The catalyst for the oxidation of carbon monoxide

 

(57) Abstract:

The invention relates to the purification of gases containing carbon monoxide. As catalyst for the oxidation of carbon monoxide used calcined manganese cake, which is obtained at the stage of purification of solutions of salts of cobalt from manganese impurities in the technology of hydrometallurgical production of hydroxide cobalt (III). The technical result - the use of waste materials and industrial products hydrometallurgical production. table 1.

The invention relates to the purification of gases from environmentally hazardous components and can be used for purification of exhaust gases of an internal combustion engine, for neutralization of exhaust gases of industrial enterprises, power plants, asphalt plants and other process industries and aggregates containing in its composition and carbon monoxide.

Known copper-manganese and zinc-copper-chromium catalysts, cement-based [Kuznetsov, I. E. Shmat K. I., Kuznetsov, S. I. Equipment for sanitary cleaning gases. Kyiv. "Technology", 1989, S. 236].

The disadvantages of the catalyst are relatively high cost and complexity of manufacture.

The disadvantage of the catalyst is the necessity of its manufacture, cost of materials and production.

Object of the invention is the use of waste materials and industrial products hydrometallurgical production of hydroxide cobalt (III) as catalyst for the oxidation of carbon monoxide.

The technical result that can be achieved by carrying out the invention, lies in the high degree of purification of exhaust gases from environmentally hazardous components with simultaneous effectiveness of the process.

This technical result is achieved by the fact that in the known catalyst for the oxidation of carbon monoxide, comprising manganese dioxide as a catalyst for the oxidation of carbon monoxide used calcined manganese cake obtained at the stage of purification of solutions of salts of cobalt from manganese impurities in the technology of hydrometallurgical hydroxide cobalt (III).

The essence of the catalytic effect of calcined manganese cake is that as a result of chemical and phase preframe oxidation of carbon monoxide.

Examples of practical application.

As the catalyst used is manganese cake obtained at the stage of purification of solutions of salts of cobalt from manganese impurities in the technology of hydrometallurgical hydroxide cobalt (III) of JSC "MMC "Norilsk Nickel".

For cleaning solutions in which the content of cobalt is significantly higher than the manganese content, apply chlorine method for selective oxidation of manganese from cobalt solutions of chlorine by the reaction:

MnSO4+Cl2+2H2O= MnO2+H2SO4+2HCl (1)

When the content of cobalt in the solution is 50 to 100 times the concentration of manganese, the reaction:

CoSO4+Cl2+6H2O= 2Co(OH)3)+2H2SO4+2HCl (2)

Co(OH)3+MnSO4+H2SO4=2CoSO4+MnO2+4H2O (3)

For the production of solutions of cobalt containing 0.3-0.6 g/DM3manganese deposition of Mno2formed by reactions 1 and 3, is carried out at a pH of 1.5 to 2.5, forming a manganese cake with weight ratio of cobalt to manganese is From:MP(2,53,0):1.

In a production environment with a small admixture of manganese precipitated his GUI SO4when the active chlorine concentration of 30-40 g/DM3and the ratio of chlorine to alkali (3-5):1. Consumption of hypochlorite set of 4 kg of chlorine per 1 kg of manganese. The deposition of lead from dilute solutions. Very active oxidant manganese is also chlorine gas cleaning which is carried out at air stirring solution and the feed to the reactor soda.

The first manganese cake with attitude:MP=(410):1 after filtering and washing from cobalt is treated with a solution containing 25-30 g/DM3H2SO4when heating it with steam to 50-60oIn the presence of sulphurous anhydride. From the resulting solution is again precipitated manganese and receive secondary manganese cake with attitude:MP=(21):1. The solution from the second filter cake contains a significant amount of cobalt and Nickel and its return to the head, i.e. the clearing of iron.

The second manganese cake is dissolved and the solution of alkali precipitated hydrates of monooxide metals. The precipitation of the hydroxide (II) is conducted by using a solution of caustic alkali (60-80 g/DM3NaOH), at the end of the precipitation the pH is 7.5. After deposition of the hydroxide (II) obtained a solution containing up to 1 g/DM3With and 2-7 g/DM3MP. This process is a solution of cobalt to manganese 5:1 are dissolved and sent to the beginning of the process.

Thus, the deposition process is multi-staged and performed with great loss of cobalt in the deposition. It is also connected with the fact that active chlorine in solution oxidizes, along with manganese, and cobalt, which results in these conditions to substantial precipitation and coprecipitation last.

According to x-ray phase analysis is used as the catalyst manganese cake contained, wt.%: Noon 20,72; UNSD 46,53; MP(OH)22,81; Co(OH)26,14; IGOs 4,60; Soo 6,39; (Co, MT) O(HE) 12,81.

According to x-ray phase analysis of calcined at 250oC for 30 min manganese cake contained, wt.%: Noon 14,31; UNSD 56,62; MP(OH)24,11; Co(OH)26,09; IGOs 4.26 Deaths; Soo 6,70; (Co, MT) O(HE)to $ 7.91.

Cleaning the gas phase from the carbon monoxide was carried out by the method of "perfect push.

For the generation of carbon monoxide used stove, which burned wood particle material by the incomplete combustion of fuel. From the furnace the obtained gas mixture was passed through an absorption flask with concentrated sulfuric acid, and then through the condenser-absorber with 10% aqueous NaOH solution through britholite with glass balls and collected in rubber the piping set with a diameter of 15 mm with a catalyst, which were placed in a sand bath with electric. The gas mixture was controlled by the content of carbon monoxide at the entrance to the U-shaped tube (before catalyst) and the output of which (after catalyst) detector brand APA-121. Temperature control in a sand bath, the catalyst and out of the tubes cleaned gas was performed using a mercury thermometer.

The powder of manganese oxide, calcined at 250oC for 30 min, a weight of 2 g were placed in each of six series-connected between a U-shaped tubes with control of the CO content in the gas stream passing through each of the tubes.

The velocity of the gas was regulated so that the gas and powder created a "fluidized bed" in one of the bends of the tubes and thus created the maximum possible contact between the catalyst surface and the cleaned gas. Due to the high density of the powder and low-speed gas flow catalyst carryover minor and controlled by the filter, filled with glass wool.

The table below gives the results of purification of the gas phase from the carbon monoxide method "perfect push.

The velocity of the gas flow 0,35-0,50 DM3With the degree of purification of gas WITH greater than 50%, with increasing temperature of the catalyst for purification of gas WITH increases and at a temperature of 175-250oWith reaches 90-99%.

According to x-ray phase analysis was used as the catalyst manganese cake contained, wt.%: Co3O453,19; (Co, Mn)(CoMn)2O436,70; Noon 10,11. This phase structure shows that in the process increases the efficiency of the use of manganese oxide as an oxidation catalyst.

Compared with the prototype using calcined manganese oxide in an inexpensive and efficient catalyst for the oxidation of carbon monoxide does not require additional expenses for its manufacturing. If necessary, manganese cake can be easily pressed into tablets.

The use of calcined manganese oxide obtained at the stage of purification of solutions of salts of cobalt from manganese impurities in the technology of hydrometallurgical production of hydroxide cobalt (III), as catalyst for the oxidation of carbon monoxide.

 

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