The catalyst for the oxidation of sulfur compounds

 

(57) Abstract:

The invention relates to the production of heterogeneous catalysts for liquid-phase oxidation of sulfur compounds (sulfur dioxide, hydrogen sulfide, mercaptans) and can be used for purification of gas emissions and wastewater, energy, refining, petrochemical, chemical and pulp and paper industries. Proposed heterogeneous catalyst for the oxidation of sulfur compounds containing active component on the carrier of the high - pressure polyethylene, characterized in that as the active component contains pyrolusite-ore composition, wt.%: manganese oxide (IV) 54,76-69,10; oxide of manganese (II) 1,80-4,85; iron oxide (III) 5,00-11,23; silicon oxide 4,05-7,52; barium oxide 3,95-5,02; aluminum oxide 0,92-5,03; titanium oxide 0,01-0,03; calcium oxide 0,50-0,82; magnesium oxide 0,40-0,70; potassium oxide 2,87-3,10; sodium oxide 0,37-0,58; oxide of phosphorus (V) 1,10-1,35; impurities - loss on ignition of the rest, and copper oxide (II) and pyrite cinder in the following catalyst components, wt. %: pyrite cinder 8-10; copper oxide (II) 5-10; pyrolusite-ore 20-25; polyethylene else. table 1.

The invention relates to the field of heterogeneous production is t to be used for the purification of gas emissions and wastewater, energy, refining, petrochemical, chemical and pulp and paper industries.

Known heterogeneous catalyst for purification of serosoderjaschei industrial waste gases by oxidation to sulfur dioxide hydrogen sulfide and organic sulfur compounds [1]

The main disadvantage of this catalyst is unsatisfactory, the depth of oxidation of hydrogen sulfide and organic sulfur compounds to sulfur dioxide. Sulfur dioxide is hard to recover highly toxic component. The cleaning gas from the sulfur dioxide is in itself no less a problem than purification from hydrogen sulfide and serverance.

The closest in technical essence and the achieved effect to the present invention is a catalyst for the oxidation of sulfur compounds, containing as an active ingredient the active sludge (35-50%) and medium high-pressure polyethylene (or polypropylene, polystyrene) [2]

The specified catalyst-prototype differs relatively little activity in the process of liquid-phase oxidation of sulfur dioxide, and also has significantly less activity in the oxidation of hydrogen sulfide and mercaptans compared to offe the

This goal is achieved by the fact that the catalyst active component contains pyrolusite-ore composition, wt.

Manganese oxide (IV) 54,76-69,10

Manganese oxide (II) 1,80-4,85

Iron oxide (III) 5,00-11,23

The silicon oxide of 4.05-7,52

The oxide of barium 3,95-5,02

Aluminum oxide 0,92-5,03

The titanium oxide 0,01-0,03

Calcium oxide 0,50-0,82

Magnesium oxide 0,40-0,70

The potassium oxide 2,87-3,10

The sodium oxide 0,37-0,58

Impurities loss on ignition Else

and copper oxide (II) and pyrite cinder in the following catalyst components, wt.

Pyrite cinder 8-10

Oxide copper (II) 5-10

Pyrolusite-ore 20-25

Polyethylene Else

A distinctive feature of the proposed catalyst is a composition of active components, which are introduced in the mass media of high-pressure polyethylene. Instead of activated sludge used a mixture of oxides of metals of variable valence oxide of manganese, which is used in the form of pyrolusite-ore of the composition, pyrite cinder and copper oxide (II).

The proposed catalyst, in comparison with the known, has a higher total activity, but most significantly the activity of the catalyst increases of sulfur compounds is carried out in the liquid phase and flows mainly to thiosulfate or sulfates, depending on the oxidation conditions.

Testing the activity of the catalyst in the process of absorption and catalytic purification of gases from sulfur dioxide was carried out in the reactor, a continuous film when the mode of conducting the process. Absorbent, which used water, was fed into the reactor from above, the gas backflow from the bottom. For experiments we used synthetic gas mixture containing sulfur dioxide 2000-2500 mg/m3and volume fraction of oxygen, 10% of This approximately corresponds to the composition of the flue gases of thermal power plants operating on brown coal. Sulfur dioxide was supplied from a cylinder, and the reduction of oxygen was carried out by dilution of the gas mixture with nitrogen.

The process of absorption and catalytic gas purification from sulfur dioxide was carried out under the following process parameters: temperature 60oC; gas velocity of 0.14 m/s; the contact time of the gas-catalyst 3.6 sec; the ratio of the flow rate of the absorbent to the gas flow 0,00015; oxygen concentration in the gas is about 10. use as an absorbent of water with a pH of 6.5-7.5.

The catalyst activity was evaluated according to the degree of purification of the gas mixture from the sulfur dioxide, for this was determined by the concentration of sulfur dioxide in the gas with in aqueous solutions is expressed by the following equation:

SO2+ 1/2 O2+ H2O _ H2SO4.

Additional controlled plant's effluent liquid-phase oxidation of SO2for completeness turning it into an H2SO4. The inspection results showed that when using the catalyst of the absorbed water SO2oxidized to sulfuric acid of not less than 96-99% vs. 5-10% in the control experiment without catalyst.

Experiments to determine the activity of the catalyst in the process of liquid-phase oxidation of hydrogen sulfide and mercaptans oxygen was carried out on real wastewater of pulp and paper production secondary condensate evaporation of black liquor, containing hydrogen sulphide 100-200 mg/DM3and methylmercaptan 60-80 mg/DM3.

The oxidation process was carried out in a batch reactor, the with the following parameters: temperature 60oC; pressure 0.3 MPa; oxidation time 3 min; the ratio (by weight) catalyst waste water 1:5; blower speed 10-20 h-1. The air in the reactor was carried out from the bottom using a special dispersant, provide good mass transfer.

The catalyst activity was evaluated according to the degree of oxidation of servodio and oxidized wastewater. Determination of the concentration of H2S and mercaptan was carried out by potentiometric method according to GOST 22985-88.

High catalytic activity of the proposed catalyst is observed at the specified mixing ratio of the active basis of the catalyst. The ratio of the mass fraction of pyrolusite to the mass fraction of copper oxide (II) must be in the range of 1:(2-5), and the content of the pyrite cinder should not exceed 10% in Addition, it is important that the mass fraction of the carrier in the catalyst was in the range of 55-67% Increase in the mass fraction of active basis over 45% leads to decrease in mechanical strength of the granules of the catalyst, and reducing the mass fraction of active bases less than 33% decrease in catalyst activity.

Example 1. The catalyst composition, wt.

Pyrite cinder 10

The copper oxide (II) 5

Pyrolusite-ore 20

Polyethylene 65

manufactured as follows. Mixing of the components and forming pellets of the catalyst is carried out at an industrial unit for the granulation of polyethylene with a minimum load of mixer 60 kg Therefore, the components of the catalyst are taken in the following quantities: pyrite cinder 6.0 kg; copper oxide (II) 3.0 kg; pyrolusite 12.0 kg; polyethylene 39,0 the La on a ball mill for 8 hours mixed with carrier - the high-pressure polyethylene (LDPE) at a temperature of 120-130oC for 20-30 minutes Duration of mixing depends on the composition of the catalyst. After mixing the resulting mass is fed into a screw extruder, where with the help of special nozzles is formed in the form of pellets or rings required shape and size. For studies were made of the samples of the catalyst in the form of spherical granules with a diameter of 4-6 mm

Example 2. The catalyst composition, wt.

Pyrite cinder 10

Oxide copper (II) 10

Pyrolusite-ore 20

Polyethylene 60

manufactured according to the technology described in example 1.

Example 3. The catalyst composition, wt.

Pyrite cinder 10

The copper oxide (II) 5

Pyrolusite-ore 20

Polyethylene 65

manufactured according to the technology described in example 1.

Example 4. The catalyst composition, wt.

Pyrite cinder 10

Oxide copper (II) 10

Pyrolusite-ore 25

Polyethylene 55

manufactured according to the technology described in example 1.

Example 5. The catalyst composition, wt.

Pyrite cinder 8

Oxide copper (II) 10

Pyrolusite-ore 20

Polyethylene 62

manufactured by technology, there are asnago oxidation of SO2H2S and mercaptan according to the method described above, as well as stability within 200 including the Results of tests on samples of the proposed catalyst (examples 1-5) and the prototype shown in the table.

Experiments to determine the activity of the samples showed that the introduction of the catalyst components in the ratio provided by the present invention (examples 1-5), allows to obtain highly active catalysts with high mechanical strength and stability. The proposed catalyst is substantially outweighed by the activity known.

The efficiency of absorption and catalytic gas cleaning and SO2in the presence of the proposed catalyst is 94-95% compared to 41.5% for the catalyst of the prototype. The proposed activity of the catalyst in a process for the oxidation of H2S is 98-99% and methylmercaptan 94-96% compared with 76.8% and 62.7 percent, respectively, for the prototype. The greatest increase in activity is observed for the oxidation of sulfur dioxide.

Additionally, for comparison, according to the technology described above, were prepared catalyst samples containing components lying outside the boundaries stipulated in the table.

The increase of mass fraction of pyrite cinder (sample 6) leads to an overall decrease in catalyst activity. The ratio of the mass fraction of copper oxide (II) mass fraction of pyrolusite should be in the range of 1:(2-5), as provided by the present invention. Change this attitude in the direction of increasing the proportion of CuO (sample 7), and in the direction of increasing the share of pyrolusite (sample 8), leads to a reduction in the overall activity of the catalyst.

The decrease in the mass fraction of the carrier in the catalyst is below 55% (sample 9 contains media 53%), while maintaining the desired ratio of metal oxides in the composition of the active basis, leads to an abrupt drop in the mechanical strength of the obtained sample of the catalyst. This entails rapid destruction of the catalyst in the catalytic reaction conditions and, therefore, reduction of service life.

The increase in the mass fraction of the carrier above 67% (sample 10 contains media 69% ), while maintaining the desired ratio of metal oxides in the composition of the active basis, entails a reduction in the overall activity of the catalyst.

The test results of samples of the catalyst vagrancy content components confirms that comprises the tee will allow to increase the efficiency of wastewater treatment and gas emissions to reduce the size of technological devices, to carry out the cleaning process in more mild conditions. All this makes it possible to reduce capital and operating costs during the implementation of the cleaning process using this catalyst.

The catalyst for the oxidation of sulfur compounds containing active component on the carrier of the high-pressure polyethylene, characterized in that as the active component contains pyrolusite-ore composition, wt.

Manganese oxide (IV) 54,76 69,10

Manganese oxide (II) 1,80 4,85

Iron oxide (III) 5,00 11,23

The silicon oxide 4,05 7,52

The oxide of barium 3,95 5,02

Aluminum oxide 0,92 5,03

The titanium oxide 0,01 0,03

Calcium oxide 0,50 0,82

Magnesium oxide 0,40 0,70

The potassium oxide 2,87 3,10

The sodium oxide 0,37 0,58

The oxide of phosphorus (V) 1,10 1,35

Impurities loss on ignition Else,

and copper oxide (II) and pyrite cinder in the following catalyst components, wt.

Pyrite cinder 8 10

The copper oxide (II) 5 10

Pyrolusite-ore 20 25

Polyethylene Ostalnoe

 

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FIELD: chemistry.

SUBSTANCE: invention relates to a homogeneous catalyst based on tetra-4-(4'-carboxyphenylsulphanium)-5-cobalt nitrophtalocyanine(II) of tetrasodium salt of formula .

EFFECT: invention allows to produce a compound having a high catalytic activity in the oxidation of sodium diethyldithiocarbamate.

4 dwg, 1 tbl, 2 ex

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