The way to fix nitrogen

 

(57) Abstract:

The method used to fix nitrogen and receiving nitrogen-containing compounds. The method of fixation of nitrogen is that gases containing nitrogen, in contact with the catalyst at atmospheric pressure and low temperatures. As catalysts carbonyl complexes of transition metals, in particular platinum group, in the form of solid products, solutions or suspensions with neutral, acidic or alkaline environment. In the composition of gases containing nitrogen may be reducing agents and/or oxidizing agents. The end products are ammonia or nitrogen oxides. 3 C.p. f-crystals.

The method relates to the field of inorganic chemistry.

As is known, molecular nitrogen under normal conditions, is chemically inert. Therefore, translating it into a bound state requires mild conditions - high temperatures and high pressure, as is the case when obtaining ammonia from nitrogen and hydrogen. This process is energy intensive and requires the use of special expensive equipment. Therefore, the development of ways of linking molecular nitrogen under mild conditions is an important task that you are trying to solve with pomoshyu ammonia from hydrogen and nitrogen at low temperatures and pressures in the presence of compounds of molybdenum, containing metallographie communication [2].

The disadvantage of this method is the low yield of the final product (0.4%) and the performance of 0.1% per hour.

The proposed method is based on the high activity of CO molecules included in carbonyl complexes of transition metals, in particular platinum group metals.

Thus, for reactions (1, 2, 3)

< / BR>
there is a high thermodynamic possibility of leakage. However, reaction (1, 2, 3) under mild conditions (room temperature and atmospheric pressure) does not occur because of the high values of activation energy.

At the same time, the CO molecule included in the carbonyl complexes, significantly activated and able to join in the reduction reaction of which with the free CO molecules does not occur.

Thus, the reaction in solution

2CuII+ CO + H2O = 2CuI+ CO2+ 2H+(4)

does not leak. But in the presence of salts of palladium (II) forming a CO carbonyl complexes, reaction (4) easily proceeds under mild conditions [3].

The essence of the proposed method lies in the fact that the gas mixture containing nitrogen comes into contact with the catalyst - carbonyl complexes of transition meta is to and in the oxidized form (NO,N2O), which is primarily determined by the composition of the gas mixture in contact with the catalyst.

The process proceeds under mild conditions at atmospheric pressure and temperatures from room temperature up to 200 - 300oC.

The catalyst may be in dry form, in the form of aqueous or aqueous-organic pulp, as well as in the form of a solution. The original liquid phase can be acidic, alkaline or neutral.

Example 1. 700 mg of carbonyl plate [Pt(CO2]nrasulovna in 150 ml of 0.1 n hydrochloric acid solution. Through this pulp at t = 60oC and atmospheric pressure with stirring missed a mixture of CO + air in a volume ratio of 1:2 at a rate of 10 ml/min for 30 minutes

In the exhaust gas was discovered 8.5 mg of N2O.

Per reaction

CO + N2+ O2= N2O + CO2< / BR>
the output of the associated nitrogen is 20%.

Example 2. 35 mg of carbonyl platinum [Pt(CO)2]nwas dissolved in 50 ml of NaOH solution. Through this solution at t=20oC, atmospheric pressure and stirring missed a mixture of CO + air in a volume ratio of 1:2 at a rate of 10 ml/min for 30 minutes

The solution was found associated oxidized nitrogen 5.1 mg the data of nitrogen is 12.3%

Example 3. 60 mg of rhodium, 40 mg of ruthenium and 12 mg of iridium in the form of its carbonyl-chloride-Rh2(CO)2Cl2Ir2(CO)2Cl2, Ru(CO)2Cl2dissolved in 35 ml of liquid, consisting of 5 ml of H2O and 30 ml of methanol and pH 9. Through this solution at 30oC, atmospheric pressure and stirring missed a mixture of CO+H2in a volume ratio of 1:1 for 1.3 hours at a rate of 10 ml/min Exhaust gas absorbed solution of hydrochloric acid. Was obtained bound nitrogen in the calculation of the ammonium chloride 9 mg

For the reaction

3CO+N2+3H2O=2NH3+3CO2< / BR>
the output of the associated nitrogen is 1.4%.

Example 4. 500 mg of carbonyl composition Pt7Pd2(CO)15in the form of crystals were placed in a boat in a tubular furnace. At t= 200oC and atmospheric pressure over a catalyst missed a gas mixture of CO, N2and water vapor in a volume ratio of 3:1:2 at a rate of 10 ml/min for 2 h

In the exhaust gas was detected 12 mg of ammonia.

Per reaction

3CO+N2+3H2O=2NH3+3CO2< / BR>
the output of the associated nitrogen was of 4.75%.

As seen from the above examples, the carbonyl complexes of transition CLASS="ptx2">

Literature.

1. Shilov, A. E. USP, 1974, T. 43, S. 863

2. Patent Germany N 956674, 1957.

3. Spitsyn, C. I., I. Fedoseev Century, Ponomarev, A. L., Elesin A. I. J. neorg. chemistry, 1978, T. 26, vol. 2, S. 454.

1. The method of fixation of nitrogen by contact with gases containing nitrogen with a catalyst, wherein the catalyst used carbonyl complexes of transition metals.

2. The method according to p. 1, characterized in that the nitrogen is part of the gases containing the reducing agents and/or oxidizing agents.

3. The method according to p. 1, characterized in that the catalyst may be dry mixed with the liquid phase or in solution.

4. The method according to p. 3, characterized in that the used water or water-organic solutions with acidic, alkaline or neutral media.

 

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