The catalyst for formic acid

 

The invention relates to the field of production of formic acid by the oxidation of the formaldehyde oxygen. The described catalyst comprises oxides of vanadium, titanium, and further comprises a modifying compound in the form of one or more oxides of alkaline-earth metal has a specific surface area of 100-250 m2/g and the following composition, wt.%:

V2O510,0-25,0

The oxide of alkaline-earth metal of 0.5-10

TiO2Else

As the modifying compound, the catalyst preferably contains an oxide selected from a number of elements : calcium, barium, strontium. The proposed modified titanium vanadium catalysts are characterized by high mechanical strength and specific surface area, high activity and selectivity in formic acid at a temperature of 110°C (from 0,60 to 1.1 sec-1). 1 C.p. f-crystals, 1 table.

The invention relates to vanadium oxide-titanium catalysts used for formic acid oxidation of formaldehyde oxygen.

Analitichnoyi catalysts should provide high activity and selectivity to the formic acid, the exception objectiu.

A known method of obtaining a granulated catalyst for the synthesis of formic acid (patent RF №2063802, 01 J 23/22, 1996), containing vanadium oxide 15-20% and titanium oxide 85-80%. The catalyst has a value of specific surface area 15-42 m2/g, the maximum mechanical strength of the pellet crush strength by forming 2.8 MPa. The catalytic activity of the catalyst is characterized by the rate constant of the first order (K, s-1), the selectivity for the reaction products (S, %), degree of conversion of formaldehyde (X %).

The best examples of the catalyst at a temperature of 120To have a rate constant K=0,35-0,40 s-1the selectivity S for formic acid 88-93%, the degree of conversion of formaldehyde 93-96%.

The disadvantage of this catalyst is the low mechanical strength and poor value of the rate constant, which indicates insufficient high activity of the catalyst.

The closest technical solution is the method of producing a catalyst for the synthesis of formic acid (U.S. Pat. Of the Russian Federation No. 2049770, IPC607 With 53/02, 1992), having the following composition. wt.%: V2About5- 17,5-89,5; Tio2- 10,5-82,5.

When the content of V2O5at the level of 15-20%, it is not a high EIT is aemono to achieve the set objective.

The problem solved by the present invention is to develop a catalyst having high strength, activity and selectivity.

The goal is solved by the use for the synthesis of formic acid catalyst, which comprises the oxides of vanadium, titanium, and further comprises a modifying compound in the form of one or more oxides of alkaline-earth metal has a specific surface area of 100-250 m2/g and the following composition, wt.%:

V2O510,0-25,0

The oxide of alkaline-earth metal of 0.5-10

TiO2Else

As the modifying compound, the catalyst preferably contains an oxide selected from a number of elements: calcium, barium, strontium.

The catalyst of the proposed structure and having a specific surface has higher catalytic and structural-mechanical properties.

The catalytic activity of the catalyst is determined in the oxidation of formaldehyde to formic acid at a flow-circulation installed in the temperature range of 110-120With the granules of the catalyst content in the reaction mixture of formaldehyde from 3.5 to 10 vol.%, when concerning About2/CH2O2. The basis of the>, carbon oxides (CO, CO2).

The catalytic activity of the catalyst was characterized by the rate constant of a first-order reaction (K, s-1), the selectivity for the reaction products (S, %), degree of conversion of formaldehyde (X %).

The specific surface of the catalyst (Sbeatsm2/g) was determined by the BET method by thermal desorption of argon.

Mechanical crushing strength along generatrix (Psec, MPa) was determined on the instrument MP-9S for limiting the force that causes the destruction of granules allocated to the conditional section granules.

The catalyst is prepared as follows.

In the mixer load hydrated titanium dioxide, vanadium pentoxide and the modifying compound is one or more oxides of alkaline-earth metal. The components are mixed until a homogeneous paste-like state in the presence of water. The resulting paste ekstragiruyut, the granules are dried, calcined and get the catalyst of the desired composition with the surface of 100-250 m2/ ,

The following examples illustrate the claimed invention.

Example 1

In a paddle mixer download powdery ingredients: Hydra-mounted titanium dioxide, vanadium pentoxide and Kava, wt.%:

V2O510,0

Tio280,0

BaO 10,0

Components lead to a homogeneous paste-like state in the presence of water. The resulting paste ekstragiruyut through the die plate hole diameter 4 mm, cut into granules with a length of 4 mm, the Obtained granules are dried at 120With 4 hours and calcined at a temperature of 400C.

The strength of the finished catalyst is 4.2 MPa, specific surface 153 m2/year Conversion of formaldehyde at a temperature of 120With its concentration in the initial mixture of 5.2% 81,3%; the rate constant of a first-order reaction under these conditions 0,86 s-1; selectivity for formic acid 93,5%.

These characteristics are presented in the table.

Example 2

Similar to example 1, the difference is that the components are loaded into the mixer was produced in an amount corresponding to the composition of the catalyst, wt.%:

V2O525,0

TiO274,5

SrO 0,5

Characteristics of the catalyst are presented in the table.

Example 3

Similar to example 1, is loaded components corresponding to the next catalyst composition, wt.%:

V2O520,0

Tio274,0

CaO 6,0

Characteristics of the catalyst performance, the content of formaldehyde in the mixture.

Example 6

Similar to example 1, is loaded components corresponding to the next catalyst composition, wt.%:

V2O518,0

TiO276,0

CaO 5,0

HLW 1,0

Characteristics of the catalyst are presented in the table.

Example 7 (prototype)

Prepare the catalyst composition of 20 wt.% V2O5, 80 wt.% TiO2as follows.

The catalyst is prepared by drying a mixture of titanium dioxide (anatase) with a solution of oxalate vanadyl forming cylinder 44 mm (diameterheight) and heat treated at 450C.

The table shows that the proposed modified vanadium-titanium catalysts are characterized by high mechanical strength and specific surface area, high activity and selectivity in formic acid at a temperature of 110With (from 0,60 to 1.1 sec-1).

Claims

1. Catalyst for the synthesis of formic acid by oxidation of formaldehyde comprising the oxides of vanadium, titanium, characterized in that the catalyst additionally contains as the modifying compound is at least one or more oxides of alkaline-Tamilnad alkaline-earth metal 0.5 to 10

TiO2Else

2. The catalyst p. 1, characterized in that as the oxide of alkaline-earth metal contains compounds selected from a number of elements (CA, BA, Sr.

 

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