Resumen
[0001] The method consists of placing in contact methanol, oxygen and optionally water with a catalyst consisting of copper (II) oxide, zinc (II) oxide, aluminium (III) oxide and copper (II) and aluminium (III) spinel, with the following molar percentages of the metals with respect to the total: Cu (15-75%). Zn (5-60%) and Al (3-50%). The catalyst is obtained by adding urea to a solution of water-soluble salts of copper (II), zinc (II) and aluminium (III) by co-precipitation of the components.
Reivindicaciones
1. A catalyst for conversion of methanol into hydrogen, comprising copper (II) oxide, zinc (II) oxide, aluminium (III) oxide and copper (II) and aluminium (III) spinel in the following molar percentages: Copper 15-75 Zinc 5-60 Aluminium 3-50 2. Catalyst as claimed in claim 1, with a composition chosen among the following: A 21.9 37.1 40.9 B 54.3 18.7 26.6 C 50.0 43.9 5.7 D 61.3 9.0 29.9 E 49.8 14.6 35.4 F 48.7 17.3 33.9 G 25.8 49.1 24.9 H 70.2 21.6 8.2 [* Molar percentages of the metals in the catalyst] 3. A method for converting methanol into hydrogen according to either of claims 1 or 2, which comprises: a) placing in contact urea and an aqueous solution of water soluble salts of copper (II), zinc (II) and aluminium (III), and heating to a temperature above 60°C; b) separating the precipitate resulting from stage a) and washing it until the wash water has a pH of approximately 6; c)drying the washed precipitate resulting from stage b); and d) calcinating the dry precipitate of stage c). 4. Method as claimed in claim 3, in which said water-soluble salts of copper, zinc and aluminium are copper (II) chloride, zinc (II) chloride and aluminium (III) chloride. 5. Method as claimed in claim 3, in which the amount of urea added in stage a) is such that the molar ratio of urea/metals is at least 1. 6. Method as claimed in claim 5, in which the amount of urea added in stage a) is such that the molar ratio of urea/metals is 3. 7. Method as claimed in claim 3 in which the mixture of urea and the water-soluble salts of copper, zinc and aluminium in stage a) is heated to a temperature of 90°C. 8. Method as claimed in claim 3, which in addition includes allowing the precipitate formed in stage a) to age before it is separated, with this precipitate maintained stirred at a temperature between 60°C and 100°C for at least 12 hours. 9. Method as claimed in claim 8, in which the ageing of the precipitate formed in stage a) is performed by maintaining said precipitate stirred at the heating temperature of stage a) for 24 hours. 10. Method as claimed in claim 3, in which drying of the washed precipitate resulting from stage b) is performed at a temperature between 50°C and 130°C. 11. Method as claimed in claim 3, in which the dry precipitate resulting from stage c) is calcined at a temperature between 300°C and 450°C for a time between 3 and 5 hours in the presence of air. 12. A method for production of hydrogen by partial oxidation of methanol which involves placing methanol, oxygen and optionally water in contact with a catalyst as claimed in any of claims 1 or 2, or obtained by the methods of any of claims 3 to 11. 13. Method as claimed in claim 12, in which said catalyst is used in the form of a powder with particle size between 0.42 and 0.59 mm. 14. Method as claimed in claim 12, in which said catalyst is activated by feeding a reducing gas and heating to a temperature between 250°C and 500°C for a time period between 1 and 5 hours. 15. Method as claimed in claim 14, in which said reducing gas is a gas which contains hydrogen. 16. Method as claimed in claim 14, in which said catalyst is activated by heating it to 450°C following a thermal cycle which involves raising the temperature to 450°C at a rate of 3°C/minute, maintaining this temperature during 2 hours and lowering the temperature to 110°C. 17. Method as claimed in claim 12, in which the reactants are methanol and oxygen. 18. Method as claimed in claim 12, in which the reactants are methanol, oxygen and water in a molar ratio of methanol:water:oxygen between 1:1.1:0.3 and 1:1.1:0.5. 19. Method as claimed in claim 12, in which the oxygen is added as such or as air, or as an oxygen-rich mixture. 20. Method as claimed in claim 12, in which conversion of methanol into hydrogen takes place at a temperature between 200°C and 400°C. 21. Method as claimed in claim 12, in which the conversion of methanol into hydrogen takes place at atmospheric pressure. 22. Method as claimed in claim 12 in which the conversion of methanol into hydrogen takes place in a reactor which is provided with means for measuring the temperature and with a heating element. 23. Method as claimed in claim 22, in which said reactor is a tubular reactor where the catalyst particles are supported between two beds of quartz wool, forming a catalytic bed, is provided with a thermocouple for measuring the temperature and uses an electric oven as the reactor heating element.
