Method of making hydroprocessing catalyst
A chelated hydroprocessing catalyst exhibiting low moisture is obtained by hearing an impregnated, calcined carrier to a temperature higher than 200° C. and less than a temperature and for a period of time that would cause substantial decomposition of the chelating agent.
1. A method for preparing a hydroprocessing catalyst comprising:
(I) providing at least the following components:
(A) at least one calcined foraminous carrier having a water pore volume;
(B) catalytically active metals useful in hydroprocessing hydrocarbons, said metals in the form of at least one component providing at least one metal from Group VIB of the periodic table and at least one component providing at least one metal from Group VIII of the periodic table;
(C) at least one chelate;
(D) water in a quantity sufficient to form a solution or dispersion comprising said catalytically active metals and said at least one chelate; and
(E) optionally, at least one phosphorus-containing acidic component;
(II) contacting said components (I)(A) with said solution or dispersion comprising (I)(B), (I)(C), (I)(D) and optionally (I)(E) for a time and at a temperature sufficient to form a mixture and to impregnate said carrier with a suitable amount of said components (I)(B) and (I)(C) and optionally (I)(E);
(III) to the extent that the volume of said solution or dispersion equals or exceeds the water pore volume of said carrier separating said impregnated carrier from said excess solution or dispersion; and
(IV) drying said impregnated carrier by heating to a temperature of 400° F. to 420° F. (204.4° C. to 215.5° C.) for a period of time less than 1 hour so that no substantial decomposition of said at least one chelate is caused, thereby forming said hydroprocessing catalyst.
2. The method of claim 1 , wherein said at least one metal from Group VIB is selected from the group consisting of molybdenum and tungsten.
3. The method of claim 1 , wherein said at least one metal from Group VIII is selected from the group consisting of cobalt and nickel.
4. The method of claim 1 wherein said chelate is selected from the group consisting of hydroxycarboxylic acids, ethylene glycol, glycerol, ethanolamine, polyethylene glycol, hydroquinone, ethylenediamine, ethylenediamine-tetraacetic acid, cysteine, alanine, methionine, gluconic acid, pyridine-2,3-dicarboxylic acid, thiophene-2- carboxylic acid, mercaptosuccinic acid, nicotinic acid, lactose, and acetone-1,3-dicarboxylic acid.
5. The method of claim 4 , wherein said at least one hydroxycarboxylic acid is selected from the group consisting of glycolic acid, hydroxypropionic acid, hydroxybutyric acid, hydroxyhexanoic acid, tartaric acid, malic acid, glyceric acid, citric acid and gluconic acid.
6. The method of claim 5 , wherein said hydroxycarboxylic acid is citric acid.
7. The method of claim 1 wherein said foraminous carrier is at least one member selected from the group consisting of silica, silica-gel, silica-alumina, alumina, titania, titania-alumina, zirconia-alumina, zirconia, boria, terrana, kaolin, magnesium silicate, magnesium carbonate, magnesium oxide, activated carbon, aluminum oxide, precipitated aluminum oxide, activated alumina, bauxite, kieselguhr, pumice, natural clays, synthetic clays, cationic clays or anionic clays, and mixtures thereof.
8. The method of claim 1 wherein the molar ratio of said Group VIII metal to Group VIB metal is about 0.05 to about 0.75, and wherein said Group VIII metal component is provided by a substantially water insoluble component.
9. The method of claim 1 wherein said at least one phosphorus-containing acidic component is substantially water soluble and is present in an amount sufficient to provide an elemental phosphorus to Group VIB metal molar ratio of about 0.01 to about 0.80.
10. The method of claim 1 wherein said heating is carried out for a time and temperature sufficient to provide a catalyst exhibiting a loss in weight on ignition (LOI) of less than about 20 wt %.
11. The hydroprocessing catalyst prepared by the method of claim 10 .
12. The method of claim 1 wherein said heating is carried out for a time and temperature sufficient to provide a catalyst exhibiting a moisture content of about 3 wt % to about 6 wt %.
13. The hydroprocessing catalyst prepared by the method of claim 12 .
14. The method of claim 1 wherein said heating is carried out for a time and temperature sufficient to provide a catalyst exhibiting a reduction in moisture content, compared to the wet catalyst following preparation of greater than 90% and wherein the catalyst is not calcined following heating.
15. The hydroprocessing catalyst prepared by the method of claim 14 .
16. The method of claim 1 wherein the amount of hydroxycarboxylic acid on the impregnated foraminous carrier prior to heating exceeds the amount desired in the catalyst after heating by about 1 wt % to about 10 wt %.
17. The method of claim 1 , wherein at least one phosphorus-containing acidic component is phosphoric acid or orthophosphoric acid.
18. The hydroprocessing catalyst prepared by the method of claim 1 .
19. A hydroprocessing catalyst formed from a mixture comprising:
(A) at least one calcined foraminous carrier;
(B) catalytically active metals useful in hydroprocessing hydrocarbons, said metals in the form of at least one component providing at least one metal from Group VIB of the periodic table and at least one component providing at least one metal from Group VIII of the periodic table;
(C) at least one organic chelate compound comprising about 0.05 to about 5 times the molar amount of said catalytically active metals;
(D) water in a quantity sufficient to form a solution or dispersion comprising said catalytically active metals and said at least one organic chelate compound; and
(E) optionally, at least one phosphorus-containing acidic component; and
wherein said catalyst exhibits a moisture content of about 3 wt % to about 6 wt %.
20. The catalyst of claim 19 wherein said organic chelate compound is at least one hydroxycarboxylic acid.
21. The catalyst of claim 20 wherein said at least one hydroxycarboxylic acid is citric acid.
22. A catalyst useful in hydroprocessing a petroleum feed, said catalyst comprising at least one catalytically active metal from Group VIB of the periodic table, at least one catalytically active metal from Group VIII of the periodic table, phosphorus and a chelating agent, wherein: (A) said metals, phosphorus and chelating agent are carried on a calcined foraminous carrier; (B) said catalyst is not calcined following impregnation with said metals and chelating agent; and
(C) the moisture content of said catalyst at the start of said hydroprocessing about 3 wt % to about 6 wt %.
23. A catalyst useful in hydrodesulfurization and hydrodenitrification of hydrocarbons, said catalyst comprising at least one catalytically active metal from Group VIB of the periodic table, at least one catalytically active metal from Group VIII of the periodic table, phosphorus and a chelating agent, wherein: (A) said metals, phosphorus and chelating agent are carried on a calcined foraminous carrier; (B) said catalyst is not calcined following impregnation with said metals and chelating agent; and (C) the moisture content of said catalyst at the start of said hydrodesulfurization and hydrodenitrification is about 3 wt % to about 6 wt %.