Process and catalyst for the hydrotreatment of a heavy hydrocarbon feedstock
View Patent ↗A method of hydrotreating a heavy hydrocarbon feedstock using a hydrotreating catalyst having specific properties that make it effective in removing nitrogen and sulfur from the feedstock is disclosed. The catalyst is composed of an alumina support particle having a specific pore diameter distribution which is achieved in part, by the use of pseudo-boehmite as the alumina source and specific calcining temperatures. The hydrotreatment catalyst also comprises a Group 6 metal component (e.g., molybdenum) and a Group 10 metal component (e.g., nickel), and optionally, a phosphorus metal component, which are supported by the alumina support particle.
1. A method of making a catalyst composition useful in the hydrotreatment of a heavy hydrocarbon feedstock, said method comprising the steps of:
providing an alumina support particle comprising gamma alumina, said support having a median pore diameter in the range of from 100 Å to 120 Å, a surface area in the range of from 280 m 2 /g to 240 m 2 /g, greater than 70% of the total pore diameter distribution between 90 Å and 130 Å, less than 5 percent of the total pore size distribution is greater than 350 Å, and a total mercury pore volume of less than 0.85 cc/g by mixing a composition comprising high purity pseudo-boehmite powder and water at a weight ratio of pseudo-boehmite-to-water in the range of from 0.1:1 to 10:1, and an acid to form an extrudable paste and extruding said paste to thereby provide a shaped support particle; and heat treating said shaped support particle at a temperature between 676° C. and 788° C.;
contacting said alumina support particle with a catalytic solution, said solution comprising a Group 6 metal component and a Group 10 metal component to thereby provide an impregnated alumina support; and
heat treating said impregnated alumina support to provide said catalyst composition having a median pore diameter in the range of from 120 Å to 150 Å, and wherein said catalyst composition has a total mercury pore volume between 0.3 and 0.6 cc/g.
2. A method according to claims 1 wherein said catalyst composition exhibits an increase in relative volumetric activity of at least 10% with respect to the kinetic rate constant for a reduction in nitrogen content to 10 ppm as compared to a catalyst comprising and alumina support particle having a surface area of at least 300 m 2 /g.
3. A method according to claims 2 wherein the total mercury pore volume of said alumina support particle is less than 0.8 cc/g.
4. A method according to claim 3 , wherein said catalyst composition contains an amount of Group 6 metal in the range of from about 3 to about 30 weight percent, calculated as a trioxide and based on the weight of said catalyst composition.
5. A method according to claim 4 , wherein said catalyst composition contains an amount of Group 10 metal in the range of from about 0.01 to about 10 weight percent, calculated as a monoxide and based on the weight of said catalyst composition.
6. A method according to claim 5 , wherein said catalyst composition further contains a phosphorous component at a concentration in the range of from about 0.01 to about 5 weight percent calculated as phosphorous.
7. A method according to claim 6 , wherein said catalyst composition has a surface area between 120 and 200 m 2 /g.
8. A method of making a catalyst composition useful in the hydrotreatment of a heavy hydrocarbon feedstock, said method comprising the steps of:
forming a shaped support particle comprising high purity pseudo-boehmite powder;
heat treating said shaped support particle at a temperature between 676° C. and 788° C. to achieve a heat treated support particle having a median pore diameter in the range of from 100 Å to 120 Å, a surface area in the range of from 280 m 2 /g to 240 m 2 /g, greater than 70% of the total pore diameter distribution between 90 Å and 130 Å, less than 5 percent of the total pore size distribution is greater than 350 Å, and a total mercury pore volume less than 0.85 cc/g; and
contacting said heat treated support particle with a catalytic solution, said solution comprising a Group 6 metal component and a Group 10 metal component to thereby provide an impregnated alumina support having a median pore diameter in the range of from 120 Å to 150 Å and a total mercury pore volume of less than 0.85 cc/g; and
heat treating said impregnated alumina support to provide said catalyst composition having a median pore diameter in the range of from 120 Å to 150 Å, and wherein said catalyst composition has a total mercury pore volume between 0.3 and 0.6 cc/g.
9. A method according to claims 8 wherein said catalyst composition exhibits an increase in relative volumetric activity of at least 10% with respect to the kinetic rate constant for a reduction in nitrogen content to 10 ppm as compared to a catalyst comprising and alumina support particle having a surface area of at least 300 m 2 /g.
10. A method according to claim 9 wherein the total mercury pore volume of the support particle is less than 0.8 cc/g.
11. A catalyst composition useful in the hydrotreatment of a heavy hydrocarbon feedstock, wherein said catalyst composition comprises:
an alumina support particle comprising gamma-alumina, wherein said alumina support particle has a median pore diameter in the range of from 100 Å to 120 Å, a surface area in the range of from 280 m 2 /g to 240 m 2 /g, greater than 70% of the total pore diameter distribution between 90 Å and 130 Å, less than 5 percent of the total pore size distribution is greater than 350 Å, and a total mercury pore volume less than 0.85 cc/g; and
wherein said alumina support particle is impregnated with a Group 6 metal component and a Group 10 metal component to provide an impregnated alumina support particle having a median pore diameter in the range of from 120 Å to 150 Å; and wherein said catalyst composition exhibits an increase in relative volumetric activity of at least 10% with respect to the kinetic rate constant for a reduction in nitrogen content to 10 ppm as compared to a catalyst comprising an alumina support particle having a surface area of at least 300 m 2 /g , and wherein said catalyst composition has a total mercury pore volume between 0.3 and 0.6 cc/g.
12. A catalyst composition according to claim 11 wherein the total mercury pore volume of said support particle is less than 0.8 cc/g.