TW200902145A - Compound catalyst composition - Google Patents

Abstract

A compound catalyst composition, useful for many chemical processes, comprises a compounding refractory 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 nonmicroporous/nonmesoporous substrate having macropores having a total surface area between about 0.1 m2/g and 50 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 refractory oxide and the precursor catalyst composition are intermixed after the precursor catalyst composition is produced.

Description

200902145 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 reticular catalyst composition comprising a refractory oxide and a precursor catalyst composition. The precursor catalyst is preferably a functional surface catalyst (FSC) composition. [Prior Art] f -

Catalyst compositions are used to promote chemical reactions that are generally described as catalytic or catalytic, and catalysis is critical to the efficient operation of various chemical processes. Hole 4 is an industrial reaction and almost all of the ', 々, Ί隹 愚, Ρ疋 ν and catalytic reactions before or after the reaction. In the case of the United States alone, the value of a product produced at a certain stage including the catalytic process is close to - US$ (USD). Products produced using catalyst compositions include: "°, clothing, pharmaceuticals, pharmaceuticals, specialty or fine chemicals", plastics, detergents, fuels and lubricants. Catalyst compositions can also be used for discharge. (eg, vehicle exhaust emissions, refinery emissions, utility plant emissions, etc.) and other process emissions to reduce the amount of harmful components that may have a negative impact on human health or the environment: _ ° amount and 3 ' The sales of solid carrier catalysts for heterogeneous catalytic reactions in the whole yard are about US$3 billion per year. The solid-loaded catalyst is usually ', ie, petroleum refining catalyst, chemical processing catalyst and row: three types of catalyst The market sales are basically three-thirds. For example, in the 126438.doc 200902145 US $1.8 billion solid catalyst market, petroleum refining, chemical processing and forestry catalysts account for 37% of the market, 3 bamboo. And Μ%. Take the petroleum refining catalyst market (about 1 billion US dollars in 1990) as an example, 56% of the proceeds come from the fluid «Fluoric acid (FCC) catalyst, and 31_5%, 65% and 45% of the proceeds From coronation treatment catalyst, hydrogenation cracking catalyst and heavy In the case of a mechanism, the catalyst can generally increase the rate at which a chemical reaction reaches equilibrium between the reactants and the product without substantially consuming itself. Therefore, for any correlation In terms of the 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 it is selected and/or selected by the appropriate method. Therefore, the catalyst is used for various purposes. Used in a wide range of commercial and practical processes' These objectives include increasing the reactivity, selectivity and energy efficiency of the process and other uses. For example, according to the specified process conditions, the desired production and production are produced. The reaction rate or reactivity can shorten the processing time, and the production capacity of the product (for example, 'increasing the volume or mass of the material per unit hour). Therefore, the 'catalytic activity means the catalyst composition in each early position. The ability to efficiently convert the reactants into the desired product over time. Also increasing the selectivity of the reaction can increase the required self-knife in the possible reaction products of the group. In (4) possible Some of the products are undesirable and require further processing for corresponding removal or conversion = this 'catalytic selectivity' is the ability of the catalyst composition to convert a portion of the reactants under specified conditions to a particular product. The catalyst combination or product is converted in a process and reduces contaminants or undesired reactants < U. Another use is to maintain or improve the overall energy efficiency of the product production I26438.doc 200902145 process And / or the selectivity of the reaction at the same time to improve the reaction range of the use of the media is very different. For example, in the reduction of money ^ r (mine is not limited to) the catalyst can be used, reduce the carbon, (3), nitrogen oxides Contaminant content such as pottery (10)), which may be present in a series of emissions (eg, gasoline or diesel combustion exhausts of vehicles, classification: coal-fired processes, etc.).婵 or (4) _ ground, the handling of hydrocarbons. This process is used for many different sources (such as the straight crane oil knives, re-salt petroleum distillate, heavy oil, transfer f, leaf rock, natural gas and contains

Conversion or upgrading of hydrocarbons from other carbonaceous materials of the material that can be catalytically reacted. The T catalytic reaction is divided into two different reaction types, namely homogeneous catalysis and heterogeneous catalysis. Homogeneous catalysis is broadly described as a type-catalyzed 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-like m. Therefore, concentration gradients and migration of reactants to the catalyst can become important factors in controlling homogeneous catalytic reactions. In some cases, the solution phase "catalytic reaction can occur across the interface of the two liquid phases' instead of forming a true solution, but forming an emulsified phase. Some general categories of homogeneous Tan &&&&&&&&&&&&&&&&&&&&&& In another aspect, heterogeneous catalysis 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 reactants produced a mixed solid-liquid phase or solid phase-gas phase reaction. Heterogeneous catalysis has many advantages over homogeneous catalysis. For example, solid catalysts are generally (a) less corrosive and therefore have lower safety and environmental risks than many homogeneous solution catalysts. (b) Scope of supply Widely economically viable temperature and pressure conditions, and (C) can control more intense exothermic chemical reactions and endothermic chemical reactions. On the other hand, solids can have mass transfer limitations that in turn significantly reduce 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, noble metals such as palladium (pd), platinum (pt), ruthenium). (Ru), Re (Re), etc.): The surface area within the catalytic component, usually on the order of hundreds of square meters per gram. Thus, conventional catalyst compositions or catalyst particles comprise a particularly porous support having a large internal surface area upon which the catalytic reaction takes place. However, such catalyst structures often produce mass transfer limits and reduce the effectiveness of catalyst particles on catalyst activity and selectivity.

Performance and trigger other catalyst performance issues. In such a more representative catalyst structure, the reactants must diffuse through the network of pores to reach the interior region of the catalyst particles, and the product must diffuse back out of the interior region of the catalyst particles. Therefore, the conventional catalyst group

The mouth hole 1± depends on the balance, among other factors, that is, it depends on the balance between the rain recordings of the conventional catalyst composition and the rain, that is, the catalyst surface area and the mass transfer. The energy of Liu Xi P bow α # α balance between the forces. For example, many catalytic components exist in the case of the type and are supplied to the carrier of "I, 八8, /, with fine and complex pore structure (often microporous structure, that is, too p 2 not, not average Maximum diameter) to increase the catalyst 126438.doc 200902145 Mao's step iL db ' coat area. This higher surface area will generally increase the catalytic activity. The activity of the catalyst due to the higher surface area of the catalyst particles increases, f ¥ will cause the problem of mass transfer resistance (that is, the movement of the reactants and products into and out of the catalyst particles), especially if the carrier comprises a higher percentage of 匕, ° 玄 ' ' ' ' ' ' ' ' ' ' The percentage of large pores (large pores of J 5 〇 not) in the carrier reduces the resistance to mass transfer (ie, speeds up mass transfer. However, this solution tends to reduce the physical strength and durability of the catalyst particles. In other words, from the point of view of mechanics, the robustness of the catalyst particles is reduced. At the same time, the right reactant is subjected to a significant mass transfer resistance in the pore structure of the catalyst particles. There should be a concentration gradient under the conditions. Therefore, in the pore structure, the anti-reservoir, when the 庳/Fucking person's / Chen is the largest around the catalyst particles, is at the center of the catalyst particles. I丨JL | „ I A. It is the smallest. On the other hand, the concentration of the reaction product is around the center of the catalyst particles. The concentration gradient provides a driving force for mass transfer. The higher the gradient becomes, the lower the rate of catalytic reaction. Such as +. Low, the effective properties of the catalyst particles (such as reactivity, selectivity, life cycle between the 5 & regeneration treatment and anti-knot隹 can also be reduced accordingly. 1 Normally, the degree of development of the catalyst composition is improved, and the β-corner or the eve processing target as described above is improved. Under certain 4b, the influence of the catalyst performance is delayed. One of the factors of θ dry-it is that it promotes the ability to react quickly and efficiently between reactants. Because of the lack of heart, the catalyst has lower diffusion limits, and &;,,,: and, in 1, he, y, "he" In order to obtain a better selection of the products for the preparation of the diacritical products, it is important to scouring 126438.doc 200902145 μ; additional processes for removing or converting undesired reaction products and related processing equipment. For example, in 1976 , ν τ cu 1 · Shah specializes in the use of acid-impregnated aluminum borosilicate fiber, which is produced by Shishida 八五为 E-glass (more specifically, E-621)

$catalyst carrier. Compared with conventional catalysts, 'the catalyst carrier has a higher f area hoarding ratio' and thus reduces the catalytic conversion for automotive exhaust systems (for example, see 0xldation of an Automobile Exhaust xture by Fiber Catalysts, Ind. Eng. Chem., Prod. = DeV"pp.29_35 v〇1 15 N〇Ή%). At the same time, _ et al. ~ generally produce reactive gases in automotive exhaust mixtures (eg carbon oxide, Carbon dioxide, nitrogen oxides 'methane, ethane, propane, ethylene, propylene, acetylene, benzene and toluene, etc.) are easily accessible to the large surface area produced in the glass.

Shah et al. showed that a relatively small number of fibers E with a relatively small surface area (7) m / g) compared to two conventional catalysts (with alumina beads as the carrier or platinum as the carrier) The performance of the glass catalyst carrier is better than that of the catalyst supported by 2 alumina or ruthenium dioxide (1 rib m2/g and 3 17 m2/g, respectively), of which e-type glass catalyst The average pore diameter is larger than the catalyst of the carrier of oxidized or the catalyst of the carrier of the dioxide. 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 type of acid-impregnated aluminum borosilicate type E glass fiber (EGF) in 1999, relative to the selective liquid phase used in benzaldehyde. Hydrogenated cerium oxide glass fiber 3 126438.doc -11 - 200902145 f

(SGF) The effect of producing benzyl alcohol (using a platinum-based catalyst) or benzene (using a catalyst based on I-bar) (see, for example, Supp0rted Giass Fibers 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 an EGF sample used to carry palladium as a catalytic component of a palladium-based catalyst composition ( The surface area is 15% and m2/g, respectively, and the surface area of SGF is kept at a low level of 2 claws 2/§. However, Mmsker et al. noted that the SGF/palladium catalyst palladium essentially has the same effective surface area concentration as its EGF/counterbatch counterpart (ie, about 丨.丨_〇1/m2) (household metal/per The square meter Moule), the SGF/|ba catalyst composition, shows that the activity or reaction rate per gram is reduced compared to its EGF/! Bar catalyst counterpart.

Kiwi-Minsker et al. suggest that such a SGF/(iv) medium-causing surface area decreases and the activity decreases 'may be interpreted as the interaction of the active ingredient (ie, the catalytic component 'in this case) with the SGF carrier (4), and Not due to the small surface area of the pot (ie 2 mVg). However, they failed to verify this argument by proving the following arguments: EGF/palladium catalyst with a small surface area (ie, comparable to 2m2/g^G Chen), at least & && On the eve, the Langerhans catalyst samples with larger surface areas (ie 15 m2/g and 75 "^, respectively, have the same catalytic activity. Therefore, Kl Wi-Minsker et al. proposed to limit the activity of SGF/(ie due to Compared with EGF, SGF has a higher 酴 3 3 3 3 , , , , , , , , , , , , , , , , , , , , 为何 为何 为何 为何 为何 为何 为何 为何 为何 为何 为何 为何 为何 , , , , , ,原因] The reason is not clear. In any case, Kiwi_Minsker does not report 126438.doc -12- 200902145, compared to 75 mVg EGF around the sample, i5 m2 / g. The mouth has increased catalytic activity due to increased diffusion rate. Otherwise, this Perhaps the benefits of the month due to the small catalyst surface area of the car. D: Recently, in US 7,060,65 1 and EP i 247 575 illusion (Ep, 575), Barelko et al. revealed the use of dioxide-rich Carrier of ruthenium (including dioxide dioxide and oxides containing non-earic dioxide For example, α12〇3, Μ], 〇, MgO, CaO, etc.) as a catalyst carrier, the beneficial (4) body has a pseudo layer in the lower surface of the carrier = (9) See EP, 575, n, 13, 15 , 17, mm paragraph content). As described more fully to the European Patent Office ("Ep〇"), in distinguishing the catalytic carrier ("Kiwi-Minsker disclosed in EP '575 and Kiwi-Minsker et al. At the time of the carrier, Barelk〇 et al. asserted that the cerium-enriched carrier they claimed had a pseudo-layered microporous structure with a narrow interlayer space, while the Kiwi_Minsker carrier did not. 5, Barelko et al. believe that in the paper by Kiwi-Minkser et al., π has a basis for assuming that (a) there is a pseudo-layered microporous structure with a narrow interlayer space in the Kiwi-Minsker carrier; (b) A pseudo-layered microporous structure with a narrow interlayer space helps to enhance the activity of the metal applied to the carrier (see, for example, paragraphs 13, 17-18, 23 and 32 of EP '575).

Barelko et al. further clarify the carrier of the cerium oxide-enriched carrier with the carrier proposed by Kiwi_Minsker et al. by explaining the following contents to the European Patent Office: due to the fact that the catalytic component has a highly dispersed active state on the surface of the carrier. Distribution (a pred〇minant distribution of the catalytic components in the subsurface layers of the support 126438.doc 13 200902145 in af highly dispersed active state)" (in the original line), the carrier rich in dioxide is more south The catalytic state of activity, and thus the more active catalytic state, enables the catalytically active component to withstand sintering, aggregation, and exfoliation from the carrier and the action of the contact agent (see, for example, EP, 575). Ep, 575 confirms that The diffusion limitation may hinder the cation mixing into the interlayer space of the carrier, and thus hinder the cation from entering the carrier by chemisorption (see, for example, 第ρι575, 1st and 7#). In order to solve the problem of diffusion limitation, et al. a carrier structure in which a thin "layer of bismuth-oxygen fragments is separated Into narrow interlayer spaces (i.e., pseudo-layered microporous structure as much), the narrow interlayer space contains = "large amount", 〇H group, the group of 〇H #: promoter may be cation exchange. - et al. reveal that a sufficiently "thin" 矽_f-fragment layer is characteristic of high Q3 to y ratios, and they further state that there are a large number of 〇H groups sandwiched between narrow interlayer spaces. The structure has been confirmed by NMR (nuclear magnetic resonance) and melon (infrared) spectrometry, ". σ argon BET and alkali titration surface area measurement. = Some of the glass catalyst compositions are the same, many conventional Catalyst attempts to solve at least one of the above confirmations, a, < force to ask 4, but in the performance of the catalyst, it is not good. Therefore, these conventional catalysts often have narrower mines. , the use period before the regeneration or replacement is required), = (4) to fill the expensive catalytic components (such as Ming, (4) precious metals:: the cost of the production of the medium and the catalytic process. And - an improved catalyst composition, Etc. The catalyst composition preferably has a wide range of process conditions and requirements for phase, selectivity and/or energy efficiency. 126438.doc 200902145 叮 进 ' ' at the same time enhances robustness and lasts for a long time, Ya Maintaining a relatively versatile 'man has found a composite catalyst composition It is contemplated that: the need for a wide range of catalytic reactions is applicable. [Invention] According to one aspect of the invention, there is provided a conjugated catalyst composition comprising: (a) at least one first composition, and b) at least one second composition, 1 and right?, 丨, ^^a, 八丹男主> 耵 耵 触 触 触 ' 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该 该a substantially microporous/non-porous matrix of the outer surface, the surface region and the subsurface region, - at least one catalytic component, and - at least one catalytically active region comprising at least one catalytic component, wherein i · only buckled The void/no-pore matrix has a total surface area measured between about 1 m2/g and 50 m2/g when measured by a method selected from the group consisting of: sA and combinations thereof; Ii. at least one catalytically active region may be continuous or discontinuous, and having a catalytically effective amount of at least one catalytic component; and iii. at least one catalytic component is substantially dispersed within or on the at least one precursor catalyst composition, wherein 'In generation After less than one precursor catalyst composition, at least one first composition is mixed with at least one second composition. 126438.doc • 15- 200902145 Based on the following technical person, [embodiment] Other aspects of the invention can be clearly understood by the scope of the invention and the accompanying drawings. The terms used in the above description have the meanings of the following definitions. "Polar," means a cavity or channel having a depth greater than the width. Represents pores that communicate with one or more other pores. The pores of the mouth represent the pores of the channel of the material in which the closed pores are located. Any other track: =:== the material of the gap _...the pore of the direct opening and closing pores). Gap associated with gaps (ie, not belonging to

The door 1 width & table does not determine the inner diameter of the pore or the distance between the relative f according to the specified method. J ” pore volume, 矣 + 0 μ > a effect, but not the total volume of all pores determined by the method of 曰疋 匕 includes the volume effect of closed pores. "Porosity, 矣_ rate. The ratio of the pore volume in the material to the total volume of the material ::::: indicates the pore whose internal width is less than 2 nm (-). , visibility of pores between 2 nm and 50 nm. The large pore "clamp + & Α" has a width greater than 50 nm. The outer surface "includes, the outer boundary of the material or the skin (thickness is close to zero), the outer boundary of the package or the rule or irregular wheel related to the defect (if any) 126438.doc -16· 200902145 ' "wall surface" means the inner boundary or skin (thickness near zero), including any regular or irregular contours on the inner boundary or skin associated with defects, if any, substantially defining at least one or more types of pores The shape of any open pores in the material. The overall surface of the garment represents the material gap, the outer surface of the material and its surface area. ''Surface area'' means the area of material that can vary depending on the material, excluding the area defined by the open pores of the material (if any open pores are present)' but the surface area (4) is less than the outer surface of the material. Or equal to ^ Nailai (preferably $ 2〇 nanometer, more preferably S 10 nanometer); when the material has any open pores, the surface area (b) is less than or equal to 30 nanometers below the pore wall surface of the material. Meters (preferably (10) nanometers are more preferably (four) nanometers. For materials with detectable surface elevation changes, whether or not such changes are along external or internal boundaries or skins, external or internal boundaries or The average elevation of the epidermis is used to determine the average depth of the surface area.

"Subsurface area, means a material that can be changed according to the material: the area is defined by the open pores of the material (if any open pores are present) =, but the subsurface area (4) is larger below the outer surface of the material (4) When the pores are taken up, the surface of the crucible wm/), under the surface of any opening 4 of the material, is larger than the surface of the pore wall of the material (preferably > 20 nm, more preferably > 1 nanometer). :: Surface area, or,, open cell wall surface area" means the surface area effect of all open cell walls in the material with the specified square. ''External surface area,' indicates the surface area effect of the material determined by the specified method that does not include the surface area effect of all pores in the material 126438.doc -17- 200902145. "Total surface area," means the sum of the internal surface area of the material and its external surface area determined by the specified method. ^ Nano-chemically adsorbed surface area, or SA"e is determined by chemisorption of sodium cations by chemical adsorption. The surface area of the material is described in GW Se (IV) Anal·chem., 1956, (10) % p ^ and R. Her, Chemistry of Silica, J〇hn Wiley & "203 and 3 53. ' ' 'Sodium-chemical adsorption surface area change rate, or "SARC ^, where sah15 / v initial" where (1) v is initially used for the initial titration of the dilute NaOH titration solution for the initial titration of the aqueous dressing mixture, at about 25 it A material that is substantially insoluble in water is included in the 3.4 M NaC1 solution at a temperature of zero time t. From the initial ρΗ4·〇 to pH 9〇, and (1))% to Μ means to make the slurry mixture in 15 minutes. Maintain the pH at 9: ^ with 5 concentrated ^ N: 〇 H titration total volume, every 5 minutes (total, minute; separate knife for t5, 〖1〇 and ti5) the total volume as needed as soon as possible The corresponding adjustment, therefore, V. "refers to the total volume of NaOH droplets m used in the titration procedure described in more detail below, where ν "~ ΐ 5 = ν total. Therefore, ~ 15 can be expressed as v total and v first Poor, where % to i5 = v total _v initial. For the purposes of this definition, 3.4 MNaCl solution is prepared by adding 3 gram NaCl (reagent grade) to 15 liters of water, and h5 gram sample material is added to the NaCl 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 earlier, a small amount of dilute acid (such as HC1) or a dilute base (such as Na〇H) can be used correspondingly to 126438.doc -18- 200902145. Titration, in order to first know that V initial, use dilute NaOH first. A titration solution (for example, 1. 1 N or 〇.〇1 N), and then use ls for SARC heart measurement. In addition, for the purposes of this definition, 'V' is the accumulation of Na〇H titration solution used in ts, ~ and ~ Volume, which is titrated with NaOH titration every 5 minutes (3 3 minute intervals), as needed, from t. To the final time. The pH of the slurry mixture was adjusted to 9. 〇 in 15 minutes.

For the purposes of this definition, it is treated with any alternative ion exchange (ΐΕχ), counter ion exchange (BIX) and/or electrostatic adsorption (ΕΑ) treatment methods to produce – or multiple type 2 component precursors (described below) The SARC; Va of the sample material is determined prior to integration onto the surface of the substrate and/or within the surface of the substrate. ''initial wetness,' indicates that for an aqueous slurry or paste mixture comprising a solid or semi-solid material, a point in time at which the isoelectric point ("IEp" of the material is being measured, at this time, deionized water substantially Covering the entire surface of the solid or semi-solid material and filling to the current extent any porous pore volume that the material may have, thereby allowing water to enter the aqueous slurry or paste mixture to provide a glass electrode contact The 液体ρ is determined by the contact with the reference electrode and the sufficient liquid contact between the two. The ''isoelectric point'' or ΙΕΡ indicates the ΡΗ value of the net surface charge of the solid or semi-solid material at initial humidity. The ΙΕρ used herein may also be referred to as a zero point charge (ZPC) or a zero charge point (PZC). The catalytically effective amount means sufficient under at least one suitable processing condition The reactants are converted to at least one predetermined product of sufficient yield to support the amount of catalytic component of the test 126438.doc -19. 200902145 factory or commercial grade process. "Chaleonide" means a group of at least one group of 16 (formerly via) derived from sulfur (s), selenium (Se) and tellurium (Te) and at least one of which is positively charged. A compound of 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), silver (1 〇, turn (), and jade (Au), unless otherwise stated, the metal is mismatched, 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 (at the same time in an unreacted state). "Anti-corrosion matrix" means that the matrix composition structure capable of resisting the subsurface region is substantially The altered matrix, 嗲, 成, 亥 4 ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ , ^ into pore size expansion, etc. However, the composition of the corrosion-resistant matrix may be substantially high-strength acid (such as thick, high-intensity test (such as concentrated NaOH) 啖 A # change from virtual high, -, humic reagent (Although alone or in combination with Α, Γ high vibration frequency conditions), for this definition 5, such a matrix is still considered to be, “corrosion resistant”. “Surface activity” means that the surface of a material is sufficient – electrical composition State The loading has, and has - or a plurality of charges (1) to promote the catalytic reaction under steady-state reaction conditions without entering the system: (9) additionally 'interacting with each other by static and/or ion exchange with - or a plurality of charged components The interaction is under the steady-state reaction conditions as a catalyzed 2-step U, which in turn can be I26438.doc •20- 200902145 "base" without any solid or semi-solid materials, including but not limited to glass and glass The sample material, 1Ep is larger than 〇 but less than or equal to 14, and the surface active state is known to be: ..., the base is modified in the intended use in the catalyst composition (having a catalytically effective amount of the catalytic component). _ + 0 indicates hunting by electronic and/or physicochemical interactions (eg, ionic, electrostatic or covalent interactions including, but not limited to, hydrogen bonding, ionic bonding, electrostatic bonding, and Van der Waals) /Dipole bonding, affinity fi

Force bonding, covalent bonding, and combinations thereof combine chemical components with a matrix. MODE FOR CARRYING OUT THE INVENTION The annotations in the Summary of the Present Embodiment are only used to illustrate the selection of the scope of the accompanying patent application and the reason why it is only used for the convenience of the brief wording. Some aspects of the implementation. Therefore, the description of this embodiment should not be construed as limiting the scope of the invention as it is attached. 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 type of catalytic vehicle composition having at least one catalytic component. The precursor catalyst composition can be prepared by ion exchange, impregnation, immersion, co-precipitation, other catalyst composition preparation methods, only: the method can produce a precursor catalyst composition, at least one of which The catalytic component remains substantially i dispersed in the precursor catalyst composition and/or composition after mixing with the refractory inorganic oxide. Knife month, the aspect of the invention relates to a composite catalyst composition comprising a high temperature inorganic oxide and a precursor catalyst composition, the precursor touch group = I26438.doc -21 - 200902145 There is no microporous/no void in the shell, but there is a matrix with large pores: the actual death may be irrelevant in quantity, and the micropores and/or mesopores which have an adverse effect on the pretreatment of the catalyst composition with k' volume. The precursor catalyst composition is preferably a functional surface catalyst composition ("FSC composition"). Another method for making novel composite catalyst compositions is preferably FSC compositions. . The invention also uses a catalyst composition for various purposes, such as smoke, hydrocarbon and/or non-hydrocarbon treatment, conversion, refining, and domain emission control and treatment: and other types. the process of. For example, 'new composite catalyst compositions can be formulated; ^ miscellaneous and / or non-hydrocarbon treatment, conversion, refining and / or emission control and treatment processes and other $i punishment beta wide cheek type of private reaction selectivity, Reaction rate, product yield and energy efficiency. Precursor Catalyst Composition The precursor catalyst composition and the ruthenium have a substrate which is substantially free of microporosity/no pores but has large pores' and a catalytically active region comprising at least one catalytic component. Generally, the matrix of the precursor catalyst composition should be substantially free of microporosity / no mesoporosity, but in fact it is not necessary to set the number of six - such as θ 匕 ,, for the catalyst ', and the pre-perform The use of micropores and or medium pore volumes without adverse effects. As noted above, the precursor-retracted human w* blade material composition is preferably an FSC composition. Thus, for purposes of illustrating this preferred embodiment, the composite catalyst compositions described herein will describe in more detail the different FSC compositions as precursor catalyst compositions. It will be appreciated, however, that other catalysts known to those skilled in the art may also be used in the manufacture of the composite catalyst group described herein: 126438.doc -22. 200902145 Precursor catalyst composition . These factors should be included in the production of FSC composition. If H s include but not limited to: (1) 霎 预期 预期 预期 预期 预期 , 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 After the sound. (Η) In view of the intended use, the degree of corrosion resistance of the substrate is again, just in the intended use, in order to obtain the desired surface properties, the matrix is much f

The degree of porosity (if any), and the associated elemental composition (especially on the surface), (iv) depends on the intended use of the composition, and where appropriate, the chemical sensitivity of the substrate to the generation of the appropriate isoelectric point, and by- Or a plurality of first forming knives having a type 2 and a matrix ion and/or an electrostatic interaction to make the substrate surface active, the substrate capable of, but not necessarily, generating a catalytically active region on the surface of the substrate and / or within the average thickness ^ about 30 nm, preferably ^ about 2 〇 nano 'more preferably S about 10 nm; (7) matrix for optional ion exchange (ΐΕχ), 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 a surface of a matrix having a second type and matrix The ions and/or electrostatic interactions, and thus the catalytically active regions, have an average thickness of about 30 nm on the surface of the substrate and/or within the surface of the substrate, preferably about 2 nm, more preferably Each about 10 nm; and I26438.doc -2 3- 200902145 (V1) Depending on the intended use of the compound, the chemical sensitivity of the substrate to the following reaction: optional calcination and / or reduction, oxidation or progress to make the treated substrate in use The catalyst composition is chemically reacted with the first or second catalytic component. I. Precursor Catalyst Matrix Description iEp selection for the general and preferred range of many potential uses

The substrate for forming the precursor catalyst composition of the present invention is preferably a bismuth-containing shell composition. In particular, when the current catalyst is FSC composition, it includes 4, if not in glass, sinusite, gas fossil. In the evening, cordierite, containing 11 pottery and its mixture 'whether it is surface active or treated to produce a surface active state' is greater than about. But less than or equal to 14, preferably sophomore: 4.5, J, at 14, and more preferably greater than or equal to 6.0 but less than 14. In these sputum'' and the mouthpiece' is preferably a glass composition. Substantially flawless compositions can also be used to produce the precursor catalyst compositions of the present invention, including but not limited to, in essence... L, e (theta) oxidation, oxidized titanium oxide, carbon and mixtures thereof, whether surface-active or treated to produce a surface active state, have an IEP greater than about 〇 but less than or equal to 14. The ability to have a suitable 1EP (suitable for the production of a precursor catalyst composition prior to the material) depends on various factors, some of which are outlined. In view of the more detailed discussion below, those skilled in the art will be more aware of other factors associated with selecting an appropriate IEp. For example, for many processes of commercial interest, the glass (or glass-like) composition and its surface active product preferably have an EP of greater than or equal to about Ο but less than 14 and an expected 1EP greater than or equal to about 6.0 but less than 14蹲 126438.doc -24- 200902145 The composition is better' and the glass composition with an IEP greater than or equal to about 7.8 but less than 14 is expected to be optimal. However, depending on the intended use of the catalyst composition and the extent and type of porosity in the matrix of the composition, the preferred range of ΙΕρ may be affected. In addition, certain catalytic processes are more sensitive to catalyst compositions that are surface active in the lower pH range. Therefore, in such cases, a substrate having a ΙΕΡ less than 7.8 (preferably $6, more preferably $45) is likely to be more suitable for such processes. Therefore, it is again stated that the selection of carbene in the appropriate range of IEp not only takes into account the intended use of the catalyst composition, but also the porosity, chemical composition and processing procedures (if any) of the substrate. In addition, depending on the intended catalytic use, many glass types can be potential candidates for the pair of bases to obtain the appropriate degree and type of IEp and porosity. The lanthanide is received as received or used in one or more of the following treatments. In general, some examples of such glass types include, but are not limited to, E glass, boron-free e-glass, S-glass, R-glass, AR glass, rare earth, acid salt glass, lock-titanium-tellurate glass, nitride glass such as germanium. Aluminum-oxygen glass, A glass, C glass and CC glass. However, the following is a description of the types of glass that are generally contemplated for use in a range of catalytic efficiencies and certain possible treatments. Macroporous glass indicates that the substrate used to produce the catalyst composition of the present invention is preferably a glass group that is substantially free of micropores & pores, but has some large pores (, without microporosity/no pores). The glass material composed of α material, whether it has surface activity & 2 疋, 匕 processed to form a surface active state, ΙΕΡ-like greater than 7.8. 无, ΙΕΡ greater than 7.8 non-microporous / no mesoporous glass combination 126438.doc -25 · 200902145 includes acidic or basic oxide type glass mesh modifiers, including (for example) but not limited to zinc (Zn), magnesium (Mg), #5 (Ca), Ming An oxide of an element such as (A1), butterfly (b), titanium (Ti), iron (Fe), sodium (Na), and potassium (K). If an organic network modifier is used, it is included in The amount in the lower IEp glass tends to <15 wt.%. The glass containing magnesium, calcium, aluminum, zinc, sodium and potassium is preferred, and the glass combination containing greater than or equal to about 70 wt.% of cerium oxide. The material is especially preferred. However, the macroporosity corresponds to less than about 98% of the total surface area, and the geometric outer surface ranges from about 2% to about 5% of the total surface area. % of the substantially microporous/no-porous glass composition can also be used to produce the catalyst composition of the present invention, and the IEp of the composition is typically greater than 7.8 but less than or equal to 14 °. Porosity indicates that the matrix is porous. Another related aspect of the catalyst composition of the present invention. Generally, the substrate should be substantially free of microporosity/no pores, but in practice it may be irrelevant for the number S, for the intended use of the catalyst composition, Microporosity and/or mesoporous volume with adverse effects. It is often difficult to determine the micropore volume in the material. Two surface area measurements are used to determine whether the matrix is substantially free of microporosity/no pores. Inventive catalyst composition. A first-surface area measurement system can be used to detect micro-pores, by means of a thermal adsorption/desorption method suitable for accepting the expected surface area range of the measurement. The extent of the pores and/or macropores. For example, for larger surface area measurements (eg > about 3 m2/g) N? BET, recognize "g) 2 hr, according to the method described in ASTM D3663-03 (SA ^-Wy"), may be Zhuo Measurement Technology Co. surface area of from ± ^. However, 126438.doc -26 - 200902145 for smaller surface area measurements (eg < about 3 m2/g) Kr BET, according to the method described in ASTm D4780-95, ("s. Anr"), may be preferred Surface area measurement technology. Those skilled in the art of analyzing the surface area of solid and semi-solid materials will be aware of the most surface area measurement methods for detecting microvoids, mesopores, and/or macroporosity. The second measurement of the _ chemical adsorption surface area ('’S.A.wn)' can use some kind of analytical method (R. Her in Chemistry 〇f

Silica, John Wiley & Sons (1979) pages 203 and 353) are expressed as the change in time versus time for NaOH titration, and in accordance with the rate of change in S Aw (nSARC 〇 more specific definition. Therefore 'as defined herein, matrix Substantially no microporosity / no mesoporosity' premise that the matrix of SAwwy ^ SA is between about (M m2 / g to about 50 m2 / g ' and its SARCyVa is less than or equal to 〇 5. As discussed in more detail above , SARC is the ratio of the two volumes of NaOH titration solution, the denominator is the volume of the initially used NaOH titration solution, that is, initially used to titrate the matrix slurry mixture at zero time t, the matrix slurry mixture is at 3 4 μ

The NaCl solution (pH 4 to pH 9) contained 1.5 g of the substrate at about 25 °C. However, as described above, before the initial Na〇H titration is started for the sarCw determination, the aqueous slurry mixture must first be adjusted to pH 4 with a small amount of acid (H(:1) or alkali (NaOH) §. Still as described above, the cumulative volume of the Na〇H titrant (for three 5 minute intervals, maintaining the matrix slurry mixture at pH 9 within 5 minutes) is ν<ί_ν initial (ie vy)), Is the molecule of the ratio SARCw. Therefore, if v total·v is less than or equal to 〇5 v at the beginning, the corresponding SARC^Va is less than or equal to 0.5. Therefore, as defined herein, the matrix of SARCw S 0.5 is substantially free of microporosity. / No mesoporosity (also known as macropores 126438.doc •27- 200902145,) A is based on the base of the SA-we-like or 兮-八士-like also in the 〇·ι m2/" spoon 50 m / g If these surface area parameters are met, there may be insufficient concentration, distribution and/or type of matrix for any other type of pore volume 'and thus may detrimental to the desired properties of the catalyst composition for the intended use. The effect of sodium surface area ("SA Qin") is an empirical titration Developed in the form of granulated, powdered and suspended sols (suspended s〇1 f〇rm) of substantially pure sulphur dioxide (3) (6). SA★ measures the reactivity and accessibility of the surface proton position (Glass-O'IT) The measure for pure silica dioxide is equivalent to the Si-〇.H+ position. The salt glass and crystal salt are significantly different in composition from pure cerium oxide (Si〇2). The stoichiometry, (4) the behavior of salt glass and crystal (tetra) acid salt can not be known or predicted according to the absolute value of the Na〇H titration solution in S·, the experiment, so the 'Se(10) and · used to test the SA ★ The equation relating the volume of niobium to the N2_bet surface area of the ceria material studied is not suitable for reliably predicting the absolute surface area of more complex tantalate compositions. This is expected because it can exist in the (7) (iv) ore with different composition of the glass. The group may include, for example, Α1-0·Η+, Β-ΟΉ+, Ti_〇-H+ u wood. U Η, Μβ-〇Ή+ and a plurality of Si-O-H+ portions combined with the early Shishi position More protons of different structures (Q2 group). m ',, 矽-like π glass combination The total surface area (eg, leached quartz) may be reliably determined using the SA·heart test, provided that the pore size of = is within the range of standard gas phase enthalpy measurements because it consists primarily of networked Si〇2 and Si. -〇-H+ part composition. + ~ • For, Glass- 〇H (4) diffusion accessibility of hydroxide ions and sodium ions, and micro-I26438.doc -28- 200902145 pore contrast medium pores, macropores And / or the percentage of the substantially non-porous area (four), should be based on the amount of NaOH (in the Μ * experiment to maintain the final positive value of 9 ' must be added in time) (titrant) (4). Therefore, in summary, the 'Glass-〇-H+ part of the 0H- and Na+ contrast between the day and the day's accessibility'\〇口 is determined in the above-mentioned SARC heart experiment, can be used as a reasonable and reliable measure of the existence of micro-pores 'including standard gas A certain type of porosity that is not comparable to the phase BET measurement. r Preferably, the surface area of the substrate will remain substantially unchanged after its ion leaching process, which is a common occurrence for most test ("AR") breaks. However, in some cases, some of the consumption from the matrix web does not significantly affect the microporous structure of the substrate, if any, thereby avoiding adverse effects on the desired performance of the catalyst composition to the desired material. ‘However, if there is significant ion depletion and associated leaching on the matrix network, microporous regions are likely to be produced in the matrix. Therefore, as mentioned above, sar. : Greater than about 〇5 indicates the presence of such a microporous structure. The fabric network of these characteristics has produced sufficient microporous structure, and (4) is injected in the base f region, which will adversely affect the ability of the substrate to maintain the surface active state. The desired properties of the composition to achieve the intended use have an adverse effect.基质. Matrix surface activation The matrix used to produce the precursor catalyst composition of the present invention, in particular, the proic acid catalyst of the FSC composition can be activated by a surface or a plurality of first components, the first component having The first type of ion and/or electrostatic interaction of the matrix (type 1 component precursor). As described in more detail below, the type 1 precursor may have catalytic activity by itself or may be further processed to produce 126438. Doc •29- 200902145 The active area 蛣, + + nano, the second =:, the average thickness on the surface and / or inside is the average thickness of the foot, the average thickness of r meters, more preferably about 10 nanometers. : In addition, for example, in some cases 'depending on the pre-composition of the catalyst composition', if the appropriate type of base is obtained, the inside of the consumption of the top use, the pore structure of X (if any) and At the isoelectric point (IEP), the substrate may have sufficient sound when it is received, and the ω is on the surface/tongue of the Du knife, which can be effectively catalyzed. Although not necessary, the 旱 '基质 substrate can be processed. Push, et慝 Come in - step to modify and / or improve its surface life. In addition, 'matrix can also By using #押卡# by processing to remove any organic coatings/contaminants that are expected to interfere with the performance of one, and the properties of the five substances. In addition, the 'in" type 2 ingredients are discussed in more detail below. Precursor integration treatment, depending on the intended use of the catalyst composition, it may be better to further treat the substrate by ion exchange () anti-ion parent (BIX) and/or electrostatic adsorption (EA) treatment. Surface treatment, such as phlegm, which integrates one or more second components onto and/or within the surface of the substrate having a second type of ionic and/or electrostatic interaction with the substrate and thereby producing a catalytically active region The average thickness on and/or within the surface of the substrate is 0 nm, preferably $2 〇 nanometer, more preferably $1 〇 nanometer. Substrate contamination removal treatment is typically on the surface of the substrate. The composition of the substance found and whether or not the substance is expected to interfere with the preparation of the catalyst composition and/or interfere with the desired performance of the catalyst composition to achieve the desired 'selection of the contaminant removal process. For example' Typically, AR type glass Manufactured using an organic coating (ie, sizing) 'The organic coating is used to facilitate processing, such as dispersion in aqueous formulations. However, even if it does not interfere with the majority of the catalyst composition 126438.doc 200902145邛) The catalytic properties of the intended use, the organic coating or sizing may also interfere with the preparation of the catalyst composition. Therefore, the organic coating should be removed. The sinter is suitable for removing such organic coatings. The preferred method is because the primary goal of the treatment is to remove contaminants from the substrate, such that the conditions of such calcination are not particularly important for successful surface activation of the substrate. In some cases, depending on the nature of the contaminant to be removed from the substrate, the solution r k = surfactant, aqueous solution cleaning or other suitable method can be used to remove the π dye and achieve satisfactory results. n The substrate is calcined in an oxidizing atmosphere, 歹1α air or oxygen, depending on the degree of use (d). It is also important to report that the calcination temperature is high enough to remove the target contamination (4), but the calcination temperature is again = reasonable to avoid the softening point of the material. Generally, the calcination temperature should be at least less than the softening point of the material. Preferably, the firing temperature is up to

(d) / The softening point of the matrix material is about 100 ° C lower. For example, when using AR, West, the majority of the glass is acceptable to remove the contaminants from about 300 ° C to about 700 ° C. Usually, the selected succulent material should be satin burned at about 2, and the choice of kiyoshi 枓 depends on the second time's better calcination for 4 to 8 hours. Nonetheless, the nature of the bismuth and the nature of the target contaminant to be removed from the substrate may vary outside of these time frames. The surface activation is achieved by ion leaching treatment::: After the potential contaminants are substantially removed from the matrix, the matrix can be used as the matrix active state and the desired isoelectric point ('-,), provided that C IEP is not present. Within the desired range 'however, a substrate that is received may have sufficient surface activity, and 126438.doc 200902145 is used - or a variety of other treatments (described in more detail below) for further step-by-step modification without the use of a first-class ion Leaching (IEX·) treatment (this will be discussed below, fine = Ming: first discussed in other treatments). 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 The IEP. However, in many cases, the elemental composition of the matrix will require some modification to change the initial wealth and obtain a suitable one (10), and then according to the predetermined composition of the catalyst composition, $ is obtained in the type and degree. a desired surface active state. The surface active state has (1) a first oxidation state and (9) a first type and a matrix ion and/or an electrostatic interaction with each other. In the case of action, it may be sufficient to produce a catalytically active region having an average thickness on and/or within the surface of the substrate of about 30 nanometers, preferably about 2 nanometers, more preferably about 1 nanometer. And thus providing the catalyst composition for the intended use: for example, but not limited to, Bronsted or Lewis acid on the surface of the substrate and/or within the Lewis and Louise The base site is effective to promote some hydrocarbons, hydrocarbons (such as oxygenated hydrocarbons) and non-hydrocarbon treatment, conversion and/or refining processes. However, in other cases, based on the intended use of the catalyst composition, a better way may be Using - or a plurality of ion exchange methods as described below: Step: Align the matrix table to achieve (1) a second oxidation state which may or may not be the same as the first oxidation state' and (ii) a second type of ion with the matrix And/or electrostatically interacting, I to produce a catalytically active region having an average thickness on the surface of the substrate and/or within S of about 30 nm, preferably about 2 nm, more preferably about 10 nm. — 126438.doc •32· 200902145 Now transferred to surface activation treatment, surface activity The treatment includes at least one of the ions' treatments to obtain a first or a class of ion exchange (ΙΕΧ-1) matrices. However, it should be understood that if the substrate being received has a suitable catalyst composition for the intended use, IEP, then IEX-i is also intended to be used to describe the first type of matrix. Typically, the ion leaching process is performed by any suitable method, and also 17: the effective removal of the entire substrate surface is required. Ion seeding without significantly eroding the matrix network (for example, avoiding the creation of any microporous structure in the surface region or subsurface region) such as, but not limited to, diterpenic acid, whether inorganic or organic, and Various chelating agents are suitable for ion leaching. Preferably, a mineral acid such as, but not limited to, nitric acid, acid, sulfuric acid, hydrochloric acid, acetic acid, peroxyacid, gas, acid, fluorescein, trifluoroacetic acid, and combinations thereof are used. The concentration of the acid solution used for ion leaching treatment depends on 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), and the substrate. The extent of the change and the intended use of the catalyst composition. Preferably, the concentration of the acid solution used for the ion leaching treatment may be between about 0.5 wt.% and about 50 wt%, more preferably between about 2.55 Wt_% and about 25 wt%, most preferably about Between 5 and (d). Chelating agents can also be used in ion leaching treatments such as, but not limited to, ethylenediaminetetraacetic acid (7) run"), words, oxalates, polyamines, polyacids, and combinations thereof. Usually used as chelate for ion leaching The concentration of the mixture solution depends on the characteristics of the substrate (for example, the affinity of the ions to be removed from the glass network, I26438.doc -33 · 200902145 the strength of the glass after removal of the network ions) and the composition of the catalyst Desirable use. Preferably, the concentration of the chelating agent solution used for the ion leaching treatment may be between about 0.001 wt.% and saturation, more preferably between about 纠1% and saturation. The heat treatment conditions for the ion leaching treatment, such as the heating temperature, the heating time, and the mixing conditions, are selected depending on the type and concentration of the acid or chelating agent used and the characteristics of the substrate. Depending on the concentration of the acid solution or the chelating agent solution The heating temperature varies widely, however, preferably, the heating temperature for the acid ion leaching treatment is between about 20 c and about 200 ° c, more preferably between about 40 〇c and about 95. Between 'best at about 6 (TC Preferably, the heating temperature for the chelating agent ion leaching treatment is in the range of about 2 (rc to about 2 〇〇t, more preferably about 40 ° C to about 90 ° C). Depending on the heating time of the acid leaching treatment of the acid solution or the chelating agent solution, the heating time can be treated between about 15 minutes and about 12 hours, depending on the temperature and the heating time, preferably for the change. For ion leaching to between about 48 hours, more preferably at about 3 Torr, usually depending on the type and concentration of the acid or meal used and the characteristics of the substrate (eg 'Isolation from the glass mesh Affinity, strength of the glass after removal of the mesh ions, etc.) and duration of the heat treatment, such as but not limited to 'mixing conditions may be continuous or broken, and may also be mechanical mixing, fluidization, tumbling, rolling Or manually mixing. In short, the 'acid or integrator doping, heat treatment conditions and mixing group 5 ' will be based on the ion or chelating agent and the target matrix ion to achieve enough 126438.doc -34- 200902145 ions and exchange (ΙΕχ Degree) is determined to produce The appropriate isoelectric point and the type and extent of surface electricity to achieve the surface active state required for the post-treatment of the substrate or the intended use of the catalyst composition. Suitable methods for separating the substrate by ion leaching, including but not limited to, by way of centrifugation, centrifugation, decantation, and combinations thereof, followed by one or more suitable cleaning solutions (eg, deionized water and/or suitable water solubility) The substrate subjected to ion leaching treatment is washed with an organic solvent such as methanol, ethanol or acetone, and dried at a temperature of about room temperature to 110 C for about 2 to 24 hours. The reverse ion exchange treatment is in some cases 'depending on the catalyst. For the purpose of the composition, it may be preferred to carry out reverse ion exchange mx") or two-step ion exchange treatment (collectively referred to herein as "ruthenium treatment") for the selected substrate. Βιχ treatment is commonly referred to as, but not limited to, “counter ion” exchange because the ion leached substrate is mixed with a salt solution (eg, NaCl) including the initially removed ions, and ion leaching treatment is performed from Zhe &; a ~ This ion removed by the shellfish (eg Na+) will then be returned or returned to the substrate. It is not clear whether the ions removed from the matrix will return to the same position originally occupied in the matrix. However, regardless of whether the initially displaced ion will completely or partially change position or not change position at all because of the hydrazine treatment, it should be understood that the machi processing described herein covers the placement of any such ionic sites. All catalyst compositions produced. Generally, the type of salt solution used to treat the substrate subjected to ion leaching treatment depends on the type of ion that will be countered by the counter ion exchange. Preferably, only one counter ion exchange of I26438.doc 35· 200902145 ions is carried out, y + ... In the case, counter ion exchange of two or more ions may be required. Any ion that can be easily removed by the method of honesty, real mountain + m i / out of the process can be counter-ion exchanged. Some examples of the _:,,. 4 ion include, but are not limited to, the first group (formerly the u-th) metal ions 'such as lithium, sodium and unloading ions, and from the second group (formerly Group IIA) The soil metal ions, such as wrinkles, towns, mother ions, NH/kunk (tetra) ions, and small organic polycations. Preferably, the metal ion and NH/ are the preferred target ions for the ruthenium treatment, while the Na+ and ΝΗ/ are preferred Βιχ ions, and the 系ιχ ions are better. Generally, the concentration of the salt solution used for the BDC treatment depends on the type of 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 retinoic ions are returned to the matrix network. Site-independent (eg, relative affinity of Na+ for matrix versus η+). For most types of glass substrates, such as, but not limited to, AR glass, bismuth glass or quartz glass, a BIX-salt solution having a concentration of about 1 m〇1/L to 5 m〇丨 is preferred, and about 〇 .〇5 m〇i/Li3 m〇1/L Βιχ_ salt solution is better. The heat treatment conditions for the BIX treatment, such as the heating temperature, the heating time, and the mixing conditions, are typically selected depending on the type and concentration of the BIX salt solution used and the characteristics of the substrate.

Preferably, the heating temperature for the β χ treatment using the BIX-salt solution may be between about 20 C and about 200 X: more preferably between about 3 Torr and about 95 ° C. 126438.doc -36- 200902145 Depending on the θN of the BIX-salt solution, the enthalpy of the array and the selected heating temperature, the heating time of the BIX treatment can be changed. Preferably, the heat treatment time of the BIX treatment is between about 5 minutes and about 24 hours, preferably between about 3 minutes and about 8. f U a depends on the type and concentration of the solution used and the nature of the substrate (for example, the affinity of the ions to be removed from the glass 4, the etched ions, the strength of the glass after the migration of the ions, etc.) and the heat treatment For the duration, select ί ° such as but not limited to 'mixing conditions can be continuous or intermittent, and can also be mechanical mixing, fluidization, tumbling, rolling or manual mixing. The combination of the barium salt, the concentration of the trough liquid, the heat treatment conditions and the mixing conditions is substantially determined based on the return of a sufficient amount and the distribution of a sufficient amount of the ionic ions back to the substrate, and the site of the ion in the matrix network Off:: Back and distribute a sufficient number of cesium-ion systems to produce the desired type and extent of surface electrical power to produce a surface active state desired for the intended use of the substrate or for the intended use of the catalyst composition. Adjusting the surface charge of the substrate by adjusting the enthalpy value 乂 $地' needs to support the positive charge with the negative surface charge on the substrate. (e.g., cationic alkaline earth metal, cationic transition metal component A) electrostatic interaction or affinity. However, for some potential touches, it is necessary to use a positive surface charge to support static electricity with a negatively charged 艾$々 (eg an anionic transition metal oxygen ion, a sulfate anion metal polydentate anion, etc.) Interaction or affinity. _ One

The surface charge of the substrate can be changed to net positive by adjusting the pH 126438.doc •37-200902145 of the ion-leached substrate/IEX mixture to a lower or higher than the substrate isoelectric point ("IEP"). State or net negative state. Think back, IEp is also known as zero charge ("ZPC"). Therefore, in other words, the IEP (or zpc) can be regarded as a {11 value of the material having a net zero surface charge on the surface at the time of initial humidity. Therefore, adjusting the pH of the Kibe/IEX water mixture to a value greater than the matrix IEp (or zpc) produces a net negative surface charge on the substrate. In addition, is the pH of the matrix/hydrophobic mixture adjusted to be less than the matrix ΙΕρ (or zpc)? A value of 11 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 AR glass subjected to the ion leaching treatment is adjusted to > 9.6? The ^! value will produce a net negative surface on the glass surface. Depending on the IEp distribution of the AR glass, the preferred way may be to adjust the pH to one or two or more pH units greater than the IEp of the substrate to ensure that its 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 (ie, to produce a net negative surface charge), and any dilute acid can be used to adjust the surface charge of the base I to the left of its IEP (ie, produce 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 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 type and density of the surface charge desired. In some cases, it may be desirable to integrate the catalytic component or precursor 126438.doc-38-200902145 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 may not occur. However, in the absence of theoretical constraints, direct ion exchange (ΙΕχ) or reverse exchange (BIX) may occur at the surface of the parent, resulting in surface integration of the catalytic component or precursor, 砀The catalytic component or precursor may be physically and/or chemically distinct from the same components that are integrated under the electrostatic adsorption (EA) mechanism. For example, certain surface portions of the matrix include cations (or anions) that may be replaced by ionic catalytic components or precursors of the same symbol. These surface portions of the substrate may be provided for proper or effective IEX or BIX with the surface portion of the substrate. Exchange location. For example and without limitation, such moieties, such as a decyloxy (-Si-0_Na+) moiety, include at least a portion of a positively charged catalytic metal or metal complex precursor (such as, but not limited to, Pd(NH3)42+ Substituting Na+ ions to produce a matrix having a catalytically effective amount of a catalytic component. The surface charge of the BIX-treated substrate is controlled by adjusting the pH as in the case of IEX processing or second: [EX processing ("ΙΕχ_2 processing, as discussed below), for some BIX processing 'may need to be adjusted pH, but not required. Similarly, depending on the type of BIX-ion that will be integrated into the surface and the exchanged BIX-ion type in the ΙΕχ_2 treatment, the degree of ipH adjustment required will generally depend on the enthalpy of the substrate, its ΙΕΡ contrast surface charge distribution curve, and the type of charge desired. 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 mobility and other factors. In general, any dilute base can be used to adjust the surface of the substrate to the right side of its IEP (ie, to produce a net negative surface charge), while 126438.doc -39- 200902145 can be used to adjust the surface charge of the substrate to The left side of its IEP (ie, produces a net positive surface charge). The inorganic acid or base or the organic acid or base can be diluted. 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. III. Type 2 component precursor integration treatment

The surface of the flawless matrix is received as is, either by ion leaching (ie, IEX-1 treated substrate) or by hydrazine treatment, preferably at (1) second ion exchange (,, ΙΕχ·2" Processing the (ii) electrostatic adsorption (EA) treatment or (m) the combination of certain IEX-2 and EA treatments using at least one second component precursor ("type 2 component precursor") to further treat the substrate so that The one or more second component precursors are integrated on and/or within the surface of the substrate having a second ion and/or electrostatic interaction with the substrate. Next, certain Type 2 component precursors may be used to produce catalytically active regions without further processing, or may be further processed to produce catalytically active regions comprising one or more Type 2 components, depending on the intended use. However, the catalytically active region is composed of (a) a type 2 component precursor composition '(b) consisting of a type 2 component derived from a type 2 component precursor' or (4) consisting of a combination of (4) and (b), catalyzing The average thickness of the regions on and/or within the surface of the substrate is about 3 nanometers nanometer, preferably 'about 20 nanometers, more preferably about 1 nanometer nanometer. As previously mentioned, in some cases, depending on the intended use of the catalyst composition, the substrate received as received or ion leached may have catalytic activity. However, it is generally preferred to 'for many potential applications' to perform IEX-2 and/or EA treatment on selected substrates. For example, but not limited to, many of the processes suitable for the process of 126438.doc 200902145 == bright catalyst composition, selectivity and / or two: seeding: fine by replacing at least a part of the first component (eight) type of ingredients ") and One component ("type 2 ingredient") is significantly increased in integration with the surface of the substrate. Without being bound by theory, 'directly or indirectly ionic phase 2 acts by a specific ion exchange site on the surface of the substrate or on the surface of the substrate, by electrostatic interaction with the surface of the oppositely charged substrate. Mutual use 'and some combination of ionic interactions and electrostatic adsorption interactions or some other type of precursor to be understood. Charge-surface interaction, type 2 component precursor ions can be integrated. However, regardless of the nature of the interaction: 'in the case of the substrate received as received, the treated substrate or the substrate treated with the ruthenium to produce a second precursor charge-surface interaction ^ 2 component The precursor may thus produce a catalytically active region having an average thickness on the surface of the substrate and/or within a range of 3 Torr, preferably about 2 Å, more preferably about 1 Å. Meter. For the convenience of the following discussion, and without intending to limit the invention as described herein, IEX_2 is used herein to collectively refer to the extensive interaction of precursor-type surface interactions or type 2 component precursor interactions commonly referred to as 2_type components. . In general, the type of salt solution used to treat the IEX-1 treated or ΒΙΧ treated substrate will depend on the type of ion to be ion exchanged in the specific 2 treatment. Either an ion will undergo ion exchange or, in some cases, exchange of two or more ions, or simultaneous ion exchange' or ion exchange in sequence. The integration of two different types of precursor ions with the matrix I26438.doc -41 · 200902145 The following is the treatment of IEX-2 called two ion exchanges or two off-2 in a different type of component precursor In the case where the ions are integrated with the substrate, the mx-2 treatment is called three-ion ion exchange or three-times. Description of Type 2 Ingredients and Precursor Any salt solution of ΙΕΧ·2 ions can be received as it is if it is chemically easy to replace. The ions on the surface of the treated or treated substrate, or ', have charge affinity to achieve electrostatic interaction with the surface of the substrate treated by IEX_W or βιχ_, can be used. Therefore, the 'EXX-2 ion can be used as a precursor to the type 2 component. As described above, according to its intended use, the plasma ΙΕχ_2 precursor (ie, type 2 into i, such as a flood) may be right he & this has catalytic effect, and if so, the plasma IEX 2 just drives It is enough to work like a type of component in a certain type of catalyst composition, and it can also be used as a precursor to Cong _2 in the process of preparing another type of catalyst composition. Work. "In general, 'ionic IEX.2 precursors (which can be used to obtain a type 2 component that is integrated with the surface of the substrate) include, but are not limited to, Blenbuter or Lewis acid, Blenzide or Lewis base, noble metal cations and t Metal mismatched cations and anions, transition metal cations and transition metal complex cations and anions, transition metal oxyanions, transition metal chalcogenide anions, main oxyanions, self ions, rare earth ions, rare earth complex cations and anions and Similarly, depending on the intended use of the catalyst composition, certain ΐΕχ_2 ions themselves have a catalytic effect in the precursor state, and when combined with a suitable matrix, a type 2 component can be produced. Alternatively, without further processing Catalytic 126438.doc -42- 200902145 Efficient ionic IEX_2 precursors 'Some examples of Sterling or Lewis acid, Brunsett or Lewis test, _^ not limited to the transition metal cation, transition metal oxyanion = cation , heterogeneous; main knowing Gong anion, halogen:: earthworm oxygen ion, rare earth oxide ion and combinations thereof. Certain precious metals and transitional golds of the precursors of the composition, including but not limited to the 7th & $ Chu〗 1 / Brother 7 to the 11th (formerly the ib, IIb, Chu^ , group % and group VI11), such as turn, put, zinc, sub"n mu, iron, short, zinc away::: mixed ion salts and combinations thereof. For coffee processing, Ji, Xu, and chain copper, silver 'gold and recorded ion salts are especially preferred. The elements of the family can be made by making the element family number of the IUPAC naming system http://pearll.lanl.gov/periodic/defaulthtmt m - Γ ^ . The chemical element of the periodic table (and not shown in the previously used family number) is queried. = Examples of certain transition metal oxyanions as precursors of type 2 components: including but not limited to groups 5 and 6 (formerly Groups Vb and VIb): salt salts 'eg W, ~·, Η2~〇4Λ, MQ〇42-, ^db6〇, ReCV and combinations thereof. For the ΐΕχ_2 treatment, ionic salts of pins, tungsten and rhenium are especially preferred. Apricot can be used as a precursor to a type 2 component. Some transition metal chalcogenide anions are not limited to the ionic salts of Group 6 (formerly the genus), such as M〇S42-, Ws42-, and combinations thereof. Examples of certain main oxygen anions that can be used as precursors for type 2 components, including (iv) (iv) the first ionic salt of Group Vla), for example, 12643S.doc • 43- 200902145 P〇4, Se〇42- and combinations thereof . For ΙΕχ_2 treatment, S (V_ ion cans are particularly preferred. Some examples of ionic ions that can be used as precursors for type 2 components, including but not limited to ionic salts of Group 17 (formerly Group VIIa), such as F ·, ci., I· and combinations thereof. For IEX_2 treatment, the ion salts of F• and C1 are especially preferred. It can be used as a type 2 “some rare earth ions and rare earth complex cations or ions examples, including but It is not limited to lanthanides and ionic salts of lanthanides such as La, Pr, Nd, Pm, Sm, Eu, (6), several, d"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 include, but are not limited to, chromium, molybdenum, tungsten, rhenium, Ion salts of iron, iron, nickel, and nickel, and combinations thereof. MX-2 treatment instructions Generally, the concentration of salt solution used for IEX-2 treatment depends on the treatment with χ-丨 or BIX- and is treated by ΙΕχ_2. Matrix type and ΐΕχ for interaction and/or integration with ΙΕΧ-1 treated matrix 2 ion relative "spray force for most types of glass substrates (such as but not limited to ar type, strontium type or soda calculus (s〇da_Hme) glass), about 〇〇 (H wt % to saturated IEX-2 salt The solution is preferred, and about 5% to 5 liters of the 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 salt The solution may be less than 0.001 Wt.%. If multiple ion types are exchanged with the matrix, either simultaneously or in sequence 126438.doc • 44- 200902145 The concentration of the salt solution will be as required for the precursors of the various components on the substrate. The loading and matrix are suitable for adjusting the relative affinity of a component precursor to another component precursor, such as, but not limited to, two IEX-2 treatments (ie, two different catalytic component precursors and - treatment of matrix integration) or three times Εχ 2 treatment (that is, the integration of three different catalytic component precursors with the matrix of the seven-go fresh processed), used to precipitate various ions, g 择, take It depends on the target relative concentration of various types of precursors with base and positive 5 and the affinity for various surface. Typically, it will be based on the characteristics of the muscle 2 salt and matrix used, π 视 ^ ^ ^ The heat treatment conditions for the IEX·2 treatment, such as the heating temperature, the heating time, and the mixing conditions. The heating temperature J for the 1ex-2 treatment using an acid may be 20 ° C to about 2 勺. , ® between the mountains is between about 30 t: to about 9 。. The concentration of the IEX-2 salt solution and the selected heating temperature are used to add to about; hour: t; The type and concentration of the 1EX_2 salt solution used and the % of the matrix such as the affinity of the ions to be removed from the broken mesh, the strength of the glass after the ion, etc., and the duration of the heat treatment are: two =:? Without limitation, the mixing conditions may be continuous or broken, ',, mechanical, fluidized, tumbling, rolling, or manual mixing. 126438.doc 45· 200902145 In summary, the concentration and combination of IEX-2 salt solution are essentially based on the base 皙, heat treatment state and mixing conditions.

And to the extent that the desired surface activity state of the catalyst composition is achieved. / Adjust the surface charge of the substrate by adjusting the pH. ('’IEX-2")

Type of charge. 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. ... as described above, considering the type of solution used to perform the pH adjustment in the second integrated type II IEP, depending on the compatibility with other reactants, the matrix is within the relevant pH range. The stability and the required density and other factors. Generally, any dilute base can be used to adjust the surface charge of the substrate to the right 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 of its IEp (ie, produce Net positive surface charge). The inorganic acid or base or organic acid or base can be made dilute in concentration: 'and usually an organic base is preferred. Generally, 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 1EX_2 treatment is completed, the IEX-2 treated substrate can be separated by any suitable means including, but not limited to, filtration, centrifugation, decant, and combination thereof. The substrate treated with ΙΕχ_2 is then washed with - or a suitable cleaning solution such as distilled or deionized water, a dilute or dilute acid and/or a suitable water-soluble organic solvent such as a mercaptan, ethanol or acetone, and Dry at a temperature of about 1 to 24 hours for about 2 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 without calcination or not calcined. In the case of oxidation. The surface metal precipitated transition metal ions, oxygen anions and/or may be subjected to a suitable reduction, sulfurization, carbonization, nitridation, squaring or aging test (-IDING reagent) as described in the gas phase or in the liquid phase. The reaction of the sulfur anion is a catalytically effective metal sulfide/sulfur oxide, metal carbide/carbon oxide, metal nitride/oxynitride, metal boride or metal phosphide component. Usually, but not limited to, the purpose of the post-precipitation calcination treatment is to substantially decompose the metal counter ion or ligand, and to integrate the metal, the metal oxide, the metal chalcogenide, etc. closely with the S-type surface, and remove any Residual water removed in the previous drying process. The calcination conditions for the IEX-2 treated substrate are not particularly important for successful surface activation of the substrate, however, these conditions should only be sufficiently stringent to produce at least one precursor with precipitated components in a catalytically effective amount. Active area. However, in the case of the use of a burn, the substrate is first calcined in an oxidizing atmosphere (e.g., in air or oxygen). In addition, it is important to select a sufficiently high calcination temperature to ensure that the 126438.doc -47- 200902145 ^ tool is oxidized and any residual water is removed (if any residual water is present), However, the calcination temperature should also be low enough to reasonably avoid the softening point of the matrix and the decomposition of the undesired precipitate component precursor. For example, without limitation, the sulphate salt requires calcination conditions to decompose the cations and immobilize the sulfate on the surface, but such conditions do not significantly decompose the sulfate into volatile sulfur oxides. Similarly, metal oxyanions require calcination conditions to decompose the bound cations and immobilize the anions as oxides on the surface, provided that the conditions are such that the metal oxides volatilize from the surface or cause the metal oxides to dissolve into the matrix. Finally, precious metals and complexes should be calcined under the following conditions: the ligands and anions present in the decomposition should 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. Generally, the calcination temperature should be at least about 〇〇 c lower than the softening point of the selected substrate. The calcination temperature should be about 100. 〇 to 700. Between 〇, it is better between about 2 〇〇 and 600 ° C, preferably at about 300. (: to between 500 ° C. Typically, the IEX-2 treated substrate is calcined from about i to about μ small days, preferably better than about 2 to about 12 hours. However, the matrix is integrated. The calcination time may vary outside of these ranges depending on the type 2 component. The use of the reduction treatment after precipitation is aimed at at least substantially, if not completely, oxidizing the catalytic component precursors (e.g., metals, metals). The material 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. Hz is preferred reduction 126438.doc -48-200902145 L/hr to about 100 The L/hr to 1 L/hr agent's flow rate is preferably between about 1 L/hr per gram of substrate, and more preferably between gram per gram of matrix 。. Typically, the reduction temperature should be Between (^(4) generations' the premise is that the selected temperature is at least 1 低 lower than the softening point of the matrix. Typically, the substrate treated with IEX-2 is subjected to a reduction treatment of from about 1 hour to about 48 hours, preferably. After about 1 hour to about 8 hours of reduction treatment. The 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 in a suitable solvent such as water or diethyl ether.

Usually, but not limited to, the purpose of the IDING reaction treatment is to reduce the metal ion, the metal oxyanion and/or the metal sulphur over the other while reacting the reduced metal with a reagent containing a lower atomic amount of _miNG element. In some cases, direct _IDING will occur without simultaneous metal oxide reduction, such as some vulcanization. Typical gas phase-IDING reagents include, but are not limited to, hydrogen sulfide, methyl mercaptan and monomethyl sulfide (sulfiding reagent), ammonia (nitriding reagent), methane, ethane, and other light hydrocarbons (carbonizing agents). The gas phase-IDING reagent can be directly reacted with the substrate treated with the ratio of \_2 under ambient pressure or under pressure, or reacted with the substrate treated with IEX-2 in a gas mixed with an inert gas or hydrogen. , which in turn produces the corresponding sulfides, carbides or nitrides. Part of the catalytically potent _IDED product (including sulphur oxides, carbon oxides and oxynitrides) can also be produced by: receiving, receiving 126438.doc • 49-200902145 as it is, The incomplete reaction was carried out by an IEX-2 treated integrated substrate, a ruthenium-based treated calcination group f or a ruthenium-2 treated reduction substrate. The metal phosphide can be produced by two ion exchange (two ΙΕΧ-2 treatments) reduction treatment of the substrate, wherein - the 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. In addition, metal scales can be produced by using a rolling phase phosphating reagent such as, but not limited to, phosphine.

The metal to be _. For example, a substrate (in a single ΐΕχ-2 treated substrate) with a desired transition metal in a suitable oxidation state can be further treated with ΡΗ3 to produce the desired metal phosphide. / combined liquid phase treatment can be used to produce metal sulfides, metal borides and metals; the typical solution treatment of this ruthenium catalyzed knife to produce metal sulfides includes, but is not limited to, in the range of temperature to reflux temperature, β, effective concentration The ruthenium disulfide organic solution is treated with a ruthenium-2 treated metal ion-integrating matrix for a time sufficient to produce a catalytically effective amount of a catalytic component on and/or within the surface of the substrate. Typical examples of cleavage formation are _, wave 4th _ 丨田->, i / 奋 / night phase treatment including, but not limited to, for IEX-2 treated metal. Ions. Integrated matrix, at room temperature to reflux The temperature of the 1 calendar is effective time for the treatment of rotten hydrogen steel or rotten nitriding bell aqueous solution. A typical solution for the production of phosphide phase step > soil/complex phase treatment includes from room temperature to reflux. 'For the treatment of IXX-2, the genus "the beta landlord (the disk-ion-integration matrix) The aqueous solution of sodium hypophosphite is treated for a sufficient period of time to achieve a catalytically effective amount of catalytic component on and/or within the surface of the substrate. V. Catalytic Active Region Description 126438.doc • 50- 200902145

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 nanometers, preferably about 2 nanometers nanometer, more preferably about 10 nanometers, 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 catalytic component versus the surface of the base of the knife. 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 this technology have a thorough understanding of XPS or TEM programs. It should be understood that in the extreme case, regardless of whether the catalytically active region is produced by treatment with ιε^ or ΙΕΧ-2 (with or without hydrazine treatment), the catalytically active region is substantially ± for any of the catalyst compositions of the present invention. , slave U) will not be in the surface area of the tooth k or (b) will not exceed the surface of the substrate about 100 meters thick, preferably * more than about 2G nanometer thick, more preferably not more than the thickness of the rice. With regard to the localization of one or more catalytic: regions on the treated substrate and/or within the catalytic region, it is also understood that the catalytically active region may: live (a) on the outer surface of the substrate, and in the presence of any pores, in the pores of the substrate (b) In the surface region of the substrate, that is, outside the matrix, it is preferably about 20 mils, and is preferably about 20 nm below the outer surface of the substrate, temporarily from the main I scale below the outer surface of the base. 10 nm; when there is any pore, about 30 nm below the surface of the pore wall, preferably in the matrix soil U soil surface is 126438.doc •51 _ 200902145 under about 20 nm' better in its皙 _ * 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在On the surface of the wall of the substrate pore or on - and partially in the surface area of the crucible, or the combination of (d) (a), (b) and (c) of π. Usually, no matter what! The type component or the type 2 component, the catalytic component is between _2. 2 wt.% to about 5 wt.%, preferably between about 〇 礼 % to about 2 wt.o / o, more preferably about 〇. _5 wt% to about i correction%. Moreover, the catalytically active regions of the catalyst compositions of the present invention can be continuous or discontinuous. Without being bound by theory, it is believed that there is discontinuity: the catalytic composition of the catalytically active region is less than the catalytic component substantially covered by a continuous or broader continuous catalytically active region. Valid ^ and in some cases more effective. The extent to which the catalytically effective region covers the outer surface of the substrate can range from as low as 0.0001% coverage to as high as 1% coverage. Preferably, the extent of surface coverage outside the catalytically active region is between about 0.0001% and about 10%, more preferably between about 1% and about 1%. However, without being bound by theory, it is believed that the catalyst composition, particularly the catalyst composition having a lower catalytic component wt% loading, is likely to be more catalytically effective because of the treated substrate. The upper and/or inner catalytically active regions become more dispersed (i.e., more widely distributed and separated between the catalytically active regions). The catalytically active regions and other characteristics of the above-described catalyst compositions are based on the best conditions of the catalyst composition for the state of the catalyst composition prior to entering the steady state reaction conditions 126438.doc -52 - 200902145 in Bellow. 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, it is believed that the functional surface activity of the catalyst compositions described herein will permit the charge and/or charge of the catalytic component integrated with the matrix as the catalyst composition promotes its intended process reaction. 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 precursor composition having at least one catalytic component. The precursor catalyst composition can be prepared by ion exchange, impregnation, precipitation, coprecipitation or other catalyst composition preparation methods, as long as the process produces a precursor catalyst composition in which at least one catalytic component is After being mixed with the high temperature resistant igniter oxide, it remains substantially dispersed in the front, in the drive catalyst composition and/or on the composition. Additionally, the preferred at least one catalytic component of the precursor catalyst composition remains substantially dispersed in the precursor catalyst composition matrix after the composite catalyst composition is exposed to steady-state reaction conditions for the intended use for at least - hour. Inside and / or on the substrate. Precursor Catalyst Description Precursor catalyst composition is produced prior to mixing with the oxide. The precursor catalyst composition matrix dispersed throughout the refractory inorganic oxide used to produce the composite catalyst composition is typically selected from the group consisting of ruthenium containing materials, substantially stone free materials, and mixtures thereof, as discussed in more detail above. More: the eve of the night. However, in any case, the matrix substance of the precursor catalyst composition is 126438.doc -53- 200902145 microporosity / no mesoporosity, but is not limited to glass breaking, carbonizing hair, nitriding; Examples of Shangjing materials include, but are not limited to, == porcelain, alpha alumina, θ alumina, shellfish..., tantalum pottery. Decrease #, niobium titanium, carbon and mixtures thereof However, the precursor catalyst composition is preferably a FSC composition prepared according to the preparation. However, in addition to the methods described herein for the description of the surfactant composition, the method of preparing the catalyst precursor composition can also be used to prepare the catalyst precursor composition to other known in '1 and for the composite contact for damage. What is the other high-quality component of the media composition? (After any 4 Tt σ, it remains substantially dispersed in the composition and/or the composition. This requirement is familiar with the catalyst.) Other methods for preparing the precursor catalyst composition will be well known. Technical use: The average size of the minimum particle size of the matrix of the precursor catalyst composition is generated. The size of the material is greater than about G.Q5. The micro (four) is less than or equal to a force of between 150 microns, preferably about 微2 micro/, and J is between microns and about 50 microns. However, depending on the intended use, matrices outside the above range may still be effective, which may adversely affect the intended performance of the combined catalyst composition. 2 Those skilled in the art should understand that 'composite operations may blend potentially large/, 'intermediate pores and/or microporosity into the composite material of the composite material: and the composite catalyst described herein. Two: Xikong: When the component is compounded, the precursor catalyst composition is not introduced into the 126438.doc-54-200902145 composite high temperature inorganic oxide for the convenience of 'for use with fully dispersed precursors The medium is formed into a complex catalyst composition, and the high-temperature benefits of the composite catalyst are also referred to herein.

Complex 5 high temperature resistant inorganic oxide, or further referred to as composite high temperature oxidation: no. The surface area of the composite refractory oxide is generally in the range of about (10) coffee m'g and preferably in the range of about 50 to 25 Torr, and the apparent bulk density is from about 0.2 g/mL to about i.8 g/ The mL, preferably from about 2 §/社 to about g/mL, but depending on the intended use of the composite catalyst composition, the surface area and apparent bulk density of the composite temperature-resistant oxide may exceed the aforementioned range. In any event, such 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. The refractory inorganic oxides forming the composite catalyst composition include, but are not limited to, gamma (gamma) alumina, δ (delta) alumina ' η (eta) alumina, yttrium alumina, alpha alumina, cerium oxide - Alumina, zeolite molecular sieves (i.e., zeolites), non-zeolitic molecular sieves (NZMS), non-screen oxides, titanium oxide, oxidization, and mixtures thereof. 〉 Examples of feldspar include, but are not limited to, zeolite Y, zeolite X, zeolite L, zeolite beta (beta), alkaloid zeolite, MFI, UZM-4 (see U.S. Patent No. 6,776,975), UFI, UZM-8 (USA) Patent No. 6,756,030), UZM-9 (U.S. Patent No. 6,713,041), zeolitic and erionite. Examples of non-zeolitic molecular sieves include, but are not limited to, aluminum arsenate (SAPO) as described in U.S. Patent No. 4,440,871, ELAPO as described in U.S. Patent No. 4,793,984, and MeAPO as described in U.S. Patent No. 4,567,029, I26438, doc-55-200902145. All of these patents are incorporated herein by reference. Examples of non-screen 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 and is described, for example, in U.S. Patent No. 3,909,450, the disclosure of which is incorporated herein by reference. Preferably, the high temperature inorganic oxide is gamma, eta alumina and zirconia. The composite refractory inorganic oxide is produced using methods well known to those skilled in the art to impart > the desired viscosity or slightly (e.g., paste, dough, etc.) for combination with precursor catalysts. Mix and mix any other optional components (described below) as appropriate. Depending on the viscosity or consistency of the composite inorganic oxide composition, the mixing method for sufficiently diffusing the pre-prepared precursor catalyst composition throughout the composite inorganic oxide includes, but is not limited to, violet mixing, ball milling, polishing paste, and Hehe. The precursor catalyst composition/composite refractory oxide mixture is used to produce the current catalyst composition and any other optional but suitable components after thorough mixing with the composite high temperature and temperature resistant inorganic oxides. Formed catalyst composition. However, at least an extrudable dough-like composition of a composite high temperature resistant oxide and precursor catalyst is generally preferred for use in the formation of a composite catalyst composition (discussed in more detail below). Forming a composite catalyst composition, thereby forming a composite contact by combining at least one composite refractory oxide and at least one pre-prepared precursor _, a sheet compound to produce a composite pair of high oxide/precursor catalyst mixture Medium composition. For example, a composite oxide 126438.doc • 56 - 200902145 high temperature oxide dough can be formed and the precursor 7 蜾 蜾 grade compound is mixed into the dough. Including but not limited to non-screening oxides kk which stone molecular sieves, non-zeolitic molecularists, sarcophagus, clay and gold g | _ oxide a other combination of other components can also be mixed with the lumps to form (you For example - ^ Mucha (for example, by extrusion) to generate a polar catalyst composition.

After the composite refractory oxide is substantially formed (for example, 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 contact. A composite refractory oxide/precursor catalyst mixture of the vehicle 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: a mixture of water and an organic solvent may also be used. The mixture may also contain certain agents which promote the diffusion of the oxides of the temperature, 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 in the aqueous slurry mixture and adding the precursor catalyst composition before or after substantially completing the milling stage. When the slurry mixture is produced, it is preferably dried and calcined into flakes. Inorganic binders can be used where appropriate. Examples of inorganic binders that may be added to the slurry include, but are not limited to, Zr〇(C2H3〇2)2, ZrCKNC)3)2, ZrO(〇H)Cl.nH20, zirconia sol, ZrOC〇3, Ζγ〇 ( 〇η)2, Zr(C5H802)4, Zr(S04)2.4H20, alumina sol, cerium oxide sol, citric acid and soft boehmite. The inorganic binder produces an inorganic oxide binder by calcination. The inorganic oxide binder can assist in strengthening the primary or virgin-protective mesh of the high-helmet composition of the 126438.doc-57-200902145 catalyst composition, or as a composite touch composite When the composition is medium, check = warm oxide. However, in the formation of organic oxide binders, especially in the case of high temperature oxides, it is often unnecessary to use a compound. For 3 & 吏 using a "combination method to form a composite catalyst group, the decomposition of the heat when the second suspect: = the appropriate agent" can be used in the addition agent. Therefore, in the appropriate Γ; = compound to form inorganic oxide viscous, oxidized, titanium oxide and _ Lu. The second inorganic oxide binder preferably provides the same high temperature oxide as the emulsion: but, in general, any compound binder can be used with any composite refractory oxide. The high temperature resistant oxide is fossil, titanium oxide, or sulphur dioxide, or an oxidized etchant can be used. However, it has been found that it is preferable to have an oxidative bonding agent when oxidizing the wrong ',, and after combining the surface temperature resistant oxide. The amount of mouth fluid = rwtrr of the binder (if any) should be in the composite catalyst composition ', ', ,, Wt. ° to about 99 wt.% of the inorganic oxide binder. Preferably, the amount of domain reduction used provides an inorganic binder from about 2 to 4 Å wt 〇 in the composite catalyst and provides an optimum amount of 5 to 30 wt. of the composite catalyst: Depending on the particle size of the composite refractory oxide, it may be necessary to grind 1 to reduce the particle size while providing a narrower particle size distribution. Grinding methods known in the art include, but are not limited to, ball and pulverized grinding to ensure adequate mixing of the various components and, if desired, to reduce the particle size of the composite high temperature resistant compound and/or precursor catalyst composition. The milling is usually carried out for about 8 hours, preferably about 2 to about 8 hours. , ', · 5 126438.doc • 58- 200902145 After the composite refractory oxide/precursor catalyst composition mixture is produced, the method known to those skilled in the art of forming materials can be made into any desired Shape forming materials, including but not limited to spherical, rod-shaped: pellets, granules, ingots, granules, extrudates, rings, saddles, three (5) large and other forms known to those skilled in the art. Composite catalyst composition one. Once formed into a desired shape (e.g., an extrudate), it will be dried at a temperature of from about 10 passages to about 3'C (preferably about 1 Torr to about 1 hour). After f is calcined at a temperature of at least about the war for about 5 to about 10 hours to = the catalyst composition. In general, the two conditions of the composite catalyst component are selected to be more complex than the composite refractory oxide and the precursor catalyst composition. In addition, depending on the intended use or process application of the composite catalyst composition, the calcination conditions can be used to optimize the properties of the composite refractory oxide such as, but not limited to, surface area, structural integrity, and pore volume. : "The degree of combustion is preferably better than the combustion temperature or structure of the precursor catalyst composition of about 20 〇V 二" 〇〇 C. However, in general, the preferred calcination temperature is from about . 〇, preferably from about 400 ° C to about; i 10 (rc, and preferably from about 4 〇〇 t to about 8 〇〇 t. 仏 eight IT two or more calcination steps 'to be in at least one catalytic group Any point after the contact of the parting machine oxide can be forged twice: 5 in the temperature range between 200 C and about 5 〇〇. 烺 „ 烺 。 。 。 煅 煅 煅 煅 煅 煅 煅 煅 煅 煅 煅 煅 煅 煅Between about 1 and f hours. In general, the composite catalyst έ is surrounded by (4) 2; the concentration of the ruthenium precursor catalyst composition is 4 (weight: $), preferably from about 1% to 9〇% (by Weight), 126438.doc •59- 200902145 Better from about 1 to about 8θ% (by weight), and the best from about i to about 7 〇 Q / (in terms of heavy weight), like the moon, The concentration of the catalyzed catalyst composition in the composite catalyst group σ depends on its intended use, the activity of the precursor catalyst composition against 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 in the composition, the lower the concentration of the precursor catalyst composition in the composite catalyst composition. The invention will be described in more detail in the following examples, which are to be construed as illustrative or equivalent. Examples of catalyst compositions with macroporous glass substrates Example 1 Palladium on macroporous glass was obtained from a large pore foamed soda lime glass sample produced by Dennert Poraver's glass having an average diameter of about 4 to 125 microns. The first step is to carry out acid leaching treatment on the macroporous glass sample received as received and not calcined. About 25 grams of macroporous glass sample and 3 liters of 5 5 wt.% of nitric acid are each placed in 4 liters of plastic. Inside the mouth container, place the plastic container in a ventilated oven at 30 ° C for 30 minutes, and shake it slightly by hand every 1 minute. After the acid leaching treatment, use Buchner with Whatman 54 1 filter paper. The sample was filtered through a funnel and washed with about 76 liters of deionized water. Then, at the temperature of the crucible, the acid leached sample was dried 126438.doc • 60· 200902145 dry 22 small The first step is the ion-exchange (IEX) treatment of the large-porosity glass in the acid-immersed treatment. In this example, p-tetramine palladium [Pd(NH3)4](〇H) is used. 2 Prepare heart-lift (M wt.% of the liquid for ion exchange (,, ΐΕχ solution)).

A 4 gram macroporous glass sample was added to the ion exchange solution ("glass/ion parent exchange mixture Ί. Measure the enthalpy of the glass/ion exchange mixture to give a Η value of about 10.3. Then 'move the mixture into 15 〇 In a milliliter plastic wide-mouth container, place the plastic container in a 5 〇 ventilated oven for 2 hours, and shake it gently with the tip of the hand every 30 minutes. After the ion exchange process is completed, use the paper with Whatman 54!1 The Buchner funnel passes through the (four) glass/ion exchange mixture' and is cleaned with about 3.8 liters of deionized water. (d), the ion exchange glass is dried for 22 hours at u (rc temperature). The second step is to reduce the ion exchange glass. The ion-exchanged glass was first calcined in an air atmosphere at an air flow rate of 2 L/hr and at a temperature of 3 Torr for 2 hours, and then at a hydrogen (Η?) atmosphere of a hydrogen (Η?) flow rate of 2 L/hr and Reduction at a temperature of 3 ° C for 4 hours. Analysis of the sample by inductively coupled plasma-atomic emission spectroscopy (icp_aes) yielded a palladium concentration of approximately 0.098 wt.%. Example 2 Palladium on macroporous glass was obtained from Dennert Poraver The macroporous foamed soda lime glass sample produced is a glass bead having an average diameter of about 40 to 125 microns. The first step is to perform acid leaching on the macroporous glass sample that is received as received and not calcined. It will be about 25 grams. Large pore glass and 3 liters 5.5 wt.% of 126438.doc -61 _ 200902145 The sulphonic acid is placed in a 4 liter plastic wide-mouth container. The plastic container is placed in a 30t ventilated oven for 30 minutes, and each 1 Shake it by hand for a few minutes. After the acid leaching process is completed, the sample is filtered using a Buchner funnel with Whatman (4) filter paper and washed with about 7.6 liters of deionized water. Then, at a temperature of 110 ° C, the The acid leached sample was dried for 22 hours. In the second step, the acid leached macroporous glass sample was subjected to ion exchange (IEX) treatment. In this example, dichlorotetramine palladium [pd (cis Aye & preparation 80 ml) was used. 0· i wt.% of palladium solution for ion exchange ("ΐΕχ solution. Add 4 gram of macroporous glass to the glass/ion exchange mixture in the ion exchange solution). Measure the value of the glass/ion exchange mixture , get 1) 1 The value of 1 is about 8.1. Then, the mixture is transferred into a 15 inch plastic wide-mouth container. The plastic container is placed in a 50 t ventilated oven for 2 hours, and shaken slightly by hand every 3 minutes. Ion exchange treatment After completion, filter the glass/ion exchange mixture using a Buchner funnel with Whatman 541 filter paper and rinse with approximately 3.8 liters of deionized water. Then dry the ion exchange glass for 22 hours at U (rc temperature). The ion-exchanged glass was subjected to a reduction treatment in which the ion-exchanged glass was first calcined in an air atmosphere at a flow rate of 2 L/hr and at a temperature of 2 L/hr in a hydrogen atmosphere and 3 Torr. Reduction at (at 4 hours). Sample analysis by 1CP AES yielded a concentration of approximately G.045 wt.%. Example 3 Palladium on macroporous glass subjected to BIX 126438.doc -62· 200902145 The large-pore foamed soda-calcium glass sample produced by Dennert Poraver' is a glass bead with an average diameter of about 40 to 125 microns. The first step is to perform acid leaching on the macroporous glass sample that is received as received and not calcined. Approximately 50 grams of macroporous glass and 4 liters of 5.5 wt% nitric acid are placed in a 4 liter glass beaker and heated at 9 ° C using a stainless steel paddle mixer at 3 to 500 rpm The machine was mixed for 2 hours. After the acid leaching treatment, the sample was filtered using a Buchner funnel with whatman 541 paper and washed with about 7.6 liters of deionized water. Then at a temperature of 110 ° C, The acid leached sample was dried for 22 hours. The second step was 'Na+_ counter ion exchange (Na-BIX) treatment on the acid leached macroporous glass. The acid leached sample from the first step was used with 4 Liter 3 liter / L gasified sodium (NaCl) solution mixed "Glass/Sodium Chloride Mixture"). Measure the pH of the glass/NaCl mixture. Add about 40 wt.% of tetrapropylammonium hydroxide as needed, and add the pn value of the glass/NaCl mixture. Withering to more than 1 〇 (in this example, the pH is about ι 〇 5). Then, the glass/NaCl mixture is transferred into a 4 liter glass beaker and heated at 50 ° C. Stirring was carried out for 4 hours at a speed of 3 Torr to 5 rpm using a stainless steel paddle mixer. After the Na_BIX treatment was completed, the glass/gasified sodium mixture was filtered using a Buchner funnel with Whatman 54 1 filter paper and Na-BIX/glass was collected. The sample was then rinsed with about 7 liters of deionized water. The Na_BIX/glass sample was then dried for 22 hours at a temperature of not. The third step was a second ion exchange of the Na-BIX/macroporous glass sample ( "IEX-2") treatment. In this example, 3 liters of 0.01 correction.% palladium solution was prepared for ion exchange ("pressure 12 solution" using diethylenetetramine 126438.doc -63 - 200902145. Add 35 grams of large pore glass sample to the ΙΕχ_2 solution ( Glass / ratio ^,). Measure the glass / ion exchange mixture value of 11 to obtain a pH of 8.1. Then 'move the mixture into a 2 liter glass beaker at 5 ° ° C While heating at a temperature, stir using a stainless steel paddle mixer at a speed of 3 Torr to 5 rpm for 4 hours. After the ion exchange treatment, filter the glass using a Buchner funnel with Whatman 54 1 filter paper / and use about 7.6 liters. After deionized water washing 1, the ion exchange glass was dried 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 hydrogen atmosphere at a hydrogen flow rate of 2 L/hr and at a temperature of 3 Torr for 4 hours. Sample analysis by ICP-AES gave a palladium concentration of about 纠21%. Example 4 Palladium on Macroporous Glass A macroporous foamed soda lime glass sample produced by Dennert Poraver, i.e., glass beads having an average diameter of about 4 to 125 microns, was obtained. In the first step, the macroporous glass sample received as it is and not calcined is subjected to acid leaching treatment. Approximately 2 gram grams of macroporous glass sample and 4 liters of 5.5 wt.% nitric acid were placed in a 4 liter glass beaker and heated at 9 〇t using a stainless steel paddle mixer at 3 to 5 The speed of the paws was mechanically stirred for 2 hours. 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 126438.doc -64-200902145 deionized water. Then, the acid immersed sample was dried at a temperature of 1 lot for 22 hours. In the second step, the acid-modified macroporous glass sample is subjected to ion exchange treatment. In this example, 3 liters of 0.01 wt.% palladium solution was prepared for ion exchange (,, hydrazine solution) using dioxetamine palladium [pd(NH3)4](cl)2. Will be about 18 grams. The acid-impregnated macroporous glass is added to the ion exchange solution ("glass/ion exchange mixture"). Measure the value of the glass/ion exchange mixture by 11. Add about 29.8 Wt_% of hydroxide as needed. Ammonium (Νη4〇η), the pH of the mixture is adjusted to greater than 1 〇 (in this example, the value is about 1 0.8). The glass/ion exchange mixture is then transferred to a 4 liter glass beaker. And heating at a temperature of 50 ° C while stirring at a speed of 300 to 500 rpm for two hours using a stainless steel paddle mixer. After the ion exchange treatment is completed, the glass/ion exchange mixture is filtered using a Buchner funnel with Whatman 541 filter paper, and The ion-exchanged glass was dried for 22 hours at a litre temperature. The third step was to reduce the ion-exchanged glass sample with a helium gas flow rate of 2 L/hr. atmosphere And reduction at a temperature of 3 〇〇t: for 4 hours. Sample analysis by ICP-AES gave a palladium concentration of about 〇.〇47. Example 5 Large pore glass was obtained on a large pore glass produced by Dennert Poraver. The soda lime glass sample 'is a glass bead having an average diameter of about 40 to 125 microns. 126438.doc -65- 200902145 Step - for large pore glass samples that are received as received, not burnt and not leached Ion exchange treatment. In this example, a 5 liter 〇〇〇1 wt% palladium solution was prepared for ion exchange using dihydrooxytetramine palladium [Pd(NH3)4](〇H)2 ("IEX Solution, |). Add 8 grams of macroporous glass to the ion exchange solution ("glass/ion exchange mixture"). Measure the pH of the glass/ion exchange of this mash. Add about 8 wt% continuously as needed. Ammonium hydroxide (ΝΗ, ΟΗ), adjust the pH of the mixture to more than 1 〇 (in this example, the pH is about 10. 5). Move the glass / ion exchange mixture into 2 liters of plastic In the mouth container, place the plastic container in a 5 0 C ventilated oven for 2 small Shake it slightly by hand every 3 minutes. After ion exchange treatment, use a Buchner funnel with whatman 541 filter paper to filter the glass/ion exchange mixture and collect the ion exchange-glass sample, and use about 7.6 liters of dilute NH4〇 h solution cleaning. The dilute NH4〇h solution was prepared by mixing 10 g of a 29.8 wt.% concentrated NH4〇H solution with about 3.8 liters of deionized water. Then, the ion exchange glass was dried at 110 ° C. 22 hours. In the next step, the ion parent glass-changing sample was subjected to reduction treatment, in which the ion-exchanged sample was reduced in a nitrogen atmosphere at a flow rate of 2 L/hr and a temperature of 3 ° C for 4 hours. Sample analysis by ICP-AES was carried out to obtain a concentration of about wt 31 wt.%. Example 6 Platinum on Large Porous Glass A large pore foamed soda lime glass sample produced by Siscor was obtained, i.e., an average of 126,438.doc •66·200902145 glass beads having a diameter of about 45 to 75 microns. In the first step, the macroporous glass sample received as it is and not calcined is subjected to acid leaching. Approximately 49.61 grams of macroporous glass sample and 4 gauge: 5.5 Wt.% nitric acid were placed in a 4 liter plastic wide mouth container. Place the plastic container in a 9 (TC venting tank) for 2 hours and shake it slightly by hand every 3 minutes. After the acid leaching process, filter the sample using a Buchner funnel with Whatman 54 丨 filter paper and use Wash about 7.6 liters of deionized water.

The acid leached sample was then dried for 22 hours at a temperature of 110 °C. In the second step, the acid-impregnated macroporous glass sample is subjected to ion exchange treatment. In this example, tetrachlorotetramine platinum [pt(NH3)4] (c...preparation of i liters of 0.66% wt% platinum solution for ion exchange ("ΙΕχ solution") was used. About 15.86 grams of gram The acid immersed macroporous glass is added to the glass/ion exchange mixture in the ion exchange solution"). The pH of the glass/ion exchange mixture was measured. The pH was adjusted as needed with about 40 wt.% of tetrapropylammonium hydroxide. The tetrapropylammonium hydroxide was continuously added to adjust the pH to more than 1 Torr (in this example, the pH obtained was about U.83). The glass/ion exchange mixture was transferred to a 4 liter plastic wide mouth container. The plastic container was placed in a 5 〇χ: ventilated oven for 2 hours. Shake the container slightly by hand every 30 minutes. After the ion exchange treatment was completed, a Brinell drain with a Whatman 541 filter paper was used = filtered glass/ion exchange mixture, and washed with about 76 liters of deionized water, and then the ion exchange glass was dried at a temperature of 1 1 〇C. Time. The sample was analyzed by ICP-AES to produce a platinum concentration of about 41.41 wt%. 126438.doc -67· 200902145 Example 7 Platinum on macroporous glass obtained a large pore foamed soda lime glass sample produced by Siscor, ie Glass beads having an average diameter of about 45 to 75 microns.

In the first step, the macroporous glass sample received as it is and not calcined is subjected to acid leaching treatment. Approximately 50.37 grams of macroporous glass and 4 liters of 5.5% of nitric acid were placed in a 4 liter plastic wide mouth container. The plastic container was placed in a 9 CTC ventilated oven for 2 hours and shaken slightly by hand every 30 minutes. After the acid leaching treatment was completed, the solution was decanted and the solid was washed with about 76 liters of deionized water. Then, at 110. The acid-impregnated sample was dried for 22 hours at a temperature of (the second step), and the acid-impregnated macroporous glass sample was subjected to ion exchange treatment. In the present example, di-tetra-tetramine platinum [Pt (NH3) was used. 4] (cl) 2 to prepare i liters of 0.18 wt.% platinum solution for ion exchange (" ΙΕχ solution.

41.79 g of acid-impregnated macroporous glass was added to the glass/ion exchange mixture in the ion exchange solution,). The p H value of the glass/ion exchange mixture was determined to be 8 In this example, the ρ Η value was not adjusted. The glass/ion exchange mixture was transferred to a 4 liter plastic wide mouth container. Place the plastic container at 9 inches. 4 hours in a ventilated oven. Shake the container slightly by hand every 30 minutes. After the ion exchange treatment was completed, the solution was decanted and the ion exchange glass was dried for 22 hours using about 76 liters of deionized water to wash the solid m temperature. Sample analysis was performed by ICP-AES. The amount of palladium on macroporous glass is obtained from a large pore foamed soda lime glass sample produced by Siscor's average diameter of about 45. Glass beads up to 75 microns. In the first step, the macroporous glass sample received as it is and not calcined is subjected to acid leaching. Approximately 20 grams of macroporous glass and 4 liters of 5.5 wt% of the acid were each placed in a 4 liter glass beaker and heated at 9 Torr using a stainless steel paddle mixer at 300 to 5 rpm. Mechanical stirring at speed for 2 hours. After the acid leaching treatment was completed, a Buchner funnel transition sample with Whatman 541 paper was used 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 〇 c. In the second step, the acid-impregnated macroporous glass sample is subjected to ion exchange treatment. In this example, 3 liters of a 0.01 wt.% palladium solution was prepared for ion exchange ("ΙΕχ solution" using dichlorotetramine palladium [Pd(NH3)4](cl)2. About 1.8 grams The acid-second macroporous glass is added to the ion exchange solution ("glass/ion exchange mixture"). The {11] value of the glass/ion exchange mixture is measured. As needed, '29.8 wt% hydrogen peroxide is added continuously dropwise. Ammonium (Νη4〇η), the pH of the mixture is adjusted to greater than 10 (in this example, the value of ρΗ is about 10.78). Then, the glass/ion exchange mixture is transferred into a 4 liter glass beaker. And use a stainless steel paddle mixer to stir at 300 to 500 rpm for 2 hours while heating at TC temperature. After the ion exchange treatment is completed, use a Buchner funnel with Whatman 541 filter paper to pass/glass/ion exchange Mix the mixture and use about 7 · 6 liters of deionized water, wash the main 126438.doc -69 - 200902145. Then 'at 110 ° C. Ion the ion exchange glass drying 22 small third step on the ion exchange glass The sample is subjected to a reduction treatment in which the sample is in The gas (H2) flow rate was 2 L/hr of hydrogen atmosphere and 3 Torr. The temperature of 匚 was 4 hours under temperature. Again, the sample was analyzed by ICP-AES to obtain a palladium concentration of about 〇〇47. Example 9

Palladium on Large Porous Glass A sample of macroporous foamed soda lime glass produced by Siscor, i.e., glass beads having an average diameter of about 45 to 75 microns, was obtained. The first step is an acid immersion treatment on the macroporous glass sample which is received as it is and which is not calcined. Approximately 49_61 grams of macroporous glassy sample 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 (TC ventilated box for 2 hours, and shake it slightly with ^ every 3 minutes. After the acid leaching process, use a Buchner funnel with Whatman 541 paper to pass the sample' and Use about 7.6 liters of deionized water, raw wash, then dry the acid immersed sample at 22 ° C at a temperature of 11 ° C. The second step is to ionize the acid leached macroporous glass sample. Exchange treatment. In this example, 1 liter of 0 · 0 0 03 wt· / 〇 of the / valley solution was prepared for ion exchange using dihydrooxoamine sharp [pd(NH3)4](OH)2 (" ΐΕχ Solution"). Add about 1 5.06 grams of acid immersed macroporous glass to the ion exchange solution ("glass/ion exchange mixture). Measure the pH of the glass/ion exchange mixture. 126438.doc -70· 200902145 About 29 8 wt% of ammonium hydroxide (nH4〇H) was added dropwise as needed, and the pH of the mixture was adjusted to be greater than 1 Torr (in this example, the pH was about 1 〇.2). Transfer the glass/ion exchange mixture into a 4 liter plastic D container. Place the plastic container in the grip. The tank was shaken for 2 hours' and shaken by hand every 3 minutes. After the ion money treatment was completed, the sample was filtered using a Buchner funnel with Whatman 541 filter paper and washed with about 7.6 liters of dilute NH4OH solution. Prepared by mixing ίο grams of 29.8 wt% concentrated NH4〇H solution with approximately 38 liters of deionized water. (iv) Drying the ion-exchanged glass sample for 22 hours at a temperature of 〇°C. -AES was subjected to sample analysis to yield a palladium concentration of about 165 wt%. A portion of the sample was examined by scanning transmission electron microscopy (STEM) analysis as described in Example CHD below, and the results showed that palladium particles ( The point where the contrast is brighter is generally dispersed within a range of less than or equal to about 30 nm from the surface of the hole wall (i.e., the perimeter of the darker shaded area relative to the material region around the substrate where the contrast is relatively bright) Example 10 Tungsten on Large Porous Glass Obtained a macroporous foamed soda lime glass sample produced by Siscor's glass beads with an average straight position of about 45 to 75 microns. The first step is as it is. The un-calcined macroporous glass sample was subjected to acid leaching treatment. Approximately 20 grams of macroporous glass sample and 4 liters of 5.5 wt.% nitric acid were placed in a 4 liter glass beaker at 9 Torr. At the same time, a stainless steel paddle mixer was used to mechanically stir 126438.doc 71 200902145 for 2 hours at a speed of 300 to 500 rpm. After the acid leaching treatment was completed, the sample was filtered using a Buchner funnel with Whatman 541 paper, and about 7. 6 liters was used. Wash with deionized water. The acid immersed sample was dried for 22 hours at a temperature of 110 ° C.

The second step is an ion exchange treatment of the acid immersed macroporous glass sample. In this example, 3 liters of 0.05 wt.% tungsten solution was prepared using ammonium metatungstate (ΝΗ4) 6Η212〇4〇·nH2〇 for ion exchange (“ΙΕχ solution”). About 18 grams of acid leaching was used. The macroporous glass is added 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 as needed (continuously 4) 〇η), adjust the pH of the mixture to 8. Move the glass/ion exchange mixture into a 4 liter glass beaker and use a non-mineral steel mixer at 300° while heating at rc. Stir at 500 rpm for two hours. After ion exchange treatment, filter the glass/ion exchange mixture using a Buchner funnel with Whatman 541 filter paper and rinse with about 5 liters of deionized water. Then, at 1HTC, ion The exchange glass is dried for one hour. In the third step, the ion-exchanged glass sample is calcined, wherein the sample is calcined for 4 hours at a gas flow rate of 2 L/lu of air and a temperature of .c. Hunting is performed by ICP-AES. Sample analysis It is expected that a tungsten concentration of about 1% is obtained. Example 11 Composite Catalyst 1 Platinum on a large-pore glass is obtained according to Example 7 3 〇 3 vouchers ifr 丄 丄 za za and u JA brother month ij drive catalyst combination , containing large pores, leaching glass beads, 1 platinum, f, / iridium platinum, the degree of about 0. 丨 3 Wt · % and the average diameter of about 126438.doc -72 - 200902145 45 to 75 nanometers Obtain 44_2 g of an alumina precursor containing non-peptized Versai_25i pseudo-soft boehmite and split it (4〇/6〇) to produce 17 7g and 26.5g each. In the Lancaster grinder丨7·7 g of a non-peptized pseudo-soft boehmite ("non-peptized V-25 1") and precursor catalyst composition and 3 〇 3 g of glass beads having a platinum concentration of about 0.13 wt·% Perform a dry mix of about 1 minute.

A 26.5 gram portion of the pseudo-soft boehmite was peptized in about 4 4 grams of 7% ην〇3 and about 25 ml of water. After the peptization is formed, the f ± peptized pseudo soft water Mingshi "gel cold V-251" is added to the previously ground mixture of the precursor catalyst composition in the Lancaster grinder and ground to form a doughy shape. a mixture of viscosities. The resulting dough is placed in a RA shut-off machine with a 16 mm 〇 / 16 inch 模板 template to make money (4), and (by hand) peeled to a length of about 6 4 mm (10) H) Up to about 9.5 mm (3/8 inch (9))

The & particles are dried on a wire mesh tray in a ventilated oven with a flow rate of about ..., "1 yjvv 1 ο 〇t" for about 2 hours. At the same air flow rate, the particles are pressed out _ Ding Jingtian Baixian After one hour, the temperature of the baking phase is raised to 300 and the temperature is increased, and the temperature is increased by the temperature of the two YHs, and then the temperature is raised to 500 C, and then at 500 V. Maintaining a three-hour stone conversion ^ oxime. " The pseudo-soft water chain is formed with a precursor sigh composition dispersed in the composite catalyst composition 126438.doc • 73· 200902145 calcined composite catalyst composition, as described below The activity test of conversion of methylcyclohexane (MCH) to toluene showed that the platinum component in the FSC composition was substantially dispersed in the pretreated macroporous glass or on the glass. Example CH-1 Analytical method re/XPS splash X-ray photoelectron spectroscopy (XPS) sputtering depth distribution method for SARCNa, electric field (IEP) and SAN2_BET or SAKr-BET

The xps sputtering depth profile was obtained using a PHI Quantum 200 Scanning ESCA MicroprobeTM (Physical Electronics) with an A1 Koc X-ray source with 1486.7 eV microfocus monochromatization. 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 10-200 μηι - X-ray beam power 2-40 W - Sample analysis area 1 0-200 μιη - The electron emission angle is 45 with the sample normal. All XPS § Jin and 深度 depth maps are recorded at room temperature, not for mouth = 仃 pre-s, but the exception is to introduce the sample into the xps instrument vacuum environment - and θ into a period of sample surface spectrum acquisition, Then, in each period, the sample table* is subjected to a 'r+_== material to generate a sputter depth distribution of a quasi-depth rate. The layer is known to have a thin film 126438.doc -74· 200902145 and The atomic concentration of Pd and Si is obtained for their respective atomic spirits. The peak area sensitivity factor of Pd 342 and Si 2p and the analyzer transfer function are used for the repair value. Those familiar with XPS analysis techniques should understand the depth of the shot. Determination of parameters

Human error is also affected by mechanical errors, and the combination of the two may result in an uncertainty of approximately 25% for each reported value of the splash* iron shot/woodness as determined by the XPS off-shoot: depth distribution technique. Therefore, this uncertainty is expressed in the depth value.

This inaccuracy is common throughout the XPS analysis technique, however, this inaccuracy is insufficient for the average thickness of the catalytically active MT, t ancient & field and other material properties disclosed herein. To prevent interference with the catalyst compositions described herein, it is also not possible to distinguish between the # compositions and other compositions not described and claimed herein. Transmission Electron Microscopy (TEM) Analysis Transmission electron microscopy (TEM) sample detection was performed using a JEOL 3000F field emission scanning transmission electron microscope (STEM) instrument operating at Accelerated C. The instrument is equipped with an inca X-ray spectrometer from Oxford Instruments to perform local chemical analysis using an energy dispersive spectrometer. Preparation of the θ sample The sample material is first familiar to the standard epoxy package known to those skilled in the art of blue analysis. After curing, the epoxy-embedded sample material was cut using a super (four) tablet to produce a slice of about 8 Å thick. The sections were collected on a film-porous carbon support and did not require further processing, and were positioned in the electron beam field of the above STEM instrument for detection and analysis. Those familiar with TEM analysis techniques should be aware that the position of the analyte and the average thickness of the relevant region relative to the surface of the substrate using TEM analysis are both affected by human error and are 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, it may cause an uncertainty of about ±20% of the TEM vertical depth measurement (relative to a specific reference point) and ±5% of the lateral measurement results (relative to a specific illuminating point) uncertainty. Therefore, this uncertainty is expressed in the distance of the measured catalytic component relative to the surface of the sample substrate, as shown in Figure 丄. This inaccuracy is common throughout the TEM analysis process, but not sufficient to interfere with the differentiation between the catalyst compositions. SARCNa determination, SARCNa empty sample and related statistical analysis For the reasons discussed above, the surface area change rate of sodium (,, sarc~") is reported as the ratio of NaOH titrant volume. According to the above SARCw procedure, the SARC duty of each sample specified in the following examples was determined. An empty sample was prepared by preparing a 35 M Naa solution (ie, adding 30 grams of NaC1 in 1" milliliter of deionized water), which contained no matrix-like mouth. However, in order to address the statistical variability in the SARC cardiac test procedure Four separate empty samples shall be titrated and adjusted using the specified concentration (0.01 N in this example) used to obtain V* and % to 丨〆, ie, V^V initial) (ie, corrected) The volume of the titration solution used for each matrix sample SARC. The pH of the empty sample was adjusted according to the same procedure as above for SAR^a_ and the empty sample was titrated, but also contained no matrix. Statistical analysis of empty sample titers is reported in each of the empty sample implementations provided below and their respective mean and standard deviation (or V total σ) analysis test results tables. Similarly, the inherent statistical fluctuations corresponding to the respective titrations 126438.doc -76- 200902145 IV, V5, V10 and Vl5 due to their respective ν totals are also reported. From the statistical point of view, the statistical t distribution is used. In the vicinity of the average value, the value other than the specified confidence interval is reliable and the degree of certainty that does not originate from the inherent deviation of the experimental method reaches 95 /〇. The initial V and Vt values measured for the base f samples in the interval were considered to be statistically indistinguishable from the empty samples. Therefore, such samples do not calculate the SARC heart value. For isoelectric point (IEP) measurement, determine the isoelectric point ("IEP") of each sample given below according to the following procedure: 1 Use Meuler Toledo SevenMulti meter with PH mW〇RP module, with & Mettler Toledo INLAB 413 pH The composite electrode is used for enthalpy measurement. The instrument is calibrated using a standard pH buffer solution with pH values of 2, 4, 7 and 10 整个 throughout the relevant 1 EP range. Quantitative 16 Μ Ω by using one of the conditions sufficient to bring the sample to a wet state. The sample is wetted in deionized water (at about 25t) and the IEP ' $ sample can be used to produce a thicker 4 slurry or paste mixture. This incipient state allows the glass electrode and its reference electrode to be contacted. Contacting liquid (contacting a sample of a solid sample (in this example, a slurry or paste mixture). Depending on the form of the sample (eg glass microfibers, granulated powder, chopped fibers, etc.) and its porosity The degree of sex (if any), the procedure requires a different amount of water, but in all cases, the amount of water added should only be sufficient to bring enough liquid into contact with the glass electrode and the reference electrode. Water should be added to the sample to be tested as far as possible 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 the production of incipient wetness) by hand until the pH is measured. Stabilize and then read the resulting pH from the meter. 126438.doc •77· 200902145 N2 BET or Kr BET Surface Area (SA) Determination According to the ASTM procedure mentioned above, each sample given below is suitably S. A. N 2 - BET or S. A. K r- BET determination. As discussed more fully above, for higher surface area measurements (eg, about 3 to 6 m2/g), as described in ASTM D366 3-03 Method, N2 BET is likely to be a preferred surface area measurement technique. For lower surface area measurements (eg, < about 3 claws 2 / §), according to eight 8 □ ^ 4 〇 478 0-95 (" 8. The method described in VIII.5^), the heart BET may be a better surface area measurement technique. The SARCNa empty sample measurement and statistical analysis for correcting the SARCN^^ value sample number dilute NaOH titration solution concentration (N) SAN2-BET (m2/g) In NaOH titration, used to make the pH at the initial value of 4.0 at tJV) The whole titration volume (ml) required to maintain the pH at 9.0 at t5, t10 and tls (VSM5) V total = V initial + V5 to 15 V initial 0 minutes Vs 5 minutes v10 10 minutes Vis 15 minutes V5il5 and the empty sample A 0.01 Not applicable 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 0.4 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 0.01 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 Large pore glass matrix - SARCNa obtained a sample of macroporous foamed soda glass produced by Dennert Poraver, a glass bead having an average diameter of about 40 to 125 microns. Sample A is a macroporous glass bead that is received as it is. Sample A was analyzed by the above-described analytical method for determining SARC- by 126438.doc -78 - 200902145. The results are shown in the table below. Sample No. Empty Sample A -------- Sample Description — 1· -------^ Dilute NaOH Titration Solution Concentration (N) In the drop;: Bu 0,: ε, make the pH at 11 When the titration of ts, ti, and ti5< is adjusted to $•t0 (V*>) from the initial value of 4.〇 to VSils), the pH is kept at 9.0. The actual volume (ml) is required. V5 5 minutes vI0 10 minutes 0.125 Vis 1 V» 15 minutes v*-v The average value of the initial space sample 0.01 2.1 0.15 〇^5T^2.5 Not commercially available as the original received glass beads 0.01 5.2 Γ 0.8 0.4 '01 1 6.5 1.3 B Leached perforated glass beads Not determined Not determined sample number Sample IEP SW For SARQvfl measurement (ml) SARC^ Description (m / g) V* 0 minutes V5 5 minutes V, 〇 10 minutes v15 15 minutes Va (V The total value of the total -V initial)/V airspace sample is not applicable. 2.1 0.15 0.125 , J 0.15 2.5 Not applicable A A holed glass bead received according to the sample 10.2 0.4 3.1 0.65 0.275 -0.05 3.97 0.28 Corrected B Acid-exposed glass beads 8.9 6.0 Not determined Unmeasured Example Composite catalyst 1 Activity test - Conversion of methylcyclohexane (MCH) to toluene Examples pointed out that when the catalyst precursor composition is dispersed in the composite catalyst composition, compared with the previous dispersed in the composite catalyst composition is not expected to adversely affect the activity of the catalyst precursor composition. The catalytic activity of the extrudate sample having the precursor of the Example 7 precursor FSC was prepared in substantial accordance with the procedure of Example Π. Additionally, in this example, the particle size distribution of the extrudate sample is maintained between about 40 and 60 mesh (i.e., 425 to 250 microns) to reduce the adverse effects of the internal diffusion channel resistance of the particles. 126438.doc -79· 200902145 The following is a general procedure for evaluating catalytic activity when I use methylation equipment to convert methylcyclohexane (MCH) to toluene. First, to provide substantially equal amounts of platinum, the precursor catalyst composition of Example 7 was dispersed therein to 250 mg of 40 to 60 mesh extrudate, or 125 mg of the sample precursor sample of Example 7, loaded into 3.5. Millimeter inner diameter tubular reactors were used for the respective catalytic activity test runs. Therefore, these two different 袤 袤 袤 提供 provide substantially the same weight hourly space velocity (WHSV) for Ming. Prior to the activity test, the catalyst was subjected to a pretreatment of about 3 minutes at 350 C using a 25 Torr "flow rate." In the first step, the molar ratio of H2 to the feed was about %. The flow rate of this feed mixture varied from >25" to 丨〇〇〇cc/min over a period of about 4 hours. The conversion of methylcyclohexane (mch) to toluene was determined. The catalyst was tested at a temperature of 325 C. The results are shown in Figure 2. Figure 2 depicts the yield of toluene (wt%) and the flow rate reciprocal.

Diagram of the relationship between (min/cc). Each flow rate has a corresponding toluene conversion yield, and the yield of the precursor catalyst composition in the sample of the extrudate is surprisingly and unexpectedly at least similar to 'and generally greater than no extrudate matrix The corresponding yield of the same precursor catalyst composition of the material (i.e., just dispersed in the kebab). Thus, the results of Figure 2 indicate that the catalytic activity of the Japanese-precursor catalyst composition dispersed in the composite catalyst composition does not adversely affect. Although in the foregoing embodiments, the invention has been described in terms of certain preferred embodiments of the present invention, and the invention has been described in the context of the present invention, it is obvious that the invention is obvious to those skilled in the art. There may be other 126438.doc-80-200902145 embodiments' and certain details described herein may vary widely without departing from the basic principles of the invention. [Simple diagram of the diagram] Figure 1 is a glass matrix sample produced by a JEOL 3000F field emission transmission electron microscope instrument with an acceleration voltage of 3 〇〇 kV, no microporosity on the f-mass, no pores, but large pores. For example, a scanning transmission electron microscope (STEM) image of a cross-section of a leached soda-lime glass, wherein the granules are generally dispersed within a range of less than or equal to about 3 angstroms from the surface of the pore walls. When the broad-spectrum green methylcyclohexane (MCH) is converted to toluene, the yield of toluene is lost. The relationship between the flow rate reciprocal (min/cc) and the dust sample in the 7 oxidation name "the activity of the precursor is dispersed before the oxidation of the sputum;; complex / resistant to the temperature oxide" and 126,438 .doc •81 -

Claims (1)

200902145 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 microporous/non-porous matrix having a large pore, an outer surface, a surface region and a subsurface region, - at least one catalytic component, and - at least one catalytically active region, It comprises the at least one catalytic component, wherein 1 the substantially microporous/non-porous matrix has a measured value of about 〇 when measured by a method selected from the group consisting of: sA; cr and combinations thereof a total surface area between .1 m2/g and 5 〇m2/gi; 11 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 the at least one catalytic component is substantially Dispersing in or on the at least one precursor catalyst composition, wherein the at least one first composition is formed after the at least one precursor catalyst composition is formed The at least one second composition are mixed. 2. A composite catalyst composition as claimed, wherein the catalytic component remains substantially substantially dispersed within the v-precursor catalyst composition or the combination after exposure to steady state reaction conditions for one hour. On the object. 3. A composite catalyst composition as claimed, wherein the precursor catalyst combination 126438.doc 200902145 has a substantially microporous/non-porous matrix having a pH in the range of greater than 6 Å but less than or equal to 14. Obtain a predetermined isoelectric point (IEp). 4. A composite catalyst composition as claimed, wherein at least one catalytically active region of the precursor catalyst composition has an average thickness of less than or equal to about 30 nanometers, and the composite catalyst composition is in a stable state After the reaction conditions, the catalytic component is substantially positioned on (a) the surface of the substantially microporous/non-porous matrix, (b) the surface region of the substantially microporous/non-porous matrix Internally, (c) is partially on the surface other than the substantially microporous/non-porous matrix and is partially in the surface region, or a combination of (d) 4 (a), (b) and (c). 5. The composite catalyst composition of claim 1, wherein the at least one catalytic component of the precursor catalyst composition is selected from the group consisting of: Bronsted or Lewis acid, Brunite or Lewis base, responsible metal cations and metal cations and anions, transition metal cations and transition metal complex cations and anions, transition metal oxyanions, transition metal chalcogenides anions, main oxygen anions, teeth Compounds, rare earth ions, rare earth complex cations and anions, noble metals, transition metals, transition metal oxides, transition metal sulfides, transition metal oxysulfides, transition metal carbides, transition metal nitrides, transition metal borides, transition metals Phosphides, rare earth hydroxides, rare earth oxides, and combinations thereof. 6. The composite catalyst composition of claim 1, wherein the precursor catalyst composition is 126438.doc 200902145 less than one catalytic component before the composite catalyst composition is under steady state reaction conditions a catalytic component having U) a first pre-reacted oxidation state, and (b) a first pre-reaction interaction with the matrix 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 acid, chalcogenide, and combinations thereof. 8. The composite catalyst composition of claim 6, wherein at least a portion of the first catalytic component is modified or displaced to form a second catalytic component before the composite catalyst composition is under steady state reaction conditions, Having (a) a second pre-reactive oxidation state, and (b) a second pre-reaction interaction with the substrate; wherein 'the second pre-reactive oxidation state of the second catalytic component is less than, greater than or equal to the first a first pre-reactive oxidation state of a catalytic component. 9. 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, All, RU, Re, Ni, c〇, Fe a group of Mn, Cr, and combinations thereof. The composite catalyst composition of claim 1, wherein the substantially microporous/non-porous matrix of the precursor catalyst composition has a SARCw of less than or equal to about 〇·5. 11. The composite catalyst composition of the present invention, wherein the substantially non-microporous/non-porous matrix of the precursor catalyst composition is selected from the group consisting of glass, tantalum carbide, tantalum nitride, cordierite, and ruthenium containing ruthenium. A group of ceramics and their combinations. The composite catalyst composition of claim 1 wherein the precursor catalyst combination 126438.doc 200902145 is substantially free of microporous/no-porous matrix selected from substantially flawless ceramics, alpha alumina, tantalum alumina a group consisting of zirconia, titania, carbon, and combinations thereof. t 126438.doc