Highly-porous honeycomb catalyst for processes of liquid-phase hydration
SUBSTANCE: invention relates to processes of catalytic hydration. Claimed is catalyst for liquid-phase hydration of organic substances of various classes i.e. nitro-compounds, aldehides, unsaturated and aromatic compounds, with molecular hydrogen, which includes unit-type carrier of low density and high porosity and metallic palladium. Carrier is made from aluminium oxide by method of doubling foam-polyurethane matrix by impregnating it with slip Al2O3 with further calcination. Layers of γ-Al2O3 are applied on carrier successively in such a way that weight of active layer from γ-Al2O3 is not less than 6% of total weight of catalyst, and of metallic palladium in amount of 0.16-3.7%. Alternatively, instead of γ-Al2O3 layer, layer of sulphated oxide of titanium or zirconium in amount of 8-9% is applied on carrier. Due to developed surface, the claimed catalyst is efficient when hydrating compounds of various classes, and has high mechanical strength, which eliminates its abrasion in the process of exploitation.
EFFECT: obtaining catalyst efficient when hydrating compounds of various classes, and having high mechanical strength, which eliminates its abrasion in the process of exploitation.
2 cl, 1 tbl, 14 ex
The present invention relates to the field of chemical technology, more narrowly to catalytic processes, in particular to catalytic hydrogenation.
Currently, the catalytic hydrogenation is the main industrial method of recovery of nitro compounds, unsaturated and aromatic compounds, various functional groups such as carbonyl, nitrile, etc.
As hydrogenation catalysts use a wide variety of media, the active components of the catalyst and promoters.
The most widespread as the media in the processes of hydrogenation of the obtained activated carbon, metal oxides, primarily Al2About3, TiO2and other, silica, zeolites, etc. Carriers are made in the form of powder, granules, tablets; in the last decade, widespread block, cell and tissue holders.
As an active part of the catalysts most often used metals of the VIII group of the periodic system (the group of iron, ruthenium and osmium), the main place among them is occupied by Ni and Pd. The hydrogenations are heavily influenced by the promoters and the environment of the reaction.
Especially in the reactivity of restorable connections lead to significant differences in the composition of the catalysts used in ishemic for hydrogenation. Therefore, the number of catalysts a wide spectrum of action is very limited. These include the catalyst proposed in patent 2095136 RF (prototype). It consists of powdered media (activated carbon, aluminum oxide, silicon oxide, and others), on the surface of which is coated with a mixture containing 0.08-0.5% Nickel, 0.05 to 0.7% of palladium and 0.3% of iron (all by weight of the carrier). The disadvantage of this catalyst is its disintegration during operation and, as a consequence, mechanical losses, reduced activity and contamination of the reaction products.
The aim of the present invention is a highly efficient catalyst for the hydrogenation of mono - and policetraining in amines, unsaturated and aromatic substances in linear and circular marginal compounds, carbonyl and carboxyl compounds to alcohols, hydrogenation of rosin, etc.
Features of the catalyst of liquid-phase catalytic hydrogenation of molecular hydrogen on the catalyst comprising metals of group VIII, characterized in that it is modular medium low density (BNP) and high porosity (porosity of more than 90%) are made of aluminum oxide by the method of duplicating a polyurethane matrix (soaking her slip Al2About3the content of Al2About3not less than 95% and subsequent annealing), and then at him the placenta is subsequently applied layers γ -Al2About3or sulfated metal oxide of group IV and then the metal palladium. Content γ-Al2About3in the catalyst is >6%, the content of sulfated oxides of titanium or zirconium 8-9%, the content of metallic palladium is equal to 0.16-3,7%.
The use of highly porous honeycomb catalyst designed as a single block or set of blocks, which passes through a gas-liquid flow solution reducible compounds and hydrogen, on the one hand, due to the developed surface provides a high rate of hydrogenation, and on the other, due to the high mechanical strength almost completely eliminates grinding and entrainment of the catalyst.
Before the experiments for the hydrogenation of preparing the catalyst according to the following technology.
Preparation of polyurethane foam impregnated by immersing it in the slip (Al2About3up to 25% water and 5% additives) and exposing cyclical effects (compression-tension). Excess slurry is removed by release of the sample to a predetermined weight. Drying the impregnated billet is carried out at a temperature of 100-120°and firing in an air atmosphere at 1450°C.
For the deposition of aluminum oxide - γ-Al2About3use a solution of hydrated aluminum nitrate [Al(NO3)3·N2O]. The sample manufactured by the th of BNP, immersed in a hot solution of hydrated and after extracting the dried first at room temperature and then in an oven at 90-100°C. is Applied sequentially two or more layers γ-Al2About3to the mass of the active layer of the γ-Al2About3was not less than 6% of the total mass of the catalyst. The firing is carried out at 500-550°to ensure that the aluminum oxide has been preserved in the γform.
The mass of the active layer of the γ-Al2About3must be at least 6% of the total mass
Application of solid acid and supercyclic catalysts is carried out in two stages. At first as a secondary coating is applied to the oxides of titanium or zirconium. The method of applying these oxides similar to that described for aluminum oxide. As the source of solutions to obtain titanium oxide used tetrabutoxide, and zirconium oxide - zirconium nitrate.
In the second stage sulfated oxide receive, immersing the carrier in a 1 n solution of sulfuric acid; after removal of the media and runoff of excess acid its calcined at 600-650°C. the Total number of marked sulfated oxides 8-9 wt.%.
The application of metallic palladium is also carried out in several stages. The resulting carrier is impregnated with a palladium nitrate solution for one or more operations, dried and calcined for p is slorenia nitrate to oxide. The palladium oxide restore molecular hydrogen in the environment of alcohol immediately before the experiments for the hydrogenation of nitro compounds at room or elevated temperature.
In the reactor, consisting of the reaction zone (equipped with a heated jacket and a vertical pipe with a diameter of 0.02 m and a height of 5 m, which rises with the speed of 1 m/s gas-liquid flow, having a density of 0.3 g/cm3; in the middle of the tube has an extension, which is the catalyst), the separation zone and the recirculation zone (similar to a pipe that moves down the reaction mass having a density of 0.9 g/cm3), continuously serves a 5% solution of nitrobenzene in isopropyl alcohol (400 ml/hour and hydrogen at a rate of 15 moles of H21 mol of nitrobenzene. The reaction proceeds in the Central part of the reaction zone, which is a pipe with an inner diameter of 50 mm and a height of 800 mm, which is 300 g of catalyst (viscoplastic block media printed on its surface 6% γ-Al2O3and 3% metallic palladium in the form of cylindrical elements with a diameter of 50 mm and height 50 mm Elements mounted close to the walls of the tube and without a gap between them, to prevent leakage of the reaction mass by catalyst. Before continuous operation in the apparatus load of 3.5 l isoprop the business of alcohol and a constant supply of hydrogen, the pressure at the end of the preparatory period reaches 6.2 kg/cm2start the dosage of the solution of nitro compounds. The experience lasted 100 hours without significant reduction in the activity of the catalyst. Despite the large number of cycles, the average duration of which was about 30 s, the accumulation of primary nitro compounds, and any by-products did not occur. Output technical aniline - 99,0%, the content of nitrobenzene in the raw product is less than 0.1%.
In the catalytic zone of the circulation loop (total contour 2.5 l) was placed 387 g of catalyst containing 2.5% of palladium metal (density of the catalyst - 0.39 g/cm3the porosity of 90%, microporosity - 25%, the material of the carrier is a mixture ofand γ-form of aluminum oxide). The catalyst was placed in the left (ascending tube path in the form of an Assembly of 10 blocks of 100 cm each. Then in the contour fill in 1600 ml of a solution of rosin in ethanol containing 200 g of rosin, and begin the flow of hydrogen into the mixer. The circulation of liquid in the circuit is provided by the difference in densities of gas-liquid flow in the ascending line and the liquid downward. Separating the reaction mixture from hydrogen is carried out in the separator. The content of abietic acid in the original rosin 53%, an acid number of 70 mg Koh/ml, color Wg. The hydrogenation was carried out at a temperature of 110°C, a hydrogen pressure of 0.4 MPa, a duration of 6 hours, the acid number 163,4 mg Koh/ml, color W, abietic acid less than 0.1%.
The recovery of a number of aromatic mono - and policetraining (nitrogroup), anilines (hydrogenation in cyclohexylamin), samalanga aldehyde (reduction of carbonyl group) conducted in the reactor, which is a cylindrical vessel with an inner diameter of 50 mm and a total volume of 400 ml, made of stainless steel. The reactor was loaded with 100 ml of ethyl or isopropyl alcohol was added 1 g of reducible compounds (the results of the experiments are presented in table 1). Highly porous honeycomb catalyst mass 18-43 g containing 1,8-3,7% palladium and 8-9% sulfated zirconium oxide or titanium, placed in the middle part of the reactor, providing its immobility due to Teflon crosses and washers. The reactor clamp is mounted on the rocking chair with the number of swings 120-160/min
Maintaining the desired temperature in the reactor was carried out by the flow of the coolant in the jacket of the reactor from thermostat. To prevent heat loss into the environment of the reactor is insulated with a layer of asbestos.
Free volume of the reactor was filled with hydrogen to the initial pressure of 0.5 MPa. The reaction rate was evaluated by the pressure drop in the reactor at a given temperature. The reaction products were analyzed by gas chromatography, the yield of the target product and its purity above 98%.
|№ p/p||Nitrocompounds||ITAK,% Pd||m cat, g||T °||t with||W50%, ml/s||G||The reaction products|
|2.||p-nitrobenzoic acid||2,13||43,07||63||107||2,70||0,39||P-aminobenzoic acid|
|10.||Polyamine THAT 113-03-22-67-83||3,4||38||126||2036||0,07||0,02||Polycyclohexylene|
|W50- the rate of hydrogen absorption at 50% conversion of the original product;|
|G - loading on the catalyst g of starting compound to grams of catalyst per hour.|
In the installation, similar to that described in examples 3-12, spent the restoration of p-nitrotoluene at low palladium catalyst. The reactor was loaded with 100 ml of ethanol was added 1 g u-NIT is toluol. The mass of catalyst - 24.4 g, the substrate of sulfated zirconium oxide, palladium content - 0,16%. The temperature of the experience 56°, the time of half-transformation 66, W50=of 4.44 ml/s, the load on the catalyst 1.1 g/g Obtained p-toluidine with a purity of more than 99%.
In the installation, similar to that described in examples 2-12, restoring gum rosin spent on low-interest palladium catalyst. The reactor was loaded with 100 ml of ethyl alcohol was added 4 g of gum rosin. The mass of catalyst - 21,5 g, the substrate of sulfated zirconium oxide, palladium content of 0.20%. The temperature of the experience 114°, the time of half-transformation 53, W50=2,75 ml/s, the load on the catalyst 8,15 g/g Content of abietic acid in the original rosin - 53%, the resulting product is less than 1%.
1. The catalyst of liquid-phase hydrogenation with molecular hydrogen, including the media and the metal of group VIII, characterized in that as the carrier using block media of low density and high porosity, which is made of aluminum oxide by the method of duplicating a polyurethane matrix by soaking her slip Al2O3with further annealing, and as the metal of group VIII use of metallic palladium on the carrier successively superimposed layers γ-Al2About3so that the mass AK the active layer of the γ -Al2O3was not less than 6% of the total mass of the catalyst, or a sulfated metal oxide is titanium or zirconium in the number of 8-9% and palladium metal in the amount of 0.16 to 3.7%.
2. The catalyst according to claim 1, characterized in that it can be used for the hydrogenation of nitro compounds to amines, unsaturated compounds to saturated aldehydes to alcohols, aromatic compounds in saturated cyclic compounds.
FIELD: chemistry, inorganic.
SUBSTANCE: invention relates to the catalytic liquid-phase processes, namely for the preparation of a catalyst to be used in the technology of obtaining products from the natural resins, for example rosin, in particular for the modification of gum rosin. Described is a highly porous catalyst for the modification of gum rosin, that consists of a carrier - a highly porous cellular block material on the basis of α-oxide of aluminium and the active part of the catalyst of the sulphated metallic oxide from the IV group and metallic palladium, thus the carrier is made to soak up soluble salts of palladium, is preliminarily processed in a constant magnetic field, and in the composition of the active part of the catalyst there is γ-Al2O3 in a quantity not less than 10% of the mass, from the quantity of α-Al2O3, sulphated zirconium dioxide in a quantity of not more than 8% of the mass, of metallic palladium in a quantity of not more than 0.2% of the mass. Technical result - reduction of the composition of metallic palladium in the active component by more than 10 times, with the retention of the load on the catalyst 5-7hr-1, and the residual content of abietic acids not more than 0.1% hydrogenated and about 3% disproportionated rosin.
EFFECT: reduction of the composition of metallic palladium in the active component.
1 cl, 6 ex
FIELD: organic synthesis catalysts.
SUBSTANCE: catalyst for modifying colophony contains, as carrier, high-porosity cellular α-alumina-based block material and, as active catalyst fraction, sulfated group IV metal oxide and metallic palladium.
EFFECT: increased modification rate due to developed catalyst surface and eliminated disintegration and carry-over of catalyst.
FIELD: natural compounds, chemical technology.
SUBSTANCE: invention relates to technology for preparing substances from the natural resins, in particular, to colophony hydrogenation. Method for catalytic hydrogenation of colophony with gaseous hydrogen is carried out on solid catalysts comprising palladium as a metal under enhanced pressure and temperature in the presence of organic solvent. Hydrogenation reaction is carried out in circulating contour wherein hydrogen is dispersed firstly in colophony alcoholic solution and the prepared gaseous-liquid mixture is passed through the catalytic zone filled with the catalyst comprising the highly porous cellular carrier made of aluminum oxide and prepared by the doubling method of polyurethane foam matrix. Method provides the complete elimination of the catalyst grinding, prolonged exploitation working life of catalyst, elimination of loss in separation of the reaction mass from the catalyst and decreasing the pressure value in the process realization.
EFFECT: improved method for hydrogenation.
1 tbl, 1 dwg, 5 ex
FIELD: resin industry.
SUBSTANCE: invention relates to production of polyterpenes, which can be used as oiling agent in manufacture of pressure-sensitive glues, in production of solid and liquid oils, etc. Polyterpene are prepared via continuous polymerization of terpene hydrocarbons in presence of zeolite catalyst by feeding starting hydrocarbons into top section of reactor through perforated cartridge, after which monomer vapors move into catalyst-filled reaction zone at a velocity in full reactor cross-section 0.3-0.4 m/s accompanied by continuous dephlegmation of unconverted part of monomer and returning it into reaction zone. Process is carried out for 7-9 h at 160-170°C. Yield of polyterpenes is 72-80%.
EFFECT: increased uniformity of polyterpene composition (98% dimers).
1 dwg, 1 tbl, 8 ex
FIELD: floatation dressing of non-sulfide ores.
SUBSTANCE: the invention is pertaining to the field of a floatation dressing of non-sulfide ores and may be used in production of floatation reagent-collectors on the basis of fatty acids. The floatation reagent-collector for non-sulfide ores is produced on the basis of saponated fatty acid. Before a saponification of a fatty acid it is heated up to 70-75°С and at stirring action as a regulator of polymerizing inject a phenolic antioxidant Ahydol-1 in amount of 0.5-5 mass %. After the saponification process a produced collector may be added with sodium alkyl sulfate in amount of 4-5 mass %. The flotation collector possesses a high-efficient and high-selective floatation of the non-sulfide ores predominantly barite-containing ores.
EFFECT: the invention ensures production of floatation reagent-collectors on the basis of fatty acids.
4 cl, 1 tbl, 2 ex
FIELD: hydrogenation-dehydrogenation catalysts.
SUBSTANCE: invention relates to novel ruthenium catalysts, method for preparation thereof, and to employment thereof for catalytic hydrogenation of mono- and oligosaccharides in production of corresponding sugar alcohols. Ruthenium hydrogenation catalyst contains ruthenium supported by amorphous silica-based carrier, content of ruthenium being 0.2 to 7% of the weight of carrier, while carrier contains at least 90% silica and less than 10% of crystalline silicon dioxide phases. Catalyst is prepared by single or multiple treatment of carrier material with halogen-free solution of low-molecular weight ruthenium compound and subsequent drying of treated material at temperature not lower than 200°C immediately followed by reduction of dried material with hydrogen at 100 to 350°C. Herein disclosed is also a process for liquid-phase production of sugar alcohols (excepting sorbitol) via catalytic hydrogenation of corresponding mono- and oligosaccharides in presence of proposed catalysts.
EFFECT: increased activity and selectivity of catalysts.
16 cl, 4 tbl, 7 ex
FIELD: chemical technology.
SUBSTANCE: invention relates to a method for synthesis of 1,3-propanediol involving the following steps: (a) formation of aqueous solution of 3-hydroxypropanal; (b) hydrogenation of 3-hydroxypropanal to form crude mixture of 1,3-propanediol, water and cyclic acetal of molecular mass 132 Da (MW 132 cyclic acetal) and/or cyclic acetal of molecular mass 176 Da (MW 176 cyclic acetal); (c) distillation (drying) of indicated crude mixture of 1,3-propanediol for water removing and formation of the second crude mixture of 1,3-propanediol (the first flow of residues after distillation) containing 1,3-propanediol and MQ 132 cyclic acetal and/or MW 176 cyclic acetal; (d) contact of the flow containing MW 132 cyclic acetal and/or MW 176 cyclic acetal with acid-base cation-exchange resin or with acid zeolite, or with soluble acid, and (e) removal of MW 132 cyclic acetal. Method provides enhancing effectiveness for extraction and purification of 1,3-propanediol.
EFFECT: improved method of treatment.
10 cl, 9 tbl, 1 dwg, 6 ex
FIELD: industrial organic synthesis and catalysts.
SUBSTANCE: invention relates to a method for processing of butanol-butyl formate fraction obtained in propylene hydroformylation process, which method comprises reduction of butanol-butyl formate fractions with hydrogen at 200-280°C, pressure 1-30 atm, and volumetric feedstock and hydrogen supply rate 0.1-0.5 and 50-500 h-1, respectively. Reaction is carried out on catalyst having following chemical analysis, wt %: copper oxide 48.0-63.0, zinc oxide 9.0-18.1, chromium oxide 19.0-34.8, graphite 1.0-5.1 and activity index below 40 to form butyl alcohols and carbon oxide as final products. Method allows using real non-diluted butanol-butyl formate fractions and achieving following results: conversion of butyl formates 94.5-99.5%, content of methanol and high-boiling products in hydrogenate 0.8-1.5 and 2.9-3.5%, respectively.
EFFECT: enhanced process efficiency.
4 tbl, 2 ex
FIELD: methods of production of 1.3 alkandiol.
SUBSTANCE: the invention is pertaining to the field of chemical industry, in particular, to production of 1.3 alkandiol by hydrogenation of the raw material, containing 3-hydroxyaldehyde at presence of a catalyst and a source of hydrogen, where as a source of hydrogen use a synthesis gas, and the catalyst represents a heterogeneous catalyst containing copper on the carrier; and also to the method of production of 1.3-alkandiol by conversion of an oxide in the process including a hydroformylation and hydrogenation. At that it is not obligatory to realize the indicated phases simultaneously in one reaction vessel. The reached technical result consists in essential reduction of the fixed value of equipment and in bringing to a "single-phase" production of 1.3-propandiol (or a similar 3-alcandil) from ethylene oxide (or a corresponding oxide).
EFFECT: the invention ensures essential reduction of the fixed value of equipment and reduction to a "single-phase" process of the propandiol or alkandiol production.
9 cl, 2 tbl, 2 ex
FIELD: organic chemistry, in particular production of high oxoalcohols.
SUBSTANCE: invention relates to method for production of high oxoalcohol from isomeric olefin mixture containing from 5 to 24 of carbon atoms. Claimed method includes hydroformylation in presence of catalyst at elevated temperature and elevated pressure. Hydroformylation in carried out in one step, and ones-through olefin conversion is limited in range of 40-90 %. Obtained reaction mixture after catalyst separation is preferably transferred to selective hydration carrying out at 120-220°C and pressure of 5-30 bar in presence of supported catalyst containing copper, nickel and chromium as active ingredients. Hydration product mixture is separated by distillation, and olefin fraction is recycled into hydroformylation step. As starting materials for hydroformylation mixtures of C8-, C9-, C12- or C16-olefins are used.
EFFECT: high olefin conversion ratio, selectivity, and capability.
15 cl, 1 dwg, 1 tbl, 2 ex
SUBSTANCE: organic solvent is used as the extractant in the processes of obtaining or using aniline, with content of aniline in the solvent of 5% mass. Putting the extractant and the water solution into the extractor is done counter-flow. Recovery of the solvent is done through distillation of the obtained extract with obtaining of a residue, containing 10-40% mass of organic solvent. In particular, benzol can be used as the organic solvent, a by-product of the process of obtaining aniline through recovery of nitrobenzol using hydrogen. Recovery of the solvent is done in a distillation column for separating the by-product benzole from the fraction in the process of obtaining aniline.
EFFECT: lowering of heat consumption in the process of recuperating aniline from concentrated solutions by 11-13 times.
2 cl, 2 ex