AU2011200003A1

AU2011200003A1 - Modified catalyst supports

Info

Publication number: AU2011200003A1
Application number: AU2011200003A
Authority: AU
Inventors: Shelly Goodman; Heinz J. Robota
Original assignee: Syntroleum Corp
Current assignee: Syntroleum Corp
Priority date: 2003-12-12
Filing date: 2011-01-04
Publication date: 2011-01-27
Also published as: AU2004299060A1; CN101060929B; AU2004299060B2; WO2005058493A1; EP1703975A1; JP2007516826A; EG24517A; BRPI0417133A; CN101060929A; WO2005058493A9; ZA200605441B

Description

AUSTRALIA Patents Act COMPLETE SPECIFICATION (ORIGINAL) Class Int. Class Application Number: Lodged: Complete Specification Lodged: Accepted: Published: Priority Related Art: Name of Applicant: Syntroleum Corporation Actual Inventor(s): Heinz J. Robota, Shelly Goodman Address for Service and Correspondence: PHILLIPS ORMONDE FITZPATRICK Patent and Trade Mark Attorneys 367 Collins Street Melbourne 3000 AUSTRALIA Invention Title: MODIFIED CATALYST SUPPORTS Our Ref: 904491 POF Code: 485049/478081 The following statement is a full description of this invention, including the best method of performing it known to applicant(s): -1- MODIFIED CATALYST SUPPORTS FIELD OF THE INVENTION The present application is a divisional application from Australian patent application 5 number 2004299060 the entire disclosure of which is incorporated herein by reference. BACKGROUND OP THE INVENTION Supported catalysts used in Fischer-Tropsch reactors, including for example, slurry bubble column reactors and continuously stirred tank reactors ("CSTR"), are subjected to 10 agitation causing significant collisions and frictional forces. Such collisions and forces can result in damage mechanisms which, over time, may cause attrition of the catalyst and/or catalyst support. Attrition of catalyst and/or catalyst support raises operating costs due to increased catalyst requirements. Moreover, attrition results in the production of fines which must be removed by filtration. The filtration process may cause loss of active catalyst in 15 addition to removal of the fines, thereby further raising operating costs. Catalyst supports used in fixed bed reactors may also be subjected to movement and collisions during batch or continuous regeneration processes, Consequently, some attrition may occur with fixed bed reactors. Moreover, catalyst supports, such as shaped extrudates, frequently show appreciable attrition during catalyst production, e.g. cobalt deposition onto 20 the support. In such instances, the attrited fines must be removed from the catalyst product prior to use to prevent reactor plugging. Attempts to reduce catalyst attrition include non-aqueous processes. Such processes require use of a non-aqueous solvent because the silicating agent used reacts rapidly with water which would displace the desired reaction of the silicate, with the hydroxyl or oxide 25 groups on or near the surface of the catalyst support. Yet another known process uses ethanol, i.e. non-aqueous, solutions of tetraethoxysilicate to deposit silicon onto catalyst supports for the purpose of suppressing the solubility of the support in aqueous acidic solutions which arc typically encountered during preparation of the supported catalyst. 30 1a 2 However, the use of non-aqueous solvents requires highly specialized equipment for commercial processing of flammable solvents as well as the costs of the solvents themselves. The above discussion of background art is included to explain the context of the present invention. It is not to be taken as an admission that any of the documents or other 5 material referred to was published, known or part of the common general knowledge at the priority date of any one of the claims of this specification. SUMMARY OF THE INVENTION Some embodiments of the invention provide catalyst composition comprising a support 10 material having between about 0.1 Si/nm 2 support surface area and about 10.6 Si/ni 2 support surface area deposited thereon wherein the Si atoms are bound to the support material through an oxygen atom. Other embodiments of the invention provide a catalyst composition comprising a support material having between about 0.1 Si/nm 2 support surface area and about 10.6 Si/nm 2 15 support surface area deposited thereon wherein less than about 10 wt% of the silicon is in polymeric form, Yet other embodiments of the invention provide a method of treating a catalyst support, comprising: contacting a support material with an attrition-suppressing composition comprising monosilicic acid thereby to provide a treated catalyst support. 20 Yet other embodiments of the invention provide a catalyst composition suitable for use in a Fischer-Tropsch process, comprising a mixture or reaction product of: an attrition resistant support prepared by contacting a support material with an attrition-suppressing composition comprising monosilicic acid; a catalyst precursor composition comprising cobalt, a first modifier selected from the group of Ca, Sc, Ba, La, Hf, and combinations thereof; and at 25 least one activator selected from the group of Ru, Rh, Pd, Re, Ir, Pt, and combinations thereof. Yet other embodiments of the invention provide A Fischer-Tropsch product, comprising: a paraffinic wax; and less than about 50 ppm of gamma alumina particles having a diameter of less than about 20 nm; wherein the concentration of gamma alumina particles is determined following primary filtration.

3 A first embodiment of the invention provides a catalyst composition comprising: a support material having between about 0.1 Si/nm.

2 support surface area and about 10.6 Si/nm 2 support surface area deposited thereon wherein the Si atoms are bound to the support material through an oxygen atom. In some such embodiments, the silicon is deposited on the support material at 5 a concentration of between about 0.55 Si/sm 2 and about 5.0 Si/nm 2 . Alternatively, in some such embodiments, the silicon is deposited on the support material at a concentration of between about 0.7 Si/nm 2 and about 3.5 Si/nm 2 . According to the invention there is also provided a catalyst composition comprising: a support material having between about 0.1 Si/nm 2 support surface area and about 1.9 Si/nm 2 support surface area deposited thereon 10 wherein the Si atoms from an aqueous acidic solution are bound directly to the support material through an oxygen atom such that the support material exhibits attrition resistance. In some embodiments, the support material is selected from the group of gamma alumina, eta alumina, theta alumina, delta alumina, rho alumina, anatase titania, rutile titania, magnesia, zirconia, refractory oxides of Groups 111, IV, V, VI and VIII elements and mixtures 15 thereof. In some embodiments, the support material is preformed. In a preferred embodiment, the support material is aggregated gamma alumina. In yet other embodiments, the support material is alumina-bound titania. In some embodiments of the invention, the catalyst has been regenerated. Some cmbodiments of the catalyst composition may further include: between about 12 wt% and about 30 wt% Co; between about 0.5 wt% and about 2 wt% of a first 20 additive selected from the group of Ca, Sc, Ba, La, and -If; and between about 0.03 wt% and about 0.3 wt% of a second additive selected from the group of Ru, Rh, Pd, Re, Jr. and Pt. In a preferred embodiment, the catalyst composition further includes: between about 12 wt% and about 30 wt% Co; between about 0.5 wt% and about 2 wt% La; and between about 0.03 wt% and about 0.3 wt% Ru. 25 Another embodiment of the invention provides a catalyst composition comprising: a support material having between about 0.1 Si/nm 2 support surface area and about 10.6 Si/nm 2 support surface area deposited thereon wherein less than about 10 wt% of the silicon is in polymeric form. In some embodiments of the invention, the silicon is deposited on the support material at a concentration of between about 0.55 Si/nm 2 and about 5.0 Si/nm 2 . In alternative 30 embodiments of the invention, the silicon is deposited on the support material at a concentration of between about 0.7 Si/nm 2 and about 3.5 Si/nm 2 . In some embodiments of the invention the support material is selected from the group of gamma alumina, eta alumina, theta alumina, delta alumina, rho alumina, anatase titania, rutile titania, magnesia, zirconia, 3a refractory oxides of Groups III, IV, V, VI and VIII elements and mixtures thereof. In a preferred embodiment of the invention, the support material is aggregated gamma alumina. In some embodiments of the invention, the support material is alumina-bound titania. In certain embodiments of the invention, less than about 5 wt% of the silicon is present in polymeric 5 form. In a preferred embodiment less than about 2.5 wt% of the silicon is in polymeric form. In some embodiments of the invention, the catalyst has been regenerated. In a preferred embodiment, the support material is preformed. In yet other preferred embodiments of the invention, the catalyst composition further includes: between about 12 wt% and about 30 wt/o Co; between about 0.5 wt% and about 2 wt% of a first additive selected 4 from the group of Ca, So, Ba, IA and Wf; between about 0.03 wtv and about 0.3 wtV% of a second additive selected from the group of a Rh, Pd, Re, Ir, and Pt In a most prefermd embodimncat of the invention, the cata3yet composition further including: between about 12 wt% and about 30 wt% Co; between about 0.5 wt% and about 2 wt% 5 La; and between about 0,03 wt% and about 0.3 w/a of R. Another embodiment of the invention provides a method of treating a catalyst support, including the stop of contacting a support material with an attrition-svppressing composition comprising monosilicic acid thereby to proyide a treated catalyst support. In some embodiments, the treated catalyst support has a surface concentration of 10 between about 0.1 and about 10.60 Si atoma/nd. In one prefrred embodiment, the attrition-suppossing composition comprises between about 0.02 .~id'about 5.4 % by weightof Si. -In another pitformd embodiment, the attrition-suppressing composition comprises between about 0.2 % and about 5.4 % by weight of Si. In yet other embodiments, the attrion-suppressing composition is prepand by contacting a silicale 15 with water under acidio conditions. In a preferred embodiment, tbe silicate comprises monosilicic acid. In yet other embodiments, the monosilicio acid is prepared by contacting tetraethoxysilane with water under acidic conditions. In some embodiments, of the method of the inventiou, the silicate is sodium orthoilicato or sodium metasilicate and the pH ranges from about 1.5 to about 3.5 at a temperaure ranging from about 0*C 20 to about 50C. In yet other embodiments of the method of the invention, the attrition suppressing composition is added to the catalyst support at a temperatun of manging from about 0*C to about 9S *C, in certain preferred embodiments of the method of the invention, the temperature muges from about 0*C to about 10C, In some embodiments of the method of the invention, the attrition-cuppressing composition comprises a 25 polyeilicio aoid species whemin concentmtion of inonosilicio acid is greater than the concentration of trisilicio acid and higher polymers of the silicio acid. In yet other embodimman of the method of the invention, the tnouosilicic acid is the predominant silicio acid species in the attrition-supprssing composition. In some embodiments of the method of the invention, the support material is preformed. 30 Yet other embodiments of the invention provide a catalyst composition suitable for use in a Fischer-Tropech process, comprising a mixture or maction product ot an attrition-resistant support prepared by contnoting a support material with an attrition suppressing composition comprising monosilicdI acid, a catalyst precursor composition 5 comprising cobalt, a first modifier selected from the group of Ca, So, Ba, La, Hf, and combinations thereof; and at least one activator selected from the group of Ru, Rh, Pd, Re, Ir, Pt, and combinations thereof. The catalyst composition according to claim 36, wherein the composition is substantially free of particles baying a diameter of lees than 5 about 20 pm under typical Fiscber-Tropsch reaction condidons. In some embodiments of the catalyst composition suitable for use in a Fischer-Topsch process of the invention, the support material comprises aggregated gamma alumina In yet other embodiments of the catalyst composition suitable for uso in a Fischer-Tropsoh process, the support material is preformed, 10 Yet another aspect of the invention provides a Pischer-Tropscb product, comaprisingma paraffmic wax; and less than about 50 ppm of gamma alumina particles having a diameter of less than about 20 nm; wherein the conceutration of gamma alumina particles is determined following primary filtration, In certain embodiments of the Fischer-Tropsch product of the invention, the Fischer-Tropsch product is produced 15 using a regenerated Fischer-Tropsch catalyst. In yet another aspect of the invention, a method for reducing the occurrence and severity of catalyst attrition is provided wheroin the method comprises the stcps of: depositing between about 0.1 Si/am 2 support surface area and about 10.6 Si/nma support surface area on a catalyst support wface wherein the SI atoms are bound to the support 20 surfae through an oxygen atom. In yet other embodiments of the method for reducing the ocurrence and seyerity of catalyst attrition of the invention, the silicon is deposited on the support mateial at a concentration of between about 0.55 Si/nm 2 and about 5.0 S/nM2. In yet other embodiments of the method for reducing the occurrene and severity of catalyst attrition of the invention, the silicon is deposited on the support 25 muaterial at a concentration of between about 0.7 Si/nm 2 and about 3,5 Si/n2. In yet other embodiments of the method for reducing the occurrence and severity of catalyst attrition of the invention, the support material is selected from the group of gamma alumina, cia alumina, theta alumina, delta alumina, rho alumina, anatase dtania, rutile titaia, magnesia, zirconle, refractory oxides of Groups MI, IV, V, VI and VIII elements 30 and mixtures thereof. In preferred embodiments of the method for reducing the occurmene and severity of catalyst attrition of the invention, the support material is aggregated gamma alumina. In yet other embodiments of the method for reducing the 6 occurrence and severity of catalyst attrition of the invention, the support material is alumina-bound titania. Yet other aspects of the invention provide a method for reducing the occurrence and severity of catalyst attrition comprising the steps of: depositing between about 0,1 S Si/and support surface area and about 10.6 Si/nm 1 support surface area on a catalyst support surface wherein less than about 10 wt% of the silicon is in polymeric forma. In yet other embodiments of the method for reducing the occurrence and severity of catalyst attrition of the invention, the silicon is deposited on the support material at a concentration of between about 0.55 Sind and about 5.0 Si/run. In yet other 10 embodiments of the method for reducing the occurrence and severity of catalyst attrition of the invention, the silicon is deposited on the support material at a concentration of between about 0.7 Si/mn 2 and about 3.5 Si/nm 2 . In yet other embodiments of the method for reducing the occurence and severity of catalyst attrition of the invention, the support material is selected from the group of gamma aluinn, eta almnina, theta aluina, delta 15 alumina, rho alumina, anatase titanla, rutile titania, magnesia, zirconia, refractory oxides of Gmups II, IV, V, VI and VI3 elements and mixtures thereof. In preferred embodiments of the method for reducing the occurrence and severity of catalyst attrition of the invention, the support material is aggregated gamma alumina. In yet other embodiments of the method for reducing the occurrence and severity of catalyst attrition 20 of the invention, the support material is alumina-bound titanin. In yet other embodiments of the method for reducing the occurrence and severity of catalyst attrition of the invention, less than about 5 wt% of the silicon is present in polymeric form. In preferred embodiments of the method for reducing the occurrence and severity of catalyst attrition of the invention, less than about 2.5 wt% of the silicon is in polymerio form. 25 Another aspect of the invention provides a method for reducing the occurrence and severity of catalyst support material deaggregation comprising the steps of. depositing between about 0.1 Si/tni support surface area and about 10.6 Si/nm 2 support surface area on a catalyst support surface wherein the Si atoms are bound to the support surface through an oxygen atom. In yet other embodiments of the method for reducing 30 the occurrence and severity of catalyst support material deaggregation of the invention, the silicon is deposited on the support material at a concenitration of between about 0.55 Si/m 1 and about 5.0 Si/rn. In yet other embodiments of the method fbr reducing the occurrence and severity of catalyst support material deaggogadon of the invention, the 7 silicon is deposited on the support material at a concentration of between about 0.7 Si/nm 2 and about 3.5 Si/nm 2 . In yet other embodiments of the method for reducing the occurrence and severity of catalyst support material deaggregation of the invention, the support material in selected from the group of gamma alumina, ea alumina, theta 5 alumina, delta alumina, iho alumina, anatssa titania, rutile titaniB, magnesia, zirconi; refctetory oxides of Groups IH, TV, V, VI and VM elements and mixtures thereof In yet other embodiments of the method for reducing the occurrence and severity of catalyst. support materal deaggregation of the invention, the support material is aggregated gamma alumina In yet other embodiments of the method for reducing the occurrence 10 and aeverity of catalyst support material deaggregation of the invention, the support material is alumina-bound titania. Yet another aspect of the invention provides a method for reducing the ocourrence and severity of catalyst support material deaggregation comprising the steps of: depositing between about 0.1 Si/nm2 support surface area and about 10.6 Si/nm 2 15 support surface area on a catalyst support surface wherein less than about 10 wt% of the silicon is in polymeric form. In yet other embodiments of the method for reducing the occurrenoe and severity of catalyst support material deaggregatlon of the invention, the silicon is deposited on the support material at a concentration of between about 0.55 Si/nm 2 And about 5.0 Si/nm2. In yet other embodiments of the method for reducing the 20 occurrence and severity of catalyst support material deaggregatdon of the inention, the silicon is deposited on the support material at a concentration of between about 0.7 Si/nm 1 and about 3.5 Si/nm 2 . In yet other embodiments of the method for reducing the occurrence and seveity of catalyst support material deaggrogation of the inYention, tho support material is selected from the group of gamma aluminA eta alumina, theta 25 alumina, delta alumina, rho alurnina, anatase titania, rutile titania, magnesia, zirconia, reftctory oxides of Groups II, IV, V, VI and VIll elements and mixtures thereof. In yet other embodiments of the method for reducing the occurrenee and severity of catalyst support material deaggregation of the invention, the support material is aggreguted gamma alumina. In yet other embodiments of the method for reducing the occurrence 30 and severity of catalyst support material deaggregMaion of the invention, the support material is alumina-bound titania, li yet other embodiments of the method for reducing the occurrence and severity of catalyst support material deaggregation of the invention, less than about 5 wf/ of the silicon is present in polymeric form. In yet other embodiments of the method for reducing the occurrence and severity of catalyst support 8 material dcaggrgation of the invention, less than about 2.5 wt% of the silicon is in polymeric form. BRIBP DESCIUPTION OF THE DRAWINGS Fig. I is a gruph of cuultive volume percent by particle size for tn untreated 5 support and for a first treated support before and after ultrasonic treatments. Fig. 2 is a graph of cumulative volume percent by particle size for an untreated support and for a second treated support before and after ultrasonic treatments, pig. 3 is a graph of cumulative volume percent by particle size for an untreated support before and following ultrasonic treatment. 10 Fig. 4 is a chart showing the properties of the catalysts discussed in Examples I 10. Fig. 5 is a graph showing ratio of Si to Al XPS intensity. DESCRIPTION OF EMBODIMBNTS OF THE INVENTION The term "support" means any pro-formed inorganic support material having 15 accessible hydroxyl and/or oxide groups and having penetrable pores. Supports, as uecd herein, may have any shape. The pores generally have openings greater than about 5 nm across the largest axis, Th term "pre,-formed" means a catalyst support which is formed, including for example extraction, wahing, drying, and setting the particle size, prior to treatment with 20 silicon compound and impregoation of an active metal, such as Group VI metals. Catalyst supports Included in the term "pro-formed" include, for example, spray driod, extruded, and pelletized supports. The tonn "Fischer-Tropsch product" means the aggregate composition of hydmearbons framed from synthesels gas by the FT synthesis proccsa and remaining 25 within the sythesi reactor vessel as a liquid at process conditions. The term "primary fIhration" means filtration of the Fischer-Tropsch product as it passes from the FT reactor and removing particles greater tian about 5 pm. The term "paraffminc wax" means a hydrocarbon consisting predominately of unbinhebed -- CH- chains wbich are semi-solid to solid at room temperature and pressure.

9 The term "directly bound to a support material through an oxygen atom" means attachment through one or more singlo bonds to one or more oxygen atoms, each oxygen atom singly bonded to the metal ofthe support material. In some embodiments of the process of the invention, monosilicic acid ("MSA") 5 is prepared in accordance with the teachings of U.S. Patent 2,588,389. In preferred embodiments of the invenlon, the MSA is made under conditions which minimize polymerization of the MSA. Such conditions are koown in the art and examples of such conditions are discussed in the above cited roforence. In some embodiments of the invention, the MSA is formed from a precursor at pHs between about 1.5 and about 3.5 10 and at temperatures between about 0*C and about 5*C. In some embodiments, the MSA is formed &om a precursor at a temperature of up to about 250C, In preferred embodiments, the MSA is formed from a prceursor at a temperature between about 0* and about 8*C; in a most preferred embodiment, the MSA is formed from a precursor at a temperature between about 0*C and about S*C, The precursor may be any aqueous 15 solution of a silicate, including sodium silloates such as sodium orthosilicato and sodium metanilicate, The MSA solution% generally contains between about 0.1% to about 1.0% Si to total solution by weight. Following formation of the MSA, the MSA solution is preferably contacted with the support within as short a time as is protiocble. The MSA is very reactive, readily forming polymers by reaction with itself or alternadvely, 20 reacting with other oxidized surfaces, such as the surfaces of typical catalyst supports. Thu contacting of the MSA and catalyst support may occur by batch mixing or by metered addition of the MSA solution to an aqueous suspension of the support materinL When batch mixing is used, the support solution is generally vigorously stirred during MSA addition to maximize contact between the MSA and support particles. When 25 metered addition is used, the MSA is added at a rate which minimi-es solf polymerization and favors reaction between the MSA and the support by maintaining a relatively low concentration of unreacted MSA to total solution. Nevertheless, the reaction between the MSA and some catalyst supports, such as alumina, may be faster than MSA self-polymerizatioA In such cases, about a monolayer of the silicon may be 30 readily deposited on the support particles even where batch addition of the MSA is used and higher MSA concentrations in the mixture occur. The MSA and support mixture may be stirred, preferably vigorously stirred, during and/or following mixing to promote contact between the MSA and the surface of the support particles. In preferred embodiments of the invention, the amount of water used to form the aqueous suspension l0 of the support Material is minimized, with only an amount necessary to permit vigorous stirring be used. Such amount of water will vary according to type, size and shape of support used. Generally, the MSA solution may be contacted with the support for a period of between about I minute to over 2 hours before subsequent processing. The 5 MSA solution may be contacted with the support at temperatures ranging from between about 0*C and about 95*C, When higher temperatures are used, the MSA rcagont may be added to the support s"rry at a higher rate due to a faster reaction rate between the MSA and the support matrix. Furthermore, even at a temperature below 5*C, the MSA reagent 10 exhibits some self-polyrmerization. 3ven with some degree of MSA self-polymerization, the active agent in the MSA reagcnt/support slurry mixture appears to be predominantly tbc monomeric form ofaillico acid. Relatively rapid hydrolysis, Le., depolymerization, of low polymers of MSA has been observed at low unreacted MSA concentrations. Even at the end of the MSA addition, where the concentration of unreacted silicate climbs to 15 about 500 ppm in the mixture, there Is a preponderance of the active monomer. Following binding of the MSA onto the support, the mixture may be cooled, excess solution may be decmtcd, and the treated support washed with water to remove excess acid. The decant-wash cycle may be repeated. Following the final decanting, the remaining dense slury may be filtered prior to drying and calcining. The alurry is then 20 dried followed by calcining at temperatures ranging from about 400*C to about 800"C and prefembly at about 600*C, The Jilter pore size used will be generally dependent upon support size and shape. Indeed, the dense slurry need not be filtered but ratbr may be sobjected to any of a nuinber of known techniques for dewatering dense slurries. For example, the dense 25 slurry maybe centrifuged, Typically, the treated support material is dried at temperatures between about 1 00*C to about 200*C, proforably at about 150*C until the mrtcrial becomes flowable. It will be understood that in commercial operations, the dewatered slurry may be dried and calcined continuously with a frout portion of a calcining zone acting as a drier by adjustment of termperato ramp and flow rate. In most applications, 30 the support will be maintained at the calclning temperature for at least about one hour. The terms "support(s)" and "support material(s)" arc used interchangeably herein. Supports useful in the invention include any prefonmed, inorganic particles having any shape, including for example substantially spherical or extrudates, having accessible 11 hydroxyl or oxide groups, and having pores penetable as necessary for use in a Fischer Tropach synthesis. Examples of suitable support materials include, for example, alumina, incohuding amma eta, thota, delta, and rho alumina, anatase and rutile titanla, magnesia, zirconia or other refructory oxides selected from Groups .11, IV, V. VI and 5 VIII. The support, prior to treatment accoiing to the invention, may have a diameter or equivalent diameter ranging from about 0.025 mm to about 0.2 mm. The amount of Si bound to the support material may range from between about 0.77 SI/em 2 to about 10.6 SiTnm As prAviously mentioned, monosilicio acid, Si(OH) 4 , may undergo self. 10 polymerization with the extent of polymerization dependent upon temperature, pressure and concentration of silicate. Consequently, preparation of practical solutions of silicki acid will contain not only the silloic acid monomer, but higher polymeric forms as well. Solutions most effective for the purposes of this invention will be composed of the lowest concentration of higher polymeric forms. The quality of solutions prepared for 15 the purposes of this invention, i.e., the less polymerio form, the higher monomeric form, the higher the quality of the solutlon, may be characterized using a colorimetric determination based on the formation of aqueous silicon molybdate species as is know in the ar, The extent of MSA polymerization may be monitored by using 20 speotrophotometric techniques known in the art. One known spectrophotometrio method relics on the depolymerization of low molecular weight polymers of SiO 2 and the formation of silicomolybdic acid wlich has a yellow color. The reaction of Si(OH)4 with nolybdic sold is extremely rapid. The rate of formation of Si(OH) 4 is inversely proportional to the length of the silicate polymer, Tlerefore, the lower the degree of 25 polymerization, the nore rapidly the solution reaebes its final color intensity. Several tests were made using this spectrophotonetrio technique in which the color change was monitored using a spectrophotometer set to 410am. MSA monomer achieved its fnal color in less than two minutes. The MSA cubic octomer requires moe than ten minutes to reach its Ilal color and exhibits ees than 50% of its final color In the 30 first two minutes. Yet higher polymers require even longer to exhibit their sal color intensity and show a correspondingly lower fraction of their color at two minutes or less. In some embodiments of the invention, the test solutions achieved about 80% of their final color within two minutes and achieved their final color within six to ten minutes.

12 Solutions were deemed suitable for use when about >900/% of the final color was developed within 5 mites. In prefermd embodiments of the invention, the test solutions produced >90% of their color within 2 minutes, indicating very high monomer Content at the outset. 5 The treated support may be used for the preparation of a catalyst, such as a Fischer-Tiopsch catalyst. Any of a number of catalyst preparation methods, for example impregnation of a Group VDI metal, am known in the art and may be utilized with the treated support. A Fischer-Tropseb catalyst incorporating the attrition-resistant catalyst support of 10 the invention hicludes a catalytically active amount of a catalytic metal, usually between about I wto and 100 wt%, preferably between 2 wt% and 60 wt%, and most preferably between about 10 wt% and about 30 wt%.. Promoters and/or iativators may be included in the catalyst composition and promoters and activators useful in Fiscber-Tropsch catalysts are well known in the art. Promoters include, for example, ruthenium, rhenium, 15 platinum, bafnium, cerimn, and zirconium. Promoters and/or activators are wuually present in amounts loss than that ofthe primary catalytic metal. One typical catalyst preparation method utiles impregnation by incipient wemess. For example, a cobalt nitrate salt may be impregnated by incipient wetness onto a titania, silica, or alumina support, optionally followed by Impregnation with a 20 promoter. The catalyst may then be calcined at about 250*C to about 500*C to covert the metal salt to its correspondiag oxide. The oxide may then be reduced by treatment with hydrogen or a hydrogen containing gas at about 300*C to about 500"C for a time sufficient to substantially reduce the oxide to the elemental or catalytic fonn of the meral. Other well known catalyst preparation methods are those disclosed in U.S. Patent Nos. 25 4,673,993; 4,717,702; 4,477,595; 4,663,305; 4,822,824; 5,036,032; 5,140,050; 5,252,613; and 5,292,705. The supports treated as described herein display improved attrition resistance over untreated supports. One method for gauging the relative attrition resistance of supports is based on the usc of an ultrasonic probe to produce conditions whorein the 30 support particles collide with one another with a high frequency and sufscient energy to potentially cause fmcture of the support particles. Such test method is discussed in 6,262,132. Figure I shows the results of such ultrasonic testing on a support, both a fuit treated ard untreated samples of such support. The curves in Fig, I show the cunTulativo 13 volume percent as a function of particle size for these samples, before and after ultrasonic testing. Specifically, the curve shown with diamond data points depicts the particle size cumulatve distribution of an untreated support before ultrasonic treatment; the curve shown with triangle data points depicts the particle size cumulative distribution 5 of a fust treated support before ultrasonic treatment; the curve ahown with box data points depicts the particle size cumulative distribution of an untreated support following ultrasonic treatment; the curve shown with "'X" data points depicts the particle size cumulative distribution of tha firt treated support following ultrasonic treatment. As can be seen fom Pig. 1, the untreated support shows a significantly greater shift to smaller 10 particle size following ultrasonic treaunent than that displayed by the treated support. The seme trend is shown in Pig, 2 with the untreated support following ultrasonic testing showing a significantly greater shift to smaller particle sizes than that of a second treated support following ultrasonic testing. The support material used in the examples shown in Pigs, I and 2 aro the same material but separate samples of such material. The 15 untreated sample is the same In both Figs. I end 2. Referring to both Figs, 1 and 2, the untreated supports following ultrasonic testing exhibit a population of particles smaller than 20 microns in diameter, Whilo the treated supports following ultrasonio testing also exhibit particles having diameters (or effective diameters) of less than 20 microns, the sub-20 micron population in the treated support is about one-half that seen in the 20 untreated supports. Moreover, the overall shift to smaller particle sizes is also less for the treated supports than for the untreated supports. The ultrasonic testing discussed above was completed on an untreated support sample and the cumulative volume percent vs. particle size of such sample before and after ultrasonic testing is shown in Fig. 3. The cumulative volume percent vs. paticle 25 size was then remeasred for the untreated sample subjected to ultrasonic testing afer about six months. The particle size distribution remain substantially identical to that measured in the earlier testing thereby demonstrating that the ultrasonic test is highly rigorous with excellent reproducibility. in addition to attrited catalyst particles, it tas bec observed that Fischer-Tropsch 30 product waxes may also contain particulate significantly smaller in size than attrition products, NMR analysis of these particulates, according to cnwn methods, shows these solids to be comprised substantially of gamrna alumina crystallites. TEM analysis of these particulates, using known methods, have a size of less than about 20 nm along any 14 rystalline axis. Such gnmma alumina crystallites am believed to be deagpggated fragments from the catalyst particles. Because the deaggregated gamma alumina fragments am significantly smaller in size than attrition products, the deaggregated gamma alumina may be separated from the attrition products. The composition of the 5 deaggregated gamma alumina product differs from the composition of the original catalyst. Whereas the catalyst typically has a composition of about 20 wta elemental cobalt, and 70 wt% AI20,, the deaggregated gamma alumina product are depleted of cobalt, typically containing about 3 wth to about 4 wt% elemental Co and about 95 wt%

A

1 O3. . 10 Examle 1 --reuaration of Catalyst Sanmlo I MSA reagent solution was prepared with 94.9g TEOS rapidly added to 4L of acidified domineralized water under vigorous string, Sufficient HNO was added to the water to bring the p1 to between 2.2 and 2.5 and beld between 3C and 8C, 15 minutes after TEOS addition, an allquot was removed and the rate of color change tested. 15 Greater than 90% of the full color dovoloped within 5 minutes. In a separate atined, heated vessel, a slurry of the alumina support containing 640g alumina suspended in 2L of dcminemlized water was beated. The surry was held at 506*5'C throughout the addition of the MSA reagent, which was added at a rate of 35ml/min. Following completion of the MSA addition, the slurry was stirred and kept at 504d5*C until >95% 20 of the silicon was meacted with the alumina. Once reaction was complete, stirring was stopped, the solids allowed to settle, and the olear mother liquor decantod from the vessel. The remaining dense slurry was vacuum filterd to remove the remainder of the solution. The filtered solid was spread onto a drying tray to a thickness less than 1.5cm and dried overnight in an oven held at 140"C. This dried powder was then ealcined in a 25 dish at 600*C for 4 hours, Catalyst was prepared to have a notninal composition of 20%Co, 1%Lo, and 0. 1%Ru in the calcined form. 200g of the Si-modified catalyst support were charged to a steam-jacketed, rotating impregnation vessel. A saturated solution prepared from Co(NOs)r6H20 and demincralized water was prepared in advance, 172.5g of this 30 saturated Co solution was used for the first impregnation pas, 6.25g of La(NO3)36H2O were dissolved in 20g of dominemlized water and combined with the Co solution. The amount of solution was selected so as to produce an incipiently wet powder when applied to the support in the rotating vessel. The impregnated powder is allowed to 15 tumble in the impregnator for one hour at ambient tempersurs and then steamed to dryness over a three hour period. The powder is cooled to ambient, weighed, and transferred to shallow calcining dishes such that the powder depth is gem. The dishes are placed Into an electrically heated oven which is ramped from ambient to 120'C, held 5 at 120'C for 2 hours, ramped to 350*C over a two hour period and held at 350*C for an additional 2 hours. After cooling to ambient, the calcined powder is again trunfer d to the impregnation vessel. To 187g of a second charge of the saturated cobalt solution, 1.8g of a 13.5% Ru solution of Ru(NO)(NQ3) is added. This second imprcgnation solution is again applied to the substrate in the tumbling impregnator and dried and 10 calcined as following the first pass. Example 2 -PManration of Catalyat Sample 2 MSA reagent solution was prepared with 73.6g TEOS rapidly added to 667ml of acidified demincralized water under vigorous stirring. Sufficient HNO was added to the water to bring the pH to between 2.2 and 2.5 and held between 3'C and S*C. 15 minutes 15 after TEOS addition, an aliquot was removed and the rate of color change tested. Greater than 90%Y1 of the full color developed within 5 minutes. In a separate tirred, heated vessel, a sluny of the aluminn support containing 100g alumina suspended in 333 ml of derineralized water was heated. 'nT sluny was held at 50'5"C throughout the addition of the MSA rmagent, which was added at a rate of 5ml/min. Following 20 completion of the MSA addition, the slurry was stirred and kept at 50'±5'C until >95% of the silicon was reacted with the alumina. Once reaction was complete, stirring was stopped, the solids allowed to settle, and the clear mother liquor decanted from the vessel. The remaining dense slurry was vacuum filtered to remove the remainder of the solution. The filtered solid was spread onto a drying tray to a thicknost less than 1.5cm 25 and dried 6 h In a static muffle funace oven held at 140*C. This dried powder was then calcined in a dish at 600"C for 4 hours. Catalyst was prepared to have a nominal composition of 20%Co, l%La, and O.lRu in the calcined form. 93.gg of the Si-modified catalyst support were charged to a steam-jacketed, rotating Impregnation vessel. A saturated solution prepared from 30 Co(NOy)r6H20 and dcrmineralized water was prepared in advance. 87.

6 g of thin saturated Co solution was used for the first impregnation pass. 4.08g of La(NO) 3 r6H 2 0 were dissolved in 1Og of deminoralized water and combined with the Co solution. The amount of solution was selected so as to produce an incipiently wet powder when 16 applied to the support in the rotating vessel. The impregnated powder is allowed to tumble in the impregnator for one hour at ambient temperature and then steamed to dryness over a three hour period. The powder is cooled to ambient, weighed, and transferred to shallow calcining dishes such that the powder depth is :2em. The dishes 5 are placed Into an electrically heated oven which Is ramped from ambient to 1209C, held at 120'C for 2 hours, ramped to 350*C over a two hour period and held at 350*C for an additional 2 hours. After cooling to ambient, the calcined powder is again tranferred to the impregnation vessel. To 87,5g of a second charge of the saturated cobalt solution, 0.97g of a 13.5% Ru solution of Ru(NO)(NO 3 )) is added. This second impregnation 10 solution is again applied to the substrate in the tumbling impregnator and dried and calcined as following the first pass. Example 3 - Preparation of Catalyst Sample 3 MSA reagent solution was prepared with 94.9g TEOS rapidly added to 4L of acidified dmrineralieCd waterunder vigorous stirring, Sufficient HNO. was added to the 15 water to bring the pH to between 2.2 and 2.5 and held between 3"C and 8"C. 15 minutes after TEOS addition, an aliquot was removed and the rate of color change tested. Greater than 90% of the full color developed within 5 minutes. A slurry of the alumina support containing 640g alumina suspended in 2L of domineralized water was added to the MSA, The mixture was then heated to 5045"C. The mixture was stirred and kept at 20 50**5*C until >95% of the silicon was reacted with the alumina. Once reaction was complete, stirring was stopped, the solids allowed to settle, and the clear mother liquor decanted frm the vessel. The remaining dense slurry was vacuum filtered to remove the reminder of the solution. The fltered solid was spread onto a drying tray to a thickness less than LSm and dried overnight In an oven held at 140 0 C. This dried powder was 25 then calcined in a dish at 600*C for 4 hours. Catalyst was prepared to have a nominal composition of 20%Co, 1%La, and 0. lRu in the calcined form, 200g of the Si-modified cntalyst support were charged to a seram-jacketed, rotating impregnation vessel. A satuated solution prepared from Co(NO)16H 2 O and domineralized water was prepared in advance. 172.Sg of this 30 saturated Co solution was used for the first impregnation pass, 6.25g of La(NOs)r-6H20 were dissolved In 20g of deminrlized water and combined with the Co solution, The amount of solution was selected so as to produce and incipiently wet powder when applied to the support in the rotating vessel. The impregnated powder is allowed to 17 tumble in the impregnator for one hour at ambient temperatures and then steamed to dryness over a three hour period. The powder is cooled to ambient, weighed, and transferred to shallow calcining dishes such that the powder depth is 52cm. The dishes are placed into an electrically heated oven which is ramped from ambient to 120'C, held 5 at 120C for 2 hours, ramped to 350'C over a two hour period and held at 350C for an additional 2 boun. After cooling to ambient, the calcined powder is again bansferred to the impregnation vessel. To 187g of a second charge of the Saturated cobalt solution, 1.8g of a 13,5% Ru solution of Rk(NO)(NO) is added. This second impregnation soludon is again applied to the substrate in the tumbling impregnator and dried and )0 calcined as following the first pass. Exnmole 4 -Prenamtion of Catalyst Samle 4 MSA reagent solution was pt.pard with 38g TEOS rapidly added to 1.62L of acidified domineralized waterunder vigorous stirring. Sufficient HN03 was added to the water to bring the pH to between 2.2 and 2.5 and held between 3"C and 8'C, 15 minutes 15 after TEOS addition, an aliquot was removed and the rate of color change tested. Greater than 90% of the full color developed within 5 minutes. This MSA solution was kept cold and held for -60 hre. A shury of the alumina support containing 640g alumina suspended in 768 ml of demineralizod water was added to the MSA. The mixture was then heated to 5 0 *5"C. The mixture was stirred and kept at 50M5'C until >95% of the 20 silicon waa reacted with the alumina Once reaction was complete, stining was stopped, the solids allowed to settle, and the clear mother liquor decauted from the vessel. The remaining dense slurry was vacuum filtered to remove the remainder of the solution. The filtered solid was spread onto a drying tray to a hikolness less than 1.5cm and dried overnight in an oven held at 140'C. 'his dried powder was then caloined in a dish at 25 600*C for 4 hours. Catalyst was prepared to have a nominal composition of 20%Co, 1%La, and 0.3 %Ru in the calcined form. 200g of the Si-modified catalyat support were charged to a atam-jacketed, rotating impregnation vessl. A saturated solution prepaed from Co(NOs>r6HO and domineralized water was prepared in advance. 172.Sg of this 30 saturated Co solution was used for the first Impregnation pass. 6,25g of LONOs)y6H20 wcre dissolved In 20g of dominemlized water and combined with the Co solution. The amount of solution was selected so as to produce and Incipiently wet powder when applied to the support in the rotating vessel. The impregnated powder is allowed to 18 tumble in the impregator for one hour at ambient temperatures and then steamed to dryness over a three hour pedod. The powder is cooled to ambient, weighed, and transferred to shallow calcining dishes such that the powder depth is :2cm. The dishes ae placed into an electrically heated oven which Is ramped from ambient to 120*C, hold 5 at 120*C for 2 hours, rmped to 350*C over a two hour period and held at 350*C for an additional 2 hours. After cooling to ambient, the calcined powder is again transferred to the impragnation vessel. To 194g of a second charge of the saturated cobalt solution, 3.82g of a 13.5% Ru solution of Ru(NO)(N%0), is added, This second Impregnation solution is again applied to the subsrate in the tumbling Impregnator and dried and 10 calcined as following the fast pass. Example 5 - Preparation of Catalyst Sample S MSA reagent solution was prepared with 38g TEOS rapidly added to 1.62L of acidified demineralized water under vigorous stirring. Sufficient HNO was added to the water to bring the pH to between 2.2 and 2.5 and held between 3*C and 80C. 15 minutes 15 after TEOS addition, an aliquot was removed and the rate of color change tested. Greater than 90% of the ful color developed within 5 minutes. A slurry of the alumina support containing 640g alumina suspended in 768 ml of demineralized water was added to the MSA. The mixture was then heated to 50%5*C. The mixture was stirred and kept at 50W5*C until >95% of the silicon was reacted with the alumina, Once reaction was 20 complete, stirring was stopped, the solid allowed to settle, and the clear mother liquor decanted from the vessel. The amaining dense slurry was vacuum filtered to remove the remainder of the solution. The filtered solid was spread onto a drying tray to a thickness loss than 1.5cm and dried overnight in an oven held at 1400C. This dried powder was then calcined in a dish at 6000C for 4 hours, 25 Catalyst was prepared to have a nominal composition of 20%Co, 1%La, and 0.1%Ru in the calcined form. 200g of the Si-modified catalyst support were charged to a steam-jacketed, rotating impregnation vessc). A saturated solution prepared from Co(N0 3

)

2 61H 2 0 and demineralied water was prepared in advance. 172.Sg of this saturated Co sohtion was used for the first impregnation pass. 6.2Sg of La(NO)61H20 30 were dissolved in 20g of demineralized water and combined with the Co solution. The amount of solution was selected so as to produce and incipiently wet powder when applied to the support in the rotating vessel The imprgnated powder is allowed to tumble in the impregnator for one hour at ambient temperatures and then steamed to 19 dryness over a three hour period. The powder is cooled to ambient, weighed, and transfered to shallow calcining dishes such that the powder depth is 52cm. The dishes are placed Into an electrically heated oven which is ramped from ambient to 120"C, held at 120*C for 2 hours, ramped to 350 9 C over a two hour period and held at 350*C for an 5 additional 2 hours. After cooling to ambient, the calcined powder is again transferred to the impregnation vessel, To 192g of a second charge of the saturated cobalt solution, 1.

82 g of a 13.5% Ru solution of Ru(NO)(NOs)s is added, This second impregnation solution is again applied to the substrate in the tumbling impregnator and dried and calcined as following the first pass. 10 Example 6 -Preparation of Catalyst Sample 6 MSA reagent solution was prepared with 94.9g TEOS rapidly added to 4L of acidified drmineralized water under vigorous stirring. Sufficient HNO) was added to the water to bring the pH to between 2.2 and 2.5 and held at room temperature ~22C. 15 minutes after TEOS addition, an aliquot was removed and the rate of color change tested. 15 Gyreater than 90% of the full color developed within 5 minutes. 640g of alumina was added to the MSA. The mixture was then heated to 5 0 h5'C. The mixture was stirred and kept at 5045 9 C until >95% of the silicon was reacted with the alumina. Once reaction was complatc, stirring was stopped, the solids allowed to settle, and the cleat mother liquor decanted from the vessel. The remaining dense slurry was vacuum filtered 20 to remove the remainder of the solution, The filtered solid was spread onto a drying tray to a thickness less than 1.5em and dried overnight in an oven held at 140"C. This dried powder was then calcined in a dish at 600'C for 4 hours. Catalyst was prepared to have a nominal composition of 20%Co, 1%La, and 0.1%Ru in the caloined form. 200g of the SI-modified catalyst support were charged to a 25 steam..jacketed, rotating impregnation vessel. A saturated solution prepared from Co(N0 3 )6140 and domineralized water was prepared in advance. 172.5g of this saturated Co solution was used for the first impregnation pass. 6.25S of La(NOj) 5 .6H;O were dissolved in 20g of demineralized water and combined with the Co solution. The amount of solution was selected so as to produce and Incipiently wet powder when 30 applied to the support in the rotating vessel. The impregnated powder is allowed to tumble In the imprepnator for one hour at ambient temperatures and then steamed to dryness over a three hour period. The powder is cooled to ambient, weighed, and transferod to shallow calcining dishes such that the powder depth is :52cm. ne dishes 20 are placed into an electrically heated oven which is ramped from ambient to 120"C, held at 120'C for 2 hours, ramped to 350'C over a two hour period and held at 350 0 C for an additional 2 hours. After cooling to ambient, the caloined powder is again transferred to the impregnation vessel, To 187g of a second charge of the spturated cobalt solution, 5 LBg of a 13.5% Ru solution of Ru(NO)(NO)t is added. This second impregnation solution is again applied to the substrate in the tumbling impregnator and dried and calcined as following the first pass. pxampte 7 -Preparation of Catalyst Sample I MSA reagent solution was prepared with 89.3g TBOS rapidly added to 2L of 10 acidified demineralized water under vigomus stirring. Sufficient HNO 3 was added to the water to bring the pH to between 2.2 and 2.5 and held between 3"C and V"C. 15 minutes after TEOS addition, an aliquot was removed and the rate of color change tested. Greater than 90% of the full color developed within 5 minutes. In a separate stirred, heated vessel, a slurry of the alumina support containing 300g alumina suspended in IL 15 of demineralized water was heated, The slurry was held at 5045'C throughout the addition of the MSA reagent, which was added a a Tate of 15mi/min. Following completion of the MSA addition, the sluny was stirred and kept at 50"*5 0 C until >95% of the silicon was reacted with the alumina. Onco reaction was complete, stirring was stopped, the solids allowed to settle, and the clear mother liquor decanted from the 20 vessel. The remaining dense slurry was vacuum filtered to remove the remainder of the solution. The filtered solid was spread onto a drying tray to a thickness less than 1.5cm and dried 6 h In a static muffle fumace held at 140"C. This dried powder was then calcined in a dish at 600C for 4 hours. Catulyst was prepared to have a nominal composition of 20%Co, 1%L, and 25 .1%Ru in the calcined form. 200g of the Si-modified catalyst support were charged to a steam-jacketod, rotating impregnation vessel. A saturated solution prepared from Co(NO3)2.6Hzo and demineralized winter was prepared in advance, 172,5g of this saturated Co solution was used for the first impregnation pass. 6.25g of La(NO3)r6H2O were dissolved in 20g of demineralized water and combined with the Co solution. The 30 amount of solution wa selected so as to produce and incipiently wet powder when applied to the support in the rotating vessel. The impregnated powder is allowed to tumble in the Impregnator for one bour at ambient temperature and then steamed to dryness over a three hour period. The powder is cooled to ambient, weighed, and 21 transferred to shallow calcining dishes such that the powder depth is 52cm. The dishes are placed into an electrically heated oven which Is ramped from ambient to 120*C, held at 120"C for 2 hours, ramped to 350 0 C over a two hour period and held at 350'C for an additional 2 hols. After cooling to ambient, the calcined powder is again transferred to 5 the impregnation vessel. To 1SSg of a second charge of the saturated cobalt solution, 1.7g of a 13.5% Ru solution of Ru(NO)(NO)h is added. This second imprgntion solution is again applied to the substrate in the tumbling impregator and dried and calcined as following the first pass, Example 8 - Prearadon of Catalyst Samole 8 10 MSA reagent solution was prepared with 68g TEOS rapidly added to 2L of acidified deomineralized water under vigorous stirring. Sufficient HNOs was added to the water to bring the pH to between 2.2 and 2.5 and held between 39C and B"C. IS minutes after TEOS addition, an aliquot was removed and the rate of color change tasted, Greater than 90% of the full color developed within 5 miutes. In a separate stihrd, 15 heated vessel, a slurry of the alumina support containing 300Sg alumina suspended in IL of demineralized water was heated. The slurry was held at 50*t5C throughout the addition of the MSA reagent, which was added at a rate of 15ml/min. Following completion of the MSA addition, the slurry was stirred and kept at 50%S'C until >95% of the silicon was reacted with the alumina. Once reaction was complete, stirring was 20 stopped, the solids allowed to aettlo, and the clear mother liquor decanted from the vessel. The remaining dense slurry was vacuum filtered to renovo the remainder of the solution. The filtered solid was spread onto a drying tray to a thickness less than 1.5cm and dried 6 h In a station muffle furnace held at 1401C. This dried powder was then caloined in a dish at 60 0 *C for 4 hours. 25 Catalyst was prepared to have a nominal composition of 20%Co, I%La, and 0,10%Ru in the calcined form. 200g of the Si-modifted catalyst support were charged to a steam-jacketed, rotating impregnatiou vessel. A saturated solution prepared from Co(NOs)6H2O and dominemlized water was prepared in advance. 172.5g of this saturated Co solution was used for the Arst imprgnation pass. 6.25g of La(NO )-6140 30 were dissolved in 20g of demineralized water and combined with the Co solution. The amount of solution was selected so as to produce sad incipiently wet powder when applied to the support in the rotating vessel. The Imprognated powder is allowed to tumble in the imprognator for ono hour at ambient temperatures and then steamed to 22 dryness over a three hour period. The powder is cooled to ambient, weighed, and transferred to shalbw calcining dishes such that the powder depth is s2cm. The dishes are placed into an electrically heated oven which Is ramped flom ambient to 120*C, held at 120*C for 2 houas, rarnped to 350'C over a two hour period and held at 350*C for an 5 additional 2 hours. After cooling to ambient, the caloined powder is again transferred to the impegnation veas cl. To 188g of a second charge of the saturated cobalt solution, 1.78g of a 13.5% Xv solution of Ro(NO)(NO3) 3 is added: This second impregnatioA solution Is again applied to the substrata in the tumbling impregnator and dried and calcined as following the firt pass. 10 L=naple 9.- PreRanatio of Catalvat Sample 9 MSA reagemt solution was prepared with 27.88 TBOS rapidly added to 1.33L of acidified deminertlied water under vigorous atirning. $uffliient HNO 3 was added to the water to bring the pH io between 2.2 and 2,5 and held between 3C and M*C. 15 minutes after TEOS additloa, an oliquot was removed and the rate of color change tested. 15 Greater than 90% of the M color developed within 5 minutes. This MSA solution was kept cold and held for -60 hrs. In a separate stirred, heated venel, a sluny of tho alumina support containing 200g alumina suspended in 667=1 of demineralized water was heated. Tte slurry was held at 5015*C throughout the addition of the aged MSA reagent, which was add-ed at a rate of 15ml/min. The mixture was stirred and kept at 20 50'5"C until >95% of the silicon was reacted with the alumina. Onco reaction was complete, stiring was stopped, the solids allowed to settle, and the clear mother liquor decanted front the vessae. The remaining denso slurry was vacuum filtered to remove tb remainder of the soludon. Tho filtered solid was spread onto a drying tray to a thickoes less than 1.5cm and dried 6 h in a static muffle futnace held at 140C. This dried powder 25 was then calcined in a dish at 600'C for 4 hours, Catalyst was pwapared to'have a nominal composition of 20%Co, I%La, and 0.1%Ru in the calciaed fnm, 160g of the Si-modificd catalyst support were charged to a steam-jacketed, rotating impregnation vessel, A saturated solution prepared from Co(NOj)h6H 4 O and domineralized water was prepared in advance, 138g of this 30 saturated Co solution was osed for the first impregnation pass. 5.00g of La(NO 3 )3-6HO were dissolved in 15g of deminerlized water and combined with the Co solution. The amount of solution as selected so as to produce and incipiently wet powder when applied to the support in the rotating vessel. The impregnated powder is allowed to 23 tumble in the impregnator for one hour at ambient temperatures and then steamed to dryness over a three hour period. The powder is cooled to ambient, weighed, and transferred to shallow calcining dishes such that the powder depth is 52cm. The dishes am placed Into an electrically beated oven which is ramped from amblent to 120*C, held 5 at 120'C for 2 hours, ramped to 350"C over a two hour period and held at 350'C for an additional 2 hours, After cooling to tabicnt, the calcined powder is again transferred to the impregnation vessel. To 151g of a second charge of the saturated cobalt solution, 1.44g of a 13.5% Ru solution of Ru(NO)(NO 3

)

3 is added. This second imprognation solution is again applied to the substrate in the tumbling impregnator and dried and 10 calcined as following the first pass. Bxample 10 - Preparation of Catalyst Samole 10 MSA reagent solution was prepared with 29.g TEOS rapidly added to 267m] of acidified demineralized water under vigorous stirring. Sufficient ENO) was added to the water to bring the pH to between 2.2 and 2.5 and held between 3*C and 8'C. 15 minutes 15 after TEOS addition, an aliquot was removed and the rate of color change tested. Greater than 90% of the Ml color developed within 5 minutes. In a separate stirred, heated vessel, a slurry of the alumina support containing 200g alurnina suspended in 667 mi of demneralized water was heated. The slurry was held at S55*C throughout the addition of the MSA reagent, which was added at a rate of 5mI/Uin. Following 20 completion of the MSA addition, the slurry was stirred and kept at 5045*C until >95% of the silicon was reacted with the alumina. Once reaction was complete, stirring was stopped, the solids allowed to settle, and the clear mother liquor decanted from the vessel. The remaining dense slurry was vacuum fatered to remove the remainder of the solution. The filtered solid was spread onto a drying tray to a thickness less than 1,5cm 25 and dried 6 h ii a static muffle furnace held at 140'C. This dried powder was then calcined in a dish at 600C for 4 hours. Catalyst was prepared to have a nominal composition of 20oCo, WLa, and 0.1%Ru in the calcined for. 200g of the Si-modined catalyst support were charged to a steam-jacketed, rotating impregnation vessel. A saturated solution prepared from 30 Co(NO) 2 6H 2 0 and demineralized water was prepared in advance, 172 .SS of this saturated Co solution was used for the first impregnation pass. 6.25g of La(NO3)r6H120 wore dissolved in 20g of demineralized water and combined with the Co solution, The amount of solution was selected so as to produce and incipiently wet powder when 24 applied to the support in the rotating vessel. The impregnated powder is allowed to tumble in the impregnator for one hour at ambient temperatures and then steamed to dryness over a three hour period. The powder is cooled to ambient, weighed, and transferred to shallow calcining dishes such that the powder depth is $2cm. The dishes 5 are placed into an electrically heated oven which is romped from ambient to 120"C, held at 120"C for 2 hours, ramped to 350'C over a two hour period and held at 350*C for an additional 2 ours. After cooling to ambient, the calcined powder is again transfod to the impregnation vessel. To IM4g of a second charge of the saturated cobalt solution, 1.78g of a 13.5% Ru solution of Ru(NO)(NO3)s is added. This second impregnation 10 solution is again applied to the substrate in the tumbling impregnator and dried and caloined as following the first pass. The catalysts produced in examples 1-10 were examined for attrition resistance according to the following method. The catalyst was activated using hydrogen gas and 20cc of the activated catalyst ire loaded into a 0.5 L CSTR and brought to synthosie 15 conditions at 410F, 300psi, GHSV 8000/hr and a stirrer speed of 1000 rpm. After 50 hours of synthesis operation, conditions are adjusted to 420*F, 400psi, G1SV 8000/hr and 4 stiner spood of 2000rpm. This condition is maintained for 150 hour. At the completion of a CSTR attrition test, the reactor is switched to a nitrogen purge and cooled to about 250"P. It is hold under these conditions for about 24 hours, during which 20 time whole catalyst and larger attrition fragments settle to the bottom of the reactor but fino attrition fragments remain suspended in the wax. The wax is then cooled until solid and rmoved from the reactor as a single plug. The catalyst-containing wax plug of the settled fraction can be separated from the overhead wax which contains the unsettled, smaller attrition-produced catalyst fragments. Once separated, the overhead wax fraction 25 is granulated and homogenized after which a representative sample is taken. This representative fraction is placed into a pyrox beaker, placed into an oven held at betwoon about 280 to about 320*F and allowed to melt. A pyrex filtration system with a vacuum receiver Is also heated to the oven temperature. The wax is filtered first through a Spm filter, the collected liquid then filtered through a 0.45pm filter, with the collected liquid 30 filtered a final time through a 0.1pm filter. At each stage of filtration, a small amount of clean isopar solvent is used to sweep all of the material from the bottom of the vessel. At the conclusion of filtration, the nitrate residual solids content is determined by eshing. The filtered solids are separated from the filter papers using a solvent in an ultrasonic bath. The solids-bearing solvent is centrifuged to concentrate the solids which a finally 25 collected, dried, and weighed. These masses oa referenced to the original mass of catalyst loaded into the reactor and the results are shown in the Table contained in Fig. 4. ExaRmple - Reaction ofMSA with Alumina d67 ml of domineralized water was acidified with HNO 3 to pH=2.0 and cooled to 5 less than 8*C with an ice bath. 74.63g of TBOS were added to the acidified water with vigorous stirring. The rate of color change was tested after 15 minutes of mixing and showed >90% of maximum color within 5 mimttes. In a separate vessel, 333ml of dcmineralized water were combined with 100g of Sasol Chemical SCCa-301 40 alumina and heated to 50C while mixing with an overhead mixer. The silicic acid reagent was 10 added to the alumina slurry using a peristaltic pump over a period of 135 minutes. After three bours of mixing, the amount of unreacted silcic acid was found to be 35% of the inidal charge. Care must be taken In this measurement to allow for the depolymerization of somewhat larger polymers of silicio acid, This higher degee of polymerization is brought about by the higher concentration of unreacted silicic acid, elevated temperature, 15 and shift of pH from the point of optimal stability in this saturation preparation. The resulting deposition was self-limiting to about 5,7% Si on the calcired alumina. Comparative Exmplo I - Reaction of MSA with Silica 667 ml of demineralized water was acidified with HNO 3 to pH=2.0 and cooled to less than 8"C with an ice bath. )3.9g of TEOS was added to the acidified water with 20 vigorous stirring. The rate of color change was tested after 15 minutes of mixing and showed >90% of maximum color within 5 minutes. In a separate vessel, 333nl of demimeralized water was combined with IOg of silica gel (Davisil Grade 64b type 150S, available ftom Davison Catalysts) and heated to 50*C while mixing with an overhead mixer. A background test of silicio acid formed in the slurry was done using the 25 molybdata color change test. The silicie acid reagent was added to the silica slurry using a peristaltic pump over a period of 60 minutes. A first test of unreacted siliO was done after one'hour of mixing. From this test, it was determined that the brkground color change fron the silica in water slurry contributed less than 5% of the total color change at thAt point. The amount of unreacted silicic acid remaining was determined hourly for 30 a total of three hours, at which point 75% of the siliic acid remained umtected in the solution. This resulting deposition was self-limiting to less than 0.5% Si on the caloined silica.

26 ConMartive Example 2 -Reaction of MSA with Titania 667 ml of demineralized water was acidified with HNOj to pWH2,0 and cooled to less than 8TC with an icc bath. 13.9g of TEOS webr added to the acidified water with vigorous stirring. The rate of color change was tested after 15 minutes of mixing and 5 showed >90% of maximum color within 5 minutes, In a separate vessel, 333ml of domineralized water was combined with 100g of titaia (Titania Type 'P-25, available from Degussa AG) and heated to 50*C while mixing with an overhead mixer. The silicio acid reagent was added to the titania slurry using a peristaltic pump over a period of 60 minutes. A first test of unreacted silica was done after one hour of mixing, indicating 10 57% of the alicio acid remained unrectod. After three hours of ridxing, the amount of unreacted silicio acid was found to be 36% of the original charge, This resulting deposition was solf-lsniting to slightly under 1% Si on the calcined titania. Comnarative Bxample 3 and Examplc I )A - Deangreated ninma alumia A semiworks batch of catalyst, Example L lA, was prepared on a Sasol Chemical 15 SCCa-30/140 alumina whieb had been modified to contain 3.0 Si/nm 2 . A semiworks batch of catalyst, Comparative Example 3, was prepared on an unmodified Sasol Chemical SCCO-30/140 alumina. Example 11 A was run in a proprietary Fischer Tropsch synthesis in a 36inch siry bubble column reactor. Three runs using Comparative Example 3 were made, one each in 42 inch, 36 inch, and 6 inch slurry 20 bubble columns using a proipietary Fiscber-Tropsch synthesis. Wax samples were obtained at the filterd product outlet and analyzed for deaggregated alumina at comparable time on stream of 45 days. The results arc given in Table I below. The deaggregated gammn alumina particles were separated from other Fiseher-Tropsch catalyst attrition solids using a progressive filtration method, The wax sample is placed 25 into a pyrex beaker, placed into an oven held at between about 280 and about 320"F and allowed to melt. A pyrex filtration system with a vacuum receiver is also heated to oven temperature. The melted wax is subjected to a series of progressive filtrations using 5pm, 0.

4 5pm, and 0.lpm pass filters, sequentially. A final filtration is done using an Anodisc aluminum oxide filter membrane with a pass size of 0.02pm. At each stage of 30 filtration, a anll amount of clean isopar solvent is used to sweep all of the material from the bottom of the vessel. The final filtrate is then ashad according to ASTM-486 and the deaggregatod particulate content determined.

27 Table 1. Sample Reactor Deaggregate Particulates Comparative Example 3 42 inch 1700 ppm Comparative Example 3 36 inch 700 ppm Comparative Bxample 3 6 inch 1400 ppm Example IIA 36 inch < 10 ppm Example 12- Distribudon of Si within the alundna bead Alumina support obtained from Sasol Chemical sold under the designation 5 SCCa-30/140 is a spray-dried material consisting of spheroidal particls between 25pm and 100pm in diameter. To determine the profile of the SI within or on the support particles after treatment with the monosiliclo acid rcagent, samples of modified support were embedded in a polymer matrix mounted to a microscope slide and polished so as to reveal exposed cross-soadona of whole particles. The polished slide wae than examined 10 with an SEM and sections along the diameter of several beads analyzed using energy dispersive X-ray analysis. When measured across many beads of different diameter, the Si/Al signal ratio was found to vary by roughly 10%, approximately consistent with the expected variability of the teolmique. Slightly higher Si/Al ratios, by approximately 15%, based on the average of several interior points on several beads, were observed at 15 the extreme exterior edge of the beads. From these observations wo conclude that the rate of reaction between the monoailcio acid and the alumina surfacO is sufficiently slow to allow for the diffusion of the reagent to all points within the beads. Exarple 13 - urface Si erichment in polymediad silicia acid reagant The supports produced by the methods of examples 4 and 5, prior to any further 20 treatment to form the catalyst particles, were analyzed using X-ray photoelectron spectroscopy (XPS). Each of the supports of examples 4 and 5 were mnodified to give 0.8% Si on the calcined support. The modified support of example 5 was prepared immediately upon preparation of the MSA reagent whereas the MSA used to produce the modified support of example 4 was first aged about 60 hours before reacting it with the 25 alumina support. The rate of color change of the aged solution used to prepare the modified support of example 4 indicated that the silica had polymerized to a very high degree. XPS is'extreincly surface sensitive, providing information about the superficial 2g surface in a layer roughly Sm deep. The catalyst beads were examined without supplemental preparation so as to restrict the analysis to only the true exterior surfaco of the beads. The Si/Al signal ratio was found to be 60% higher in the modified support of example 4 than in the modified support of example 5, indication that the polymerized 5 siliclo acid was unable to penetrate the entire support particle before reacting with the alumina. As can be seen In the Tablo attached in Fig. 4, the modified support example 4 io less effective at mitigating attrition than the modified support of example 5. Example 14--Retained Attrition Rkesistance with Regeneration 200g of Sasol Puralex SCCa-30/140 alumina was charged into a steam jacketed 10 impregnation vessel. 37.04S TEOS was added to 75cc ethanol. The TEOS/EtOH mixture was added drop-wise to the alumina in the impregnation vessel. The mixture was allowed to mix at ambient temperature for I hour. Steam drying was started and continued for 3 hour, The alumina mixture was cooled and then transferred to ceramic calcining dishes. The alumina bed depth was <1.5 cm. he alumina was put into a static 15 muffle furnace and ramped to 140*C over -30 mins, ne alumina was held for 2 hours at 140*C. This dried powder was then ramped to 600 0 C and calrined for 4 hours, This support rnaterial contained 2,5 Si/nu2. Catalyst was prepared to have a nominal composition of 20%Co, l%I.a, and 0.1%Ru in the calcined form. 100g of the Si-modified catalyst support were charged to a 20 steam-jacketed, rotating impregnation vessel. A sntumted solution prepared from Co(N0 3 )r6H20 and dominteralized water was prepared in advance, 70.8g of this saturated Co solution was used forthe ferst impregnation pass. 3.13g of La(NO 3

)

3 6H 2 O were dissolved in lOg of domineralized water and combined with the Co solution. The amount of solution was selected so as to produce an incipiently wet powder when 25 applied to the support in the rotating vessel. The impregnated powder is allowed to tumble in the impregnator for one hour at ambient temperatures and then steamed to dryness over a three hour period, The powder Is cooled to ambient, weighed, and transferred to shallow calcining dishes such that the powder depth is 2cm. The dishes ar placed into an electrically heated oven which is ramped from ambient to 120*C, held 30 at 120*C for 2 hours, ramped to 350"C over a two hour period and held at 350*C for an additional 2 houn. After cooling to ambient, the calcined powder is again transferrd to the impregnation vessel. To 106.7g of a second charge of the saturated cobalt solution, 0.9g of a 13,5% Ru solution of Ru(NO)(NO 3

)

3 is added. This second impregnation shiution is again applied to the substrate in the tumbling impregnator and dried and calcined as following the first pass. An initial 80cc charge of catalyst prepared on a support treated with TOS/EtOH, as described above i this Example, was run in a 1 liter CSTR under typical FT synthesis 5 conditions, adjusting temperature and GHSV in order to maintain conversion above 55%. Following in initial operating period of 2000 hour, the catalyst was rgnerated in accordanco with procedures described in US, Patent No. 6,812,179. The regenerated charge was again operted for 2000 bours and again regenerated. Following a third operating pedod of 2000 hours, the catalyst was recovered, dewaxed, and the particle 10 size distribution measured. Thc tridaily loaded catalyst bad a distribution with >99% of the particles larger than 2Opm in diameter, After the 6000 operating hours and 2 regenerations, the recovered catalyst still exhibited no detectable fine, still with >99% of the particles larger than 20pm. An itial 80cc charge of catalyst prepared on a support treated with MSA so as 15 to deposit 3.0 Si/nm 2 , was run in a I liter CSTR under typical PT synthesis conditions, adjusting temperatum and GIHSV in order to maintain conversion above 55%. Following an initial operating period of 2000 hours, the catalyst was regenerated in accordance with procedures described in U.S. Patent No. 6,812,179. The regenerated charge was again operated for 2000 hours and agin regenerated. Following a third opemting period of 20 1800 hours, the catalyst was recovered, dewaxed, and the particle size distribution measured. The initially loaded catalyst had a distribution with >99% of the particles larger than 20pm in diameter. After the 5800 operating bours and 2 regenerations, the recovered catalyst still exhibited no detectable fnes, with >99% of the particles larger than 20pm. 25 Exanmpe IS - Prepartion of Catalyst Sample 15 C(TES/BtOH method) 350g of Sasol SCCa-30/140 alnmina was charged into a steam jacketed impregnation vessel. 25.98 TEOS was added to 168cc ethanol. The TBOS/EIOH mixture was added drop-wise to the alumian in the impregnation vessel. The inixtue was allowed to mix at ambient temperature for I hour. Sean drying was started and 30 continued for 3 hours. The alumina mixture was cooled and then transferred to ceramic calcining dishes. The alumina bed depth was <1.5 cm. The alumina was put into a static muftie furnace and ramped to 1400C over -30 mins. The alumina was held for 2 hours at 1400C. This dried powder was then ramped to 600"C and calcined for 4 hours.

30 Catalyst was prepared to have a nominal composition of 20%Co and 0.1%Ru in the calcined form. 200g of the Si-modified catalyst support were charged to a eteam jacketed, rotating impregation vessel. A sarwated solution prepared frm Co(NO)a6H20 and dormineralized water was prepared in advance, 172.45g of this 5 saturated Co solution was used for the first impregnation pass. The amount of solution woe selected so ca to produce an incipiently wet powder when applied to the support in the rotating vessel. The impregnated powder is allowed to tumble in the impregnator for one hour at ambient temperatues and then steamed to dryness over a three hour period. The powder is cooled to ambient, weighed, and transfered to shallow calcining dishes 10 such that the powder depth Is 42cm. The dishes are placed Into an electrically heated oven which is ramped from ambient to 120"C, held at 120"C for 2 hours, ramped to 350'C over a two hour period and held at 350C for an additional 2 hours. After cooling to ambient, the calcined powder is again transferred to the impregnation vessel. To 176.67g of a second charge of the saturated cobalt solution, 1.75g of a 13.5% Ru solution 15 of Ru(NO)(NO3) 3 is added. This second impregnation solution is again applied to the substrate in the tumb]iAg impregnator and dried and calcined as following the first pass. Example 16- Dispersion of Si on the Alumina Surface throgb XPS Since the iicic acid is prone to polymerize, a question arises as to the possibility that higher oligomers begin to form as the concentration of Si on the alumina surface is 20 increased. X-ray photoelectron spectroscopy (XPS) can be used to address this quc'stion. Since the signal observed by XPS derives from the outermost surface exposed to the excitation X-ray beam, usually 3-5m in depth, it is well suited to detect such changes in morpbology. Even in the event that a single layer structure converts to a two layer structure, the second layer signal will be attenuated relative to the signal from the first 25 layer. Consequently, a ratio of the observed Si/Al ratio as a function of aurface coverage should abow a deviation toward diminishing SI/Al detected as layered structure form, even if these layered stmuctumas are islands and not contiguous surfaces. Since XPS is so superficial surface sensitive, the interior surfaces of the support needs to be made available for analysis. This was accomplished through mechanical 30 grinding of the calcined supports followed by sieving through a 20pm opening sIev, Particles fractued to be smaller than this dimension must expose a relatively high proportion of interior surface.

31 Figue 5 shows the change in Si/Al ratio observed for samples with nominal Si loadings ranging from 0.3 Si/wun through 6.2 Si/nm 2 . The high degree of linearity clearly indicates that the morphology of the SiO% entities formed at the lowest, 0.3 Si/ni, Si concentration am the same as those formed at the highest concentration, 6.2 5 Shem. These observations indioato that the SiO 2 deposited most likely binds a individual entities in a single layer on the A1 2 0 surface. Example I-Tetgm Evidecie for UniforM Deposition Nitrogen adsorption ean be used to monitor change in surface area, pore volume, and avcMge pore diameter as a function of Si loading onto the alumina surface. In the 10 event that polymeric entities begin to form, blockage of pores can occur, resulting in a discontinuous change in pore volume with increased loading. Similarly, blockages change the effective average poro diameter. The followhig table shows the textual data obtained at several different nominal Si loadings. All three texturnl parameters show continuous behavior, particularly the average pore diam ter, consistent with a continuous 15 deposition of SiO2 onto the alumina surface. Surface BJI DesorptIon N 2 Pore BJH DesorptIon Average Pore Sample Ares m/g Volume(c/g) Diameter(nm) unmodIflod 140.49 0.44 8.28 3.1 Si/vrnron 301140 138.4 0.41 8.42 4.6 Si/nr2 301140 133.15 0.38 7.84 6.2 Si/nm 2 on 30/140 135.6 0.37 7.67 8.5 Si/mron 301140 139.3 0.3- 7.08 8.8 Si/2nn on 30/140 142.08 0.32 6.75 While the invention has been described with a Limited number of embodiments, thoso specific embodiments are not intended to limit the se"pe of the invention as otherwise described and claimed herein. Modification and variations from the described embodiments exist. A person of ordinary skill in the art recognizes parameters for the 20 formation of semiconductor materials processes may vary, for example, in temperature, pressure, gas flow rates, and so on. Therefore, materials -which do not fulfill the selection criteria under one set of process conditions may nevertheless be used in embodiments of the invention under another set of process conditions. The incorporation of additional elements may result in beneficial properties which are not otherwise 32 available. Also, while the processes are described as comprising one or more steps, it should be understood that these steps may be practiced in any order or sequence unless otherwise indicated. These steps may be combined or separated. Finally, any number disclosed herein should be construed to mean approximate, regardless of whether the word "about" or 5 "approximate" is used in describing the number. The appended claims intend to cover all such variations and modifications as falling within the scope of the invention. Where the terms "comprise", "comprises" or "comprising" are used in this specification (including the claims) they are to be interpreted as specifying the presence of the stated features, integers, steps or components, but not precluding the presence of one or more 10 other features, integers, steps or components, or group thereof. 15 20

Claims

1. A catalyst composition comprising: a support material having between about 0.1 Si/nm2 support surface area and 5 about 1.9 Si/nm 2 support surface area deposited thereon wherein the Si atoms from an aqueous acidic solution are bound directly to the support material through an oxygen atom such that the support material exhibits attrition resistance. 10

2. The catalyst composition of claim I wherein the silicon is deposited on the support material at a concentration of between about 0.55 Si/nm 2 and about 1.75 Si/nm 2 .

3. The catalyst composition of claim I wherein the silicon is deposited on the support material at a concentration of between about 0.7 Si/nm 2 and about 1.5 Si/nm 2 . 15

4. The catalyst composition of any one of claims I to 3 wherein the support material is selected from the group of gamma alumina, eta alumina, theta alumina, delta alumina, rho alumina, anatase titania, futile titania, magnesia, zirconia, refractory oxides of Groups Ill, IV, V, VI and VIII elements and mixtures thereof. 20

5. The catalyst composition of claim 4 wherein the support material is aggregated gamma alumina.

6. The catalyst composition of claim 4 wherein the support material is alumina-bound 25 titania.

7. The catalyst composition of any one of claims I to 6 wherein the catalyst has been regenerated. 30

8. The catalyst composition of any one of claims 1 to 6 wherein the support material is preformed.

9. The catalyst composition of any one of claims I to 8 further comprising: 34 between about 12 wt % and about 30 wt % Co; between about 0.5 wt % and about 2 wt % of a first additive selected from the group of Ca, Sc, Ba, La, and Hf; between about 0.03 wt % and about 0.3 wt % of a second additive selected from the group of Ru, Rh, Pd, Re, Ir, and Pt. 5

10. The catalyst composition of any one of claims I to 8 further comprising: between about 12 wt % and about 30 wt % Co; between about 0.5 wt % and about 2 wt % La; and between about 0.03 wt % and about 0.3 wt % Ru. 10

11. A catalyst composition comprising: a support material having between about 0.1 Si/nm2 support surface area and about 1.9 Si/nm 2 support surface area deposited thereon wherein less than about 10 wt % of the silicon is in polymeric form. 15

12. The catalyst composition of claim 11 wherein the silicon is deposited on the support material at a concentration of between about 0.55 Si/nm 2 and about 1.75 Si/nm 2

13. The catalyst composition of claim 11 wherein the silicon is deposited on the support material at a concentration of between about 0.7 Si/nm 2 and about 1.5 Si/nm 2 20

14. The catalyst composition of any one of claims 11 to 13 wherein the support material is selected from the group of gamma alumina, eta alumina, theta alumina, delta alumina, rho alumina, anatase titania, rutile titania, magnesia, zirconia, refractory oxides of Groups III, IV, V, VI and VIII elements and mixtures thereof. 25

15. The catalyst composition of claim 14 wherein the support material is aggregated gamma alumina.

16. The catalyst composition of claim 14 wherein the support material is alumina-bound 30 titania.

17. The catalyst composition of any one of claims 11 to 16 wherein less than about 5 wt % of the silicon is present in polymeric form. 35

18. The catalyst composition of any one of claims I1 to 16 wherein less than about 2.5 wt % of the silicon is in polymeric form.

19. The catalyst composition of any one of claims 11 to 18 wherein the catalyst has been 5 regenerated.

20. The catalyst composition of any one of claims 11 to 18 wherein the support material is preformed. 10

21. The catalyst composition of any one of claims 11 to 20 further comprising: between about 12 wt % and about 30 wt % Co; between about 0.5 wt % and about 2 wt % of a first additive selected from the group of Ca, Sc, Ba, La, and Hf; between about 0.03 wt % and about 0.3 wt % of a second additive selected from the group of Ru, Rh, Pd, Re, Ir, and Pt. 15

22. The catalyst composition of any one of claims 11 to 20 further comprising: between about 12 wt % and about 30 wt % Co; between about 0.5 wt % and about 2 wt % La; and between about 0.03 wt % and about 0.3 wt % of Ru. 20

23. A method of treating a catalyst support, comprising: contacting a support material with an attrition-suppressing composition comprising monosilicic acid thereby to provide a treated catalyst support material having between about 0.1 Si/nm 2 support surface area and about 1.9 Si/nm 2 support surface area deposited thereon wherein the Si atoms from an 25 aqueous acidic solution are bound directly to the support material through an oxygen atom such that the support material exhibits attrition resistance.

24. The method according to claim 23, wherein the attrition-suppressing composition comprises between about 0.02% and about 6.9% by weight of Si. 30

25. The method according to claim 23 wherein the attrition-suppressing composition comprises between about 0.2% and about 6.9% by weight of Si. 36

26. The method according to any one of claims 23 to 25 wherein the attrition-suppressing composition is prepared by contacting a silicate with water under acidic conditions.

27. The method according to claim 26 wherein the silicate comprises monosilicic acid. 5

28. The method according to claim 27 wherein the monosilicic acid is prepared by contacting tetraethoxysilane with water under acidic conditions.

29. The method according to claim 26, wherein the silicate is sodium orthosilicate or 10 sodium metasilicate and the pH ranges from about 1.5 to about 3.5 at a temperature ranging from about 0*C to about 5*C.

30. The method according to any one of claims 26 to 29 wherein the attrition-suppressing composition is added to the catalyst support at a temperature ranging from about 0*C 15 to about 95*C.

31. The method according to any one of claims 26 to 29 wherein the temperature ranges from about 00C to about 10C. 20

32. The method according to claim 23, wherein the attrition-suppressing composition comprises a polysilicic acid species wherein concentration of monosilicic acid is greater than the concentration of trisilicic acid and higher polymers of the silicic acid.

33. The method according to claim 27 wherein the monosilicic acid is the predominant 25 silicic acid species in the attrition-suppressing composition.

34. The method of any one of claims 23 to 33 wherein the support material is preformed.

35. A catalyst composition comprising: 30 a support material having between about 0.1 Si/nm 2 support surface area and about 1.9 Si/nm 2 support surface area deposited thereon wherein the Si atoms from an aqueous solution are bound directly to the support material through an oxygen atom such that the support material exhibits attrition resistance, 37 substantially as herein described with reference to the Examples, excluding the Comparative Examples.

36. A method of treating a catalyst support, comprising: 5 contacting a support material with an attrition-suppressing composition comprising monosilicic acid thereby to provide a treated catalyst support material having between about 0.1 Si/nm 2 support surface area and about 1.9 Si/nm 2 support surface area deposited thereon wherein the Si atoms from an aqueous acidic solution are bound directly to the support material through an 10 oxygen atom such that the support material exhibits attrition resistance, substantially as herein described with reference to the Examples, excluding the Comparative Examples. 15