The preparation method of catalyst for steam reforming of carbon monoxide and a catalyst for steam reforming of carbon monoxide

 

(57) Abstract:

The invention relates to the production of catalysts for steam reforming of carbon monoxide in the processes of hydrogen and nitric mixture in the chemical and petrochemical industries. The invention consists in the mixture of compounds of iron with a water solution of chromic acid and a manganese salt with subsequent formation of granules, drying and calcination, while having steam reforming catalyst containing the oxides of chromium and manganese. In an aqueous solution of chromic acid is further added at least one connection alkaline earth metal selected from the group comprising Mg, Ca, and at least one compound of rare earth metal selected from the group including Ce, La, Nd, Pr, and optional connection of copper, as well as compounds of iron using iron oxide. The catalyst additionally contains at least one oxide of the alkali earth metal General formula MeO selected from the group Mg, Ca, and at least one oxide of rare earth metal General formula Ln2O3selected from the group Ce, La, Nd, Pr. The technical result consists in increasing the stability of the catalyst when the save is of catalysts steam reforming of carbon monoxide in the processes of hydrogen and nitric mixture in the chemical and petrochemical industries.

A known method of producing catalyst for steam reforming of carbon monoxide containing 7.2 wt.% Cr2O3, a mixture of iron oxide Fe2O3with chromic acid, followed by molding, drying and calcination. The activity of the catalyst, expressed in terms of the rate constant for the reaction of carbon monoxide with water vapor at a temperature of 350oC, is 1.35-1,55 cm3/(g). (A. C. USSR N 651838, IPC 01 J 37/04, publ. 15.03.79).

A method of obtaining a catalyst, characterized by the additional introduction of magnetite (Fe3O4in the amount of 15 to 100% by weight of iron oxide. Get the catalyst activity 1,22-1,35 cm3/(g). (A. C. RF N 1790064 F1, IPC 01 J 37/04, 23/86, publ. 20.05.96).

The disadvantage of this method is the low activity obtained with the help of catalysts.

A known catalyst for steam reforming of carbon monoxide on the basis of iron oxide containing 6.5 to 7.5 wt.% Cr2O3, 2 to 10 wt.% CuO and 1 to 4 wt.% Al2O3. The catalyst was prepared by mixing the carbonate of iron - FeCO3with a solution of copper nitrate Cu(NO3)2or ammonium carbonate copper - Cu(NH4)4CO3, nitrate aluminum - Al2(NO3)filling (before the introduction of chromic acid) with annealing. (RF patent N 2059430 C1 IPC 01 J 23/885, publ. 10.05.96).

The disadvantage of this catalyst is the low stability, resulting in the loss of activity after overheating in the reaction medium containing hydrogen and steam (Red/Ox). The term "stability" is a characteristic of the performance of catalyst (E. L. Furin, H. C. Komova and other stability studies elekronnogo the catalyst for carbon monoxide conversion. Sat. Catalysis and catalysts. Kyiv. - Naukova Dumka, 1985, vol. 23, S. 90-93).

Closest to the proposed invention to the technical essence and the achieved result is a method for preparing a catalyst comprising a mixture of compounds of iron with a water solution of chromic acid and a salt of manganese, followed by molding, drying and calcination. The catalyst obtained by this method contains of 6.5 - 7.5 wt.% Cr2O3, 1.6 to 1.7 wt.% MnO2and 0.9 to 1.0 wt.% K2O, Fe2O3the rest and has a fairly high activity of 2.5 - 3.5 cm3/HS). (A. C. USSR N 518941 A, IPC 01 J 37/04, publ. 07.07.84).

The disadvantage of the catalyst obtained by this technology is the low stability.

The technical problem to be solved, predlagaemy and stability during operation.

This technical problem is solved in the method of preparation of catalyst for steam reforming of carbon monoxide, comprising a mixture of compounds of iron with a water solution of chromic acid and a salt of manganese, with the subsequent formation of granules, drying and calcination, in which an aqueous solution of chromic acid is further added at least one connection alkaline earth metal selected from the group Mg, Ca, and at least one compound of rare earth metal selected from the group including Ce, La, Nd, Pr, and optional connection of copper, as well as compounds of iron using iron oxide.

The preparation of the catalyst as the metal compounds selected from the group Mg, Ca, Ce, La, Nd, Pr, Cu, use at least one compound from the series: oxide, hydroxide, carbonate, chromate, bichromate and use iron oxide containing magnetite (Fe3O4and/or chromite iron - Fe[CrFe] O4in the amount of 5-50% by weight of iron oxide. When mixed in the catalyst mass is further added a solution of chromate of urea - 2 CO(NH2)2H2CrO4or urea in the amount of 0.5 to 1.5% by weight of iron oxide and/or carbon-containing material in an amount of 1.0 to 4.0 wt.and/or colloidal graphite. In this way we obtain a catalyst for steam reforming of carbon monoxide containing oxides of iron, chromium and manganese, which additionally contains at least one oxide of the alkali earth metal General formula MeO selected from the group Mg, Ca, and at least one oxide of rare earth metal General formula Ln2O3selected from the group Ce, La, Nd, Pr, at the following content, wt.%:

Cr2O3- 7,0 - 12,0

MnO2- 0,2 - 1,0

MeO - 0,1 - 0,8

Ln2O3- 0,05 - 1,0

Iron oxide - Rest.

The catalyst additionally contains from 1.0 to 3.0 wt.% copper oxide CuO.

The main distinguishing features of the present invention is that the preparation of the catalyst in an aqueous solution of chromic acid is further added at least one connection alkaline earth metal selected from the group comprising Mg, Ca, and at least one compound of rare earth metal selected from the group including Ce, La, Nd, Pr, and optional connection of copper, as well as compounds of iron using iron oxide. The catalyst additionally contains at least one oxide of the alkali earth metal General formula MeO, vybaveneho from the group Ce, La, Nd, Pr, at the following content, wt.%:

Cr2O3- 7,0 - 12,0

MnO2- 0,2 - 1,0

MeO - 0,1 - 0,8

Ln2O3- 0,05 - 1,0

Iron oxide - Rest

Additional distinctive features is that the preparation of the catalyst as the metal compounds selected from the group Mg, Ca, Ce, La, Nd, Pr, Cu, use at least one compound from the series: oxide, hydroxide, carbonate, chromate, bichromate and use iron oxide containing magnetite (Fe3O4and/or chromite iron - Fe[CrFe]O4in total an amount of 5 to 50% by weight of iron oxide. When mixed in the catalyst mass is further added a solution of chromate of urea - 2 CO(NH2)2H2CrO4or urea in the amount of 0.5 to 1.5% by weight of iron oxide and/or carbon-containing material in an amount of 1.0 to 4.0 wt.% by weight of iron oxide. The carbonaceous component activated carbon is used stamps BAU and/or colloidal graphite. The catalyst additionally contains from 1.0 to 3.0 wt.% copper oxide CuO.

The proposed set of features for a method of producing catalyst for steam reforming of carbon monoxide corresponds to the condition of paternopoli "From the e was not known, the proposed set of features leads to the solution of the aforementioned problem, namely that the introduction of an aqueous solution of chromic acid, at least one connection alkaline earth metal selected from the group comprising Mg, Ca, and at least one compound of rare earth metal selected from the group including Ce, La, Nd, Pr, Mn, and optionally a compound of copper, by mixing this solution with iron oxide, provides improved stability of the catalyst for steam reforming of carbon monoxide while maintaining its high activity. Studies show that promotion of catalyst for steam reforming of carbon monoxide ions of alkaline earth metals (Mg, Ca), transition metals (Mn, Cr, Cu), lanthanides (Ce, La, Nd, Pr) allows to stabilize the ratio of Fe2+/Fe3+at the optimal level.

Example 1.

In an aqueous solution of chromic acid (H2CrO4dissolve the carbonate of manganese, magnesium oxide, neodymium carbonate and urea.

The catalyst is prepared by mixing 350 g of iron oxide with 85 cm3prepared aqueous solution of chromic acid containing, in terms of oxides: 40 g CrO3, 1.0 g of MnO2, 1.2 g of MgO, about 0,45 graphite and stirring is continued for another 1 h These granules are dried at temperatures up to 100oC and calcined at a temperature of 450oC for 3 h

Get the catalyst containing Cr2O3- 7.8 wt.%, MnO2- 0.26 wt.%, MgO - 0.3 wt.%, Nd2O3and 0.12 wt.%, iron oxide rest.

The activity of the catalyst, expressed by the rate constant of the reaction is first order with respect to carbon monoxide (cm3CO/HS), is determined by THE 113-03-317 in the reaction of steam reforming gas containing 50 vol.% CO and 50% vol. N2at atmospheric pressure, flow rate 6000 h-1, molar ratio water/gas to 3.0 at a temperature of 350oC.

To determine the stability of spend processing catalyst providerone mixture with the molar ratio of H2O/H2= 2.26 and, at atmospheric pressure, the flow rate of hydrogen 8000 h-1at a temperature of 500oC for 4 h, followed by determination of the activity as described above. The stability is expressed by the dimensionless value as the ratio of activity after providerone heat treatment to the activity of the original catalyst.

The results of determining the activity and stability obtained in examples 1-8 catalysts, as well as the content promotionat as in example 1, but the solution chromic acid contains in terms of oxides: 41 g CrO3, 1.0 g of MnO2, 1.2 g CaO, 0.4 g of MgO, 1.1 g Ln2O3and 0.2 g CeO2. When preparing the solution using the carbonate of manganese, chromium, calcium and magnesium hydroxides of lanthanum and cerium. To the catalyst mass after stirring 1.5 h add 6.0 g of ground activated charcoal brand BAU.

Get the catalyst containing Cr2O3to 8.1 wt.%, MnO2- 0.26 wt.%, CaO - 0.3 wt.%, MgO is 0.1 wt.%, La2O3- to 0.29 wt.%, Ce2O3to 0.05 wt.%, iron oxide - rest.

Example 3.

The catalyst is prepared as in example 1, but the iron oxide contains 18% chromite iron, a solution of chromic acid contains in terms of oxides: 41 g CrO3, 1.0 g of MnO2, 1.2 g of MgO, 1.0 g Pr2O3and 3.7 g of urea (1,1% by weight of iron oxide). When preparing the solution using manganese carbonate, magnesium hydroxide and praseodymium. To the catalyst mass after stirring for 1.5 h add 6.0 g of colloidal graphite and 6.0 g of ground activated charcoal brand BAU.

Get the catalyst containing Cr2O3to 8.1 wt.%, MnO2- 0.26 wt.%, MgO - 0.3 wt.%, Pr2O3- 0.26 wt.%, iron oxide rest.

3, 2 g of MnO2, 0.5 g of CaO, 0.5 g MgO, 2.0 g Ln2O3and 10 g of CuO. When preparing the solution using the carbonate of manganese, oxides of calcium and magnesium, lanthanum carbonate and copper bichromate. To the catalyst mass after stirring for 1.5 h add 5 g of urea.

Get the catalyst containing Cr2O3is 8.5 wt.%, MnO2- 0.50 wt.%, CaO - 0.1 wt.%, MgO is 0.1 wt.%, La2O3to 0.5 wt.%, CuO - 2.5 wt.%, iron oxide rest.

Example 5.

The catalyst is prepared as in example 1, but the iron oxide contains 15% magnetite and 5% chromite iron, a solution of chromic acid contains in terms of oxides: 42 g CrO31 g MnO2, 0.5 g CaO, 40.6 g La2O3and 10 g of CuO. When preparing the solution using manganese carbonate, calcium oxide, lanthanum carbonate and carbonate of copper. To the catalyst mass after stirring for 1.5 h, add 1.8 g urea.

Get catalyst containing: Cr2O3is 8.5 wt.%, MnO2- 0,26, CaO - 0.1 wt.%, La2O3to 0.15 wt.%, CuO - 2.5 wt.%, iron oxide rest.

Example 6 (with a maximum content of components).

The catalyst is prepared as in example 1, but the solution chromic acid contains in terms of oxides: 36 g is xidi calcium and cerium and copper carbonate.

Get the catalyst containing Cr2O3- 7.0 wt.%, MnO2to 0.2, CaO - 0.8 wt.%, CeO2to 1.0 wt.%, CuO - 1.0 wt.%, iron oxide - rest.

Example 7 (nearest equivalent).

The catalyst is prepared as in example 1, but the solution chromic acid contains in terms of oxides: 38 g CrO3, 6.5 g of MnO2< / BR>
Get the catalyst containing Cr2O3- 7.5 wt.%, MnO2- 1.7 wt.%.

From the comparison of examples 1-5 with example 6 (the closest analogue) shows that obtained in examples 1-5 catalyst has a high stability, in comparison with the closest analogue, while maintaining its high activity.

Example 8 (with the beyond the content of the components).

The catalyst is prepared as in example 1, but the solution chromic acid contains in terms of oxides: 36 g CrO3, 1.0 g of MnO2, 3.5 g CaO, 4.5 g La2O3. When preparing the solution using manganese carbonate, calcium oxide, lanthanum carbonate.

Get the catalyst containing Cr2ABOUT3- 7.4 wt.%, MnO2is 0.27, CaO - of 0.82 wt.%, La2O31.2 wt.%, iron oxide rest.

As can be seen from the test results, when going beyond the content of oxides deliciosamente remains high.

Industrial applicability

The present invention can be implemented using known means and used in the chemical and petrochemical industry for the production of catalysts for steam reforming of carbon monoxide.

1. The preparation method of catalyst for steam reforming of carbon monoxide, comprising a mixture of compounds of iron with a water solution of chromic acid and a salt of manganese, the subsequent formation of granules, drying and calcination, characterized in that an aqueous solution of chromic acid is further added at least one connection alkaline earth metal selected from the group comprising Mg, Ca, and at least one compound of rare earth metal selected from the group including Ce, La, Nd, Pr, and optionally, a compound of copper, as compounds of iron using iron oxide.

2. The method of preparation of the catalyst under item 1, characterized in that compounds of metals selected from the group Mg, Ca, Ce, La, Nd, Pr, Cu, use at least one compound from the series: oxide, hydroxide, carbonate, chromate, bichromate.

3. The method of preparation of the catalyst under item 1, characterized in that the use of iron oxide containing dlese.

4. The method of preparation of the catalyst under item 1, characterized in that the catalyst mass by mixing further added a solution of chromate of urea 2CO(NH2)2H2CrO4or urea in the amount of 0.5 to 1.5% by weight of iron oxide and/or carbon-containing component in an amount of 1.0 to 4.0 wt.% by weight of iron oxide.

5. The method of preparation of the catalyst under item 1, characterized in that the carbonaceous component used activated charcoal brand BAU and/or colloidal graphite.

6. The catalyst for steam reforming of carbon monoxide containing the oxides of chromium and manganese, characterized in that it additionally contains at least one oxide of the alkali earth metal General formula MeO selected from the group Mg, CA, and at least one oxide of rare earth metal General formula Ln2O3selected from the group Ce, La, Nd, Pr, at the following content, wt.%:

Cr2O3- 7,0 - 12,0

MnO2- 0,2 - 1,0

MeO - 0,1 - 0,8

Ln2O3- 0,05 - 1,0

Iron oxide - Rest

7. The catalyst p. 6, characterized in that it additionally contains from 1.0 to 3.0 wt.% copper oxide CuO.

 

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