressure for 30-32 h, and wherein cobalt stearate is used as catalyst taken in the amount 1.5-1.7 wt.-% of the reaction mass. Invention provides increasing rate in carrying out the reaction and simplifying the method.

EFFECT: improved method of synthesis.

5 ex

FIELD: industrial organic synthesis.

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

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

5 cl, 1 dwg, 10 ex

FIELD: 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

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to the improved method for oxidation of (C2-C4)-alkane and preparing the corresponding alkene and carboxylic acid. Method involves addition of this alkane to contact with molecular oxygen-containing gas in oxidative reaction zone and optionally at least one corresponding alkene and water in the presence of at least two catalysts with different selectivity. Each catalyst is effective in oxidation of alkane to corresponding alkene and carboxylic acid resulting to formation of product comprising alkene, carboxylic acid and water wherein the molar ratio between alkene and carboxylic acid synthesized in the reaction zone is regulated or maintained at the required level by regulation the relative amounts of at least two catalyst in the oxidative reaction zone. Also, invention relates to the combined method for preparing alkyl carboxylate comprising abovementioned stage in preparing alkene and carboxylic acid in the first reaction zone. Then method involves the stage for addition of at least part of each alkene and carboxylic acid prepared in the first reaction zone to the inter-contacting in the second reaction zone the presence of at least one catalyst that is effective in preparing alkyl carboxylate to yield this alkyl carboxylate. Also, invention relates to a method for preparing alkenyl carboxylate comprising the abovementioned stage for preparing alkene and carboxylic acid in the first reaction zone and stage for inter-contacting in the second reaction zone of at least part of each alkene and carboxylic acid synthesized in the first reaction zone and molecular oxygen-containing gas in the presence of at least one catalyst that is effective in preparing alkenyl carboxylate and resulting to preparing this alkenyl carboxylate.

EFFECT: improved method for oxidation.

30 cl, 1 dwg, 5 tbl, 14 ex

FIELD: chemistry.

SUBSTANCE: invention relates to composition based on gold and reducible oxide, method of its production and its application as catalyst, in particular in carbon monoxide oxidation. Described is composition based on gold on carrier based on reducible oxide, as such composition contains titanium or iron (III) oxide, content of halogen in composition, expressed by molar ratio halogen/gold, constitutes not more than 0.05, content of gold in it constitutes not more than 1%, gold is in form of particles with size not more than 10nm, and composition is subjected to reducing processing. Described is method of composition production, which contains following stages: bringing in contact compound based on reducible titanium or iron (III) oxide and compound based on gold halogenated and, in case of necessity, compound based on silver, with formation of suspension of said compounds, pH of obtained medium being set not lower than 8; separation of solid substance from reaction medium; washing solid substance with alkaline solution; in addition method includes reducing processing after mentioned above washing stage. Described is method of carbon monoxide oxidation, method of air purification and method of cigarette smoke purification using described above composition as catalyst.

EFFECT: elaboration of catalysts, efficient at low temperatures and/or high hour volume rates.

16 cl, 12 tbl, 15 ex

FIELD: industrial organic synthesis catalysts.

SUBSTANCE: invention provides catalyst containing vanadium, at least one alkali metal compound, and, if necessary, one or several promoters on porous carrier, said catalyst being prepared by applying at least one palladium compound onto porous carrier, in particular titanium dioxide, followed by reduction at 300-500°C. According to invention, before or after reduction, at least one alkali metal compound and, if necessary, one or several promoters are applied. Catalyst is used in gas-phase production of vinyl acetate from ethylene, aqueous, and oxygen or oxygen-containing gases.

EFFECT: increased selectivity and productivity of catalyst.

12 cl, 1 tbl, 10 ex

The invention relates to a method for producing vinyl acetate and a catalyst intended for use in this method

The invention relates to a method for preparing a catalyst which comprises a noble metal and a metal, which is the promoter of catalysis, in combination with the compound of the alkali or alkaline-earth metal deposited on the outer surface of the carrier

The invention relates to methods of producing a catalyst containing metallic palladium and gold, to obtain a vinyl acetate by reaction of ethylene, oxygen and acetic acid, and a process for the production of vinyl acetate using the obtained catalyst

The invention relates to catalysts for production of vinyl acetate by reaction of ethylene, oxygen and acetic acid

The invention relates to a new method of preparation of the catalyst for vapor-phase reaction of ethylene, oxygen and acetic acid to form vinyl acetate, wherein said catalyst comprises metallic palladium and gold deposited on a suitable porous media

The invention relates to a method for producing a catalyst for production of vinyl acetate by reaction of ethylene, oxygen and acetic acid containing porous media, porous surfaces of which is coated with an effective amount of copper, palladium and gold
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