The catalyst receiving nitrous oxide and method

 

The invention relates to catalysts and methods of producing nitrous oxide (N2O) by oxidation of ammonia with oxygen or oxygen-containing gas. Nitrous oxide is widely used in various fields of national economy: in a semiconductor, perfume, medical and food industries. The described catalyst and method for producing nitrous oxide by oxidation of ammonia with oxygen or oxygen-containing gas, comprising the mn containing the active ingredient, iron oxide, lanthanum oxide, oxide or mixture of oxides, alkaline earth metal and aluminum oxide. The catalyst contains as an active ingredient composition, a mixed amorphous oxide phase non-stoichiometric composition MnBixOy(0,05x2,24; 2,08yare 5.36) or a mixture of amorphous oxide phase composition MnBixOyand mn containing crystalline phase. The process of obtaining nitrous oxide by oxidation of ammonia with oxygen or oxygen-containing gas in the presence of mn containing catalyst of the above composition is carried out at a temperature of 250-450oC. Technical affinage component. 2 S. and 4 C.p. f-crystals, 1 table.

The invention relates to catalysts and methods of producing nitrous oxide (N2O) by oxidation of ammonia with oxygen or oxygen-containing gas. Nitrous oxide is widely used in various industries such as semiconductor, perfume, medical and food industries. In recent years there has been another area of application of catalytic oxidation of nitrogen oxide benzene to phenol.

Needs of nitrous oxide in various fields have resulted in increased interest in the development of various methods of its receipt. There are several ways of obtaining nitrous oxide, among which we can highlight a number of catalytic methods: 1. Catalytic reduction of nitrogen monoxide (NO) or carbon monoxide (CO) or hydrogen or a mixture of carbon monoxide and hydrogen (synthesis gas) in the presence of homogeneous catalysts [EP 54965, 01 21/22, 1982]; 2. Catalytic reduction of nitrogen monoxide or carbon monoxide, or hydrogen, or a mixture of carbon monoxide and hydrogen (synthesis gas) in the presence of heterogeneous catalysts, which are used noble metals of the platinum group deposited on carriers, for example, (1-5) wt is oxygen in the presence of heterogeneous catalysts based on metal oxides.

A known number of oxide catalysts for production of nitrous oxide by oxidation of ammonia, in particular, on the basis of manganese dioxide: MnO2-Bi2O3[Pat. DE, 503200, 1930; Pat. CSR, 158091, 1973]; MnO2-CuO [EP 799792, C 01 B 21/22, 1997]; MnO2-Bi2O3-Fe2O3[Pat. DE, 503200, 1930; EP 799792, C 01 B 21/22, 1997]; MnO2-CoO-NiO [ EP 799792, C 01 B 21/22, 1997].

The number of known catalysts containing manganese oxide, namely: Co3O4-A12O3[Reference: Catalytic properties of substances. / Ed. by C. A. Reuter, 1968 ]; Pr2O3-Nd2O3-CeO2[EP 799792, C 01 B 21/22, 1997].

Closest to the proposed catalyst is the catalyst for getting the nitrous oxide comprising oxides of manganese, bismuth and aluminum content, wt.%: (5,035,0) MnO2- (4,530,0) Bi2About3- (90,535) Al2About3[Pat. RF 2102135, B 01 J 23/18, 1998; WO 9825698, B 01 J 23/18, 1998]. The catalyst used for obtaining nitrous oxide by oxidation of ammonia oxygen-containing gas. In particular, the catalyst containing, wt.%: 13 Mno2- 11 Bi2O3- 76 Al2About3when processing of the reaction mixture composition is about 9. the following process parameters: the degree of conversion of ammonia99.2%, and the selectivity for N2Oand NO (SNO) - 87% and 2.8%, respectively.

The disadvantages of this catalyst is relatively high lower limit of the content of the oxides Mno2and Bi2O3in the catalyst, at least a 9.5 wt.%, to obtain the required selectivity for N2O. a Known catalyst shows a sufficiently high output of NO in the oxidation of ammonia, which is harmful impurities for subsequent use of the target product. Known catalyst has a fairly high bulk density in the range of 0.9-1.4 g/cm3that complicates its use in the apparatus of the fluidized bed because of the impossibility of the realization of the turbulent mode.

The invention solves the problem of obtaining an active and selective catalyst in the ratio of nitrous oxide by oxidation of ammonia with oxygen or oxygen-containing gas, including low content of the active component.

The problem is solved by catalyst receiving nitrous oxide comprising mn containing the active ingredient, an oxide or mixture of oxides, alkaline earth metal, iron oxide, lanthanum oxide and aluminum oxide. The catalyst contains as AK composition MnBixOy(0,05x2,24; 2,08are 5.36) or a mixture of amorphous oxide phase composition MnBixOyand mn containing crystalline phase. The content of components in the catalyst, wt. %: MnBixOyor a mixture of MnBixOyand mn containing crystalline phase - 0,75 - 65,0
Alumina - 99,235 - 0,005
Iron oxide - 0,005 - 99,235
The oxide of lanthanum - 0,005 - 99,235
The oxide or mixture of oxides of the alkaline earth metal - 0,005 - 99,235
As a mn containing crystalline phases it contains manganese oxide MP2About3and/or connection of the composition of Bi2Mn4O10. The content of mn containing crystalline phase is, wt.%: 0,005-25,0.

The catalyst contains an oxide or mixture of oxides of alkaline earth metals selected from a number of: Mg, Ca, Sr, Ba.

The catalyst may optionally contain a spinel type MAl2O4, where M is an alkaline earth metal.

The task is also solved by a method of obtaining nitrous oxide by oxidation of ammonia with oxygen or oxygen-containing gas in the presence of mn containing catalyst of the above composition, the process is carried out at those who Ganz, bismuth, iron, lanthanum and alkaline earth metal with subsequent stages of drying at 120-150oC and calcination at 400-750oC. Or prepared by impregnation of the granules containing oxides of alkaline earth metals and aluminum oxide with subsequent stages of drying at 120-150oC and calcination at 400-750oC. Or deposition with subsequent mixing and forming of the catalyst components into pellets of the desired shape with the subsequent stages of drying at 120-150oC and calcination at 400-750oC. the Finished catalyst after calcination according to the RFA does not contain in its structure phases of oxides MnO2and Bi2O3observed the presence of a characteristic "Gallo" mixed amorphous phase MnBixOy. In the case of calcination of the catalyst at temperatures above 550-600oWith the structure of the catalyst can be observed the formation of crystalline oxide phases MP2About3and mixed compounds of Bi2Mn4O10. The resulting catalysts are characterized by a high selectivity for N2O in the oxidation of ammonia-oxygen mixtures, even for samples with a relatively low content of active ingredient: mixed amorphous Mn-Bi oxide phase; give demoted the ora MVxAbouty/MO-Fe2About3-La2About3-Al2About3significantly smaller than the catalyst of the prototype Mno2-Bi2About3/Al2About3the selectivity for nitrous oxide in the oxidation of ammonia to the above catalyst is 87-88% at the reaction temperature of 350-360oC.

Salient features of the proposed catalyst is a catalyst composition and structure of the active component.

The catalytic properties of the proposed catalysts in the oxidation of ammonia-oxygen mixtures are examined in running the install and evaluate the selectivity to the target product N2O and on the presence of incidental impurities NO. The reaction mixture of 8 vol.% NH3, 9.% About2Not - the rest is passed through the catalyst bed fractional composition of 0.25-0.50 mm at flow rate of 3600 h-1. The reaction temperature is 350oC. the Composition of the initial reaction mixture and the reaction products analyzed chromatographically; the NO concentration is determined using an analyzer ECOM-Omega (Austria).

The invention is illustrated by the following examples.

Example 1. 60 g of the granules media Al2About3containing 0,004 is of 39,59 g of salt MP(NO3)26N2O and 16,65 g of salt Bi(NO3)35H2O a 5% solution of HNO3. The wet granules are dried under IR-dryer to dry friable state, then dried in a drying Cabinet at a temperature of 120oC for 4 hours. The sample was then calcined in a furnace at a temperature amounts to 400-650oC for 6 hours. The resulting catalyst has a composition, by weight. %: 25,0 MnBi0.25O2,38- 74,985 Al2About3- 0,005 MgO - 0,005 La2O3- 0,005 Fe2O3. The XRD pattern indicates the absence of a catalyst composition of the crystalline phase of oxides Mno2and Bi2O3. The catalyst was tested in the oxidation of ammonia oxygen-containing mixture in the test conditions described above. Selectivity for nitrous oxideand nitrogen oxide (SNO) respectively 87,4% and 2.4%.

Example 2. 58,4 g granules media Al2About3containing 0.004 g Fe2O3and 0.004 g La2About3, nitrate impregnated with a solution obtained by dissolving 39,59 g of salt MP(NO3)26N2O, 16,65 g of salt Bi(NO3)35H2O and 10,24 g of salt Mg(NO3)2and nitrogen oxide (SNO) respectively of 87.8% and 0.2%.

Example 3. 60 g of the granules media MgO containing 0.004 g La2About3, 0.004 g Al2About3and 0.004 g Fe2O3, nitrate impregnated with a solution obtained by dissolving 39,59 g of salt MP(NO3)26N2O and 16,65 g of salt Bi(NO3)35H2O a 5% solution of NGO3. The wet granules are dried under IR-dryer to dry friable state, then dried in a drying Cabinet at a temperature of 120oC for 4 hours. The sample was then calcined in a furnace at a temperature amounts to 400-650b>O3- 0,005 Fe2O3- 0,005 Al2About3. The XRD pattern of the catalyst shows the absence of the catalyst composition of the crystalline phase of oxides Mno2and Bi2O3. The catalyst was tested in the oxidation of ammonia oxygen-containing mixture in the test conditions described above. Selectivity for nitrous oxideand nitrogen oxide (SNO) respectively 87,0 and 0.3%.

Example 4. 60 g of the granules media Al2About3containing 0.003 g Fe2O3, 0.0024 g of MgO and 0.024 g of Cao, nitrate impregnated with a solution obtained by dissolving 1.0 g of salt MP(NO3)26N2O, 0.32 g of salt Bi(NO3)35H2O and 0.003 g of oxide of La2O3a 5% solution of NGO3. The wet granules are dried under IR-dryer to dry friable state, then dried in a drying Cabinet at a temperature of 120oC for 4 hours. The sample was then calcined in a furnace at a temperature amounts to 400-650oC for 6 hours. The resulting catalyst has a composition, by weight. %: 0,75 MnBi0,19O229- 0,004 MgO - 0,04 Cao - 0,005 Fe2O3-0,005 La2About3- 99,196% Al2O3. The XRD pattern of the catalyst shows a lack with the oxidation of ammonia oxygen-containing mixture in the test conditions, described above. Selectivity for nitrous oxideand nitrogen oxide (SNO) respectively of 80.6% and 0.9%.

Example 5. 60 g of the granules media Al2About3containing 0.0024 g of MgO and 0,0016 g Cao, nitrate impregnated with a solution obtained by dissolving 39,59 g of salt MP(NO3)26N2O, 13,32 g of salt Bi(NO3)35H2O, 0.004 g La2About3and 8.08 g of salt Fe(NO3)3N2O a 5% solution of NGO3. The wet granules are dried under IR-dryer to dry friable state, then dried in a drying Cabinet at a temperature of 120oC for 4 hours. The sample was then calcined in a furnace at a temperature amounts to 400-650oC for 6 hours. The resulting catalyst has a composition, wt.%: 25,0 MnBiof 0.25O2,38- 72,99 Al2About3- 0,003 MgO - 0,002 Cao - 0,005 La2About3- 2,0 Fe2About3. The XRD pattern indicates the absence of a catalyst composition of the crystalline phase of oxides Mno2and Bi2About3. The catalyst was tested in the oxidation of ammonia oxygen-containing mixture in the test conditions described above. Selectivity for nitrous oxideand sub>, 0.004 g Fe2O3and 0.004 g La2About3, 104,97 g MP(NO3)26N2O, 56,76 g Bi(NO3)35H2O in nitric acid solution, neutralized with lime water to pH 7. Leave to stand for 30 min and filtered. The wet precipitate formed into pellets and dried in air. Then dried in an oven at 120-140oC and calcined at 400-500oC for 4 hours. The resulting catalyst has a composition, wt.%: 65,0 MnBi0,32O2,48to 2.0 CaO - 0,005 Fe2O3- 0,005 La2About3- 32,99 Al2About3. The XRD pattern of the catalyst shows the absence of the catalyst composition of the crystalline phase of oxides Mno2and Bi2O3. The catalyst was tested in the oxidation of ammonia oxygen-containing mixture in the test conditions described above. Selectivity for nitrous oxideand nitrogen oxide (SNO) respectively and 82.2% and 2.0%.

Example 7. 60 g of the granules media MgAl2O4impregnated with a nitric acid solution obtained by dissolving 29,69 g of salt MP(NO3)26N2O, of 10.93 g of salt Bi(NO3)35H2O, 0.75 g of oxide of La2O the uly dried under IR-dryer to dry friable state, then dried in a drying Cabinet at a temperature of 120oC for 4 hours. The sample was then calcined in a furnace at a temperature amounts to 400-650oC for 6 hours. The resulting catalyst has a composition, wt.%: 18,0 MnBi0,19Oto 2.29to 1.0 Fe2O3- 1,0 La2O3- 22,5 MgO - 57,5 Al2About3. The XRD pattern indicates the absence of a catalyst composition of the crystalline phase of oxides Mno2and Bi2O3. The catalyst was tested in the oxidation of ammonia oxygen-containing mixture in the test conditions described above. Selectivity for nitrous oxideand nitrogen oxide (SNO) respectively of 87.5% and 0.2%.

Example 8. 60 g of the granules media Al2About3containing 0.004 g MgO, 0.004 g La2O3and 0.004 g Fe2O3, nitrate impregnated with a solution obtained by dissolving 42,23 g of salt MP(NO3)26N2O and 15,32 g of salt Bi(NO3)35H2O a 5% solution of NGO3. The wet granules are dried under IR-dryer to dry friable state, then dried in a drying Cabinet at a temperature of 120oC for 4 hours. The sample was then calcined in a furnace at a temperature amounts to 400-650oWith over 6 About3- 0,005 MgO - 0,005 La2About3- 0,005 Fe2O3. The XRD pattern showed the absence of the catalyst composition of the crystalline phase of oxides Mno2and Bi2O3. The catalyst was tested in the oxidation of ammonia oxygen-containing mixture in the test conditions described above. Selectivity for nitrous oxideand nitrogen oxide (SNO) respectively 87,2% and 1.2%.

Example 9. 60 g of the granules media Al2About3containing 0.004 g MgO, 0.004 g La2About3and 0.004 g Fe2About3, nitrate impregnated with a solution obtained by dissolving with 40.2 g of salt MP(NO3)26N2O and 16,65 g of salt Bi(NO3)35H2O a 5% solution of NGO3. The wet granules are dried under IR-dryer to dry friable state, then dried in a drying Cabinet at a temperature of 120oC for 4 hours. The sample was then calcined in a furnace at a temperature amounts to 400-650oC for 6 hours. The resulting catalyst has a composition, wt.%: 20,0 MnBiof 0.25O2,38is 1.58 MP2About3- 3,42 Bi2Mn4O10- 74,985 Al2About3- 0,005 MgO - 0,005 La2O3- 0,005 Fe2O3. The XRD pattern showed the absence of cccii oxidation of ammonia oxygen-containing mixture in the test conditions, described above. Selectivity for nitrous oxideand nitrogen oxide (SNO) respectively 87,0 and 1.1%.

Example 10. 60 g of the granules media MgAl2O4impregnated with a nitric acid solution obtained by dissolving 29,69 g of salt MP(NO3)26N2O, 12,49 g of salt Bi(NO3)35H2O and 1.54 g of oxide of La2O3an 8% solution of NGO3. The wet granules are dried under IR-dryer to dry friable state, then dried in a drying Cabinet at a temperature of 120oC for 4 hours. The sample was then calcined in a furnace at a temperature amounts to 400-650oC for 6 hours. The resulting catalyst has a composition, by weight. %: 19,6 MnBiof 0.25O2,38- 2,0 La2About3- 78,4 MgAl2O4. The XRD pattern showed the absence of the catalyst composition of the crystalline phase of oxides Mno2and Bi2O3. The catalyst was tested in the oxidation of ammonia oxygen-containing mixture in the test conditions described above. Selectivity for nitrous oxideand nitrogen oxide (SNO) respectively 87,4 and 0.5%.

Thus, the present invention allows to reduce the release of NO in the process and with a lower bulk weight at a level of 0.65-0.7 g/cm3.


Claims

1. The catalyst for obtaining nitrous oxide by oxidation of ammonia with oxygen or oxygen-containing gas, comprising the mn containing active component and aluminum oxide, characterized in that it contains as an active ingredient composition, a mixed amorphous oxide phase non-stoichiometric composition MnBixOy(0,05x2,24; 2,08yare 5.36) or a mixture of amorphous oxide phase composition MnBixOyand mn containing crystalline phases, as well as lanthanum oxide, iron oxide and the oxide or mixture of oxides of the alkaline earth metal content, wt. %:
MnBixOyor a mixture of MnBixOyand mn containing crystalline phase - 0,75-65,0
Alumina - 99,235-0,005
Iron oxide - 0,005-99,235
The oxide of lanthanum - 0,005-99,235
The oxide or mixture of oxides of the alkaline earth metal - 0,005-99,235
2. The catalyst p. 1, characterized in that as the mn containing crystalline phases it contains the oxide of manganese Mn2O3and/or connection of the composition of Bi2Mn4O10hat from 0.005 to 25.0 wt. %.

4. The catalyst PP. 1-3, characterized in that it contains an oxide or mixture of oxides of alkaline earth metals selected from a range of Mg, Ca, Sr, Ba.

5. The catalyst PP. 1-4, characterized in that it further comprises a spinel type l2O4, where M is an alkaline earth metal.

6. The method of obtaining nitrous oxide by oxidation of ammonia with oxygen or oxygen-containing gas in the presence of mn containing catalyst, wherein the process is carried out at a temperature of 250-450oWith, and as a catalyst using the catalyst according to any one of paragraphs. 1-5.

 

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