Catalyst and ammonia production process

FIELD: industrial inorganic synthesis and catalysts.

SUBSTANCE: invention provides ammonia synthesis catalyst containing VII group and group VIB metal compound nitrides. Ammonia is produced from ammonia synthesis gas by bringing the latter into contact with proposed catalyst under conditions favoring formation of ammonia.

EFFECT: increased ammonia synthesis productivity.

8 cl, 2 tbl, 19 ex

 

The present invention relates to a process for the synthesis of ammonia, in particular to a catalyst and method of producing ammonia.

Known catalyst to produce ammonia, which represent clusters of transition metals of group VIII deposited on a zeolite carrier with embedded two ions and monovalent metals. The specified zeolite carrier can additionally contain alkali metal ions (see application WO 96/38222 A1, 01 J 8/00, 01 1/02, 31.05.1996). Receiving ammonia by contacting containing nitrogen and hydrogen gas mixture with the specified catalyst at a temperature and pressure sufficient for the reaction gases of nitrogen and hydrogen resulted in the formation of NH3. Typically, the ammonia synthesis is carried out at a pressure in the range from 100 to 400 bar and a temperature in the range from 300°to 600°C. the closest of the invention is a catalyst to produce ammonia containing oxidic compound of a metal of group VIII and a metal of the sixth group and the promoter is a metal oxide selected from the group comprising metals of IA, IIA, VIB, VIII group, and lanthanides (see application WO 95/32798 A1, 07.12.1995). This application also describes a method of producing ammonia using a specified catalyst.

Object of the invention is the expansion of the range of highly active catalysts, designed to receive the deposits of ammonia.

The problem is solved by the proposed catalyst to produce ammonia containing compound of a metal of group VIII and VIB metal link band, a distinctive feature of which is that as compounds of a metal of group VIII and metal compounds VIB group it contains nitrides of these metals.

The catalyst according to the invention can be promotional one or more metals selected from IA and IIA groups, or one or more metals selected from the lanthanides.

The nitrides of these metals preferably have the General formula:

M'xMyN

where

M' represents a metal of group VIB (according to CAS),

M" is a metal of group VIII and

x and y mixed number from 1 to 10.

The preferred metals of group VIII are iron, cobalt, Nickel and mixtures thereof. The preferred metals of group VIB is molybdenum and/or tungsten. Preferred promoting metals IA and IIA groups are, respectively, cesium and barium.

The catalyst according to the present invention can be applied to any known media.

The task is also solved by the proposed method of producing ammonia from ammonia synthase gas by contacting the synthesis gas with the proposed catalyst under conditions ensuring formation of ammonia.

the ri carrying out the proposed method, the catalyst load, as a rule, in the form of a fixed layer in the Converter to produce ammonia. The catalyst may be loaded in its oxidized form, which is in contact with hydrogen and nitrogen and ammonia in the reaction of the synthesis gas is converted in the active nitride form according to the following reaction scheme:

M'xMyOz+H2⇒M'xMy

M'xMy+H2+NH3⇒M'xMyN

where

M', M", x and y have the above meaning and z is a number corresponding to the valence of the metals.

Working conditions of the proposed method, such as temperature, pressure, are conventional and well-known specialist in this field.

Below the present invention is illustrated by the following examples in more detail describing the preparation and use of the catalyst.

Example 1

Preparation of oxide SNF predecessor.

An aqueous solution containing Co(NO3)2(0.1 mol)is added dropwise to an aqueous solution containing 0.1 mol Mo (NH4)6Mo7O24·4H2O. Upon completion of addition, the reaction mixture is evaporated to dryness and dried at 110°C. the Product calicivirus for 4 hours at 600°With air and analyze rentgenograficheski. According to the analysis of the product is a h is a simple CoMoO 4.

Example 2

Preparation of NiMo oxide predecessor.

Preparation of NiMoO4produced analogously to example 1 using Ni(NO3)2instead of Co(NO3)2.

Example 3

Preparation of NiMo oxide predecessor.

Preparation of Ni2Mo3About11produced analogously to example 2 with the use of 0.066 mol of Ni(NO3)2instead of 0.1 mol of Co(NO3)2.

Example 4

Preparation of oxide SNF predecessor.

Preparation of Co4Moo7produced analogously to example 1 with the use of 0.4 mol of Co(NO3)2instead of 0.1 mol of Co(NO3)2.

Example 5

Preparation of oxide FeMo-predecessor.

Preparation of Fe2Mo3About12produced analogously to example 3 with the use of 0.066 mol of Fe(NO3)3instead of 0.066 mol of Ni(NO3)2.

Example 6

Preparation of oxide NiW predecessor.

Preparation NiWO4produced analogously to example 2 with the use of 0.1 mol W in the form (NH4)10[H2W12O40]·7H2O instead of 0.1 mol of Mo in the form of (NH4)6Mo7O24·4H2O.

Example 7

Preparation of promoted with cesium oxide SNF predecessor.

Preparation of Coof 0.95Cs0,10MoO4is an is logical to example 1 using 0,095 mole of Co(NO 3)2and 0.010 mol CsNO3instead of 0.10 mole of Co(NO3)2.

Example 8

Preparation of modified barium oxide SNF predecessor.

Preparation of Co0,90VA0,10MoO4produced analogously to example 1 with the use of 0.09 mol of Co(NO3)2and 0.010 mol of BA(NO3)2instead of 0.10 mole of Co(NO3)2.

Example 9

Preparation of promoted with lanthanum oxide NiMo predecessor.

Preparation of Niof 0.85La0,05MoO4produced analogously to example 1 using a 0.85 mol of Ni(NO3)2and 0.005 mol of La(NO3)3instead of 0.10 mole of Co(NO3)2.

Example 10

Nitrotyrosine oxide SNF predecessor in pure ammonia.

CoMoO4example 1 pressed into tablets, fracture and sieved to a particle size of 0.3 to 0.8 mm, 5.0 g of material placed in the reactor for ammonia synthesis. The catalyst is heated with a speed of 0.1°C/min to 650°in the stream of gaseous ammonia is passed at 50 l/h. The catalyst support at a temperature of 650°C for 24 hours and then cooled to room temperature.

Example 11

Nitrotyrosine oxide SNF predecessor in dilute ammonia.

The experiment is carried out similarly to experiment 10, except that nitrotyrosine spend the camping in noise at 50 l/h thread containing 4.5% ammonia, 71.6% of hydrogen and 23.9% of nitrogen.

Example 12

Nitrotyrosine NiMo oxide-precursor in dilute ammonia.

The experiment is carried out similarly to experiment 11, except that as starting material used 3.1 g NiMoO4example 2.

Example 13

Nitrotyrosine non-oxide SNF predecessor in dilute ammonia.

The experiment is carried out similarly to experiment 11, except that as the starting material using 4.3 g of Co(NH3)6Mo(CN)8.

Example 14

Promotion SOMO-nitride catalyst is cesium.

2.5 g of the product from example 10 is impregnated with an aqueous solution CsNO3before the initial moisture content. Then the obtained product is dried at 110°and chemically analyzed. According to analysis, the product contains 6.2% of cesium.

Example 15

Promotion NiMo-nitride catalyst is barium.

1.4 g of product from example 12 is impregnated with the aqueous solution of BA(OH)2before the initial moisture content. Then the obtained product is dried at 110°and chemically analyzed. According to analysis, the product contains 5.4% of barium.

Example 16

Oxide SNF-catalyst on the carrier.

Spinel media MgO·xAl2O3in which the spinel has a specific surface area of Asp[g/m2] above 400·exp(-TC/400° (C)obtained KAHL what inacia at the temperature Tc=700° With soaks up the content of 10.5% (wt.) With and 16.2% Mo after calcination at 500°C. the Impregnation is carried out by multiple impregnations to the initial humidity solutions With(NO3)2·6N2O and (NH4)6Mo7O24·4H2O.

Example 17

Promoted with cesium SOMO-the catalyst on the carrier.

The impregnation is conducted as in example 16, except that the final impregnation aqueous solution of CsOH to perform content of 4.1% Cs in the catalyst precursor.

Example 18

Test the activity of the catalyst in the process of ammonia synthesis.

The test is performed using the apparatus used in experiments on nitrotyrosine mentioned in example 10. All test experiments was charged to the reactor 3 to 8 g of the catalyst. Before testing, all the catalysts were nitrotyrosine using the method described in example 10-12. Testing of the catalysts was carried out at a temperature of 400°and the total pressure of 100 bar. The source gas contained 4.5% of ammonia in a hydrogen-nitrogen mixture containing components in the ratio 3:1. The flow rate was adjusted to obtain in the flue gas 12% ammonia. Typical flow velocities were in the range of 2000 ml/h to 50 l/h.

The following table 1 shows the tested catalysts and the corresponding results ispy is any.

Table 1
Catalyst12The output of ammonia, N ml/hour·g
SOMO according to example 1 and 10120
SOMO according to example 1 and 11210
SOMO according to example 13120
CsCoMo according to example 7 and 11650
CsCoMo according to example 14680
VA/SNF according to example 8 and 11520
NiMo according to example 2 and 1280
La/NiMo according to example 9 and 10310
FeMo according to example 5 and 1085
Cs/FeMo according to example 5, 14 and 10540
NiW according to example 6 and 1150
CoMo/MgAl2O4according to example 1670
CsCoMo/MgAl2O4according to example 17210
1Examples refer to the method of preparation of the precursor and the activation method, respectively.

2Activity in terms of the mass of catalyst loaded in the reactor.

Example 19

The test was carried out analogously to example 18, but using 4.5% of ammonia in a hydrogen-azotnoyi, contains the components in a 1:1 ratio.

The following table 2 shows the tested catalysts and the corresponding test results.

Table 2
Catalyst12The output of ammonia, N ml/hour·g
SOMO according to example 1 and 10230
Cs/CoMo according to example 7 and 111040
1Examples refer to the method of preparation of the precursor and the activation method, respectively.

2Activity in terms of the mass of catalyst loaded in the reactor.

1. Catalyst to produce ammonia containing compound of a metal of group VIII and compound VIB group, characterized in that compounds of the metal of group VIII and VIB compounds of group it contains nitrides of these metals.

2. The catalyst according to claim 1, characterized in that as the metals of group VIII it contains iron, cobalt or Nickel and mixtures thereof, and the metal of group VIB is molybdenum and/or tungsten.

3. The catalyst according to claim 1, characterized in that it promotional one or more metals selected from IA and IIA groups.

4. The catalyst according to claim 1, characterized in that it promotional one or more metals, selected and of the lanthanides.

5. The catalyst according to claim 3, characterized in that as the metals of groups IA and IIA it contains, respectively, cesium and barium.

6. The catalyst according to claim 3, characterized in that it is selected from the group comprising Co3Mo3N, promotional caesium or barium and Fe3Mo3N, promotional caesium.

7. The catalyst according to one of claims 1 to 6, characterized in that it is supported on a carrier.

8. The method of producing ammonia from ammonia synthesis gas by contacting the synthesis gas with the metal-containing catalyst under conditions ensuring formation of ammonia, characterized in that the metal-containing catalyst using the catalyst according to one of claims 1 to 7.



 

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