Highly-porous honeycomb catalyst for processes of liquid-phase hydration

FIELD: chemistry.

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.

Example 1.

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%.

Example 2.

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%.

Examples 3-12

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%.

1,8-dinitronaphthalene
Table
№ p/pNitrocompoundsITAK,% Pdm cat, gT °t withW50%, ml/sGThe reaction products
1.nitrobenzene2,1341,43601162,420,37Aniline
2.p-nitrobenzoic acid2,1343,07631072,700,39P-aminobenzoic acid
3.p-nitroaniline2,1340,82631262,450,35P-diaminobenzoic
4.p-nitrotoluene2,1340,90651072,680,46P-toluidine
5.2,4-dinitrotoluene2,1341,33651263,090,35Diaminotoluene
6/2,5818,0064684,821,471,8-diaminonaphthalene
7.2,4,6-trinitrotoluene2,1335,4255854,960,602,4,6-triaminotoluene
8.Somelady aldehyde3,4382613290,180,042-methylpropanol
9.Aniline1,729,012015400,890,04Cyclohexylamin
10.Polyamine THAT 113-03-22-67-833,43812620360,070,02Polycyclohexylene
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.

Example 13

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%.

Example 14

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.



 

Same patents:

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1 cl, 6 ex

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16 cl, 4 tbl, 7 ex

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4 tbl, 2 ex

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9 cl, 2 tbl, 2 ex

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15 cl, 1 dwg, 1 tbl, 2 ex

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2 cl, 2 ex

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