The method of preparation of the catalyst to remove oxygen from the hydrogen sulfide-containing gases

 

(57) Abstract:

The invention relates to a method for producing a catalyst to remove oxygen in the processing technology for hydrogen sulfide gas in the sulfur method Claus.

The method differs in that the aluminum hydroxide, or aluminum hydroxide with a pore-forming additives, or aluminum hydroxide mixed with up to 30% - Al2O3mixed with the salt of iron, then add nitric acid to acid module Mto=0,1 - 0,01, then a lot ekstragiruyut, dried and calcined at a temperature of 450 - 600oC.

As salts of iron using iron sulfate, iron oxalate, iron nitrate, iron acetate.

As a pore-forming additives used sawdust softwood up to 20%.

As a pore-forming additives used carboxymethylcellulose, carboximetilzellulozu.

The proposed method for the preparation of the catalyst allows to reduce energy consumption, to simplify the technology of preparation of the catalyst retaining the activity and stability of the catalyst. 4 C.p. f-crystals, 1 table.

The invention relates to a method for producing a catalyst to remove oxygen in technologiesthis in gases, burn partially to sulfur and sulfur dioxide, sulfur is separated and the gas containing H2S, SO2H2O and nitrogen, is directed to the catalytic step (I)

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The presence of traces of oxygen in the gas leads to sulfate crystallization catalyst Claus on the basis of aluminum oxide and diminished activity in the reaction (1).

Known methods of decreasing sulfate crystallization catalyst Claus on the basis of aluminum oxide by introducing various additives.

For example, a catalyst containing 2.5% sodium oxide and calcined at 100oC [1] and the catalyst containing alkaline or alkaline-earth metals in a quantity of 50 to 400 mg/m3media [2] First, however, characterized by a low specific surface, the second high content of active additives, which leads to lowering the porosity of the catalyst.

In addition, the deposition of oxides of alkali metals leads to their interaction with sulphurous anhydride. The catalysts more resistant to sulfate crystallization than aluminum oxide, but inferior in the degree of obezkislorazhivaniya gases.

A known way of increasing the stability of the catalyst Claus due to the absorption of oxygen supplements deposited on the catalyst in the pores is not less than 0.2 cm3/g and sulfides, oxides or other compounds of molybdenum, cobalt, iron, copper and so on [3]

However, the catalyst obtained by this method showed low activity and stability as the Claus reaction, and the absorption of oxygen, which is required in the first place, increasing the contact time up to 8 and above.

Closest to the claimed is the catalyst for the removal of oxygen from gases to protect the catalyst Claus from sulfate crystallization containing at least one metal from the group of Fe, Ni, Co, Zn and other media with a specific surface area not less than 100 m2/g and specific porosity greater than 0.2 cm3/g [4] the metal Content in the catalyst is 0.5 to 10% wt. The contacting gas containing H2S, SO2and oxygen, occurs in one catalytic reaction zone.

Catalyst protection loaded into the reactor immediately before the layer of aluminum oxide and with the passage of process gases oxygen contained in the gas interacts with the hydrogen sulfide by the reaction rather than the oxide catalyst Claus:

2H2S+2O2_ S+SO2+2H2O

The application of the protective layer prevents oxygen from entering into the zone of the main reaction is aetsa its high initial activity.

The catalyst was prepared by impregnation of alumina aqueous or organic solutions of metal salts of excess solution, followed by decantation, dried at a temperature of 120oC for 3 h and calcination in air at 350oC for 3 h

A significant drawback of this method is that the catalyst showed lower activity.

In addition, the use of excess impregnating solution leads to the presence of waste water after phase adsorption of the active ingredient aluminum oxide containing metals. It should be noted, and a significant flow of metal salts when applied, which leads to higher catalyst.

A significant drawback is the duration of stage adsorption-impregnation, especially for the deposition of significant quantities of metals.

The purpose of the present invention, the reduction of energy consumption, simplification of preserving the activity and stability of the catalyst.

This objective is achieved in that for obtaining the catalyst for the removal of oxygen from hydrogen sulfide gas as a binder is used, the aluminum hydroxide or aluminum hydroxide up to 30% - Al2O3mixed with with the 450 600oC.

As salts of iron using iron sulfate, iron oxalate, iron acetate, iron nitrate.

As a pore-forming additives used sawdust softwood up to 20%

As a pore-forming additives used carboxymethylcellulose, carboximetilzellulozu.

As aluminum hydroxide use aluminum hydroxide, past termomekhanicheskoe activation.

The active component in terms of the metal is 1 to 10% can increase the metal content of up to 20% but this leads to a decrease in strength of the catalyst.

Thus, the proposed method in contrast to the known is characterized by a number of significant differences:

the use of aluminum hydroxide or aluminum hydroxide with a pore-forming additives or aluminum hydroxide mixed with up to 30% c - Al2O3;

mix with salt iron at acidic module Mto=0,01 0,01;

the calcination at a temperature of 450 -600oC;

as a pore-forming additives used sawdust softwood up to 20%

as a pore-forming additives used carboxymethylcellulose, carboxin iron, acetate of iron, nitrate of iron.

As aluminum hydroxide use aluminum hydroxide, past termomekhanicheskoe activation.

A new set of distinctive features leads to achievement.

The catalyst is prepared as follows.

The aluminum hydroxide or aluminum hydroxide + 30% c Al2O3or aluminum hydroxide with a pore-forming additives are mixed in dry form with a compound of iron with the subsequent introduction of nitric acid (Mto=0,1 - 0,01), the mixture is stirred, molded, dried and calcined at a temperature of 450 - 600oC.

The distribution of the pore radii were conducted by the method of mercury porometry on the device 2000 of the company "Carlo Erba (Italy).

Testing of catalyst stability were conducted in flow-through laboratory setting at a temperature 22010oC for a contact time of 0.3 C. the Composition of the initial gas mixture in all tests was constant and consisted of 3% vol. H2S, 1,5% vol. SO2, 0,5% vol. O2, argon else.

Analysis of the initial mixture and the composition of the gas after contact with the catalyst was carried out on the chromatograph LHM-MD.

Example 1 (the prototype).

To 200 ml of oxide is an increase of 3 h are adsorption. Then the excess solution containing ferric sulphate is poured, the catalyst is dried at 120oC 3 h and calcined at 350oC 3 o'clock

Example 2.

To 280 g of aluminum hydroxide, past termomekhanicheskoe processing, add 40 g of pore-forming additives c Al2O3, salt iron. Mix the dry ingredients for 10 minutes Then add a solution of nitric acid in water (10 ml concentrated acid in 150 ml of water). Stirred for 15 minutes Then a lot ekstragiruyut, dried, calcined at a temperature of 450 600oC.

Example 3.

Similar to example 2, only the acid module is equal to 0.005 and the amount of pore-forming additive is 25% wt

Example 4.

Similar to example 2, only the acid module is equal to 0.15 and the number of pore-forming additive is 27% wt.

Example 5.

Similar to example 2, the temperature of calcination is 400oC.

Example 6.

Similar to example 2, the temperature of calcination is equal to 700oC.

Example 7.

Similar to example 2, only a pore-forming additive is a 10% wt

Example 8.

Similar to example 2, only serve as a pore-forming sawdust, acid module is equal to 0.02 and the amount of sawdust is 20% wt

Example 10.

Similar to example 2, only as salts of iron using iron sulfate, but as a pore-forming additives used carboxymethylcellulose in an amount of 30 wt.%

Example 11.

Similar to example 2, only as salts of iron using iron-oxalate and acid module is 0.05.

Example 12.

Similar to example 2, only as salts of iron using iron nitrate.

Example 13.

Similar to example 2, only the porous structure regulate acid unit, which is equal to 0.01.

All the catalysts are summarized in table.

As can be seen from the table, the reduction of acid module (example 3) leads to a decrease in the strength and stability of the catalyst, and its increase to obtain porous catalyst with a low volume of macropores, which leads to difficulty of removal of the reaction products and reduce stability.

Lowering the temperature of the annealing up to 400oC (example 5) leads to lower stability of the catalyst, the temperature of annealing to 700oC (example 6) results >the amount of this additive is up to 30% When used as a pore-forming additives sawdust softwood their number is reduced to 20%

With increasing mixing time in more than 15 min pasta relaxes (diluted), and at lower (5 min) pasta mixed.

To make the active component may use a dry iron compounds.

As iron compounds are used, preferably, iron sulfate (example 10), iron oxalate (example 11) and iron nitrate (example 12).

Thus, the proposed method in comparison with the known is less energy - and time-consuming.

In the preparation method of catalyst for the cost of the preparation of a carrier, a porous structure is formed in the process of preparation of the catalyst.

1. The method of preparation of the catalyst to remove oxygen from the hydrogen sulfide-containing gases, including drying and calcination, wherein the aluminum hydroxide, or aluminum hydroxide with a pore-forming additives, or aluminum hydroxide mixed with up to 30% X Al2O3mixed with the salt of iron, then add nitric acid to acid module Mto0,1 is m, as salts of iron using iron sulfate, iron oxalate, iron nitrate, iron acetate.

3. The method according to p. 1, characterized in that as a pore-forming additives used sawdust softwood up to 20%

4. The method according to p. 1, characterized in that as a pore-forming additives used carboxymethylcellulose, carboximetilzellulozu.

5. The method according to p. 1, characterized in that the aluminum hydroxide use aluminum hydroxide, past termomekhanicheskoe activation.

 

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4 cl, 1 tbl, 8 ex

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