WO2008060979A2 - Composition de catalyseur composé - Google Patents

Composition de catalyseur composé Download PDF

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Publication number
WO2008060979A2
WO2008060979A2 PCT/US2007/084211 US2007084211W WO2008060979A2 WO 2008060979 A2 WO2008060979 A2 WO 2008060979A2 US 2007084211 W US2007084211 W US 2007084211W WO 2008060979 A2 WO2008060979 A2 WO 2008060979A2
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Prior art keywords
glass
catalyst composition
iex
substrate
treatment
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PCT/US2007/084211
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WO2008060979A3 (fr
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Dean E. Rende
Robert L. Bedard
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Uop Llc
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Publication of WO2008060979A3 publication Critical patent/WO2008060979A3/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/08—Silica
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/12—Silica and alumina
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/30—Tungsten
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/42—Platinum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/48—Silver or gold
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/75—Cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/58—Fabrics or filaments
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0207—Pretreatment of the support
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/06—Washing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/28—Phosphorising
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/30—Ion-exchange
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/26—Chromium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/32—Manganese, technetium or rhenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/72—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/394—Metal dispersion value, e.g. percentage or fraction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/396—Distribution of the active metal ingredient
    • B01J35/397—Egg shell like
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/612—Surface area less than 10 m2/g

Definitions

  • This invention relates to a compound catalyst composition, and its method of making and manufacture, useful for a diversity of chemical production processes as well as various emission control processes. More specifically, it relates to a compound catalyst composition comprising a refractory oxide and a precursor catalyst composition.
  • the precursor catalyst composition is a functional surface catalyst (FSC) composition.
  • Catalyst compositions are used to promote a class of chemical reactions generally described as catalytic reactions or catalysis. Catalysis is important to efficiently operating a wide range of chemical processes.
  • solid, supported catalysts used in heterogeneous catalysis reactions, represent about $3 billion/year worldwide market.
  • Solid, supported catalysts generally fall in three groups, petroleum refining, chemical processing and emission control catalysts. Between these three classes of catalyst markets, sales are roughly split in thirds. For example, in 1990, of the $1.8 billion U.S. solid catalyst market, petroleum refining, chemical processing and emission control catalysts comprised 37%, 34% and 29% of the market, respectively. And of the petroleum refining catalyst market, for example, (about $1 billion in 1990) 56% of revenue came from fluid catalytic cracking (FCC) catalysts, while 31.5%, 6.5% and 4.5% of revenue came from hydrotreating, hydrocracking and reforming catalysts, respectively.
  • FCC fluid catalytic cracking
  • a catalyst From a chemical mechanism standpoint, without being substantially consumed itself, a catalyst generally works to increase the rate at which a chemical reaction reaches a state of equilibrium between reactants and products. So, although a catalyst cannot alter the state of equilibrium between reactants and product, for any given reaction of interest, it can, if properly designed and/or selected, accelerate the rate of chemical reactions. [0006] Consequently, catalysts are used in a wide range of commercially useful processes for an array of purposes including improving the reactivity, selectivity, and energy efficiency of the process, among other purposes.
  • improving the rate of reaction or reactivity of reactants to produce the desired product(s) under specified process conditions can reduce processing time, so higher product throughputs (e.g., increased product volume or mass per unit hour) can be obtained.
  • catalyst activity indicates the catalyst composition's ability to effectively convert reactants to the desired product(s) per unit time.
  • improving reaction selectivity can improve the percentage yield of desired product(s) across a range of possible, reaction products, some of which may be undesired and require further processing to either remove or convert, accordingly.
  • catalyst selectivity is the catalyst composition's ability to convert a fraction of reactant(s) to a particular product under specified process conditions.
  • catalyst compositions can be used to convert and reduce levels of contaminants or undesired reactants or products in a process. And still another purpose is to improve the overall energy efficiency of the reaction process, while either maintaining or improving product throughputs and/or reaction selectivity.
  • the scale at which catalysts can be used can vary widely.
  • catalysts can be used for reducing pollutant levels such as hydrocarbons, carbon monoxide (CO), nitrogen oxides (NO x ) and sulfur oxides (SO x ), which may be found in the emissions for a range of processes, from gasoline or diesel combustion exhausts of vehicles to assorted petroleum refining or coal-burning processes.
  • catalysts can be used in hydrocarbon treatment processes used for converting or modifying hydrocarbon process streams from many different sources including, for example, virgin petroleum fractions, recycle petroleum fractions, heavy oil, bitumen, shale, natural gas, among other carbon containing materials susceptible to catalytic reactions.
  • Catalytic reactions generally fall in one of two distinct classes of reaction types - homogeneous catalysis and heterogeneous catalysis.
  • Homogeneous catalysis broadly describes a class of catalytic reactions in which the reactants and catalyst are mixed together in a solution-phase, which is typically a liquid- phase system, though gas-phase catalytic reactions have been used in some cases. Consequently, concentration gradients and the transport of the reactants to the catalyst can become important considerations in controlling a homogeneous catalytic reaction. Also, in some instances "solution-phase" catalytic reactions can occur across the interface of two liquid phases, not forming a true solution, but rather an emulsion phase.
  • Some general categories of homogeneous catalysis include acid-base catalysis, organometallic catalysis and phase-transfer catalysis, among others.
  • Heterogeneous catalysis describes a class of catalytic reactions in which the reactants, in either a gas or liquid phase, are exposed to a catalyst that's in a substantially solid or semi-solid phase. So, in heterogeneous catalysis, the catalyst and reactants produce a mixed solid-liquid or solid-gas phase reaction.
  • Heterogeneous catalysis has a number of advantages versus homogeneous catalysis including, for example, the tendency for solid catalysts to (a) be less corrosive and hence present relatively lower safety and environmental risks versus many homogeneous solution- phase catalysts, (b) allow a wider range of economically viable temperature and pressure conditions and (c) allow better control of more strongly exothermic and endothermic chemical reactions, among other advantages.
  • a solid can have mass transport limitations that could significantly reduce the catalyst's ultimate effectiveness.
  • a solid catalyst (or catalyst particle, as it's sometimes called) comprises one or more catalytic constituents (e.g., a noble metal such as Pd, Pt, Ru, Re, etc.) on a porous material with very high internal surface areas, usually on the order of hundreds of square meters per gram, where the catalytic constituent resides.
  • a conventional catalyst composition or catalyst particle includes a particularly porous support with high internal surface area where the catalytic reaction occurs.
  • this type of catalyst structure can, and often does, create a mass transport limitation that can reduce the catalyst particle's effective performance, both with respect to catalyst activity and selectivity, among other catalyst performance issues.
  • the concentration of the reactant(s) in the pore structure is a maximum at the catalyst particle's periphery and minimum at its center.
  • the reaction product concentration will be higher at the catalyst particle's center than at its periphery.
  • These concentration gradients provide the driving force for the transport. The larger these concentration gradients become, the lower the rate of the catalytic reaction becomes.
  • the catalyst particle's effective performance e.g., reactivity, selectivity, life cycle between regeneration treatments, resistance to coking, etc.
  • catalyst compositions are developed to improve on one or more processing objectives like those noted above from a commercial standpoint.
  • one factor affecting catalyst performance is its ability to promote a rapid, but effective, reaction between reactants. Accordingly, a catalyst composition with reduced diffusion limitations is frequently desired. In other instances, however, selectivity towards producing particular products may be relatively more important so that the preferred product(s) are obtained. In turn, additional process steps and related processing equipment, used to remove or convert undesired reaction products, may be eliminated. [0015] For example, in 1976 YT. Shah et al.
  • the SGF was not susceptible to obtaining an increased surface area from acid-leaching so its surface area remained low at 2 m 2 /g versus EGF sample surface areas of 15 m 2 /g and 75 m 2 /g, respectively, used for supporting Pd as a catalytic constituent for a Pd-based catalyst composition.
  • Kiwi-Minsker et al. noted that the SGF/Pd catalyst had substantially the same effective surface concentration of Pd (millimoles of metal per m 2 ) as its EGF/Pd catalyst counterparts (i.e., about 0.1 mmol/m 2 ) and yet the SGF/Pd catalyst composition demonstrated a lower activity or reaction rate per gram of Pd vs. its EGF/Pd catalyst counterparts.
  • a compound catalyst composition comprising:
  • the substantially nonporous substrate has a total surface area, as measured by a method selected from the group consisting of S.A. N2 - BET , S.A. ⁇ r - ⁇ E7 - and combinations thereof, between about 0.01 nrVg and 10 m 2 /g; ii.
  • the at least one catalytically-active region may be contiguous or discontiguous and has a catalytically effective amount of the at least one catalytic constituent; and iii. the at least one catalytic constituent is dispersed substantially in or on the at least one precursor catalyst composition wherein the at least one first composition and the at least one second composition are intermixed after the at least one precursor catalyst composition is produced.
  • FIG. 1 is an XPS Sputter Depth Profile corresponding to each of four samples comprising Pd on/in an AR-glass substrate, wherein the Sputter Depth Profile is obtained using a PHI Quantum 200 Scanning ESCA MicroprobeTM (Physical Electronics, Inc.) with a micro-focused, monochromatized Al Ka X-ray source at 1486.7 eV.
  • FIG. 1 is an XPS Sputter Depth Profile corresponding to each of four samples comprising Pd on/in an AR-glass substrate, wherein the Sputter Depth Profile is obtained using a PHI Quantum 200 Scanning ESCA MicroprobeTM (Physical Electronics, Inc.) with a micro-focused, monochromatized Al Ka X-ray source at 1486.7 eV.
  • FIG. 1 is an XPS Sputter Depth Profile corresponding to each of four samples comprising Pd on/in an AR-glass substrate, wherein the Sputter Depth Profile is obtained using a PHI Quantum 200 Scanning ESCA Micro
  • FIG. 2 an XPS Sputter Depth Profile corresponding to each of three samples comprising Pd on/in an A-glass substrate, wherein, the Sputter Depth Profile obtained using a PHI Quantum 200 Scanning ESCA MicroprobeTM (Physical Electronics, Inc.) with a micro- focused, monochromatized Al Ka X-ray source at 1486.7 eV.
  • PHI Quantum 200 Scanning ESCA MicroprobeTM Physical Electronics, Inc.
  • STEM 4 are scanning transmission electron microscopy (STEM) images produced by a JEOL 3000F Field Emission TEM instrument operated at 300 kV accelerating voltage on a cross-sectioned portion sample of a precursor catalyst composition dispersed in a calcined gamma alumina base, wherein the precursor catalyst composition comprises a substantially nonporous glass substrate (e.g., leached A glass) with Pt particles generally dispersed within a distance less than or equal to about 30 nm from the surface of the precursor catalyst composition.
  • a substantially nonporous glass substrate e.g., leached A glass
  • FIG. 5 plots the toluene yield (wt.%) vs. the inverse flow rate (min/cc) for conversion of methylcyclohexane (MCH) to toluene using an extrudate sample of precursor catalyst composition in a gamma alumina, as a compounding refractory oxide, as compared to its activity before dispersion in the gamma alumina.
  • Pore means a cavity or channel that is deeper than it is wide.
  • Interconnected Pore means a pore that communicates with one or more other pores.
  • Closed Pore means a pore without any access to the external surface of the material in which the closed pore is located.
  • Open Pore means a pore with access, whether directly or via another pore or interconnected pore(s), to the external surface of a material in which the open pore is located (i.e., a pore that's not a closed pore).
  • Pore Width means an internal diameter or distance between opposite walls of a pore, as determined by a specified method.
  • Pore Volume means the total volume contribution of all pores excluding the volume contribution of closed pores, as determined by a specified method.
  • Porcity means the ratio of pore volume in a material to the overall volume occupied by the material.
  • Micropore means a pore of internal width less than 2 nanometers (nm).
  • Micropore means a pore of internal width in the range from 2 nm to 50 nm.
  • Micropore means a pore of internal width greater than 50 nm.
  • Extra Surface means the external boundary or skin (with a near-zero thickness) of a material including regular or irregular contours associated with defects, if any, on the external boundary or skin.
  • Pore Wall Surface means the internal boundary or skin (with near-zero thickness), including regular or irregular contours associated with defects, if any, on the internal boundary or skin, substantially defining the shape of any open pore in a material having at least one or more types of pore(s).
  • “Surface” means, collectively, a material's pore wall surface (if any open pores are present), the material's external surface and its surface region.
  • “Surface Region” means the region of material, excluding any region or regions defined by the material's open pores (if any open pores are present), which may vary depending on the material, but that is (a) less than or equal to 30 nm (preferably, ⁇ 20 nm and more preferably, ⁇ 10 nm) beneath a material's external surface and, to the extent any open pores are present in the material, that is (b) less than or equal to 30 nm (preferably, ⁇ 20 nm and more preferably, ⁇ 10 nm) beneath the material's pore wall surface.
  • Subsurface Region means the region of a material, excluding any region or regions defined by the material's open pores (if any open pores are present), which may vary depending on the material, but that is (a) greater than 30 nm (preferably, > 20 nm and more preferably, > 10 nm) beneath the material's external surface and, to the extent any open pores are present in the material, that is (b) greater than 30 nm beneath the material's pore wall surface (preferably, > 20 nm and more preferably, > 10 nm).
  • Internal Surface Area or "Open Pore Wall Surface Area” means the surface area contribution of all open pore walls in a material, as determined by a specified method.
  • External Surface Area means the surface area contribution of a material excluding the surface area contribution of all pore walls in the material, as determined by a specified method.
  • Total Surface Area means the sum of a material's internal surface area and its external surface area, as determined by a specified method.
  • V 1 is an initial volume of dilute NaOH titrant solution used to initially titrate an aqueous slurry mixture, comprising a substantially water-insoluble material in a 3.4M NaCI solution at about 25°C, from an initial pH 4.0 to pH 9.0 at time zero, t 0
  • V 5 to is is the total volume of the same strength NaOH titrant used to maintain the slurry mixture at pH 9 over a 15 minute period, adjusted, as needed and as rapidly as possible, at each of three 5 minute intervals, t 5 , t 10 and t 15 , accordingly.
  • the 3.4M NaCI solution is prepared by adding 30 g NaCI (reagent grade) to 150 ml. H 2 O and 1.5 g of the sample material is added to the NaCI solution to produce an aqueous slurry mixture.
  • the aqueous slurry mixture must be first adjusted to pH 4.0. Either a small amount of dilute acid (e.g., HCI) or base (e.g., NaOH) is used, accordingly, for this adjustment before titration begins with dilute NaOH titrant (e.g., 0.1 N or 0.01 N) for first obtaining V, and, thereafter, V 5 to i5 for making the SARC/va determination.
  • dilute NaOH titrant e.g., 0.1 N or 0.01 N
  • V 5 to i 5 is the cumulative volume of NaOH titrant used at t 5 , t 10 and t 15 , wherein the NaOH titrant used is titrated, as rapidly as possible, at each of three 5 minute intervals, to adjust, as needed, the slurry mixture's pH to 9.0 from t 0 to the final time at 15 minutes, t 15 .
  • SARC Wa is determined for a sample material prior to treatment by any optional ion exchange (IEX), back ion exchange (BIX) and/or electrostatic adsorption (EA) treatment method that may be used for integrating one or more Type-2 constituent precursors (described below) on and/or in the substrate surface.
  • IEX ion exchange
  • BIX back ion exchange
  • EA electrostatic adsorption
  • IEP isoelectric point
  • IEP Isoelectric Point
  • ZPC zero point charge
  • PZC point of zero charge
  • Catalytically Effective Amount means a mass of catalytic constituent(s) sufficient to convert, under suitable processing conditions, at least one reactant to at least one predetermined product in sufficient yield to support either a pilot plant or commercial- grade process.
  • Chalconide means a compound containing at least one Group 16 (formerly Group VIA) element from the group consisting of sulfur (S), selenium (Se) and tellurium (Te) and at least one element or radical that's more electropositive than its corresponding Group 16 element.
  • Noble Metal means a transition metal from the group of rhodium (Rh), palladium (Pd), silver (Ag), iridium (Ir), platinum (Pt) and gold (Au), each in a zero oxidation state (while in an unreacted state) unless otherwise indicated as having a charged state in the form of a metal complex, metal salt, metal cation or metal anion.
  • Corrosion Resistant Substrate means a substrate resistant to a substantial alteration in the substrate's compositional structure in its subsurface region, arising from alteration and/or loss of structural constituent elements, new pore production, pore size expansion and the like, by most acids or dilute bases under standard temperature and pressure conditions.
  • a corrosion resistant substrate's compositional structure might be substantially altered by high-strength acids (e.g., concentrated HF), bases (e.g., concentrated NaOH) or other highly corrosive reagents, whether alone or in combination with intense temperature, pressure and/or vibrational frequency conditions and still be considered “corrosion resistant” for purposes of this definition.
  • “Surface Active” means a state in which a material's surface is sufficiently charged with one or more charged constituents to either (i) promote a catalytic reaction under a steady state reaction condition, without further modification, or (ii) otherwise, is adaptable to further modification by either an electrostatic and/or ion exchange interaction with one or more charged constituents, which can subsequently function as catalytic constituent(s) under a steady state reaction condition.
  • Substrate means any solid or semi-solid material, including without limitation, glass and glass-like materials, with an IEP greater than 0 but less than or equal to 14, whose surface active state can be modified, as appropriate, for the substrate's intended use in a catalyst composition having a catalytically effective amount of catalytic constituent(s).
  • IEP greater than 0 but less than or equal to 14
  • IEP greater than 0 but less than or equal to 14
  • Surface active state can be modified, as appropriate, for the substrate's intended use in a catalyst composition having a catalytically effective amount of catalytic constituent(s).
  • “Integrate” means to associate, for example, a chemical constituent with a substrate through an electronic and/or physicochemical interaction such as, for example, ionic, electrostatic or covalent interactions, including, without limitation, hydrogen bonding, ionic bonding, electrostatic bonding, Van der Waals/dipole bonding, affinity bonding, covalent bonding and combinations thereof.
  • a compound catalyst composition (discussed more fully below) comprises at least one refractory oxide and at least one precursor catalyst composition having at least one catalytic constituent.
  • the precursor catalyst composition may be prepared by ion exchange, impregnation, precipitation, coprecipitation or other catalyst composition preparation methods to the extent the method produces a precursor catalyst composition in which at least one catalytic constituent remains dispersed substantially in and/or on the precursor catalyst composition after it is intermixed with the refractory inorganic oxide.
  • One aspect of the invention relates to a compound catalyst composition comprising a refractory inorganic oxide and a precursor catalyst composition having a substrate that is substantially nonporous, though materially insignificant amounts of micro-, meso-and/or macro-pore volume may exist without adversely affecting the catalyst composition's intended use.
  • the precursor catalyst composition is a functional surface catalyst composition ("FSC composition").
  • Another aspect of the invention relates to various methods of making the novel compound catalyst composition, preferably with a FSC composition.
  • Another aspect of the invention relates to using the catalyst composition in various processes, such as, for example, hydrocarbon, hetero-hydrocarbon and/or non- hydrocarbon treatment, conversion, refining and/or emission control and treatment processes, among other types of processes.
  • the novel compound catalyst composition can improve reaction selectivity, reaction rate, product yield and energy efficiency of hydrocarbon, hetero-hydrocarbon and/or non-hydrocarbon treatment, conversion, refining and/or emission control and treatment processes, among other types of processes.
  • the precursor catalyst composition has a substantially nonporous substrate and a catalytically-active region comprising at least one catalytic constituent.
  • the substrate of the precursor catalyst composition should be substantially nonporous, though materially insignificant amounts of micro-, meso-and/or macro-pore volume may exist without adversely affecting the catalyst composition's intended use.
  • the precursor catalyst composition is a FSC composition. So to illustrate this preferred embodiment, the compound catalyst composition described herein will describe in greater detail various FSC compositions as a precursor catalyst composition. But it should be understood that catalyst compositions prepared by other methods known to those skilled in the art can also be used for making precursor catalyst compositions useful for making precursor catalyst compositions of the compound catalyst compositions described herein.
  • Several factors that should be considered in producing a FSC composition include, without limitation, (i) obtaining a substrate with a predetermined isoelectric point ("IEP"), whether as received or after undergoing subsequent treatment(s), in view of the intended use; (ii) the extent of the substrate's corrosion resistance, in view of the intended use;
  • IEP isoelectric point
  • the treated substrate depending on the composition's intended use, the treated substrate's chemical susceptibility to, optionally, calcining and/or either reducing, oxidizing, or further chemically reacting the treated substrate with the first or second catalytic constituent prior to using the catalyst composition.
  • Substrates used for producing a precursor catalyst composition of the invention are preferably silicon- containing substrate compositions including, without limitation glass, silicon carbide, silicon nitride, cordierite, silicon-containing ceramics and mixtures thereof having an IEP greater than about 0 but less than or equal to 14, preferably greater than or equal to about 4.5, but less than 14, and more preferably greater than or equal to about 6.0, but less than 14, whether surface-active, as-received, or treated to produce a surface-active state.
  • silicon-containing compositions glass compositions are preferred.
  • Substantially silicon-free compositions may also be used for producing a precursor catalyst composition of the invention including, without limitation, substantially silicon-free ceramics, alpha alumina, zirconia, titania, carbon and mixtures thereof, having an IEP greater than about 0 but less than or equal to 14, whether surface-active, as-received, or treated to produce a surface- active state.
  • substantially silicon-free ceramics alpha alumina, zirconia, titania, carbon and mixtures thereof, having an IEP greater than about 0 but less than or equal to 14, whether surface-active, as-received, or treated to produce a surface- active state.
  • glass (or glass-like) compositions and their surface-active products will preferably have an IEP greater than or equal to about 4.5, but less than 14, while glass compositions with an IEP greater than or equal to about 6.0, but less than 14 are often expected to be more preferred and those compositions with an IEP greater than or equal to about 7.8 but less than 14 are often expected to be most preferred.
  • the preferred IEP range can be affected. Also, for example, some catalytic processes may be more responsive to a catalyst composition that's surface-active in a lower pH range.
  • a substrate with an IEP less than 7.8, preferably ⁇ 6, and more preferably, ⁇ 4.5 is likely to be more suitable for such processes.
  • selecting a substrate in a suitable IEP range in view of the catalyst composition's intended use will be one factor, in combination with the substrate's porosity, chemical composition and treatment procedures (if any), among other factors.
  • numerous glass types can be potential substrate candidates for obtaining the suitable IEP and degree and type of porosity, whether as-received, or using one or more of the treatment methods described below.
  • some examples of such glass types include, without limitation, E-glasses, boron- free E-glasses, S-glasses, R-glasses, AR-glasses, rare earth-silicate glasses, Ba-Ti-silicate glasses, nitrided glasses such as Si-Al-O-N glasses, A-glasses, C-glasses and CC-glasses.
  • E-glasses boron- free E-glasses
  • S-glasses S-glasses
  • R-glasses R-glasses
  • AR-glasses rare earth-silicate glasses
  • Ba-Ti-silicate glasses nitrided glasses such as Si-Al-O-N glasses
  • A-glasses A-glasses
  • C-glasses C-glasses
  • CC-glasses CC-glasses
  • AR-type glass is one broad group of substantially nonporous glass compositions with an IEP greater than 7.8.
  • AR- type glass will contain basic oxide type glass network modifiers in substantial amounts, often 10 wt. % or more of the total glass composition.
  • These basic oxide network modifiers include, for example, without limitation, oxides of Zr, Hf, Al, lanthanides, actinides, alkaline earth oxides (group 2), alkali oxides (group 1 ), and the like.
  • Zr, Hf, Al, lanthanide, alkaline earth oxide, and alkaline oxide containing glasses are preferred, while Zr containing glass compositions, such as, without limitation, AR-glasses, are particularly preferred.
  • A-type glass is another broad group of, substantially nonporous glass compositions having an IEP greater than 7.8 but less than 14, whether surface active, as-received, or treated to produce a surface-active state.
  • A-type glass will contain either acidic or basic oxide type glass network modifiers including, for example, without limitation, oxides of Zn, Mg, Ca, Al, B, Ti, Fe, Na and K and the like. In the case of basic network modifiers, the amount incorporated in these lower IEP glasses tends to be ⁇ 12 wt.%. Mg, Ca, Al, Zn, Na and K containing glasses are preferred.
  • Non-leached ⁇ -type" glass is still another non-limiting example of a broad group of substantially nonporous glass compositions having an IEP greater than 7.8 but less than 14, whether surface active, as-received, or treated to produce a surface-active state.
  • non-leached E-type glass will contain either acidic or basic oxide type glass network modifiers including, for example, without limitation, oxides of Zn, Mg, Ca, Al, B, Ti, Fe, Na and K and the like. In the case of basic network modifiers, the amount incorporated in these non-leached E-type glasses tends to be ⁇ 20 wt.%. Mg, Ca, Al, Zn, Na and K containing glasses are preferred. Porosity Description
  • the substrate's porosity is another relevant aspect to producing a precursor catalyst composition of the invention.
  • the substrate should be substantially nonporous, though materially insignificant amounts of micro-, meso-and/or macro-pore volume may exist without adversely affecting the catalyst composition's intended use. Because micropore volume in a material is often difficult to detect, two surface area measurements are used herein to determine whether a substrate is substantially nonporous for identifying the catalyst composition of the invention.
  • the first surface area measurement useful for detecting the extent of micro-, meso- and/or macro-porosity, is determined by a thermal adsorption/desorption method suitable for the expected surface area range being measured.
  • N 2 BET for higher surface area measurements (e.g., > about 3 m 2 /g) N 2 BET, according to the method described by ASTM D3663-03, ("S.A. W2 - BET "), would likely be a preferred surface area measurement technique. While for lower surface area measurements (e.g., ⁇ about 3 m 2 /g) Kr BET, according to the method described by ASTM D4780-95, ⁇ "S ⁇ . Kr . BET "), would likely be a preferred surface area measurement technique. The most preferred surface area measurement for detecting the extent of micro-, meso- and/or macro-porosity will be apparent to one skilled in the art of analyzing solid and semi-solid material surface areas.
  • the second measurement is a sodium-chemisorption surface area ("S.A. Wa "), which can be expressed as a change vs. time in NaOH titrant using the type of analytical method described by R. Her in Chemistry of Silica, John Wiley & Sons (1979) at p. 203 and 353 and defined more specifically above under the S.A. Wa rate of change (“SARC Wa ”)- [0078] Accordingly, as defined herein, the substrate will be substantially nonporous, provided the substrate's SA. N2 - BET or S ⁇ . Kr .
  • B E ⁇ is in a range from about 0.01 m 2 /g to about 10 m 2 /g and its SARCwa is less than or equal to 0.5, which, as discussed more fully above, is the ratio of two volumes of NaOH titrant, wherein the denominator of the ratio is the volume of NaOH titrant solution used initially, to titrate at time zero, t 0 , a substrate slurry mixture containing 1.5 g of the substrate in 3.4M NaCI solution from pH 4 to pH 9 at about 25°C.
  • the aqueous slurry mixture must first be adjusted to pH 4, using either a small amount of acid (HCI) or base (NaOH), accordingly.
  • HCI acid
  • NaOH base
  • the cumulative volume of NaOH titrant used at three 5-minute intervals, to maintain the substrate slurry mixture at pH 9 over 15 minutes is V tota ⁇ - V 1 (i.e., V 510 15 ), the numerator of the ratio SARC W/ ⁇ . So, if V tota ⁇ - V 1 is less than or equal to 0.5V 1 , the corresponding SARC Wa is less than or equal to 0.5.
  • a substrate with a SARC Wa ⁇ 0.5 will be substantially non-porous as defined herein, provided, again, that the substrate's S.A. W2-B£7 - or S ⁇ . Kr . BET is also in a range from about 0.01 m 2 /g to about 10 m 2 /g. Provided these surface area parameters are satisfied, to the extent the substrate has any micropore, mesopore and/or macropore volume, it would be an insufficient concentration, distribution and/or type to adversely affect the precursor catalyst composition's expected performance for its intended use.
  • the sodium surface area (“S.A. Wa ”) is an empirical titration procedure developed for essentially pure forms of SiO 2 in the granular, powder, and suspended sol form.
  • the S.A./va is a measure of the reactivity and accessibility of surface protonic sites (Glass-O ⁇ + ), which for pure SiO 2 would correspond to Si-0 ⁇ + sites.
  • the behavior of silicate glasses and crystalline silicates which markedly differ in composition from pure SiO 2 with respect to the stoichiometry of this titration procedure, is not known or predictable in terms of the absolute value of the NaOH titrant measured in the S.A. Wa experiment.
  • the substrate's surface area will remain substantially unchanged after its ion leach treatment, which is often the case with most alkali resistant (“AR") glasses.
  • AR alkali resistant
  • microporous regions in the substrate are likely created. Accordingly, as noted above, this microporous structure is indicated by a SARC Wa greater than about 0.5.
  • a substrate network exhibiting these properties has developed sufficient micropore structure, particularly in the subsurface region, that would likely have an adverse effect on the substrate's capacity to sustain its surface active state, and hence, adversely affect the catalyst composition's expected performance for its intended use.
  • Substrates used for producing the precursor catalyst composition of the invention can be made surface active with one or more first constituents having a first type of ionic and/or electrostatic interaction with the substrate ("Type-1 constituent precursor").
  • a Type-1 constituent precursor may itself be catalytically effective or may be further treated to produce a catalytically active region, having a mean thickness ⁇ about 30 nm, preferably, ⁇ about 20 nm and more preferably, ⁇ about 10 nm, on and/or in the substrate surface.
  • the substrate obtained has the appropriate type and degree of pore structure (if any) and an isoelectric point (IEP) in the range suitable for the intended use
  • the substrate may be sufficiently surface active, as received, to be catalytically effective.
  • the substrates can be treated to further modify and/or enhance their surface activity.
  • the substrates can be treated to remove any organic coatings or other possible contaminants that would be expected to interfere with the catalyst composition's performance.
  • IEX ion exchange
  • BIX back ion exchange
  • EA electrostatic adsorption
  • a contaminant removal treatment may be optional depending on the composition of the substances typically found on the surface of the substrate and whether such substances would be expected to interfere with catalyst composition's preparation and/or its expected performance for the intended use.
  • AR-glass is typically manufactured with an organic coating (i.e., sizing) used to facilitate its processing, such as dispersion in aqueous formulations. This organic coating or sizing, however, may interfere with the catalyst composition's preparation, if not its catalytic performance for at least most, if not, all intended uses. Accordingly, the organic coating should be removed.
  • Calcination is a preferred method for removing such an organic coating. Because the primary objective of this treatment is contaminant removal from the substrate, the conditions for this type of calcination treatment are not particularly crucial to the substrate's successful surface activation. In certain instances, depending on the nature of the contaminant to be removed from the substrate a solvent, surfactant, aqueous wash or other suitable means can be used to satisfactorily remove the contaminant. [0084] To the extent calcination is used, however, it's preferable to calcine the substrate in an oxidizing atmosphere (e.g., under air or O 2 ).
  • an oxidizing atmosphere e.g., under air or O 2 .
  • the calcination temperature should be at least about 50 0 C below the selected substrate material's softening point. Preferably, the calcination temperature should be at least about 100 0 C below the selected substrate material's softening point.
  • an acceptable contaminant removal calcination temperature can range from about 300°C to about 700 0 C for most AR-glass types.
  • the selected substrate material should be calcined for about 2 to 14 hours and preferably about 4 to 8 hours. Nonetheless, this calcination time can vary beyond these times, depending on the nature of the substrate obtained and the contaminants targeted for removal from the substrate.
  • the substrate can then be treated to produce a surface active state and a desired isoelectric point ("IEP"), provided the initial IEP obtained with the substrate is not in the desired range.
  • IEP isoelectric point
  • a substrate, as-received may be sufficiently surface active to be further modified by one or more of the other treatments described more fully below, without a first-type ion-leach (IEX-1 ) treatment, first discussed in more detail among the other treatments described more fully below.
  • IEX-1 first-type ion-leach
  • the elemental composition of the substrate particularly at or substantially near the external surface, may be sufficient to obtain the desired IEP.
  • the substrate's elemental composition will require some modification to shift its initial IEP and obtain an IEP suitable, in turn, for the desired surface active state, in type and degree, depending on the catalyst composition's intended use.
  • This surface active state with one or more first constituents having (i) a first oxidation state and (ii) a first type of ionic and/or electrostatic interaction with the substrate may be sufficient for producing a catalytically active region, having a mean thickness ⁇ about 30 nm, preferably, ⁇ about 20 nm and more preferably, ⁇ about 10 nm, on and/or in the substrate surface, and accordingly, providing the catalyst composition's expected performance for the intended use.
  • Bronsted or Lewis acid sites and Bronsted or Lewis base sites on and/or in the substrate's surface can be effective for promoting some hydrocarbon, hetero-hydrocarbon (e.g., oxygen containing hydrocarbon) and non-hydrocarbon treatment, conversion and/or refining processes.
  • hetero-hydrocarbon e.g., oxygen containing hydrocarbon
  • a second oxidation state which can be the same or different from that of the first oxidation state and (ii) a second type of ionic and/or electrostatic interaction with the substrate sufficient for producing a catalytically active region, having a mean thickness ⁇ 30 nm, preferably, ⁇ 20 nm and more preferably, ⁇ 10 nm, on and/or in the substrate surface.
  • the treatment involves at least one ion-leaching treatment to obtain a first type or Type-1 ion exchanged (IEX-1 ) substrate.
  • IEX-1 Type-1 ion exchanged
  • this ion-leaching treatment is performed by any suitable method effective for removing the desired ionic species in a substantially heterogeneous manner across the substrate surface without significantly eroding the substrate network (e.g., avoiding production of any micropore structure either in the surface region and/or subsurface region).
  • inorganic acids are used, for example, without limitation, nitric acid, phosphoric acid, sulfuric acid, hydrochloric acid, acetic acid, perchloric acid, hydrobromic acid, chlorosulfonic acid, trifluoroacetic acid and combinations thereof.
  • the strength of an acid solution used in an ion-leaching treatment depends on the properties of the substrate (e.g., affinity of ion(s) to be removed from the glass network, strength of the glass after certain network ions are removed, etc.), the extent to which the substrate's IEP needs to be shifted and the catalyst composition's intended use.
  • the strength of an acid solution used in an ion-leaching treatment can range from about 0.5 wt. % to about 50 wt.%, more preferably ranges from about 2.5 wt.% to about 25 wt. % and most preferably ranges from about 5 wt.% to about 10 wt.%.
  • Chelating agents may also be used in an ion-leaching treatment.
  • ethylenediaminetetraacetic acid EDTA
  • crown ethers oxalate salts
  • polyamines polycarboxylic acids and combinations thereof.
  • the strength of a chelating agent solution used in an ion-leaching treatment depends on the properties of the substrate (e.g., affinity of ion(s) to be removed from the glass network, strength of the glass after certain network ions are removed, etc.) and the catalyst composition's intended use.
  • the strength of an chelating agent solution used in an ion-leaching treatment can range from about 0.001 wt.% to saturation, more preferably ranges from about 0.01 wt.% to saturation.
  • heat treatment conditions such as heating temperature, heating time and mixing conditions, for the ion-leaching treatment are selected in view of the type and strength of the acid or chelating agent used and the properties of the substrate.
  • the heating temperature can be widely varied.
  • the heating temperature for an acidic, ion-leaching treatment ranges from about 20 0 C to about 200 0 C and more preferably from about 40°C to about 95°C and most preferably from about 60 0 C to about 90°C.
  • the heating temperature for chelating, ion-leaching treatment ranges range from about 20 0 C to about 200°C and more preferably from about 40°C to about 90 0 C. [0095] Depending on the strength of the acid or chelating agent solution and the heating time, the heating time for the ion-leaching treatment can be varied. Preferably, the heating time for the ion-leaching treatment ranges from about 15 minutes to about 48 hours, more preferably ranges from about 30 minutes to about 12 hours.
  • mixing conditions are selected in view of the type and strength of the acid or chelating agent used and the properties of the substrate (e.g., affinity of ion(s) to be removed from the glass network, strength of the glass after certain network ions are removed, etc.) and the duration of the heat treatment.
  • mixing conditions may be continuous or intermittent, and may be mechanical, fluidized, tumbling, rolling, or by hand.
  • the combination of acid or chelating strength, heat treatment conditions and mixing conditions are determined in view of obtaining a sufficient degree of ion- exchange ("IEX") between the acid or chelating agent and the targeted substrate ion(s) necessary for producing a suitable isoelectric point and type and degree of surface charge needed to produce the surface active state desired for either the substrate's subsequent treatment(s) or the catalyst composition's intended use.
  • IEX ion- exchange
  • the ion-leach treated substrate is preferably isolated by any suitable means, including, without limitation, filtration means, centrifuging means, decanting and combinations thereof. Thereafter, the ion-leach treated substrate is washed with one or more suitable rinsing liquid(s), such as deionized water and/or suitable water-soluble organic solvent (e.g., methanol, ethanol or acetone) and dried at about room temperature to 1 10 0 C for about 20 to 24 hours.
  • suitable rinsing liquid(s) such as deionized water and/or suitable water-soluble organic solvent (e.g., methanol, ethanol or acetone)
  • BIX treatment a back-ion exchange
  • a BIX treatment is described as a "back-ion" exchange, without limitation, generally because ions of one type (e.g., Na + ) that are removed from the substrate with an ion-leach treatment are subsequently put back into or returned to the substrate by mixing the ion-leached substrate with a salt solution (e.g., NaCI) comprising ions of the type initially removed.
  • a salt solution e.g., NaCI
  • the types of salt solutions used for treating an ion-leach treated substrate will depend on the type of ion(s) to be back-ion exchanged. Preferably, only one type of ion will be back-ion exchanged, but it may be desirable in certain instances to back- ion exchange two or more ions.
  • any ions susceptible to removal using the ion-leaching treatment described above can be back-ion exchanged.
  • Some examples of such ions include, without limitation, ions of alkali metals from Group 1 (formerly Group IA), such as Li, Na and K, and alkaline earth metals from Group 2 (formerly Group NA), such as Be, Mg, Ca, NH 4 + and alkylammonium cations, and small organic polycations.
  • alkali metal ions and NH 4 + are preferred target ions for a BIX treatment, while Na + and NH 4 + are preferred BIX ions and Na + is a particularly preferred BIX ion.
  • the concentration of the salt solutions used for the BIX treatment will depend on the type of ion-leach treated substrate undergoing a BIX treatment and the BIX ion's relative affinity for returning to the ion-leach treated substrate, again, regardless of the site the BlX-ion returns to in the substrate network (e.g., Na + relative affinity for the substrate vs. H + ).
  • the concentration of the salt solutions used for the BIX treatment will depend on the type of ion-leach treated substrate undergoing a BIX treatment and the BIX ion's relative affinity for returning to the ion-leach treated substrate, again, regardless of the site the BlX-ion returns to in the substrate network (e.g., Na + relative affinity for the substrate vs. H + ).
  • glass substrates such as, without limitation, AR, A or quartz glass, about a 0.001 mol/L to 5 mol/L strength BlX-salt solution is preferred, while about a 0.05
  • heat treatment conditions such as heating temperature, heating time and mixing conditions, for the BIX treatment are selected in view of the type and strength of the BlX-salt solution used and the properties of the substrate.
  • the heating temperature for BIX treatment using BlX-salt solution can range from about 20 0 C to about 200 0 C and more preferably from about 30°C to about 95°C.
  • the heating time for the BIX treatment can be varied.
  • the heating time for the BIX treatment ranges from about 5 minutes to about 24 hours, more preferably ranges from about 30 minutes to about 8 hours.
  • mixing conditions are selected in view of the type and strength of the BIX salt solution used and the properties of the substrate (e.g., affinity of ion(s) to be removed from the glass network, strength of the glass after certain network ions are removed, etc.) and the duration of the heat treatment.
  • mixing conditions may be continuous or intermittent, and may be mechanical, fluidized, tumbling, rolling or by hand.
  • the combination of BIX salt solution strength, heat treatment conditions and mixing conditions are based substantially on returning a sufficient amount and distribution of BlX-ion back to the substrate, regardless of its siting in the substrate network, necessary for producing the type and degree of surface charge needed to produce the surface active state desired for either the substrate's subsequent treatment(s) or the catalyst composition's intended use.
  • a negative surface charge on the substrate is desired to sustain an electrostatic interaction or affinity with a positively charged constituent(s) (e.g., cationic alkali earth metal, a cationic transition metal constituent, etc.).
  • a positively charged constituent(s) e.g., cationic alkali earth metal, a cationic transition metal constituent, etc.
  • a positive surface charge may be desirable to support an electrostatic interaction or affinity with a negatively charged constituent (e.g., an anionic transition metal oxyanion, sulfate anion, noble metal polyhalide anion, etc.).
  • the surface charge of the substrate can be shifted to either a net positive or net negative state by adjusting the pH of an ion-leach treated substrate/I EX mixture either below or above the substrate's isoelectric point ("IEP").
  • IEP is also known as zero point charge (“ZPC”). So, put another way the IEP (or ZPC) can be viewed as the pH at which the surface of a material at incipient wetness has a net zero surface charge. So, adjusting the pH of a substrate/I EX water mixture to a pH greater than the substrate's IEP (or ZPC) produces a net negative surface charge on the substrate.
  • adjusting the pH of a substrate/I EX water mixture to a pH less than the substrate's IEP produces a net positive surface charge on the substrate.
  • adjusting the pH of an ion-leach treated AR-glass to a pH > 9.6 will produce a net negative surface charge on the surface of the glass.
  • any dilute base can be used to adjust the substrate's surface charge to the right of its IEP (i.e., to produce net negative surface charge) and any dilute acid can be used to adjust the substrate's surface charge to the left of its IEP (i.e., to produce net positive surface charge).
  • Either inorganic or organic acids and bases can be used in a dilute strength, with inorganic acids generally being preferred.
  • the strength of the dilute acid or base solution will depend on the type of acid or base used and its dissociation constant and the pH suitable for obtaining the desired type and density of surface charge.
  • IEX IEX
  • BIX back exchange
  • EA electrostatic adsorption
  • certain substrate surface moieties containing a cation (or anion) susceptible to displacement by an ionic catalytic constituent or precursor of the same sign can provide the exchange sites for discreet, but nonetheless effective, IEX or BIX with the substrate's surface moieties.
  • moieties such as, siloxy (- Si-O " Na + ) moieties contain Na + ions that can be displaced, at least in part, by a positively charged catalytic metal or metal complex precursor, such as, without limitation, Pd(NH 3 ) 4 2+ , to produce a substrate with a catalytically effective amount of catalytic constituents.
  • a positively charged catalytic metal or metal complex precursor such as, without limitation, Pd(NH 3 ) 4 2+
  • IEX-2 treatment As in the case of the IEX treatment or a second IEX treatment ("IEX-2 treatment", discussed below), a pH adjustment may also be desired for certain BIX treatments, though not necessarily required. Again, the extent of pH adjustment required will depend generally on the substrate's IEP, its IEP vs. surface charge profile curve and the type of charge desired, in view of a second constituent to be integrated with the surface in an IEX-2 treatment, as well as the type of B ⁇ X-ion(s) exchanged.
  • any dilute base can be used to adjust the substrate's surface charge to the right of its IEP (i.e., to produce net negative surface charge) and any dilute acid can be used to adjust the substrate's surface charge to the left of its IEP (i.e., to produce net positive surface charge).
  • Either inorganic or organic acids and bases can be used in a dilute strength.
  • the strength of the dilute acid or base solution will depend on the type of acid or base used and its dissociation constant and a pH suitable for obtaining the desired type and density of surface charge.
  • the substrate is surface active, as received, or is an ion-leach treated substrate (i.e., IEX-1 treated substrate), or BlX-treated substrate, preferably, the substrate is further treated with at least one second constituent precursor ("Type-2 constituent precursor") in either (i) a second ion exchange (“IEX-2") treatment, (ii) an electrostatic adsorption (EA) treatment or (iii) some combination of an IEX-2 and EA treatment, for integrating one or more second constituent precursors on and/or in the substrate surface having a second type of ionic and/or electrostatic interaction with the substrate.
  • IEX-2 second ion exchange
  • EA electrostatic adsorption
  • some Type-2 constituent precursors without further treatment, can produce a catalytically active region or, subject to further treatment, can produce a catalytically active region comprising one or more Type-2 constituents.
  • the catalytically active region is comprised of (a) a Type-2 constituent precursor, (b) a Type-2 constituent, arising from Type-2 constituent precursor(s), or (c) some combination thereof, the catalytic region has a mean thickness ⁇ about 30 nm, preferably, ⁇ about 20 nm and more preferably, ⁇ about 10 nm on and/or in the substrate surface.
  • an as received substrate or ion-leach treated substrate can be catalytically effective depending on the catalyst composition's intended use.
  • the reaction rate, selectivity and/or energy efficiency of many processes suitable for using the catalyst compositions of the invention can be significantly enhanced by displacing at least a portion of the first constituent ("Type-1 constituent") and integrating a second type of constituent ("Type-2 constituent”) with the substrate surface.
  • Type-2 constituent precursor ions can be integrated by direct or indirect ionic interaction with oppositely charged specific ion exchange sites on and/or in the substrate surface, by electrostatic adsorption interaction with an oppositely charged substrate surface, some combination thereof or some other type of precursor-charge-to-surface interaction, yet to be understood.
  • Type-2 constituent precursor(s) may have with an as-received substrate, IEX-1 treated, or BlX-treated substrate, a second type of precursor charge-to- surface interaction is produced that will, accordingly, produce a catalytically active region, having a mean thickness ⁇ about 30 nm, preferably, ⁇ about 20 nm and more preferably, ⁇ about 10 nm, on and/or in the substrate surface.
  • IEX-2 will be used herein to collectively refer to the diverse range of interactions generally described as Type-2 constituent precursor charge-to-surface interaction or Type-2 constituent precursor interactions.
  • the types of salt solutions used for treating an IEX-1 treated or BIX- treated substrate will depend on the type of ion(s) to be ion exchanged in the IEX-2 treatment. Either one type of ion will be ion exchanged, or it may be desirable in certain instances to ion exchange two or more ions, either concurrently or sequentially.
  • the IEX-2 treatment is referred to herein as a double ion-exchange or double IEX-2 treatment. Accordingly, where three different types of constituent precursor ions are integrated with substrate, the IEX-2 treatment is called a triple ion-exchange or triple IEX-2 treatment.
  • Any salt solutions of IEX-2 ions chemically susceptible to either displacing ions on the as-received, IEX-1 treated, or BlX-treated substrate surface or having a charge affinity for electrostatically interacting with IEX-1 treated or BlX-treated substrate surface can be used.
  • IEX-2 ions are precursors to constituents that can be used as Type-2 constituents.
  • these ionic IEX-2 precursors i.e., Type-2 constituent precursors
  • these ionic IEX-2 precursors may be catalytically effective and, if so, can work, in their precursor state, like Type-2 constituents in one type of catalyst composition, even though such ions can also work as IEX-2 precursors in the preparation of another type of catalyst composition.
  • IEX-2 precursors include, without limitation, Bronsted or Lewis acids, Bronsted or Lewis bases, noble metal cations and noble metal complex cations and anions, transition metal cations and transition metal complex cations and anions, transition metal oxyanions, transition metal chalconide anions, main group oxyanions, halides, rare earth ions, rare earth complex cations and anions and combinations thereof.
  • certain IEX-2 ions can themselves be catalytically effective in the precursor state, when integrated with the appropriate substrate, to produce a Type-2 constituent.
  • ionic IEX-2 precursors that, optionally, without further treatment, can be catalytically effective include, without limitation, Bronsted or Lewis acids, Bronsted or Lewis bases, noble metal cations, transition metal cations, transition metal oxy anions, main group oxyanions, halides, rare earth hydroxides, rare earth oxides, and combinations thereof.
  • noble and transition metals useful as precursors to Type-2 constituents include, without limitation, ionic salts and complex ion salts of Groups 7 through 11 (formerly Groups Ib, lib, Vb, VIb, Vb, VIII), such as Pt, Pd, Ni, Cu, Ag, Au, Rh, Ir, Ru, Re, Os, Co, Fe, Mn, Zn and combinations thereof.
  • Ionic salts of Pd, Pt, Rh, Ir, Ru, Re, Cu, Ag, Au, and Ni are particularly preferred for an IEX-2 treatment.
  • transition metal oxyanions useful as Type-2 constituent precursors include, without limitation, ionic salts of Group 5 and 6 (formerly Groups Vb and VIb), such as VO 4 3" , WO 4 2" , H 2 W 12 O 40 6" , MoO 4 2" , Mo 7 O 24 6" , Nb 6 Oi 9 6" , ReO 4 " , and combinations thereof.
  • Ionic salts of Re, Mo, W and V are particularly preferred for an IEX-2 treatment.
  • Some examples of transition metal chalconide anions useful as Type-2 constituent precursors include, without limitation, ionic salts of Group 6 (formerly Group VIb), such as MoS 4 2" , WS 4 2" , and combinations thereof.
  • Type-2 constituent precursors include, without limitation, ionic salts of Group 16 (formerly Group Via), such as SO 4 2" , PO 4 3" , SeO 4 2" , and combinations thereof. Ionic salts of SO 4 2" are particularly preferred for an IEX-2 treatment.
  • ionic salts of Group 16 (formerly Group Via), such as SO 4 2" , PO 4 3" , SeO 4 2" , and combinations thereof. Ionic salts of SO 4 2" are particularly preferred for an IEX-2 treatment.
  • halides useful as Type-2 constituent precursors include, without limitation, ionic salts of Group 17 (formerly Group Vila), such as F “ , Cl “ , Br “ , I “ and combinations thereof. Ionic salts of F “ and Cl " are particularly preferred for an IEX-2 treatment.
  • rare earth ions and rare earth complex cations or ions useful as Type-2 constituent prescursors include, without limitation, ionic salts of the lanthanides and actinides, such as La, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Th, U, and combinations thereof.
  • transition metals that can be used to produce transition metal- carbides, -nitrides, -borides, and -phosphides useful as Type-2 constituents include, without limitation, ionic salts of Cr, Mo, W, Nb, Ta, Fe, Co, Ni, and combinations thereof.
  • the concentration of the salt solutions used for the IEX-2 treatment will depend on the type of IEX-1 treated or BlX-treated substrate undergoing a IEX-2 treatment and the IEX-2 ion's relative affinity for interacting and/or integrating with the IEX-1 treated substrate.
  • concentration of the salt solutions used for the IEX-2 treatment will depend on the type of IEX-1 treated or BlX-treated substrate undergoing a IEX-2 treatment and the IEX-2 ion's relative affinity for interacting and/or integrating with the IEX-1 treated substrate.
  • glass substrates such as, without limitation, AR, A or soda- lime glass
  • about a 0.001 wt.% to saturation of the IEX-2 salt solution is preferred, while about a 0.001 wt.% to 5 wt.% IEX-2 salt solution is more preferred.
  • IEX-2 salt solutions may be less than 0.001 wt.%.
  • the concentration of salt solutions will be adjusted according to the relative loading desired for each type of constituent precursor on the substrate and the substrate's relative affinity for one type of constituent precursor vs. another.
  • the concentration of the salt solutions used for depositing each ion type will depend on the relative concentration targeted for each type of constituent precursor integrated with the substrate's surface and the surface's affinity for each ion.
  • heat treatment conditions such as heating temperature, heating time and mixing conditions, for the IEX-2 treatment are selected in view of the type and strength of the IEX-2 salt solution used and the properties of the substrate.
  • the heating temperature for IEX-2 treatment using an acid can range from about 20 0 C to about 200 0 C and more preferably from about 30°C to about 90 0 C.
  • the heating time for the IEX-2 treatment can be varied.
  • the heating time for the IEX-2 treatment ranges from about 5 minutes to about 48 hours, more preferably ranges from about 30 minutes to about 5 hours.
  • mixing conditions are selected in view of the type and strength of the IEX-2 salt solution used and the properties of the substrate (e.g., affinity of ion(s) to be removed from the glass network, strength of the glass after certain network ions are removed, etc.) and the duration of the heat treatment.
  • mixing conditions may be continuous or intermittent, and may be mechanical, fluidized, tumbling, rolling, or by hand.
  • the combination of IEX-2 salt solution strength, heat treatment conditions and mixing conditions are based substantially on integrating a sufficient amount and distribution of IEX-2 ions on and/or in the substrate, regardless of the nature of its physicochemical association with the substrate's surface, necessary for producing the type and degree of surface charge needed to produce the surface active state desired for the catalyst composition's intended use.
  • the extent of pH adjustment required will depend generally on the substrate's IEP, its IEP vs. surface charge profile curve and the type of charge desired, in view of Type-2 constituent precursor(s) to be integrated with the surface in a second IEX ("IEX-2") treatment.
  • IEX-2 IEX
  • the pH of the substrate/I EX-2 mixture is preferably adjusted to within a range from about 8 to about 12 and more preferably, from about 9 to about 1 1.
  • the types of solutions used for making such a pH adjustment will depend on compatibility with other reagents, substrate stability in the pH range of interest and desired charge density, among other factors.
  • any dilute base can be used to adjust the substrate's surface charge to the right of its IEP (i.e., to produce net negative surface charge) and any dilute acid can be used to adjust the substrate's surface charge to the left of its IEP (i.e., to produce net positive surface charge).
  • Either inorganic or organic acids and bases can be used in a dilute strength, with organic bases generally being preferred.
  • the strength of the dilute acid or base solution will depend on the type of acid or base used, its dissociation constant, and pH suitable for obtaining the desired type and density of surface charge.
  • the IEX-2 treated substrate is preferably isolated by any suitable means, including, without limitation, filtration means, centrifuging means, decanting and combinations thereof. Thereafter, the IEX-2 treated substrate is washed with one or more suitable rinsing liquid(s), such as distilled or deionized water, dilute base or acid and/or suitable water-soluble organic solvent (e.g., methanol, ethanol or acetone) and dried at about 110 0 C for about 20 to 24 hours.
  • suitable rinsing liquid(s) such as distilled or deionized water, dilute base or acid and/or suitable water-soluble organic solvent (e.g., methanol, ethanol or acetone)
  • the IEX-2 treated substrate may be dried, calcined only, calcined under oxidizing conditions and subsequently reduced or further oxidized, reduced without calcination or oxidized without calcination.
  • Reaction of surface deposited transition metal ions, oxyanions and/or thioanions in the gas or liquid phase with suitable reducing, sulfiding, carbiding, nitriding, phosphiding, or bonding reagents can be carried out as desired to produce the respective catalytically effective metal sulfide/oxysulfide, metal carbide/oxycarbide, metal nitride/oxynitride, metal boride, or metal phosphide constituent.
  • the purpose of the post-deposition calcination treatment is to substantially decompose the metal counterion or ligands and more intimately integrate the metal, metal oxide, metal chalconide, and the like with the substrate surface and remove any residual water that may not have been removed from the previous drying treatment.
  • the conditions for such a calcination treatment for an IEX-2 treated substrate are not particularly crucial to the substrate's successful surface activation, however, they should only be severe enough to produce at least one catalytically-active region with the deposited constituent precursor(s) in a catalytically effective amount.
  • the substrate is first calcined in an oxidizing atmosphere (e.g., under air or O 2 ). Also, it's important to select a calcination temperature high enough to ensure the Type-2 constituent precursor of interest is oxidized and any residual water removed (if any is still present), but low enough to reasonably avoid the substrate's softening point and undesired decomposition of the deposited constituent precursor(s).
  • an oxidizing atmosphere e.g., under air or O 2
  • deposited sulfate requires calcination conditions to decompose associated cations and anchor the sulfate to the surface but the conditions must not significantly decompose the sulfate to volatile sulfur oxides.
  • metal oxyanions require calcination conditions that decompose the associated cations and anchor the anion to the surface as an oxide, but the conditions must not be severe enough to volatilize the metal oxide from the surface or cause the metal oxide to dissolve into the substrate.
  • noble metals and complexes should be calcined under conditions that decompose the ligands and anions present, but not severe enough to agglomerate the noble metal on the surface. For this reason, preferably, noble metals are directly reduced, without calcination, as described more fully below.
  • the calcination temperature should be at least about 100 0 C below the selected substrate's softening point.
  • the calcination temperature should be from about 100 0 C to 700 0 C, preferable from about 200 0 C to 600 0 C, and most preferably from about 300 0 C to 500 0 C.
  • the IEX-2 treated substrate is calcined for about 1 to about 24 hours and preferably about 2 to about 12 hours. Nonetheless, this calcination time can vary beyond these times, depending on the Type-2 constituent integrated with the substrate.
  • the purpose of the post-deposition reducing treatment is to, at least substantially, if not fully, reduce catalytic constituent precursors such as metals, metal oxides or metal sulfides to a lower oxidation state integrated with the substrate surface.
  • suitable reducing agents include, without limitation, CO and H 2 .
  • H 2 is a preferred reducing agent, preferably at a flow rate in a range from about 0.01 L/hr. to about 100 L/hr. per gram of substrate, and more preferably at a flow rate of about 0.1 L/hr. to 1 L/hr. per gram of substrate.
  • the reducing temperature should be about 0 0 C to 600 0 C, provided the chosen temperature is at least 100 0 C below the softening point of the substrate.
  • the IEX-2 treated substrate undergoes a reducing treatment for about 0.1 to about 48 hours and preferably about 1 to about 8 hours.
  • the IEX-2 treated substrate may be reduced by a solution phase treatment with a soluble reducing agent such as, without limitation, hydrazine, sodium hydride, lithium aluminum hydride and combinations thereof in a suitable solvent such as water or an ether.
  • a soluble reducing agent such as, without limitation, hydrazine, sodium hydride, lithium aluminum hydride and combinations thereof in a suitable solvent such as water or an ether.
  • the purpose of the post deposition -IDING reaction treatment simultaneously reduces the metal ions, metal oxyanions, and/or metal thioanions while additionally reacting the reduced metal with a lower atomic weight -IDING element- containing reagent. In certain cases direct -IDING takes place without simultaneous reduction of the metal oxidation state, for instance in certain sulf-IDING treatments.
  • Typical gas phase -IDING reagents include, without limitation, hydrogen sulfide, methyl mercaptan and dimethylsulfide (sulf-IDING reagents), ammonia (nitr-IDING reagent), methane, ethane, and other light hydrocarbons (carb-IDING reagents). These gas-phase - IDING reagents can be reacted directly or in a gas blend with an inert gas or hydrogen at ambient or elevated pressure with an IEX-2 treated substrate to produce the corresponding sulfide, carbide or nitride.
  • Partially -IDED species including oxysulfides, oxycarbides, and oxynitrides, which may be catalytically effective, can also be produced by incomplete reaction with either substrates in a substantially as-received/obtained condition, integrated IEX-2 treated substrates, calcined IEX-2 treated substrates, or reduced IEX-2 treated substrates.
  • Metal phosphides can be made by reducing treatment of doubly ion exchanged (double IEX-2 treatment) substrates wherein one of the IEX-2 treatments is one or more transition metal ions and the other IEX-2 treatment is phosphate ion.
  • the two IEX-2 treatments can be carried out sequentially.
  • metal phosphides can be made by using gas-phase phosph-IDING reagent for example, without limitation, phosphine (PH 3 ), to produce the desired metal phosphide.
  • gas-phase phosph-IDING reagent for example, without limitation, phosphine (PH 3 ), to produce the desired metal phosphide.
  • a single ion exchanged substrate with the desired transition metal in the suitable oxidation state can be further treated with PH 3 to produce the desired metal phosphide, accordingly.
  • Solution phase treatments can be used to produce metal sulfide, metal boride, and metal phosphide catalytic constituents.
  • Typical solution treatments that produce metal sulfides include, without limitation, treatment of IEX-2 treated metal-ion-integrated substrate with effective concentrations of organic solutions of hexamethyldisilthiane from room temperature to reflux temperature for a time sufficient to yield a catalytically effective amount of catalytic constituent on and/or in the substrate surface.
  • Typical solution phase treatments that produce borides include, without limitation, aqueous sodium borohydride or potassium borohydride treatment of IEX-2 treated metal-ion- integrated substrate at temperatures from room temperature to reflux for an effective time.
  • Typical solution phase treatments that produce phosphides include aqueous sodium hypophosphite treatment of IEX-2 treated metal-ion-integrated substrate at temperatures from room temperature to reflux for a time sufficient to yield a catalytically effective amount of catalytic constituent on and/or in the substrate surface.
  • the catalytically-active region arising from any of the above-described substrate treatments, will have (i) a mean thickness less than or equal to about 30 nm, preferably, ⁇ about 20 nm and more preferably, ⁇ about 10 nm and (ii) a catalytically effective amount of at least one type of catalytic constituent.
  • the mean thickness of the catalytic region is preferably determined using XPS spectroscopy using a technique of layer-by-layer etching known as sputter depth profiling (discussed more fully under the Analytic Methods in the Examples provided below).
  • sputter depth profiling discussed more fully under the Analytic Methods in the Examples provided below.
  • other analytical techniques known to those skilled in the art may be used to determine the general locus of a catalytic constituent versus the surface of the constituent's related substrate.
  • the mean thickness of a substrate's catalytic region may be determined for example, without limitation, using transmission electron microscopy (TEM) or scanning TEM (STEM, also described more fully below).
  • TEM transmission electron microscopy
  • STEM scanning TEM
  • the XPS or TEM procedures are each well understood by those skilled in the art.
  • the thickness of a catalytically-active region will not, on average, (a) penetrate substantially beyond the substrate's surface region or (b) exceed about a 30 nm thickness, preferably, about a 20 nm thickness and more preferably, about a 10 nm thickness, above the substrate's external surface, for any catalyst composition of the invention.
  • the catalytically- active region(s) may be:
  • amounts of catalytic constituents can range from about 0.0002 wt.% to about 5 wt.%, preferably from about 0.0002 wt.% to about 2 wt.% and more preferably from about 0.0005 wt.% to about 1 wt.%.
  • the catalytically-active region(s) of the catalyst compositions of the invention may be contiguous or discontiguous.
  • catalyst compositions with discontiguous coverage of catalytically-active regions are at least equally, and in some cases, more effective, than catalyst composition's with substantially contiguous or more extensive areas of contiguous coverage of catalytically-active regions.
  • the extent of the catalytically-active region's external surface coverage on the substrate can range from as low as about 0.0001 % coverage to as high as 100% coverage.
  • the extent of the catalytically-active region's external surface coverage ranges from about 0.0001 % to about 10% and more preferably from about 0.0001% to about 1%.
  • catalyst composition's, particularly those with lower wt it is believed that catalyst composition's, particularly those with lower wt.
  • catalytically-active region and other catalyst composition attributes described above are based on the inventors' best available information about the catalyst composition's state before entering a steady-state reaction condition. The extent to which one or more of the described attributes may change is uncertain and in large measure unpredictable.
  • a compound catalyst composition comprises at least one refractory inorganic oxide and at least one precursor catalyst composition having at least one catalytic constituent.
  • the precursor catalyst composition may be prepared by ion exchange, impregnation, precipitation, coprecipitation or other catalyst composition preparation methods to the extent the method produces a precursor catalyst composition in which at least one catalytic constituent remains dispersed substantially in and/or on the precursor catalyst composition after it is intermixed with the refractory inorganic oxide. Also, preferably at least one catalytic constituent of the precursor catalyst composition remains substantially dispersed in and/or on the substrate of the precursor catalyst composition after the compound catalyst composition is exposed for at least one hour to a steady state reaction condition for its intended use.
  • the precursor catalyst composition is produced before mixing with the refractory oxide.
  • Substrates for precursor catalyst compositions which are dispersed throughout the refractory inorganic oxide used to produce the compound catalyst composition, are generally chosen from the groups of silicon-containing materials, substantially silicon-free materials, and mixtures thereof, having the porosity attributes more fully discussed above. But in any case, the substrate for the precursor catalyst composition is substantially nonporous.
  • silicon-containing substrates include, without limitation, glass, silicon carbide, silicon nitride, cordierite, silicon-containing ceramics and mixtures thereof.
  • substantially silicon-free materials include, without limitation substantially silicon-free ceramics, alpha alumina, zirconia, titania, carbon and mixtures thereof.
  • the precursor catalyst composition is a FSC composition prepared in view of the description provided herein.
  • FSC composition prepared in view of the description provided herein.
  • other methods known in the art for making a precursor catalyst composition can be used, again provided that at least one catalytic constituent remains substantially dispersed in and/or on the precursor catalyst composition after it's intermixed with the refractory inorganic oxide, among any other suitable materials, used for making a compound catalyst composition.
  • other methods of making precursor catalyst compositions will be apparent to those skilled in art.
  • the minimum size of the substrate (i.e., substrate particle's mean maximum dimension) used for producing the precursor catalyst composition are generally in a range from greater than about 0.05 microns to less than or equal to about 150 microns, preferably from about 0.2 microns to less than or equal to about 150 microns and more preferably from about 0.2 microns to about 50 microns.
  • substrates outside this range could still be effective without adversely affecting the compound catalyst composition's expected performance.
  • the refractory inorganic oxide used in forming the compound catalyst composition with the precursor catalyst composition dispersed throughout may also be referred to herein for convenience as the compounding refractory inorganic oxide or further abbreviated to the compounding refractory oxide.
  • This compounding refractory oxide is one which generally has a surface area in the range of about 1 to about 1000 m 2 /g, and preferably in the range of about 50 to 250 m 2 /g and an apparent bulk density of about 0.2 g/ml_ to about 1.8 g/mL, preferably from about 0.2 g/mL to about 1.0 g/ml_.
  • the compounding refractory oxide may have a surface and an apparent bulk density outside the aforementioned ranges. In any case, these properties of the compounding refractory oxide are selected to ensure that the precursor catalyst composition(s) can be sufficiently dispersed throughout the compounding refractory oxide, without adversely affecting the compound catalyst composition's performance.
  • Refractory inorganic oxides that can be used to form the compound catalyst composition include, without limitation, gamma alumina, delta alumina, eta alumina, theta alumina, alpha alumina, silica-alumina, zeolitic molecular sieves (i.e., zeolites), non-zeolitic molecular sieves (NZMS), non-sieve oxides, titania, zirconia and mixtures thereof.
  • zeolites include, without limitation, zeolite Y, zeolite X, zeolite L, zeolite beta, ferrierite, MFI, UZM-4 (see U.S. Patent No. 6,776,975), UFI, UZM-8 (U.S. Patent No.
  • NZMS examples include, without limitation, silicoaluminophosphat.es (SAPOs) described in U.S. Patent No. 4,440,871 , ELAPOs described in U.S. Patent No. 4,793,984, and MeAPOs described in U.S. Patent No. 4,567,029 all of which are incorporated by reference.
  • SAPOs silicoaluminophosphat.es
  • ELAPOs described in U.S. Patent No. 4,793,984
  • MeAPOs described in U.S. Patent No. 4,567,029 all of which are incorporated by reference.
  • non-sieve oxides include, without limitation, silica and aluminophosphates.
  • silica-alumina is not a physical mixture of silica and alumina but rather is an acidic and amorphous material that's formed by cogellation or coprecipitation. This term is well known in the art, see e.g., U.S. Patent Nos. 3,909,450; 3,274,124; and 4,988,659, all of which are incorporated by reference.
  • Preferred refractory inorganic oxides are gamma, eta alumina and zirconia.
  • the compounding refractory inorganic oxide is produced using methods well known to those skilled in art to form the desired viscosity or consistency (e.g., paste, dough, etc.) for mixing with the precursor catalyst composition and any other suitable compounding components (described below).
  • mixing means for producing a good dispersion of the pre-prepared precursor catalyst composition throughout the compounding refractory inorganic oxide include, without limitation, paddle mixing, ball milling, mulling and kneading.
  • this precursor catalyst composition/compounding refractory oxide mixture is used to produce the formed compound catalyst composition.
  • an extrudable dough-like composition of at least the compounding refractory oxide and precursor catalyst is generally preferred to produce a compound catalyst composition (as discussed more fully below).
  • the compound catalyst composition is produced by intermixing at least one compounding refractory oxide and at least a pre-prepared precursor catalyst composition to produce a compounding refractory oxide/precursor catalyst mixture.
  • a dough of the compounding refractory oxide may be formed and the precursor catalyst composition mixed into the dough.
  • Other components including without limitation, non-sieve oxides, zeolitic molecular sieves, non-zeolitic molecular sieves, titanium silicates, clays and metal oxides and combinations thereof, may be mixed with the dough as well to produce the compound catalyst composition prior to forming (e.g., by extrusion).
  • a compounding refractory oxide/precursor catalyst mixture for producing an compound catalyst composition is produced by intermixing the precursor catalyst composition with the compounding refractory oxide, substantially after the compounding refractory oxide is formed (e.g., by peptizing alumina powder with water and suitable peptizing agent such as HCI).
  • the compounding refractory oxide and precursor catalyst can be mixed using a variety of mixing methods known to those skilled including, without limitation, paddle mixing, ball milling, mulling and kneading.
  • a preferred solvent is water, although organic solvents can also be used as well as mixtures of water and an organic solvent(s).
  • the mixture can also contain an agent that will enhance dispersion of the refractory oxide such as, but not limited to, nitric acid, hydrochloric acid, sulfuric acid and acetic acid.
  • the compounding refractory oxide may be formed by attrition milling a metal oxide in an aqueous slurry mixture and adding precursor catalyst composition before or after the attrition milling phase is substantially complete. In the case where a slurry mixture is produced, preferably it is dried and calcined as a sheet.
  • an inorganic binder agent can be used.
  • Nonlimiting examples of inorganic binder agents that can be added to the slurry are ZrO(C 2 H 3 O 2 ⁇ , ZrO(NO 3 ) 2 , ZrO(OH)CLnH 2 O, zirconia sol, ZrOCO 3 , ZrO(OH) 2 , Zr(C 5 H 8 O 2 ) 4 , Zr(SO 4 ) 2 .4H 2 O, alumina sol, silica sol, aluminum nitrate and boehmite.
  • the inorganic oxide binder give the same refractory oxide as the compounding refractory oxide, generally any inorganic oxide binder can be used with any compounding refractory oxide.
  • an inorganic binder agent produces an inorganic oxide binder.
  • Such an inorganic oxide binder can help strengthen the network of refractory inorganic oxides of the compound catalyst composition or function as either the primary or only compounding refractory oxide of the compound catalyst composition.
  • often many compounding refractory oxides will not require an inorganic oxide binder, particularly, for example, where an extrusion process is used to form the compound catalyst composition.
  • an inorganic binder agent is appropriate, a sol, a gel or a compound of a metal, which will decompose on heating to form an inorganic oxide binder may be used, for example.
  • inorganic oxide binders that can be used include, without limitation, alumina, silica, zirconia, titania and aluminum phosphate.
  • an alumina binder can be used when the compounding refractory oxide is a zeolite, titania, silica or alumina.
  • zirconia it's preferred to have a zirconia binder.
  • the amount of inorganic binder agent present in the compounding mixture is that amount which will provide from about 1 wt. % to about 99 wt. % inorganic oxide binder in the compound catalyst composition.
  • the amount of inorganic binder agent used will provide from about 2 to 40 wt. % of inorganic binder of the compound catalyst and most preferably the amount that will provide from 5 to 30 wt. % of the compound catalyst.
  • a variety of mills are known in the art including, without limitation, ball milling and impact milling. Milling is conducted to ensure adequate blending of the various components and to optionally reduce the particle size of the compounding refractory oxide and/or precursor catalyst composition. Milling is usually performed for times of about 0.5 to about 8 hours, preferably from about 2 to about 8 hours.
  • the compounding refractory oxide/precursor catalyst composition mixture After the compounding refractory oxide/precursor catalyst composition mixture is produced it can be formed into any desired shape of formed material including, without limitation, spheres, rods, pills, pellets, tablets, granules, extrudates, rings, saddles, trilobes and other forms known to those skilled in the art, by methods well known to the practitioners of the catalyst material forming art.
  • the compound catalyst composition is dried at a temperature of about 100 0 C to about 320 0 C, preferably from about 100 0 C to about 150 0 C, for a time of about 1 to about 24 hours and then calcined at a temperature of at least about 200 0 C for a time of about 0.5 to about 10 hours to produce compound catalyst composition.
  • the calcination conditions for the compound catalyst composition are selected to stabilize and integrate the compounding refractory oxide with the precursor catalyst composition..
  • calcination conditions can be used to optimize characteristics of the compounding refractory oxide, such as, without limitation, its surface area, structural integrity and pore volume.
  • the calcination temperature is at least about 100 0 C below the combustion or structural decomposition temperature of the precursor catalyst composition.
  • preferred calcination temperatures are from about 200 0 C to about 1500 0 C, preferably from about 400°C to about 1100°C and most preferably from about 400°C to about 800 0 C.
  • One or more calcining steps may be used, such that at any point after at least one catalytic component compound is contacted with the compounding refractory inorganic oxide, it may be calcined.
  • the calcining step is carried out at a temperature in the range of about 100°C to about 700°C, preferably between about 200 0 C and about 500°C in a non-reducing atmosphere. Calcination times may vary but preferably are between about 1 and 5 hours.
  • the concentration of precursor catalyst composition in the calcined compound catalyst composition can range from about 1 % to 99% (by wt.), preferably from about 1 % to 90% (by wt.), more preferably from about 1 to about 80% (by wt.) and most preferably from about 1 to about 70% (by wt.). But more generally, the concentration of the precursor catalyst composition in the compound catalyst composition will depend on its intended use, the precursor catalyst composition's activity towards the targeted reactants and the desired rate of production for the targeted product(s). Also, generally the higher the concentration of catalytic constituent(s) on and/or in the precursor catalyst composition the lower the precursor catalyst composition can be in the compound catalyst composition.
  • AR-glass Cem-FIL Anti-Crak TM HD sample, as glass fibers having a mean diameter of about 17-20 microns, produced by Saint-Gobain Vetrotex, is obtained.
  • the as-received AR-glass sample undergoes a calcination heat treatment. In that treatment, the AR-glass is calcined at 600 0 C for 4 hrs in air under an air flow rate of 1 L/hr.
  • the calcined AR-glass undergoes an acid-leach treatment.
  • palladium tetraamine-dihydroxide [Pd(NHs) 4 ](OH) 2
  • IEX solution 80 ml. 0.1 wt.% palladium solution for ion exchange
  • 4 g of AR- glass is added to the IEX solution ("glass/IEX mixture”).
  • the pH of the glass/IEX mixture is measured, resulting in a pH of about 1 1.4.
  • the mixture is then transferred to a 150-mL wide neck plastic container. The container is placed in an air-draft oven at 50 0 C for 2 hrs and shaken briefly by hand every 30 minutes.
  • the glass/IEX mixture is filtered on a Buchner funnel with Whatman 541 paper and washed with about 3.8 L deionized water. Thereafter, the IEX-glass is dried at 110°C for 22 hrs.
  • the IEX-glass undergoes a reducing treatment in which the IEX-glass is initially calcined at 300°C for 2 hrs in air at an air flow rate of 2 L/hr and thereafter reduced at 300°C for 4 hrs in hydrogen (H 2 ) under a H 2 flow rate of 2 L/hr.
  • the sample is analyzed by Inductively Coupled Plasma-Atomic Emission Spectroscopy (ICP-AES), resulting in a palladium concentration of about 0.016 wt.%.
  • ICP-AES Inductively Coupled Plasma-Atomic Emission Spectroscopy
  • the sample is analyzed by an XPS Sputter Depth Profiling method (as described below), demonstrating, as depicted in Fig. 1 , that the thickness of the region in which a substantial portion of the palladium is detected by this method is about 10 nm.
  • AR-glass Cem-FIL Anti-Crak TM HD sample, as glass fibers having a mean diameter of about 17-20 microns, produced by Saint-Gobain Vetrotex, is obtained and prepared according to the procedure of Example 1.
  • the sample is analyzed by ICP-AES, resulting in a palladium concentration of about 0.032 wt.%.
  • AR-glass Cem-FIL Anti-Crak TM HD sample, as glass fibers having a mean diameter of about 17-20 microns, produced by Saint-Gobain Vetrotex, is obtained.
  • the as-received AR-glass sample undergoes a calcination heat treatment. In that treatment, the AR-glass is calcined at 600 0 C for 4 hrs in air under an air flow rate of 1 L/hr.
  • the calcined AR-glass undergoes an acid-leach treatment.
  • 25 g of the calcined AR-glass and 3 L 5.5 wt.% nitric acid are each placed in a 4-L wide-neck plastic container.
  • the plastic container is placed in an air draft oven at 60 0 C for 1 hr and shaken briefly by hand every 15 minutes.
  • the sample is filtered on a Buchner funnel with Whatman 541 paper and washed with about 7.6 L deionized water. Thereafter, the acid-leached sample is dried at 110°C for 22 hrs.
  • the acid-leach treated AR-glass undergoes an IEX treatment.
  • palladium tetraamine-dichloride [Pd(NH 3 ) 4 ](CI) 2
  • IEX solution 40 ml. 0.1 wt.% palladium solution for IEX
  • 4 g of AR-glass is added to the IEX solution ("glass/IEX mixture”).
  • the pH of the glass/IEX mixture is measured, resulting in a pH of about 7.7.
  • the mixture is then transferred to a 100-mL wide neck plastic container and placed in an air-draft oven at 50 0 C for 2 hrs and shaken briefly by hand every 30 minutes.
  • the glass/IEX mixture is filtered on a Buchner funnel with Whatman 541 paper and washed with about 3.8 L deionized water. Thereafter, the IEX- glass sample is dried at 1 10°C for 22 hrs.
  • the IEX-glass sample undergoes a reducing treatment in which the IEX- glass is initially calcined at 300°C for 2 hrs in air at an air flow rate of 2 L/hr and thereafter reduced at 300 0 C for 4 hrs in hydrogen (H 2 ) under a H 2 flow rate of 2 L/hr.
  • AR-glass Cem-FIL Anti-Crak TM HD sample, as glass fibers having a mean diameter of about 17-20 microns, produced by Saint-Gobain Vetrotex, is obtained.
  • the as-received AR-glass sample undergoes a calcination heat treatment. In that treatment, the AR-glass is calcined at 600 0 C for 4 hrs in air under an air flow rate of 1 L/hr.
  • the calcined AR-glass undergoes an acid-leach treatment.
  • the acid-leached sample from the second step is mixed with 4 L 3 mol/L sodium chloride (NaCI) solution ("glass/NaCI mixture").
  • NaCI sodium chloride
  • the pH of the glass/NaCI mixture is measured. As needed, the pH of the mixture is adjusted with a continuous drop-wise addition of about 40 wt.% tetrapropylammonium-hydroxide to greater than pH 10 (in this example, resulting in a pH of about 11.0).
  • the glass/NaCI mixture is transferred to a 4-L wide neck plastic container. The container is subsequently placed in an air-draft oven at 50 0 C for 4 hrs and shaken briefly by hand every 30 minutes.
  • Na-BIX/AR-glass sample undergoes a second ion-exchange ("IEX-2") treatment.
  • IEX-2 solution palladium tetraamine-chloride, [Pd(NH 3 ) 4 ](CI) 2 , is used to prepare 3 L 0.01 wt.% palladium solution for ion exchange ("IEX-2 solution").
  • the dilute NH 4 OH solution is prepared by mixing 10 g of a concentrated 29.8 wt.% NH 4 OH solution with about 3.8 L of deionized water. Thereafter, the IEX-2-glass sample is dried at 110 0 C for 22 hrs. [00200] Fifth, the IEX-2-glass sample undergoes a reducing treatment in which the sample is reduced at 300 0 C for 4 hrs in hydrogen (H 2 ) under a H 2 flow rate of 2 L/hr. [00201] The sample is analyzed by ICP-AES, resulting in a palladium concentration of about 0.015 wt.%.
  • the sample is analyzed by an XPS Sputter Depth Profiling method (as described below), demonstrating, as depicted in Fig. 1 , that the thickness of the region in which a substantial portion of the palladium is detected by this method is about 10 nm.
  • AR-glass Cem-FIL Anti-Crak TM HD sample, as glass fibers having a mean diameter of about 17-20 microns, produced by Saint-Gobain Vetrotex, is obtained.
  • the as-received AR-glass sample undergoes a calcination heat treatment. In that treatment, the AR-glass is calcined at 600 0 C for 4 hrs in air under an air flow rate of 1 L/hr.
  • the calcined AR-glass undergoes an acid-leach treatment.
  • 90.03 g of the calcined AR-glass and 4 L 5.5 wt.% nitric acid are each placed in a 4-L wide-neck plastic container.
  • the plastic container is placed in an air draft oven at 90 0 C for 2 hr and shaken briefly by hand every 15 minutes.
  • the sample is filtered on a Buchner funnel with Whatman 541 paper and washed with about 7.6 L deionized water. Thereafter, the acid-leached sample is dried at 110°C for 22 hrs.
  • the acid-leach treated AR-glass undergoes an ion-exchange (IEX) treatment.
  • IEX ion-exchange
  • palladium tetraamine-dihydroxide [Pd(NHa) 4 ](OH) 2
  • IEX solution 2000 ml. 0.1 wt.% palladium solution for ion exchange
  • 80.06 g of AR-glass is added to the IEX solution ("glass/IEX mixture”).
  • the pH of the glass/IEX mixture is measured, resulting in a pH of about 10.6.
  • the mixture is then transferred to a 4000-mL wide neck plastic container. The container is placed in an air-draft oven at 50 0 C for 72 hrs and shaken briefly by hand every 30 minutes.
  • the glass/IEX mixture is filtered on a Buchner funnel with Whatman 541 paper and washed with about 7.6 L a dilute NH 4 OH solution.
  • the dilute NH 4 OH solution is prepared by mixing 10 g of a concentrated 29.8 wt.% NH 4 OH solution with about 3.8 L of deionized water. Thereafter, the IEX-glass sample is dried at 110°C for 22 hrs.
  • the IEX-glass undergoes a reducing treatment in which the IEX-glass is reduced at 300°C for 4 hrs in hydrogen (H 2 ) under a H 2 flow rate of 2 L/hr.
  • the sample is analyzed by ICP-AES, resulting in a palladium concentration of about 0.019 wt.%.
  • AR-glass Cem-FIL Anti-Crak TM HD sample, as glass fibers having a mean diameter of about 17-20 microns, produced by Saint-Gobain Vetrotex, is obtained.
  • the as-received AR-glass sample undergoes a calcination heat treatment. In that treatment, the AR-glass is calcined at 600 0 C for 4 hrs in air under an air flow rate of 1 L/hr.
  • the calcined AR-glass undergoes an acid-leach treatment.
  • 250 g of the calcined AR-glass and 3 L 5.5 wt.% nitric acid are each placed in a 1-L wide-neck glass container.
  • the open plastic container is heated for 2 hrs on a Corning hotplate to a temperature of 90-100 0 C on the bottom of the container an to at least 75°C at the top of the container, measured with thermocouples placed at several places in the container; 5.5 wt.% nitric acid is added to keep the volume at 3 L as solution evaporates during the treatment.
  • the sample is filtered on 200 mesh stainless steel screen and washed with about 15 L deionized water. Thereafter, the acid-leached sample is dried at 100 0 C for several hours.
  • the acid-leach treated AR-glass undergoes an ion-exchange (IEX) treatment.
  • IEX solution 2000 ml. 0.1 wt.% palladium solution for ion exchange
  • 80 g of AR- glass is added to the IEX solution ("glass/I EX mixture”).
  • the pH of the glass/IEX mixture is measured, resulting in a pH of about 9.4.
  • the mixture is then transferred to a 4000-mL wide neck plastic container. The container is placed in an air-draft oven at 50°C for 2 hrs and shaken briefly by hand every 30 minutes.
  • the glass/IEX mixture is filtered on a Buchner funnel with Whatman 541 paper and washed with about several liters of deionized water. Thereafter, the IEX-glass is dried at 110 0 C for 22 hrs. [00213] Fourth, the IEX-glass undergoes a reducing at 300 0 C for 4 hrs in hydrogen (H 2 ) under a H 2 flow rate of 2 L/hr. [00214] The sample is analyzed by ICP-AES, resulting in a palladium concentration of about 0.019 wt.%.
  • the sample is analyzed by an XPS Sputter Depth Profiling method (as described below), demonstrating, as depicted in Fig. 1 , that the thickness of the region in which a substantial portion of the palladium is detected by this method is about 10 nm.
  • AR-glass Cem-FIL Anti-Crak TM HD sample, as glass fibers having a mean diameter of about 17-20 microns, produced by Saint-Gobain Vetrotex, is obtained.
  • the milled, acid-leach treated AR-glass undergoes an IEX treatment.
  • platinum tetraamine-dichloride [Pt(NH 3 ) 4 ](CI) 2
  • IEX solution 1 L 0.3 wt.% platinum solution for ion exchange
  • glass/IEX mixture 1 L 0.3 wt.% platinum solution for ion exchange
  • the pH of the glass/IEX mixture is measured.
  • the pH of the mixture is adjusted with a continuous drop- wise addition of about 29.8 wt.% ammonium hydroxide (NH 4 OH) to greater than pH 10 (in this example, resulting in a pH of about 10.6).
  • the glass/IEX mixture is transferred to a 4-L beaker and heated at 50 0 C for 2 hrs with continuous mechanical stirring with a stainless steel paddle stirrer at 300-500 rpm. After 1 hr of heating the pH is again measured, and as needed, adjusted again with about 29.8 wt.% NH 4 OH solution to a pH greater than 10. At the completion of the 2 hr. heating period, the glass/IEX mixture's pH is again measured, resulting in a pH of about 10.1.
  • the glass/IEX mixture is filtered and IEX-glass sample collected on a Buchner funnel with Whatman 541 paper and washed with about 7.6 L of a dilute NH 4 OH solution.
  • the dilute NH 4 OH solution is prepared by mixing 10 g of a concentrated 29.8 wt.% NH 4 OH solution with about 3.8 L of deionized water.
  • the IEX-glass sample is dried at 110°C for 22 hrs.
  • the IEX-glass sample undergoes a reducing treatment in which the ion- exchanged sample is reduced at 300°C for 4 hrs in hydrogen (H 2 ) under a H 2 flow rate of 2 L/hr.
  • AR-glass Cem-FIL Anti-Crak TM HD sample, as glass fibers having a mean diameter of about 17-20 microns, produced by Saint-Gobain Vetrotex, is obtained.
  • the as-received, AR-glass sample undergoes a calcination heat treatment. In that treatment, the AR-glass is calcined at 600 0 C for 4 hrs in air under an air flow rate of 1 L/hr.
  • the calcined AR-glass undergoes an acid-leach treatment.
  • About 30 g of the calcined AR-glass and 4 L 5.5 wt.% nitric acid are each placed in a 4-L wide neck plastic container.
  • the plastic container is placed in an air draft oven at 90 0 C oven for 2 hrs and shaken briefly by hand every 30 minutes.
  • the sample is filtered on a Buchner funnel with Whatman 541 paper and washed with about 7.5 L deionized water. Thereafter, the acid-leached sample is dried at 110°C for 22 hrs.
  • acid-leach treated AR-glass undergoes an IEX treatment.
  • platinum tetraamine-dichloride [Pt(NH 3 ) 4 ](CI) 2
  • IEX solution 3 L 0.01 wt.% platinum solution for ion exchange
  • About 15.01 g of acid-leach treated AR-glass is added to the IEX solution ("glass/IEX mixture”).
  • the pH of the glass/IEX mixture is measured. As needed, the pH of the mixture is adjusted with a continuous drop-wise addition of about 29.8 wt.% ammonium hydroxide (NH 4 OH) to greater than pH 10 (in this example, resulting in a pH of about 10.6).
  • the glass/IEX mixture is transferred to a 4-L wide neck plastic container.
  • the plastic container is placed in an air draft oven at 50 0 C oven for 2 hrs and shaken briefly by hand every 30 minutes. After 1 hr of heating the pH is again measured, and as needed, adjusted again with about 29.8 wt.% NH 4 OH solution to a pH greater than 10. At the completion of the 2 hr. heating period, the glass/IEX mixture's pH is again measured, resulting in a pH of about 10.19. After the IEX treatment is completed, the glass/IEX mixture is filtered and IEX-glass sample collected on a Buchner funnel with Whatman 541 paper and washed with about 7.6 L of a dilute NH 4 OH solution.
  • the dilute NH 4 OH solution is prepared by mixing 10 g of a concentrated 29.8 wt.% NH 4 OH solution with about 3.8 L of deionized water. Thereafter, the IEX-glass sample is dried at 1 10 0 C for 22 hrs.
  • the IEX-glass undergoes a reducing treatment in which the IEX-glass is reduced at 300°C for 4 hrs in hydrogen (H 2 ) under a H 2 flow rate of 2 L/hr.
  • H 2 hydrogen
  • the sample is analyzed by ICP-AES, resulting in a platinum concentration of about 0.0032 wt.%.
  • AR-glass Cem-FIL Anti-Crak TM HD sample, as glass fibers having a mean diameter of about 17-20 microns, produced by Saint-Gobain Vetrotex, is obtained.
  • the as-received, AR-glass sample undergoes a calcination heat treatment. In that treatment, the AR-glass is calcined at 600 0 C for 4 hrs in air under an air flow rate of 1 L/hr.
  • the calcined AR-glass undergoes an acid-leach treatment.
  • About 30 g of the calcined AR-glass and 4 L 5.5 wt.% nitric acid are each placed in a 4-L wide neck plastic container.
  • the plastic container is placed in an air draft oven at 90 0 C oven for 2 hrs and shaken briefly by hand every 30 minutes.
  • the sample is filtered on a Buchner funnel with Whatman 541 paper and washed with about 7.5 L deionized water. Thereafter, the acid-leached sample is dried at 110°C for 22 hrs.
  • Third, acid-leach treated AR-glass undergoes an IEX treatment.
  • platinum tetraamine-dichloride [Pt(NH 3 ) 4 ](CI) 2
  • IEX solution 3 L 0.01 wt.% platinum solution for ion exchange
  • glass/IEX mixture 3 L 0.01 wt.% platinum solution for ion exchange
  • the pH of the glass/IEX mixture is measured. As needed, the pH of the mixture is adjusted with a continuous drop-wise addition of about 40 wt.% tetrapropylammonium-hydroxide to greater than pH 10 (in this example, resulting in a pH of about 11.38).
  • the glass/IEX mixture is transferred to a 4-L wide neck plastic container.
  • the plastic container is placed in an air draft oven at 100 0 C oven for 22 hrs and shaken briefly by hand every 30 minutes.
  • the glass/IEX mixture is filtered and IEX-glass sample collected on a Buchner funnel with Whatman 541 paper and washed with about 7.6 L of a dilute NH 4 OH solution.
  • the dilute NH 4 OH solution is prepared by mixing 10 g of a concentrated 29.8 wt.% NH 4 OH solution with about 3.8 L of deionized water.
  • the IEX-glass sample is dried at 110°C for 22 hrs.
  • the IEX-glass undergoes a reducing treatment in which the IEX-glass is reduced at 300 0 C for 4 hrs in hydrogen (H 2 ) under a H 2 flow rate of 2 L/hr.
  • the sample is analyzed by ICP-AES, resulting in a platinum concentration of about 0.038 wt.%.
  • AR-glass Cem-FIL Anti-Crak TM HD sample, as glass fibers having a mean diameter of about 17-20 microns, produced by Saint-Gobain Vetrotex, is obtained.
  • platinum tetraamine-dichloride [Pt(NH 3 ) 4 ](CI) 2
  • IEX solution 3 L 0.01 wt.% platinum solution for ion exchange
  • About 8.79 g of acid-leach treated AR-glass is added to the IEX solution ("glass/IEX mixture”).
  • the pH of the glass/IEX mixture is measured. As needed, the pH of the mixture is adjusted with a continuous drop-wise addition of about 29.8 wt.% ammonium hydroxide (NH 4 OH) to greater than pH 10 (in this example, resulting in a pH of about 10.4).
  • the glass/IEX mixture is transferred to a 4-L wide neck plastic container.
  • the plastic container is placed in an air draft oven at 100 0 C oven for 22 hrs and shaken briefly by hand every 30 minutes.
  • the glass/IEX mixture is filtered and IEX-glass sample collected on a Buchner funnel with Whatman 541 paper and washed with about 7.6 L of a dilute NH 4 OH solution.
  • the dilute NH 4 OH solution is prepared by mixing 10 g of a concentrated 29.8 wt.% NH 4 OH solution with about 3.8 L of deionized water. Thereafter, the IEX-glass sample is dried at 1 10°C for 22 hrs.
  • the IEX-glass undergoes a reducing treatment in which the IEX-glass is reduced at 300°C for 4 hrs in hydrogen (H 2 ) under a H 2 flow rate of 2 L/hr.
  • H 2 hydrogen
  • the sample is analyzed by ICP-AES, resulting in a platinum concentration of about 0.022 wt.%.
  • AR-glass Cem-FIL Anti-Crak TM HD sample, as glass fibers having a mean diameter of about 17-20 microns, produced by Saint-Gobain Vetrotex, is obtained.
  • the as-received, AR-glass sample undergoes a calcination heat treatment. In that treatment, the AR-glass is calcined at 600°C for 4 hrs in air under an air flow rate of 1 L/hr.
  • the calcined AR-glass undergoes an acid-leach treatment.
  • About 30 g of the calcined AR-glass and 4 L 5.5 wt.% nitric acid are each placed in a 4-L wide neck plastic container.
  • the plastic container is placed in an air draft oven at 90 0 C oven for 2 hrs and shaken briefly by hand every 30 minutes.
  • the sample is filtered on a Buchner funnel with Whatman 541 paper and washed with about 7.5 L deionized water. Thereafter, the acid-leached sample is dried at 110 0 C for 22 hrs.
  • acid-leach treated AR-glass undergoes an IEX treatment.
  • cobalt (II) nitrate hexahydrate Co(NO 3 ) 2 -6H 2 O
  • IEX solution 1 L 0.1 wt.% cobalt solution for ion exchange
  • the IEX solution is prepared by bubbling N 2 through 1 L of deionized water in an Erlenmeyer flask for 30 minutes to minimize the amount of air present to prevent cobalt from changing oxidation states upon addition.
  • cobalt nitrate hexahydrate is added to the N 2 -purged deionized water.
  • the pH of the IEX solution is measured.
  • the pH of the mixture is adjusted with a continuous drop-wise addition of about 29.8 wt.% ammonium hydroxide (NH 4 OH) to greater than pH 10 (in this example, resulting in a pH of about 10.2).
  • the IEX solution is transferred to a 1-L wide neck plastic container. About 20 g of acid-leach treated AR-glass is added to the IEX solution ("glass/I EX mixture").
  • the plastic container is placed in an air draft oven at 50 0 C oven for 2 hrs and shaken briefly by hand every 30 minutes. After the IEX treatment is completed, the glass/IEX mixture is filtered on a Buchner funnel with Whatman 541 paper. The mother liquor is collected and pH measured (in this example pH is about 9.70).
  • the filtered glass is then washed with about 6 L of a dilute NH 4 OH solution.
  • the dilute NH 4 OH solution is prepared by mixing 10 g of a concentrated 29.8 wt.% NH 4 OH solution with about 3.8 L of deionized water. Thereafter, the IEX-glass sample is dried at 110°C for 16 hrs. [00244] The sample is analyzed by ICP-AES, resulting in a cobalt concentration of about 0.64 wt.%.
  • the as-received, AR-glass sample undergoes a calcination heat treatment.
  • the AR-glass is calcined at 600 0 C for 4 hrs in air under an air flow rate of 1
  • the calcined AR-glass undergoes an acid-leach treatment.
  • About 30 g of the calcined AR-glass and 4 L 5.5 wt.% nitric acid are each placed in a 4-L wide neck plastic container.
  • the plastic container is placed in an air draft oven at 90 0 C oven for 2 hrs and shaken briefly by hand every 30 minutes.
  • the sample is filtered on a Buchner funnel with Whatman 541 paper and washed with about 7.5 L deionized water. Thereafter, the acid-leached sample is dried at 110°C for 22 hrs.
  • Third, acid-leach treated AR-glass undergoes an IEX treatment.
  • cobalt (II) nitrate hexahydrate Co(NO 3 ) 2 -6H 2 O
  • IEX solution 1 L 0.1 wt.% cobalt solution for ion exchange
  • the IEX solution is prepared by bubbling N 2 through 1 L of deionized water in an Erlenmeyer flask for 30 minutes to minimize the amount of air present to prevent cobalt from changing oxidation states upon addition.
  • cobalt nitrate hexahydrate is added to the N 2 -purged deionized water.
  • the pH of the IEX solution is measured.
  • the pH of the mixture is adjusted with a continuous drop-wise addition of about 29.8 wt.% ammonium hydroxide (NH 4 OH) to greater than pH 10 (in this example, resulting in a pH of about 10.24).
  • NH 4 OH ammonium hydroxide
  • the IEX solution is transferred to a 1-L wide neck plastic container. About 20 g of acid-leach treated AR-glass is added to the IEX solution
  • glass/I EX mixture The plastic container is placed in an air draft oven at 50 0 C oven for 45 minutes, shaken briefly by hand after 25 minutes. After the completion of the IEX treatment, the glass/IEX mixture is filtered on a Buchner funnel with Whatman 541 paper. The mother liquor is collected and pH measured (in this example pH is about 9.88). The filtered glass is then washed with about 6 L of a dilute NH 4 OH solution. The dilute NH 4 OH solution is prepared by mixing 10 g of a concentrated 29.8 wt.% NH 4 OH solution with about 3.8 L of deionized water. Thereafter, the IEX-glass sample is dried at 110 0 C for 17 hrs. [00249] The sample is analyzed by ICP-AES, resulting in a cobalt concentration of about 0.15 wt.%. EXAMPLE 13
  • AR-glass Cem-FIL Anti-Crak TM HD sample, as glass fibers having a mean diameter of about 17-20 microns, produced by Saint-Gobain Vetrotex, is obtained.
  • the as-received, AR-glass sample undergoes a calcination heat treatment. In that treatment, the AR-glass is calcined at 600 0 C for 4 hrs in air under an air flow rate of 1 L/hr.
  • the calcined AR-glass undergoes an acid-leach treatment.
  • About 30 g of the calcined AR-glass and 4 L 5.5 wt.% nitric acid are each placed in a 4-L wide neck plastic container.
  • the plastic container is placed in an air draft oven at 90 0 C oven for 2 hrs and shaken briefly by hand every 30 minutes..
  • the sample is filtered on a Buchner funnel with Whatman 541 paper and washed with about 7.5 L deionized water. Thereafter, the acid-leached sample is dried at 110°C for 22 hrs.
  • acid-leach treated AR-glass undergoes an IEX treatment.
  • ammonium metatungstate (NH 4 ) 6 H 2 W 12 O 40 *nH 2 O, is used to prepare 3 L 0.05 wt.% tungsten solution for ion exchange ("IEX solution”).
  • IEX solution 3 L 0.05 wt.% tungsten solution for ion exchange
  • glass/IEX mixture 3 L 0.05 wt.% tungsten solution for ion exchange
  • the pH of the glass/IEX mixture is measured.
  • the pH of the mixture is adjusted with a continuous drop-wise addition of about 29.8 wt.% ammonium hydroxide (NH 4 OH) to pH 8.
  • the glass/IEX mixture is transferred to a 4-L wide neck plastic container. The plastic container is placed in an air draft oven at 50 0 C oven for 2 hrs and shaken briefly by hand every 30 minutes.
  • the glass/IEX mixture is filtered and IEX-glass sample collected on a Buchner funnel with Whatman 541 paper and washed with about 5 L of deionized water. Thereafter, the IEX-glass sample is dried at 110 0 C for 22 hrs.
  • the IEX-glass undergoes a calcination treatment in which the IEX-glass is calcined at 500 0 C for 4 hrs in air flow at a rate of 2 L/hr.
  • the sample is analyzed by ICP-AES, which is expected to result in a tungsten concentration of about 0.01 wt.%.
  • the as-received, non-calcined A-06F glass sample undergoes an acid-leach treatment.
  • About 21 g of the A-06F glass and 4 L 5.5 wt.% nitric acid are each placed in a 4- L wide neck plastic container.
  • the plastic container is placed in an air draft oven at 90 0 C oven for 2 hrs and shaken briefly by hand every 30 minutes.
  • the sample is filtered on a Buchner funnel with Whatman 541 paper and washed with about 7.6 L deionized water. Thereafter, the acid-leached sample is dried at 110°C for 22 hrs.
  • the acid-leach treated A-06F glass undergoes an IEX treatment.
  • platinum tetraamine-chloride [Pt(NH 3 ) 4 ](CI) 2
  • IEX solution 1 L 0.01 wt.% platinum solution for ion exchange
  • 20 g of A-06F glass is added to the IEX solution ("glass/IEX mixture”).
  • the pH of the glass/IEX mixture is measured.
  • the pH of the mixture is adjusted with a continuous drop-wise addition of about 29.8 wt.% ammonium hydroxide (NH 4 OH) to greater than pH 10 (in this example, resulting in a pH of about 1 1.1.
  • the glass/IEX mixture is transferred to a 2-L wide neck plastic container.
  • the container is placed in an air-draft oven at 100°C oven for 23 hrs.
  • the container is shaken several times over the 23 hr heating period.
  • the glass/IEX mixture is filtered and IEX-glass sample collected on a Buchner funnel with Whatman 541 paper and washed with about 7.6 L of a dilute NH 4 OH solution.
  • the dilute NH 4 OH solution is prepared by mixing 10 g of a concentrated 29.8 wt.% NH 4 OH solution with about 3.8 L of deionized water. Thereafter, the IEX-glass sample is dried at 1 10 0 C for 22 hrs.
  • the IEX-glass sample undergoes a reducing treatment in which the ion- exchanged sample is reduced at 300 0 C for 4 hrs in hydrogen (H 2 ) under a H 2 flow rate of 2 L/hr.
  • A-06F-glass fibers having a mean diameter of 500-600 nm produced by Lauscha Fiber International is obtained.
  • the as-received, non-calcined A-06F glass sample undergoes an acid-leach treatment. About 50 g of the A-06F glass and 4 L 5.5 wt.% nitric acid are each placed in a 4- L wide neck plastic container. The plastic container is placed in an air draft oven at 90 0 C oven for 2 hrs and shaken briefly by hand every 30 minutes. After the acid-leach treatment is completed, the sample is filtered on a Buchner funnel with Whatman 541 paper and washed with about 7.6 L deionized water. Thereafter, the acid-leached sample is dried at 110°C for 22 hrs.
  • the acid-leach treated A-06F-glass sample undergoes an IEX treatment.
  • palladium tetraamine-hydroxide [Pd(NH 3 ) 4 ](OH) 2
  • IEX solution 3 L 0.001 wt.% palladium solution for ion exchange
  • About 10 g A-06F glass is added to the IEX solution ("glass/IEX mixture”).
  • the pH of the glass/IEX mixture is measured.
  • the pH of the mixture is adjusted with a continuous drop-wise addition of about 29.8 wt.% ammonium hydroxide (NH 4 OH) to greater than pH 10 (in this example, resulting in a pH of about 10.5).
  • NH 4 OH ammonium hydroxide
  • the glass/IEX mixture is transferred to a 4-L wide neck plastic container.
  • the container is placed in an air-draft oven at 50°C oven for 2 hrs and shaken briefly by hand every 30 minutes.
  • the glass/IEX mixture is filtered on a Buchner funnel with Whatman 541 paper and a filtercake is obtained, which is remixed with about 3 L of a dilute NH 4 OH solution and filtered again. This remixing/filtering step is repeated two times.
  • the dilute NH 4 OH solution is prepared by mixing 10 g of a concentrated 29.8 wt.% NH 4 OH solution with about 3.8 L of deionized water. Thereafter, the IEX-glass sample is dried at 110°C for 22 hrs.
  • the IEX-glass sample undergoes a reducing treatment in which the IEX- glass sample is reduced at 300 0 C for 4 hrs in hydrogen (H 2 ) under a H 2 flow rate of 2 L/hr.
  • the sample is analyzed by ICP-AES, resulting in a palladium concentration of about 0.062 wt.%.
  • A-06F-glass fibers having a mean diameter of 500-600 nm produced by Lauscha Fiber International is obtained.
  • the as-received, non-calcined A-06F glass sample undergoes an acid-leach treatment. About 51 g of the A-06F glass and 4 L 5.5 wt.% nitric acid are each placed in a 4- L wide neck plastic container. The plastic container is placed in an air draft oven at 90 0 C oven for 2 hrs and shaken briefly by hand every 30 minutes. After the acid-leach treatment is completed, the sample is filtered on a Buchner funnel with Whatman 541 paper and washed with about 7.6 L deionized water. Thereafter, the acid-leached sample is dried at 110°C for 22 hrs.
  • the acid-leach treated A-06F glass undergoes Na + -back-ion exchange (“Na-BIX”) treatment.
  • the acid-leached sample from the first step is mixed with 4 L 3 mol/L sodium chloride (NaCI) solution ("glass/NaCI mixture").
  • NaCI sodium chloride
  • glass/NaCI mixture 4 L 3 mol/L sodium chloride
  • the pH of the glass/NaCI mixture is measured.
  • the pH of the glass/NaCI mixture is adjusted with a continuous drop- wise addition of about 40 wt.% tetrapropylammonium hydroxide to greater than pH 10 (in this example, resulting in a pH of about 10.9).
  • the glass/NaCI mixture is transferred to a 4-L wide-neck plastic container.
  • the plastic container is subsequently placed in an air-draft oven at 50 0 C for 4 hrs and shaken briefly by hand every 30 minutes.
  • the glass/NaCI mixture is filtered and the Na-BIX/A-06F sample collected on a Buchner funnel with Whatman 541 paper and washed with about 7.6 L deionized water. Thereafter, the Na-BIX/ A-06F-glass sample is dried at 1 10°C for 22 hrs.
  • IEX-2 second ion-exchange
  • palladium tetraamine-chloride [Pd(NH 3 ) 4 ](CI) 2
  • IEX-2 solution 1 L 0.01 wt.% palladium solution for ion exchange
  • 35 g of A-06F glass is added to the IEX-2 solution ("glass/I EX-2 mixture”).
  • the pH of the glass/IEX-2 mixture is measured, resulting in a pH of about 8.5.
  • the glass/IEX-2 mixture is transferred to a 2-L wide neck plastic container. The plastic container is placed in an air-draft oven at 50 0 C oven for 4 hrs and shaken briefly by hand every 30 minutes.
  • the glass/IEX-2 mixture is filtered on a Buchner funnel with Whatman 541 paper and the IEX-2-glass sample collected is washed with about 7.6 L of a dilute NH 4 OH solution.
  • the dilute NH 4 OH solution is prepared by mixing 10 g of a concentrated 29.8 wt.% NH 4 OH solution with about 3.8 L of deionized water. Thereafter, the ion-x2 sample is dried at 1 10 0 C for 22 hrs.
  • the IEX-2-glass sample undergoes a reducing treatment in which the sample is reduced at 300 0 C for 4 hrs in hydrogen (H 2 ) under a H 2 flow rate of 2 L/hr.
  • the sample is analyzed by ICP-AES, resulting in a palladium concentration of about 0.09 wt.%.
  • the sample is analyzed by an XPS Sputter Depth Profiling method (as described below), demonstrating, as depicted in Fig. 2, that the thickness of the region in which a substantial portion of the palladium is detected by this method is about 15 nm.
  • A-06F-glass fibers having a mean diameter of 500-600 nm produced by Lauscha Fiber International is obtained.
  • the A-06F-glass fiber undergoes an IEX treatment.
  • palladium tetraamine-hydroxide, [Pd(NH 3 ) 4 ](OH) 2 is used to prepare 2 L 0.001 wt.% palladium solution for ion exchange ("IEX solution”).
  • IEX solution 2 L 0.001 wt.% palladium solution for ion exchange
  • About 5.4 g A-06F glass is added to the IEX solution ("glass/IEX mixture"). The pH of the glass/IEX mixture is measured.
  • the pH of the mixture is adjusted with a continuous drop-wise addition of about 29.8 wt.% ammonium hydroxide (NH 4 OH) to greater than pH 10 (in this example, resulting in a pH of about 10.1 ).
  • the glass/IEX mixture is transferred to a 4-L glass beaker container and placed on a hotplate. The container is mechanically stirred at 59°C oven for 2 hrs. After the IEX treatment is completed, the glass/IEX mixture is filtered on a Buchner funnel with Whatman 541 paper and a filtercake is obtained, which is remixed with about 3 L of a dilute NH 4 OH solution and filtered again. This remixing/filtering step is repeated two times.
  • the dilute NH 4 OH solution is prepared by mixing 10 g of a concentrated 29.8 wt.% NH 4 OH solution with about 3.8 L of deionized water. Thereafter, the IEX-glass sample is dried at 100 0 C for 22 hrs. [00275] Second, the IEX-glass sample undergoes a reducing treatment in which the IEX- glass sample is reduced at 300 0 C for 4 hrs in hydrogen (H 2 ) under a H 2 flow rate of 2 L/hr. [00276] The sample is analyzed by ICP-AES, resulting in a palladium concentration of about 0.035 wt.%.
  • A-06F-glass fibers having a mean diameter of 500-600 nm produced by Lauscha Fiber International is obtained.
  • the as-received, non-calcined A-06F glass sample undergoes an acid-leach treatment. About 50 g of the A-06F glass and 4 L 5.5 wt.% nitric acid are each placed in a 4- L wide neck plastic container. The plastic container is placed in an air draft oven at 90 0 C oven for 2 hrs and shaken briefly by hand every 30 minutes. After the acid-leach treatment is completed, the sample is filtered on a Buchner funnel with Whatman 541 paper and washed with about 7.6 L deionized water. Thereafter, the acid-leached sample is dried at 110 0 C for 22 hrs.
  • the acid-leach treated A-06F-glass sample undergoes an IEX treatment.
  • palladium tetraamine-hydroxide [Pd(NHs) 4 ](OH) 2
  • IEX solution 3 L 0.001 wt.% palladium solution for ion exchange
  • About 10 g A-06F glass is added to the IEX solution ("glass/IEX mixture”).
  • the pH of the glass/IEX mixture is measured.
  • the pH of the mixture is adjusted with a continuous drop-wise addition of about 29.8 wt.% ammonium hydroxide (NH 4 OH) to greater than pH 10 (in this example, resulting in a pH of about 10.5).
  • NH 4 OH ammonium hydroxide
  • the glass/IEX mixture is transferred to a 4-L wide neck plastic container.
  • the container is placed in an air-draft oven at 50 0 C oven for 2 hrs and shaken briefly by hand every 30 minutes.
  • the glass/IEX mixture is filtered on a Buchner funnel with Whatman 541 paper and a filtercake is obtained, which is remixed with about 3 L of a dilute NH 4 OH solution and filtered again. This remixing/filtering step is repeated two times.
  • the dilute NH 4 OH solution is prepared by mixing 10 g of a concentrated 29.8 wt.% NH 4 OH solution with about 3.8 L of deionized water. Thereafter, the IEX-glass sample is dried at 110 0 C for 22 hrs.
  • the IEX-glass sample undergoes a reducing treatment in which the IEX- glass is initially calcined at 300 0 C for 2 hrs in air at an air flow rate of 2 L/hr and thereafter reduced at 300°C for 4 hrs in hydrogen (H 2 ) under a H 2 flow rate of 2 L/hr.
  • the sample is analyzed by ICP-AES, resulting in a palladium concentration of about 0.059 wt.%.
  • A-06F-glass fibers having a mean diameter of 500-600 nm produced by Lauscha Fiber International is obtained.
  • the as-received, non-calcined A-06F glass sample undergoes an acid-leach treatment. About 8.43 g of the A-06F glass and 1.5 L 5.5 wt.% nitric acid are each placed in a 2-L glass beaker and mechanically stirred with a stainless steel paddle stirrer at 300-500 rpm at 22°C for 30 min. After the acid-leach treatment is completed, the sample is filtered on a Buchner funnel with Whatman 541 paper and washed with about 7.6 L deionized water. Thereafter, the acid-leached sample is dried at 110 0 C for 22 hrs.
  • the acid-leach treated A-06F-glass sample undergoes an IEX treatment.
  • palladium tetraamine-hydroxide [Pd(NHs) 4 ](OH) 2
  • IEX solution 500 ml. 0.01 wt.% palladium solution for ion exchange
  • glass/IEX mixture About 4.2 g A-06F glass is added to the IEX solution ("glass/IEX mixture”).
  • the pH of the glass/IEX mixture is measured.
  • the pH of the mixture is adjusted with a continuous drop-wise addition of about 29.8 wt.% ammonium hydroxide (NH 4 OH) to greater than pH 10 (in this example, resulting in a pH of about 10.2).
  • the glass/IEX mixture is transferred to a 1-L beaker and stirred at 50 0 C for 2 hrs. After the IEX treatment is completed, the glass/IEX mixture is filtered on a Buchner funnel with Whatman 541 paper and washed with about 7.6 L deionized water. Thereafter, the IEX-glass sample is dried at 110 0 C for 22 hrs.
  • the IEX-glass sample undergoes a reducing treatment in which the IEX- glass is initially calcined at 300 0 C for 2 hrs in air at an air flow rate of 2 L/hr and thereafter reduced at 300 0 C for 4 hrs in hydrogen (H 2 ) under a H 2 flow rate of 2 L/hr.
  • the sample is analyzed by ICP-AES, resulting in a palladium concentration of about 0.57 wt.%.
  • A-06F-glass fibers having a mean diameter of 500-600 nm produced by Lauscha Fiber International is obtained.
  • the as-received, non-calcined A-06F glass sample undergoes an acid-leach treatment. About 30 g of the A-06F glass and 4 L 5.5 wt.% nitric acid are each placed in a 4- L wide neck plastic container. The plastic container is placed in an air draft oven at 90°C oven for 2 hrs and shaken briefly by hand every 30 minutes. After the acid-leach treatment is completed, the sample is filtered on a Buchner funnel with Whatman 541 paper and washed with about 7.6 L deionized water. Thereafter, the acid-leached sample is dried at 110°C for 22 hrs.
  • the acid-leach treated A-06F glass undergoes an IEX treatment.
  • platinum tetraamine-chloride [Pt(NH 3 ) 4 ](CI) 2
  • IEX solution 3 L 0.01 wt.% platinum solution for ion exchange
  • 15.1 g of acid-leached A-06F glass is added to the IEX solution ("glass/IEX mixture”).
  • the pH of the glass/IEX mixture is measured.
  • the pH of the mixture is adjusted with a continuous drop-wise addition of about 29.8 wt.% ammonium hydroxide (NH 4 OH) to greater than pH 10 (in this example, resulting in a pH of about 10.07).
  • the glass/IEX mixture is transferred to a 4-L wide neck plastic container.
  • the container is placed in an air-draft oven at 50 0 C oven for 2 hrs.
  • the container is shaken briefly by hand every 30 minutes.
  • the glass/IEX mixture is filtered and IEX-glass sample collected on a Buchner funnel with Whatman 541 paper and washed with about 7.6 L of a dilute NH 4 OH solution.
  • the dilute NH 4 OH solution is prepared by mixing 10 g of a concentrated 29.8 wt.% NH 4 OH solution with about 3.8 L of deionized water.
  • the IEX-glass sample is dried at 110 0 C for 22 hrs.
  • the IEX glass sample undergoes a reducing treatment in which the sample is reduced at 300 0 C for 4 hrs in hydrogen (H 2 ) under a H 2 flow rate of 2 L/hr.
  • the sample is analyzed by ICP-AES, resulting in a platinum concentration of about 0.33 wt.%.
  • A-06F-glass fibers having a mean diameter of 500-600 nm produced by Lauscha Fiber International is obtained.
  • the as-received, non-calcined A-06F glass sample undergoes an acid-leach treatment. About 30 g of the A-06F glass and 4 L 5.5 wt.% nitric acid are each placed in a 4- L wide neck plastic container. The plastic container is placed in an air draft oven at 90 0 C oven for 2 hrs and shaken briefly by hand every 30 minutes. After the acid-leach treatment is completed, the sample is filtered on a Buchner funnel with Whatman 541 paper and washed with about 7.6 L deionized water. Thereafter, the acid-leached sample is dried at 110°C for 22 hrs.
  • the acid-leach treated A-06F glass undergoes an IEX treatment.
  • platinum tetraamine-chloride [Pt(NH 3 ) 4 ](CI) 2
  • IEX solution 3 L 0.01 wt.% platinum solution for ion exchange
  • 9.3g of acid-leached A-06F glass is added to the IEX solution ("glass/IEX mixture").
  • the pH of the glass/IEX mixture is measured.
  • the pH of the mixture is adjusted with a continuous drop-wise addition of about 40 wt.% tetrapropylammonium hydroxide to greater than pH 10 (in this example, resulting in a pH of about 11.07).
  • the glass/IEX mixture is transferred to a 4-L wide neck plastic container.
  • the container is placed in an air-draft oven at 100 0 C oven for 22 hrs.
  • the container is shaken briefly by hand every 30 minutes.
  • the glass/IEX mixture is filtered and IEX-glass sample collected on a Buchner funnel with Whatman 541 paper and washed with about 7.6 L of a dilute NH 4 OH solution.
  • the dilute NH 4 OH solution is prepared by mixing 10 g of a concentrated 29.8 wt.% NH 4 OH solution with about 3.8 L of deionized water.
  • the IEX-glass sample is dried at 110 0 C for 22 hrs.
  • the IEX glass sample undergoes a reducing treatment in which the sample is reduced at 300 0 C for 4 hrs in hydrogen (H 2 ) under a H 2 flow rate of 2 L/hr.
  • the sample is analyzed by ICP-AES, resulting in a platinum concentration of about 0.59 wt.%.
  • A-06F-glass fibers having a mean diameter of 500-600 nm produced by Lauscha Fiber International is obtained.
  • the as-received, non-calcined A-06F glass sample undergoes an acid-leach treatment. About 30 g of the A-06F glass and 4 L 5.5 wt.% nitric acid are each placed in a 4- L wide neck plastic container. The plastic container is placed in an air draft oven at 90°C oven for 2 hrs and shaken briefly by hand every 30 minutes. After the acid-leach treatment is completed, the sample is filtered on a Buchner funnel with Whatman 541 paper and washed with about 7.6 L deionized water. Thereafter, the acid-leached sample is dried at 110 0 C for 22 hrs.
  • the acid-leach treated A-06F glass undergoes an IEX treatment.
  • platinum tetraamine-chloride [Pt(NH 3 ) 4 ](CI) 2
  • IEX solution 3 L 0.01 wt.% platinum solution for ion exchange
  • 21 g of acid-leached A-06F glass is added to the IEX solution ("glass/IEX mixture").
  • the pH of the glass/IEX mixture is measured.
  • the pH of the mixture is adjusted with a continuous drop-wise addition of about 29.8 wt.% ammonium hydroxide (NH 4 OH) to greater than pH 10 (in this example, resulting in a pH of about 10.38).
  • the glass/IEX mixture is transferred to a 4-L wide neck plastic container.
  • the container is placed in an air-draft oven at 100 0 C oven for 22 hrs.
  • the container is shaken briefly by hand every 30 minutes.
  • the glass/IEX mixture is filtered and IEX-glass sample collected on a Buchner funnel with Whatman 541 paper and washed with about 7.6 L of a dilute NH 4 OH solution.
  • the dilute NH 4 OH solution is prepared by mixing 10 g of a concentrated 29.8 wt.% NH 4 OH solution with about 3.8 L of deionized water. Thereafter, the IEX-glass sample is dried at 110°C for 22 hrs.
  • the IEX glass sample undergoes a reducing treatment in which the sample is reduced at 300 0 C for 4 hrs in hydrogen (H 2 ) under a H 2 flow rate of 2 L/hr.
  • the sample is analyzed by ICP-AES, resulting in a platinum concentration of about 0.71 wt.%.
  • the as-received, non-calcined A-06F glass sample undergoes an acid-leach treatment.
  • 15 g of the A-06F glass and 4 L 5.5 wt.% nitric acid are each placed in a 4-L wide neck plastic container.
  • the plastic container is placed in an air draft oven at 90 0 C oven for 2 hrs and shaken briefly by hand every 30 minutes.
  • the sample is filtered on a Buchner funnel with Whatman 541 paper and washed with about 7.6 L deionized water. Thereafter, the acid-leached sample is dried at 1 10 0 C for 22 hrs.
  • the acid-leach treated A-06F glass undergoes a double-IEX treatment.
  • 3 L 0.0005 wt.% total metal solution is used for double-IEX ("double-IEX solution").
  • the double IEX solution is prepared by mixing 1.5 L 0.0005 wt.% palladium solution and 1.5 L 0.0005 wt.% copper solution.
  • palladium tetraamine hydroxide is used to prepare 1.5 L 0.0005 wt.% palladium solution
  • copper nitrate is used to prepare 1.5 L 0.0005 wt.% copper solution
  • About 14 g of A-06F glass is added to the double-IEX solution ("glass/IEX mixture").
  • the pH of the glass/IEX mixture is measured. As needed, the pH of the mixture is adjusted with a continuous drop-wise addition of about 29.8 wt.% ammonium hydroxide (NH 4 OH) to greater than pH 10 (in this example, resulting in a pH of about 10.9).
  • the glass/IEX mixture is transferred to a 4-L wide neck plastic container. The container is placed in an air-draft oven at 50°C oven for 2 hrs and shaken briefly by hand every 30 minutes. After the double-IEX treatment is completed, the glass/IEX mixture is filtered on a Buchner funnel with Whatman 541 paper and double-IEX-glass sample collected is washed with about 7.6 L of a dilute NH 4 OH solution.
  • the dilute NH 4 OH solution is prepared by mixing 10 g of a concentrated 29.8 wt.% NH 4 OH solution with about 3.8 L of deionized water. Thereafter, the double-IEX-glass sample is dried at 110 0 C for 22 hrs. [00307] Third, the double-IEX-glass sample undergoes a reducing treatment in which the double-IEX-glass sample is reduced at 300 0 C for 4 hrs in hydrogen (H 2 ) under a H 2 flow rate of 2 L/hr.
  • the sample is analyzed by ICP-AES, resulting in a palladium concentration of about 0.019 wt.% and a copper concentration of about 0.02 wt.%.
  • A-06F-glass fibers having a mean diameter of 500-600 nm produced by Lauscha Fiber International is obtained.
  • the as-received, non-calcined A-06F glass sample undergoes an acid-leach treatment. About 51 g of the A-06F glass and 4 L 5.5 wt.% nitric acid are each placed in a 4- L wide neck plastic container. The plastic container is placed in an air draft oven at 90 0 C oven for 2 hrs and shaken briefly by hand every 30 minutes. After the acid-leach treatment is completed, the sample is filtered on a Buchner funnel with Whatman 541 paper and washed with about 7.6 L deionized water. Thereafter, the acid-leached sample is dried at 110°C for 22 hrs.
  • the acid-leach treated A-06F glass undergoes an IEX treatment.
  • silver nitrate is used to prepare 4 L 0.001 wt.% silver solution for ion exchange ("IEX solution”).
  • 10 g of A-06F glass is added to the IEX solution ("glass/IEX mixture”).
  • the pH of the glass/IEX mixture is measured.
  • the pH of the mixture is adjusted with a continuous drop-wise addition of about 29.8 wt.% ammonium hydroxide (NH 4 OH) to greater than pH 1 1 (in this example, resulting in a pH of about 1 1.5).
  • the glass/IEX mixture is transferred to a 4-L wide neck plastic container.
  • the plastic container is placed in an air- draft oven at 50 0 C oven for 2 hrs and shaken briefly by hand every 30 minutes.
  • glass/IEX mixture is filtered and the IEX-glass sample collected on a Buchner funnel with Whatman 541 paper and washed with about 7.6 L of a dilute NH 4 OH solution.
  • the dilute NH 4 OH solution is prepared by mixing 10 g of a concentrated 29.8 wt.% NH 4 OH solution with about 3.8 L of deionized water. Thereafter, the IEX-glass sample is dried at 110°C for 22 hrs.
  • the IEX-glass sample undergoes a reducing treatment in which the IEX- glass sample is reduced at 300°C for 4 hrs in hydrogen (H 2 ) under a H 2 flow rate of 2 L/hr.
  • the sample is analyzed by ICP-AES, resulting in a silver concentration of about 0.053 wt.%.
  • EXAMPLE 25 Platinum on A-06F glass
  • A-06F-glass fibers having a mean diameter of 500-600 nm produced by Lauscha Fiber International is obtained.
  • the as-received, non-calcined A-06F glass sample undergoes an acid-leach treatment. About 100 g of the A-06F glass and 4 L 5.5 wt.% nitric acid are each placed in a 4-L wide neck plastic container. The plastic container is placed in an air draft oven at 90 0 C oven for 2 hrs and shaken briefly by hand every 30 minutes. After the acid-leach treatment is completed, the sample is filtered on a Buchner funnel with Whatman 541 paper and washed with about 7.6 L deionized water. Thereafter, the acid-leached sample is dried at 110 0 C for 22 hrs.
  • the acid-leach treated A-06F glass undergoes an IEX treatment.
  • platinum tetraamine-chloride [Pt(NH 3 ) 4 ](CI) 2
  • IEX solution 3 L 0.016 wt.% platinum solution for ion exchange
  • 48.17g of A-06F glass is added to the IEX solution ("glass/IEX mixture”).
  • the pH of the glass/IEX mixture is measured.
  • the pH of the mixture is adjusted with a continuous drop-wise addition of about 29.8 wt.% ammonium hydroxide (NH 4 OH) to greater than pH 10 (in this example, resulting in a pH of about 10.06).
  • the glass/IEX mixture is transferred to a 4-L wide neck plastic container.
  • the container is placed in an air-draft oven at 50 0 C oven for 2 hrs.
  • the container is shaken briefly by hand every 30 minutes.
  • the glass/IEX mixture is filtered and IEX-glass sample collected on a Buchner funnel with Whatman 541 paper and washed with about 7.6 L of a dilute NH 4 OH solution.
  • the dilute NH 4 OH solution is prepared by mixing 10 g of a concentrated 29.8 wt.% NH 4 OH solution with about 3.8 L of deionized water. Thereafter, the IEX-glass sample is dried at 110°C for 22 hrs.
  • the IEX glass sample undergoes a reducing treatment in which the sample is reduced at 500 0 C for 4 hrs in hydrogen (H 2 ) under a H 2 flow rate of 2 L/hr.
  • the sample is analyzed by ICP-AES, resulting in a platinum concentration of about 0.147 wt.%.
  • the as-received, non-calcined A-06F glass sample undergoes an acid-leach treatment.
  • About 21 g of the A-06F glass and 4 L 5.5 wt.% nitric acid are each placed in a 4- L wide neck plastic container.
  • the plastic container is placed in an air draft oven at 90 0 C oven for 2 hrs and shaken briefly by hand every 30 minutes.
  • the sample is filtered on a Buchner funnel with Whatman 541 paper and washed with about 7.6 L deionized water. Thereafter, the acid-leached sample is dried at 110 0 C for 22 hrs.
  • the acid-leach treated A-06F glass undergoes an IEX treatment.
  • platinum tetraamine-chloride [Pt(NH 3 ) 4 ](CI) 2
  • IEX solution 4 L 0.02 wt.% platinum solution for ion exchange
  • About 21 g of acid-leached A-06F glass is added to the IEX solution ("glass/IEX mixture”).
  • the pH of the glass/IEX mixture is measured.
  • the pH of the mixture is adjusted with a continuous drop-wise addition of about 29.8 wt.% ammonium hydroxide (NH 4 OH) to greater than pH 10 (in this example, resulting in a pH of about 10.90).
  • the glass/IEX mixture is transferred to a 4-L wide neck plastic container.
  • the container is placed in an air-draft oven at 100 0 C oven for 22 hrs.
  • the container is shaken briefly by hand every 30 minutes.
  • the glass/IEX mixture is filtered and IEX-glass sample collected on a Buchner funnel with Whatman 541 paper and washed with about 7.6 L of a dilute NH 4 OH solution.
  • the dilute NH 4 OH solution is prepared by mixing 10 g of a concentrated 29.8 wt.% NH 4 OH solution with about 3.8 L of deionized water.
  • the IEX-glass sample is dried at 110 0 C for 22 hrs.
  • the IEX glass sample undergoes a reducing treatment in which the sample is reduced at 300 0 C for 4 hrs in hydrogen (H 2 ) under a H 2 flow rate of 2 L/hr.
  • the sample is analyzed by ICP-AES, resulting in a platinum concentration of about 0.67 wt.%.
  • EXAMPLE 27 Palladium on E-06F glass Non-leached [00324] E-06F-glass fibers having a mean diameter of 500-600 nm produced by Lauscha Fiber International, is obtained.
  • the unleached E-06F-glass sample undergoes an IEX treatment.
  • palladium tetraamine- hydroxide [Pd(NH 3 ) 4 ](OH) 2
  • IEX solution 2 L 0.00008 wt.% palladium solution for ion exchange
  • IEX solution 2 L 0.00008 wt.% palladium solution for ion exchange
  • about 15.45 g E-06F glass is added to the IEX solution ("glass/IEX mixture”).
  • the pH of the glass/IEX mixture is measured.
  • the pH of the mixture is adjusted with a continuous drop-wise addition of about 29.8 wt.% ammonium hydroxide (NH 4 OH) to greater than pH 10 (in this example, resulting in a pH of about 10.99).
  • the glass/IEX mixture is transferred to a 4-L wide neck plastic container.
  • the container is placed in an air-draft oven at 50°C oven for 2 hrs.
  • the container is shaken briefly by hand every 30 minutes.
  • the glass/1 EX mixture is filtered and IEX-glass sample collected on a Buchner funnel with Whatman 541 paper and washed with about 7.6 L of a dilute NH 4 OH solution.
  • the dilute NH 4 OH solution is prepared by mixing 10 g of a concentrated 29.8 wt.% NH 4 OH solution with about 3.8 L of deionized water. Thereafter, the IEX-glass sample is dried at 110°C for 22 hrs.
  • the IEX-glass undergoes a reducing treatment in which the IEX-glass is reduced at 300 0 C for 4 hrs in hydrogen (H 2 ) under a H 2 flow rate of 2 L/hr.
  • the sample is analyzed by ICP-AES, resulting in a palladium concentration of about 0.014 wt.%.
  • EXAMPLE 28 Compound Catalyst-1
  • a gamma alumina precursor comprising unpeptized Versal-251 pseudoboehmite is obtained and split (40/60) to produce two portions of 7.2 g and 10.7 g, respectively.
  • the 7.2 g portion of unpeptized pseudoboehmite ("unpeptized V-251 ") is dry- mixed with the precursor catalyst composition, 13.4 g of the A-06F glass fibers with about 0.67 wt. % Pt, and 1.6 g of MTW type zeolite (described above) in a Lancaster muller for about 10 minutes.
  • the 10.7 g portion of the pseudoboehmite is peptized with about 1 g of 70% HNO 3 and about 10 ml. water.
  • the substantially peptized pseudoboehmite (“peptized V-251") is added to the previously mulled mixture of the precursor catalyst composition and MTW zeolite in the Lancaster muller and mulled to produce a mixture having a dough-like consistency.
  • the resulting dough is placed in a RAM extruder with a 1.6 mm (1/16 in) die plate to produce an extrudate, which is broken (by hand) into extrudate particles having a length of ranging from about 6.4 mm (1/4 in) to about 9.5 mm (3/8 in).
  • the extrudate particles are dried on wire mesh tray in an air-draft oven with an air flow rate of about 8.5 m 3 /hr (300 ft 3 /hr) at 100° C for about 2 hours.
  • the extrudate particles are calcined by first ramping the oven temperature to 300° C over 1 hour and holding for 1 hour. The first temperature ramp is followed by a second temperature ramp up to 500° C over 2 hours and subsequently held at 500° C for an additional 3 hours to convert the pseudoboehmite substantially to gamma alumina.
  • a calcined compound catalyst composition is produced having a MTW-type zeolite and precursor FSC composition dispersed in the compound catalyst composition, while the Pt constituent of the FSC composition is dispersed substantially in or on the pre- treated A glass, as indicated by the methycyclohexane to toluene activity test results described below.
  • the extrudate sample is examined by scanning transmission electron microscopy (STEM) analysis as described under Example CH-1 (below), indicating in Figs. 3 and 4 that Pt particles (brighter points of contrast) are generally dispersed within a distance less than or equal to about 30 nm from the surface of precursor catalyst composition having a substantially nonporous substrate, in this case, leached A glass fibers.
  • STEM scanning transmission electron microscopy
  • XPS X-Rav Photoelectron Spectroscopy
  • the XPS Sputter Depth Profiles are obtained using a PHI Quantum 200 Scanning ESCA MicroprobeTM (Physical Electronics, Inc.) with a micro-focused, monochromatized Al Ka X-ray source at 1486.7 eV.
  • a dual neutralization capability using low energy electrons and positive ions to provide charge compensation during spectral acquisition is standard in this instrument.
  • XPS spectra are generally measured under the following conditions:
  • Electron emission angle 45° to sample normal [00341] All XPS spectra and sputter depth profiles are recorded at room temperature without sample pretreatment, with the exception of introducing the samples in the vacuum environment of the XPS instrument.
  • Sputter depth profiles are generated by alternating cycles of spectral acquisition of the sample surface, followed by 2 kV Ar + sputtering of the sample surface for 15 - 30 s in each cycle to remove surface material.
  • the sputter depth rate is calibrated using a silica thin film of known thickness.
  • Atomic concentration values for Pd and Si shown in Fig. 1 and 2 are obtained by taking the Pd 3d3/ 2 and Si 2p peak areas and correcting for their respective atomic sensitivity factors and the analyzer transmission function.
  • TEM Transmission electron microscopy
  • STEM Field Emission scanning transmission electron microscopy
  • Samples are prepared by first embedding the sample material in a standard embedding epoxy known to those skilled in the art of TEM analysis. After curing, the epoxy- embedded sample material is sectioned using an ultra-microtome sectioning device to produce ⁇ 80 nm thick sections. Sections are collected on thin film holey carbon supports and, without further processing, are properly oriented in the electron-beam field of the above-described STEM instrument for examination and analysis.
  • the determination of a target analyte's location and the mean thickness of a region of interest versus a substrate's surface using TEM analysis is subject to both human and mechanical error, which can impose uncertainty in the TEM vertical depth measurement (vs. a specific reference point) of about ⁇ 20% and a lateral position measurement (vs. a specific reference point) of about ⁇ 5%, depending the sample's image resolution, target analyte's physicochemical characteristics and sample morphology, among other factors. Accordingly, the uncertainty is manifested in the distance measured for the catalytic constituent vs. the sample substrate surface. This imprecision is general throughout the art of TEM analysis and is not sufficient to preclude differentiation between catalyst compositions.
  • SARC Wa The sodium surface area rate of change
  • a SARC/va is determined for each of the samples specified below in the following examples according to the procedure described above for SARC Wa .
  • a blank sample is prepared by producing a 3.5M NaCI solution (i.e, 30 g NaCI in 150 ml. deionized water), but contains no substrate sample.
  • four independent blank samples are titrated and the mean value of the titrant volumes for the specified concentration (0.01 N in this case) used to obtain a V, and V 510 is (i.e., V to tai - V 1 ) are used to adjust (i.e., correct) the volume of titrant used in the SARC/va determination of each substrate sample.
  • the blank sample is pH adjusted and titrated according to the same procedure described above for SARC/va determinations, but again, without substrate present.
  • IEP Isoelectric Point
  • IEP isoelectric point
  • the instrument is calibrated with standard pH buffer solutions of pH 2, 4, 7 and 10 over the entire IEP range of interest.
  • the IEP is determined for each sample by wetting the samples with an amount of 16 M ⁇ deionized water (at about 25°C) sufficient to bring the sample to a state of incipient wetness, which will result in producing a relatively dense aqueous slurry-like or paste-like mixture.
  • this state of incipient wetness will allow liquid contact of both the glass electrode and its reference electrode junctions with the liquid (in this case, water of the slurry- or paste-like mixture) in contact with the solid sample being tested.
  • This procedure will require variable amounts of water, depending on the form of the sample (e.g.
  • the volume of added water should be only enough to allow sufficient liquid contact with both glass electrode and reference electrode junctions. In other words, adding water beyond a sample's state of incipient wetness should be avoided, to the extent reasonably possible to do so, for the sample being tested.
  • the solid sample is mixed, by hand, with the deionized water (added to produce incipient wetness) using the electrode tip in each case until the measured pH stabilizes, then the resulting pH is read from the meter.
  • S.A.M2-BET or S.A. Kr- BE ⁇ determinations are made, as appropriate, for each of the samples specified below according to the ASTM procedures referenced above.
  • higher surface area measurements e.g., about 3 to 6 m 2 /g
  • N 2 BET e.g., N 2 BET
  • ASTM D3663-03 e.g., ⁇ about 3 m 2 /g
  • Kr BET e.g., ⁇ about 3 m 2 /g
  • ASTM D4780-95 e.g., ⁇ about 3 m 2 /g Kr BET, according to the method described by ASTM D4780-95, (“S.A./o-W)
  • S.A./o-W is likely to be the preferred surface area measurement technique.
  • E-06F glass sample as glass fibers having a mean diameter of 500-600 nm produced by Lauscha Fiber International, is obtained.
  • Sample A-1 is the as-received E-glass sample, while A-2 is prepared by calcining, but not leaching, the as-received E-glass.
  • the non- leached E-glass sample undergoes a calcination heat treatment. In that treatment, the non- leached E-glass is calcined at 600 0 C for 4 hrs in air under an air flow rate of 1 L/hr.
  • Comparative Sample Comp-B is prepared by acid-leach treating the as-received, non-calcined, E-glass.
  • Comparative Sample Comp-B For Comparative Sample Comp-B, about 15 g of the E-glass and 1.5 L 9 wt.% nitric acid are each placed in a 4-L wide-neck plastic container. The plastic container is placed in an air draft oven at 95°C for 4 hr and shaken briefly by hand every 30 minutes. After the acid-leach treatment is completed, the sample is filtered on a Buchner funnel with Whatman 541 paper and washed with about 7.6 L deionized water. Thereafter, the acid-leached sample is dried at 110 0 C for 22 hrs.
  • Samples A-1 , A-2 and Comp-B are analyzed by the Analytical Method for Determining SARC Wa described above. The results are presented in the table below.
  • AR-glass Cem-FIL Anti-Crak TM HD sample, as glass fibers having a mean diameter of about 17-20 microns, produced by Saint-Gobain Vetrotex, is obtained. This glass is used for Samples A, B and C in this example.
  • ARG 6S-750 glass sample, as glass fibers having a mean diameter of about 13 microns produced by Nippon Electric Glass is obtained. This glass is used for Samples D and E in this example.
  • Samples A and D are prepared by calcining the as-received AR- and ARG-glass, respectively.
  • the AR- and ARG-glass samples undergo a calcination heat treatment. In that treatment, the AR-glass and ARG-glass is calcined at 600 0 C for 4 hrs in air under an air flow rate of 1 L/hr.
  • Samples B, C and E are prepared by acid-leach treating the as-received, non- calcined, AR-glass and ARG-glass, respectively.
  • Samples B and C about 101 g of the AR-glass and 4 L 5.5 wt.% nitric acid are each placed in a 4-L wide-neck plastic container. The plastic container is placed in an air draft oven at 90 0 C for 2 hr and shaken briefly by hand every 30 minutes. After the acid- leach treatment is completed, the sample is filtered on a Buchner funnel with Whatman 541 paper and washed with about 7.6 L deionized water. Thereafter, the acid-leached sample is dried at 110°C for 22 hrs.
  • Sample E about 58 g of the ARG-glass and 4 L 5.5 wt.% nitric acid are each placed in a 4-L wide-neck plastic container. The plastic container is placed in an air draft oven at 90 0 C for 2 hr and shaken briefly by hand every 15 minutes. After the acid- leach treatment is completed, the sample is filtered on a Buchner funnel with Whatman 541 paper and washed with about 7.6 L deionized water. Thereafter, the acid-leached sample is dried at 110°C for 22 hrs.
  • V, and Vt measured for the substrate samples are within the 95% confidence interval for the mean value so the SARCwa values are considered statistically indistinguishable from the blank mean. Accordingly, a SARC Wa determination is not considered applicable for these samples.
  • A-06F-glass fibers having a mean diameter of 500-600 nm produced by Lauscha Fiber International is obtained. This glass is used for Samples A, B and C in this example.
  • Sample A is a sample of as-received A-06F-glass fibers.
  • Samples B and C are prepared by acid-leach treating the as-received, non- calcined, A-06F-glass.
  • Samples B and C about 58.5 g of the A-06F-glass and 4 L 5.5 wt. % nitric acid are each placed in a 4-L wide-neck plastic container. The plastic container is placed in an air draft oven at 90 0 C for 2 hr and shaken briefly by hand every 30 minutes.
  • the sample is filtered on a Buchner funnel with Whatman 541 paper and washed with about 7.6 L deionized water. Thereafter, the acid- leached sample is dried at 110 0 C for 22 hrs.
  • the following non-limiting example indicates that dispersing a precursor catalyst composition in a compound catalyst composition is not expected to adversely affect the precursor catalyst composition's activity as compared to its activity before dispersion in the compound catalyst composition.
  • the catalytic activity for an extrudate sample having the precursor FSC composition of Example 26 is prepared substantially according to Example 28. Also, in this example, the particle size distribution of the extrudate sample is maintained between about 40 to 60 mesh (i.e., 425 to 250 microns) to reduce adverse affects introduced from intra-particle diffusion path resistance.
  • the catalyst is pre-treated prior to the activity test with a H 2 flow rate of 250 cc/min at 350 0 C for about 30 minutes.
  • the H 2 to feed molar ratio is about 56 to 1.
  • the flow rate of this feed mixture is varied over about a 4 hour period in the range of 125 cc/min to 1000 cc/min.
  • the conversion of MCH to toluene is determined.
  • the catalyst is tested at a temperature of
  • Fig. 5 plots the toluene yield (wt.%) against the inverse flow rate (min/cc). For each flow rate with a related toluene conversion yield, the yield for a precursor catalyst composition dispersed in the extrudate sample is substantially similar to, if not coincident with, the respective yield for the same precursor catalyst composition free of an extrudate base material (i.e., before dispersion in the base). Accordingly, the results of Fig. 5 indicate that the catalytic activity of the precursor catalyst composition is not expected to be adversely affected when dispersed in the compound catalyst composition.

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Abstract

La présente invention concerne une composition de catalyseur composé utilisée dans de nombreux processus chimiques. La composition comprend un oxyde réfractaire de composition et une composition de catalyseur précurseur, un ou plusieurs constituants tensio-actifs fonctionnels étant intégrés à la surface du substrat et/ou dans cette surface. La composition de catalyseur précurseur comprend un substrat sensiblement non poreux qui présente une surface active totale située entre environ 0,01 m2/g et 10 m2/g et de préférence un point isoélectrique (IEP) prédéfini, obtenu dans une gamme de pH supérieure à 0, de préférence supérieure à 6,0, mais inférieure ou égale à 14. Au moins une région à activité catalytique peut être contiguë ou non contiguë et présente une épaisseur moyenne ≤ à environ 30 nm. La composition de catalyseur précurseur est de préférence une composition de catalyseur de surface fonctionnel qui comprend un verre présentant un SARCNa ≤ à environ 0,5. L'oxyde réfractaire de composition et la composition de catalyseur précurseur sont entremêlés une fois que la composition de catalyseur précurseur est produite.
PCT/US2007/084211 2006-11-11 2007-11-09 Composition de catalyseur composé WO2008060979A2 (fr)

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US11084021B2 (en) 2015-10-27 2021-08-10 W.R. Grace & Co.—Conn Acid-resistant catalyst supports and catalysts

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KR102604873B1 (ko) 2015-07-22 2023-11-23 바스프 코포레이션 아세트산비닐 단량체 생산을 위한 높은 기하학적 표면적 촉매
SG11202000709TA (en) * 2017-07-28 2020-02-27 Rohm & Haas A method for production of methyl methacrylate by oxidative esterification using a heterogeneous catalyst
CN115025781B (zh) * 2022-06-13 2023-08-29 中国石油大学(华东) 一种用于催化非临氢加氢的催化剂及其制备方法和应用

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US20020035033A1 (en) * 1997-09-30 2002-03-21 Herbert Muller Process for preparing a shell-type catalyst
EP1044935A1 (fr) * 1999-04-13 2000-10-18 Ecole Polytechnique Federale De Lausanne Fibre de verre poreuse, résistante à poids léger ayant des propriétés physiques, chimiques ou biologiques
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11084021B2 (en) 2015-10-27 2021-08-10 W.R. Grace & Co.—Conn Acid-resistant catalyst supports and catalysts
US11691124B2 (en) 2015-10-27 2023-07-04 W.R. Grace & Co.-Conn Acid-resistant catalyst supports and catalysts

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CN101583419A (zh) 2009-11-18
WO2008060965A3 (fr) 2008-08-07
TW200843852A (en) 2008-11-16
TW200902146A (en) 2009-01-16
WO2008060965A2 (fr) 2008-05-22
EP2081678A2 (fr) 2009-07-29
WO2008060979A3 (fr) 2008-10-02
WO2008060977A2 (fr) 2008-05-22
WO2008060977A3 (fr) 2008-07-03

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