Extruded Titania-Based Materials Comprising Quaternary Ammonium Compounds and/or Prepared Using Quaternary Ammonium Compounds

Abstract

Porous, extruded titania-based materials further comprising one or more quaternary ammonium compounds and/or prepared using one or more quaternary ammonium compounds, Fischer-tropsch catalysts comprising them, uses of the foregoing, processes for making and using the same and products obtained from such processes.

1 . A porous, extruded titania-based material further comprising one or more quaternary ammonium compounds. 
     
     
         2 . A porous, extruded titania-based material according to  claim 1 , in the form of symmetrical cylinders, dilobes, trilobes, quadralobes or hollow cylinders. 
     
     
         3 . A porous, extruded titania-based material according to  claim 1 , having a crush strength of greater than 3.0 lbf, preferably greater than 5.0 lbf. 
     
     
         4 . A porous, extruded titania-based material according to  claim 1 , wherein the one or more quaternary ammonium compounds comprises tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide or cetyltrimethylammonium hydroxide. 
     
     
         5 . A porous, extruded titania-based material according to  claim 1 , comprising mesopores and macropores. 
     
     
         6 . A porous, extruded titania-based material according to  claim 5 , wherein the mesopores have a pore diameter of 2 to 50 nm, preferably 15 to 45 nm or 30 to 45 nm, more preferably 25 to 40 nm or 30 to 40 nm. 
     
     
         7 . A porous, extruded titania-based material according to  claim 5 , wherein the macropores have a pore diameter of greater than 50 nm, preferably 60 to 1000 nm, more preferably 100 to 850 nm. 
     
     
         8 . A porous, extruded titania-based material according to  claim 5 , wherein the total pore volume is at least 0.3 ml/g, preferably at least 0.40 ml/g. 
     
     
         9 . A porous, extruded titania-based material according to  claim 5 , wherein the surface area is at least 30 m 2 /g, preferably at least 40 m 2 /g. 
     
     
         10 . A process for the preparation of a porous, extruded titania-based material having a crush strength greater than 3.0 lbf, said process comprising:
 a) mixing titanium dioxide and a solution of one or more quaternary ammonium compounds to form a homogenous paste;   b) extruding the paste to form an extrudate; and   c) drying and/or calcining the extrudate.   
     
     
         11 . A process according to  claim 10 , wherein the solution of one or more quaternary ammonium compounds comprises tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide or cetyltrimethylammonium hydroxide. 
     
     
         12 . A porous, extruded titania-based material obtainable by the process of  claim 10 . 
     
     
         13 . A process for the preparation of a porous, extruded titania-based material comprising mesopores and macropores and having a crush strength greater than 3.0 lbf, said process comprising:
 a) mixing titanium dioxide and one or more porogens to form a homogenous mixture;   b) adding a solution of one or more quaternary ammonium compounds to the homogenous mixture, and mixing to form a homogenous paste;   c) extruding the paste to form an extrudate; and   d) drying and/or calcining the extrudate at a temperature sufficient to decompose the one or more porogens.   
     
     
         14 . A process according to  claim 13 , wherein the solution of one or more quaternary ammonium compounds comprises tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide or cetyltrimethylammonium hydroxide. 
     
     
         15 . A process according to  claim 13  or claim H, wherein the one or more porogen comprises cellulose or a derivative thereof, such as methyl cellulose, ethyl cellulose and ethyl methyl cellulose; alginic acid or a derivative thereof, such as ammonium alginate, sodium alginate and calcium alginate; latex or polyvinyl chloride. 
     
     
         16 . A process according to  claim 13 , wherein the weight ratio of titanium dioxide to porogen is from 1:0.1 to 1:1.0, preferably 1:0.1 to 1:0.8, more preferably 1:0.15 to 1:0.6. 
     
     
         17 . A porous, extruded titania-based material obtainable by a process according to  claim 13 . 
     
     
         18 . A Fischer-Tropsch synthesis catalyst comprising a porous, extruded titania-based material according to  claim 1 , and further comprising at least one metal selected from cobalt, iron, nickel, ruthenium or rhodium. 
     
     
         19 . A Fischer-Tropsch synthesis catalyst comprising a porous, extruded titania-based material according to  claim 5 , and further comprising at least one metal selected from cobalt, iron, nickel, ruthenium or rhodium. 
     
     
         20 . A Fischer-Tropsch synthesis catalyst according to  claim 18 , further comprising one or more promoters, preferably wherein the one or more promoters are selected from rhenium, ruthenium, platinum, palladium, molybdenum, tungsten, boron, zirconium, gallium, thorium, manganese, lanthanum, cerium or mixtures thereof. 
     
     
         21 . A process for the preparation of a Fischer-Tropsch synthesis catalyst according to  claim 18 , said process comprising:
 a) mixing titanium dioxide, a solution of one or more quaternary ammonium compounds and a solution of at least one thermally decomposable cobalt, iron, nickel, ruthenium or rhodium compound, to form a homogenous paste;   b) extruding the paste to form an extrudate;   c) drying and/or calcining the extrudate at a temperature sufficient to convert the one or more thermally decomposable cobalt, iron, nickel, ruthenium or rhodium compound to an oxide thereof or to the metal form; and, where an oxide is formed, optionally   d) heating the dried and/or calcined extrudate under reducing conditions to convert the one or more cobalt, iron, nickel, ruthenium or rhodium oxide to the metal form.   
     
     
         22 . A process for the preparation of a Fischer-Tropsch synthesis catalyst according to  claim 19 , said process comprising:
 a) mixing titanium dioxide and one or more porogens to form a homogenous mixture;   b) adding a solution of one or more quaternary ammonium compounds and a solution of at least one thermally decomposable cobalt, iron, nickel, ruthenium or rhodium compound to the mixture, and mixing to form a homogenous paste;   c) extruding the paste to form an extrudate;   d) drying and/or calcining the extrudate at a temperature sufficient to decompose the one or more porogens and to convert the at least one thermally decomposable cobalt, iron, nickel, ruthenium or rhodium compound to an oxide thereof, or to the metal form; and, where an oxide is formed, optionally e) heating the dried and/or calcined extrudate under reducing conditions to convert the one or more cobalt, iron, nickel, ruthenium or rhodium oxide to the metal form.   
     
     
         23 . A process according to  claim 21 , wherein the solution of one or more quaternary ammonium compounds comprises tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide or cetyltrimethylammonium hydroxide. 
     
     
         24 . A process for the preparation of a Fischer-Tropsch synthesis catalyst according to  claim 18 , said process comprising:
 a) impregnating a porous, extruded titania-based material with a solution of at least one thermally decomposable cobalt, iron, nickel, ruthenium or rhodium compound;   b) drying and/or calcining the impregnated porous, extruded titania-based material at a temperature sufficient to convert the at least one thermally decomposable cobalt, iron, nickel, ruthenium or rhodium compound to an oxide thereof or to the metal form; and where an oxide is formed, optionally   c) heating the dried and/or calcined porous, extruded titania-based material under reducing conditions to convert the at least one cobalt, iron, nickel, ruthenium or rhodium oxide to the metal form.   
     
     
         25 . A Fischer-Tropsch synthesis catalyst obtainable by the process of  claim 21 , preferably having a crush strength of greater than 5.0 lbf. 
     
     
         26 . (canceled) 
     
     
         27 . (canceled) 
     
     
         28 . (canceled) 
     
     
         29 . (canceled) 
     
     
         30 . A process for converting a mixture of hydrogen and carbon monoxide gases to hydrocarbons, which process comprises contacting a mixture of hydrogen and carbon monoxide with a Fischer-Tropsch synthesis catalyst according to  claim 18 . 
     
     
         31 . A composition, preferably a fuel composition, comprising hydrocarbons obtained by a process according to  claim 30 . 
     
     
         32 . A process for producing a fuel composition, said process comprising blending hydrocarbons obtained by a process according to  claim 30  with one or more fuel components to form the fuel composition.