The method of obtaining 2-methyl-1-naphthol

 

(57) Abstract:

Usage: catalytic alkylation of 1-naphthol with methanol in the gas phase, the development of catalysts. The inventive 1-naphthol will was identified in the ortho-position by passing a vapor mixture of methanol and naphthol through the layer of oxide catalyst at elevated temperatures with subsequent condensation of the reaction products and their separation. In the reaction mass of water is added and the process is conducted at a molar ratio of 1-naphthol: methanol: water, equal 1:(2-5):(1-5), at a temperature of 300-400°C with volumetric feed rate of the reaction mixture 460-1570 h, and as a catalyst a mixture of oxides of iron, vanadium and manganese in an atomic ratio Fe:V:Mn(0,5-1): (0,5-1): (0-0,5), either tabletirujut or granularit in a mixture with a binder, or put on a silica gel. The SiO content in the catalyst 70-75 mA. Finally, the catalyst was calcined at 500-800°C. table 1.

The invention relates to a process for the catalytic methylation of 1-naphthol in the ortho-position with the formation of 2-methyl-1-naphthol and catalysts for this process.

Methylpropane Naftalan are valuable compounds precursors used in the various organizations of the production of elastomers, fragrances and so on [1,2] More valuable it is as a starting substance for the synthesis of b vitamins To the catalytic method, developed in the Institute of catalysis SB RAS [3]

The most efficient method of obtaining 2-methyl-1-naphthol is a vapor-phase catalytic alkylation of 1-naphthol with methanol. The well-known series of works devoted to this reaction. In [4] the alkylation of 1-naphthol with methanol is carried out in the presence of aluminum oxide with different acidity of the surface at temperatures 275-550aboutWith a molar ratio of the naphthol:methanol 1:10 and the load naphthol 0.18 g/g of catalyst per hour. The highest yield of 2-methyl-1-naphthol (21-37%) was obtained at the reaction temperature below 350aboutC. under these conditions, the degree of conversion of 1-naphthol was 37-79% selectivity of the formation of 2-methyl-1-naphthol not exceed 60% and the maximum catalyst productivity on this product reached 0.07 g/,h

Higher methylation reaction 1 Napoli achieved in [5] using the complex oxide catalyst containing the oxides of germanium, antimony, tin or magnesium. At a temperature of 425aboutWith a molar ratio of the naphthol:methanol 1:6 and flow rate 1000 soba methylation is high reaction temperature and a relatively low degree of conversion of 1-naphthol.

The aim of the invention is to develop a more effective method of obtaining 2-methyl-1-naphthol.

In the result, found that the selective methylation of 1-naphthol in the ortho-position can be carried out in the vapor phase at elevated temperatures (300-400about(C) in the presence of two - or three-component oxide catalysts based on iron, vanadium and manganese. Also found that the reaction mixture should contain higher compared with the stoichiometric amount of methanol. Adding the reaction mixture to water in an amount of from 1 to 5 mol per 1 mol of 1-naphthol contributes to a more stable and continuous operation of the catalyst.

The catalysts proposed for obtaining 2-methyl-1-naphthol with high yield, must contain the original components in this range of atomic ratios of Fe:Y:Mn(0,5-1):(1-0,5):(0-0,5). They should be crystallizability and having pores with a total volume of 0.5-1.5 cm3/g after calcination in the temperature range 500-800aboutC.

For the preparation of iron-vanadium-manganese oxide catalysts can be used any soluble salts of these elements, preferably nitrates of iron and manganese and the oxalate vanadocene, any way co-precipitation followed by filtration, spray drying the solution or suspension obtained from this solution at elevated pH. The resulting powder or plastificator with a binder, followed by granulation of pasta by extrusion through a die plate of a given size and shape, or from it to prepare tablets also certain size. As a binder used various substances, including those containing silicon. The extrudate and the tablets are dried and calcined at a temperature of 500-800aboutC.

In addition to these catalysts in this process are encouraged to apply and catalysts on carriers. As the carrier used broad porous silica gel obtained by granulation of Aerosil and its hydrothermal treatment in autoclave at a temperature of 250-350aboutC. the pore silica gel is 30-4000 nm, and their volume of 0.5-1 cm3/, Calcined granules of silica gel impregnated with at capacity with a solution of iron salts, vanadium and manganese in specific molar ratios. After impregnation, the samples are dried and calcined at a temperature of 500-800aboutC.

The methylation reaction of 1-naphthol is carried out in a flow reactor with a fixed bed of caqueza with a particle size of 3-5 mm The catalyst in the reactor calcined in a flow of nitrogen (1-15 l/h) at a temperature of 350-550aboutC for 1 h and Then, without stopping the flow of nitrogen into the reactor serves a mixture of 1-naphthol (H), methanol (M) and water (). The relationships between the components of the reaction mixture H:M:B 1:(2-5):(1-5). The reaction is carried out at a temperature of 300-400aboutC. the reaction Products are collected in a cooled trap and analyze method getaccountinfo chromatography. The contact time varies by changing the feeding speed of the reaction mixture and the amounts of catalyst.

According to the results of chromatographic analysis of phenolic part of the reaction products to determine the degree of reaction of naphthol and selectivity of methylation. The degree of transformation (X, ) is defined as the ratio of the number of moles of unreacted 1-naphthol and missed, the selectivity of the formation of 2-methyl-1-naphthol (MN) (SMN, or 2,4-dimethyl-1-naphthol (DMN) (SDMN,) as the ratio of the numbers of moles formed a certain product and unreacted 1-naphthol.

P R I m e R 1. In a reactor equipped with a mixer, poured 1.2 l of distilled water and bring the temperature up to 70-90aboutWith, and then dissolved under stirring in her 300 g of oxalic acid. Then this is astory add 399,8 g Fe(NO3) 9H2O and to 63.1 g of Mn(NO3)26H2O. the Atomic ratio of Fe:Y:Mn 1:1,1:0,2. After the dissolution of salts in the solution with vigorous stirring, add 12% ammonia solution to achieve a pH of 4. The resulting suspension is sprayed on the spray dryer. The powder calcined at 250aboutWith, and binder is placed in a Z-shaped mixer and plastificator mixture for 0.5 h, the resulting paste granularit by extrusion through a die plate with a diameter of 3 mm Cylindrical pellets of size 3x3 mm, dried, and then calcined at 650aboutC. the Content of SiO2in the catalyst is more than 20 wt. the volume of pores with a radius greater than 15 nm 0.5 cm3/,

4 g of catalyst loaded into the reactor from top to fall asleep layer (3-4 cm) of quartz, which is used as the evaporator of the reaction mixture. The catalyst was calcined in a stream of nitrogen at 400aboutWith, then reduce the temperature to 350aboutWith and into the reactor serves a mixture of naphthol, methanol and water in a molar ratio of N: M:B1:3:1. The reaction products are collected in the trap and analyze chromatographic method. The volumetric feed rate of the nitrogen-steam mixtures 1100 h-1.

P R I m m e R 2. The catalyst is prepared analogously to example 1. Nuclear zootoxin who is 20 wt. Test activity carried out analogously to example 1, the volumetric feed rate of the reaction mixture is 1570 h-1.

P R I m e R 3. The catalyst is prepared analogously to example 1. The atomic ratio of Fe:Y:Mn 1:0,5:0.2, a volume of pores with a radius greater than 15 nm 0.5 cm3/, Test activity carried out analogously to example 1, reaction temperature of 330aboutC.

P R I m e R 4. The catalyst is prepared analogously to example 2. Test activity carried out analogously to example 1, reaction temperature of 330aboutWith, the molar ratio of the components in the reaction mixture H:M:B1:5:2, the volumetric rate filing 1360 h-1.

P R I m e R 5. A mixture of solutions of oxalate vanadyl, nitrate iron (III) and manganese nitrate (II) with an atomic ratio of Fe:Y:Mn 1:0,7:0,1 sprayed on the spray dryer. The resulting powder was tabletirujut, tablet size 3x3 mm Heat treatment pills similar to example 1. The volume of pores with a radius greater than 15 nm 1.5 cm3/, Test activity carried out analogously to example 1.

P R I m e R 6. To a solution of nitrate salts of iron (III) and manganese (II), and metavanadate ammonium with the atomic ratio of Fe:Y:Mn 1:1:0.2 to add 12% aqueous ammonia solution to pH 4, the resulting suspension is dried under inprobable catalyst similar to example 1. The volume of pores with a radius greater than 15 nm is 1.5 cm3/, Test activity carried out analogously to example 1, the volumetric feed rate of the reaction mixture 420 h-1.

P R I m e R 7. The catalyst is prepared analogously to example 6. As a source of vanadium use the oxalate vanadyl. Pore volume in the catalyst with a range greater than 15 nm is 1.5 cm3/, Test activity carried out analogously to example 1, the volumetric feed rate of the reaction mixture 770 h-1.

P R I m e R 8. The catalyst is prepared analogously to example 5, but without manganese atomic ratio of the components in the Fe solution:Y 1:1. Pore volume in the catalyst with a range greater than 15 nm is 1.5 cm3/, Test activity carried out analogously to example 1, the volumetric feed rate of the reaction mixture 700 h-1.

P R I m e R 9. The catalyst is prepared analogously to example 8, the atomic ratio of the components in solution Fe:Y 0.8, the pore volume in the catalyst with a range greater than 15 nm is 1.5 cm3/, Test activity carried out analogously to example 8.

P R I m e R 10. The catalyst is prepared analogously to example 8, the atomic ratio of Fe:Y 1,2, pore volume in the catalyst with a range greater than 15 nm is 1.5 cm3/year / Test>/BR>P R I m e R 11. The catalyst is prepared by impregnation of a broad porous silica gel with a solution of iron salts, vanadium and manganese atomic ratio of Fe:Y:Mn of 1.1: 1:0,2. Silica gel is prepared by mixing 1 kg of Aerosil grades a-175, 2 liters of water and 30 g of ammonium acetate in Z-shaped mixer. The mass is stirred until the formation of plastic paste, then it granularit by extrusion through a die plate with a diameter of 3 mm Pellets 3x3 mm air-dried first at 20aboutAnd then at 110aboutWith, and then subjected to hydrothermal treatment in an autoclave water vapor at 350aboutC for 24 h Received the silica gel has a pore radius 30-4000 nm displacement of 1 cm3/g, specific surface of 10 m2/, Calcined silica gel twice impregnated by capacity solution of compounds of iron, vanadium and manganese with intermediate drying of the pellets at 110aboutC. the Content of SiO2in the catalyst 75 wt. Heat treatment of the granules of the catalyst is similar to example 1. The volume of pores of radius greater than 15 nm is 1.0 cm3/, Test activity carried out analogously to example 1, the volumetric feed rate of the reaction mixture 490 h-1.

P R I m e R 12. The catalyst is prepared analogously to example 11. Use broad porous illinoi processing 250aboutC. the Atomic ratio of the components in the impregnating solution is Fe:Y:Mn of 1.4: 1.0 to:0,2. The content of SiO2in the catalyst 72 wt. The volume of pores larger than 15 nm is 1.0 cm3/, Test activity carried out analogously to example 1, the volumetric feed rate of the reaction mixture 460 h-1.

The results of testing the activity of the catalyst shown in the table. As can be seen from the above results, the use of iron-manganese vanadium oxide catalysts obtained by the described method allows to significantly increase the methylation of 1-naphthol. In addition, these catalysts allow the methylation reaction at lower temperatures, which reduces the formation of resins as of naphthol and of the products of methylation.

The METHOD of OBTAINING 2-METHYL-1-NAPHTHOL-methylation of 1-naphthol in anthopology by passing a vapor mixture of methanol and naphthol through the layer of oxide catalyst at elevated temperatures with subsequent condensation of the reaction products and their separation, characterized in that the reaction mass is added water and the process is conducted at a molar ratio of 1-naphthol methanol water equal 1 (2 5) (1 5), at a temperature of 300 - 400oWith sydnaya compositions based on iron, vanadium and manganese atomic ratio of the elements Fe, V, Mn(0,5 1) (0,5 1) (0 0,5), either tabletirujut or granularit in a mixture with a binder, or put on a broad porous silica gel, and then calcined at 500 800oWith and receive catalysts, which have the largest pores of radius greater than 15 nm, and 0.5 to 1.5 cm3/g and contain SiO2from 70 to 75 wt.

 

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