Catalyst for oxidation of sulfur compounds

 

(57) Abstract:

The invention relates to the production of heterogeneous catalysts for liquid-phase oxidation of sulfur compounds, in particular sulfidogenic solutions, natural and waste water, and can be used in power, metallurgical, gas, refining, petrochemical and pulp and paper industries. The essence of the invention lies in the fact that the proposed active, stable, mechanically strong heterogeneous catalyst for oxidation of sulfidogenic solutions having a solids containing microsphere, chromium oxide, and optionally a polymeric binder, in a ratio of components, wt.%: microsphere 10-15, chromium oxide 3-5, the polymeric binder is rest. 3 table.

The invention relates to the production of heterogeneous catalysts for liquid-phase oxidation of sulfur compounds, in particular sulfidogenic solutions, natural and waste water, and can be used in power, metallurgical, gas, refining, petrochemical and pulp and paper industries.

Known electrochemical oxidation sulfidogenic obrazovanie hydrogen ions and, therefore, sulfuric acid occurs at the anode.

The disadvantage of this process are the high cost of electricity, a limited amount of oxidizable solution and the absence of impurities in the oxidized solution.

Closest to the invention on the achieved result and the technical nature of is use in the oxidation sulfidogenic solutions as a catalyst of activated carbon modified with Nickel, silver or platinum (UK Application N 1602218, B 10 D 53/36, published. 30.04.77).

The disadvantage of this process is the low mechanical strength of the activated carbon in the process of liquid-phase oxidation in the conditions of the bubbling regime and the high sensitivity of the activated carbon to mechanical impurities.

The gradual destruction of the active carbon will be accompanied by loss of modifying components, which are expensive metals and as a consequence the decrease of catalytic activity and stability of the catalyst.

Clogged pores mechanical impurities will lead to blocking of active sites and deactivation of the active carbon and a catalyst and a sorbent.

To resolve the above shortcomings, the oxidation sulfidogenic solutions proposed active, stable, mechanically robust, does not require filtering of impurities oxidized solutions of the heterogeneous catalyst containing microsphere, chromium oxide, and optionally a polymeric binder, wt.

the microsphere 10-15

the chromium oxide 3-5

the rest of the binder polymer

The microsphere is part of the fly ash of thermal power stations and represents the gas aluminosilicates with a smooth external surface. The main components of the microspheres are steklovata, mullite, quartz, hematite, magnetite, an oxide of calcium. The composition of the microspheres include, wt.

Al2O323,8

Fe3O46,24

FeO 1,37

TiO20,53

MgO 3,44

SiO2the rest of it.

Example 1. The microsphere fly ash feed coal took the place of discharge of ash pulp in shlakozalivnyye with a specific gravity <1 t/m3dried in air at room temperature and then in an oven at 105oC to a residual moisture content of 7-/BR>Fe3O46,24

FeO 1,37

TiO 0,53

MgO 3,44

SiO2else,

kept in chromic acid at room temperature and periodic stirring for 2 h, and then dried to a residual moisture content of 3-7 wt. and progulivali in a muffle oven at 350-400oC, then added to the polymer binder and molded spherical catalyst pellet. As the polymer binder used high-pressure polyethylene.

Similarly produced catalysts containing chromium oxide and the microsphere in different mass ratio, mixing the respective components of the catalyst.

Example 2. 500 ml sulfanilamide of structure solution 1000 mg/l sulfite ions were oxidized in the presence of 20 g of the catalyst prepared according to example 1.

The catalyst was loaded into a glass reactor with recurring action dispergating plate at the bottom of the reactor to air. The air was applied from the block through the gearbox, the dosage was carried out using a rheometer at the exit of the reactor. Otdelochnye gases passed through the system sinks control the sulfur dioxide.

Salpicaduras the solutions were oxidized in static mode PRA.

Evaluation of catalytic activity of the prepared catalyst composition of example 1 was carried out in comparison with activated carbon modified with Nickel (prototype).

The residual concentration of the sulfite ions and the concentration of sulfate ions in the oxidized solution was determined by conventional methods (Lurie Y. Y. A. Rybnikov I. Chemical analysis of industrial wastewater. Chemistry, 1974). Data on the catalytic activity of the catalysts are presented in table. 1.

Example 3. 500 ml sulfanilamide solution containing 1,000 mg/l sulfite ions were oxidized in the presence of 20 g of the catalyst prepared according to example 1. The oxidation of the sulfite ions were carried out in static mode, at room temperature, atmospheric pressure, when the air flow of 10 l per 1 l of oxidized solution at the time of oxidation 1, 3, 5, 7, 10, 15, 25, 30, 40, 60, 80 minutes of the Received data with a known catalyst are presented in table. 2.

Example 4. In this example determined the duration of the work proposed and the known catalysts. As oxidizable solution used the drains of getsomevalue with the content of the sulfite ions 300 mg/l and the concentration of mechanical impurities (ash) up to 2 g/l Effluent oxidized ID of chrome 3

the rest of the binder polymer

The catalyst was loaded into the reactor in example 2. Oxidation sulfidogenic wastewater was carried out at room temperature, atmospheric pressure, air flow of 10 l per 1 l of oxidized solution for 30 min, then the solution was decanted and analyzed for the residual content of the sulfite ions and the presence of sulfate ions. In this mode, the catalyst has worked for 40 hours Analysis of the presence of sulfite ions and sulfate ions were carried out in each 10-m experience.

Comparative data for the determination of catalytic activity of the proposed catalyst in comparison with the known are given in table. 3.

When used as a catalyst carrier activated carbon is mainly the adsorption of sulfate ions. After 6 hours of catalyst on active coal catalyst must partly be replaced because there is a saturation of the pores of the carrier, sulfite, sulfate ions, pores become clogged with ash and catalyst practically deactivated.

Mechanical destruction of the granules of catalyst on charcoal when working in conditions of fluidized bed starts already after 3 h of operation catalyst. After 40 h of operation of the catalyst is enhanced by the above, and from data presented in the table, the claimed catalyst composition has a sufficiently high mechanical strength at the operating conditions of the fluidized bed, is not clogged with ash and superior to the catalyst-the prototype for catalytic activity in the oxidation of solutions containing sulfite ion and mechanical impurities.

High catalytic activity of the proposed catalyst is achieved due to the significant dispersion caused active component and oxides of metals of variable valence, within the framework of the microspheres provided by the structure of the microspheres.

Catalyst for oxidation of sulfur compounds containing active component on the carrier, characterized in that the active ingredient it contains chromium oxide as a carrier microsphere fly ash of thermal power stations and optionally a polymeric binder in the following ratio, wt.

Microsphere fly ash of thermal power plants 10 15

The chromium oxide 3 5

The Rest of the binder polymer

 

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