Mass for capturing mercaptans which is prepared using molten salts
The invention describes a mass for scavenging mercaptans which is particularly suitable for the treatment of olefinic gasoline cuts containing sulfur such as gasolines resulting from catalytic cracking. The scavenging mass comprises an active phase based on group VIII, IB or IIB metal particles which is prepared by a step of bringing a porous support into contact with a metal salt of said group VIII, IB or IIB metal and a step heating the resulting mixture to a temperature above the melting point of said metal salt. The invention also relates to a process for using said scavenging mass for the adsorption of mercaptans.
1. A process for preparing a scavenging mass comprising an active phase based on at least one group VIII, IB or IIB metal, at least partially in reduced form, and a porous support chosen from aluminas, silica, silica-aluminas, or titanium or magnesium oxides alone or as a mixture with alumina or silica-alumina, said scavenging mass having been obtained by at least the following steps:
a) bringing into contact said porous oxide support with at least one metal salt comprising at least one group VIII, IB or IIB metal for which the melting point of said metal salt is between 2° and 150° C. to form a solid mixture, the mass ratio between said metal salt and said porous oxide support being between 0.1 and 2.5;
a′) bringing the porous support into contact with an organic compound comprising oxygen and/or nitrogen;
b) heating the solid mixture obtained on conclusion of step a) with stirring to a temperature between the melting point of said metal salt and 200° C. to obtain a scavenging mass precursor;
c) optionally drying the solid obtained on conclusion of step b) at a temperature below 200° C. to obtain a dried scavenging mass precursor;
d) optionally calcining the solid obtained on conclusion of step b) or c) at a temperature greater than 200° C. and less than or equal to 1100° C. under an inert atmosphere or under an atmosphere containing oxygen to obtain a calcined scavenging mass precursor;
e) reducing the solid obtained on conclusion of step b), c) or d) to obtain said scavenging mass.
2. The process as claimed in claim 1 , in which steps a) and a′) are performed simultaneously, said organic compound being in solid form to form a solid mixture.
3. The process as claimed in claim 1 , in which step a′) is performed after the sequence of steps a) and b).
4. The process as claimed in claim 1 , in which the mole ratio of said organic compound relative to the group VIII, IB or IIB element is between 0.01 and 5.0 mol/mol.
5. A process for scavenging mercaptans contained in a partially desulfurized hydrocarbon fraction containing sulfur obtained from a catalytic hydrodesulfurization step by the scavenging mass as claimed in claim 1 , comprising bringing into contact said scavenging mass with a feedstock at a temperature of 40 to 250° C., and a pressure of 0.2 to 5 MPa.
6. The scavenging process as claimed in claim 5 , in which the feedstock is a partially desulfurized catalytic cracking gasoline with a boiling point below 350° C. and containing between 5% and 60% by weight of olefins and less than 100 ppm by weight of sulfur.
7. The process as claimed in claim 1 , in which the organic compound comprising oxygen and/or nitrogen is chosen from oxalic acid, malonic acid, glutaric acid, glycolic acid, lactic acid, succinic acid, tartronic acid, citric acid, acid tartaric, pyruvic acid and γ-ketovaleric acid.
8. A process for scavenging mercaptans contained in a partially desulfurized hydrocarbon fraction containing sulfur obtained from a catalytic hydrodesulfurization step by a scavenging mass, comprising bringing into contact said scavenging mass with a feedstock at a temperature of 40 to 250° C., and a pressure of 0.2 to 5 MPa,
wherein said scavenging mass comprises an active phase based on at least one group VIII, IB or IIB metal, at least partially in reduced form, and a porous support chosen from aluminas, silica, silica-aluminas, or titanium or magnesium oxides alone or as a mixture with alumina or silica-alumina, said scavenging mass having been obtained by at least the following steps:
a) bringing into contact said porous oxide support with at least one metal salt comprising at least one group VIII, IB or IIB metal for which the melting point of said metal salt is between 2° and 150° C. to form a solid mixture, the mass ratio between said metal salt and said porous oxide support being between 0.1 and 2.5;
b) heating the solid mixture obtained on conclusion of step a) with stirring to a temperature between the melting point of said metal salt and 200° C. to obtain a scavenging mass precursor;
c) optionally drying the solid obtained on conclusion of step b) at a temperature below 200° C. to obtain a dried scavenging mass precursor;
d) optionally calcining the solid obtained on conclusion of step b) or c) at a temperature greater than 200° C. and less than or equal to 1100° C. under an inert atmosphere or under an atmosphere containing oxygen to obtain a calcined scavenging mass precursor;
e) reducing the solid obtained on conclusion of step b), c) or d) to obtain said scavenging mass.
9. The scavenging process as claimed in claim 8 , in which the feedstock is a partially desulfurized catalytic cracking gasoline with a boiling point below 350° C. and containing between 5% and 60% by weight of olefins and less than 100 ppm by weight of sulfur.
10. The scavenging process as claimed in claim 8 , wherein, in said scavenging mass, said group VIII, IB or IIB metal is nickel, copper or zinc.
11. The scavenging process as claimed in claim 8 , wherein, in said scavenging mass, the content of group VIII, IB or IIB metal, expressed as group VIII, IB or IIB metal element, is between 5% and 65% by weight relative to the total mass of the scavenging mass.
12. The scavenging process as claimed in claim 8 , wherein, in said scavenging mass, the content of group VIII, IB or IIB metal, expressed as group VIII, IB or IIB metal element, is between 12% and 34% by weight relative to the total mass of the scavenging mass.
13. The scavenging process as claimed in claim 8 , wherein the total pore volume of said scavenging mass is greater than or equal to 0.3 mL/g and the BET specific surface area of said scavenging mass is at least 40 m 2 /g.
14. A process for scavenging mercaptans contained in a partially desulfurized hydrocarbon fraction containing sulfur obtained from a catalytic hydrodesulfurization step by a scavenging mass, comprising bringing into contact said scavenging mass with a feedstock at a temperature of 100° C. to 250° C., and a pressure of 0.2 to 5 MPa, wherein said scavenging mass comprises an active phase based on at least one group VIII, IB or IIB metal, at least partially in reduced form, and a porous support chosen from aluminas, silica, silica-aluminas, or titanium or magnesium oxides alone or as a mixture with alumina or silica-alumina, said scavenging mass having been obtained by at least the following steps:
a) bringing into contact said porous oxide support with at least one metal salt comprising at least one group VIII, IB or IIB metal for which the melting point of said metal salt is between 2° and 150° C. to form a solid mixture, the mass ratio between said metal salt and said porous oxide support being between 0.1 and 2.5;
b) heating the solid mixture obtained on conclusion of step a) with stirring to a temperature between the melting point of said metal salt and 200° C. to obtain a scavenging mass precursor;
c) optionally drying the solid obtained on conclusion of step b) at a temperature below 200° C. to obtain a dried scavenging mass precursor;
d) optionally calcining the solid obtained on conclusion of step b) or c) at a temperature greater than 200° C. and less than or equal to 1100° C. under an inert atmosphere or under an atmosphere containing oxygen to obtain a calcined scavenging mass precursor;
e) reducing the solid obtained on conclusion of step b), c) or d) to obtain said scavenging mass.
15. The scavenging process as claimed in claim 14 , in which the feedstock is a partially desulfurized catalytic cracking gasoline with a boiling point below 350° C. and containing between 5% and 60% by weight of olefins and less than 100 ppm by weight of sulfur.