The method of producing methylformate, the catalyst for its implementation and the method of producing catalyst


B01J35B01J23/72 -

 

(57) Abstract:

The invention relates to a method of producing methylformate used as an intermediate product when receiving the organic acid is formic, acetic, propionic and their esters, as well as formamido, and to a method of preparation of the catalyst to obtain methylformate. Mailformat obtained by dehydrogenation of methanol in the gas phase at a temperature of 150-350oAnd atmospheric pressure in the presence of a copper-containing catalyst, the content of elements in which, in terms of metals, is, at.%: copper 10-30, zinc 10-50, aluminum and/or chromium and/or zirconium, or silicon. The catalyst receiving methylformate the dehydrogenation of methanol in the gas phase obtained by termomaslyanym in a stream of air hydroxocobalamine copper, zinc, aluminum and/or chromium and/or zirconium, or silicon structure type hydrozincite, or hydrotalcite, or stevensite, at a temperature of 350-550oWith subsequent reduction in hydrogen and exhibits high selectivity and the rate of conversion of methanol in methylformate. 3 S. p. f-crystals, 1 table.

The invention relates to methods for producing methylformate by dehydrogenation of methanol in gatewaysm product and can be used as an intermediate connection when receiving valuable organic acids - formic, acetic, propionic and their esters, as well as various formamido.

In industry mailformat get in two ways - by the esterification of formic acid with methanol and carbonyliron methanol. The most common industrial method for the synthesis of methylformate by carbonylation of methanol [J. S. Lee, J. C. Kim, Y. G. Kim, Y. G. Kim, Methyl Formate as a New Building Block in C1Chemistry, Appl. Catal. 57 (1990) 1].

Known more effective way to get methylformate the dehydrogenation of methanol by the reaction: 2CH3HE=CH3BASED+2H2[U.S. patent 1400195, 1975853, 2160064].

The process uses the available raw materials are methanol, and in addition methylformate in the reaction produces hydrogen, which can be used in the future as in chemical synthesis, and as a clean fuel.

For dehydrogenation of methanol in methylformate proposed different catalysts based on the platinum group metals [U.S. patent 4778923, C 07 C 045/38, 18.10.1988] and copper-based [U.S. patent 4149009, C 07 C 067/40, 10.04.1979; USA 5144062, C 07 C 067/40, 1.09.1992; USA 4480122, C 07 C 067/40, 30.10.1984; USA 5144062, C 07 C 067/40, 1.09.1992].

The main disadvantage of obtaining methylformate the dehydrogenation of methanol is low selectivity about the possible formation of methane and dimethyl ether. Copper-containing catalysts are the most selective.

The closest technical solution to the present invention is a method of obtaining methylformate the dehydrogenation of methanol using a catalyst of copper-magnesium-silicon oxide-modified zinc, chromium and/or barium [U.S. patent 5194675, C 07 C 67/00, 16.03.1993]. The catalyst contains components in wt.%: 30-80 - CuO, 20-80 - magnesium silicate (calculated for MgO+SiO2), with the molar ratio of oxides from 0.3 to 1.5, and 1.5 wt.% oxide of zinc, chromium and/or barium.

The catalyst was prepared by precipitation from a mixture of aqueous solutions of nitrate salts of the components of baking soda in their suspension of magnesium silicate, calcined at temperatures of from 250oAnd restore nitric mixture at 200oC.

Dehydrogenation of methanol in methylformate carried out in the following way: propasny methanol passes through the catalyst bed (in a tubular reactor or fluidized bed reactor) at a temperature of 150-300oWith, preferably 200-290oC, a pressure of 0.1-10 bar, preferably atmospheric and feed rate of methanol 2700-7500 h-1(1.3 to 0.5 seconds). Methanol vapor can be diluted with an inert gas. A mixture of the l return to the reactor.

The disadvantage of this method is its low efficiency: 180oWith contact time of 0.6 sec achieved the degree of conversion of 7% with a selectivity for methylformate 98%, contact time 1 sec achieved the degree of conversion of 30% with a selectivity to methylformate 70%, at 200oWith contact time of 0.6 sec achieved the degree of conversion of methanol 14%, the selectivity is 93%, removal of methylformate with 1 g of catalyst per hour at 750 g at 260oWith contact times of 0.5-0.6 sec achieved the degree of conversion of methanol 36-43%, the selectivity is 80-76% and removal of methylformate with 1 g of catalyst per hour to 2000, At higher temperatures the removal of product with 1 g of the catalyst can be increased, however, this increases the yield of CO and H2i.e. decreases the overall efficiency of the process.

The problem solved by the present invention is to develop a more effective method of dehydrogenation of methanol in methylformate.

The solution is to develop ways to obtain methylformate by dehydrogenation of methanol in the gas phase at a temperature of 150-350oAnd atmospheric pressure in the presence of a copper-containing catalyst, the content of the/or chromium, and/or zirconium, or silicon obtained by termomaslyanym in a stream of air hydroxocobalamine copper, zinc and aluminum and/or chromium and/or zirconium, or silicon, with the structure type hydrozincite, or hydrotalcite, or stevensite, at a temperature of 350-550oC, followed by reduction in hydrogen, or

Copper - 10-30

Zinc - 20-50

aluminum and/or chromium and/or zirconium, or silicon obtained by termomaslyanym in a stream of air hydroxocobalamine copper, zinc and aluminum and/or chromium and/or zirconium, or silicon, with the structure type hydrozincite, or hydrotalcite, or stevensite, at a temperature of 350-550oC, followed by reduction in hydrogen.

According to [L. Schlegel, D. Gostick, A. I. Rozovsky. The decomposition of methanol on cu-containing catalysts for methanol synthesis. Kinetics and catalysis, 1990, T. 31, 4, S. 1000-1003] curve accumulation methylformate passes through a maximum, typical of the intermediate product in a sequential reaction, and the shape of the curve of accumulation WITH reference to his education in the secondary reaction. That is, the process is complicated by the collapse of methylformate on CO and H2. The scheme of the observed sequence of transformations of the analyzed substances can be written Cora consider the following:

The equilibrium conversion of methanol in methylformate increases with Rostov temperature and the conversion of methanol in methylformate at 170oWith approximately 25% and 270oWith about 45% [A., Krasnyanskaya, Y. C. lander, C. E. stork. The equilibrium of this reaction is receiving methylfolate from methanol. Chemical industry, 5, pp. 264-265, 1986]. Therefore, the process of obtaining methylformate at temperatures substantially below 170oSince it is impractical.

The most effective will be the catalyst for which high selectivity for methylformate value of the speed of reaction (1) will be greatest, that is, achieved the greatest degree of conversion of methanol each time.

In the proposed method of obtaining methylformate the dehydrogenation of methanol using a catalyst containing copper, zinc and aluminum and/or zirconium and/or chromium, or silicon obtained by termomaslyanym in a stream of air at 300-550oFrom hydroxocobalamine (hydroxocobalamin) copper-zinc-aluminum and/or chromium and/or zirconium, with the structure type hydrozincite, Zn5-x-yCxAly(OH)6(CO3)2[S. Ghose, Acta Cryst., 17, 1051-1057, (1964)] or hydrotalcite, Zn6-xCuxAl23-xCuxSi4O10(OH)24H2O [PCPDFWIN JCPDS-25-1498; Minerals. The Handbook. The layered structure, M: Nauka, so 4, vol. 2, 100-101 C., (1992)]. These catalysts after reduction with hydrogen exhibit high selectivity and high speed conversion of methanol in methylformate.

The invention is illustrated by examples.

Example 1. The process of dehydrogenation of methanol in methylformate carried out by passing a mixture of 15% vol. methanol vapors with an inert gas through the catalyst bed at a temperature of 170-260oAnd atmospheric pressure. Use of an oxide catalyst containing ions of copper, zinc, chromium in at.% Cu:Zn:Cr= 30: 10: 60 received termomaslyanym in a stream of air at a temperature of 550oFrom gidroksicarbonata copper-zinc-chromium with structure type hydrotalcite (Cu3Zn1Cr6(OH)16CO3nH2O) and restored in a stream of hydrogen at 350oC. Gidroksicarbonat copper-zinc-chromium receive joint precipitation of metal ions from solutions of their nitrates with sodium carbonate solution at pH about 6.5-6.8, and a temperature of 75-78oC. by the Method of x-ray fluorescence analysis shows that the structure of the obtained gidroksicarbonata copper-zinc-chromium identical structure which provides the rate of conversion of methanol is significantly greater than the rate of conversion in a known way (prototype). The selectivity in respect of methylformate at high degrees of conversion is also greater than the selectivity in a known way (see table 1).

Example 2. Analogously to example 1, but the process is performed using an oxide catalyst containing ions of copper, zinc, silicon in at.% Cu:Zn: Si= 13: 30: 57. The catalyst was prepared termomaslyanym in a stream of air at a temperature of 400oFrom hydroxoselenite copper-zinc structure type stevensite (CuZn)3Si4O10(OH)2nH2O and restore in a stream of hydrogen at 350oC.

Hydrochloricum receive deposition at 90oWith and gradually changing the pH in the mixture of aqueous solutions of nitrate salts of copper and zinc, silicon dioxide and urea. Method the IRS found that the precipitate was a connection structure stevensite.

The catalyst provides the rate of conversion of methanol is significantly greater than the rate of conversion in a known way (prototype). The selectivity in respect of methylformate at high degrees of conversion is also greater than the selectivity in a known way (see table 1).

Example 3. Analogously to example 1, but the process is performed on the oxide catalysis is of oxocarbons copper-zinc-aluminum with structure type hydrozincite (C2Zn3.6Al(Oh)6.6(CO3)2). Gidroksicarbonat copper-zinc-aluminium receive joint precipitation of metal ions from solutions of their nitrates solution of sodium carbonate at pH 6.6-6.8 and a temperature 79-81oC. by the Method of x-ray fluorescence analysis shows that the obtained gidroksicarbonat copper-zinc-aluminium has a structure identical to the structure of hydrozincite.

The characteristic operation of the catalyst are shown in table 1. The catalyst provides the rate of conversion of methanol, far exceeding the rate of conversion in a known way (prototype). The selectivity in respect of methylformate at high degrees of conversion is also greater than the selectivity in a known way (see table 1).

Example 4. Analogously to example 3, but the process is performed on the oxide catalyst with a ratio of Cu:Zn:Zr=20:20:60. The catalyst was prepared by heat treatment at 450oFrom hydrooxicarbonate copper-zinc-zirconium structure type hydrotalcite (Cu1Zn1Zr3(OH)14CO3nH2O). Gidroksicarbonat copper-zinc-zirconium produced by the method of coprecipitation at pH of 6.8 to 7.0, temperature 73-75oWith the formation of compound given this structure is confirmed by metadiorite transformations in a certain way. The selectivity in respect of methylformate at 200oWith 30% conversion of methanol is 92%, which also exceeds the index of the known method.

Example 5. Analogously to example 1, but the process is performed on the oxide catalyst with a ratio of Cu:Zn:Al:Zr=40:40:10:10. The catalyst was prepared by heat treatment at 450oFrom hydrooxicarbonate copper-zinc-aluminum-zirconium structure hydrozincite (Cu4Zn4Al1Zr1(OH)19(CO3)2nH2O).

Gidroksicarbonat copper-zinc-aluminum-zirconium produced by the method of coprecipitation at pH of 6.8 to 7.0, temperature 73-75oWith the formation of compound given this structure is confirmed by xfa (see table 1).

The catalyst is the rate of conversion of methanol, far exceeding the rate of conversion in a known way. The selectivity in respect of methylformate at 200oWith the achievement of a 33% conversion of methanol is 93%, which also exceeds the index of the known method.

Example 6. Analogously to example 1, but the process is performed on the oxide catalyst with a ratio of Cu:Zn:Cr:Zr=40:40:10:10. The catalyst was prepared by heat treatment at 450oSince g is UB>(OH)19(CO3)2nH2O).

Gidroksicarbonat copper-zinc-chromium-zirconium produced by the method of coprecipitation at pH of 6.8 to 7.0, temperature 73-75oWith the formation of compound given this structure is verified by the xfa (see table 1).

The catalyst is the rate of conversion of methanol, far exceeding the rate of conversion in a known way. The selectivity in respect of methylformate at 200oWhen reaching 31% conversion of methanol is 91%, which also exceeds the index of the known method.

Example 7. Analogously to example 1, but the process is performed on the oxide catalyst with a ratio of Cu:Zn:Al:Cr:Zr=50:30:10:5:5. The catalyst was prepared by heat treatment at 450oFrom hydrooxicarbonate copper-zinc-aluminium-chromium-zirconium structure hydrotalcite (Cu5Zn3Al1Cr0.5Zr0.5(OH)20.5CO3nH2O). Gidroksicarbonat copper-zinc-aluminium-chromium-zirconium produced by the method of coprecipitation at pH of 6.8 to 7.0, temperature 73-75oWith the formation of compound given this structure is confirmed by xfa (see table 1).

The catalyst is the rate of conversion of methanol, far exceeding the speed of pnii 30% conversion of methanol is 92%, that also exceeds the index of the known method.

1. The method of producing methylformate by dehydrogenation of methanol in the gas phase at a temperature of 150-350oAnd atmospheric pressure in the presence of a copper-containing catalyst, wherein the used catalyst, the content of elements in which, in terms of the metals is at. %:

Copper - 10-30

Zinc - 10-50

aluminum and/or chromium and/or zirconium, or silicon obtained by termomaslyanym in a stream of air hydroxocobalamine copper, zinc and aluminum and/or chromium and/or zirconium, or silicon, with the structure type hydrozincite, or hydrotalcite, or stevensite, at a temperature of 350-550oWith subsequent reduction in hydrogen.

2. The catalyst receiving methylformate by dehydrogenation of methanol in the gas phase at a temperature of 150-350oAnd atmospheric pressure, containing copper, characterized in that it additionally contains zinc and aluminum and/or chromium and/or zirconium, or silicon, the content of elements in the catalyst, calculated on the metal is at. %:

Copper - 10-30

Zinc - 20-50

aluminum and/or chromium and/or zirconium, or silicon obtained by termomaslyanym in the current wondogenet, or hydrotalcite, or stevensite, at a temperature of 350-550oWith subsequent reduction in hydrogen.

3. The method of preparation of the catalyst receiving methylformate by dehydrogenation of methanol in the gas phase, containing copper, wherein conducting thermal decomposition in a stream of air hydroxocobalamine copper, zinc and aluminum and/or chromium and/or zirconium, or silicon, with the structure type hydrozincite, or hydrotalcite, or stevensite, at a temperature of 350-550oWith subsequent reduction in hydrogen.

 

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