Process for producing a reforming catalyst and the reforming of methane

Patent metadata

Field	Value
Publication number	US-9259712-B2
Application number	US-201213671159-A
Country	US
Kind code	B2
Filing date	Nov 7, 2012
Priority date	Nov 8, 2011
Publication date	Feb 16, 2016
Grant date	Feb 16, 2016

Abstract

The present invention relates to a process for producing a catalyst for the reforming of hydrocarbons, preferably methane, in the presence of CO 2 , water and/or hydrogen. The production of the catalyst is based on contacting of a hydrotalcite-comprising starting material with a fusible metal salt. The compounds which have been brought into contact with one another are intimately mixed and treated thermally, resulting in the fusible metal salt forming a melt. After molding, the material is subjected to a high-temperature calcination step. The metal salt melt comprises at least one metal selected from the group consisting of K, La, Fe, Co, Ni, Cu and Ce, preferably Ni. The metal salt melt more preferably comprises nickel nitrate hexahydrate. In addition, the invention relates to the use of the catalyst of the invention for the reforming of hydrocarbons, preferably methane, in the presence of CO 2 , water and/or hydrogen at elevated pressures which are greater than 5 bar, preferably greater than 10 bar, particularly preferably greater than 20 bar. The catalyst according to the invention is distinguished from the prior art by particular, preferred physicochemical properties.

First claim

The invention claimed is:

1. A catalyst, comprising:
nickel-magnesium mixed oxide;
magnesium spinel; and
optionally aluminum oxide hydroxide,
wherein the nickel-magnesium mixed oxide has an average crystallite size of ≦100 nm,
the magnesium spinel has an average crystallite size of ≦100 nm,
a proportion of nickel in the catalyst is in the range of 6-30 mol %,
a proportion of magnesium in the catalyst is in the range of 8-38 mol %,
a proportion of aluminum in the catalyst is in the range of 50-70 mol % and
an intensity of the diffraction reflection of the catalyst at 43.09°2θ is less than or equal to an intensity of the diffraction reflection at 44.82°2θ.

2. The catalyst according to claim 1 ,
wherein a BET surface area of the catalyst is in the range of from 10 to 200 m 2 /g.

3. The catalyst according to claim 1 ,
wherein the catalyst has a bimodal pore structure with mesopores and macropores.

4. The catalyst according to claim 3 ,
wherein a diameter of the mesopores is in the range 4-40 nm and a diameter of the macropores is in the range 30-120 nm, wherein diameter is determined according to DIN 66133.

5. The catalyst according to claim 4 ,
wherein the catalyst has a trimodal pore structure which additionally has macropores whose diameter is in the range from 100to 2000 nm, wherein diameter is determined according to DIN 66133.

6. The catalyst according to claim 1 ,
wherein an average pore diameter of the catalyst is >15 nm.

7. The catalyst according to claim 1 ,
wherein a characteristic tamped density of the catalyst is <1500 g/l, and/or
starting materials for producing the catalyst comprise a nickel-comprising salt and a hydrotalcite-comprising compound.

8. The catalyst according to claim 7 ,
wherein the characteristic tamped density of the catalyst is <1350 g/l and/or
the starting materials for producing the catalyst comprise nickel nitrate and hydrotalcite.

9. The catalyst according to claim 1 ,
wherein a BET surface area of the catalyst is in the range of from 15to 150 m 2 /g.

10. A catalyst according to claim 1 , obtained by a process comprising:
(i) contacting of a fusible metal salt comprising a nickel salt and/or cobalt salt, and a finely divided hydrotalcite-comprising starting material,
(ii) intimate mixing of the fusible metal salt and the finely divided hydrotalcite-comprising starting material, thereby forming a mixture,
(iii) thermal treatment of the mixture and heating of the mixture under conditions under which the fusible metal salt is present in the form of a melt,
(iv) low-temperature calcination of the mixture at a temperature of <500° C.,
(v) molding or shaping, and
(vi) high-temperature calcination of the mixture at a temperature of >500° C., Where an intensity of diffraction reflection at 43.08°θ is less than or equal to an intensity of diffraction reflection at 44.82°θ, and the BET surface of the catalyst is in the range of from 10to 200 m 2 /g.

11. A process for producing a catalyst, comprising:
(i) contacting of a fusible metal salt and a finely divided hydrotalcite-comprising starting material,
(ii) intimate mixing of the fusible metal salt and the finely divided hydrotalcite-comprising starting material, thereby forming a mixture,
(iii) thermal treatment of the mixture and heating of the mixture under conditions under which the fusible metal salt is present in the form of a metal salt melt,
(iv) low-temperature calcination of the mixture at a temperature of <500° C.,
(v) molding or shaping, and
(vi) high-temperature calcination of the mixture at a temperature of >500° C to form the catalyst according to claim 1 .

12. The process according to claim 11 ,
wherein the fusible metal salt comprises a nickel salt and/or cobalt salt.

13. The process according to claim 11 ,
wherein the intimate mixing (ii) is carried out simultaneously with the thermal treatment (iii).

14. The process according to claim 11 ,
wherein the thermal treatment (iii) and the low-temperature calcination (iv) are carried out in one coherent process.

15. The process according to claim 11 ,
wherein the fusible metal salt is present in the form of the metal melt when carrying out the contacting (i).

16. A process, comprising:
reforming a hydrocarbon-comprising compound and CO 2 with the catalyst according to claim 1 or a catalyst produced by the process according to claim 11
wherein the reforming is carried out in a temperature range of from 500° C. to 1100° C.

17. The process according to claim 16 ,
wherein the process is carried out at a pressure in the range of from 2 to 70 bar.

18. The process claim 16 , the process, comprising:
reforming a hydrocarbon compound and CO 2 with a feed fluid,
wherein the feed fluid has a CH 4 content and a CO 2 content which are each in the range of from 20 to 45% by volume, and water vapor in the range of from 0 to 40% by volume.

19. The process according to claim 16 ,
wherein a molar CO 2 /CH 4 ratio is in the range of from 0 to 1.5, and/or an H 2 O/CH 4 ratio is <2.0.

20. The process according to claim 16 ,
wherein a synthesis gas having an H 2 /CO ratio of <2 is produced.

Assignees

• Basf Se

Inventors

• Schwab Ekkehard
• Milanov Andrian
• Schunk Stephan
• Roussiere Thomas
• Wasserschaff Guido
• Strasser Andreas

Classifications

• B01J35/77

  Compounds characterised by their crystallite size · CPC title

• B01J35/45

  Nanoparticles · CPC title

• B01J35/70

  characterised by their crystalline properties, e.g. semi-crystalline (catalysts comprising carbon B01J21/18; molecular sieves B01J29/00) · CPC title

• B01J2235/15

  X-ray diffraction · CPC title

• B01J35/393

  Metal or metal oxide crystallite size · CPC title