Catalysts for demetallization treatment of hydrocarbons supported on sepiolite

Abstract

This invention relates to a catalyst for hydrotreatment of hydrocarbons comprising one or more of metals selected from the group consisting of transition metals and metals of group IIb of the periodic table supported on sepiolite. More particularly it relates to a catalyst effective in the selective demetallization treatment of hydrocarbons.

What is claimed is: .[.1. A hydrodemetallization catalyst comprising an effective amountof a catalyst metal component supported on a sepiolite carrier, the catalyst metal being selected from the group consisting of 
     
        Mo, W and V..]. .[.2.  The hydrodemetallization catalyst of claim 1 wherein the catalyst metal is Mo..]. .[.3. A hydrodemetallization catalyst comprising an effective amount of catalyst metal components supported on a sepiolite carrier, the catalyst metal being (1) at least one member selected from the group consisting of Co., Ni, Fe, Cu and lanthanides and   (2) at least one member selected from the group consisting of Mo, W and V..]. .[.4. The hydrodemetallization catalyst of claim 3 wherein the catalyst metal (1) comprises at least 0.1 wt. % based on the weight of the catalyst and the catalyst metal (2) comprises at least 0.5 wt. % based on the weight of the catalyst..]. .[.5. The hydrodemetallization catalyst of claim 3 wherein the catalyst metal (1) is Cu and the catalyst metal (2) is Mo..]. .[.6. The hydrodemetallization catalyst of claim 3 wherein the catalyst metal (1) is Co and the catalyst metal (2) is Mo..]. .[.7. The hydrodemetallization catalyst of claim 3 wherein the catalyst metal (1) is Co and Ni and the catalyst metal (2) is Mo..]. .[.8. The hydrodemetallization catalyst of claim 3 wherein the catalyst metal (1) is Ni and the catalyst metal (2) is Mo..]. .[.9. The hydrodemetallization catalyst of claim 3 wherein the catalyst metal (1) is Cu and the catalyst metal (2) is V..]. .[.10. The hydrodemetallization catalyst of claim 3 wherein the catalyst metal (1) is Co and the catalyst metal (2) is V..]. .[.11. The hydrodemetallization catalyst of claim 3 wherein the catalyst metal (1) is Co and Ni and the catalyst metal (2) is V..]. .[.12. The hydrodemetallization catalyst of claim 3 wherein the catalyst metal (1) is Ni and the catalyst metal (2) is V..]. .[.13. A sepiolite carrier prepared according to a process comprising:   (a) grinding sepiolite to a fine powder, 50% or more by weight of which has a particle size of 100-mesh or finer;   (b) adding water to the sepiolite obtained in (a) to adjust the water content thereof to about 20 to about 350% by weight;   (c) kneading the resulting mixture in (b), and subsequently   (d) air-drying or heat-treating the resulting mixture in (c) at a temperature lower than about 1000° C..]. .[.14. A hydrodemetallization catalyst comprising an effective amount of one or more catalyst metal components supported on sepiolite, the catalyst metal being selected from the group consisting of the metals of the IIb group and the transition metals of the Periodic Table, and wherein said catalyst is prepared according to a process comprising the steps of:   (a) grinding sepiolite to a fine powder, 50% or more by weight of which has a particle size of 100-mesh or finer;   (b) adding water to the ground sepiolite to adjust the water content thereof to about 20 to about 350% by weight;   (c) kneading the resulting mixture;   (d) air-drying or heat-treating the moist kneaded sepiolite at a temperature lower than about 1000° C.; and   (e) supporting one or more of said catalyst metal components on the sepiolite, the sequence of steps being (a), (b), (c), (d), and (e) or (e),   
     
     
        (a), (b), (c) and (d)..]. .[.15.  The hydrodemetallization catalyst of claim 14, wherein in step (e) the sepiolite is contacted with an aqueous acidic solution containing ions of one or more metals selected from the group consisting of the metals of Ib, IIb, IIIa and iron groups of the 
     
     
        Periodic Table..]. 16. The hydrodemetallization catalyst of claim .[.14.]. .Iadd.36.Iaddend., wherein the aqueous acidic solution has a pH of less than or equal to 7 and wherein said one or more metals are selected from the group consisting of Co, Ni, Fe, Cu and lanthanides. .[.17. The hydrodemetallization catalyst of claim 14, wherein the catalyst metal is selected from the group consisting of Cu and the metals of the Va, VIa and iron groups of the Periodic Table..]. .[.18. The hydrodemetallization catalyst of claim 17, wherein the catalyst metal is selected from Mo, W and V..]. .[.19. The hydrodemetallization catalyst of claim 14, wherein step (e) comprises a two-stage treatment consisting essentially of a first step of contacting the sepiolite with an acidic aqueous solution containing ions of one or more metals selected from the group consisting of the metals of the Ib, IIb, IIIa and iron groups of the Periodic Table, and a second step of contacting the resulting sepiolite with a basic aqueous solution containing ions of one or more metals selected from the group consisting of Cu and the metals of the Va, VIa and iron groups of 
     
     
        the Periodic Table..]. 20. The hydrodemetallization catalyst of claim .[.19.]. .Iadd.37.Iaddend., wherein the aqueous acidic solution has a pH of less than or equal to 7 and wherein said one or more metals are 
     
     
        selected from the group consisting of Co, Ni, Fe, Cu and lanthanides. 21. The hydrodemetallization catalyst of claim .[.19.]. .Iadd.37.Iaddend., wherein in said second step an aqueous ammonia and/or amine solution containing ions of one or more metals selected from Mo, W and V is 
     
     
        employed. 22. The hydrodemetallization catalyst of claim .[.19.]. .Iadd.37.Iaddend., wherein said acid aqueous solution has a pH of less than or equal to 7 and contains ions of one or more metals selected from Co, Ni, Fe, Cu and lanthanides; and wherein said basic aqueous solution is an aqueous ammonia and/or amine solution containing ions of one or more 
     
     
        metals selected from Mo, W and V. 23. The hydrodemetallization catalyst of claim .[.19.]. .Iadd.37.Iaddend., wherein the sepiolite treated in the first step is rinsed with a rinsing liquid before the treated sepiolite is 
     
     
        subjected to the second-step treatment. 24. The hydrodemetallization catalyst of claim 23, wherein the rinsing liquid is water, a basic aqueous solution, or an acidic aqueous solution. .[.25. The hydrodemetallization catalyst of claim 14, wherein the sequence of steps is (a), (b), (c), (d) and (e) and the sepiolite is molded after step (d) and before step (e) or after step (e)..]. .[.26. The hydrodemetallization catalyst of claim 25, wherein one or more additives are added to the sepiolite in step (b) or step (c) to enhance the molding properties and molded part strength; said additives being selected from the group consisting of aluminium hydroxide sol, alumina silica sol, silica sol, bauxite, kaoline, montmorillonite, allophane, bentonite, attapulgite, higher alcohols, esters of higher alcohols, ethers of higher alcohols, urea, starch, sucrose and organic 
     
     
        molding auxiliaries..]. .[.27.  The hydrodemetallization catalyst of claim 26, wherein before or in step (c) the sepiolite is treated with an aqueous solution containing one or more members selected from the group consisting of inorganic acids, organic acids, ammonium salts, salts of ammonium derivatives and magnesium salts, said aqueous solution being capable of removing impurities contained in the sepiolite..]. .[.28. The hydrodemetallization catalyst of claim 14, wherein the sepiolite is pretreated with an aqueous solution containing one or more members selected from the group consisting of inorganic acids, organic acids, ammonium salts, salts of ammonium derivatives and magnesium salts, said aqueous solution being capable of removing impurities contained in the 
     
     
        sepiolite..]. 29. The hydrodemetallization catalyst of claim 16, wherein the sepiolite is treated with an aqueous solution containing one or more members selected from the group consisting of inorganic acids, organic acids, ammonium salts, salts of ammonium derivatives and magnesium salts, said aqueous solution being capable of removing impurities contained in the sepiolite. .[.30. The hydrodemetallization catalyst of claim 17, wherein the sepiolite is treated with an aqueous solution containing one or more members selected from the group consisting of inorganic acids, organic acids, ammonium salts, salts of ammonium derivatives and magnesium salts, said aqueous solution being capable of removing impurities 
     
     
        contained in the sepiolite..]. 31. The hydrodemetallization catalyst of claim .[.19.]. .Iadd.37.Iaddend., wherein the sepiolite is treated with an aqueous solution containing one or more members selected from the group consisting of inorganic acids, organic acids, ammonium salts, salts of ammonium derivatives and magnesium salts, said aqueous solution being capable of removing impurities contained in the sepiolite. .[.32. The sepiolite carrier of claim 13, wherein one or more additives are added to the sepiolite in step (b) or step (c) so as to enhance its molding properties and molded part strength; said additives being selected from the group consisting of aluminium hydroxide sol, alumina silica sol, silica sol, bauxite, kaoline, montmorillonite, allophane, bentonite, attapulgite higher alcohols, esters of higher alcohols, ethers of higher alcohols, urea, starch, sucrose and organic molding auxiliaries..]. .[.33. The sepiolite carrier of claim 32, wherein before or in step (c), the sepiolite is treated with an aqueous solution containing one or more members selected from the group consisting of inorganic acids, organic acids, ammonium salts, salts of ammonium derivatives and magnesium salts, said aqueous solution being capable of removing impurities contained in 
     
     
        the sepiolite..]. 34. The hydrodemetallization catalyst of any of claims .[.27, 28,.]. 29.[., 30.]. or 31, wherein said inorganic acids are selected from the group consisting of nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid and carbonic acid; the organic acids are selected from formic acid, oxalic acid, acetic acid and tartaric acid; the ammonium salts are selected from ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium carbonate, ammonium oxalate, ammonium acetate and ammonium tartarate and the salts of ammonium derivatives are selected from trimethylamine hydrochloride and aniline hydrochloride. .[.35. The sepiolite carrier of claim 33 wherein said inorganic acids are selected from the group consisting of nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid and carbonic acid; the organic acids are selected from formic acid, oxalic acid, acetic acid and tartaric acid; the ammonium salts are selected from ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium carbonate, ammonium oxalate, ammonium acetate and ammonium tartarate and the salts of ammonium derivatives are selected from trimethylamine hydrochloride and aniline hydrochloride..]. .Iadd. 36. A hydrodemetallization catalyst comprising an effective amount of one or more catalyst metal components supported on sepiolite, the catalyst metal being selected from metals of the IIb group and transition metals of the Periodic Table, and wherein said catalyst is prepared according to a process comprising the steps of: (a) grinding the sepiolite to a fine powder, 50% or more by weight of which has a particle size of 100-mesh or finer;   (b) adding water to the ground sepiolite to adjust the water content thereof to about 20 to about 350% by weight;   (c) kneading the resulting mixture;   (d) air-drying or heat-treating the moist kneaded sepiolite at a temperature lower than about 1000° C.; and   (e) supporting one or more of said catalyst metal components on the sepiolite by contacting the sepiolite with an aqueous acidic solution containing ions of one or more metals selected from the group consisting of metals of the Ib, IIb, IIIa and iron groups of the periodic Table, the sequence of steps being (a), (b), (c), (d), and (e), (a), (b), (c), and (d). .Iaddend..Iadd. 37. A hydrodemetallization catalyst comprising an effective amount of one or more catalyst metal components supported on sepiolite, the catalyst metal being selected from metals of the IIb group and transition metals of the Periodic Table, and wherein said catalyst is prepared according to a process comprising the steps of:   (a) grinding the sepiolite to a fine powder, 50% or more by weight of which has a particle size of 100-mesh or finer;   (b) adding water to the ground sepiolite to adjust the water content thereof to about 20 to about 350% by weight;   (c) kneading the resulting mixture;   (d) air-drying or heat-treating the moist kneaded sepiolite at a temperature lower than about 1000° C.; and   (e) supporting one or more of said catalyst metal components on the sepiolite by a two-stage treatment consisting essentially of a first step of contacting the sepiolite with an acidic aqueous solution containing ions of one or more metals selected from the group consisting of metals of the Ib, IIb, IIIa and iron groups of the Periodic Table, and a second step of contacting the resulting sepiolite with a basis aqueous solution containing ions of one or more metals selected from the group consisting of Cu and the metals of the Va, VIa and iron groups of the Periodic Table; the sequence of steps being (a), (b), (c), (d) and (e), or (e), (a), (b), (c) and (d). .Iaddend.