The method of obtaining formic acid

 

(57) Abstract:

Usage: the oxidation of aldehydes, obtaining formic acid from formaldehyde. The inventive formic acid is obtained gas-phase oxidation of formaldehyde oxygen nitrogen mixture at 110-180°C above the layer of the heterogeneous catalyst composition, wt. V2O517,5 89,5 and TiO210,5 82,5. table 2.

The invention relates to the chemical industry and can be used for the production of formic acid by enterprises with sufficient quantities of formaldehyde. In turn, formic acid is used in pharmacology for the production of drugs, in the chemical industry to obtain odoriferous substances, solvents, some types of fibers in animal conservation animal feed and so on [1, 2]

A method of obtaining formic acid from carbon monoxide and sodium hydroxide over sodium formate

NaOH+CO ___ HCOONa HCOOH

Also known is a method of obtaining formic acid by oxidation of aliphatic hydrocarbons (per tonne of primary product of acetic acid will receive 50 kg of formic acid).

In industry also get muravyiny the BR>HCOOCH3HCOOH+CH3OH

However, all these methods are characterized by high complexity of the technological cycles and low (20%) yield of formic acid that does not give reason to hope for rapid growth in the scale of production of formic acid.

The closest number of similar features with the claimed invention, a method of obtaining the formic acid is a method consisting in the oxidation of formaldehyde by oxygen in the presence of an oxide of vanadium-titanium catalyst [3] When this reaction takes place:

CH2O+0.5 O2____ HCOOH

Studies of this method is carried out by passing vapors of formaldehyde in the air above the surface of the oxide vanadium-titanium catalyst. We used two samples of catalysts differing in chemical composition, and the tests were carried out at different temperatures. The data are given in table.1.

While sample 1 receive the output of formic acid 19,0% and undesirable side product of methylformate -12,0% For sample 2 obtained the release of formic acid of 14.5% and methylformate of 13.1% (table.1 and 2 [3]). The described method is selected as a prototype of the invention.

Given the ukta formic acid;

the formation of undesirable side products methylformate in large quantities (comparable to the yield of the target product).

The aim of the invention is to increase the yield of formic acid and the almost complete elimination of the formation of undesirable side products methylformate.

This goal is achieved by the fact that formic acid is obtained by passing gaseous formaldehyde together with oxygen (or air) at 110-180aboutWith through the layer of oxide of vanadium-titanium catalyst in the following ratio, wt. V2O517,5-89,5; TiO210,5-82,5.

The catalysts are prepared by drying a mixture of titanium dioxide (anatase) with a solution of oxalate vanadyl followed by manufacture of granules of the desired size and shape and heat treated at 450aboutC.

The process is as follows. Formaldehyde in the gas phase obtained by any known method, for example, the oxidation of methanol [4] in a mixture with gaseous oxygen or air in any ratio, but preferably in stoichiometric 2:1 (formaldehyde oxygen) or above stoichiometric, miss at 110-180aboutWith through a fixed or pseudo the Main reaction products are formic acid, oxides of carbon and methylformate. All components of the reaction mixture were analyzed by chromatography. Formic acid from the reaction mixture allocate any known method, for example, by distillation [1, 2]

The catalyst layer may be formed from particles of various shapes and sizes, commonly used in the chemical industry. The shape and the particle size and form of the layer do not affect the achievement of this goal. In any case, the yield of the target product formic acid compared with the prototype will increase the formation of methylformate will be virtually eliminated (see examples).

Significant factors influencing the achievement of this goal are:

the chemical composition of the catalyst;

the temperature regime of the process.

Thus, in the catalyst composition, wt. 15.62 WIDE V2O584,38% TiO2the goal is not achieved due to the low activity of the catalyst (example 6). For the same reason, is not achieved the goal and on the catalyst composition, wt. 90,2 V2O59,8 TiO2(example 7).

When the temperature of the reaction mixture below 110aboutWith the process impractical because of the extremely low activity obratno, because there is a significant increase in the homogeneous velocity of decomposition of formic acid, leading to a dramatic reduction of its output (example 11).

The invention has the following similar to the prototype features:

formic acid is obtained by oxidation of the formaldehyde oxygen;

the process is conducted in a layer of an oxide of vanadium-titanium catalyst; and the following distinctive features:

oxide catalyst containing vanadium and titanium in the following ratio, wt. V2O517,5-89,5; TiO210,5-82,5;

the process is carried out at 110-180aboutC.

The combination of similar and distinctive characteristics of the inventive method, is not known from the prior art that demonstrates compliance of the claimed invention, the criterion of "novelty".

The inventive method also meets the criterion of "inventive step", because not obvious from the prior art. Known from the publication [3] the method of obtaining the formic acid by oxidation of formaldehyde with oxygen in the presence of an oxide of vanadium-titanium catalyst was carried out at others concerning the claimed compositions of the catalyst and the other is defined in the characterizing part of the formula, and can be achieved only at the specified chemical composition of the catalysts and temperatures.

The invention is industrially applicable, because it can be used in chemical plants for the production of formic acid on an industrial scale.

P R I m e R 1. The original reaction mixture, containing about 6. formaldehyde, about 8. oxygen and the rest nitrogen or another inert gas, with a temperature of 110aboutWith send in the reactor with internal heat exchange (tubular reactor). In the contact tube reactor load oxide vanadium-titanium catalyst composition, wt. 32,8 V2O567,2 TiO2made in the form of cylinders 4x4 mm (diameter x height). The main process parameters: the linear velocity in the tubes of 0.2 m/s; the inner diameter of the contact tube 20 mm; conditional contact time is 8; the maximum temperature in the tube 135aboutC; coolant temperature of -115aboutC; outlet temperature -125aboutC. Conversion of formaldehyde 98% selectivity for formic acid -88,8% selectivity for products of deep oxidation of 11.15% methylformate -0,05% Yield of formic acid is 87% yield of methylformate traces ( not more than 0.05%). After use in accordance with the/P> P R I m m e R 2. The initial reaction mixture containing 0.5 vol. formaldehyde, about 15. oxygen and the rest nitrogen or another inert gas, with a temperature of 115aboutWith send in the reactor with adiabatic layer of oxide analitichnogo catalyst composition: 22,1 V2O577,9 TiO2. Form of granules ring HH mm (external diameter x height x thickness). The main process parameters: the conditional contact time of 1 s; casting speed in the layer of 0.1 m/s; the temperature at the exit 155aboutC. Conversion of formaldehyde to 95.3% selectivity for formic acid of-89.2% products of deep oxidation of 10.75% methylformate 0.05% Output formic acid is 85,0% output methylformate traces (not more than 0.05%).

P R I m e R 3. The original reaction mixture, containing about 20. formaldehyde, about 10. oxygen and the rest nitrogen or another inert gas, with a temperature of 130aboutTo send in a reactor with a fluidized bed of oxide analitichnogo catalyst composition, wt. 53,2 V2O546,8 TiO2made in the form of spheres with a diameter of 0.25 x 1 mm, heat Removal is accomplished using a heat exchanger, placed in a fluidized bed. The main process parameters: the linear velocity of the gas in the apparatus 1 m/s; conventionally, there is a deep oxidation 14,15% methylformate 0.05% Output formic acid 85% yield of methylformate not more than 0.05%

P R I m e R 4. Similar to example 1, the difference lies in the fact that you are using the oxide vanadium-titanium catalyst composition, wt. 17,5 V2O5; 82,5 TiO2. Conversion of formaldehyde is 85.2% selectivity for formic acid 82,1% selectivity for products of deep oxidation 17,85% selectivity for methylformate 0.05% Output formic acid 70% yield of methylformate traces (not more than 0.05%).

P R I m e R 5. Similar to example 2, the difference is that the oxide vanadium-titanium catalyst composition, wt. 89,5 V2O5; 10,5 TiO2conditional contact time is 5 sec.

Conversion of formaldehyde is 73,7% selectivity for formic acid and 70.5% for the products of deep oxidation 29,45% methylformate 0.05% Output formic acid 52% yield of methylformate traces (not more than 0.04%).

P R I m e R 6. Similar to example 3, the difference consists in that the catalyst has a composition, by weight. 15.62 WIDE V2O5; 84,38 TiO2. Conversion of formaldehyde is 30% selectivity for formic acid 66,7% products of deep oxidation 33,25% methylformate 0.05% Output formic acid is 20% output methylformate traces (not more than 0.02%). The conduct process is Chiyo is the catalyst has a composition, by weight. 90,2 V2O5; 9,8 TiO2. Conversion of formaldehyde to 20.5% selectivity for formic acid to 34.1% for the products of deep oxidation 65,75% methylformate 0,15% Yield of formic acid is 20.5% output methylformate 3.0% process impractical because of the low yield of formic acid and the reaction products of methylformate.

P R I m e R 8. Similar to example 3, the difference is that the process is carried out at a temperature of 110aboutC. Conversion of formaldehyde is 61,1% selectivity for formic acid 90.0% of the products of deep oxidation 9,95% methylformate 0.05% Output formic acid is 55,0% output methylformate less than 0.03% (mol%).

P R I m e R 9. Similar to example 3, the difference is that the process is carried out at 180aboutWith conventional contact time is 3 C. Conversion of formaldehyde is 99.0% selectivity for formic acid, and 75.5% for the products of deep oxidation 24,45% methylformate 0.05% Output formic acid is 75% Yield of methylformate traces (not more than 0.05%).

P R I m e R 10. Similar to example 3, the difference is that the process is carried out at 105aboutC. Conversion of fatalpharmacy 0,05% Yield of formic acid was 5.2% output methylformate less than 0.03%

P R I m e R 11. Similar to example 3, the difference is that the process is carried out at 200aboutC. Conversion of formaldehyde is 100% selectivity for formic acid 20,0% products of deep oxidation 79,95% methylformate 0.05% Output formic acid is 20.0% of the Output methylformate of 0.05% (traces). The process is impractical because of the sharp increase in the rate of decomposition of formic acid.

The METHOD of OBTAINING FORMIC ACID, comprising passing gaseous reaction mixture containing formaldehyde and oxygen through the layer of oxide of vanadium-titanium catalyst, wherein the process is carried out at 110-180oTo use a catalyst in the following ratio, wt.

V2O517,5-89,5

TiO210,5-82,5

 

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