TW200902146A - Compound catalyst composition - Google Patents

Abstract

A compound catalyst composition, useful for many chemical processes, comprises a compounding refractor oxide and a precursor catalyst composition, with one or more functional surface active constituents integrated on and/or in the substrate surface. The precursor catalyst composition comprises a substantially non-porous substrate having a total surface area between about 0.01 m2/g and 10 m2/g; and, preferably, a predetermined isoelectric point (IEP) obtained in a pH range greater than 0, preferably greater than 6.0, but less than or equal to 14. At least one catalytically-active region may be contiguous or discontiguous and has a mean thickness ≤ about 30 nm. Preferably, the precursor catalyst composition is a functional surface catalyst composition comprising a glass having a SARCNa ≤ about 0.5. The compounding refractor oxide and the precursor catalyst composition are intermixed after the precursor catalyst composition is produced.

Description

200902146 IX. Description of the Invention: [Technical Field] The present invention relates to a composite catalyst composition and a preparation method thereof, which are applicable to various chemical production methods and various emission control methods. In particular, the present invention relates to a composite catalyst composition comprising a refractory oxide and a precursor catalyst composition. The precursor catalyst composition is preferably a functional surface catalyst (FSC) composition. [Prior Art] Catalyst compositions are used to promote a class of chemical reactions that are generally described as catalytic or catalytic, and catalysis is critical for efficient operation of various chemical processes. Most industrial reactions and almost all biological reactions, if not catalytic, are pre- or post-reaction treatments involving catalytic reactions. The value of the product produced by the process of including catalysis in only one stage in the United States is close to one trillion dollars (USD). Products produced using catalyst compositions include, for example, food, clothing, pharmaceuticals, household chemicals, specialty or fine chemicals, plastics, detergents, fuels, and lubricants. Catalyst compositions can also be used to treat emissions (such as vehicle exhaust emissions, refinery emissions, utilities, and plant emissions) and other process emissions to reduce potential negative impacts on human health or the environment. The content of harmful ingredients. Guangzhe's sales and §, the sales of solid-loaded catalysts for heterogeneous reactions in the global market are approximately US$3 billion per year. The solid carrier catalyst is usually divided into three oil refining catalysts, chemical processing catalysts and emission control catalysts. The market for such catalysts is basically three-thirds of the world. For example, in 1990, in the solid catalyst market of 126437.doc 200902146 US 1 81⁄4, US TL, 37%, 34% and 29% of the petroleum refining, chemical processing and emission control catalyst market. For example, in the petroleum refining catalyst market (about $1 billion in 1990), 56% of the revenue comes from fluid-vehicle cracking (FCC) catalysts, while 31.5%, 65% and 45% of the revenue comes from hydrogenation. Treatment of catalyst, hydrocracking catalyst and reforming catalyst. From a chemical mechanism point of view, the catalyst can generally bring a chemical reaction to a rate of equilibrium between the reactants and the product in the case of itself, which is substantially free of consumption. Therefore, for any relevant reaction, although the catalyst cannot change the equilibrium state between the reactants and the product, the catalyst can accelerate the rate of the chemical reaction if properly designed and/or selected. Thus, catalysts are used for a wide variety of commercial and practical processes for a variety of purposes, including improving process reactivity, selectivity and energy efficiency, and other materials. For example, the reaction rate or reactivity of the reactants produced to produce the desired product in accordance with the specified process conditions can reduce the processing time to achieve higher product throughput (e.g., increase product volume or mass per unit hour). ). Thus, catalyst activity refers to the ability of the catalyst composition to effectively convert the reactants to the desired product at a unit time. Similarly, the selectivity of the ruthenium reaction can be increased, and the yield of the desired house can be increased by the 反应 瘟 Α 姑 姑 姑 姑 姑 在 在 在 在 在 姑 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在It is desirable and requires further processing to effect the corresponding removal or conversion =: the selectivity of the catalyst composition is the ability of the catalyst composition to convert a portion of the reactants to a specific product. In addition, the catalyst is converted into a process to reduce the amount of contaminants or undesired reactions. Another use is to improve the overall energy efficiency of the reaction process while maintaining or improving the product's production and/or reaction selectivity. The range of use of the catalyst varies widely. For example, but not limited to, a catalyst can be used to reduce contaminant levels such as hydrocarbons, carbon monoxide (CO), nitrogen oxides (N〇x) & sulfur oxides (sox), which can be present in a series of Processes (such as gasoline or diesel combustion of vehicles, classified petroleum refining or coal burning processes, etc.). Similarly, catalysts can be used in hydrocarbon processing processes. The process is used for many different sources (eg straight-run petroleum fractions, recycled petroleum fractions, heavy oils), bitumen, rock, natural gas, and materials that contain catalytic reactions. The hydrocarbon process stream of other carbonaceous materials is converted or upgraded. The catalytic reaction is usually divided into two different reaction types, namely homogeneous catalysis and heterogeneous catalysis. Homogeneous catalysis broadly describes a type of catalytic reaction in which reactants and catalysts are mixed in a solution phase. Although gas phase catalytic reactions have been used in some cases, homogeneous catalysis is typically a liquid phase system. Therefore, concentration gradients and migration of reactants to the catalyst can become important factors in controlling homogeneous catalytic reactions. In addition, in some cases, the "solution phase" catalyzed reaction can occur across the interface between the two liquid phases, rather than forming a true solution, but forming an emulsified phase. Homogeneous catalysis in certain general classes includes acid-base catalysis, organometallic catalysis, phase transfer catalysis, and the like. Heterophasic catalysis, on the other hand, describes a type of catalytic reaction in which a reactant in a gas phase or a liquid phase is exposed to a substantially solid or semi-solid phase catalyst. Therefore, in the heterogeneous catalysis process, the catalyst and the reactants produce a mixed solid phase-pan soil a_^m^ and a phase or solid phase-oxygen phase reaction. Compared with homogeneous catalysis, heterogeneous catalysis has the advantage of allowing you to sweat. For example, solid catalysts are generally less corrosive, and thus with many mooring, six or six 4 scoops/liquid phase Compared with the media, the safety and environmental risks are relatively low' (b) providing |& a wide range of economically viable temperature and pressure conditions, and (4) more control of the more intense exothermic chemical reactions and endothermic chemical reactions. In addition: the aspect m body can have a mass transfer limit, which in turn significantly reduces the ultimate effectiveness of the catalyst. Typically, solid catalysts (sometimes referred to as catalyst particles) include one or more catalytic components on a porous material having a high internal surface area (eg, 'precious metals, such as (Pd), turn (Pt), Peak u), : (4), etc. 'The internal surface area where the catalytic component is located, usually on the order of a square foot per square foot. Therefore, conventional catalyst compositions or catalyst particles comprise a particularly porous support having a large internal surface area on which the catalytic reaction takes place. However, such catalyst structures often produce a mass transfer system that reduces the effective performance of the catalyst particles with respect to catalyst activity and selectivity' and triggers other catalyst performance problems. In a more representative, representative catalyst structure, the reactants must diffuse through the pores, and the ruthenium can reach the inner region of the catalyst particles, and the product must be expanded into the inner region of the catalyst particles. Because &, the known catalyst group. The porosity is not dependent on other factors, but also depends on the balance.

Known Catalyst Composition > $ # M The trade-off between the characteristics of the catalyst is the trade-off between the catalyst's surface area and the ability to promote the penalty. For example, many catalytic components are in the carrier of the fine-grained and complex pore structure (via "microporous structure, ie < 2 nm average maximum diameter") to increase the catalyst 126437.doc 200902146

The surface area of the particles. This higher surface area will in turn generally increase catalyst activity. : The increase in catalyst activity due to the higher surface area of the catalyst particles often causes problems with mass transfer resistance (ie, prevents movement of reactants and ruthenium products into and out of the catalyst particles), particularly carriers including This problem is more pronounced with a high percentage of microporous structure. By increasing the percentage of larger size pores (e.g., > 50 nm large pores) in the carrier, the resistance to mass transfer can be reduced (i.e., the mass transfer is accelerated). However, the solution tends to reduce the catalyst particles. Physical strength and durability. In other words, from the viewpoint of mechanics, the robustness of the catalyst particles is lowered. At the same time, if the reactants are subjected to significant mass S transfer resistance in the pore structure of the catalyst particles, a concentration gradient will exist under steady state reaction conditions. Because in the pores, and so on, the concentration of the reactants is the largest around the catalyst particles, and the center of the catalyst particles is the smallest. In other respects, the concentration of the reaction product is higher in the center of the catalyst particles than the catalyst particles. The concentration gradients provide a driving force for mass transfer. The greater the concentration gradient becomes, the lower the rate of catalytic reaction. Thus, the effective properties of the catalyst particles (eg, reaction selectivity, regeneration treatment) The life cycle and anti-coking properties are also reduced accordingly. In general, the purpose of developing a catalyst composition is to improve one or more of the processing objectives described above from a commercial point of view. In some cases, One of the factors affecting the performance of the catalyst is its ability to promote a fast and efficient reaction between reactants. Therefore, a catalyst composition having a lower diffusion limit is often required. However, in other cases, in order to obtain a better product, It may be more important to produce the selectivity of a particular product. Thus, it is possible to scouring 126437.doc -10- 200902146; too much to remove or convert undesired reactions Additional processes and associated processing equipment. For example, in 1976, YT Shah et al. proposed the use of acid leached aluminum boron phthalic acid "" fibers, specifically E-glass (more specifically, E-621) Producing a seed carrier. The catalyst carrier has a higher surface area to volume ratio than conventional catalysts, thereby reducing the size of the catalytic converter used in automotive exhaust systems (eg, I Oxidation of An Automobile Exhaust

Gas Mixture by Fiber Catalysts, Ind. Eng. Chem., Prod. ReS. DeV·, PP·29.35, Vol. 15, No. 1, 1976). At the same time, he believes that reactive gases (such as oxidized gorge, carbon dioxide, nitrogen oxides, methane, ethane, propane, ethylene propylene, acetylene, benzene, toluene, etc.) are generally produced in automobile exhaust mixtures. Easy access to the large surface area produced in acid immersion e-glass.

Shah et al. showed that a relatively small amount of fiber e with a relatively small surface area (75 m2/g) compared to two conventional catalysts (platinum supported on alumina beads or platinum supported on silica beads) The performance of the glass-catalyst carrier is better than that of the alumina-supported or cerium oxide-supported catalyst (8 〇m2/g and 317 m2/g, respectively), of which the E-type glass catalyst The average pore diameter is larger than that of the catalyst supported by oxidized or supported by cerium oxide. Despite this, Shah et al. did not propose or suggest that effective vehicle exhaust oxidation can occur at surface areas of less than 75 m2/g. Nearly 25 years later, Kiwi-Minsker et al. studied the reduction of surface area in another acid-impregnated aluminum borosilicate type E glass fiber (EGF) in 1999, relative to the selective liquid phase used in benzene. Hydrogenated cerium oxide glass fiber 126437.doc 200902146 (SGF) Effect on the formation of benzyl alcohol (using a platinum-based catalyst) or toluene (using a catalyst based on 1 bar) (see, for example, Swpporied G/) Aw FAea

Catalysts for Novel Multi-phase Reactor Design, Chem. Eng. Sci. pp. 4785-4790, Vol. 54, 1999). In this study, Kiwi-Minsker et al. found that SGF does not achieve an increased surface area from acid leaching, so it is relative to the EGF sample used to carry the catalytic component of the catalyst composition. The surface area is 15 m 2 /g and 75 m 2 /g, respectively, and the surface area of SGF is kept at a low level of 2 m 2 /g. However, Kiwi-Minsker et al. noted that the SGF/palladium catalyst palladium essentially has the same effective surface area concentration as its EGF/palladium catalyst counterpart (ie, about 0.1 mmol/m2) (mole metal per square metric) The SGF/palladium catalyst composition shows a decrease in activity or reaction rate per gram of palladium compared to its EGF/palladium catalyst counterpart.

Kiwi-Minsker et al. suggest that the SGF/palladium catalyst has a reduced surface area due to reduced surface area, which may be explained by the enhanced interaction of the active ingredient (ie, the catalytic component, in this case palladium) with the SGF carrier. Not because of its small surface area (ie 2 m2/g). However, they failed to verify this argument by proving the following argument: EGF/palladium catalysts with a small surface area (ie, comparable to 2 m2/g of SGF/palladium), at least with a larger surface area (ie, respectively The EGF/palladium catalyst samples of 15 m2/g and 75 m2/g) have the same catalytic activity. Therefore, Kiwi-Minsker et al. proposed a limitation on the activity of SGF/ (ie, because SGF has a higher acidity than EGF, and the interaction between palladium and SGF is enhanced), not because of The surface area of SGF/Pd is small for unknown reasons. In any case, Kiwi-Minsker did not 126437.doc •12- 200902146 reported that the 15 m2/g egf& sample increased catalytic activity due to increased diffusion rate relative to the 75 m2/g EGF/sample. Otherwise, this may indicate a beneficial effect due to the smaller catalyst surface area. Recently, in US 7,060,651 and EP 1 247 575 A1 (EP, 575),

Barelko et al. disclose the beneficial effects of using a cerium oxide-rich carrier, including cerium oxide and an oxide comprising non-cerium oxide (eg, ai2o3, B2〇3, Na2〇, MgO, CaO, etc.) as a catalyst carrier. Wherein the cerium-enriched support has a pseudo-layered microporous structure in the lower surface of the support (see, for example, paragraphs U, 13, 15, 17, 18, 23, 31 and 32 of EP '575) As explained in more detail to the European Patent Office ("EP〇"), in distinguishing the catalytic carrier (''Kiwi-Minsker carrier') disclosed in the above document by ΕΡ5 75 and Kiwi-Minsker et al. Barelko et al. assert that the cerium-enriched carrier they claim has a pseudo-layered microporous structure with a narrow interlayer space, whereas the Kiwi-Minsker carrier does not. For example, Barelko et al. In Kiwi-Minkser et al., there is no basis for assuming that (a) there is a pseudo-stratified microporous structure with a narrow interlayer space in the Kiwi-Minsker carrier; (b) the pseudo-separated space with pseudo-separation Layered microporous structure helps to enhance The active metal on the carrier (see, e.g. EP '575 and 32 of the first piece of content 13,17-18,23).

Barelko et al. further differentiated their carrier rich in dioxide dioxide from the carrier proposed by Kiwi-Minsker et al. by explaining the following to the European Patent Office: due to the fact that the catalytic component is highly dispersed in the active state. a dominant distribution of the catalytic components in the subsurface layers of the support 126437.doc -13 - 200902146 in a highly dispersed active state" (on the Ai 蛰 line), the carrier containing cerium oxide The catalytic state with higher activity, and thus the catalytic state of higher activity, enables the catalytic component to withstand sintering, aggregation and self-carrier flaking and the action of contact agents (see, for example, EP 11 5 75). EP '5 75 confirms that the diffusion limit may hinder the intercalation of the cation into the support and thus hinder the entry of the cation into the support by chemisorption (see, for example, paragraph 17 of ι 575575). In order to solve this diffusion limitation problem, Barelk et al. propose (and advocate) a carrier structure in which the "thin" layer of the diarrhea-oxygen fragments are separated to form a narrow interlayer space (i.e., the number of pseudo-layers) Pore structure), the narrow interlayer space contains &quot;a large number of &quot;〇H groups, the protons of which H group can be exchanged by cations. Barelko et al. revealed that the full II thin &quot; 氧-oxygen fragment layer is unique for high Q3 to Q4 ratios, and they further declare that there are a large number of pseudo-layers with a large number of 〇H groups sandwiched between narrow interlayer spaces. The microporous structure has been confirmed by 29Si NMR (nuclear magnetic resonance) and krypton (infrared) spectrometry combined with argon BET and titration surface area measurements. Like some of these glass catalyst compositions A, many conventional catalysts attempt to solve at least one of the above identified processing problems, but perform better in other aspects of catalyst performance. Therefore, such conventional catalysts are often limited to a narrow process reaction range, have a limited life cycle before regeneration or replacement is required, and/or require a large amount of expensive catalytic components (e.g., precious metals such as platinum, palladium, etc.), and thus are significant. Increase the cost of catalyst production and catalytic processes. Thus, there is a need for an improved catalyst composition that can be used in a variety of processing reactions while improving such as process responsiveness, selectivity and/or energy efficiency. The catalyst composition is preferably improved over a wide range of process conditions and requirements while enhancing robustness and durability while maintaining a relatively long shoot-up period. Applicants have discovered a composite catalyst composition that is expected to meet the need for this broad range of catalytic reactions. SUMMARY OF THE INVENTION According to one aspect of the invention, a composite catalyst composition is provided comprising: '(a) at least one first composition, and (b) at least one second composition having at least one precursor a catalyst composition comprising: - a substantially non-porous substrate having an outer surface, a surface region and a subsurface region, - at least one catalytic component, and - at least one catalytically active region comprising at least one a catalytic component, wherein L the substantially non-porous substrate has a measured value of about 0.01 m2/g when measured by a method selected from the group consisting of SAW^, SA·heart_β£; Γ and combinations thereof a total surface area between 1 〇m2/g; 11. the at least one catalytically active region may be continuous or discontinuous, and having a catalytically effective amount of at least one catalytic component; and ni. the at least one catalytic component is substantially dispersed In or on at least one precursor catalyst composition, wherein 'after the at least one precursor catalyst composition is formed, the at least one first composition is mixed with the at least one second composition . 126437.doc • 15· 200902146 Based on the following embodiments and the accompanying claims, the scope of the patents and the accompanying drawings will be apparent to those skilled in the art. ‘,’, [Embodiment] Definitions The terms used herein have the meanings defined below. "Pore" means a cavity or channel having a depth greater than the width. "Interconnected pores" means pores that communicate with a plurality of other pores of the 砹 甘 甘 甘. ''Closed pores' means that there is no channel pores on the outer surface of the material with the closed pores new * $. "Open pores'' means that there is a direct passage or the outer surface of the material in which the open pores are located. Interconnecting pores connected by pores (ie, pores that are not part of the closed pores). "Pore width," means the inner diameter of the pore or the distance between the opposing walls as determined by the specified method. "Pore volume" means the total volume effect of all pores determined by the specified method 'but does not include the volume effect of the closed pore." "Porosity" means the ratio of the pore volume in the material to the total volume of the material. 'Microporosity' indicates the pores with an internal width of less than 2 nm. ''Mesopores', the internal width of the surface is not less than 2 nm. Pore between 5 nanometers. ', large pores', indicating pores with an internal width greater than 50 nm. ', outer surface, 'not the outer boundary or skin of the material (thickness close to zero), including the outer boundary or A regular or irregular contour on the epidermis associated with a defect, if any. 126437.doc -16 - 200902146 ,, the wall surface of the hole, the inner boundary or the skin (near thickness), including the inner boundary or the skin Any regular or irregular profile associated with a defect, if any, substantially defines the shape of any open pore in the material having at least one or more types of pores. The overall representation of the pore wall surface of the material (if any open pores exist), the outer surface of the material and its surface area. The surface area represents the area of the material that can vary depending on the material, and does not include any open pores from the material (if any openings are present) The area defined by the pores, but the surface area (4) is less than or equal to Kawana below the outer surface of the material (preferably - <20 nm' is preferably _&lt;1 〇 nanometer); When the aperture is open, the surface area (8) is less than or equal to 30 nm below the surface of the pore wall of the material (preferably &lt; 20 nm, more preferably better than illusion 0). For a change with a change of == The material, whether or not the change is regular, along the boundary or internal boundary or skin, the outer or inner ridge or the skin's mean square is used to determine the average depth of the surface area. Included ^ 2: Zone: The table cannot be changed according to the material Material area, but no., by the open pores of the material (if there is any open area 'but the surface area (4) is on the outer surface of the material, 1 疋m (preferably > 20 nm, more preferably > ; 1〇太^. When the surface below the surface is larger than 30 nanopores, the table "', no"), in the material has any opening meter (four) for > 2G nanometer, more preferably > 1G nanometer) wall table big (4) Nai's internal surface area or, surface area of the open pore wall in the material makes all the open pore walls', the surface area effect of the soil determined by the private method. The absence of all pore surface areas in the material '' indicates the material surface area effect determined by the specified method 126437. d〇c 200902146 Wall surface area effect. "Total surface area, means the sum of the internal surface area of the material and its external surface area determined by the specified method. , Sodium - chemisorption surface area" or SA center means the surface area of the material determined by chemical adsorption of sodium cations by chemical adsorption. , the (etc.) dropout adsorption method in GW Sears such as β/. C/zem·, 1956, ν〇ι. 28, ρ 1981 and R. Her, C/zem(6)r_y o/W/ica, John Wiley &amp; S〇ns 1979 ρ 203 and 353 are explained. "Sodium-chemosorption surface area change rate" or, SARC^, where SARQfVy ls/v is initially, where (1)v is initially the initial volume of the dilute NaOH titration solution used to initially titrate the aqueous slurry mixture, at a temperature of about 25 &lt; t

A material that is substantially insoluble in water is included in the 3.4 M NaCl solution, and the pH of the solution is at time t. From the initial pH 4.0 to pH 9.0, and (ii) V5ii5 means the same concentration used to maintain the slurry mixture at pH 9 for a period of 15 minutes.

The total volume of the NaOH titrant is adjusted every 5 minutes (a total of 3 5 minute intervals for t5, tl 0 and ti s). ~ 斤 乂 V refers to the total volume of his titrant used in the titration procedure described in more detail below, where V is initially + V5M5 = V total. Therefore, v5il5 can be expressed as the difference between the total and the beginning of V, where V5 &amp; 15 = v total - V initial. For the purposes of this, a 3.4 M NaCl solution was prepared by adding 3 gram NaCl (reagent grade) to 150 liters of water, and 1 &gt; 5 gram of sample material was added to the NaC1 a solution to produce an aqueous slurry mixture. The aqueous slurry mixture must first be adjusted to pH 4.0. In order to make this adjustment before titration, a small amount of dilute acid (such as HCl) or a dilute base (such as Na〇H) can be used accordingly. Titration, in order to obtain the initial v first, first use a dilute Na0H titration solution (for example, 〇^ N or 0.01 N), and then use Vpu for SARC heart measurement. In addition, for the purposes of this definition, Vs to is the cumulative volume of the NaOH titrant used in ts, ~ and tls, wherein the NaOH titration solution is titrated as quickly as possible every 5 minutes (3 3 minute intervals) to follow Need to be from t. The pH of the slurry mixture was adjusted to 9. 丨 within 5 minutes of the final time t15. For the purposes of this definition, it is treated with any alternative ion exchange (ΙΕχ), counter ion exchange (BIX) and/or electrostatic adsorption (ΕΑ) treatment to produce one or more Type 2 component precursors (described below) The SARCjva of the sample material is determined prior to integration onto the surface of the substrate and/or within the surface of the substrate. "Incipient wetness" means that for an aqueous slurry or paste mixture comprising a solid or semi-solid material, the time point of the material's isoelectric point (&quot;IEp&quot;) is being measured, at which point the deionized water is substantially covered. The entire surface of the solid or semi-solid material, and to the present extent, fills any water-permeable pore volume that the material may have, thereby allowing water to enter the aqueous slurry or paste mixture to provide a glass electrode contact and its reference The electrode contact surface and sufficient liquid contact between the two, thereby determining the IEP of the material. The 'isoelectric point' or IEP indicates the pH at which the solid surface charge of the solid or semi-solid material is zero at the initial humidity. The IEp used herein may also be referred to as a zero point charge 'ZPC' or a point 〇f zer〇 charge (PZC). ''Catalytic effective amount, means at least enough to convert at least one of the reactants into sufficient yield under appropriate processing conditions to support the test 126437.doc •19- 200902146 Catalytic or commercial grade process catalysis The amount of ingredients. ', Chalconide, denotes at least one element from the group consisting of sulfur (S), selenium (Se) and tellurium (Te), and a group of at least one positive A compound that is stronger than the element or group of its corresponding Group 16 element. "Precious metal" means a transition metal from the group of rhodium (Rh), palladium (Pd), silver (Ag), iridium (Ir), platinum (Pt), and gold (Au), unless otherwise stated, with a metal complex, The form of the metal salt, metal cation or metal anion is in a charged state - otherwise the various transition metals are in a zero oxidation state (while in an unreacted state). Anti-corrosion matrix', a matrix that is capable of resisting substantial changes in the matrix composition of the subsurface region. These changes are due to changes and/or loss of structural constituent elements due to most acids or tests under standard temperature and pressure conditions. 'New pore formation, pore size expansion, etc. However, the composition of the corrosion-resistant matrix may be substantially composed of a high-strength acid (eg, a high-strength base (eg, concentrated NaOH) or other highly corrosive agent (whether alone or in combination with high temperature, high pressure, and/or high vibration frequency conditions) Altered, for the purposes of this definition, such a matrix is still considered "corrosion resistant, matrix. ''Surface activity' means that the surface of a material is sufficiently filled with - or a plurality of charged components, one or more charged The material of the component is used to (1) promote the catalytic reaction under steady-state reaction conditions without- (ii) additionally, for further modification by interaction with one or more charged components and/or ion exchange interaction As a catalytic component under steady-state reaction conditions. Step-up, or electrostatic interactions, and then s. 126437.doc -20- 200902146 ''matrix, means any solid or semi-solid material, including but not limited to glass and glass-like materials , IEP is greater than 〇 but less than or equal to 14, and the surface active state may be predetermined according to the matrix in the catalyst composition (having a catalytically effective amount of catalytic component) Changes are made. 'Integration,' means electronic and/or physicochemical interactions (eg, ionic, electrostatic or covalent interactions including, but not limited to, hydrogen bonding, ionic bonding, electrostatic bonding, van der Waals) Van der Waals / dipole bonding, affinity

C force bonding, covalent bonding, and combinations thereof combine chemical components with a substrate. MODES FOR CARRYING OUT THE INVENTION The notes under the Summary of the Present Embodiment are only used to illustrate selected aspects and factors related to the scope of the accompanying claims, and are therefore only used to facilitate the presentation of possible implementations that may be of potential interest to the reader in a simplified wording. Some aspects of it. Therefore, the description of the present embodiment should not be construed as limiting the scope of the appended claims. The composite catalyst composition (described in more detail below) includes at least one high temperature resistant oxide and at least one of the at least one precursor catalyst composition having at least one of the catalytic components. The precursor catalyst composition can be prepared by ion exchange, impregnation, sedimentation, coprecipitation or other catalyst composition preparation methods, as long as the method can produce a precursor catalyst composition, at least one catalytic component in (4) The high temperature inorganic oxide remains substantially dispersed within the precursor catalyst composition and/or composition after mixing. The present invention relates to a composite catalyst composition comprising a refractory inorganic oxide and a precursor catalyst composition, the precursor catalyst group 126437.doc 200902146 having substantially non-porous The matrix, but in practice there may be microvoids, mesopores and/or macropore volumes that are not quantitatively significant and do not adversely affect the intended use of the catalyst composition. The precursor catalyst composition is preferably a functional surface catalyst composition ("FSC composition,"). Another aspect of the invention pertains to various methods of making novel composite catalyst compositions, preferably having FSC Compositions. Yet another aspect of the invention relates to the use of catalyst compositions in various processes, such as hydrocarbon, hydrocarbon and/or non-hydrocarbon treatment, conversion, refining, and/or emission control and treatment processes, and Other types of processes. For example, novel composite catalyst compositions can improve the reaction selectivity, reaction rate, and finished product of hydrocarbon, hydrocarbon, and/or non-hydrocarbon treatment, conversion, refining, and/or emission control and treatment processes, as well as other types of processes. Yield and Energy Efficiency. Precursor Catalyst Matrix Composition The precursor catalyst composition has a substantially non-porous substrate and a catalytically active region comprising at least one catalytic component. Typically, the matrix of the precursor catalyst composition should be substantially There are no pores, but there may actually be micropores, mesopores and/or macropores that do not adversely affect the intended use of the catalyst composition. Volume. As described above, the precursor catalyst composition is preferably an FSC composition. Thus, for purposes of illustrating the preferred embodiment, the composite catalyst compositions described herein will be described in more detail as precursor precursor compositions. Different Fsc compositions. However, it is to be understood that a catalyst composition prepared by other methods known to those skilled in the art can also be used in the manufacture of precursor catalyst compositions of the composite catalyst compositions described herein. Doc -22· 200902146 Several factors should be considered in the production of FSC compositions, including but not limited to: ω Obtain a matrix with a predetermined isoelectric point (&quot;IEP" for the intended use, whether obtained as is Or obtained after subsequent treatment; (ii) the degree of anti-corrosion of the substrate for the intended use; (iii) the degree of porosity (if any) of the substrate in order to obtain the desired surface properties in view of the intended use, and Elemental composition (particularly on the surface), (iv) depending on the intended use of the composition, where appropriate, the chemical sensitivity of the substrate to the generation of the appropriate isoelectric point, and by means of - or There is a first type of first component that interacts with the ions and/or statics of the matrix to render the substrate surface active, and the matrix can, but does not necessarily, produce a catalytically active region having an average on and/or within the surface of the substrate. The thickness is about 30 nm, preferably &lt; about 2 〇 nanometers, more preferably &lt; about 丨❶ nanometer; (v) matrix for optionally ion exchange (ΙΕχ), counter ion exchange ( Chemical susceptibility of BIX) and/or electrostatic adsorption (ΕΑ) treatment methods for integrating one or more second components onto and/or within the surface of the substrate having a second type and matrix ions And/or electrostatically interacting, and thus producing a catalytically active region having an average thickness on and/or within the surface of the substrate of from about 3 nanometers, preferably about 2 to about 20 nanometers, more preferably S. About 10 nm; and (vi) depending on the intended use of the composition, the chemical sensitivity of the treated substrate to the following reactions: optional calcination and/or reduction, oxidation or further treatment of the substrate in use Media composition before and first or 126437.doc -23- 200902146 two catalyst components chemically react. I. Precursor Matrix Description The matrix selected for use in the formation of the precursor catalyst composition of the present invention, which is generally preferred and preferred for many potential applications, is preferably a ruthenium-containing matrix composition, particularly current precursors. When the medium is a FSC composition, including but not limited to glass, tantalum carbide, tantalum nitride, cordierite, cerium-containing ceramics and mixtures thereof, whether surface-active or treated to produce a surface active state, the IEP is greater than about 〇 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 〇 but less than 14. The sigma t' at these 3 shi stagnation groups is preferably a glass composition. Substantially no 7 compositions can also be used to produce the precursor catalyst compositions of the present invention, including, but not limited to, substantially no shi tao taman, a (alpha) oxidized, oxidized, oxidized, carbon, and mixtures thereof. Whether surface-active or treated to produce a surface active state '纟IEP is greater than about 〇 but less than or equal to &quot;. @否的基贝 with a suitable IEP (suitable for the production of a pre-catalyst catalyst composition) is dependent on various factors, some of which are outlined. The game provides a more detailed discussion below, and those familiar with the art will have a clearer understanding of other factors associated with choosing an appropriate IEP. For example, for many processes of commercial interest, the glass (or glass-like) «object and/or surface-active product preferably has a enthalpy greater than or equal to about * 5 but less than 14, and is expected to be greater than or equal to about but less than μ. Glass ', and the mouth is better, and it is expected that 1 ΕΡ is greater than or equal to about 7.8 but less than 14" and the mouth is best. However, depending on the intended use of the catalyst composition and the porosity in the matrix of the composition The extent and type, the preferred range of ΐΕρ may be affected by the effect: In addition, certain catalytic processes are more sensitive to surfactant compositions that are surface active at lower pH ranges. In other cases, a substrate having an IEP of less than 7.8 (preferably &lt;6, more preferably £4.5) is likely to be more suitable for such processes. Therefore, it is again stated that when selecting a substrate within the appropriate IEP range, 'not only must be considered The intended use of the catalyst composition is also combined with the porosity of the substrate, the chemical composition and processing procedures (if any), etc. In addition, many glass types can be potential depending on the intended catalytic use. The matrix candidate 'to obtain the appropriate degree and type of IEP and porosity' is received or used as one or more of the following treatment methods. Typically, some examples of such glass types include, but are not limited to, E-glass, boron-free. Glass, S glass, R glass, AR glass, rare earth-tellurate glass '钡 _ titanium-tellurate glass, nitride glass such as 矽_aluminum_oxygen-nitrogen glass, A glass, C glass and CC glass. The following is a description of the types of glass that are generally expected for a range of catalytic applications and some possible treatments. AR type glass descriptions such as, but not limited to, "AR type", a group of glass systems with an IEp greater than 78, a wide range and substantially Non-porous glass composition. Typically, the AR-type glass contains a significant amount of a basic oxide type glass mesh modifier, typically 1% by weight or more based on the weight of the total glass composition. Such basic oxide network modifiers include, but are not limited to, (9), (4), Ming (10), lanthanide and _ element oxides, soil metal oxides (Group 2), metal oxides (class j) and so on. A glass system containing the wrong (Zr), yttrium (Hf), aluminum (A1), lanthanide, alkaline earth oxide, and alkali metal oxide is preferred, and a glass composition containing the wrong (Zr) (for example, but not limited to eight anti- Type glass) is especially preferred. ° I26437.doc •25- 200902146 Type A broken glass Description In addition, for example but not limited to, “Type A” glass is another broad and substantially non-porous glass composition, whether the surface active system is received as received or Treatment results in a surface active state 'IEP is greater than about 7.8 but less than 丨4. Typically 'type A glass will include acidic or basic oxide type glass mesh modifiers' such glass mesh modifiers include, for example, but are not limited to, zinc (Zn), magnesium (Mg), calcium ( Oxides of elements such as Ca), Ming (A1), boron (B), titanium (Ti), iron (Fe), nano (Na) and potassium (K). If an anionic network modifier is used, the amount included in the lower IEP glass tends to &lt;12 wt.〇/. . Glass containing magnesium, calcium, aluminum, zinc, sodium and unloading is preferred. The un-dipped E-glass indicates the unsimmered &quot;E-type&quot; glass is another broad and substantially non-porous glass composition' which includes infinite examples, whether the surface active system is received as received or The treatment produces a surface active state, the IEP is greater than about 7.8 but less than 14 〇 typically 'un-leached E-glass will include acidic or basic oxide-type glass mesh modifiers' including, for example, but not limited to zinc ( Oxides of elements such as Zn), magnesium (Mg), calcium (Ca), aluminum (A1) 'butter (B), titanium (Ti), iron (Fe), sodium (Na) and potassium (K). If an alkaline mesh modifier is used, the amount included in the unsimmered E-glass tends to be &lt; 2 〇 wt %. Glass containing magnesium, calcium, aluminum, zinc, sodium and potassium is preferred. Porosity indicates that the porosity of the matrix produces another relevant aspect of the catalyst composition of the present invention. In general, the matrix should be substantially non-porous, but there may actually be a number of 126437.doc -26 - 200902146 irrelevant 'microporosity, mesopores and/or no adverse effects on the intended use of the sputum sputum sputum composition.戋 Large a large pore volume. Due to the micropore volume in the material, &amp; often difficult to detect 'this description uses two surface area measurements to determine whether the matrix is non-porous on the shell' to memorize the catalyst composition of the present invention. The first surface area is measured by means of a thermal adsorption/desorption time (four) that is suitable for the range of expected surface areas to be measured, and can be expressed in the degree of micropores, mesopores and/or large pores of acne. For example, for large surface area measurements (eg &gt; about 3 m2/g) Ni RPT nr,

BET, the method described in ASTM D3663_〇3 (&quot;S.Aim&quot;)' may be a preferred surface area measurement technique. However, for smaller surface area measurements (e.g., < about 3 m2/g) Kr ΒΕΤ, the method described in ASTM D4780.95, m, may be a preferred surface area measurement technique. Those skilled in the art of analysing the surface area of solid and semi-solid materials will be well aware of the optimum enthalpy area measurement method for micropores, mesopores and/or macroporosity.帛mj is a nano-chemical adsorption surface area (&quot;S.A.h"), which can be used in some sort of analytical method (R.

Iler is described in C/zewbiry o/A/zca, John Wiley &amp; Sons (1979) on pages 203 and 353) for changes in NaOH titrant versus time &amp; and according to SA - rate of change (&quot;SARCO A specific definition. Thus, as defined herein, the matrix is substantially non-porous, provided that the matrix or SAor is between about m1 m2/g to about 1 〇m2/g and its SARCw is less than or equal to 〇5. As discussed in more detail above, the ratio of the two volumes of the SARCNa-based NaOH titrant, the denominator is the volume of the initially used NaOH titration solution' is initially used to titrate the matrix slurry mixture at zero time t, the matrix slurry mixture is The 3 4 M NaC1 solution (pH 4 126437.doc 27· 200902146 9) contains 15 grams of matrix in about 25 〇c. However, as described above, 'before the initial NaOH titration is used for SARC, The water-containing, mosquito-like substance must first be adjusted with a small amount of acid (HC1) or alkali (NaOH) to adjust P 4. In addition, as described above, the NaOH titration solution (for three 5 minute intervals, within 15 minutes) The cumulative volume of the base f slurry mixture maintained at pH 9) is V total _V initial ( VP"), which is the molecule of the ratio SARCw. Therefore, if Vife_v is less than or equal to 0.5 V at the beginning, the corresponding SARCw is equal to or greater than 0.5. Therefore, as defined herein, the matrix is substantially non-porous, provided that the matrix is 8 people _ (four) or H tear is also between about 0.01 m / g to about 1 〇 m2 / g. If the surface area parameters are met, in terms of any microporosity, mesoporosity and / or large pore volume of the matrix, There may be insufficient concentration, distribution, and/or type to adversely affect the desired performance of the precursor catalyst composition for the intended use. Nano surface area (&quot;SA·;^&quot;) is an empirical titration The procedure was developed for the substantially pure cerium oxide (Si〇2) in the form of granulated, powdered and suspended sol forms. S_A. The determination of the surface proton position (Glass-cnr) and its reactivity And the measure of the purity, the pure silica dioxide eve 'is equivalent to the Si-CTH + position. The oxalate glass and the crystal lithic acid salt and the pure one gas fossil eve (Si 〇 2) are significantly different in composition, The stoichiometry of this titration procedure The behavior of the crystal citrate cannot be known or predicted from the absolute value of the NaOH titration solution determined in the SAw experiment. Therefore, Sears and Her are used to measure the NaOH volume of the S_A.jva experiment with the N2_BET of the ceria material studied. The equation for surface area correlation is not suitable for reliably predicting the absolute surface area of more complex tantalate compositions. This is 126437.doc -28- 200902146 expected, because Giass.〇H+ groups which can exist in different compositions of glass can include, for example, A1-〇-H+, b_〇-h+, Ti_〇.H+, Mg 〇 .H+ and a plurality of Si_0-Hs in a single Shishi position, and a more proton group (Q2 group) with different structures. On the other hand, the total surface area of the "Shi Xi-like" glass composition (for example, leached quartz) may be reliably determined using the SA·heart test, provided that the minimum pore size is within the range achievable by the standard gas phase BET measurement. Because it is mainly composed of networked Si〇2 and Si_〇-H+ parts. However, (1) trace Η·Η+ part of the diffusion accessibility of hydroxide ions and steel ions, and microporous contrast in the pores The relative percentage of macropores and/or substantially non-porous areas shall be detectable based on the amount of NaOH (in the sA known experiment, to maintain the final positive value of 9' must be added over time) (titrant). Therefore, the total ancient '(1)ass-0-mine part for the 〇H- and Na+ contrast between the daytime, the second in the above SAR "experimental determination, can be used as a reasonable and reliable micro-porosity" including standard gas A certain type of porosity that is not measurable by phase BET. Preferably, the surface area of the substrate will remain substantially unchanged after its ion leaching treatment. For most of the durability (&quot;AR&quot;) glass, this is Common. However, 'in some cases, some of the ions consumed from the matrix network do not significantly affect the microporous structure of the matrix, if any, thus avoiding the desired performance of the intended use of the catalyst plant. Adverse effects. However, if there is significant ion depletion and associated leaching on the matrix network, it is likely that a microporous region will be produced in the matrix. Therefore, as described above, _~ greater than about 0.5 indicates the presence of such a Microporous structure. The plastid network showing these properties has produced sufficient microporous structure, especially in the matrix region; this microporous structure will be detrimental to the ability of the substrate to maintain a surface active state. 126437. Do c • 29- 200902146 Sweat, thus achieving a desired effect on the intended use of the catalyst composition. This production is not II. Matrix surface activation is used to produce the matrix of the precursor catalyst composition of the present invention. The FSC composition 眛-T iirh ^ ^ ^ ^ m when the object can be hunted by one or more of the first components to make the surface = use, the composition has the first type of ion and / or electrostatic phase with the matrix (type 1 component precursor) ). As described in more detail below, the Type 1 precursor may itself have catalytic potency or may be further processed to produce an active region having an average thickness on and/or within the surface of the substrate such as ❹ The average thickness of %2 〇 nanometer is better than the average thickness of the ΜN. For example, in some cases, depending on the intended use of the catalyst composition; the substrate to be obtained has a suitable 3L and degree of pore structure (if any) and isoelectricity in a range suitable for the intended use. At point (iEp), the matrix may be sufficiently surface active upon receipt and is effectively catalyzed. Preferably, although not necessary, the substrate can be treated to further modify and/or improve its surface activity. Alternatively, the substrate can be treated to remove any organic coating or other possible contaminants that are expected to interfere with the performance of the catalyst composition. In addition, as described below, in the case of &quot;2 component precursor integration treatment&quot;, depending on the stereotype of the catalyst composition, it may be better to use ion exchange (IEX), reverse Ion exchange (ΒΙχ) and/or electrostatic adsorption (ea) treatment methods further processing the surface of the substrate. The treatments integrate one or more second components onto the surface of the substrate and/or within the surface of the substrate having a second type The ions and/or electrostatic interactions of the matrix, and thus the catalytically active regions, have an average thickness on the surface of the substrate and/or within (10) nanometers, preferably 126437.doc * 30 - 200902146 nm, more preferably &lt;10 nm. The substrate contaminant removal is determined by the composition of the material typically found on the surface of the substrate and whether the material is expected to interfere with the preparation of the catalyst composition and/or interfere with the desired performance of the catalyst composition for the intended use, Optional contaminant removal. For example, typically, the AR-type glass is made using an organic coating (i.e., sized). The organic coating is used to facilitate processing, such as dispersion in aqueous formulations. However, the organic coating or sizing may interfere with the preparation of the catalyst composition, even if it does not interfere with most, if not all, of the catalytic properties of the intended use of the catalyst composition. Therefore, the organic coating should be removed. Calcination is a preferred method for removing such organic coatings. Since the primary goal of this treatment is to remove contaminants from the matrix, the conditions of such calcination treatments are not particularly important for successful surface activation of the matrix. In some cases, depending on the nature of the contaminant to be removed from the substrate, solvents, surfactants, aqueous cleaning or other suitable methods can be used to remove contaminants&apos; to achieve satisfactory results. However, depending on the degree of calcination used, the substrate is preferably calcined in an oxidizing atmosphere (e.g., in dioxane or oxygen). It is also important to select a high calcination temperature to remove the target contaminant, but the calcination temperature is low enough to avoid the softening point of the material. Generally, the calcination temperature should be at least about 5 (rc lower than the softening point of the selected matrix material. Preferably, the calcination temperature should be at least about 1 〇〇〇 C lower than the softening point of the selected matrix material. For example, in the use of the AR type When glass is used, most of the AR type glass can be used to remove contaminants with a calcination degree of between about 300 c and about 700. (Between: usually, the selected matrix material 126437.doc -31 · 200902146 should be calcined about 2 Preferably, calcination is carried out for 4 to 8 hours up to 14 hours. Nevertheless, depending on the nature of the substrate obtained and the nature of the target contaminant to be removed from the substrate, the calcination time may vary outside of these time ranges. Treatment to achieve surface activation After any potential contaminants are substantially removed from the substrate, the substrate can be treated to produce a surface active state and the desired isoelectric point (&quot;IEp&quot;), provided that the initial IEP obtained from the substrate is not Within the desired range, however, in some cases, the substrate received may have sufficient surface activity and require further modification using one or more other treatments (described in more detail below) without Use the first type of ion leaching (ί EX 丨 ) process (this will be discussed first in other processes described in more detail below). In other words, the elemental composition of the matrix, especially on the outer surface or substantially close to the outer surface , may be sufficient to obtain the desired IEP. However, in many cases, the elemental composition of the matrix will require some modification to change the original IEP and obtain a suitable IEP, followed by the type and extent of the intended use of the catalyst composition. The surface active state is satisfactory. The surface active state may be sufficient to produce one or more of the first components having (1) the first oxidation state and (ii) the first species and the matrix ions and/or electrostatic interactions. The catalytically active region has an average thickness on and/or within the surface of the substrate of {about 30 nanometers, preferably &lt; about 2 nanometers, more preferably about 1 nanometer, and thus provides a catalyst composition. Achieving the desired properties for the intended use, such as, but not limited to, Bronsted or Lewis acid sites on the surface of the substrate and/or within the Laminate or Lewis base. It can effectively promote some hydrocarbons, hydrocarbons (such as oxygenated hydrocarbons) and non-hydrocarbon treatment, and 126437.doc -32-200902146 and/or refining process. In other cases, based on the intended use of the catalyst composition, &quot; The substrate surface is further processed by one or more ion exchange methods as described below to achieve (1) the 盥 盥 method to enter the τ and the first gasification state is the same or different [[2] 35' and U) the second type and the ion and/or electrostatic phase of the group f are sufficient to produce a catalytically active region having an average thickness on the surface and/or within the substrate of M30 nm, preferably about 2 () nm, more preferably 10 nm. / / See the surface activation treatment 'Surface activation treatment includes at least one kind of ion, and the treatment is treated to obtain a first type or J type ion exchange (IEX)) matrix. However, it should be understood that if the substrate received has an IEP suitable for the intended use of the catalyst composition, then the 汨-丨 is also intended to be used to illustrate the first type of substrate. Typically, the ion leaching process is performed by any suitable method, i.e., effective removal of the desired ionic species from the entire substrate surface without substantial erosion of the matrix network (e.g., avoiding surface The region and/or subsurface region produces any microporous structure). For example, but not limited to, most of the acids, whether inorganic or organic, and various chelating agents, are suitable for ion leaching. Preferably, mineral acids such as, but not limited to, nitric acid, phosphoric acid, sulfuric acid, hydrochloric acid, acetic acid, peroxyacid, hydrobromic acid, gas sulfonic acid, trifluoroacetic acid, and combinations thereof are used. Generally, the concentration of the acid solution used for the ion leaching treatment depends on the characteristics of the substrate (eg, the affinity of the ions to be removed from the glass network, the strength of the glass after removal of the network ions), the IEP of the substrate The intended use of the modified process and catalyst composition. Preferably, the concentration of the 126437.doc-33.200902146 acid solution used for the ion leaching treatment may be between about 55 wt% to about 5 wt%, more preferably about 2.5 wt. /. Between about 25 wt·%' optimally between about 5 wt.% and about 10 wt.%. The integrator can also be used in ion leaching processes such as, but not limited to, ethylenediaminetetraacetic acid ("EDTAM"), crown ethers, oxalates, polyamines, polycarboxylic acids, and combinations thereof. Typically, for ion leaching treatment The concentration of the chelating agent solution depends on the nature of the substrate (e.g., the affinity of the ions to be removed from the glass network, the strength of the glass after removal of the network ions) and the intended use of the catalyst composition. The concentration of the chelating agent solution for ion leaching treatment may range from about 0.001 wt.% to saturation, more preferably from about 1% to saturation. Usually, depending on the acid or chelate used. The type and concentration of the mixture and the characteristics of the substrate 'Select the heat treatment conditions for the ion leaching treatment, such as the heating temperature, the heating time, and the mixing conditions. The heating temperature varies widely depending on the concentration of the acid solution or the chelating agent solution. However, preferably, the heating temperature suitable for the acid ion leaching treatment is about 20% (between about 20 and about rc, more preferably between about 4 〇t and about 95 Å, and most preferably about 6). (TC to about 9 (between rc. preferably The heating temperature suitable for the chelating agent ion leaching treatment is about 2 Torr. (: to about 20 (the range of TC, more preferably about 40 &lt;&gt; C to about 90 ° C.) Depending on the acid solution or the chelating agent solution The heating time suitable for the ion leaching treatment may vary depending on the concentration and the heating time. Preferably, the heating time for the ion leaching treatment is between about 15 minutes and about 48 hours, more preferably about 3 〇 126437. 34- 200902146 minutes to about 12 hours. Usually, depending on the type of acid or chelating agent used and the nature of the concentration and quality (for example, the affinity of the ions to be removed from the glass mesh, removed) The mixing conditions are selected, such as, but not limited to, the mixing conditions may be continuous or intermittent, or may be mechanical mixing, fluidization, tumbling, rolling, or manual mixing. In short, the combination of acid or chelating agent concentration, heat treatment conditions and mixing conditions will be determined according to the degree of sufficient ion exchange ("IEX") between the acid or chelating agent and the target matrix ion. The appropriate isoelectric point and the type and extent of surface charge are generated to achieve the surface active state required for the post-treatment of base f or the intended use of the catalyst composition.

The ion fip treatment base f is separated by ion dipping treatment, preferably by a suitable method, including but not limited to transition mode, centrifugal decantation, and combinations thereof. The ion-leaching treated substrate is then washed with one or more suitable cleaning solutions (eg, deionized water and/or a suitable water-soluble organic solvent such as methanol, ethanol or propyl) and heated to about 110 in a room temperature. Dry at a temperature of about 20 to 24 hours. In some cases, the counter-ion exchange treatment may be counter-ion exchanged ('BIX··) or two-step two-A* exchange treatment depending on the substrate of the catalyst composition. This article is collectively referred to as BIX processing). The BIX treatment is usually exchanged with the package:: limited to "reverse ion" because the ion-leached matrix is separated from the early reading: the initially removed salt solution of the ion (eg NaCi) is mixed and removed from the substrate by treatment. Such ions (e.g., Na+) are then returned or returned to the substrate at 126437.doc 35·200902146. It is still unclear - will definitely return to the original matrix in the second order, whether the ions of the silk will be replaced or not change at all, it should be understood, this article;; t part of the change bit covers due to any such possibility Ionization: The BIX treatment of the month has a catalytic composition. ‘The result of the change in the placement of the point = the type of solution (4) of the material (four) and the fourth (four) solution, depending on the (4) _. More money, only the counter ion exchange of the sub-child is carried out 'but in some cases' counter-ion exchange of two or more ions may be required. Any ions that are easily removed by the above ion leaching process can be subjected to lamp counter ion exchange. Some examples of such plasmas include, but are not limited to, Group 5 (former Group VIII) metal ions, such as clock, nano, and potassium ions, and soiled metal ions from Group 2 (formerly Group III), such as Wrinkles, magnesium, about ions, ΝΗ4+ and hospital base cations' and small organic polycations. Preferably, the alkali metal ions and ruthenium/series are preferred target ions for the ruthenium treatment, while Na+ and ΝΗ/ are preferred ruthenium ions, and Na+ is the preferred Βιχ ion. Generally, the concentration of the salt solution used for the BIX treatment depends on the type of the substrate to be treated by the BIX by the ion leaching treatment and the relative affinity of the BIX ions for returning to the ion leaching treatment substrate, and, similarly, the ruthenium ion return matrix reticular Site-independent (eg 'N+ relative affinity for matrix versus Η+). For most types of glass substrates, such as, but not limited to, AR glass, A glass, or quartz glass, the BIX-salt solution is about 0.001 m 〇 1 /L to 5 ❶丨 ❶丨 126437.doc -36 - 200902146 degrees Good, and about 5 moi / L to 3 m 〇 1 / L ΒΙχ salt solution is better. Typically, the heat treatment conditions for the hydrazine treatment, such as the heating temperature, the heating time, and the mixing conditions, are selected depending on the type and concentration of the strontium salt solution used and the characteristics of the substrate. Preferably, the heating temperature for the hydrazine treatment using the BIX-salt solution may be between about 20 C and about 200 ° C, more preferably between about 3 ° C and about 95 ° C. Depending on the concentration of the BIX salt solution and the heating temperature selected, the heating time for the BIX treatment can be varied. Preferably, the heating time of the Βιχ treatment is between about 5 minutes and about 24 hours, more preferably between about 3 minutes and about 8 hours. Usually, depending on the type and concentration of the BIX solution used and the characteristics of the substrate (for example, the affinity of the ions to be removed from the glass network, the strength of the glass after removal of the network ions, etc.) and the duration of the heat treatment , choose the mixing conditions. For example, without limitation, the mixing conditions can be continuous or intermittent, or mechanical mixing, fluidization, tumbling, rolling, or manual mixing. In summary, the combination of 'BIX salt solution concentration, heat treatment conditions, and mixing conditions' is substantially determined based on the return of a sufficient amount and the distribution of a sufficient amount of ruthenium-ion back to the substrate, irrespective of the site of ions in the matrix network. A sufficient amount of ruthenium-ion is used to return and distribute the desired surface charge type and extent to produce the surface active state desired for the intended use of the post-treatment or catalyst composition of the substrate. Adjusting the surface charge of the substrate by adjusting the pH 126437.doc -37- 200902146 Preferably, the negative surface charge on the substrate is required to support positively charged components (eg, cationic alkaline earth metals, cationic transition metal components, etc.) Electrostatic interaction or affinity. However, for some potential catalyst composition applications, it may be necessary to use a positive surface charge to support electrostatic interactions with negatively charged components such as anionic transition metal oxygen ions, sulfate anions, noble metal polyhalide anions, etc. Or affinity. Generally, the surface charge of the substrate can be changed to a net positive state or a net negative by adjusting the pH of the ion-leached substrate/IEX mixture to be lower or higher than the isoelectric point of the substrate (&quot;IEP"). Sexual state. Think back, IEP is also known as zero charge (&quot;ZPC"). Therefore, in other words, IEP (or ZPC) can be regarded as the pH of the material having a net zero surface charge on the surface at the time of initial humidity. Therefore, adjusting the pH of the matrix/IEX water mixture to a pH greater than the matrix IEP (or ZPC) produces a net negative surface charge on the substrate. Additionally, adjusting the pH of the matrix/IEX water mixture to less than the pH of the matrix IEP (or ZPC) produces a net positive surface charge on the substrate. For example, but not limited to, if the IEP of the AR glass is equal to 9.6, if the pH of the ion-treated AR glass is adjusted to a pH of &gt; 9.6, a net negative surface charge will be produced on the glass surface. Depending on the IEP distribution of the AR glass, it may be preferred to adjust the pH to be greater than the IEP of the substrate - or two or more pH units to ensure that the surface charge is fully supported.

The type of solution used to effect the pH adjustment will depend on compatibility with other reactants, glass stability, and required charge density and other factors. In general, any dilute base can be used to adjust the surface charge of the substrate to the right of its IEP 126437.doc •38· 200902146 (ie, to produce a net negative surface charge) and any dilute acid can be used to adjust the surface charge of the substrate to its The left side of the IEP (ie, produces a net positive surface charge). The inorganic acid and the base or the organic acid and the base can be used in a dilute concentration, and a mineral acid is usually preferred. Generally, the concentration of a dilute acid solution or a dilute solution will depend on the type of acid or base used, its dissociation constant, and the pH at which it is suitable to obtain the type and density of the surface charge desired. In some cases, it may be desirable to integrate the catalytic component or precursor at a pH that causes the surface charge to produce the same sign as a catalytic component or precursor. Under these conditions, the electrostatic adsorption (EA) type integration mechanism is likely to not occur. However, without being bound by theory, direct ion exchange (IEX) or reverse exchange (BIX) may occur at the exchangeable surface location resulting in surface integration of the catalytic component or precursor, which is a catalytic component or precursor. It may be physically and/or chemically different from the same components that are integrated under the electrostatic adsorption (EA) mechanism. For example, certain substrate surface portions include cations (or anions) that may be replaced by ionic catalytic components or precursors of the same symbol, which may provide an appropriate but effective exchange of IEX* 与 with the surface portion of the substrate. . For example, without limitation, such moieties, such as a decyloxy (_Si-CTNa+) moiety, can be at least partially replaced by a positively charged catalytic metal or metal complex precursor such as, but not limited to, Pd(NH3)42+ The Na+ ions, in turn, produce a matrix having a catalytically effective amount of catalytic component. The surface charge of the B1X treated substrate is controlled by adjusting the pH as in the case of IEX treatment or second treatment (&quot;ΙΕχ_2 treatment, as discussed below). For some treatments, it may be necessary to adjust the pH. 126437.doc -39- 200902146 But not required. Similarly, depending on the type of BIX_ion to be integrated into the surface and exchanged in the IEX-2 treatment, the degree of 2pH adjustment required usually depends on the 1EP of the substrate, its 1EP. Comparing the surface charge distribution curve with the desired charge type. The type of solution used to effect the pH adjustment will depend on compatibility with other reactants, stability of the matrix over the relevant pH range, and desired charge density. And other factors. Generally, any rare test can be used to adjust the surface charge of the substrate to the right side of its IEP (ie, to produce a net negative surface charge), and any dilute acid can be used to adjust the surface charge of the substrate to the left side of its IEp. (ie, a net positive surface charge is produced.) The inorganic acid or base or organic acid or base can be diluted. Usually, the concentration of the dilute acid solution or the dilute alkali solution will depend on The type of acid or base used, its dissociation constant, and the pH suitable for obtaining the type and density of the surface charge to be obtained. 2. Integral treatment of type 2 precursors, whether the surface of the substrate is received as it is, or is subjected to ion leaching ( That is, the substrate treated by IEX-1) or treated by BIX, preferably, in (1) second ion exchange (&quot;IEX·2&quot;) treatment, (Π) electrostatic adsorption (EA) treatment or (Hi) The combination of IEX-2 and EA treatment uses at least one second component precursor (&quot; type 2 precursor&quot;) to further process the substrate to integrate one or more second component precursors with a second The ionic and/or electrostatic interaction of the substrate is on and/or within the surface of the substrate. Next, certain Type 2 component precursors may be catalytically active without further treatment, or further processed, depending on the intended use. The catalytically active region comprising one or more type 2 components is produced. However, 'the catalytically active region is composed of 126437.doc -40-200902146 (4) type 2 component precursor '(8) is derived from the type 2 component precursor The composition of the type 2 component, or (4) consists of a combination of (4) and (8), the average thickness of the catalytic region on the surface of the substrate and/or is nanometer, and the car is preferably about 2 nanometers. 5 is about 1 nanometer. As mentioned above, in some cases, depending on the intended use of the catalyst composition, the base f received as received or treated by ion leaching may have catalytic efficacy. However, for many potentials In practice, it is generally preferred to subject the selected substrate to a ΙΕΧ2 and/3 wolf treatment, such as, but not limited to, a plurality of reaction rates, selectivities, and/or energy efficiencies suitable for use in the process of using the catalyst composition of the present invention, It can be significantly improved by replacing at least a portion of the first component ("type component") and integrating one of the components ("type 2 component") with the surface of the substrate. Without being bound by theory, direct or indirect ionic interactions are carried out by specific ion exchange sites on the surface of the substrate and/or in the opposite charge, by electrostatic adsorption to the surface of the oppositely charged substrate. Role, and the combination of certain ionic interactions and electrostatic adsorption interactions or some other type of precursor-charge-surface interaction to be understood, the type 2 precursor precursor ions can be integrated, however, regardless of the interaction ! • How the biomass 'the type 2 component precursor may produce catalytic activity in the case where the substrate received as received, the treated substrate or the mx-treated substrate produces a second precursor charge-surface interaction The region 'the catalytically active region has an average thickness on and/or within the surface of the substrate of from about 1 to about 30 nm, preferably &lt; about 2 nanometers, more preferably &lt; about 1 nanometer. - It is convenient to carry out the following discussion 'and is not intended to limit the use of ΙΕχ_2 in this essay. This is commonly referred to as the type component precursor 126437.doc -41 · 200902146 charge-surface interaction or type 2 component precursor The broad interaction of interactions. In general, the type of salt solution used to treat the IEX-1 treated or BIX-treated substrate will depend on the type of ion to be ion exchanged in the ΙΕΧ2 treatment. Either an ion will undergo ion exchange, or in some cases two or more ions need to be exchanged, or ion exchanged at the same time, or ion exchange in sequence.

In the case where two different types of component precursor ions are integrated with the matrix, the ΙΕΧ-2 treatment herein is referred to as two ion exchanges or two ΙΕχ_2 treatments. Therefore, the ΙΕΧ·2 treatment in the case of the integration of the precursor ions of the three different types of components with the matrix is referred to as tertiary ion exchange or tertiary ΐΕχ_2 treatment. Type 2 Ingredients and Precursor Description Any salt solution of ΙΕΧ-2 ion, if chemically easy to replace, received as received, treated by I, or treated with ions on the surface of the substrate treated with ΒΙχ_ or with charge affinity to achieve Or the electrostatic interaction of the surface of the substrate treated by Βιχ. Soil, and therefore, ΙΕΧ-2 ion can be used as a type 2 component (IV). As described above, 'according to its pre-; t with it, the plasma precursor 2 (ie, type 2 component precursor) may have catalytic effect, and if so, the plasma-2 can be like a certain type of touch Form 2 in the vehicle composition operates as its mash, but the ions can also serve as a precursor for the preparation of another type of catalyst composition. “In general, ionic εεχ_2 precursors (which can be used to obtain surface-integrated 126437.doc •42- 200902146 type 2 components) include but not limited to Lewisine, precious metal cations, and bristles Or transition metal cations and ruthenium and anion MM, metal sterol 3 cations and anions, transition metal emulsion anions, transition granules &amp; m metal chalcogenide anions, main oxyanions, tooth ions, rare earth ions, rare earths Cationics and anions and combinations thereof. = "Depending on the intended use of the catalyst composition, certain Z-coded ion bodies have catalytic potencies in the precursor state and can form a type 2 component when integrated with a suitable matrix. An ionic IEX-2 precursor with catalytic potency without further treatment, some examples including, but not limited to, Blenzel or Lewis acid, Blenz or Lewis, noble metal cations, transition metal cations, Transition metal oxyanion, main group oxygen anion, tooth ion, rare earth hydroxide ion, rare earth oxide ion and combinations thereof. Examples of certain precious metals and transition metals of type component precursors, including but not limited to Groups 232 to U (formerly Groups lb, lib, Group II, Group VIb, Group Vb, and Group VIII), such as platinum, palladium, nickel, copper, silver, gold, ruthenium, osmium, iridium, osmium, cobalt, iron, manganese, zinc ionic salts and complex ion salts and combinations thereof. For IEX-2 For the treatment, ionic salts of palladium, platinum, rhodium, ruthenium, osmium, iridium, copper, silver, gold and nickel are especially preferred. For the sake of convenience, the elements of these groups can be used by using international theory and applied chemistry. · The element family number of the 1 (IUPAC) naming system is queried in the periodic table of chemical elements displayed in 2 http.//pearll.lanl.gov/periodie/default_htm (and shows the family number used previously). Examples of certain transition metal oxyanions of the component precursors, including but not limited to Groups 5 and 6 (formerly Groups Vb and VIb) 3 126437.doc 200902146 ionic salts 'eg V〇43-, w 〇2- „ a 6. 4 , h2w12o40 , m〇o42·, Mo7024 -, Nb60196-, Re〇甘〇4 and combinations thereof. For the IEX-2 treatment, yttrium salts of molybdenum, tungsten and vanadium are particularly preferred. Some transition metal chalcogenide anions which may be used as precursors of the type 2 component include, but are not limited to, the ionic salts of Group 6 (formerly the mth group), such as MoS42., WS42, and combinations thereof.

Examples of certain main group oxygen anions which may be used as precursors of the type 2 component include, but are not limited to, the ionic salts of Group 16 (formerly Group Vla), such as s〇, P(V 'Se042, and combinations thereof. For the ΙΕχ 2 treatment, the ionic salt of 2 _ is particularly preferred. Some examples of halides which can be used as precursors of the type 2 component include, but are not limited to, the ionic salts of the steroidal group (formerly the Vila group), such as F- , α_, Br-, r and combinations thereof, for the ΙΕΧ_2 treatment, the ionic salts of F· and α_ are particularly preferred. Some rare earth ions and rare earth cations or ions may be used as precursors of type 2 components, including but It is not limited to lanthanides and ionic salts of lanthanides such as La, pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, H〇, Er, Tm, Yb, Lu, Th, U, and combinations thereof. Examples of certain transition metals that can be used to produce transition metal carbides, transition metal-nitrides, transition metal-borides, and transition metal-phosphides as type 2 components, including but not limited to chromium, molybdenum, tungsten, rhenium, Button, iron, ionic, nickel ionic salts and combinations thereof. 1EX-2 treatment instructions are usually 'for IEX-2 The concentration of the salt solution 'depends on the type of substrate treated with ΐΕχ 1 or BIX - and treated with ΙΕΧ 2 and the IEX-2 used for interaction and/or integration with the substrate treated by 126437.doc -44 - 200902146 IEX_1 Relative affinity of ions. For most types of glass substrates (such as, but not limited to, Bahan, A or Sdda_lime), about 〇〇〇1. To saturated IEX-2 salt solution Preferably, about 0.001 wt% to 5 wt% of the IEX-2 salt solution is preferred. However, depending on the functional surface concentration of the catalytic component necessary to achieve the intended use of the catalyst composition, ΙΕχ·2 The salt solution may be less than 0.001 wt%. If multiple ion types are exchanged with the matrix, either simultaneously or sequentially, the concentration of the salt solution will be applied to the relative loading and matrix required for the precursors of the various components on the substrate. The relative affinity of a component precursor to another component precursor is adjusted, such as, but not limited to, two IEX-2 treatments (ie, two different catalytic component precursors and a hydrazine or a BIX-treatment). In the case of matrix integration) or tertiary ΙΕχ_2 treatment (that is, the integration of three different catalytic component precursors with IEX-1 or BIX-treated matrix), the concentration of the salt solution used for the various ions of the shoal will depend on the type of application. Target relative concentration of component precursors integrated with the surface of the substrate and surface affinity for various ions. Typically, depending on the type and concentration of the IEX-2 salt solution used and the properties of the matrix, 'select for IEX-2 treatment. Heat treatment conditions such as heating temperature, heating time, and mixing conditions. Preferably, the heating temperature suitable for the treatment with a certain acid may range from about 20 ° C to about 200 ° C, more preferably from about 3 (rc to about 9 〇 (&gt; Depending on the concentration of the IEX-2 salt solution and the selected heating temperature, the heating time for the 126437.doc -45-200902146 IEX-2 treatment may vary. Preferably, the heating time is suitable for the pressure and _2 treatment. Between about 5 minutes and about 48 hours, more preferably between about 3 minutes and about 5 hours. Usually 'depending on the type and concentration of the IEX-2 salt solution used and the characteristics of the substrate (eg 'from glass The affinity of the ions removed by the mesh, the strength of the glass after removal of the mesh ions, etc., and the duration of the heat treatment, the mixing conditions are selected. For example, but not limited to, the mixing conditions may be continuous or broken.

Continued, it can also be mechanical mixing, fluidization, tumbling, rolling or manual mixing. ~Q, IEX-2 salt solution concentration, heat treatment state and mixing conditions of the group 0 'substantially based on the integration of a sufficient number of ΙΕΧ-2 ions and ΙΕχ_2 ions on the substrate and / or within the matrix to determine, and the matrix The nature of the physicochemical bonding of the surface is independent of the type and extent of surface charge required to produce the surface active state required to achieve the intended use of the catalyst composition. ' Adjusting the surface charge of the substrate by adjusting the pH. As mentioned above, the degree of positive adjustment required for the type 2 component precursor to be integrated with the surface in the second 1EX (&quot;IEX-2&quot;) treatment will usually be Depends on the soil IEP, the IEp contrast surface charge distribution curve of the matrix and the type of charge required. For example, without limitation, for a substrate having an IEp equal to 8, preferably, the pH of the matrix/IEX-2 mixture is adjusted to be between about 8 and about 12, more preferably between about 9 and about 11. The (4)_ used to carry out the pH value (4) will depend on compatibility with other inverses (IV), the stability of the base f in the range of pH values (4), and the desired m-degree and other g-forms. In general, any thin test can be used to adjust the surface charge of the matrix table 126437.doc •46·200902146 to the right side of its IEP (ie, to produce a net negative surface charge), and any dilute acid can be used to adjust the surface charge of the substrate to Its left side of the IEp (ie, produces a net positive surface charge). The inorganic acid or organic acid or organic acid may be used in a dilute concentration, and an organic base is usually preferred. Generally, the concentration of the dilute acid solution or the dilute alkali solution will depend on the type of acid or base used, its dissociation constant, and the pH at which it is suitable to obtain the desired surface charge type and density. Preferably, after the IEX-2 treatment is completed, the substrate treated by ΙΕχ_2 can be separated by any suitable method including, but not limited to, filtration, centrifugation, decantation, and combinations thereof. The substrate treated with ΙΕΧ_2 is then washed with one or more suitable cleaning solutions (eg, distilled or deionized water, dilute or dilute acid and/or a suitable water-soluble organic solvent such as methanol, ethanol or acetone) and Dry at a temperature of 110 ° C for about 20 to 24 hours. IV. Post-precipitation treatment description If necessary, after the IEX-2 treated substrate is separated, it can be dried only, calcined, calcined under oxidizing conditions, then reduced or further oxidized, reduced or not calcined. Oxidation in the case of calcination. Transition metal ions, oxyanions and/or sulfur anions can be surface-precipitated in the gas or liquid phase with suitable reduction, sulfurization, carbonization, nitridation, phosphating or boration reagents (-IDING reagents) as needed The reaction produces a corresponding catalytically effective metal sulfide/sulfur oxide, metal carbide/carbon oxide, metal nitride/nitrogen oxide, metal boride or metal phosphide component. Usually, but not limited to, the purpose of the post-precipitation calcination treatment is essentially to decompose the metal counterion or the ligand 'silk metal, metal oxide, metal chalcogenization 126437.doc -47- 200902146 and remove any undried dry matter, etc. More closely integrated with the surface of the substrate, residual water removed during the drying process.

The calcination conditions for the IEX-2 treated substrate are not (4) important for successful surface activation of the matrix. However, these conditions should only be sufficiently stringent to produce at least one precipitated component precursor in a catalytically effective amount. Catalytic active region. However, in the case of calcination, the &amp; mass is first calcined in an oxidizing atmosphere (e.g., in air or oxygen). In addition, it is important to choose a high calcination temperature to ensure that the precursor of the type 2 component of interest is oxidized and any residual water is removed (if any residual water is present), but the calcination temperature should also be low enough' It can reasonably avoid the softening point of the matrix and the decomposition of the undesired precursor components. For example, but not limited to, the sulphate of the sulphate requires calcination conditions to decompose the cations formed and the sulphate is compared to the surface, but such conditions do not significantly decompose the sulphate into volatile sulphur oxides. Similarly, the metal anion requires calcination conditions to decompose the bound cations and fix the anions to the surface as oxides, provided that the metal oxides are volatilized from the surface or the metal oxides are dissolved into the matrix. Finally, the precious metals and complexes should be calcined under the following conditions: decomposition of the ligands and anions present, c must not be so strict that the shellfish accumulate on the surface. For this reason, as explained in more detail below, the noble metal is preferably directly reduced without calcination. The sling, service, and JBL should be at least about 1 低 lower than the softening point of the selected substrate. The calcination temperature should be between about loot and 700 〇c, more preferably about 2 Torr. (: between 6 ° °c, preferably between about 300 ° C and 500X: 126437.doc •48· 200902146 Typically, the substrate treated with IEX-2 is calcined for about i to about 24 hours. 'It is preferred to calcine for about 2 to about 12 hours. However, depending on the type 2 component integrated with the matrix, the calcination time can vary outside of these ranges. Usually, but not limited to, the purpose of the reduction treatment after precipitation is at least Substantially, if not completely, the catalytic component precursor (e.g., metal, metal oxide or metal sulfide) is reduced to a lower oxidation state integrated with the surface of the substrate. Examples of suitable reducing agents include, but are not limited to, CO and H2. Preferably, the reducing agent has a flow rate of from about 0.01 L/hr. to about 100 L/hr per gram of substrate. More preferably, the flow rate is in the range of gram per gram of 〇.1 [Chemical to 丨L/hr ^ Between. Typical h conditions 'reduction temperature should be between 〇C and 600, provided that the selected temperature is at least 1 低 lower than the softening point of the matrix. 〇. Usually, the substrate treated by IEX-2 is After about 5% to about the hour of reduction, preferably from about 1 hour to about 8 Alternatively, the IEX-2 treated substrate can be reduced by solution phase treatment using a soluble reducing agent such as, but not limited to, hydrazine, sodium hydride, lithium aluminum hydride, and combinations thereof. The solvent (for example, water or diethyl ether) is usually carried out. Usually, but not limited to, the purpose of the post-precipitation-IDING reaction treatment is to reduce the metal ions while additionally reacting the reducing metal with a low atomic weight-IDING element. Metal oxyanions and/or metal sulphide anions. In some cases, direct-IDING can occur without simultaneous metal oxide reduction, such as some vulcanization treatments. 126437.doc -49- 200902146 Typical gas phase - IDING reagents include, but are not limited to, hydrogen sulfide, methyl mercaptan and dimercaptosulfur (vulcanization reagent), ammonia (nitriding reagent), methane, ethane, and other light hydrocarbons (carbonizing agents). IDING reagent can react directly with IEX_2 treated substrate under ambient pressure or under pressure' or in a gas mixed with inert gas or hydrogen and with ΙΕχ_2 The substrate reacts to produce the corresponding sulfide, carbide or nitride. The portion of the catalytically effective part - IDED products (including sulfur oxides, carbon oxides and nitrogen oxides) can also be produced by: Substantially incomplete reaction of the substrate received/obtained as it is, the integrated matrix treated with IEX-2, the calcined substrate treated with ΙΕχ_2 or the reduced substrate treated with IEX-2. By two ion exchanges (two IEX_2 treatments) The reduction treatment of the substrate produces a metal phosphide, wherein one ΙΕχ·2 treatment is one or more transition metal ions, and the other ΙΕΧ·2 treatment is a phosphate ion. Preferably, the two ΙΕΧ-2 processes can be performed in sequence. Alternatively, the metal phosphide can be produced by using a gas phase phosphating agent such as, but not limited to, phosphine (ρ Η 3). For example, a single ion exchanged substrate (matrix treated with mono-?2) with the desired transition metal in the appropriate oxidation state can be further treated with hydrazine 3 to produce the desired metal phosphide. Solution phase treatment can be used to produce metal sulfides, metal borides, and metal phosphide catalytic components. Typical solution treatment for the production of metal sulfides includes, but is not limited to, treatment of the metal ion-integrated matrix treated with ruthenium-2 at an effective concentration of the organic solution of hexamethyldisulfanethione over a range of room temperature to reflux temperature over time. Sufficient to produce a catalytically effective amount of a catalytic component on and/or within the surface of the substrate. 126437.doc •50· 200902146 Typical solution phase treatment for shed formation includes, but is not limited to, for IOX-2 treated metal-ion-integrated matrices, between room temperature and reflux temperature, for a period of time effective for sodium borohydride Or treated with aqueous potassium borohydride solution. Typical solution phase treatment for the formation of the fill comprises treatment of the IOX-2 treated metal-ion-integrated substrate with an aqueous solution of sodium hypophosphite for a time sufficient to be on and/or within the surface of the substrate, from room temperature to reflux. A catalytically effective amount of a catalytic component is produced. V. Catalytic active region indicates that the catalytically active region resulting from any of the above substrate treatments will have an average thickness of (1) less than or equal to about 30 nm, preferably &lt; about 2 nanometers, more preferably &lt; about 10 Nano, and (ii) catalyzing an effective amount of at least one catalytic component. Preferably, XPS spectroscopy is used to determine the average thickness of the catalytic region, and XPS spectroscopy uses a layered etching technique known as a sputter depth profile (described in more detail below in the analytical methods provided in the Examples below). However, other analytical techniques known to those skilled in the art can be used to determine the approximate location of the substrate surface associated with the catalytic component. Therefore, the average thickness of the matrix catalytic region can be determined using, for example, but not limited to, transmission electron microscopy (TEM) or scanning TEM (STEM, also described in more detail below). Those skilled in the art have a thorough understanding of the XPS or the program. It should be understood that in the extreme case, regardless of whether the catalytically active region is produced by treatment or IEX-2 treatment (with or without hydrazine treatment), the thickness of the catalytically active region is generally the same for any of the catalyst compositions of the present invention ( a) does not substantially pass through the surface area of the substrate or (b) does not exceed the surface of the substrate by a thickness of about 3 nanometers, preferably no more than about 2 nanometers, more preferably no more than 126437.doc -51· 200902146 meters thickness. It is also understood that the catalytically active region may be on the treated mass and/or one or more catalytic domains m: (4) on the surface outside the substrate, and in the presence of any pores, on the surface of the wall; (b) on the surface of the substrate In the area of the area, the field is taken from the field, that is, about 3 inches below the outer surface of the substrate.

Preferably, the rice is preferably about 2G nanometers below the outer surface of the substrate, more preferably below the outer surface of the substrate. (4) (4); # When any pores are present, about 3 hours below the surface of the matrix pore wall, preferably below the surface of the base pore wall About 20 nm is more preferably about 10 nm below the surface of the substrate pore wall, but above the surface of the substrate surface; (4) above or above the surface of the substrate, when there is any pore, part is on the surface of the pore wall of the substrate or Above, and partly in the surface area of the matrix, or (d) a combination of (a), (b) and (c). Generally, the amount of the catalytic component may be about 0.0002 wt·/, whether it is a quinoid component or a type 2 component. Between about 5 wt.%, preferably between about wt2 wt% and about 2 wt.%, more preferably between about 〇5〇〇〇% to about 丨"%. The catalytically active region of the catalyst composition of the present invention may be continuous or discontinuous. Without being bound by theory, it is believed that the catalyst composition covered with the discontinuous catalytically active region is substantially continuous or The catalytic composition of the broader continuous catalytically active region is at least as effective and, in some cases, more effective. The extent of the catalytically effective region covering the outer surface of the substrate can be as low as 〇.〇〇〇1 The % coverage is between up to 1% coverage. Preferably, the extent of surface coverage outside the catalytically active area is between about 126437.doc 52-200902146 0.00013⁄4 to about 10%, more preferably about 0.0001% to about Between 1%. However, without being bound by theory, it is believed that the catalyst composition, especially the catalyst composition with a lower catalytic component wt_% loading, may be more catalytically effective because The catalytically active regions on and/or within the treated substrate become more For dispersion (i.e., greater distribution and separation between catalytically active regions).

The catalytically active regions and other characteristics of the above-described catalyst compositions are based on the best available information for the state of the catalyst composition prior to entering the steady state reaction conditions. The degree to which one or more of the described characteristics can vary is not certain and is largely unpredictable. Nevertheless, without being bound by theory, the catalyst, and the sigma of the sigma, will allow the catalytic component to be integrated with the matrix, as the catalyst composition promotes its intended process reaction. The electrical and/or geometric positioning and other component characteristics vary significantly. Thus, it is to be understood that the scope of the invention described herein extends to all of the catalyst compositions produced by the claimed compositions under steady state reaction conditions. VI. Composite Catalyst Composition Description The composite catalyst composition comprises at least one refractory inorganic oxide and at least one to v catalytic component precursor catalyst composition. The precursor catalyst composition can be prepared by ion exchange, impregnation, immersion, co-precipitation or other catalyst composition preparation methods, as long as the method can produce a precursor catalyst composition in which at least one catalytic component is After mixing with the refractory inorganic oxide, it remains substantially dispersed within the precursor catalyst composition and/or composition. In addition, Hetong Renxu;, Gan A person, Bu Tian composite catalyst composition exposed to the intended use of steady-state reaction conditions for at least - hour after the precursor catalyst composition of 126437.doc •53·200902146 Preferably at least one catalytic component remains in the matrix and/or on the substrate. The catalyst-combined precursor catalyst indicates that the peak pin s "&amp; lead-and-spinning catalyst composition" before mixing with the genomic temperature oxide. The entire high temperature resistance used to produce the composite catalyst composition The precursor catalyst composition matrix of the prosthetic machine is typically selected from the group consisting of a mesophyll material, a substantially innocuous material, and mixtures thereof, having the porous genus discussed in more detail above.

Sex. In any event, however, the matrix of the precursor catalyst composition is substantially non-porous. Examples of the inclusions include, but are not limited to, glass, carbon carbide, nitrogen: Shixi, cordierite, inclusion, and mixtures thereof. Examples of substantially no stone materials include, but are not limited to, substantially flawless ceramics, alpha alumina, cerium oxide, oxidized chin, carbon, and mixtures thereof. D. However, the precursor catalyst composition is preferably according to the description provided herein. Prepared FSC composition. However, the methods of preparing functional surface catalyst compositions described herein can also be used in the art: other methods of preparing catalyst precursor compositions, as long as at least one of the catalysts is used in the preparation of the composite The high temperature resistant inorganic oxide (especially any other suitable material) of the catalyst composition remains substantially dispersed within the precursor catalyst composition and/or composition after mixing. In view of this need, other methods of preparing precursor catalyst compositions will be apparent to those skilled in the art. The minimum size of the matrix used to produce the precursor catalyst composition (i.e., the average maximum size of the matrix particles) is typically between 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 Between 15 and 10 microns and preferably between about 0.2 microns and about 50 microns. However, depending on the intended use of the composition of 126437.doc • 54· 200902146, matrices outside the above range may still be effective without adversely affecting the expected performance of the composite catalyst composition. Those skilled in the art will appreciate that the composite operation may introduce potential macropores, mesopores, and/or micropores into the finished composite. However, this porosity is not introduced into the precursor catalyst composition when the precursor catalyst composition is formulated and complexed with the other components of the composite catalyst composition described herein. Composite High Temperature Inorganic Oxide Description Γ For convenience, the high temperature resistant inorganic oxide used to form the composite catalyst composition together with the fully dispersed precursor catalyst composition may also be referred to herein as composite high temperature inorganic oxidation. 'or' is further referred to as a composite refractory oxide. The surface area of the composite refractory oxide is generally in the range of from about i to about (eight) m 2 /g and preferably in the range of from about 5 Torr to about 25 Å, and the apparent bulk density is from about 0.2 g/mL to about 丨. _8 g/mL, preferably from about 〇·2 g/mL to about 1.0 g/mL. However, depending on the intended use of the composite catalyst composition, the surface area and apparent bulk density of the complex U 纟 refractory oxide may exceed the foregoing ranges. In any case, these characteristics of the composite refractory oxide are selected to ensure that the precursor catalyst composition can diffuse well throughout the composite refractory oxide without adversely affecting the performance of the composite catalyst composition. . ', y can be used to form a composite catalyst composition of high temperature resistant inorganic oxides including but not limited to Y (gamma) alumina, S (delta) alumina, - Yihua Ming, "Oxidation Ming, dioxide plant II" (also known as buddha), non-zeolitic molecule _(NZMS), (iv) oxide, gasification 126437.doc •55· 200902146 Titanium, zirconia and mixtures thereof. Examples of zeolites include, but are not limited to, zeolite Y, zeolite X, zeolite L, zeolite p (beta), ferrierite, Mn, UZM_4 (see U.S. Patent No. 6,776,975), UFI, UZM_8 (U.S. Patent No. 6,756,030), UZM-9 (U.S. Patent No. 6,713, No. 41), luminescent zeolite and erionite. Examples of non-zeolitic molecular sieves include, but are not limited to, aluminum bismuth phosphate (SAp®) as described in U.S. Patent No. 4,440,871, ELAP0, which is incorporated in U.S. Patent No. 4,793,984, and MeAPO, which is incorporated herein by reference. The patents are hereby incorporated by reference. Examples of non-oxides include, but are not limited to, ceria and aluminum phosphate. It should be noted that cerium oxide-alumina is not a physical mixture of cerium oxide and aluminum oxide, but an acidic amorphous material formed by co-gelation or co-precipitation. The term is well known in the art, for example, see U.S. Patent Nos. 3,9,9,9,5,5, 3, 274,124, and 4, 988, 659, the disclosures of each of which are incorporated herein by reference. Preferred high temperature resistant inorganic oxides are cerium, eta alumina and zirconia. The composite refractory inorganic oxide is produced using methods well known to those skilled in the art to form the desired viscosity or consistency (e.g., paste, dough, etc.) for use with precursor catalyst compositions and any other Suitable for mixing of composite components (described below). Depending on the viscosity or consistency of the composite refractory inorganic oxide composition, the mixing method for sufficiently diffusing the pre-prepared precursor catalyst composition throughout the composite: high temperature inorganic oxide includes, but is not limited to; Ball milling, polishing and blending. After the current catalyst composition is thoroughly mixed with the composite refractory inorganic oxide, the precursor catalyst combination and the composite temperature-resistant compound mixture are used for the generation of the composite catalyst combination 126437.doc -56 - 200902146. However, an extrudable dough-like composition that at least retries the high temperature oxide and the precursor touch is generally preferred for forming a composite catalyst composition (discussed in more detail below). Formation of the composite catalyst composition illustrates the formation of a composite catalyst composition by mixing at least one composite refractory oxide and at least one pre-prepared precursor catalyst composition to produce a composite refractory oxide/precursor catalyst mixture&apos;. For example, a composite high temperature resistant oxidation (tetra) 16 can be formed first, and a precursor catalyst composition is mixed into the agglomerate. Other components including, but not limited to, non-screen oxides, zeolite molecular sieves, non-zeolitic molecular sieves, titanium tantalate, clay, and metal oxides, and combinations thereof, may also be mixed with the dough to form (eg, by extrusion) ) A composite catalyst composition was previously produced. After the composite refractory oxide is substantially formed (for example, the alumina powder is peptized with water and a suitable peptizing agent such as HCl), the precursor catalyst composition is mixed with the composite refractory oxide to produce a composite. A composite enthalpy resistant oxide/precursor catalyst mixture of the catalyst composition. The composite refractory oxide and precursor catalyst can be mixed using a variety of mixing methods known to those skilled in the art including, but not limited to, paddle mixing, ball milling, polishing, and kneading. The preferred solvent is water, but an organic solvent and a mixture of water and an organic solvent may also be used. The mixture may also contain some agent which promotes resistance to diffusion of the oxide of the dish, such as, but not limited to, nitric acid, hydrochloric acid, sulfuric acid, and acetic acid. In another embodiment, the composite refractory oxide can be formed by milling the metal oxide &amp; in the aqueous slurry mixture and adding the precursor catalyst composition before or after the milling stage substantially m. It is preferred to dry and calcine it into flakes when producing a polymer blend 126437.doc • 57· 200902146. Inorganic binders can be used where appropriate. Examples of inorganic binders to which slurry 10 can be added include, but are not limited to, Zr0(C2H3〇2)2, Ζα(Ν〇3)2, ZrO(OH)Cl.nH20, cerium oxide sol, Zr〇c〇3, Ζγ 〇(〇η)2

Zr(C5H8〇2)4, Zr(S〇4)2.4H2(), alumina sol, cerium oxide sol, aluminum nitrate and soft boehmite. Although in some cases, the inorganic oxide binder can provide the same high temperature oxidation resistance as the composite high temperature oxide, and any inorganic oxide binder can be combined with any composite high resistance and oxide. use. The inorganic binder produces an inorganic oxide binder by gunming. The inorganic oxide binder can assist in strengthening the &lt;high temperature inorganic oxide network of the composite catalyst composition, or as the primary or sole composite refractory oxide of the composite catalyst composition. However, many composite refractory oxides do not require an inorganic oxide binder when forming a composite catalyst composition, particularly when a composite catalyst composition is formed using some dusting method. However, as long as the inorganic binder is appropriate, a sol, a gel or a metal complex which decomposes upon heating can be used to form an inorganic oxide binder. Thus, if appropriate, inorganic oxide binders which may be used include, but are not limited to, oxidized, dioxin, oxidized, titanium oxide and linonic acid. For example, when the composite refractory oxide is stagnation, oxidized, oxidized or oxidized, an oxidized binder can be used. However, it has been found that when the oxidation is used as a composite refractory oxide, it is preferred to have an oxidative misclay. The amount of inorganic binder (if present) present in the composite mixture should be provided in the composite catalyst composition about! From wt.% to about 99% by weight of the inorganic oxide binder. Preferably, the amount of inorganic binder used provides the optimum amount of inorganic binder wt% in the composite catalyst from about 126437.doc -58 to 200902146 of from about 2 to 40 wt.%. And provide 5 to 3 复合 of composite catalyst

Depending on the particle size of the high temperature resistant oxide, it may be necessary to grind the material. Various grinding methods for "negative and at the same time providing a narrower particle size distribution range include, but are not limited to, ball and pulverized grinding = :: grinding 乂 ensures different The components are thoroughly mixed and the particle size of the composite refractory oxide and/or precursor catalyst composition is reduced as appropriate. Grinding = about 5 to about 8 hours, preferably about 2 to about 8 hours. After the composite refractory oxide/precursor catalyst composition mixture is formed, it can be formed into a shaped material of any desired shape by methods well known to those skilled in the art of forming materials, including but not limited to spheres, rods Shapes, pellets, granules, ingots, granules, extrudates, rings, saddles, bilobes, and other forms known to those skilled in the art. The composite catalyst composition is opened/formed into the desired shape. After (e.g., extrudate), it will be dried at a temperature of from about 1 〇〇〇c to about 320 ° C (preferably about 10 (rc to about 15 〇〇 c) for about i to about hour' then at least about 20 (at a temperature of TC, simmering for about 5 to about 1 hour to generate a complex a catalyst composition. In general, the calcination conditions of the composite catalyst component are selected to stabilize the composite refractory oxide and integrate with the precursor catalyst composition. In addition, the intended use or process of the composite catalyst composition is determined. Application-specific 'calcining conditions can be used to optimize the properties of the composite refractory oxide, such as, but not limited to, its surface area, structural integrity, and pore volume. The firing temperature is preferably better than the combustion of the precursor catalyst composition. The temperature or structural decomposition temperature is at least about a loot. However, in general, the preferred calcining temperature is from about 200 ° C to about 15 Torr. Preferably, from about 400 ° C to about lioot, and preferably 126437.doc - 59- 200902146 From about 40 ° C to about 80 ° C. One or more calcination steps can be performed so that any point after at least one catalytically componentized mouth is contacted with the composite surface temperature resistant inorganic oxide can be Cannon burning. For example, 'in a non-reducing environment, about l 〇 (rc to about 7 〇 (the calcination step in the temperature of rc is preferably performed at about 200. (: to about 500.): between The burning time can be different 'but preferably about 1 to 5 hours In the calcined composite catalyst composition, the concentration of the precursor catalyst composition ranges from about 1% to 99% by weight, preferably from about 1% to about 9% by weight, more preferably from about 1 to about 80% by weight, and most preferably from about 1 to about 7 % by weight. However, in general, the concentration of the precursor catalyst composition in the composite catalyst composition depends on its The intended use, the activity of the precursor catalyst composition for the target reactant, and the desired target product productivity. In addition, in general, the higher the concentration of the catalytic component on the precursor catalyst composition and/or the composition, The lower the concentration of the precursor catalyst composition in the composite catalyst composition. EXAMPLES The invention will now be described in more detail in connection with the following examples which illustrate or analogize various aspects of the practice of the invention. It is to be understood that all changes that come within the spirit of the invention are intended to be protected, and thus the invention is not to be construed as limited to the examples. Alkali-resistant (AR) glass matrix catalyst composition Example 1 AR glass

Obtained AR glass produced by Saint-Gobain Vetrotex Cem-FIL 126437.doc 200902146

Anti-CrakTM HD samples, i.e., glass fibers having an average diameter of about 17 to 2 microns. The first step is to perform a calcination heat treatment on the AR glass sample received as it is. In this treatment, the AR glass was calcined for 4 hours in an air atmosphere having an air flow rate of 1 L/hr and a temperature of 600 °C.

In the second step, the simmered AR glass is subjected to acid leaching treatment. Place 25 grams of calcined AR glass and 3 liters of 5.5 wt.% nitric acid in a 4 liter plastic wide-mouth container. Place the plastic container in a 6 inch. Shake it in your hand for 15 hours every 15 minutes. After the acid leaching treatment was completed, the sample was filtered using a Buchner funnel with Whatman 541 filter paper and washed with about 7.6 liters of deionized water. The acid leached sample was then dried for 22 hours at a temperature of 丨1〇. In the third step, the acid-impregnated AR glass is subjected to ion exchange treatment. Prepare 80 ml (M wt.% solution for ion exchange (&quot;ΐΕχ solution") in this solid H-hydrogen tetraamine _3)4]_)2. Add 4 g of AR glass to the ion Exchange solution (&quot;glass/ion exchange mixture"). Measure the glass/ΙΕΧ ion exchange mixture _, get a value of ρ 约为. Money 'move the mixture into a 15 〇 ml plastic wide-mouth container. The container was placed in a ventilated oven for two hours, and it was shaken by hand every 30 minutes. After the ion exchange treatment was completed, the use was carried out.

The Whatman 5411 paper Buchner funnel is passed through a glass/ion exchange mixture and rinsed with deionized water using approximately 3 · 8 liters to ^, too % λ. Then, the ion exchange glass was dried at a temperature of 1 HTC for 22 hours. The fourth step is to reduce the ion exchange glass, ion exchange break 126437.doc • 61 - 200902146 First calcined in an air atmosphere with an air flow rate of 2 L / hr and a temperature of 300 ° C for 2 hours, then in hydrogen (H2 A hydrogen (H2) atmosphere at a flow rate of 2 L/hr and a temperature of 300 ° C for 4 hours. The sample was analyzed by inductively coupled plasma-atomic emission spectroscopy (ICP-AES) to give a concentration of about 0.016 wt.%. Sample analysis was carried out by XPS sputtering depth distribution method (described below). As shown in Fig. 1, the results showed that the thickness of the region where a large amount of palladium was detected by the method was about 10 nm. Example 2 Application on AR glass A sample of AR glass Cem-FIL Anti-CrakTM HD produced by Saint-Gobain Vetrotex, i.e., glass fibers having an average diameter of about 17 to 20 microns, was obtained and prepared according to the procedure of Example 1. Sample analysis by ICP-AES gave a palladium concentration of about 0.032 wt.%. Sample analysis was carried out by XPS sputtering depth distribution method (described below). As shown in Fig. 1, the results showed that the thickness of the region where a large amount of palladium was detected by the method was about 10 nm. Example 3 AR glazed glass A sample of AR glass Cem-FIL Anti-CrakTM HD produced by Saint-Gobain Vetrotex, a glass fiber having an average diameter of about 17 to 20 microns, was obtained. In the first step, the AR glass sample received as received is subjected to calcination heat 126437.doc -62- 200902146. In this treatment, the AR glass was calcined for 4 hours in an air atmosphere having an air flow rate of 1 L/hr and a temperature of 6 °C. In the second step, the calcined AR glass is subjected to acid leaching treatment. 25 g of calcined AR glass and 3 liters of 5.5 wt.% nitric acid were each placed in a 4 liter plastic wide-mouth container. Place the plastic container at 60. (: Inside the ventilated oven - hour's shaking slightly by hand every 15 minutes. After the acid leaching process, filter the sample using a Buchner funnel with Whatman 541 filter paper and rinse with about 7.6 liters of deionized water. Then, 11 (The temperature of rc, the sample after acid leaching is dried for 22 hours. The third step is to carry out ion exchange treatment on the acid-impregnated AR glass. In this example, '4 〇 ml is prepared using di-halo-tetraamine palladium. 0.1 wt_% palladium solution for ion exchange ("ΙΕχ solution"). Add 4 g of ar glass to the ion exchange solution ("glass/ion exchange mixture"). Measure the pH value of the glass/ion exchange mixture to obtain The 2ρΗ value was about 77. Then, the mixture was transferred into a 100 ml plastic wide-mouth container and placed in a ventilated oven at C for two hours and shaken slightly by hand every 3 minutes. After the ion exchange treatment was completed, use Whatman with 54 丨 filter paper Buchner funnel filter glass / ion exchange mixture, and use about 3 · 8 liters of deionized water to clean. Then, at 11 (rc temperature, ion exchange glass samples Drying for 22 hours. In the fourth step, the ion exchange glass sample is subjected to reduction treatment, in which the ion parent glass is first simmered in an air atmosphere at an air flow rate of 2 L/hr and a temperature of 3 ° C for 2 hours, and then The hydrogen gas flow rate was 2 L/hr in a hydrogen atmosphere and at a temperature of 3 ° C for 4 hours. 126437.doc -63 - 200902146 Sample analysis by ICP-AES gave a palladium concentration of about 0.0012 wt.%. Example 4 An AR glass Cem-FIL Anti-CrakTM HD sample produced by Saint-Gobain Vetrotex, a glass fiber having an average diameter of about 17 to 20 microns, was obtained on the AR glass. The first step was to receive the AR as it is. The glass sample was subjected to calcination heat treatment. In this treatment, the AR glass was calcined for 4 hours in an air atmosphere having an air flow rate of 1 L/hr and a temperature of 600 ° C. In the second step, the calcined AR glass was subjected to acid leaching treatment. Place about 50 grams of calcined AR glass and 4 liters of 5.5 wt.% nitric acid in a 4 liter plastic wide-mouth container. Place the plastic container in a 90 ° C ventilated oven for two hours, every 30 minutes. Shake your hand a little. The acid leaching process is complete. Thereafter, the sample was filtered using a Buchner funnel with Whatman 54 1 filter paper and washed with about 7.6 liters of deionized water. Then, the acid immersed sample was dried for 22 hours at a temperature of 11 ° C. The acid-impregnated AR glass is subjected to Na+-reverse ion exchange (&quot;Na-BIX"). The acid leached sample from the second step is mixed with 4 liters of 3 mol/L sodium chloride (NaCl) solution. Mix ("glass/sodium chloride mixture"). The pH of the glass/NaC blend was measured. About 40 wt.% of tetrapropylammonium hydroxide was added dropwise as needed, and the pH of the mixture was adjusted to be greater than 10 (in the present example, the pH was about 11.0). The glass/gasified sodium mixture was transferred to a 4 liter plastic wide mouth container. The container was then placed in a ventilated oven at 126437.doc -64 - 200902146 50 °C for 4 hours with a slight shake of the hand every 30 minutes. After the Na-BIX treatment was completed, the glass/sodium chloride mixture was filtered using a Brinell funnel with Whatman 541 filter paper and the Na-BIX/AR glass sample was collected and then washed with about 7.6 liters of deionized water. Then, the Na-BIX/AR glass sample was dried at a temperature of 1 l ° C for 22 hours. In the fourth step, a second ion exchange (ΠΙΕΧ_2Π) treatment was performed on the Na-BIX/AR glass sample. In this example, 3 liters of a 0.01 wt.% palladium solution was prepared for ion exchange (&quot;IEX-2 solution" using dichlorotetramethylene palladium [Pd(NH3)4](Cl)2. 42 gram Na -BIX/AR glass is added to the IEX-2 solution (&quot;glass/IEX-2 mixture&quot;). The pH of the glass/IEX-2 mixture is measured to give a pH of about 8.5. Then, the mixture is transferred 4 liters of plastic wide-mouth container. Place the container in a ventilated oven at 100 ° C for 22 hours, shake it slightly by hand during 22 hours of heating. After IEX-2 treatment, use with Whatman 541 Filter paper Buchner funnel filter glass / IEX-2 mixture and collect IEX-2 glass sample, then use about 7.6 liters of dilute ammonium hydroxide (! ^ 114011) solution to clean. Rare 1 ^ 4011 solution by 1 gram The 29.8 wt···. concentrated 4Οίϊ solution was prepared by mixing with about 3.8 liters of deionized water. Then, the ΙΕΧ-2 glass sample was dried at 110 ° C for 22 hours. Step 5, for IEX-2 glass The sample was subjected to a reduction treatment in which the sample was reduced in a hydrogen atmosphere at a hydrogen flow rate of 2 L/hr and a temperature of 300 C for 4 hours. Sample analysis by ICP-AES yielded a palladium concentration of approximately 0.015 wt.%. Sample analysis was performed by XPS sputtering depth profile (described below), as shown in Figure 1, 126437.doc-65. 200902146, The results show that the thickness of the region where a large amount of palladium is detected by the method is about 10 nm. Example 5 The AR glass is obtained from the AR glass Cem-FIL Anti-CrakTM HD sample produced by Saint-Gobain Vetrotex. , that is, a glass fiber having an average diameter of about 17 to 20 μm. In the first step, the AR glass sample received as it is is subjected to a calcination heat treatment. In this treatment, the AR glass is at an air atmosphere having an air flow rate of 1 L/hr and 600. Calcination at a temperature of ° C for 4 hours. In the second step, the calcined AR glass is subjected to acid leaching treatment. 90.03 g of calcined AR glass and 4 liters of 5.5 wt.% of nitric acid are each placed in a 4 liter plastic wide mouth. Inside the container, place the plastic container in a ventilated oven at 90 ° C for two hours, shake it slightly by hand every 15 minutes. After the acid leaching process, filter the sample using a Buchner funnel with Whatman 54 1 filter paper, and Use about 7.6 liters to go Ion water cleaning. The acid leached sample is then dried for 22 hours at a temperature of 110 ° C. In the third step, the acid leached AR glass is subjected to ion exchange (IEX) treatment. In this example, Dihydrooxytetramine palladium [Pd(NH3)4](OH)2 was prepared in 2000 ml of a 0.1 wt.% palladium solution for ion exchange (&quot;IEX solution"). Add 8 0.06 g of AR glass to the ion exchange solution ("glass/ion exchange mixture"). Measure the pH of the glass/ion exchange mixture to give a pH of about 10.6. Then, transfer the mixture to 4000 ml of plastic. In a wide-mouth container, place the plastic container in a ventilated oven at 50 ° C for 72 hours, shaking it slightly by hand every 30 minutes 126437.doc -66 - 200902146. After ion exchange treatment, use with Whatman 54 1 The filter and paper Buchner funnel was passed through a glass/ion exchange mixture and washed with a solution of about 7.6 liters of dilute 1^1140^1. The solution was diluted with 10 gram of 29.8 wt·% concentrated NH4OH solution. Prepare by mixing 3.8 liters of deionized water. Then, dry the ion exchange glass sample for 22 hours at 11 °C. The fourth step is to reduce the ion exchange glass, where the ion exchange glass has a hydrogen flow rate of 2 L/hr. The hydrogen atmosphere was reduced at 300 ° C for 4 hours. Sample analysis by ICP-AES gave a palladium concentration of about 0.019 wt·%. Example 6 The AR glass was obtained by Saint-Gobain Vetrotex. The AR glass Cem-FIL Anti-Crak TM HD sample, which is a glass fiber having an average diameter of about 17 to 20 microns. In the first step, the AR glass sample received as received is subjected to a calcination heat treatment. In this treatment, the AR glass is produced. Calcined for 4 hours in an air atmosphere at an air flow rate of 1 L/hr and at a temperature of 600 ° C. In the second step, the calcined AR glass is subjected to acid leaching treatment, 250 g of calcined AR glass and 3 liters of 5.5 wt. ·% of nitric acid is placed in a 1 liter glass wide-mouth container. The open plastic container is heated on a Corning hot plate for two hours to bring the bottom of the container to a temperature of 90-100 ° C. The top of the container is at least 75. The temperature of °C is measured by thermoelectricity 126437.doc 67· 200902146 located in several places in the container; since there is evaporation of the solution during the treatment, 5.5 wt% of nitric acid is added to keep the volume at 3 liters. After the acid leaching treatment was completed, the sample was filtered using a 200 mesh stainless steel mesh and washed with about 5 liters of deionized water. Then, the acid immersed sample was dried for several hours at a temperature of TC. step, The acid-impregnated AR glass was subjected to ion exchange treatment. In this example, 2000 ml (pwt(NH3h)(1)) was used to prepare 2000 ml (M wt.% palladium solution for ion exchange ( &quot;ΐΕχsolution&quot;). Add 80 grams of AR glass to the ion exchange solution (&quot;glass/ion exchange mixture) to measure the pH of the glass/ion exchange mixture to give a pH of about 9.4 and then transfer the mixture to 4 _ml of plastic wide-mouth container will be placed in a 5 〇〇c ventilation box for 2 hours (1) every minute (s) shaking slightly with the hand. After the ion exchange treatment was completed, a Buchner funnel glass/ion exchange mixture with Whatman 5411 paper was used, and washed with about several liters of grammatic deionized water. Then, the ion exchange glass was dried at a temperature of 110 ° C for 22 hours. The ion exchange surface was reduced for 4 hours under a hydrogen atmosphere with a hydrogen flow rate of 2 ^ and a bribe. Concentration: Sample analysis by ICP-AES yielded approximately ο. Example of μ·% 7 126437.doc -68- 200902146 The glass on the AR glass obtained the AR glass Cem-FIL Anti-Crak TM HD sample produced by Saint-Gobain Vetrotex, ie the average diameter is about 17 to 20 microns. Glass fiber. In the first step, the AR glass sample is subjected to a calcination heat treatment as it is. In this treatment, the AR glass is calcined for 4 hours in an air atmosphere having an air flow rate of 1 L/hr and a temperature of 600 ° C. The calcined AR glass was subjected to acid leaching treatment. About 1 60 g of calcined AR glass and 12 liters of 5.5 wt.% nitric acid were each placed in a 15 liter round bottom flask, and a stainless steel paddle mixer was used. Mechanical mixing was carried out for two hours while heating at 90 rpm at 90 ° C. After the acid leaching treatment, the sample was filtered using a Buchner funnel with Whatman 54 1 paper and washed with about 7.5 liters of deionized water. The acid leached sample was then dried for 22 hours at a temperature of 110 ° C. The acid immersion sample was then ground to a fine powder by passing through a small hammer mill at one time. Grinding and acid immersion AR glass Row ion exchange treatment. In this example, 1 liter of 0.3 wt.% platinum solution was prepared using platinum tetraamine platinum [Pt(NH3)4](Cl) 2 for ion exchange ruthenium solution &quot;). 58 grams of ground and acid immersed AR glass was added to the ion exchange solution ("glass/ion exchange mixture"). The pH of the glass/ion exchange mixture was measured. About 29.8 wt% of ammonium hydroxide (NH4OH) was added dropwise as needed, and the pH of the mixture was adjusted to be greater than 10 (in the present example, the pH was obtained to be about 10.6). The glass/ion exchange mixture was then transferred to a 4 liter beaker and heated at 50 °C for two hours, using a stainless steel paddle mixer at 126437.doc -69-200902146 for continuous mechanical operation at 300 to 500 rpm. Stir. After heating for one hour, the pH was measured again and, as needed, the pH was adjusted to greater than 10 using about 29.8 wt.% NH4OH solution. After the two hour heating process was completed, the pH of the glass/ion exchange mixture was again measured and the pH was measured to be about 1 0.1. After the ion exchange treatment was completed, the glass/ion exchange mixture was filtered, and the ion exchange-glass sample was collected using a Buchner funnel with Whatman 541 filter paper, and washed with about 7.6 liters of a dilute NH4OH solution. The dilute NH4OH solution was prepared by mixing 10 grams of a 29.8 wt.% concentrated NH4OH solution with about 3.8 liters of deionized water. Then, the ion-exchanged glass sample was dried at a temperature of 11 ° C for 22 hours. In the fourth step, the ion-exchanged glass sample was subjected to a reduction treatment in which the ion-exchanged sample was reduced in a hydrogen atmosphere at a hydrogen flow rate of 2 L/hr and at a temperature of 300 ° C for 4 hours. Sample analysis by ICP-AES gave a platinum concentration of about 0.0033 wt.%. Example 8 AR ray on the glass obtained from the Saint-Gobain Vetrotex AR glass Cem-FIL Anti-CrakTM HD sample, a glass fiber having an average diameter of about 17 to 20 microns. In the first step, the AR glass sample is received as it is subjected to a calcination heat treatment. In this treatment, the AR glass was calcined for 4 hours in an air atmosphere having an air flow rate of 1 L/hr and a temperature of 600 °C. 126437.doc -70- 200902146 In the second step, the calcined AR glass is subjected to acid leaching treatment. Each of the gram calcined AR glass and 4 liters of 5.5 wt.% nitric acid were placed in a 4 liter plastic wide-mouth container. Place the plastic container in a 9 〇 ventilated oven for two hours and shake it slightly by hand every 30 minutes. After the acid leaching treatment was completed, the sample was filtered using a Buchner funnel with Whatman 541 filter paper and washed with about 7.5 liters of deionized water. Then, the acid-impregnated sample is dried for 22 hours at a temperature of 丨1 (at a temperature of 3. The third step is an ion exchange treatment of the acid-impregnated AR glass. In this example, dichlorotetramine is used. Platinum [Pt(NH3)4](cl)2 was prepared to prepare 3 liters of 0.01 wt.% platinum solution for ion exchange ("ΙΕχ solution"). Add about Μg of acid-impregnated AR glass to the ion exchange solution. ("glass/ion exchange mixture"). Measure the pH of the glass/ion exchange mixture. Add about 29.8 wt.% ammonium hydroxide (NH4〇h) dropwise as needed to adjust the pH of the mixture. To more than 10 (in this example, the ipH value is about 10.6). Move the glass/ion exchange mixture into a 4 liter plastic wide-mouth container. Place the plastic container in a 5 (rc ventilated oven for 2 hours, every 3 hours) 〇The bell is shaken slightly by hand. After heating for one hour, measure the pH again' and adjust the pH to more than 1 再次 using about 29 8 wt% of nH4〇h solution as needed. In two hours. After the heating process is completed, measure the glass/ion exchange mixture again. A value of 11 gives a pH of about 1 〇 19. After the ion exchange treatment is completed, the glass/ion exchange mixture is filtered using a Buchner funnel with a 541 filter paper and the ion exchange _ glass sample is collected and used about 7 · 6 liters of diluted NH4 〇 h solution. Dilute NH4 〇 H solution by using 1 〇 gram of μ 』 wt. 0 / (^ NH 4 〇 H solution and 126437.doc -71 - 200902146 about 3.8 liters of deionized water Prepared by mixing. Then, the ion exchange glass sample was dried for 22 hours at a temperature of 110 ° C. In the fourth step, the ion exchange glass was subjected to reduction treatment, wherein the ion exchange glass was under a hydrogen atmosphere at a hydrogen flow rate of 2 L/hr and Reduction at 300 ° C for 4 hours. Sample analysis by ICP-AES gave a platinum concentration of approximately 0.0032 wt. ° / 。. Example 9 The glass on the AR glass obtained the AR glass Cem- produced by Saint-Gobain Vetrotex FIL Anti-Crak TM HD sample, a glass fiber having an average diameter of about 17 to 20 microns. In the first step, the AR glass sample is subjected to a calcination heat treatment as it is. In this treatment, the AR glass has an air flow rate of 1 L/ Hr air atmosphere and 600 ° C Calcination at temperature for 4 hours. In the second step, the calcined AR glass is subjected to acid leaching treatment. About 30 g of calcined AR glass and 4 liters of 5.5 wt.% of nitric acid are each placed in a 4 liter plastic wide-mouth container. Place the plastic container in a ventilated oven at 90 ° C for two hours, shaking it slightly by hand every 30 minutes. After the acid leaching process, filter the sample using a Buchner funnel with Whatman 54 1 filter paper, and use about 7.5. Liter deionized water for cleaning. The acid leached sample was then dried for 22 hours at a temperature of 110 °C. In the third step, the acid-impregnated AR glass is subjected to ion exchange treatment. In this example, 3 liters of 126437.doc -72 - 200902146 0.01 wt.% platinum solution was prepared for ion exchange ("IEX solution") using tetrachlorotetramine platinum [Pt(NH3)4](Cl)2. Approximately 9.8 grams of acid leached AR glass was added to the ion exchange solution ("glass/ion exchange mixture π." The pH of the glass/ion exchange mixture was measured. As needed, about 40 wt.% was added dropwise continuously. Tetrapropylammonium hydroxide, the pH of the mixture was adjusted to greater than 10 (in this example, the pH obtained was about 11.38). The glass/ion exchange mixture was transferred to a 4 liter plastic wide mouth container. The plastic container was placed in a ventilated oven at 100 ° C for 22 hours and shaken slightly by hand every 30 minutes. After ion exchange treatment, use a Buchner funnel transition glass/ion exchange mixture with Whatman 5 41 filter, paper and collect. Ion exchange-glass samples were washed with approximately 7.6 liters of dilute NH4OH solution prepared by mixing 10 gram of 29.8 wt.0/. The ion-exchanged glass sample was dried for 22 hours at a temperature of 11 ° C. In the fourth step, the ion-exchanged glass sample was subjected to a reduction treatment, and the ion-exchanged glass was subjected to a hydrogen atmosphere at a hydrogen flow rate of 2 L/hr. Reduction at 300 ° C for 4 hours. Sample analysis by ICP-AES gave a platinum concentration of approximately 0.038 wt·%. Example 10 The glass on the AR glass was obtained from the Saint-Gobain Vetrotex AR glass Cem-FIL Anti -Crak TM HD sample, a glass fiber having an average diameter of about 17 to 20 microns. In the first step, the AR glass sample is subjected to a calcination heat treatment as it is. 126437.doc -73· 200902146 In this treatment, 'AR glass is in the air. The air atmosphere at a flow rate of 1 L/hr and calcination at a temperature of 600 ° C for 4 hours. The second step 'acid-dipped the calcined AR glass. About 30 g of calcined AR glass and 4 liters of 5.5 wt· The % nitric acid is placed in a 4 liter plastic wide-mouth container. Place the plastic container at 9 〇. (: 2 hours in a ventilated oven, shake it slightly by hand every 30 minutes. After the acid leaching treatment is completed) The Buchner funnel with Whatman 541 filter paper was used to filter the sample and rinse with about 7.5 liters of deionized water. Then, the acid immersed sample was dried for 22 hours at rc1 (the temperature of rc. The third step, the acid leaching Treated AR glass for ionization Exchange treatment. In this example, 3 liters of 0.01 wt.% platinum solution was prepared for ion exchange (&quot;ΙΕχsolution&quot;) using dioxetamine platinum [Pt(NH3)4](cl)2. 8 79 g of acid-impregnated AR glass is added to the ion exchange solution ("glass/ion exchange mixture"). Is the glass/ion exchange mixture measured? 11 values. About 29-8 wt% of ammonium hydroxide (ΝΗ4〇Η) was added dropwise as needed, and the pH of the mixture was adjusted to be greater than 1 Torr (in this example, a value of about 10.4 was obtained). The glass/ion exchange mixture was transferred to a 4 liter plastic wide-mouth container. Place the plastic container in a 10 (rc ventilated oven for 22 hours:

Thereafter, it was prepared by mixing about 3·8 liters of deionized water at a temperature of 110 °C. The ion exchange glass samples were dried for 22 hours. 126437.doc •74· 200902146 In the fourth step, the ion-exchanged glass sample was subjected to a reduction treatment in which the ion-exchanged glass was subjected to a hydrogen atmosphere at a hydrogen flow rate of 2 L/hr and a temperature of 300 ° C for 4 hours. Sample analysis by ICP-AES gave a platinum concentration of about 0.022 wt.%. Example 11 On the glass of AR Glass An AR glass Cem-FIL - Anti-Crak TM HD sample produced by Saint-Gobain Vetrotex was obtained, i.e., a glass fiber having an average diameter of about 17 to 20 μm. In the first step, the AR glass sample is received as it is subjected to a heat treatment. In this treatment, the AR glass was calcined for 4 hours in an air atmosphere having an air flow rate of 1 L/hr and a temperature of 600 °C. In the second step, the calcined AR glass is subjected to acid leaching treatment. Approximately 30 grams of calcined AR glass and 4 liters of 5.5 wt.% nitric acid were each placed in a 4 liter plastic wide mouth container. The plastic container was placed in a ventilated oven at 90 ° C for 2 hours, and the hand tip was shaken slightly every 30 minutes. After the acid leaching treatment was completed, a Buchner funnel transition sample with Whatman 541 crepe paper was used and washed with about 7.5 liters of deionized water. The acid leached sample was then dried for 22 hours at a temperature of 110 °C. In the third step, the acid-impregnated AR glass is subjected to ion exchange treatment. In this example, 1 liter of a 0.1 wt.% cobalt solution was prepared for ion exchange (&quot;IEX solution) using cobalt(II) nitrate hexahydrate Co(N03)2'6H20. In an Erlenmeyer flask Form N2 bubbles through 1 liter of deionized water 30 minutes 126437.doc -75- 200902146 clocks, prepare ion exchange solution, try to minimize the amount of air present, so as to avoid the change of oxidation state of cobalt after addition. Then hexahydrate hexahydrate Cobalt is added to deionized water purified by A. Measure the value of 1) 11 of the ion exchange solution. Add about 29.8 wt% ammonium hydroxide (NH4〇h) continuously as needed, and adjust the pH of the mixture to More than 1 〇 (in this example, the ipH value is about 10.2). Then, the ion exchange solution is transferred into an i liter plastic wide-mouth container. About 20 grams of acid-impregnated eight-foot glass is added to the ion exchange solution. (&quot;glass/ion exchange mixture"). The plastic container was placed in a ventilated oven at 5 ° C for 2 hours and shaken slightly by hand every 30 minutes. After the ion exchange treatment was completed, the glass/ion exchange mixture was filtered using a Buchner funnel with Whatman 541 filter paper. The mother liquor was collected and the port 11 value was measured (in this example, the pH was about 9.70). The filtered glass is then washed with about 6 liters of a dilute ΝΗβΗ solution. The dilute NH4〇H solution was prepared by mixing 1 gram of a concentrated 29.8 wt.% NH4〇H solution with about 3.8 liters of deionized water. The ion exchange glass samples were then dried for 16 hours at a temperature of liot. A sample analysis by ICP-AES&apos; yielded a concentration of about 0 64 wt.%. Example 12 The beginning of AR glass

Acquired AR glass by Saint-Gobain Vetrotex Cem-FIL

Anti-CrakTM HD samples, i.e., glass fibers having an average diameter of about 17 to 2 microns. In the first step, the AR glass sample is received as it is subjected to a calcination heat treatment. 126437.doc •76- 200902146 In this treatment, AR glass was calcined for 4 hours in an air atmosphere having an air flow rate of i L/hr and a temperature of 600 °C. In the second step, the calcined AR glass is subjected to acid leaching treatment. Approximately 3 ounces of calcined AR glass and 4 liters of 5.5 wt.% nitric acid were each placed in a 4 liter plastic wide-mouth container. Place the plastic container in a 9 (rc ventilated oven for 2 hours, shake it slightly by hand every 30 minutes. After the acid leaching process, filter the sample using a Buchner funnel with Whatman 541 filter paper and use about 7.5 liters. The ion-washed water is washed. Then, the acid-impregnated sample is dried for 22 hours at a temperature of 丨丨〇t. In the second step, the acid-impregnated AR glass is subjected to ion exchange treatment. In this example, six are used. Hydrated cobalt nitrate (II) c〇(N〇3)2.6H2〇 Preparation of 0.1 wt·% cobalt solution for ion exchange (&quot;ΙΕχsolution"). Formation of Ν2 bubbles in the Ehrlich flask Liter deionized water for 3 minutes, prepare ion exchange solution, try to minimize the amount of air present, so as to avoid the change of oxidation state of cobalt after addition. Then add cobalt nitrate hexahydrate to deionized water purified by hydrazine. {) 11 value of the ion exchange solution. Add about 29.8 wt.% ammonium hydroxide (ΝΗ4〇Η) dropwise as needed, and adjust the pH of the mixture to be greater than ι (in this example, The pH is about 1 〇.24). Then The ion exchange solution was transferred to a 1 liter plastic wide-mouth container. About 20 grams of the acid-impregnated ar glass was added to the ion exchange solution ("glass/ion exchange mixture"). Place the plastic container in a 5 〇〇c air supply box for 45 minutes, and shake it slightly by hand after 25 minutes. After completion of the ion exchange treatment, a Buchner funnel filter glass/ion exchange mixture with Whatman 54 1 filter paper was used. The mother liquor was collected and the pH was measured (in this example 126437.doc -77. 200902146, the pH was about 9.88). The filtered glass was then cleaned using about 6 liters of dilute NH4OH solution. The dilute NH4OH solution was prepared by mixing 10 grams of a 29.8 wt.% concentrated ΝΙ4 ί solution with about 3.8 liters of deionized water. The ion exchange glass samples were then dried at a temperature of 110 ° C for 17 hours. Sample analysis by ICP-AES yielded a cobalt concentration of about 0.15 wt.%. Example 13 Town on AR glass A sample of AR glass Cem-FIL Anti-CrakTM HD produced by Saint-Gobain Vetrotex, a glass fiber having an average diameter of about 17 to 20 microns, was obtained. In the first step, the AR glass sample is received as it is subjected to a calcination heat treatment. In this treatment, the AR glass was calcined for 4 hours in an air atmosphere having an air flow rate of 1 L/hr and a temperature of 600 °C. In the second step, the calcined AR glass is subjected to acid leaching treatment. Approximately 30 grams of calcined AR glass and 4 liters of 5.5 wt.% nitric acid were each placed in a 4 liter plastic wide mouth container. The plastic container was placed in a ventilated oven at 90 ° C for two hours and shaken slightly by hand every 30 minutes. After the acid leaching treatment was completed, the sample was filtered using a Buchner funnel with Whatman 54 1 filter paper and washed with about 7.5 liters of deionized water. The acid leached sample was then dried for 22 hours at a temperature of 110 °C. In the third step, the acid-impregnated AR glass is subjected to ion exchange treatment. In this example, 3 liters of 0.05 wt.% tungsten solution was prepared using ammonium metatungstate (NH4)6H2W12O40 · η Η 20 for ion exchange (&quot;IEX solution). Will be about 126437.doc •78- 200902146 2 gram Acid-leached AR broken glass plus human ion exchange solution (&quot;glass

= ion exchange mixture &quot;). The pH of the glass/ion exchange mixture was measured. About 29 8 wt% of hydrogen hydroxide (NH 4 〇 H) was added dropwise as needed, and the pH of the glass/ion exchange mixture was adjusted to 8. After the absence, the glass/ion exchange mixture was transferred to a 4 liter plastic wide-mouth container. Place the plastic container in a 5 () t ventilated box for 2 hours, and (4 minutes) shake it slightly with the hand tip. At the end of the two-hour heating process, use

The Whatman 541 crepe Buchner funnel was passed through the glass/ion exchange mixture and the ion exchange-glass sample was collected and washed with about 5 liters of deionized water and then the ion exchange glass samples were dried for 22 hours at uot temperature. In the fourth step, the ion-exchanged glass was subjected to calcination treatment, in which the ion-exchanged glass was calcined for 4 hours in an air atmosphere having an air flow rate of 2 L/hr and a temperature of 5 Torr. Sample analysis by ICP-AES is expected to yield a crane concentration of about 〇1. A glass matrix catalyst composition Example 14 A-06F glass on the A-06F glass fiber produced by Lauscha Fiber International with an average diameter of about 500-600 nm. First, the A-06F glass sample received as received and not calcined was subjected to acid leaching treatment. Approximately 21 grams of A-06F glass and 4 liters of 5.5 wt.% of the auxiliary acid were each placed in a 4 liter plastic wide mouth container. The plastic container was placed in a ventilated oven at 126437.doc -79.200902146 90 °C for 2 hours, shaking it slightly by hand every 30 minutes. After the acid leaching treatment was completed, the sample was filtered using a Brinell filter with Whatman 54 1 filter, paper, and washed with about 7.6 liters of deionized water. Then, the acid immersed sample was dried at a temperature of 110 ° C for 22 hours. In the second step, the ion exchanged A-06F glass is ion exchanged.

Reason. In the present example, 1 liter of 0.01 wt_°/ was prepared using tetrachlorotetramine platinum [Pt(NH3)4](cl)2. The platinum solution was used for ion exchange (ι, ΙΕχ solution). 2 〇g of A-06F glass was added to the ion exchange solution ("glass/ion exchange mixture"). The pH value of the glass/ion exchange mixture was measured. As needed, about 29.8 wt.% of ammonium hydroxide (ΝΗ4〇Η) was added dropwise, and the pH of the mixture was adjusted to be greater than 10 (in this example, the positive value was about 11.1). Transfer the glass/ion exchange mixture into a 2 liter plastic wide-mouth container. Place the barn at 1 inch. 23 hours in a ventilated oven. After shaking for a few hours of ion exchange for a period of 23 hours, the glass/ion exchange mixture was filtered using a Buchner funnel with Whatman 54 lj paper and the ion exchange glass samples were collected and the 7.6 liters of dilute NH4 was shut off. 〇H solution is cleaned. The dilute nh4〇h solution was prepared by mixing 1 gram of 29 Å % concentrated NH 4 〇 H solution with about 3.8 liters of deionized water. The ion exchange glass samples were then dried at 110 u degrees for 22 hours. The third step was to carry out a reduction treatment on the ion-exchanged glass sample in which the ion-parent exchanged sample was reduced for 4 hours at a hydrogen atmosphere having a hydrogen flow rate of 2 L/hr and a temperature of 3 sails. Sample analysis was performed by ICP-AES. A platinum concentration of approximately 0.96 wt.% was produced. 126437.doc 200902146 Example 15 A-06F glass was obtained from Lauscha Fiber International with an average diameter of about 500-600 nm A-06F glass fiber. First, the A-06F glass sample which was received as it was and which was not calcined was subjected to acid leaching treatment. Approximately 50 grams of A-06F glass and 4 liters of 5.5 wt.% of the acid were each placed in a 4 liter plastic wide mouth container. The plastic container was placed in a ventilated oven at 90 ° C for 2 hours, and shaken slightly by hand every 3 minutes. After the acid leaching treatment was completed, the sample was filtered using a Brinell flask with Whatman 541 paper and washed with about 7.6 liters of deionized water. The acid leached sample was then dried for 22 hours at a temperature of 11 0 C. The second step was an ion exchange treatment of the acid leached A-06F glass sample. In the present example, 3 ml of 0.001 wt. ° / was prepared using dihydrooxytetraamine palladium [Pd(NH3)4](〇H)2. The palladium solution was used for ion exchange (&quot;ΙΕχ solution,,). Approximately 10 grams of A-06F glass was added to the ion exchange solution (&quot;glass/ion exchange mixture&quot;). The pH of the glass/ion exchange mixture was measured. The pH of the mixture was adjusted to greater than 1 Torr (in this example, the pH was about 10.5), as needed, by continuously adding about 29.8 wt. ° / Torr of ammonium hydroxide (NH 4 OH) dropwise. The glass/ion exchange mixture was transferred to a 4 liter plastic wide-mouth container. Place the plastic container at 50. (:In a ventilated oven for two hours, shake it slightly by hand every 3 minutes. After the ion exchange treatment is completed, filter the glass/ion exchange mixture using a Buchner funnel with Whatman 54 1 filter paper and obtain a crepe cake' Approximately 3 liters of dilute NH4〇H solution was remixed and then filtered again. Repeat the two steps of remixing/filtering. Dilute NH4〇h dissolve 126437.doc -81 - 200902146 Liquid system by 10 g of 29_8 wt·% concentrated NH4 The 〇H solution was prepared by mixing with about 38 liters of deionized water. Then, the ion exchange glass sample was dried at 11 〇ts for 22 hours. In the second step, the ion exchange glass sample was subjected to reduction treatment in which the ion exchange-glass sample was Reduction was carried out for 4 hours in a hydrogen atmosphere (HO flow rate of 2 L/hr hydrogen atmosphere and 3 Torr). Sample analysis by ICP-AES gave a palladium concentration of about 62 wt%. Example 16 A- The 06F glass was obtained from A-06F glass fiber produced by Lauscha Fiber International with an average diameter of about 500-600 nm. First of all, the acid immersion was performed on the A- 〇6 F glass sample received as received and not calcined. At Place approximately 51 grams of A-06F glass and 4 liters of 5.5 wt.% nitric acid in a 4 liter plastic wide-mouth container. Place the plastic container in a 90 ° C ventilated oven for 2 hours, every 30 minutes. Shake it slightly. After the acid leaching process is completed, use a Buchner funnel with Whatman 541 crepe paper to filter, sample, and rinse with about 7 -6 liters of deionized water. Then, at a temperature of 1 l ° ° C, The acid leached sample was dried for 22 hours. In the second step, the acid leached A-06F glass was subjected to Na+-reverse ion exchange (&quot;Na-ΒΙΧ&quot;) treatment. The acid leaching from the first step Mix the sample with 4 liters of 3 mol/L sodium chloride (NaCl) solution (&quot;glass/sodium chloride mixture&quot;). Measure the pH of the glass/NaCH mixture. Add about 40 wt% as needed. • % tetrapropylammonium hydroxide, adjusting the pH of the glass/NaCl mixture 126437.doc • 82- 200902146 to greater than 10 (in this example, the pH obtained is approximately 10.9). Glass/sodium chloride The mixture was transferred to a 4 liter plastic wide-mouth container. The plastic container was then placed at 50 ° C for air drying. Shake it by hand for 4 hours every 4 hours. After Na-BIX treatment, filter with a Buchner funnel with Whatman 541 crepe paper, glass/chloride mixture and collect Na-BIX/A-06F samples. And use about 7.6 liters of deionized water for cleaning. Then, the Na-BIX/A-06F glass sample was dried at a temperature of 11 ° C for 22 hours. In the third step, a second ion exchange (&quot;IEX-2&quot;) treatment was performed on the Na-BIX/A-06F glass sample. In the present example, 1 liter of a 0.01 wt.% palladium solution was prepared for ion exchange (πΙΕΧ-2 solution '') using dioxetamine palladium [Pd(NH3)4](Cl)2. 35 grams of A-0 6F glass was added to the IEX-2 solution ("glass/IEX-2 mixture"). The pH of the glass/IEX-2 mixture was measured to give a pH of about 8.5. The glass AEX-2 mixture was transferred to a 2 liter plastic wide mouth container. The plastic container was placed in a ventilated oven at 50 ° C for 4 hours and shaken slightly by hand every 30 minutes. After the ion exchange treatment was completed, the glass/IEX-2 mixture was filtered using a Buchner funnel with Whatman 541 filter paper and the IEX-2 glass sample was collected and washed with a solution of about 7.6 liters of dilute ammonium hydroxide. The dilute NH4OH solution was prepared by mixing 10 grams of a 29.8 wt. ° / 〇 concentrated NH 4 OH solution with about 3.8 liters of deionized water. Then, the ion-x2 sample was dried at a temperature of 110 ° C for 22 hours. In the fourth step, the IEX-2 glass sample was subjected to reduction treatment, in which the sample was reduced in a helium atmosphere at a hydrogen flow rate of 2 L/hr and at a temperature of 300 ° C for 4 hours. 126437.doc -83 - 200902146 Sample analysis by ICP-AES yielded a palladium concentration of approximately 〇 9 wt %. Sample analysis was carried out by XPS sputtering depth distribution method (described below), as shown in Fig. 2, and the results showed that the thickness of the region where a large amount of palladium was detected by the method was about 15 nm. Example 17 Fun on A-06F Glass A-06F glass fiber produced by Lauscha Fiber International with an average diameter of about 500-600 nm was obtained. In the first step, the A-06F glass fiber was subjected to ion exchange treatment. In this example, 2 liters of 〇〇〇1 wt% palladium solution was prepared for ion exchange using dihydrooxytetraamine palladium [Pd(NH3)4](〇H)2 (&quot;ΙΕχsolution&quot; 54 g of Α·06F glass was added to the ion exchange solution ("glass/ion exchange mixture"). Measure the pH value of the glass/ion exchange mixture. Add about 29.8 wt.% ammonium hydroxide continuously as needed (ΝΗ4 〇Η), the ipH value of the mixture was adjusted to be greater than 1 〇 (in this example, a 2ρ Η value of about 1 〇 1 was obtained.) The glass/ion exchange mixture was transferred into a 4 liter glass vessel and placed on a hot plate. The vessel was mechanically stirred in an oven at 59 ° C for 2 hours. After ion exchange treatment, the glass/ion exchange mixture was filtered using a Buchner funnel with Whatman 541 filter paper, and a filter cake was obtained, which was approximately 3 liters. Dilute 4 Η 'The solution is re-mixed and then smashed again. Repeat the two steps of re-mixing/filtering. The diluted NH4 〇H solution is made by adding 10 grams of 29 8 wt% concentrated NH4 〇H solution to about 38 liters. Prepared by mixing ionic water. Then, at 100 C, ion exchange The glass sample was dried for 22 hours. 126437.doc -84 - 200902146 The second step was to reduce the ion exchange glass sample, where the ion parent-glass sample was at a helium atmosphere with a hydrogen flow rate of 2 L/hr and 3 Torr. The temperature was reduced for 4 hours at a temperature of 〇. Sample analysis by ICP-AES gave a palladium concentration of about wt35 wt%. The sample was analyzed by XPS sputtering depth distribution method (described below), as shown in Fig. 2. The results show that the thickness of the region where a large amount of palladium is detected by the method is about 15 nm. Example 18 The A-06F glass is produced by Lauscha Fiber International, and the average diameter is about 500-600 nm. A-06F glass fiber. In the first step, the A-06F glass sample received as received and not calcined is subjected to acid leaching treatment. About 50 grams of A_〇6F glass and 4 liters of 55 correction.% = nitric acid Place in a 4 liter plastic wide-mouth container. Place the plastic container in a 9 (TC ventilated oven for 2 hours, shake it slightly by hand every 3 minutes. After acid leaching, use - (4) filter paper The Buchner funnel filters the sample and uses 7.6 liters of deionized water was washed. Then, the acid leached sample was dried for 22 hours at iio ° C. In the second step, the acid leached glass sample was subjected to ion exchange treatment. Prepare 3 liters of a 0.001 wt.% palladium solution for ion exchange (, hydrazine solution) using palladium dihydrooxytetramine. Add 10 gram of A-06F glass to the ion exchange solution ("glass/ion exchange Mixture &quot;). Measuring glass/ion exchange mixture? 11 values. According to the need, this 126437.doc •85· 200902146 continuously added about 29.8 wi.% ammonium hydroxide (nh4〇h), and adjusted the pH of the mixture to more than 1 〇 (in this example, it is obtained? The value is approximately 10.5). The glass/ion exchange mixture was transferred to a 4 liter plastic wide mouthpiece. Place the plastic container in a ventilated oven for two hours, shaking each hand slightly with a hand. After the ion exchange treatment was completed, the glass/ion exchange mixture was filtered using a Buchner funnel with Whatman 541 crepe paper and a filter cake was obtained, which was remixed with about 3 liters of dilute NH4 〇H solution and then filtered again. Repeat the steps of re-mixing/over-twisting. The dilute nh4〇h solution was prepared by mixing 10 g of a 29.8 wt.% concentrated NH4〇h solution with about 38 liters of deionized water. The ion exchange glass samples were then dried for 22 hours at a temperature of i 1 〇〇c. In the third step, the ion exchange glass sample is subjected to reduction treatment, and the ten ion exchange glass is first calcined in an air atmosphere at an air flow rate of 2 L/hr and a temperature of 3 Torr for 2 hours' and then at a hydrogen flow rate of 2 L. /hr of hydrogen old 2) atmosphere and reduction at 300 ° C for 4 hours. Sample analysis by ICP-AES gave a concentration of about 59 wt%. Sample analysis was carried out by XPS sputtering depth profile (described below), as shown in Figure 2, which showed that the thickness of the region present by the method was approximately 15 nm. Example 19 A-06F glass-on-glass A-06F glass fiber produced by Lauscha Fiber International with an average weight of about 500-600 nm was obtained. 126437.doc • 86 - 200902146 The first step is to carry out acid leaching on the A-06F glass sample 0 that has been received as received and not burnt. Approximately 8.43 grams of A-06F glass and liters of 5 5 wt. ° / 〇 of nitric acid were placed in a 2 liter glass beaker and mechanically dropped at 22 ° C using a stainless steel mixer at 300 to 500 rpm. 3 minutes. After the acid leaching treatment was completed, the sample was filtered using a Buchner funnel with Whatman 541 crepe paper and washed with about 7.6 liters of deionized water. The acid leached sample was then dried at a temperature of 110 ° C for 22 hours. In the second step, the acid-impregnated A_〇6F glass sample was subjected to ion exchange treatment. In the present example, 500 ml of a 0.01 wt% palladium solution was prepared using ion dihydrooxytetraamine palladium [Pd(NH3)4](〇H)2 for ion exchange (&quot;ΙΕχsolution&quot;). 4_2 grams of A-06F glass was added to the ion exchange solution ("glass/ion exchange mixture"). The value of the glass/ion exchange mixture is measured only. About 29.8 wt.% of ammonium hydroxide (Νη4〇η) was added dropwise as needed, and the pH of the mixture was adjusted to be greater than 10 (in the present example, the obtained pΗ value was about 10.2). The glass/ion exchange mixture was transferred to a liter liter beaker at 50. . Stir at temperature for 2 hours. After the ion exchange treatment was completed, the glass/ion exchange mixture was filtered using a Buchner funnel with Whatman 541 filter paper and washed with about 7.6 liters of deionized water. Then, the ion exchange glass sample is dried for 22 hours at u (rc temperature. The third step is to reduce the ion exchange glass sample, wherein the ion exchange glass is first placed in an air atmosphere having an air flow rate of 2 L/hr and The calcination was carried out for 2 hours at a temperature of 2 hours, and then reduced at a hydrogen flow rate of 2 ['hydrogen (4) atmosphere and at a temperature of 300 ° C for 4 hours. Sample analysis by ICP-AES gave a concentration of about 12657 .doc &lt;87- 200902146 degrees. Example 20 A-06F glass was obtained from Lauscha Fiber International to produce 500-600 nm A-06F glass fibers.

First, the A-06F glass sample received as received and not calcined was subjected to acid leaching treatment. Approximately 30 grams of A-06F glass and 4 liters of 5.5 wt% of nitric acid were each placed in a 4 liter plastic wide mouth container. The plastic container was placed in a ventilated oven at 90 ° C for 2 hours, and shaken slightly by hand every 30 minutes. After the acid leaching treatment was completed, the sample was filtered using a Brinell flask with Whatman 541 filter paper and washed with about 7.6 liters of deionized water. Then, the acid immersed sample was dried at a temperature of 110 C for 22 hours. Step 2 'Ion exchange treatment of acid-leached A-06F glass. In this example, 3 liters of 0.01 wt.% platinum solution was prepared using one gas tetraamine [Pt(NH3)4](Cl)2. For ion exchange (&quot;ΙΕχsolution&quot;). Will be 151

The acid-impregnated A-06F glass is added to the ion exchange solution (&quot;glass/ion exchange mixture"). Measure the pH value of the glass/ion exchange mixture. Add about 29,8 wt.% continuously as needed. Ammonium hydroxide (ΝΗ4〇Η), the pH of the mixture is adjusted to be greater than 1 〇 (in this example, the positive value is about 10.07). The glass/ion is exchanged, and the dicing is changed again. Transfer the material into a 4 liter plastic wide-mouth container. Place the plastic container in a 5 (rr + 1 , 3 ° C ventilated oven for two hours. Shake the container slightly by hand every 30 minutes with Brinell with Whatman 541 filter paper. After leaking the compound and collecting the ion exchange-glass σ ion exchange treatment, the filter glass/ion exchange is mixed and cleaned with a solution of about 7.6 liters of 126437.doc •88· 200902146 NH4〇H. Dilute NH4〇H The solution was prepared by mixing 1 gram of a 298 wt.% concentrated NH4 〇H solution with about 3.8 liters of deionized water. Then, the ion exchange glass sample was dried at 110 ° C for 22 hours. , the ion parent glass sample is subjected to reduction treatment, wherein the sample is sampled The product was reduced in a hydrogen atmosphere at a hydrogen flow rate of 2 L/hr and at a temperature of 30 (rc) for 4 hours. Sample analysis by ICP-AES gave a platinum concentration of about 3333 wt%.

Example 21 A-06F Glass Breaking A06F glass fiber produced by Lauscha Fiber International with an average diameter of about 500-600 nm was obtained. In the first step, the A-06F$ glass sample that was received as received and not calcined was subjected to acid leaching. Approximately 3 ounces of A-06F glass and 4 liters of 5.5 wt.% of the tribasic acid were each placed in a 4 liter plastic wide-mouth container. The plastic container was placed in a 90 C ventilated oven for 2 hours and shaken slightly by hand every 30 minutes. After the acid leaching treatment was completed, the sample was filtered using a Buchner funnel with whatman 541 filter paper and washed with about 7.6 liters of deionized water. The acid leached sample was then dried at a temperature of 110 ° C for 22 hours. In the first step, the acid-impregnated A-06F glass was subjected to ion exchange treatment. In this example, '3 liters of 0.01 wt.% platinum solution was prepared for ion exchange (ι, ΙΕΧ solution) using tetrachlorotetramine platinum [Pt(NH3)4](Cl) 2 . 93 g of acid leached The A-06F glass is added to the ion exchange solution ("glass/ion exchange mixture"). The pH value of the glass/ion exchange mixture was measured. According to the need 126437.doc -89· 200902146 to 'continuously add about 40 wt.% of tetramethyl oxynitride to adjust the pH of the mixture to more than 10 (in this example, the pH obtained) For 11.07). The glass/ion exchange mixture was transferred to a 4 liter plastic wide-mouth container. The plastic container was placed in a ventilated oven at 100 ° C for 22 hours. Shake the container slightly by hand every 30 minutes. After the ion exchange treatment was completed, the glass/ion exchange mixture was filtered using a Buchner funnel with Whatman 541 filter paper and the ion exchange-glass sample was collected and washed with a solution of about 7.6 liters of dilute NH4OH. The dilute NH4OH solution was prepared by mixing 10 grams of a 29.8 wt% Η4ΟΗ solution with about 3.8 liters of deionized water. The ion exchange glass samples were then dried for 22 hours at a temperature of 11 °C. In the third step, the ion-exchanged glass sample was subjected to a reduction treatment in which the sample was reduced in a hydrogen atmosphere at a hydrogen flow rate of 2 L/hr and at a temperature of 300 ° C for 4 hours. Sample analysis by ICP-AES gave a platinum concentration of about 0.59 wt.%. Example 22 A-06F glass on the A-06F glass fiber produced by Lauscha Fiber International with an average diameter of about 500-600 nm. In the first step, the A-06F glass sample received as it is and not calcined is subjected to acid leaching. Place 30 g of A-06F glass and 4 liters of 5.5 wt.% nitric acid in 4 liter plastic wide-mouth containers. The plastic container was placed in a ventilated oven at 90 °C for 2 hours and shaken slightly by hand every 30 minutes. After the acid leaching treatment was completed, the sample was filtered using a cloth with Whatman 54 1 filter paper 126437.doc -90-200902146 funnel and washed with about 7.6 liters of deionized water. The acid leached sample was then dried for 22 hours at a temperature of not. In the second step, the acid-impregnated A_06F glass was subjected to ion exchange treatment. In the present example, '10% wt.% platinum solution was used for ion exchange (&quot;ΙΕχsolution&quot;) using 'diox tetraamine pt(10)山)(a). The galvanic acid-impregnated glass is added with a human ion exchange solution towel ("glass/ion exchange mixture"). The cation value of the glass/ion exchange mixture is measured. As needed, continuous addition and subsequent addition of about 29.8 wt.% Ammonium hydroxide (ΝΗ40Η), the enthalpy of the cough mixture is adjusted to greater than 1G (in this example, the positive value is about 138). The glass/ion exchange mixture is transferred to a liter plastic wide-mouth container. The plastic container was placed in a 10 inch ventilated chess box for 22 hours. The micro-shake-down container was weighed by hand every 3 minutes. Ion (four) treatment mu was used and collected by a Buchner funnel with Whatman 5411 paper (four) glass/ion exchange mixture. Ion exchange-glass sample, and washed with about 7.6 liters of dilute NH4〇H solution. The solution was diluted with W gram 8 and mixed with about 3·8 liters of deionized water. The ion-exchanged glass sample was dried (four) hours at _ temperature...., the second step 'restores the ion-exchanged glass sample, where the sample is at a gas flow rate of 2 L/hr. Hole rolling and 30 (reduction of temperature at rc 4 Sample analysis by ICP-AES. Approximately 0.71 wt% of platinum concentration Example 23 A-06F palladium on copper and copper 126437.doc 200902146 Obtained by Lauscha Fiber International, the average diameter is approximately 500-600 nm A-06F glass fiber. First, the A-06F glass sample received as received and not calcined is subjected to acid leaching treatment. 15 g of A-06F glass and 4 liters of 5.5 wt·% tannic acid Place them in a 4 liter plastic wide-mouth container. Place the plastic container in a 9 ° C ventilated oven for 2 hours and shake it slightly by hand every 30 minutes. After acid treatment, use with Whatman 54 U Filter the sample with a Buchner funnel and clean it with about 7.6 liters of deionized water. Then, dry the acid leached sample for 22 hours at a temperature of 11 ° C. The second step is to acid leaching. A-06F glass was subjected to dual ion exchange treatment. In this example, 3 liters of 0.0005 wt% total metal solution was used for double ion exchange ("double ion exchange solution"). The double ion exchange solution was mixed by 1.5 liters of 0.0005 wt. .% palladium solution and Prepared by 1.5 liters of 0.0005 wt.% copper solution. In this example, 1.5 liters of 0.0005 wt.% palladium solution was prepared using palladium dihydrooxytetraamine, and 15 liters of 0.0005 wt.% copper solution was prepared using copper nitrate. The gram A-06F glass is added to the double ion parent exchange solution ("glass/ion exchange mixture"). The pH of the glass/ion exchange mixture is measured. As needed, about 29 8 wt% of hydrazine oxide (NH 4 〇 H) was continuously added dropwise, and the pH of the mixture was adjusted to be greater than ι (in the present example, the pH was about 1 〇 9). . The glass/ion exchange mixture was transferred to a 4 liter plastic wide mouth container. Place the plastic container in the ventilated box of (9) for two hours. Shake it slightly by hand every 30 minutes. After the double ion exchange treatment was completed, the glass/IEX mixture was filtered using a Buchner funnel with Whatman 54 1 filter paper and collected with a solution of about 7.6 liters of dilute ammonium hydroxide 126437.doc -92.200902146 (NH4〇H). Double ion exchange - glass sample. dilute

The dual ion exchange-glass samples were dried for 2 hours.

It was reduced at a temperature of 300 C for 4 hours. The wt.% sample was analyzed by ICP-AES to obtain a copper concentration of about 〇19 and about 0.02 wt.%. Example 24 Silver on A-06F Glass A-06F glass fiber produced by Lauscha Fiber International having an average diameter of about 500-600 nm was obtained. In the first step, the _061? glass sample received as received and uncalcined is subjected to acid leaching. Approximately 51 grams of A_06F glass and 4 liters of 55 wt% nitric acid were each placed in a 4 liter plastic wide mouth container. The plastic container was placed in a 90C ventilated oven for 2 hours and shaken slightly by hand every 30 minutes. After the acid leaching treatment was completed, the sample was filtered using a Buchner funnel with Whatman 541 filter paper and washed with about 7.6 liters of deionized water. The acid immersed sample was then dried for 22 hours at a temperature of 110 °C. In the second step, the acid-impregnated A-06F glass is subjected to ion exchange treatment. In this example, 4 liters of 〇·001 wt.% silver solution was prepared using silver nitrate for ion exchange (&quot;IEX solution&quot;). One gram of A-06F glass was added to the ion exchange solution ("glass/ion exchange mixture"). Measuring glass/ion exchange 126437.doc •93· 200902146 pH of the mixture. As needed, about 29.8 wt.% of ammonium hydroxide (ΝΗβΗ) was continuously added dropwise to adjust the pH of the mixture to be greater than u (in the present example, the pH obtained was about 11.5). The glass/ion exchange mixture was transferred to a 4 liter plastic wide mouth container. Place the plastic container in a 5 (rc ventilated oven for 2 hours and shake it slightly by hand every 30 minutes. After the ion father has been replaced) use a Buchner funnel transition glass/ion exchange with Whatman 54 1 遽 paper The mixture was collected and the ion exchange-glass sample was collected and washed with approximately 7.6 liters of dilute NhOH solution. The diluted Nh4 〇h solution was prepared by mixing 10 gram of 29.8 wt.% concentrated ΝΗβΗ solution with approximately 3·8 liters of deionized water. The ion exchange glass sample was then dried for 22 hours at a temperature of 110 ° C. In the third step, the ion exchange glass sample was subjected to a reduction treatment in which the ion parent-glass sample was at a hydrogen flow rate of 2 L/hr. The hydrogen atmosphere was reduced for 3 hours at a temperature of 〇〇. The sample was analyzed by ICP-AES to obtain a silver concentration of about 53 wt.%. Example 25 A-06F glass was given by Lauscha. Produced by Fiber International, A-06F glass fiber with an average diameter of about 500-600 nm. The first step is for acid leaching of a_〇6F glass sample received as received and uncalcined. It will be about 1 gram. A_〇6F glass 4 liters of 5 5 nitric acid were placed in a 4 liter plastic wide-mouth container. Place the plastic container in a 90 ° ventilated oven for 2 hours and shake it slightly by hand every 30 minutes under 126437.doc -94- 200902146. After the acid leaching treatment was completed, the sample was filtered using a Buchner funnel with Whatman 54 1 crepe paper and washed with about 7.6 liters of deionized water. The acid leached sample was then dried at a temperature of 110 C for 22 hours. The second step is to carry out ion exchange treatment on the acid leached A-06F glass. In this example, tetrachlorotetramine platinum [Pt(NH3)4] is used (c 丨 to prepare 3 liters of 0.016 wt.% platinum solution). For ion exchange (ι, ΙΕχ solution,,). Will be 48 17

Add grams of A-06F glass to the ion exchange solution (&quot;glass/ion exchange mixture"). Measure the pH value of the glass/ion exchange mixture. Add about 29.8 wt.% ammonium hydroxide continuously as needed (ΝΗ4〇 Η), adjust the pH of the mixture to greater than 10 (in this example, the positive value is about 10.06). Move the glass/ion exchange mixture into a 4 liter plastic wide-mouth container. Place the plastic container at 5. (The TC is ventilated for two hours in the box. Shake it slightly by hand every 3 minutes - the lower container. After the ion exchange treatment is completed, the Buchner funnel glass/ion exchange mixture with Whatman 54U paper is used and the ion exchange is collected. - Glass sample, and washed with about 76 liters of dilute NH4 〇H solution. The diluted NH4 〇h solution was prepared by mixing 298 〇 〇 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 After the 'ion exchange temperature, the ion exchange glass sample was dried for 22 hours. Step, the ion exchange glass sample was subjected to reduction treatment, wherein the sample was reduced in hydrogen atmosphere at a hydrogen flow rate of 2 L/hr and at a temperature of 4 hours. Samples were analyzed by ICP-AES at a rate of approximately 0.147 wt.%. Example 26 126437.doc •95· 200902146 The surface of the A-06F glass was obtained by Lauscha Fiber International with an average diameter of approximately 500- 600 nm A_06F glass fiber. The first step is to carry out acid leaching treatment on the A-06F glass sample which is received as received and not calcined. About 21 g of A-06F glass and 4 liters of 5.5 wt.% nitric acid are placed. Place in a 4 liter plastic wide-mouth container. Place the plastic container in a ventilated oven at 90 °C for 2 hours, shake it slightly by hand every 30 minutes. After acid leaching, use Brinell with Whatman 541 filter paper. The sample was filtered through a funnel and washed with about 7.6 liters of deionized water. The acid leached sample was then dried for 22 hours at a temperature of 110 ° C. The second step was to acid leaching the A-06F glass. Ion exchange treatment was carried out. In this example, 4 liters of a 0.02 wt.% platinum solution was prepared for ion exchange ("ΙΕχ solution") using tetrachlorotetramine platinum [Pt(NH3)4](cl)2. 21 g of acid-impregnated A-06F glass is added to the ion exchange solution (& Quot [glass/ion exchange mixture"). Measure the value of the glass/ion exchange mixture by 11. If necessary, add about 29.8 wt.% ammonium hydroxide (ΝΗ4〇η) continuously, and mix the mixture. The pH was adjusted to greater than 1 Torr (in this example, the ?11 value was approximately 10.90). The glass/ion exchange mixture was transferred to a 4 liter plastic wide-mouth container. Place the plastic container in a ventilated box for 1 hour for 22 hours, shaking it with your hands every 30 minutes. After the ion exchange treatment was completed, a Brinell glass/ion exchange mixture with a phase of 11 541 m was used and an ion exchange-glass sample was collected and washed with a solution of about 7.6 liters of dilute Η4Ηη. The dilute NH4〇h solution was prepared by mixing 1 gram of 298% concentrated NH4OH solution with about 3.8 liters of deionized water. After 126437.doc -96- 200902146, the ion exchange glass samples were dried for 22 hours at a temperature of 1 l ° °C. In the third step, the ion-exchanged glass sample was subjected to reduction treatment, and the sample was reduced in a hydrogen atmosphere at a hydrogen flow rate of 2 L/hr and at a temperature of 300 ° C for 4 hours. Sample analysis by ICP-AES gave a platinum concentration of about 0.67 wt.%. Example 27: Unbleached E-06F glass The E-06F glass fiber produced by Lauscha Fiber International having an average diameter of about 500-600 nm was obtained. In the first step, the unleached E-06F glass sample was subjected to ion exchange treatment. In the present example, 2 liters of a 0.00008 wt.% palladium solution was prepared for ion exchange (&quot;IEX solution π) using dihydrooxytetraamine palladium [Pd(NH3)4](OH)2. 15.45 grams of E-06F glass was added to the ion exchange solution ("glass/ion exchange mixture"). The pH of the glass/ion exchange mixture was measured. As needed, about 29.8 wt.% ammonium hydroxide was added dropwise continuously. (NH4OH), the pH of the mixture was adjusted to greater than 10 (in this example, the pH was obtained to be about 10.99). The glass/ion exchange mixture was transferred into a 4 liter plastic wide-mouth container. The container was shaken in a ventilated oven at 50 ° C for two hours. The container was shaken slightly by hand every 30 minutes. After the ion exchange treatment was completed, the glass/ion exchange mixture was filtered using a Buchner funnel with Whatman 54 1 filter paper and the ion exchange-glass was collected. The sample was washed with a solution of about 7.6 liters of dilute NH4OH. The dilute NH4OH solution was prepared by mixing 10 grams of a 29.8 wt.% concentrated ΟΗ4 ΟΗ solution with about 3.8 liters of deionized water. Then, at a temperature of ll 〇 ° C The ion exchange glass sample was dried for 22 hours. 126437.doc -97- 200902146 The first step was to reduce the ion exchange glass sample, wherein the ion exchange glass was at a hydrogen flow rate. 2 L/hr hydrogen atmosphere and 300 ° C temperature for 4 hours. Sample analysis by ICP-AES gave a palladium concentration of about 0.014 wt%. Example 28 composite catalyst 1 leached on A-06F glass According to Example 26, a 1 3 _4 gram precursor catalyst composition was obtained which contained leached A-06F glass fibers having a platinum concentration of about 〇67 wt% and an average diameter of 500 to 600 nm. 1.6 g of MTW structure was obtained. Type, zeolite with a cerium/aluminum atomic ratio of about 18.5 to 1. Obtain 17.9 grams of alumina precursor containing non-peptized Versal_251 pseudo-soft boehmite and split it (4〇/6〇) to form separately 7 2 g and 10.7 g each. In a Lancaster grinder, 7.2 g of a non-peptized pseudo-boehmite ("non-peptized V-25 1") and precursor catalyst composition, 丨 3 4 A-06F glass fiber with a rolling capacity of about 0.67 wt.%, and a type of Buddha stone (as described above) for dry mixing for about 1 minute. A 10.7 gram portion of fake soft boehmite at about i grams 7〇% HN... and about 10 ml of water peptized. After the peptization is substantially completed, it will be substantially peptized. Fake soft boehmite (&quot;Plastant V-25 1&quot;) was added to the previously ground mixture of the precursor catalyst composition and MTW zeolite in a Lancaster mill and ground to give a doughy shape 126437.doc •98· 200902146 Viscosity The resulting dough is placed in a RAM extruder with a 1.6 mm (1/16 inch) template, to produce an extrudate (millimeter (10) inches) to about 9.5 mm (10) inches. Dust particles in the range: The extrudate particles were dried on a wire mesh tray in a ventilated oven at an air flow rate of about 8 5 m3/hr (3 ft, (10) °C for about 2 hours. At the same air flow rate, the extrudate particles were calcined by first raising the oven temperature to 3 G () t for an hour. After the first temperature rise, the temperature was raised to 50 passages for the second time in two hours, and then maintained at 5 GG ° C for another three hours, and the pseudo soft water was converted to gamma oxide. A calcined composite catalyst composition having a MTW-type zeolite and a precursor FSC composition dispersed in the composite catalyst composition is produced, and the activity test results such as the following conversion of methylcyclohexane (MCH) to toluene show that the FSC combination The platinum component is substantially dispersed in the pretreated eight glass or on the glass. Further, as described in Example CH-1 (below), the extrudate samples were examined by scanning transmission electron microscopy (STEM), and Figures 3 and 4 show that platinum particles (higher contrast points) are generally dispersed. Within a range of less than or equal to about 30 nanometers from the surface of the precursor catalyst composition, the composition has a substantially non-porous matrix (in this case, a leached A glass fiber). Example CH-1 analytical method re/XPS sputtering, SARCNa, isoelectric point (IEP) and SAN2-BET or SAKr-BET determination X-ray photoelectron spectroscopy (XPS) sputtering depth distribution method 126437.doc -99- 200902146 The xps sputter depth profile was obtained using a PHI Quantum 200 Scanning ESCA MicroprobeTM (Physical Electronics) with a 1486.7 eV microfocus monochromatization Α1 Κα X-ray source. In this instrument, the dual neutralization capability of charge compensation using low energy electrons and cations during spectral acquisition is standard. The XPS spectrum is usually measured under the following conditions:

• X-ray beam diameter 1〇_2〇〇 μιη - X-ray beam power 2-40 W - Sample analysis area 10-200 - The electron emission angle is 45 compared to the sample normal. All XPS spectra and sputter depth profiles were recorded at room temperature without pretreatment of the sample, with the exception of the introduction of the sample into the xps instrument vacuum environment. The in-depth depth profile is generated by alternately collecting the sample surface spectra for several cycles and then performing a 15 to 3 (seconds) 2 kv Ar+ ride on the surface of the sample at each cycle to remove the surface material. The sputter depth rate is calibrated using a __ layer of known thickness. By taking the peak areas of Pd 3 (^2 and Si 2p and correcting their respective atomic sensitivity factors and the force analyzer wheel function, the values of the ^ and Si atoms shown in Fig. 2 and 2 are obtained. Familiar with XPS analysis technique It should be understood that (4) the determination of the depth parameter is affected by both human error and mechanical error, and the combination of the two may cause an uncertainty of about 25% for each reported value of the depth measured by the XPS sputter depth distribution technique. Therefore, this uncertainty is shown in the depth value of 126437.doc •100-200902146 shown in Figure (1). This inaccuracy is common in the entire XPS analysis technique 'however' for the catalytic activity disclosed herein. Such inaccuracies in the region's average thickness and other material properties are not sufficient to interfere with the differentiation of the catalyst compositions described herein, nor do they affect the compositions and other compositions not described and claimed herein. Transmission electron microscopy (TEM) analysis Transmission electron microscopy (TEM) sample detection using a JEOL 3000F field emission scanning transmission electron microscope (STEM) instrument operating at 300 kV accelerating voltage The instrument is equipped with Oxford Instniments' lnca X-ray spectrometer system, which performs local chemical analysis using an energy dispersive spectrometer. Sample preparation First, the sample material is embedded in a standard epoxy embedding agent known to those skilled in TEM analysis. After curing, the epoxy-embedded sample material is cut using an ultra-thin slicer to produce a slice of about 80 nm thick. The slice is collected on a film-porous carbon support without further processing, suitably positioned above. The electron beam field of the STEM instrument is used for detection and analysis. Those familiar with TEM analysis should understand that the TEM* analysis method is used to determine the position of the object and the average thickness of the relevant area relative to the surface of the substrate. The effect is also affected by mechanical errors, depending on the image resolution of the sample, the physicochemical properties of the target analyte, and the morphology of the sample, which may result in a tem vertical depth measurement of about ±20% (relative to a certain The specific reference point) the uncertainty and the lateral measurement of 5% of the soil (relative to a specific reference point) uncertainty. Therefore, the uncertainty is measured by the distance of the measured catalytic component relative to the surface of the sample substrate. This 126437.doc 200902146 is very common throughout the TEM analysis, but not enough to hinder the catalyst combination. Distinction between objects. SARCh determination, SARCi empty sample and related statistical analysis. The surface area change rate of sodium ("sarc heart") is reported as the ratio of NaOH titrant volume due to the above reasons. According to the above SARC& SARSARC^ for each sample specified in the following example. Prepare a blank sample by preparing a 3.5 Μ Naa solution (ie, adding 30 gram of NaCl in 15 liters of deionized water), however, without matrix To resolve the statistical variability in the SARCw experimental procedure, four separate empty samples should be titrated and used to obtain the initial and V5q5 (ie, the specified concentration for V^v illusion (〇〇1 本 in this example) The titration average is used to adjust (ie, correct) the volume of the titrant used to determine the core sample from the heart. According to the same procedure as the above SAR (W), the pH value of the empty sample is adjusted and the empty sample is titrated, but the matrix is also not included. In the length of the ^: the execution of each empty sample and their respective average values and targets (or V Zhen analysis) The statistical scores of the empty sample titers in the test results table = also reported the inherent statistical fluctuations corresponding to the respective V-spots, V5, V10 and Vl5 due to the respective Vss. From the statistical point of view 'Use Statistical t distribution, near the average value, the value outside the specified confidence interval is reliable and does not originate from the inherent deviation of the experimental method itself, the degree of certainty is 95%. So 'measured for the matrix sample in the confidence interval near the average of the empty sample The V4Vt value is considered to be statistically indistinguishable from the empty sample. Therefore, the sample does not calculate the SARC heart value. The isoelectric point (IEP) measurement 126437.doc -102- 200902146 The following samples are determined according to the following procedure. The isoelectric point (&quot;ΙΕρ&quot;). The Mettler Toledo SevenMulti meter with pH mv/ORP module was used with the Mettler Toledo INL AB 413 pH composite electrode for enthalpy measurement. Calibrate the meter with a standard pH buffer solution at pH 2, 4, 7 and 10. Quantify 16 Μ Ω deionized water (at approximately 25 ° C) by using one of the samples to achieve the initial wet state Wet the sample and determine the IEP of each sample to produce a thicker slurry or paste mixture. This incipient state allows the glass electrode and its reference electrode to contact the liquid with the solid sample being tested. Liquid contact is achieved between the slurry or paste mixture in this example. Depending on the morphology of the sample (eg glass microfibers, granulated powder, chopped fibers, etc.) and its porosity (if any), the procedure needs to be different. In all cases, the amount of water added should only be sufficient to bring sufficient liquid into contact with the glass electrode and the reference electrode. In other words, 'water should be added to the sample to be tested to avoid exceeding the initial humidity. In all cases, the electrode tip is used, and the solid sample is mixed with deionized water (added for generating incipient wetness) by hand until the measured pH value is stable, and then the value obtained from the meter is read. N2 BET or Kr BET Surface Area (SA) Determination According to the ASTM procedure mentioned above, each sample given below is suitably subjected to SAN2_BET or SA, Kr_BET determination. As discussed more fully above, for higher surface area Measured values (e.g., about 3 to 6 m'g), & BET is likely to be a preferred surface area measurement technique in accordance with the method described in ASTM D3 663-03. For lower surface area measurements (for example, &lt;about 3 m2/g), Kr BET 126437.doc -103 - 200902146 can be a preferred surface area measurement technique according to the method described in ASTM D4780-95 ("SA Shi-5"). SARCNa empty sample measurement and statistical analysis for correcting SARCnp^ sample number sample A dilute NaOH titrant solution _ (N) SAN2-BET (m2/g) used to make pH in NaOH titration In te (the initial value of V* is adjusted to 9·0, and at ts, t10, and tls&lt; the pH is maintained at 9.0, the required titration liquid shift) is from 4.0 vsils) (ml) V is suspected = V initial + Vsiis V Initial minute Vs 5 minutes Vio 10 minutes V1S 15 minutes v5il5 The sum does not apply 1.5 0.3 0.1 0.2 0.6 2.1 Empty sample B 0.01 Not applicable 2.2 0.1 0,1 0.2 U.4 2.6 Empty sample C 0.01 Not applicable 2.4 0.1 0.1 0.1 0.3 2.7 Empty sample D 0.01 Not applicable 2.2 0.1 0.2 0.1 0.4 2.6 Empty sample average not applicable 2.075 0.15 0.125 0.15 0.325 2.5 Empty sample standard deviation 0.01 Not applicable 0.3947 0.1 0.05 0.0577 Not applicable 0.2708 Empty sample 95% Trust interval 1.45-2.70 2.07-2.93 Example CH-2 E Glass - SARCjva obtained a sample of E-06F glass produced by Lauscha Fiber International, a glass fiber with an average diameter of 500 to 6 nanometers. Sample A-1 was an E glass sample received as received, and A-2 was an E glass which was received as received by calcination but not leached. Samples A_1 and A_2' were non-leached E glass samples for calcination heat treatment. During the treatment, the non-leaching E glass was calcined for 4 hours in an air atmosphere having an air flow rate of 1 liter/hr and a temperature of 600 °C. Comparative sample Comp-B was prepared by acid immersion treatment of the non-calcined E glass received as received. For the comparative sample Comp-B, approximately 15 grams of E-glass and 1.5 liters of 9 wt.% of nitric acid were each placed in a 4 liter plastic wide-mouth container. The plastic container was placed in a ventilated oven at 95 ° C for 4 hours and shaken slightly by hand every 3 minutes. After the acid leaching treatment was completed, the sample was filtered using a Buchner funnel with Whatman 541 126437.doc 104·200902146 filter paper and washed with about 7.6 liters of deionized water. The acid leached sample was then dried for 22 hours at a temperature of 110 °C. Samples A-1, A-2 and Comp-B were analyzed by the above analytical method for determining SARCWa. The results are shown in the table below. Sample No. Sample Describes Dilute NaOH Titration Concentration (N) In pNaOH titration, the initial value of 4.0 is adjusted to 9.0 when the pH is at UV*), and the pH is maintained at ts, t10, and t15 (Vsil5). The actual volume of the titrant required in 9.0 (ml) V initial minute v5 5 minutes 锗 Vio 10 minutes Vis 15 minutes V* V*-V initial sample empty sample 0.01 2.1 0.15 0.125 0.15 ~~2.5 Not applicable A -1 E-06F received as received 0.01 20.5 0.5 0.4 0.3 21.7 1.2 A-2 Calcined E-06F 0.1 0.7 0 0.1 〇0.8 0.1 Comp-B Leach E-06F 0.1 22.6 1.9 0.9 0.4 25.8 3.2 Sample No. IEP SA* N2.bet (rn2/g) Titration liquid species (ml) for SARC^» determination* SARC^a (V*-V*)/ V phase description V initial 0 minutes Vs 5 minutes V, 〇 10 minutes VI5 15 minutes 镂V* Average sample empty value Not applicable Not applicable 2.1 0.15 Bu 0.125 ^0.15 ΤΓ Not applicable A-1 Corrected as received E-06F 8.9 &lt;7 18.4 0.35 0.25 0.15 19.2 0.04 Uncorrected A -2* Calcined E-06F 9.5 幺7 0.7 0 0.1 0 0.8 &lt; 〜0.2* Uncorrected Comp-B* Leach E-06F 4.1 &lt;250 22.6 1.9 0.9 0.4 25.8 &lt; -0.2* * Empty sample using the correction value based 〇1 square-N concentration of NaOH titrant obtained, rather than such a special sample used in the analysis of SARC · 0.1 N NaOH titrant 'it is not empty for correcting this sample titration sample titration. EXAMPLE CH-3 AR Glass - SARCNa A sample of AR glass Cem-FIL Anti-CrakTM HD produced by Saint-Gobain Vetrotex was obtained, i.e., glass having an average diameter of about 17 to 20 microns. 126437.doc -105 - 200902146 Glass fiber. In this example, the glass was used for samples A, B, and C. An ARG 6S-750 glass sample as produced by Nippon Electric Glass was obtained, i.e., a glass fiber having an average diameter of about 13 microns. In this example, the glass was used for samples D and E. Sample A and ruthenium were prepared by calcining AR glass and ARG glass which were received as they were. For samples a and d, AR glass and ARG glass samples were subjected to calcination heat treatment. In this treatment, AR glass and ARG glass were calcined for 4 hours in an air atmosphere at an air flow rate of 1 liter/hour and at a temperature of 60 (TC). Acid immersion was performed on the as-received, non-calcined AR glass and ARG glass, respectively. Prepare samples B, C and e. For samples B and C', place approximately 1 〇 1 gram of AR glass and 4 liters of 5.5 wt. 0 / 硝酸 of nitric acid in 4 liter plastic wide-mouth containers. Place in a 90 ° ventilated oven for 2 hours' and shake gently with hands every 30 minutes. After acid leaching, 'filter the sample with a Buchner funnel with Whatman 541 , paper and rinse with about 7.6 liters of deionized water. Then, the acid leached sample was dried for 22 hours at a temperature of 110. (Also, for sample E, about 5 8 grams of ARG glass and 4 liters of 5.5 wt% of nitric acid were each placed at 4 liters. In a plastic wide-mouth container, place the plastic container in a ventilated oven for 901 for 2 hours, and shake it slightly by hand every 15 minutes. After the acid leaching treatment, filter the sample using a Buchner funnel with Whatman 541 filter paper, and Use about 7.6 liters of deionized water to clear Then, the acid immersed sample was dried for 22 hours at a temperature of not: The sample a_e was analyzed by the above analysis method for measuring SARCjva. The results are shown in the following table. 126437.do. -106- 200902146 Sample No. Sample Describes Dilute NaOH Titration Concentration (N) In titration, used to adjust the initial value of 4.0 to 9.0 at pH κν*) and to maintain pH at ts, ί10Αί15 (ν5*15) The actual volume of the titrant required at 9.0 (ml) V initial split cone V5 5 minutes V10 10 minutes V15 15 minutes V* νΛ-ν* Average sample empty sample 0.01 2.1 0.15 0.125 0.15 2.5 Not applicable 95% empty sample Trust interval statistical confidence interval 1.44- 2.70 2.07-2.93 A Calcination AR 0.01 2.4 0 0 0.1 2.5 0.1 B Leaching AR 0.01 2.2 0.1 0.1 0.1 2.5 0.3 C Leaching AR 0.01 1.7 0.1 0.1 0.1 2.0 0.3 D Calcination ARG 6S-750 0.01 1.6 0.4 0.3 0.4 2.7 1.1 E Leaching ARG 6S-750 0.01 2.1 0.2 0.1 0.1 2.5 0.4 Sample sample ffiP SAKr-BET (m2/g) For SARQy« test 5 II Correction titration hoarding f ml) Modified SARCNa ( ΛΛ-ν^)/ν^ Description V* 0 minutes Vs 5 Minute V, 0 10 minutes V15 15 minutes Empty sample Average value Not applicable Not applicable 2.1 0.15 0.125 0.15 2.5 Not applicable Correction A Calcination AR 9.9 0.13 0.30 • 0.15 -0.13 -0.05 0 Not applicable t Corrected B Leaching AR 9.6 0.16 0.10 -0.05 -0.03 -0.05 0 Not applicable ' Corrected C Leaching AR Not determined 0.16 -0.40 -0.05 -0.03 -0.05 -0.5 Not applicable t Corrected D Calcined ARG 6S-750 Not determined 0.11 -0.50 0.25 0.18 0.25 0.2 — Not applicable ^ --- Corrected E Leaching ARG 6S-750 Not determined 0.12 0.0 0.05 -0.025 -0.05 0 Not applicable ' Ο &quot;Because of the 95% confidence interval of the V initial and Vt measured on the matrix sample Inside, therefore, 8 8 11 (: ^ value is considered to be statistically different from the average of the empty sample, there is a difference. Therefore, the SARC^ assay is considered unsuitable for these samples. EXAMPLE CH-4 A-Glass-SARCpja A-06F glass fiber produced by Lauscha Fiber International with an average diameter of about 50,000-600 nm was obtained. In this example, the glass was used for samples A, B, and C. 126437.doc • 107- 200902146 Obtained A-26F glass samples from Lauscha Fiber International, namely glass fibers with an average diameter of 2.6 microns. In this example, the glass was used for sample D. Sample A is an A - 0 6 F -glass fiber sample received as received. Samples B and C were prepared by acid immersion treatment of the non-calcined A-06F-glass received as received. For samples B and C, approximately 58.5 grams of A-06F-glass and 4 liters of 5.5 wt.% nitric acid were each placed in a 4 liter plastic wide-mouth container. The plastic container was placed in a ventilated oven at 90 ° C for 2 hours and shaken slightly by hand every 30 minutes. After the acid leaching treatment was completed, the sample was passed through a Buchner funnel with Whatman 5 41 filter paper and washed with about 7.6 liters of deionized water. Then, the acid immersed sample was dried at a temperature of 1 l ° C for 22 hours. A-26F glass fibers having an average diameter of about 2.6 microns (2600 nm) produced by Lauscha Fiber International were obtained. In the present example, the glass was used as it was for sample D. Samples A-D were analyzed by the above analytical method for determining SARC. The results are shown in the table below. Sample No. Sample Describes Dilute NaOH Titration Concentration (N) In titration, the pH is adjusted from initial value of 4.0 to 9.0 at αν*〇 and pH is maintained at t5, t10 and tls (Vsils) The actual volume of the titration required at 9·0 (ml) V first 0 minutes V5 5 minutes V10 10 minutes V15 15 minutes V» v*-v Primary air sample average value 0.01 2.1 0.15 0.125 0.15 2.5 Not applicable A A-06 0.01 16.7 1.5 1.2 0.5 19.9 3.2 B Leaching A_06 0.01 15.4 1.4 0.9 1.0 18.7 3.3 C Leaching A-06 0.01 15.7 2.3 1.2 1.3 20.5 4.8 D A-26F as it is 0.01 5.4 0.7 0.5 0.3 6.9 1.5 126437. Doc -108- 200902146 Sample sample 修正 For correction of SARCmJ in the titration solution (ml) SARC^vc (Vifc-V^) / V* description (m2/g) V4, 〇 minute V5 5 minutes V, 0 10 minutes 锸 V15 15 minutes V* Average value of the average value of the sample is not applicable 2.1 0.15 0.125 0.15 2.5 Not applicable Correction A received as received Α-06 10.1 3.1 14.6 1.35 1.075 0.35 17.4 0.19 Corrected B -06 10.6 3.1 13.3 1.25 0.775 0.85 16.2 0.18 Corrected C Leaching Α-06 Not Determination 3.1 13.6 2.15 1.075 1.15 18.0 0.32 Corrected D A-26F Not determined as usual <5 3.3 0.55 0.375 0.15 4.4 0.25 Example Composite Catalyst 1 Activity Test - Methylcyclohexane (mch> Conversion to Toluene The following non-limiting The examples indicate that when the precursor catalyst composition is dispersed in the composite catalyst composition, it is not expected to adversely affect the activity of the precursor catalyst composition as compared to prior to dispersion in the composite catalyst composition. The catalytic activity of the extrudate sample having the precursor FSC composition of Example 26 was prepared as in Example 28. In addition, in this example, the particle size distribution of the extrudate sample was maintained between about 4 Å and 60 mesh (i.e., 425 to 250 μm) to reduce the adverse effects of the internal diffusion channel resistance of the particles. The following is a general procedure for evaluating catalytic activity when converting methylcyclohexane (?) to anthraquinone using an experimental apparatus. In order to provide substantially equal amounts of platinum, the precursor of Example 26 was catalystd. The knives are dispersed in the 丨 04 mg 4 〇 to 6 〇 mesh extrudate, or the MG sample 2.6 as the catalyzed catalyst sample, loaded into a 35 mm inner diameter tubular reactor for 'each catalysis The activity test was run. Due to &amp;, the two different sample test loads provide substantially the same weight hourly space velocity for platinum 126437.doc 200902146 (WHSV). After the activity test, use 25 〇 cc / 3 to take a pre-treatment of the catalyst for minutes. The ratio of H2 to the molar ratio of the H2 to the feed is about %. The flow rate of the mixture varies within about 4 hours of the target range of (2) ee/mi cc/mm in about 4 hours. The contact line was tested under the conversion of methyl hexane (MCH) to toluene. As a result, (4) shows the relationship between the yield of toluene (heart) and the flow of (4). Each flow rate has a corresponding toluene conversion yield, and the yield of the precursor catalyst composition in the extrudate sample is substantially similar (if not coincidental), 5 ^ Q) without extrudate matrix material The corresponding yield of the same precursor catalyst composition (i.e., prior to dispersion in the matrix). Thus, the results of Figure 5 indicate that the catalytic activity of the precursor catalyst composition does not adversely affect when dispersed in the composite catalyst composition. Although in the foregoing embodiments, certain preferred embodiments of the present invention have been described in accordance with the present invention, and for the purpose of description (d), many of the succincts have been proposed. It will be apparent to those skilled in the art that the present invention is likely to have other Some of the details described herein may vary widely, without departing from the basic principles of the invention. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is an XPS sputter depth profile corresponding to each of four samples on/in an AR-type glass substrate, wherein the in-depth depth profile is PHI Quantum 200 Scanning ESCA ( Chemical analysis using photoelectron spectrometer) MiCr〇probeTM (Physical Ε1_〇η^, —) obtained two

The MicroprobeW has a microfocus, 1 126437.doc •110- 200902146 colorization 在1 Κα X body ten-line source operating at 1486 7 electron volts (ev). 2 is an XPS sputter depth profile corresponding to each of three samples including palladium on/in a bismuth-type glass substrate, wherein the sputter depth profile is a PHI Quantum 200 Scanning ESCA (photoelectron for chemical analysis) Obtained by MicroprobeTM (Physical Electronics, Inc.), which has a microfocus, monochromated Α1 Κα X-ray source operating at 1486.7 electron volts. Figures 3 and 4 are based on the JEOL 3000F field emission transmission electron microscope instrument.

A scanning transmission electron microscope (STEM) image of a cross-sectional portion of a sample of a precursor catalyst composition dispersed in a calcined niobium alumina matrix, generated at an acceleration voltage of 300 kV, wherein the precursor catalyst composition comprises substantially For non-porous glass matrices (e.g., leached A glass), the facing granules are typically dispersed within a range of less than or equal to about 3 angstroms from the surface of the squirting composition. Figure 5 is a graph showing the relationship between the methyl group (wt.%) and the flow rate reciprocal (min/cc) when the methylcyclohexane (MCH) is converted to toluene, using the pre-media composition in the pressure of gamma alumina. The sample 〇^ material sample °° is used as a composite refractory oxide, compared with the activity before being dispersed in gamma alumina. 126437.doc 111 ·

Claims (1)

200902146 X. Patent Application Range: 1. A composite catalyst composition comprising: (a) at least one first composition, and (b) at least one second composition having at least one precursor catalyst composition The precursor catalyst composition comprises, - a substantially non-porous substrate having an outer surface, a surface region and a subsurface region, - at least one catalytic component 'and at least one catalytically active region comprising at least one catalytic component Wherein L the substantially non-porous substrate has a measured value of from about 0.01 m2/g to 1 〇m2/g when measured in a group selected from the group consisting of VIII.., and combinations thereof The total surface area between; the at least one catalytically active region may be continuous or discontinuous and having a catalytically effective amount of the at least one catalytic component; and 111. the at least one catalytic component is substantially dispersed in the at least one precursor Within or on the composition, wherein 'at least one first composition is mixed with the at least one second composition after the at least one precursor catalyst composition is formed. 2. The composite catalyst composition of claim 1 wherein the catalytic component remains substantially dispersed substantially within the at least one precursor catalyst composition or the composition after exposure to steady state reaction conditions for one hour on. 3. The composite catalyst composition of claim 1 wherein the substantially non-porous matrix of the precursor catalyst composition has a predetermined isoelectricity obtained within a pH range of 126437.doc 200902146 of greater than 6.0 but less than or equal to 14. Point (IEp). 4. The composite catalyst composition of claim 1 wherein at least one catalytically active region of the precursor catalyst composition has an average thickness of less than or equal to about 3 nanometers and the composite catalyst composition is at After the steady state reaction conditions, the catalytic component is substantially positioned on (a) the outer surface of the substantially non-porous substrate, (b) within the surface region of the substantially non-porous substrate, (part of the a surface of the non-porous substrate, and partially in the surface region, or a combination of (d) 4(a), (b) and (c). 5. The composite catalyst composition of claim 1, wherein At least one catalytic component of the precursor catalyst composition is selected from the group consisting of Bronsted or Lewis acid, Blenz or Lewis, noble metal cations and noble metal cations and Anions, transition metal cations and transition metal complex cations and anions, transition metal oxyanions, transition metal chalcogenide anions, main oxygen p ions, _ compounds, rare earth ions, rare earth complex cations and anions, expensive Genus, transition metal, transition metal oxide, transition metal sulfide, transition metal oxysulfide, transition metal carbide, transition metal vapor, transition metal boride, transition metal phosphide, rare earth oxide, rare earth oxide and 6. The combination of claim 1, wherein the at least one catalytic component of the precursor catalyst composition is a first catalytic component, before the composite catalyst composition is in a steady state reaction condition, It has 126437.doc 200902146 (a) a first pre-reacted oxidation state, and (b) a pre-reaction interaction with a matrix, which is selected from the group consisting of ionic charge interactions, electrostatic charge interactions, and combinations thereof. 7. The composite catalyst composition of claim 6, wherein the first catalytic component is selected from the group consisting of acids, bases, chalcogenides, and combinations thereof. The composite catalyst composition of claim 6 And wherein at least a portion of the first catalytic component is modified or displaced to form a second catalytic component, wherein the composite catalyst composition is under steady state reaction conditions, (a) a second pre-reaction oxidation state, and (b) a second pre-reaction interaction with the substrate; wherein the second pre-reaction oxidation state of the second catalytic component is less than, greater than or equal to The first pre-reactive oxidation state of the first catalytic component. The composite catalyst composition of claim 8, wherein the second catalytic component is selected from the group consisting of pd, Pt, Rh, Ir, Ru, OS, Cu, Ag, a group consisting of AuRu, eNi, co, Fe, Mn, Cr, and combinations thereof. The composite catalyst composition of claim i wherein the precursor catalyst composition: substantially non-porous matrix has less than or equal to about U. The composite catalyst composition of claim 1, wherein the substantially non-porous matrix of the precursor catalyst composition is selected from the group consisting of glass, tantalum carbide, and cordierite nitride. , a group consisting of tantalum ceramics and combinations thereof. A composite catalyst composition of the present invention, wherein the substantially non-porous matrix of the precursor catalyst composition is selected from the group consisting essentially of no ceramsite, alpha alumina, oxidized oxidization, titanium oxide, carbon, and combinations thereof. group. 126437.doc