TW200836831A - Selective hydrogenation processes using functional surface catalyst composition - Google Patents

Abstract

Selective hydrogenation processes using a catalyst composition which, preferably comprises a glass substrate, with one or more functional surface active constituents integrated on and/or in the substrate surface. A substantially nonmicroporous/nonmesoporous substrate having macropores has (I) a total surface area between about 0.1 m<SP>2</SP>/g and 50 m<SP>2</SP>/g; and (ii) a predetermined isoelectric point (IEP) obtained in a pH range greater than 0, preferably greater than or equal to 4.5, or more preferably greater than or equal to 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 less than or equal to about 30 nm, preferably less than or equal to 20 nm and more preferably less than or equal to 10 nm. Preferably, the substrate is a glass composition having a SARCNa less than or equal to about 0.5.

Description

200836831 IX. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a catalyst composition and a method of preparing the same, which can be used in various chemical manufacturing methods and various emission control methods. More particularly, the present invention relates to a catalyst composition comprising a glass substrate and incorporating one or more functional surface active ingredients on the surface of the substrate and/or in the surface of the substrate. The catalyst composition can be used in various Application of selective hydrogenation methods. [Prior Art] Catalyst compositions are used to promote a class of chemical reactions that are generally described as catalytic or catalytic, and catalysis is critical for efficient operation of various chemical processes. Most industrial reactions and almost all biological reactions, if not catalyzed, involve pre- or post-reaction treatments that are catalytic reactions. For the United States alone, σ's products at a certain stage including catalytic processes are close to a dead dollar (USD). Products produced using catalyst compositions include, for example, foods, clothing, pharmaceuticals, pharmaceuticals, specialty or fine chemicals, plastics, detergents, fuels, and lubricants. Catalyst compositions can also be used to treat emissions (such as vehicle exhaust emissions, refinery emissions, utilities, and plant emissions) and other process emissions streams to reduce potential negative impacts on human health or the environment. The content of harmful ingredients. In terms of market sales, the sales of solid carrier catalysts for heterogeneous catalytic reactions in the global market are approximately $3 billion per year. The solid-carrying catalysts are generally classified into three categories, namely, petroleum refining catalysts, chemical processing catalysts, and emission control catalysts. The 126432.doc 200836831

The market sales of the three types of catalysts are basically three-thirds. For example, in the year of i99, in the US$1.8 billion solid catalyst market, petroleum refining, chemical processing and emissions control catalysts accounted for 37%, 34% and 29% of the market. Take the petroleum refining catalyst market (about 100 million U.S. dollars in 1990) as an example. Na’s income comes from ' _ , „ 31.50/0 . 6.5〇/〇^4.5〇/〇^^^^, J3, L From hydrotreating catalysts, hydrocracking catalysts, and reforming catalysts. • As far as the mechanism is concerned, the catalyst can generally improve the chemical reaction in the reactants and products without substantially eliminating it. The rate at which equilibrium is reached. Therefore, for any relevant reaction, the catalyst does not change the equilibrium state between the reactants and the product, but if properly designed and/or selected, the catalyst accelerates the chemical reaction. The rate of use of the catalyst for a wide range of commercial and practical purposes for a variety of purposes includes improving the reactivity, selectivity and energy efficiency of the process and other uses. For example, producing the plant according to the specified process conditions. When the product is desired, increasing the reaction rate or reactivity of the reactants can shorten the processing time, and # is used to obtain higher product productivity (for example, increase the volume or mass per unit hour). Therefore, the catalytic activity Catalyst group The ability of the material to effectively convert the reactants to the desired product in each morning time. Similarly, increasing the selectivity of the reaction increases the desired amount of the desired reaction product. Percentage of output of the product: at such possible Of the reaction products, some of the products 11b are not required and require further processing for corresponding removal or re-transfer. The catalyst selectivity is a catalyst composition that converts a portion of the reactants to a specific product under standard process conditions. In addition, the combination of catalysts; the conversion and reduction of pollutants or undesired reactants in a process 126432.doc 200836831 or the content of the product. The other use is to maintain or improve product production capacity and / or Selective reaction while increasing the overall energy efficiency of the reaction process〇

The range of use of the catalyst varies greatly. For example, but not limited to, the catalyst can be used to reduce the amount of contaminants such as hydrocarbons, carbon monoxide (co), nitrogen oxides (tetra) X), and sulfur oxides (sox). These contaminants may exist in the series. The process (1) is such as emissions from a combustion exhaust gas in an engine or a diesel engine, a classified petroleum refining or a coal burning process, and the like. Similarly, catalysts can be used in hydrocarbon processing processes. The process is used for many different sources (eg, direct petroleum fractions, recycled petroleum fractions, heavy oil, bitumen, phyllo, natural gas, and materials containing catalytic reactions). The hydrocarbon process stream of other carbonaceous materials is converted or upgraded. The catalytic reaction is usually divided into two different reaction types, namely homogeneous catalysis and heterogeneous catalysis. Homogeneous catalysis broadly describes a type of catalytic reaction in which the reactants and catalyst are mixed in a solution phase. Although gas phase catalytic reactions have been used in some cases, the phrase phase catalysis is typically a liquid phase system. Therefore, concentration gradients and migration of reactants to the catalyst can become important factors in controlling homogeneous catalytic reactions. In addition, in some cases, the "solution phase" catalytic reaction can occur across the interface between the two liquid phases, rather than forming a true solution, but forming an emulsified phase. Some general classes of homogeneous catalysis include acid-base catalysis, organic Metal catalysis, phase transfer catalysis, etc. 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 phase or a half 126432.doc 200836831 alpha phase H Therefore, in the heterogeneous catalytic process, the catalyst and the reactants produce a solid phase-liquid phase or solid phase gas phase reaction of U. Compared with homogeneous catalysis, heterogeneous catalysis has many advantages, such as solid catalyst (4) rot.钕 is less than 1 and compared with many homogeneous solution catalysts, safety and environmental wind. 彳目 provides n a wide range of economically feasible temperature and pressure conditions for ffii and (C) is more controllable Strong exothermic chemical reactions and endothermic and chemical reactions, etc. • In other respects, 'solids can have mass transfer restrictions' and thus significantly reduce the most specific and reproducible. Typically, solid catalysts (sometimes referred to as catalyst particles) includes one or more catalytic components (eg, 'precious metals' such as he (four), _〇, (10) U), 铢 (four), etc.) in a porous material having a high internal surface area, in a catalytic component The internal surface area is typically on the order of hundreds of square meters per gram. Therefore, conventional catalyst compositions or catalyst particles comprise a special porous support having a large internal surface area. The catalytic reaction occurs on the porous support. However, such catalyst structures often produce mass transports that limit it and reduce the activity and performance of the catalyst particles with respect to the catalyst and cause other catalyst performance problems. The latter is more effective in this more representative catalyst. In the structure, the reactants must diffuse through the network of pores to reach the inner region of the catalyst particles, and the product must be dispersed to exit the inner region of the catalyst particles. Therefore, the porosity of the conventional catalyst composition is other than The factors also depend on the balance, that is, on the trade-off between the two characteristics of the conventional catalyst composition, namely the trade-off between the ability of the catalyst surface area fish to promote mass transfer. For example, 'many catalytic components are typically present in carriers with fine and complex pore structures (via 126432.doc 200836831 for microporous structures, ie &lt; 2 nm average maximum diameter) to increase catalyst particles Surface area. This higher surface area will generally increase the activity of the catalyst. However, due to the increased catalyst activity due to the higher surface area of the catalyst particles, #^ causes a problem of mass transfer resistance (ie, preventing reactants and products from entering). The problem is more pronounced when the carrier comprises a higher percentage of microporous structure. By increasing the size of the pores (for example, &gt; 50 nm large pores) in the carrier Percentage, which reduces the resistance of the 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 viewpoint of mechanics, the robustness of the catalyst particles is lowered. At the same time, if the reactants are subjected to significant texture transfer resistance in the pore structure of the catalyst particles, a concentration gradient will exist under steady state reaction conditions. In the pores and structures, the concentration of the reactants is the largest around the catalyst particles and the smallest at the center of the catalyst particles. On the other hand, the concentration of the reaction product is higher in the center of the catalyst particles than in the vicinity of the catalyst particles. These concentration gradients • provide a driving force for mass transfer. The greater the concentration gradient becomes, the lower the rate of the catalytic reaction. As a result, the effective properties of the catalyst particles (e.g., reactivity, selectivity, life cycle between the regeneration treatment, and anti-coking ability, etc.) are also reduced accordingly. • In general, the purpose of developing catalyst compositions is to improve the above-mentioned or multiple processing objectives from a commercial perspective. In some cases, the factor that affects the performance of the catalyst is its ability to promote rapid and efficient reaction between reactants. Therefore, a catalyst composition having a lower diffusion limit is often required. However, in other cases, in order to obtain a better product, 126432.doc -10- 200836831 may be more important for the selectivity of a particular product. Thereby, additional processes and associated processing equipment for removing or converting undesired reaction products can be eliminated. For example, in 1976, Y.T. Shah et al. proposed the use of acid leached aluminum borosilicate fibers, specifically E-glass (more specifically, E-621) to produce a catalyst carrier. The catalyst carrier has a higher surface area to volume ratio than conventional catalysts, thereby reducing the size of the catalytic converter used in automotive exhaust systems (see, for example, Oxidation of an Automobile Exhaust Gas Mixture by Fiber Catalysts, Ind. Eng. Chem., Prod. Res. Dev., pp. 29-35, Vol. 15, No. 1, 1976). At the same time, Shah et al. believe that reactive gases (such as carbon monoxide, carbon dioxide, nitrogen oxides, decane, ethane, propane, ethylene, propylene, acetylene, benzene, toluene, etc.) are generally accessible in automotive exhaust mixtures. To the large surface area produced in acid leached E-glass.

Shah et al. showed that a relatively small number of fibers E with a relatively small surface area (75 m2/g) compared to two conventional catalysts (platinum supported on alumina beads or platinum supported on silica beads) The performance of the glass-catalyst carrier is better than that of alumina-supported or cerium oxide-supported catalyst (1 80 m2/g and 317 m2/g, respectively), and the average pore size of the E-type glass catalyst It is larger than the catalyst supported by alumina or the catalyst supported by cerium oxide. Despite this, Shah et al. did not propose or suggest that effective vehicle exhaust oxidation can occur at surface areas of less than 75 m2/g. Nearly 25 years later, Kiwi-Minsker et al. studied the reduction of surface area in another acid-impregnated aluminum borosilicate type E glass fiber (EGF) in 1999, phase 126432.doc -11 - 200836831 for benzene The selective liquid phase hydrogenation of cerium oxide glass fiber (SGF) for formaldehyde is related to the effect of producing benzyl alcohol (using a platinum-based catalyst) or toluene (using a catalyst for the main one) (see, for example, Supported Glass Fibers). Catalysts for Novel Multi-phase Reactor Design, Chern. 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 m2/g and 75 m2/g, respectively, and the surface area of SGF is kept at a low level of 2 m2/g. However, Kiwi-Minsker et al. noted that the SGF/palladium catalyst palladium essentially has the same effective surface area concentration as its EGF/catalyst counterpart (ie about 0.1 mmol/m2) (mole metal/square The MGF/Palladium catalyst composition shows a decrease in activity or reaction rate per gram of palladium compared to its EGF/palladium catalyst counterpart.

Kiwi-Minsker et al. suggest that such SGF/reduction of the activity of the catalyst due to reduced surface area may be explained by the enhanced interaction of the active ingredient (ie, the catalytic component, in this case palladium) with the SGF carrier. Not because of its small surface area (ie 2 m2/g). However, they failed to verify this argument by proving the following argument: EGF/palladium catalysts with a small surface area (ie, comparable to 2 m2/g SGF/bar), at least with a larger surface area (ie, respectively The EGF/catalyst samples of 15 m2/g and 75 m2/g) have the same catalytic activity. Therefore, Kiwi-Minsker et al. proposed a limitation on the activity of SGF/ (ie, because SGF has a higher acidity than EGF, and the interaction between palladium and SGF is enhanced), not because of SGF/Palladium Table 126432.doc -12· 200836831 The area is small, the reason is not clear. In any case, Kiwi-Minsker did not report that the 15 m2/g EGF/palladium sample has enhanced catalytic activity due to increased diffusion rates relative to the 75 m2/g EGF/palladium sample. Otherwise, this may indicate a beneficial effect due to the smaller catalyst surface area. Recently, in US 7,060,651 and EP 1 247 575 A1 (EP '575), Barelko et al. disclose the use of a cerium-rich-rich carrier (including cerium oxide and an oxide comprising non-cerium oxide (for example, Al2〇3). , B203, Na20, MgO, CaO, etc.) as a catalyst carrier, wherein the cerium-enriched carrier has a pseudo-layered microporous structure in the lower surface of the carrier (see, for example, the first? Sections 11, 13, 15, 17, 18, 23, 31 and 32), as explained in more detail to the European Patent Office, in the distinction between ΕΡ '575 and Kiwi-Minsker et al. In the case of the catalytic carrier (nKiwi-Minsker carrier), Barelko et al. asserted that their claimed ceria-rich carrier has a pseudo-layered microporous structure with a narrow interlayer space, whereas the Kiwi-Minsker carrier does not. More specifically, Barelko et al. believe that there is no basis in Kiwi-Minkser et al.'s paper that (a) a pseudo-layered microporous structure with a narrow interlayer space is formed in the Kiwi-Minsker carrier; (b) said with a narrow clip The pseudo-layered microporous structure of the layer 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 to the European Patent Office that the catalytic component is on the surface of the carrier in a highly dispersed active state. a dominant distribution of the 126432.doc -13-200836831 catalytic components in the sub-surface layers of the support in a highly dispersed active state), (in the original line), a carrier rich in cerium oxide A catalytic state with higher activity, and thus the catalytic state of higher activity allows the catalytic component to withstand sintering, aggregation and self-carrier flaking and contact agents (see, for example, paragraph 11 of EP, 575). EP '575 confirmation 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, paragraph 17 of £?575). To solve this diffusion limitation problem,]8&1^1] &lt;:0 et al. propose (and claim) a carrier structure in which "thin, layer 矽-oxygen fragments Forming a narrow space separating interlayer (i.e., pseudo-layered microporous structure as much), the narrow interlayer space contains a large amount of ,, ,, 〇H group, such 〇H groups of protons can be cation exchange. Barelko et al. revealed that a sufficiently thin &quot;thin&quot; layer of bismuth-oxygen fragments is unique for high Q3 to Q4 ratios, and they further clarify that f has a large pseudo-point of 〇H groups sandwiched between narrow interlayer spaces. The layered microporous structure has been confirmed by 29Si NMR (nuclear magnetic resonance) and spectroscopy (infrared) spectroscopy combined with argon BET and alkali titration surface area measurements, such as those in the glass catalyst composition, Many conventional catalysts attempt to solve the processing problems identified in the 7th, but they are not good in other aspects of the performance of the female. Therefore, these conventional catalysts are often limited to a narrow range of process reactions. The use period is limited before the regeneration or replacement is required and/or a large amount of expensive catalytic components (such as (4), precious metals) are required to be charged, thereby significantly increasing the cost of catalyst production and catalytic process. Therefore, it is necessary to improve Catalysts can be used in a variety of processing reactions while improving such as process responsiveness, selectivity and/or energy efficiency 126432.doc -14-200836831, etc. The catalyst composition is preferably suitable for a wide range of process strips. Improvements in requirements and requirements while enhancing robustness and durability, and maintaining a relatively long life cycle. Applicants have discovered a functional surface catalyst composition that is expected to meet the needs of this wide range of catalytic reactions. An aspect of the invention provides a process for the selective hydrogenation of a process stream, comprising: selectively Φ hydrogenating at least a portion of a process stream using a catalyst composition comprising at least one target hydrogenatable group having at least one target a compound of a point, wherein the catalyst composition comprises: - a substantially microporous/non-porous matrix having a large pore, an outer surface, an open pore wall surface, a surface region, and a subsurface region, - at least one catalytic component, and At least one catalytically active region comprising the at least one catalytic component, wherein the ruthenium is substantially free of microporous/non-porous matrix having 10 1) ▲ selected from the group consisting of S · Α·ΑΓ2-ΜΓ 'S · AD-MT and The total surface area measured between about 〇·1 m2/g to 50 m2/g when measured by a combination of methods; and u) Predetermined • isoelectric point (IEP) obtained at a pH range of 0 but less than or equal to 14; b) at least one catalytically active region may be continuous or discontinuous and have an average thickness of 0 less than or equal to about 30 nm. And U) catalytically effective amount of at least one catalytic component; and (c) at least one catalytically active region positioned substantially 126432.doc -15-200836831 D on the outer surface, i〇 on the open pore wall surface, in the surface region Inside, iv) is partially on the open pore wall surface, partially in the surface region and combinations thereof; or V) (C) (i), (ii), (in) and (iv). Other aspects of the invention will be apparent to those skilled in the art from the <RTIgt; [Embodiment] Definition The terms used herein have the meanings defined below. "Pore" means a cavity or channel having a depth greater than the width. ''Interconnecting pore π denotes a pore that communicates with one or more other pores. '▼ Closed pore, indicating that there is no pore in the outer surface of the material where the closed pore is located • ''Open pores') means direct passages to the outer surface of the material in which the open pores are located, or pores connected through another pore or interconnected pores (ie, pores that are not part of the closed pores). The π pore width '' indicates the inner diameter of the pore or the distance between the opposing walls determined by the specified method. The pore volume product represents the total volume effect of all pores determined by the specified method, but does not include the volume effect of the closed pores. π Porosity &quot; denotes the ratio of the pore volume in a material to the total volume of the material. 126432.doc -16- 200836831 Micropores '' denote pores having an internal width of less than 2 nanometers (nm). Mesoporous &quot; denotes an internal width between 2 nm and 50 nm. The "large pores" indicate pores with an internal width greater than 50 nm. The outer surface '' indicates the outer boundary or skin of a material (thickness is near zero) ), including the outer boundary or the surface of the skin with respect to the defect (if any) or the irregular wheel wall surface" refers to the inner boundary or skin (thickness near zero), including any defects on the inner boundary or the skin (if There are related rules or irregular contours that are substantially defined in the shape of any open pores in a material having at least one or more types of pores. ''Surface' generally indicates the surface of a pore wall of a material (if any open pores exist), the surface of the material and its surface area. The surface area means that it may vary depending on the material and does not include any open pores of the material (if present) The material region of the region defined by any open pores' but the surface region (4) is less than or equal to 咐 (preferably (four) nanometers below the outer surface of the material, more preferably when the carbon nanotube has any open pores in the material, The surface region (b) is below the surface of the pore wall of the material: (4) nanometer (preferably (four) nanometer, more preferably 0, and there is a material that can be said to have a surface elevation change, regardless of whether the change is: External boundary or internal boundary or skin, external or internal edge ^ The average elevation of the skin is used to determine the average depth of the surface area. One material = subsurface area, indicating that it can be changed according to the material does not include any open pores of the material (If there is any open pores), the surface of the material under the surface is less than 3 〇 126432.doc -1 below the surface of the material. 7-200836831: for &gt;=m, more preferably &gt;1〇N); in the material there is any open hole 2:: subsurface area (b) below the pore wall surface of the material (preferably &gt; 20 nm, more preferably &gt; 1 〇 nanometer. ^ Surface area pores (4) Surface area, which represents the surface area effect of all open pore walls in the material determined by the specified method. The gap table / product" means determined by the specified method It does not include the material surface area effect of the surface area effect of all pores in the material.

"Total surface area" means the sum of the internal surface area of the material and its external surface area determined by the specified method. The sodium chemisorption surface area, or SA*, represents the surface area of the material as determined by chemisorption of sodium cations using a chemisorption method. (4) chemisorption method in Gw·Sears Anal. Chem, 1956, vQl 28, p and R · Iler, Chemistry of Silica, J〇hn Wiley & s〇ns 1979, p 203 and 353. "Sodium chemisorption surface area change rate" or "SARC^", where SARQfVy U/V is initially, where (1)v is initially the initial volume of the dilute NaOH titration solution used to initially titrate an aqueous slurry mixture, at about 25 at its temperature at 3 • The 4 M NaCl solution includes a material that is substantially insoluble in water, and the pH of the solution reaches pH 9 最初 from the initial pH 4 零 at zero time t0, and (ϋ)% to &quot; is used to make the slurry mixture at 15 The total volume of the same / / NaOH titration solution maintained at pH 9 for a period of 5 minutes, every 5 minutes (a total of 3 5 minute intervals, respectively ts, t1 () and tH) the total volume as needed Adjust accordingly. Therefore, the term "V" refers to the total volume of NaOH titration solution used in the titration procedure described in more detail below, where V^+V5q5=v total. Therefore, it can be expressed as the difference between v total and v initial, where V5q5=v total _v phase. For the purposes of this definition, a 3.4 M NaCl solution was prepared by adding 3 gram grams of NaCl (reagent grade) to 150 liters of water, and 1 gram of sample material was added to the NaCl solution to produce an aqueous slurry mixture. The aqueous slurry mixture must be adjusted to pH 4.0 first. In order to carry out this adjustment before titration, a small amount of a dilute acid (e.g., HCl) or a dilute base (e.g., Na〇H) may be used accordingly. For the timing of the titration, in order to obtain the V initial, first use a dilute NaOH titration solution (for example, 0.1 N or 0,01 N), and then use Vy for the SARC heart measurement. Further, for the purposes of this definition, Vs to 15 is the cumulative volume of the NaOH titration solution used at t5, 〇1〇, and 115, wherein the NaOH titration solution is titrated as quickly as possible every 5 minutes (3 3 minute intervals). Take t as needed. The pH of the slurry mixture was adjusted to 9.0 within 15 minutes of the final time. For the purposes of this definition, it is treated with any alternative ion exchange (ΙΕχ), counter ion exchange (BIX) and/or electrostatic adsorption (ΕΑ) treatment to produce one or more Type 2 component precursors (described below) Determine the Sarc^ of the sample material before it is integrated onto the surface of the substrate and/or before the surface of the substrate. "Incipient wetness" means that for an aqueous slurry or a paste mixture comprising a solid or semi-solid material, a point in time at which the isoelectric point (&quot;IEp" of the material is being measured, at which point the deionized water substantially covers The entire surface of a solid or semi-solid material, and to the present extent, fills any water-permeable pore volume that the material may have, thereby allowing water to enter the aqueous slurry or paste mixture to provide contact between the glass electrode contact and its reference electrode The surface and the sufficient liquid contact between the two, and then determine the IEP of the material. 126432.doc -19- 200836831 π isoelectric point π or IEP represents the pH of a solid or semi-solid material with zero net surface charge at initial humidity. The value used herein may also be referred to as a zero point charge (ZPC) or a point 〇f zero charge (PZC). "Catalytic effective amount" means sufficient under appropriate processing conditions The at least one reactant is converted to at least one predetermined product in sufficient yield to support the amount of catalytic component of the pilot plant or commercial grade. ''Chalconide' table Illustrated to include at least one Group 16 (formerly Group VIA) element from a group consisting of sulfur (S), cerium (Se), and cerium (Te) and at least one element having a positive charge that is stronger than its corresponding Group 16 element a compound of the element or group. The shell metal '' indicates a transition metal from the group of lanthanum, palladium (Pd), silver (Ag), lanthanum (lr), platinum (Pt), and gold (Au), unless otherwise specified as a metal complex. The form of the metal salt, metal cation or metal anion is in a state of charge, otherwise the various transition metals are in a zero oxidation state (at the same time in an unreacted state). ', corrosion-resistant matrix' means a matrix that can resist substantial changes in the matrix composition of the subsurface region. The change in the structure is due to changes in the structural elements of most acids or dilute bases under standard temperature and pressure conditions and/or The structure of the loss, new pore formation, pore size expansion, etc. may be high-strength acid (such as concentrated HF), high-intensity test (such as concentrated NaOH) or other strong-resistance reagents (regardless of It is changed either alone or in combination with the local temperature 'high pressure and/or high vibration frequency conditions. For the purposes of this definition, such a matrix is still considered to be &quot;corrosion resistant&quot; matrix. 126432.doc 200836831 Surface activity" means The surface of the material is sufficiently filled with - or a plurality of charged knives &amp; ' $ _ or a plurality of charged components of the material used to (1) promote the catalytic reaction under the conditions of stable reaction without further modification, or (^ In addition, the error is caused by electrostatic interactions with / or a plurality of charged components and/or ions are exchanged for further modification, and then can be used under steady state reaction conditions. Catalytic component. ''Substrate' means any solid or semi-solid material, including but not limited to glass

And the glass material, IEP is greater than ❹ but less than or equal to 14, and the surface active state can be modified according to the intended use of the substrate in the catalyst composition (having a catalytically effective amount of the catalytic component). "Integration, means (9) mu, electrostatic or covalent interactions by electron and/or physicochemical, including but not limited to hydrogen bonding, ionic bonding, electrostatic bonding, Van der Waals / Dipole bonding, affinity bonding, covalent bonding, and combinations thereof) Combining chemical components with a substrate. 0. Overview of the Embodiments The subtraction of the annotations in this embodiment is based on (4) selected aspects related to the patent scope of the accompanying towel. And the factors are therefore only used in a concise manner to facilitate the presentation of certain aspects of the embodiments that may be related to the potential benefits of the reader. Therefore, the description of this embodiment should not be construed as limiting the scope of the invention. One aspect of the invention is directed to a catalyst composition having a surface active catalytically active region having an average thickness of less than or equal to about 30 nanoliters, preferably about 20 nanometers and more preferably (four) 10 nanometers (,, Catalyst composition &quot;). Another aspect of the invention is 126432.doc-21-200836831 for various methods of making novel catalyst compositions. Another aspect of the invention is to produce a composite form of a catalyst composition ,no There is no forming medium. Yet another aspect of the invention relates to the use of catalyst compositions in various processes, such as hydrocarbon, hydrocarbon and/or non-hydrocarbon treatment, conversion, refining and/or emission control and treatment. Processes and other types of processes. For example, new catalyst compositions can increase the selectivity of reactions, reaction rates, hydrocarbons, hydrocarbons, and/or non-hydrocarbon treatment, conversion, refining, and/or emission control and treatment processes, and other types of processes. Yield and energy efficiency of the finished product. Several factors should be considered in the production of the catalyst composition, including but not limited to: (In view of the intended use, obtain a substrate with a predetermined isoelectric point ("IEP&quot;)" Obtained as it is or after subsequent processing; (ii) the degree of corrosion resistance of the substrate for the intended use of the cloud; (iii) the degree of porosity (if any) of the substrate in order to obtain the desired surface properties for the intended use, and Related elemental composition (particularly on the surface), (iv) depending on the intended use of the composition, and where appropriate, the chemical sensitivity of the substrate to the generation of an appropriate isoelectric point, and The substrate is surface active by one or more first components having a first type of ion and/or electrostatic interaction with the substrate, the substrate being capable of, but not necessarily, producing a catalytically active region on the surface of the substrate and / or within the average thickness of about 30 nanometers, preferably about 2 〇 nanometers 'better than about 10 nanometers; (V) matrix for - optional ion exchange (ΙΕχ), counterion exchange 126432.doc -22- 200836831 (BIX) and/or chemical susceptibility of electrostatic adsorption (EA) treatment methods for integrating one or more second components onto and/or within the surface of a substrate The surface has a second type of interaction with the matrix ions and/or electrostatics and thus produces a catalytically active region having an average thickness on the surface of the substrate and/or within the substrate of about 30 nanometers, preferably about $about 2 〇 nanometers, more preferably about 10 nanometers; and (vi) depending on the intended use of the composition, the chemical sensitivity of the treated substrate to the following reactions: optional calcination and/or reduction, oxidation or Further processing the treated substrate in use The composition of the media prior to chemically react with the first or second catalytic component. I. Substrate Description IEp selection for the general and preferred ranges of many potential applications. Preferably, the matrix used to produce the catalyst composition of the present invention is a glass composition, whether the surface activity is received as received or processed. The state of surface activity, IEP is greater than about 〇 but less than or equal to 14. The availability of a matrix with a suitable IEP (suitable for producing a catalyst composition for the intended use) depends on various factors, some of which have been outlined above (in the "Overview of the Implementation"). In more detail, those skilled in the art will be more aware of other factors associated with the selection of an appropriate IEP. For example, for many processes of commercial interest, glass (or glass-like) compositions and their surface active products preferably have A glass composition greater than or equal to about 4. 5 but less than 14, and a glass composition having a ΙΕΡ greater than or equal to about 6 〇 but less than 14 is preferred, and a glass having a ΙΕΡ greater than or equal to about 7.8 but less than 14 is expected to be 126432.doc -23- 200836831 The composition is 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 IEP may be affected. In addition, certain catalytic processes are A surfactant composition having a surface activity at a lower pH range is more sensitive. Therefore, in such cases, a substrate having an IEP of less than 7.8 (preferably, more preferably $4·5) It is likely to be more suitable for such processes. Therefore, it is again stated that when selecting a matrix within the appropriate range, it is not only necessary to consider the intended use of the catalyst composition, but also to combine the porosity of the substrate, the chemical composition and Processing procedures, if any, etc. In addition, depending on the intended catalytic use, many glass types can be potential matrix candidates to achieve the appropriate degree and type of porosity and porosity' whether received or used as received Various treatment methods. Usually, examples of such glass types include, but are not limited to, bismuth-type glass, boron-free ε-type glass, S-type glass, R-type glass, AR-type glass, rare earth-silicate glass, strontium-titanium-stone. Niobate glass, nitride glass such as Shixi-aluminum-oxygen-nitrogen glass, bismuth glass, C-glass and CC-type glass. However, the following examples are generally intended for a range of catalytic applications and some possible treatments. The glass type 0 macroporous glass indicates that the substrate used to produce the catalyst composition of the present invention preferably has substantially no microporosity, no mesoporosity, but some macropores ( No microvoids / pores ,, No Glass) made of the glass composition, whether originally having a surface active 'or a surfactant treated formed state, the IEP is generally greater than 7,8. Bypassing, the microporous/no-porous glass composition having an IEP greater than 7.8 will include 126432.doc -24-200836831 including an acidic or basic oxide type glass mesh modifier, including, for example, but not Limited to oxidation of elements such as zinc (Zn), magnesium (Mg), calcium (Ca), aluminum (A1), boron (B), titanium (Ti), iron (Fe), sodium (Na), and potassium (&amp;) Things. If an alkali network modifier is used, the amount included in the lower IEp glass tends to be &lt;15 wt.%. A glass containing magnesium, calcium, aluminum, zinc, sodium, and potassium is preferred, and a glass combination containing more than or equal to about 70 wt.% of ceria is preferable. However, the macroporosity corresponds to less than about 98% of the total surface area, and the substantially geometrically non-porous, void-free glass composition having a corresponding geometric outer surface ranging from about 2% to about 50% of the total surface area can also be used to produce the present invention. Catalyst composition 'and the composition (10) Piif is greater than 78 but less than or equal to 14. Porosity indicates that the porosity of the matrix produces another relevant aspect of the catalyst composition of the present invention. Generally, the matrix should be substantially non-microporous and free of mesopores, but the actual f can be in the presence of the number of b, irrespective of the microporosity and/or mesoporosity of the intended use of the catalyst composition. . Since the 10 (four) (four) product in the material is often difficult to prepare, the description uses two surface area measurements, 疋i 7C, which is substantially free of microporosity/non-woven pores to identify the catalyst composition of the present invention. The term surface area is measured by the thermal adsorption 7 desorption method applicable to the measurement, and can be used for (4) the degree of microporosity, pores and/or macropores. For example, for larger surface area measurements (eg, >3 V/g) N2 bribes, as described in ASTM D3663_〇3, (&quot;SA &quot;, , (may be a preferred surface area measurement technique) However, for smaller surface area measurements (eg &lt; about 3 m2/g) Kr BET, the method described in 126432.doc -25 - 200836831 ASTM D4780-95 may be a preferred surface area measurement technique. The surface area measurement method for solid and semi-solid materials will be clear for the best surface area measurement method for detecting microporosity, mesoporosity and/or macroporosity. The second measurement system is sodium-chemical adsorption surface area C'S.AO A certain type of analytical method (r·Iler described in chemistry of Silica, John Wiley &amp; Sons (1979) pp. 203 and 353) is expressed as the change in time for the NaOH titrant and in accordance with the rate of change of sAw (''SARC〇) More specifically defined. Thus, as defined herein, the matrix is substantially free of microporosity/no mesoporosity's two-battery-based lamps or §·Α·^: γ-5£γ is at about 0·1 m2/g Up to about 50 m2/g, and its SARCw is less than or equal to 0.5. More details above For a detailed discussion, SARCN "f, the ratio of the two volumes of NaOH titrant, the denominator is the volume of the initially used NaOH titration solution, that is, initially used to titrate a matrix slurry mixture at zero time t, the matrix slurry mixture is A 3.4 M NaCl solution (pH 4 to pH 9) contains 1·5 gram of matrix at about 25 ° C. However, as described above, the initial NaOH titration is used for 8 8 11 (: The slurry mixture must first be adjusted accordingly to a pH of 4 with a small amount of acid (HCi) or base (NaOH). In addition, as described above, the NaOH titrant (for three 5 minute intervals, the matrix slurry in 15 minutes) The cumulative volume of the mixture maintained at pH 9) is initial (i.e., v#i5), which is the numerator of the ratio SARCw. Therefore, if the initial value of V-V is less than or equal to 0.5 V, the corresponding SARC is less than or equal to 0.5. Therefore, as defined herein, the matrix of the SARC core '0.5 is substantially free of microporosity/no mesoporosity (ie, macropores)' premise that the matrix SA#2· is destroyed by SAu£r also in about 〇·ι m2/ g to 126432.doc -26- 200836831 between about 50 m / g. The right surface area parameters are satisfied For any matrix will have a pore volume of other types, it may be insufficient concentration, distribution and / or type, which can achieve a desired performance produce adverse effects on the intended use of the catalyst composition. The sodium surface area (&quot;S.A.a^&quot;) is an empirical titration procedure developed for substantially pure silica dioxide (Si〇2) in the form of granules, powders and suspended sol forms. 8. VIII. The measure of the reactivity and accessibility of the surface proton position (Glass-CTH+) is equivalent to the Si-0 H+ position for pure silica. The composition of the sulphate glass and the crystalline sulphate is significantly different from that of the pure cerium oxide (Si〇2). The stoichiometry of the titration procedure, the behavior of bismuth silicate glass and crystalline citrate It cannot be known or predicted based on the absolute value of the NaOH titration solution measured in the SA·. experiment. Therefore, the equations used by Sears and Iler to correlate the NaOH volume of the S·Α· experiment with the ΒΕΤ^ΒΕΤ surface area of the ceria material studied are not suitable for reliably predicting the absolute surface area of more complex citrate compositions. This is expected [because the Giasss_〇-H+ groups that can exist in different compositions of glass can include, for example, Α1_ΟΉ+, Β-ΟΉ+, Ti-0_H+, Mg_CTH+, and multiple Si-0_H+ portions with a single Shishi position. A combination of more different structures of protons (Q2 group). On the other hand, the total surface area of a "glass-like" glass composition (such as acid-impregnated quartz) may be reliably determined using SA·- experiments, provided that the minimum pore size is within the range achievable by standard gas-phase BET measurements. Because it is mainly composed of networked Si〇2 and Si-CTH+ parts. However, part of the diffusion accessibility of hydroxide ions (OH) and sodium ions, and microporous contrast in the pores, macropores and / Or the phase of the substantially non-porous area 126432.doc •27- 200836831 The percentage should be based on the Na 〇 desire (in the experiment, if the experiment is to keep the most _9' must be added in time) (titrant). Therefore, in summary, the accessibility of GW〇.H+ for OH· and Na+ contrast time, as determined by the above SAR' experiment, can be used as a reasonable guilty read of microporosity, including standard vapor brittle measurements. A certain type of porosity that is not accessible. Preferably, the surface area of the substrate will remain substantially unchanged after its ion leaching process, which is common for most test (, AR) glasses.

However, in some cases, some of the ions consumed from the matrix network do not sway the microporous structure of the base, if any, thereby avoiding the desired performance of the intended use of the catalyst composition. Negative Effects. However, if there is significant ion depletion and associated leaching on the matrix network, it is reported that a microporous region is produced in the matrix. Therefore, as described above, (10) 'greater than about 〇·5 守 守 indicates that such a microporous structure exists. The matrix network exhibiting such properties has produced sufficient microporous structure, particularly in the matrix region, which will adversely affect the ability of the radical f to maintain a surface active state, thus the catalyst composition The desired performance to achieve the intended use has an adverse effect. Matrix Shape, Form and Size Description The matrix used to produce the catalyst composition of the present invention has a variety of shapes and forms. Examples of suitable shapes include, but are not limited to, fibers, fibrillated fibers, cylindrical particles (eg, pellets), spherical particles (eg, spheres), elliptical particles (eg, ellipsoids), flat particles (eg, sheets), no Regular broken particles, spiral or helical particles, and combinations thereof. Examples of suitable shaped bodies or composites that can form such matrix shapes 126432.doc -28 - 200836831 include but are not limited to: woven composites, non-woven composites, mesh fabrics, extrudates, rings, saddles Objects, cylinders, membranes, spiral bonded membranes, filters 'fiber filaments, chopped fibers, and combinations thereof. In some cases, depending on the intended use of the catalyst composition, any suitable material may be used as the forming medium to form a shaped body or composite with the catalytic matrix (collectively &quot;composite &quot;), including but not limited to Soft water|boehmite, hydrated titanium dioxide and Ti〇2, hydrated oxidized hammer and Ζγ〇2,γ

Alumina, alpha alumina, ceria, clay, natural and synthetic polymeric fibers, polymeric resins and solvents, and water soluble polymers, whether or not the matrix comprises a Type 1 or Type 2 catalytic component (described in more detail below). Preferably, the catalytic substrate should be at or substantially adjacent to the outer surface of the composite (i.e., at the outer periphery of the composite). Without being bound by theory, it is believed that if a substantial portion of the catalytic substrate is placed on and/or within the outer surrounding region of the catalyst composite (&quot;composite material'), it will reduce the occurrence of unwanted The extent of the internal composite diffusion effect. Therefore, it should be noted that the proper distance for positioning a substantial portion of the catalytic substrate within and/or over the periphery of the composite material will depend on the intended use of the catalytic composite, the overall size and shape of the catalytic composite, and the catalysis. The overall size and shape of the substrate. Therefore, in various composite shapes and sizes, the average thickness of the periphery of the composite (the catalytic group may be placed on and/or within the periphery of the composite, usually between about 四 (4) and about tens of micrometers. The average thickness of the periphery of the composite is preferably between about m and about 250 microns, more preferably between about m and about 15 microns. However, depending on the intended use of the composition, in some cases Next, 126432.doc -29- 200836831 may require the matrix to be substantially distributed throughout the forming medium. For example, but not limited to, 'in the process of expanding the exposure of reactants and/or reaction intermediates', preferably on the entire forming medium The composite matrix (whether type 1 or type 2 catalytically active matrix) has a controlled pore size distribution which is preferred but not essential. The minimum size of the matrix used to produce the shaped body or composite (ie the average maximum size of the matrix particles) Typically between about 〇〇5 microns and less than or equal to about 150 microns, preferably between about 〇2 microns to less than or equal to about 15 microns, more preferably from about 2 microns to about 5 microns. Between microns. However, depending on the intended use of the composition and other process variables that may be affected by the shape and form of the combination of catalysts, substrates outside this range may still be effective, for example, in the continuous fiber form described above, The desired performance of the catalyst composition is adversely affected. Those skilled in the art will appreciate that the composite operation may introduce potential mesopores and/or microporosity into the finished composite. However, in composite operating systems, such as this article Said porosity is not introduced into the functionalized surface component of the catalyst composition. II. Matrix surface activation The matrix used to produce the catalyst composition of the invention can be activated by - or a plurality of first adult surface, The first component has a first-class ion and/or electrostatic interaction with the matrix (!-type component precursor &quot;). As described in more detail below, the !-component precursor may have catalytic activity or may pass through Rationally to produce catalytically active regions, everywhere

The average I degree on and/or within the surface of the oyster shell is about 3 〇 nanometers, preferably &lt; horse = an average thickness of about 20 nanometers, more preferably 126432.doc -30 - 200836831: about 1 inch The average thickness of the nano. For example, in some cases, depending on the intended composition of the conjugate, if the substrate obtained has a suitable type and degree of pore structure (if any) and an isoelectric point _) in a dry perimeter suitable for the intended use, The matrix may be sufficiently surface active upon receipt, and may be effectively catalyzed, although not necessarily, but preferably, the substrate may be treated to further modify and/or improve its surface activity. In addition, the substrate can also be treated to remove any organic coating that is expected to interfere with the performance of the catalyst composition.

In addition, as discussed in more detail below, in the &quot;type 2 precursor precursor integration: , depending on the intended use of the catalyst composition, it may be better to use ion exchange (IEX), counter ion exchange ( ΒΙχ) and/or electrostatic adsorption (ea): the method further processes the surface of the substrate, the processing method integrating one or more second components onto the surface of the substrate and/or β, the surface of the I having a second type and matrix The ions and/or electrostatic interactions, and thus the catalytically active regions, have an average thickness on the surface and/or within the substrate of $3 nanometers, preferably $20 nanometers, more preferably $1 nanometers. Substrate contaminant removal treatment depends on the composition of the material typically found on the surface of the substrate and whether the material is expected to interfere with the preparation of the catalyst composition and/or interfere with the desired properties of the catalyst composition for the intended use. , optional for removal of contaminants. For example, typically, AR-type glass is made using an organic coating (i.e., sized) that is used to facilitate processing, such as dispersion in aqueous formulations. However, the organic coating or sizing may interfere with the preparation of the catalyst composition, even if it does not interfere with most, if not all, of the catalytic properties of the intended use of the catalyst composition. Therefore, the organic coating should be removed. 126432.doc •31- 200836831 Wave Burner is a preferred method for removing such organic coatings. Because the primary goal of this treatment is to remove contaminants from the matrix, the conditions of such sinter treatment are not particularly important for successful surface activation of the matrix. In some cases, depending on the nature of the contaminant to be removed from the substrate, solvents, surfactants, aqueous washes, or other suitable methods can be used to remove contaminants for satisfactory results. However, depending on the degree of calcination used, the substrate is preferably calcined in an oxidizing atmosphere (e.g., in dioxane or oxygen). In addition, it is important to select a sufficient calcination temperature to remove the target contaminant, but the calcination temperature is low enough to avoid the softening point of the material. Generally, the calcination temperature should be at least about 5 ° C lower than the softening point of the selected matrix material. Preferably, the calcination temperature is at least about 1 Torr lower than the softening point of the selected matrix material. For example, when using ar-type glass, the majority of the AR-type glass can be cured to remove contaminants at a calcination temperature of between about 300 C and about 700 °C. Typically, the selected matrix material should be calcined for about 2 to 14 hours, preferably for 4 to 8 hours. Nonetheless, the calcination time depending on the nature of the substrate obtained and the target contaminant to be removed from the substrate can vary outside of these time ranges. Surface activation by ion leaching treatment After any potential contaminants are substantially removed from the substrate, the substrate can be treated to produce a surface active state and a desired isoelectric point, provided that the initial IEP obtained from the substrate is not desired. Within the scope. However, in some cases, the substrate being received may have sufficient surface activity to be further modified using other treatments (described in more detail below) without the use of first-class ion leaching (ΙΕχ) treatment. (This will be discussed first in the other processing described in more detail below, 126432, doc-32-200836831). In other words, the composition of the elements of the matrix, particularly on the outer surface or substantially close to the outer surface, can be sufficient to obtain the desired IEP. However, in many cases, the composition of the matrix will require some modification to alter the original IEP and obtain a suitable intended use of the subsequent photocatalyst composition to achieve surface activity that meets the requirements in terms of type and degree. status. • a surface active state in which one or more of the first components have (1) a first oxidation state and (丨丨) a first type of ion and/or electrostatic interaction with the substrate, which may be sufficient to generate a catalytically active region, The average thickness on and/or within the surface of the substrate is about 30 nanometers, preferably about 2 nanometers, more preferably about 10 nanometers, and thus provides the desired properties of the catalyst composition for the intended use. For example, but not limited to, Bronsted or Lewis acid sites and Brunsett or Lewis bases on and/or within the surface of the substrate are effective to promote some hydrocarbons, hydrocarbons (eg, oxygenated hydrocarbons). And non-hydrocarbon treatment, conversion and / or refining processes. _ However, in other cases, based on the intended use of the catalyst composition, it may be preferable to further treat the substrate surface by one or more ion exchange methods as described below to achieve (1) the same as the first oxidation state. Or a different second oxidation state, and (ϋ) the second type interacts with the ion and/or electrostatic phase of the substrate to produce a catalytically active region having an average thickness of about 30 on and/or within the surface of the substrate. The nanometer is preferably about 2 nanometers, more preferably about 10 nanometers. Turning now to surface activation treatment, the surface activation treatment comprises at least one ion leaching treatment to obtain a first type or class I ion exchange (IEX_0 matrix. 126432.doc -33 - 200836831 However, it should be understood that if the substrate received has The IEP suitable for the intended use of the catalyst composition is also intended to be used to describe the first type of substrate. Generally, the ion leaching treatment is performed by any suitable method, that is, in a substantially heterogeneous manner. The entire substrate surface effectively removes the desired ionic species without significantly eroding the matrix network (eg, avoiding the creation of any microporous structures in the surface region and/or subsurface regions), such as, but not limited to, large P-knife Anthraquinones, whether inorganic or organic, and various chelating agents, are suitable for ion leaching. Preferably, inorganic acids such as, but not limited to, nitric acid, phosphoric acid, sulfuric acid, hydrochloric acid, acetic acid, chloric acid, Hydrobromic acid, chlorosulfonic acid, trifluoroacetic acid, and combinations thereof. Generally, the concentration of the acid solution used for ion leaching treatment depends on the characteristics of the substrate (for example, from a glass mesh) The affinity of the removed ions, the strength of the glass after removal of the network ions, the extent to which the IEP of the substrate needs to be altered, and the intended use of the catalyst composition. Preferably, the acid, valley for ion leaching treatment The concentration of the liquid may range from about 0. 5 Wt% to about 5 〇 wt. Q/G, more preferably between about 2.5 wt./〇 to about 25 wt.%, most preferably about 5 wt·. Between about 1 〇 wt %. The integrator can also be used in ion leaching treatments such as, but not limited to, ethylenediaminetetraacetic acid (&quot;EDTA&quot;), crown ethers, oxalates, polyamines, polycarboxylic acids And its combination 0. Usually the concentration of the chelating agent solution used for ion leaching depends on the properties of the substrate (eg, the affinity of the ions to be removed from the glass network, the strength of the glass after removal of the network ions) And the intended use of the catalyst composition. The concentration of the chelating agent solution used for ion leaching treatment by the rider may be between 126432.doc -34 - 200836831 about 0 · 0 01 wt · % to the sum More preferably at about 0·01 Wt·% to saturation

Usually, depending on the characteristics of the acid used, the heat treatment conditions for the handy, type and concentration, and the matrix, and the sound of “钣(9) ^, such as heating/dish, heating time and mixing conditions are selected. The temperature of the solution or the chelating agent is again/decreased, and the heating temperature varies widely. W, and preferably, the heating temperature of the ^^^^^^^^^ is about 20 C to the secondary treatment. About 200 ρ bow ^, between WL, better at about 4 〇ΐ: to about %. Between the best between about 6 〇. 〇 to about 9 〇. Factory 卩 卩 卩 ^ 7 L between. Preferably, the heating temperature suitable for the chelating agent ion leaching treatment is in the range of about 2 (rc to about fine t, more preferably in the range of about 40 ° C to about 90 ° C. Depending on the concentration of the acid solution or the chelating agent solution The heating time suitable for the ion/removal treatment may vary depending on the heating time. Preferably, the heating time for the ion leaching treatment is between about 15 minutes and about 48 hours, more preferably about 3 minutes to Between about 12 hours. ^ ^ depending on the type and concentration of the acid or chelating agent used and the characteristics of the substrate (for example, from glass) The affinity of the ion removed by the glass mesh, the strength of the glass after removing the mesh ions, etc., and the duration of the heat treatment, and the mixing conditions are selected. For example, but not limited to, the mixing condition may be continuous or broken, It can be mechanical mixing, fluidization, tumbling, rolling or manual mixing. In short, 'the combination of acid or chelating agent concentration, heat treatment conditions and mixing conditions' will be based on the formation of sufficient ions between the acid or chelating agent and the target matrix ions. The degree of exchange (,, IEX) is determined to produce the appropriate isoelectric point and the type and extent of surface charge to achieve the intended use of the substrate for post-treatment or catalyst group 126432.doc-35-200836831 The surface active state is required. After the ion leaching treatment is completed, the ion leaching substrate is preferably separated by any suitable method, including but not limited to filtration, centrifugation, decantation, and combinations thereof. Ion leaching treatment with a variety of suitable cleaning solutions (such as deionized water and / or a suitable water-soluble organic solvent such as methanol, ethanol or acetone) The substrate is dried for about 2 to 24 hours at a temperature of about room temperature to 11 G C. The reverse ion exchange treatment may, in some cases, be based on the intended use of the catalyst composition, possibly in a preferred manner for the selected substrate. Perform reverse ion exchange ("Βιχ") or two-step ion exchange treatment (collectively referred to herein as "ruthenium treatment"). βΙχ treatment is often referred to as (in addition to) counterion &quot;parent replacement, because the ion-leached matrix Mixing with a salt solution (eg, NaCl) that includes one of the ions initially removed, such ions (eg, Na+) removed from the substrate by ion/texture treatment are then returned or returned to the base. It is not clear from Whether the ions removed from the matrix will necessarily 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 due to BIX treatment, it should be understood that the BIX treatment described herein covers the placement of any such possible 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 ions that will undergo reverse ion exchange. Preferably, only one type of ion counter ion exchange is performed, but in some cases, counter ion exchange of two or more ions may be required. 126432.doc -36· 200836831 Any ion that is easily removed by the above ion leaching process can be subjected to counter ion exchange. Some examples of such plasmas include, but are not limited to, Group 1 (former Group IA) metal ions, such as chain, nano and Shu ions, and alkaline earth metal ions from Group 2 (former Group IIA), such as ruthenium. , magnesium, calcium ions, NH4+ and alkylammonium cations, and small organic polycations. Preferably, alkali metal ions and NEU+ are preferred target ions for BIX treatment, while Na+ and NH/ are preferred BIX ions, and Na+ is preferred for BIX ions. Generally, the concentration of the salt solution used for the BIX treatment depends on the type of the substrate to be treated by the BIX by the ion leaching treatment and the relative affinity of the BIX ion for returning to the ion leaching treatment substrate, and, similarly, the BIX ion return matrix network. Site-independent (eg, Na+ relative affinity for matrix versus H+). For most types of glass substrates, such as, but not limited to, AR-type glass, A-glass or quartz glass, a BIX-salt solution having a concentration of about 0.001 mol/L to 5 mol/L is preferred, and about 0.05 mol/L to about A 3 mol/L BIX-salt solution is preferred. Typically, the heat treatment conditions for the BIX treatment, such as the heating temperature, the heating time, and the mixing conditions, are 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 BIX treatment using the BIX-salt solution may be between about 20 ° C and about 200 ° C, more preferably between about 30 ° C and about 95 ° C. Depending on the concentration of the BIX salt solution and the heating temperature selected, the heating time for the BIX treatment can be varied. Preferably, the heating of the BIX treatment is between 126,432.doc -37 and 200836831 between about 5 minutes and about 24 hours, more preferably between about 30 minutes and about 8 hours. Usually 'will depend on the type and concentration of the BIX solution used and the characteristics of the substrate (eg, the affinity of the ions to be removed from the glass mesh, the strength of the glass after removing the mesh ions, etc.) and the duration of the heat treatment , choose the mixing conditions. For example, without limitation, the mixing conditions can be continuous or intermittent, or mechanical mixing, fluidization, tumbling, rolling, or manual mixing. In summary, the combination of BIX salt solution concentration, heat treatment conditions, and mixing conditions is determined by returning a sufficient amount and dispensing a sufficient amount of ions back to the matrix to correlate with the ions in the matrix network. Returning and distributing a sufficient amount of Βιχ_ion is used to produce the desired type and extent of surface charge to produce the surface active state desired for the intended use of the post-treatment or catalyst composition of the substrate. Adjusting the surface charge of the substrate by adjusting the pH Preferably, the negative surface charge on the substrate is required to support electrostatic interaction or affinity with positively charged components (e.g., cationic alkaline earth metals, cationic transition metal components, etc.). However, for some potential touch composition applications, it may be necessary to use a positive surface charge to support the negative charge. (Example # an anionic transition metal oxygen ion, a rock anion anion, a noble metal polyanion anion, etc.) Electrostatic interaction or affinity. By hanging, the substrate/germanium mixture subjected to ion leaching treatment is rounded to a lower or higher than the base f isoelectric point (tube, and), and the surface of the substrate is electrically: a net positive property Evil or net negative state. Think back, also known as 126432.doc -38- 200836831 Zero charge (nZPCn). Therefore, in other words, IEP (or ZPC) can be regarded as the pH of the material having a net zero surface charge on the surface at the time of initial humidity. Therefore, adjusting the pH of the matrix/IEX water mixture to a pH greater than the matrix IEP (or ZPC) produces a net negative surface charge on the substrate. Additionally, adjusting the pH of the matrix/IEX water mixture to less than the pH of the matrix IEP (or ZPC) produces a net positive surface charge on the substrate. For example, but not limited to, if the IEP of the AR-type glass is equal to 9.6, if the pH of the AR-type glass subjected to the ion leaching treatment is adjusted to a pH of &gt; 9.6, a net negative surface charge will be generated on the surface of the glass. . Depending on the IEP distribution of the AR-type glass, it may be preferred to adjust the pH to be greater than the IEP of the substrate - or two or more pH units to ensure that the surface charge is adequately supported. The type of solution used to effect the pH adjustment will depend on compatibility with other reactants, glass stability and desired 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 substrate 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 at a pH that causes the surface charge to produce the same sign as a catalytic component or precursor. Under these conditions, the electrostatic adsorption (EA) type integration mechanism is likely to occur without 126432.doc -39- 200836831. However, without being bound by theory, direct ion exchange (IEX) or reverse exchange (BIX) may occur at the exchangeable surface location resulting in surface integration of the catalytic component or precursor, which is a catalytic component or precursor. It may be physically and/or chemically different from the same components that are integrated under the electrostatic adsorption (EA) mechanism. For example, certain substrate surface portions include cations (or anions) that may be replaced by ionic catalytic components or precursors of the same symbol, which may provide an appropriate but effective exchange of IEX or BIX with the surface portion of the substrate. . For example, without limitation, such moieties, such as a decyloxy (-Si-〇·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 +) Substituted Na+ ions, which in turn produce a matrix having a catalytically effective amount of catalytic component. Controlling the surface charge of the BIX treated substrate by adjusting the pH is as in the case of IEX processing or second; [EX processing ("ΙΕχ_2 processing", as discussed below), for some BIX processing, adjustments may be required 1 11 value, but not required. Similarly, depending on the type of BIX-ion that will be integrated into the surface and the exchange of BIX-ions in the ΙΕχ_2 treatment, the degree of ipH adjustment required will usually depend on the IEP of the matrix and its IEP versus 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 density and other factors. 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, yielding 126432. Doc 40- 200836831 net positive surface charge). Inorganic acid or organic acid or test can be used in dilute concentrations. Usually, the concentration of dilute acid solution or dilute alkali solution will be taken The type of acid or base used, its dissociation constant, and the pH suitable for obtaining the type and density of the surface charge. ΪΙΙ· Type 2 component precursor integration treatment Whether the substrate surface active system is received as it is, or is ion leached (ie, the substrate treated with IEX-1), or treated with BIX, preferably, (1) second ion exchange (&quot;IEX_2&quot;), (ii) electrostatic adsorption (EA) treatment or (iii) certain The combination of IEX-2 and EA treatment further processes the substrate using at least one second component precursor (''type 2 component precursor&quot;) to integrate one or more second component precursors with the second and matrix Ion and/or electrostatic interaction on and/or within the surface of the substrate. Next, according to the intended use, certain 2 type component two-drivers can produce catalytically active regions without further treatment, or can be further processed. Producing a catalytically active region comprising one or more Type 2 components. However, the catalytically active region is composed of (a) a type 2 component precursor, and (b) is composed of a type 2 component derived from a type 2 component precursor. Or (c) consisting of a combination of (a) and (b), the average thickness of the catalytic region on the surface of the substrate and/or within the substrate is about 3 nanometers, preferably about 2 nanometers, more preferably Preferably, it is about 10 nanometers. As mentioned above, in some cases, depending on the intended use of the catalyst composition, the substrate received as received or ion-leached may have catalytic efficacy. However, for many potential applications It is generally preferred to subject the selected substrate to IEX-2 and/or EA treatment, such as, but not limited to, many reaction rates, selectivities, and/or 126,432.doc suitable for use in the process of using the catalyst composition of the present invention. -41 - 200836831 The efficiency of the month can be significantly improved by replacing at least a portion of the first component (&quot;ι-type component) and integrating the second component (&quot;2 component,) with the surface of the substrate. Without being bound by theory, direct or w-bonded ionic interactions are carried out by the age of the material on the surface of the substrate and/or the inner band of the f-loaded by the surface of the oppositely charged substrate Type 2 component precursor ions can be integrated by electrostatic adsorption interactions, and combinations of certain ionic interactions with electrostatic adsorption interactions or some other type of precursor, charge, and surface interactions to be understood. However, regardless of the nature of the interaction, in the case of a substrate received as received, a substrate treated with a ruthenium or a matrix treated with a BIX-form, a second precursor charge-surface interaction is produced. It is thus possible to produce a catalytically active region having an average thickness on the surface of the substrate and/or within the substrate having a thickness S of about 30 nm, preferably about 2 Å nm, more preferably about 1 Å nm. It is only for the convenience of the following discussion 'and is not intended to limit the scope of the invention as described herein'. This article uses ΙΕΧ·2 to collectively refer to the broad range of charge-surface interactions or type 2 component precursor interactions commonly referred to as 2_type component precursors. Interaction. μ In general, the type of ruthenium solution used to treat IEX-丨 treated or ΒΙχ-treated substrates will depend on the subtype of ion exchange to be performed in the press _2 treatment. Either an ion will undergo ion exchange or, in some cases, exchange of two or more ions, or simultaneous ion exchange, or sequential ion exchange. In the case where two different types of component precursor ions are integrated with the matrix, the ΙΕΧ-2 treatment herein is referred to as two ion exchanges or two pressures at _2 126432.doc -42-200836831. Thus, in the case where three different types of component precursor ions are integrated with the substrate, the 'EXEX-2 treatment is referred to as three-ion ion exchange or three positive-thickness treatments. Type 2 ingredients and precursor description

Any salt solution of IEX-2 ion, if it is chemically sensitive to the substrate surface-replacement ion received as it is, treated with ΙΕχβ1 or treated with BIX·, or has charge affinity to achieve or Βΐχ treatment The electrostatic interaction of the surface of the substrate can be used. Therefore, ΙΕΧ-2 ion can be used as a precursor to the type 2 component. As described above, the plasma mx_2 precursor (i.e., the type 2 component precursor) may have catalytic efficiency depending on its intended use, and if so, the plasma IE X-2 precursor can be like a certain type of catalyst composition. The type 2 component is the same as its precursor state X. 'But the ion can also function as a bulk 2 precursor in the preparation of another type of catalyst composition process. However, in general, ionic ΙΕΧ·2 precursors (which can be used to obtain a type 2 component integrated with the surface of the substrate) include, but are not limited to, Blenzel or Lewis acid, Blenz or Lewis, precious metal cations and precious metals. Mismatched cations and anions, transition metal cations and transition metal complex cations and anions, transitional oxyanions, transition metal chalcogenide anions, main oxyanions, functional ions, rare earth ions, rare earth complex cations and anions and combination. Also, depending on the intended use of the catalyst composition, certain ΐΕχ2 ions themselves have catalytic potencies in the precursor state and can form a type 2 component when combined with a suitable matrix. Selective ionic ΙΕΧ 2 precursors with catalytic potency without further processing, some examples include but are not limited to Bu 126432.doc -43- 200836831, =: Road "Acid, Blenz or Louis Test, precious metal cation, k to the genus, ion, sputum, and, is a milk anion, main oxygen anion, halogen

Sub-rare hydroxide ions, rare earth oxide ions, and combinations thereof. Examples of certain precious gold layers and transition metals that can be used as precursors for type 2 components, including but not limited to groups 7 through _ (formerly the first, the first, the first, the sixth, the fourth, and the And the Techu), such as the beginning, full, recorded, copper, silver, gold, bismuth, bismuth, bismuth, chain, iron, abundance, iron, fission, zinc ionic salts and complex ion salts and combinations thereof. For the ΐΕχ_2 treatment, palladium, inscription, money, silver, #, bismuth, copper, silver, gold and recorded ionic salts are especially preferred. For the sake of convenience, the elements of these groups may be obtained by using the element family number of the International Union of Theoretical and Applied Chemistry (IUPAC) nomenclature system ^ httP://pearll.lanl g〇v/peri〇dic/defauh The query is displayed in the chemical element periodic table (and shows the previously used family number). Examples of certain transition metal oxyanions that can be used as precursors for type 2 components, including but not limited to ionic salts of Groups 5 and 6 (formerly Groups Vb and VIb), such as VO, W (V- Chatting 12〇4.6_,Μ.#, M〇7〇246·' Nb6〇196-, Re〇4- and combinations thereof. For the treatment of ΐΕχ·2, especially the ionic salts of strontium, barium, tungsten and hunger Some transition metal chalcogenide anion examples which may be used as precursors of type 2 components include, but are not limited to, ionic salts of Group 6 (formerly Group vib), such as MoS42., WS42-, and combinations thereof. Examples of certain main oxygen anions that may be used as precursors for type 2 components, including but not limited to ionic salts of Group 16 (formerly Via), such as sa^, P〇43, Se〇42, and combinations thereof For the ΙΕΧ·2 treatment, s〇42• ionic salt 126432.doc -44- 200836831 is especially preferred. Some examples of halides that can be used as precursors for type 2 components, including but not limited to group 17 (formerly Ion salts of the Vila family, such as F_, Cl·, Br·, ruthenium, and combinations thereof. For the IEX-2 treatment, an ionic salt of F_&amp;Cr is particularly preferred. Examples of certain rare earth ions and rare earth misaligned cations or ions that can be used as precursors for type 2 components, including but not limited to lanthanides and lanthanides, such as La, Pr, Nd, Pm, Sm , Eu, Gd, Tb, Dy,

Ho, 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 slats, and transition metal-fillers as type 2 components, including but not limited to chromium, molybdenum, iron, niobium Ion salts of barium, iron, cobalt, nickel and combinations thereof. IEX-2 Treatment Description Generally, the concentration of the salt solution used for IEX_2 treatment depends on the type of substrate treated by IEX-1 or BIX-treated and treated with IEX-2 and used to interact with the substrate treated with 0 IEX-1. The relative affinity of the action and/or integrated IEX-2 ions. For most types of glass substrates (such as, but not limited to, AR type, A type, or soda-lime glass), about 0.001 wt.% to saturated • IEX-2 salt solution is preferred, and about 0.001 wt.% to 5 wt.% IEX-2 salt solution. The liquid system is better. However, depending on the functional surface concentration of the catalytic component necessary to achieve the intended use of the catalyst composition, the IEX-2 salt solution may be less than G · 0 G1 wt. % 〇 if multiple ion types are exchanged with the substrate Whether carried out simultaneously or sequentially, the concentration of the salt solution will be relative to the relative load required for the precursors of the various components on the substrate 126432.doc -45-200836831 and the matrix is suitable for the relative of one component precursor versus the other precursor. Affinity adjustments. For example, but not limited to, two ΙΕΧ-2 treatments (ie, two different catalytic component precursors integrated with a BIX-treated substrate) or three IEX-2 treatments (also: π & & & 禋 禋 禋The concentration of the salt solution used to precipitate the various ions in the catalytic component precursor and the ruthenium-1 or BIX-treated substrate will depend on the target relative concentration of the component precursors that are suitable for various types of surface integration with the aesthetic surface and Surface affinity for various ions.

Typically, the heat treatment conditions suitable for the ΙΕΧ·2 treatment, such as the heating temperature, the heating time, and the mixing conditions, are selected depending on the type and concentration of the IEX_2 salt solution used and the characteristics of the substrate. Preferably, the heating temperature suitable for the IEX 2 treatment using an acid may be between about 20 C and about 200 C, more preferably about 3 Torr. 〇 to about 90 ° C. The heating time for the IEX-2 treatment can vary depending on the concentration of the IEX-2 salt solution and the selected heating temperature. Preferably, the heating time for the κΐΕχ·2 treatment is between about 5 minutes and about 48 hours, more preferably between about 3 minutes and about 5 hours. Usually, depending on the type and concentration of the ΙΕΧ2 salt solution used and the characteristics of the substrate (for example, the affinity of the ions to be removed from the glass mesh, the strength of the glass after removal of the network ions, etc.) and heat treatment For the duration, choose this δ condition. For example, without limitation, the mixing conditions can be continuous or broken, mechanical mixing, fluidization, tumbling, rolling, or manual mixing. ~^, ΙΕΧ-2 salt solution concentration, heat treatment state and mixing conditions, the ear is based on the integration of a sufficient amount on the substrate and / or within the 126432.doc -46-200836831 IEX-2 ion and ΙΕΧ · 2 ion The distribution μ is determined irrespective of the nature of the physicochemical bonding of the substrate surface to produce the desired surface charge type and twist to produce the surface active state required to achieve the intended use of the catalyst composition. / Adjusting the surface charge of the substrate by adjusting the pH As mentioned above, what is required for the type 2 component drive that will be integrated with the surface in the second , (, ΙΕχ_2,,) treatment? The degree of adjustment of the }1 will usually depend on the IEP of the matrix, the ιΕρ versus surface charge distribution curve and the type of charge required. For example, without limitation, for a substrate having an IEp equal to 8, preferably, the pH of the matrix/IEX-2 mixture is adjusted to be between about 8 and about 12, more preferably between about 9 and about 11. The 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 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, to produce a net Positive surface charge). The inorganic acid or base or the organic acid or base can be used in a dilute manner, and an organic base is usually preferred. Generally, the concentration of the dilute acid solution or the dilute alkali solution will depend on the type of acid or base used, its dissociation constant, and the pH at which it is suitable to obtain the desired surface charge type and density. Preferably, after the IEX-2 treatment is completed, the substrate treated by ΙΕχ_2 can be separated by any suitable method including, but not limited to, filtration, centrifugation, decantation, and combinations thereof. The ΙΕΧ-2 treated substrate is then treated with one or more suitable cleaning solutions (eg distilled or deionized water, dilute or dilute acid and / 126432.doc • 47-200836831 or a suitable water-soluble organic solvent such as methanol, Wash with ethanol or acetone and dry at about iio °c for about 20 to 24 hours. IV. Post-precipitation treatment description If necessary, after the IEX-2 treated substrate is separated, it can be dried only, calcined, calcined under oxidizing conditions, then reduced or further oxidized, reduced without calcination or not calcined. In the case of oxidation. Surface precipitation of transition metal ions, oxyanions and/or sulfur in the gas or liquid phase can be carried out as appropriate using suitable reduction, sulfurization, carbonization, nitridation, phosphating or boring reagents (-IDING reagents) The anion is reacted to produce the corresponding catalytically effective metal sulfide/sulfur oxide, metal carbide/carbon oxide, metal nitride/nitrogen oxide, metal boride or metal phosphide component. Typically, but not limited to, the purpose of the post-precipitation calcination treatment is essentially to decompose the metal counterion or ligand and to more closely integrate the metal, metal oxide, metal chalcogenide, etc. with the surface of the substrate and remove any previously unreceived Residual water removed during the 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 calcination, the substrate is first calcined in an oxidizing atmosphere (e.g., in air or oxygen). In addition, the important system is to choose a high calcination temperature to ensure that the precursor of the type 2 component of interest is oxidized and any residual water is removed (if any residual water remains), but the calcination temperature should be low enough. It can reasonably avoid the softening point of the matrix and the undesired decomposition of the precursor component of the 126432.doc -48-200836831.

For example, but not limited to, 'precipitated sulfates require calcination conditions to decompose the bound cations and set the sulfuric acid on the surface, but such conditions do not lead to the good solution of sulfuric acid to volatile sulfur oxides. Metal oxyanions require calcination conditions to decompose the bound cations and immobilize the anions as oxides on the surface, provided that the conditions are not critical to volatilize the metal oxides from the surface or cause the metal oxides to dissolve in the matrix. Finally, the precious metals and The complex should be calcined under the following conditions: decomposition of the ligands and anions present, but not so strict that the precious metals accumulate on the surface. For this reason, as explained in more detail below, the responsible metal is preferably directly in the absence of calcination. Reduction 0 苇, the calcination temperature should be at least about 50 lower than the softening point of the selected matrix. The calcination temperature should be about 100. (: to 700. 〇: between, more preferably between about 2 〇〇 and 600 C Preferably, it is between about 3 Torr and 5 Torr. Typically, the IEX-2 treated substrate is calcined for about i to about μ hours, preferably for about 2 to about 12 hours. Nonetheless, depending on the type 2 component of the matrix integration, the calcination time can vary outside of these ranges. Typically, but not limited to, the post-precipitation reduction treatment aims to at least substantially (if not completely) catalyze the component precursor ( For example, metals, metal oxides or metal sulfides are reduced to a lower oxidation state integrated with the surface of the substrate. Examples of suitable reducing agents include, but are not limited to, C〇 and h2. The preferred reducing agent for h2 is a preferred flow rate. Between about 0.01 L/hr and about 1 〇〇L/hr per gram of matrix 'better flow rate is between 1 L/hril L/hr• per gram of substrate. 126432.doc -49- 200836831 Typical The reduction temperature should be between 0 ° C and 600 ° C, provided that the selected temperature is at least 100 ° C lower than the softening point of the substrate. Typically, the substrate treated with IEX-2 is passed for about 0.1 hour. The reduction treatment is carried out for about 48 hours, preferably for about 1 hour to about 8 hours. Alternatively, the substrate treated with IEX-2 can be reduced by solution phase treatment using a soluble reducing agent (for example, Not limited to hydrazine, sodium hydride, hydrogen Lithium and combinations thereof are carried out in a suitable solvent such as water or diethyl ether. Usually, but not limited to, after precipitation, the purpose of the IDING reaction treatment is to additionally react the reduced metal with a reagent containing a lower atomic weight-IDING element. At the same time, metal ions, metal oxyanions and/or metal sulphide anions are reduced. In some cases, direct-IDING can occur without simultaneous reduction of the metal oxidation state, such as some sulphurization treatments. -IDING reagents include, but are not limited to, hydrogen sulfide, sulfonium thiol and dimethyl sulfide (vulcanization-IDING reagent), ammonia (nitriding-IDING reagent), methane, ethane and other light hydrocarbons (carbonization-IDING reagent) . The gas phase-IDING reagents can be directly reacted with the IEX-2 treated substrate under ambient pressure or under pressure, or in a gas mixed with an inert gas or hydrogen and with an IEX-2 treated substrate. The reaction, which in turn produces the corresponding sulfide, carbide or nitride. Part of the catalytically potent component - IDED products (including sulfur oxides, carbon oxides and nitrogen oxides) can also be produced by: Substrate received/obtained as it is, IEX-2 treated integrated matrix The incomplete reaction was carried out by the IEX-2 treated calcined substrate or the IEX-2 treated reducing substrate. Metal phosphide can be produced by two ion exchange (two IEX-2 treatments) substrate reduction treatment, 126432.doc -50-200836831, wherein one ΙΕχ-2 treatment is one or more transition metal ions, and the other The ΙΕΧ-2 treatment is a phosphate ion. Preferably, the two ΙΕΧ-2 processes can be performed in sequence. Alternatively, the metal fill can be produced by using a gas phase phosphating reagent such as, but not limited to, phosphine (ρη3) to produce the desired metal phosphide. For example, a single ion exchanged substrate (matrix treated with mono-indole_2) with the desired transition metal in the appropriate oxidation state can be further treated with hydrazine 3 to produce the desired metal phosphide.

Solution phase treatment can be used to produce metal sulfides, metal borides, and metal phosphide catalytic components. The typical solution treatment for producing metal sulfides includes, but is not limited to, treating the metal-ion-integrated matrix treated with cerium-2 at an effective concentration of a hexamethyldisulfide-sintered organic solution at a temperature ranging from room temperature to reflux temperature. The time is sufficient to produce a catalytically effective amount of catalytic component on and/or within the surface of the substrate. Typical solution phase treatments for the production of boride include, but are not limited to, treatment of a sodium borohydride or potassium borohydride aqueous solution over a period of effective time between room temperature and reflux temperature for a ruthenium-2 treated metal-ion-integrated substrate. Typical solution phase treatment for the production of phosphides comprises treatment of a ruthenium-2 treated metal-ion-integrated substrate with an aqueous solution of sodium hypophosphite for a time sufficient to be on and/or within the surface of the substrate, from room temperature to reflux. A catalytically effective amount of a catalytic component is produced. V. The catalytically active region indicates that the catalytically active region resulting from any of the above substrate treatments will have (1) an average thickness of less than or equal to about 30 nm, preferably about 2 () of rice, more preferably about $ a catalytically effective amount of at least one of nano and (Π) catalyzed to 126432.doc -51· 200836831

Minute. Preferably, the average thickness of the catalytic region is determined using XPS spectroscopy, and XPS spectroscopy uses a layered etching technique known as sputter depth distribution (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 general location of the substrate surface associated with the catalytic component contrast component. Therefore, the average thickness of the matrix catalytic region can be determined using, for example, but not limited to, transmission electron microscopy (TEM) or scanning TEM (STEM, also described in more detail below). Those skilled in the art have a thorough understanding of XPS or TEM programs. It should be understood that in the extreme case, regardless of whether the catalytically active region is produced by a reciprocating treatment or an IEX-2 treatment (with or without BIX treatment), the thickness of the catalytically active region for any of the catalyst compositions of the present invention. Generally, (a) does not pass through the surface area of the substrate on the κ mass or exceeds the surface of the substrate by about 3 Å, preferably not more than about 2 Å, more preferably not more than 丨〇 nanometer. thickness. 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: (a) be on the outer surface of the substrate, and in the presence of any pores, in the pore walls of the substrate Surface; '(b) in the surface region of the base f, i.e., about 30 nm below the outer surface of the substrate, preferably about 20 nm below the outer surface of the base f, more preferably about 10 nm below the outer surface of the substrate. When there is any pore in the winter left soil, the lower, the field is about 30 half below the surface of the pore wall of the matrix, and the shot is from the upper soil. 'It is preferably about 20 nm below the surface of the pore wall of the matrix, preferably in the base soil. # Beside the surface of the pore wall, about 1 〇 is not more than the area below the surface of the substrate; (C) Above or above the surface of the substrate, when there is any pore in Hetian, 126432.doc •52- 200836831 Part of the pore wall of the matrix On the surface or above, partially in the surface area of the matrix, or (d) a combination of (a), (b) and (c). Usually 'whether it is a type 1 component or a type 2 component, the amount of the catalytic component can be Between about 0.0002 wt.% to about 5 wt.%, preferably about 0.0002 wt.% Between about 2 wt ·%, more preferably between about billion-〇〇〇5 wt ·% to about 1 wt ·%. Further, the catalyst composition of the catalytically active region of the present invention may be continuous or discontinuous.

Without being bound by theory, it is believed that the catalyst composition covered with the discontinuous catalytically active region is at least as effective as the catalytic component substantially covered with a continuous or broader continuous catalytically active region, and In some cases it is more effective. The extent to which the catalytically effective region covers the outer surface of the substrate can range from as low as 1% 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, in the absence of cultural constraints, it is believed that the catalyst composition,

A catalyst composition having a lower catalytic component of ~.% loading is likely to be more catalytically effective because of catalytic activity on and/or within the treated substrate.

The sexual regions become more dispersed (i.e., more widely distributed and separated between catalytically active regions). X The catalytically active region and other above-mentioned sensitizers have access to steady-state reaction conditions. One or more of the described characteristics can be largely unpredictable. Nonetheless, since the catalyst composition promotes its pre-polymer composition characteristics, the degree of optimal change based on the state of the uranium-catalyst composition is not determined, and is not subject to theoretical constraints. The proprietary reaction, the functional surface activity of the 126432.doc •53-200836831 media composition described herein will allow for significant changes in the charge and/or geometric positioning and other component characteristics of the catalytic component integrated with the base f. 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. Application of νι·catalyst composition in selective hydrogenation method

In general, catalyst compositions of the above type are most advantageous for processes in which catalyst activity and selectivity are limited (i.e., diffusion limited) due to intraparticle diffusion resistance of the product or reactant. However, such catalyst compositions can also be used in processes that are not necessarily limited by diffusion. For example, if not limited, some processes require only a single type of catalytic composition to provide a single type of catalytic interaction to help reduce the activation energy of a process reaction. Therefore, the lower activation energy allows the process to have good thermodynamic properties (e.g., less energy required to drive the process), so commercial production is also more cost effective. The selective hydrogenation process (i.e., SHp treatment) is a process for treating the smoke, hydrocarbons, and mixtures thereof. As used herein, a smoke refers to a group of compounds consisting only of an atom (C) and a hydrogen atom (H), and a heteroalkyl as used herein means mainly composed of a carbon atom (c) and a hydrogen atom (8), but at the same time Also included is a group of compounds other than carbon and hydrogen, such as, but not limited to, oxygen (oxime), nitrogen (8), and/or sulfur (S). In SHP processing, a process stream comprising hydrocarbons or, or a heterohydrocarbon, suitable for selective hydrogenation using a catalyst composition of the above type generally comprises from about to about 30 stone counter atoms but in some cases may have a hydrocarbon having at least one hydrogenatable group in the above carbon atom and a hydrocarbon which may be one or more heteroatoms (e.g., oxygen (nitrogen), nitrogen (N), sulfur (S), etc.), 126,432.doc -54 - 200836831 The point (i.e., the target hydrogenatable site) is readily hydrogenated under appropriate hydrogenation conditions (described in more detail below) for the desired product, yield, and/or process efficiency.

Process streams include, but are not limited to, feed stream 'intermediate transfer streams, recycle streams, and/or streams. As used herein, a target hydrogenatable site refers to an atomic position having at least one carbon atom (c) or a hetero atom, but is generally a carbon-containing atomic position, and the hetero atom may be, but is not limited to, oxygen (0), Nitrogen (N) or sulfur (s). In any case, the target hydrogenatable sites have at least one degree of unsaturation, and under appropriate reaction conditions, it is easy to achieve at least partial saturation with the participation of the catalyst composition. In addition, the extent and type of unsaturation in the hydrocarbons may vary. Thus, multiolefins, polyacetylenes and cyclic olefins may have continuous (only continuous double-double bonds), a total of one or more double bonds and/or substitutions of one or more saturated and/or substituted carbons. Of the hydrogenatable sites that may be present in the hydrocarbon of interest, two of them are preferentially saturated (at least in part) than the other hydrogenatable sites. Process streams suitable for SHP treatment may also be a mixture of olefins or fluffy and aromatic or terpene olefins, for selective hydrogenation of olefins or multiolefins or mixtures of olefins or multiolefins and fast hydrocarbons or polyacetylenes, For selective hydrogenation of fast smoke or multiple pieces of cigarettes. Thus, for hydrocarbons and/or heterocarbon mixtures having at least two hydrogenatable sites of at least two types of hydrocarbons or heterohydrocarbons, the hydrogenatable sites predetermined for selective hydrogenation are regarded as target hydrogenatable sites (10) For example, &gt; aromatic hydrocarbons + dilute hydrocarbons where the dilute hydrocarbons contain the target hydrogenatable sites and the phase aromas are preferentially hydrogenated. ' Thus, suitable for SHP treatment using a catalyst composition of the above type 126432.doc -55 - 200836831 Hydrocarbons and hydrocarbons include, but are not limited to, olefins, diolefins, multiolefins, alkynes, polyalkynes, rings Olefins, aromatic hydrocarbons, unsaturated vegetable oils and hydrogenated oxygenates. Hydrogen-containing oxygenates include, but are not limited to, ketones, aldehydes, hydroxy acids, hydrazines, and other heteroatoms having one or more nitrogen or sulfur-containing heteroatoms other than oxygen. A preferred class of hydrocarbons suitable for SHP treatment using a catalyst composition of the above type is a normal chain olefin having from about 2 to 20 carbon atoms, a normal chain multiolefin and a normal chain alkyne and having from 6 to 12 (substituted or not) Substituting an aromatic hydrocarbon of a carbon atom. More noble hydrocarbons are normal chain olefins having from 2 to 15 carbon atoms, normal chain multiolefins, olefin substituted aromatic hydrocarbons, normal chain alkyne, alkene aldehydes and olefin ketones. As such, the SHP treatment can be performed using a variety of reactors having one or more hydrogenation zones such that the reaction hydrocarbon feed stream can be combined with a catalyst composition maintained in a selective hydrogenation zone under selective hydrogenation conditions. Full contact (described in more detail below). The contacting can be carried out in a fixed catalyst bed system, a mobile catalyst = system, a fluidized bed system, or a plurality of different catalyst composites as described above, in batch operations. In general, a fixed bed system is preferred. In a fixed bed system, the hydrocarbon: stream is first preheated to the desired reaction temperature and then passed to a hydrogenation zone containing a bed of fixed catalyst complex. The selective hydrogenation zone itself may include one or more separate reaction zones with heating means to ensure that the desired reaction temperature is maintained at the input of each reaction zone. The hydrocarbon can contact the catalyst bed in an upward, downward or radial flow. Preferably, the hydrocarbon flows radially through the catalyst bed. The smoke may be in the liquid phase 'gas-liquid mixed phase or gas phase when contacting the catalyst, preferably 126432.doc -56-200836831. Under the selective hydrogenation conditions, the catalyst composition can be tested for many options. The method, also depends on the desired product, yield, and/or process efficiency. The hydrogenation conditions include (4) temperature ranges, generally from about to about. c, and better to catch about. c; (b) The pressure range is generally from about 101 kPa to about 13,789 kPa, and (4) the molar ratio of hydrogen to the target hydrogenatable hydrocarbon is generally from about 0.1:1 to about 20:1, preferably about 〇5: 1 to about 51, and preferably: about 0.8:1 to about and (4) the liquid hourly space velocity (10) sv) in the reactor generally ranges from about 0.1 hr1 to about 20 hr.1. EXAMPLES The present invention will now be described in more detail by the following examples in which the following examples illustrate or simulate various aspects of the practice of the invention. It is to be understood that all changes in the spirit of the invention are intended to be protected, and therefore the invention is not to be construed as limited to the examples. Catalyst Composition with Large Porous Glass Substrate Example 1 Palladium on Large Porous Glass A macroporous soda lime calcium glass sample produced by Dennert Poraver was obtained, i.e., glass beads having an average diameter of about 40 to 125 microns. In the first step, the macroporous glass sample received as it is and not calcined is subjected to acid leaching. Approximately 25 grams of macroporous glass and 3 liters of 5.5 wt.% nitric acid were placed in a 4 liter plastic wide mouth container. The plastic container was placed in a ventilated oven at 30 ° C for 30 minutes, and shaken slightly by hand every 10 minutes. After the acid leaching treatment was completed, a sample was taken using a Buchner funnel with Whatman 541 filter paper and washed with about 7.6 liters of deionized water 126432.doc -57-, 200836831. Then, at 11 (the temperature of rc, the acid immersed sample is dried. In the second step, the acid leached macroporous glass is subjected to ion exchange (IEX) treatment. In this example, dihydrogen oxygen is used. Tetraamine [Pd(NH3)4](〇H)2 was prepared by using 80 ml of a 0.1 wt.% palladium solution for ion exchange (&quot;ΊΕΧsolution&quot;). 4 g of macroporous glass was added to the ion exchange solution ( π glass/ion exchange mixture"). Measurement of glass/ion exchange mixture

The pH was measured to be about 10.3. The mixture was then transferred to a 15 inch plastic wide mouthed container. The plastic container was placed in a ventilated oven at 501 for 2 hours. The mother was shaken slightly by hand for 30 minutes. After the ion exchange treatment was completed, the mixture was filtered using a Buchner funnel with Whatman 541 paper, a glass/ion exchange mixture, and washed with about 3.8 liters of deionized water. Then, the ion exchange glass sample was dried at a temperature of 110 ° C for 22 hours. The third step is to reduce the ion-exchanged glass, wherein the ion-exchanged glass is first calcined in an air atmosphere at an air flow rate of 2 L/hr and at a temperature of 300 ° C for 2 hours, and then at a hydrogen (h 2 ) flow rate of 2 L / The hydrogen (H2) atmosphere of hr was reduced at a temperature of 300 ° C for 4 hours. The sample was analyzed by inductively coupled plasma-atomic emission spectroscopy (ICP-AES) and the palladium concentration was about 0.098 wt.%. Example 2 Palladium on Macroporous Glass A macroporous sodium foam #5 glass sample produced by Dennert Poraver, a glass bead having an average diameter of about 40 to 125 microns, was obtained. In the first step, the macroporous glass sample 126432.doc -58 - 200836831, which was received as received and not calcined, was subjected to acid leaching treatment. Approximately 25 grams of macroporous glass and 3 liters of 5·5 to % of nitric acid were placed in a 4 liter plastic wide mouth container. Place the plastic container in a 30 C ventilated oven for 3 minutes, shake it slightly by hand every 1 minute. After processing the ingredients, filter the sample using a Buchner funnel with Whatman 541 filter: paper. Wash with approximately 7.6 liters of deionized water. The acid immersed sample was then dried for 22 hours at a temperature of uo °c. In the second step, the acid-impregnated macroporous glass is subjected to ion exchange (IEX) treatment. In this example, 80 ml of oi was used as a .% palladium solution for the ion exchange (palladium solution) using dichlorotetramethylene palladium [pd(NH仏](ci) 2 ). 4 gram of macroporous glass was added to the ion. Exchange the solution (, glass/ion exchange of this compound). Measure the value of 卩11 of the glass/ion exchange mixture and measure about 8.1. Then, transfer the mixture into a 15 liter plastic wide-mouth container. The plastic container was placed in a 5 (TC ventilated oven for 2 hours, shaken by hand every 3 minutes. After the ion exchange treatment was completed, filter the glass/ion exchange mixture using a Buchner funnel with Whatman 541 filter paper, and use Approximately 3.8 liters of deionized water was cleaned. Then, at 11 Torr (the temperature of the ion exchange glass sample was dried for 22 hours. The third step, the ion exchange glass was reduced, wherein the ion exchange glass was first at an air flow rate of 2 The air atmosphere of L/hr and the temperature of 300 ° C were satin-sintered for 2 hours, and then reduced under a nitrogen gas atmosphere of 2 L/hr at a flow rate of 2 L/hr and a temperature of 300 ° C for 4 hours. Sample analysis, results of saturating concentration 0.045 wt.% 〇Example 3 126432.doc 59- 200836831 Palladium on Porous Ion Exchanged Porous Glass Obtains a sample of macroporous soda sap from Born, made by Dennert Poraver, a glass with an average diameter of about 40 to 125 microns. The first step is to perform acid leaching on the macroporous glass sample received as received and uncalcined. Place about 50 grams of macroporous glass and 4 liters of 5.5 wt.% nitric acid in a 4 liter glass beaker. Mechanically agitate at a temperature of 300 to 500 rpm at 90 ° C for 2 hours using a stainless steel paddle mixer. After the acid leaching process, the sample was filtered using a Buchner funnel with Whatman 541 filter paper and used approximately 7.6 liters. The ion-washed water is washed. Then, the acid-impregnated sample is dried for 22 hours at a temperature of 11 ° C. The second step is to carry out Na + - counter ion exchange on the acid-impregnated macroporous glass (&quot;Na- BIXn) Treatment. Mix the acid leached sample obtained in the first step with 4 liters of 3 mol/L sodium chloride (NaCl) solution (&quot;glass/sodium chloride mixture"). Measure glass/NaCl mixture pH value. , about 40 wt.% of tetrapropylammonium hydroxide was added dropwise continuously, and the pH of the glass/NaCl mixture was adjusted to be greater than 1 Torr (in this example, the obtained pH was about 10.5). Then, The glass/NaCl mixture was transferred to a 4 liter glass beaker and heated at 50 ° C for 4 hours while stirring at 300 to 500 rpm using a stainless steel paddle mixer. After Na-BIX treatment was completed, the belt was used. Whatman 541 filter, paper Buchner funnel filter glass / chloride mixture and collect Na-BIX / glass samples, then rinse with about 7.6 liters of deionized water. The Na-BIX/glass sample was then dried for 22 hours at a temperature of 11 °C. In the third step, a second ion 126432.doc -60-200836831 exchange (&quot;ΙΕΧ·2&quot;) treatment was performed on the Na-BIX/large pore glass sample. In the present example, 3 liters of a palladium solution of ruthenium ruthenium (1 wt.%) was prepared for ion exchange ("IEX_2 solution") using [Pd(NH3)4](Cl)2. Add 35 grams of macroporous glass to the ΙΕχ_2 solution (&quot;glass/ΙΕΧ-2 mixture"). Measure the ρΗ value of the glass/ion exchange mixture to measure about 8.1. Then 'move the mixture into 2 liters of glass. Heat in a beaker and heat at 50 °C for 4 hours while stirring at 300 to 500 rpm using a stainless steel forcing mixer. After the ion exchange treatment, use a Buchner funnel transition glass with Whatman 541 filter paper / The ion exchange mixture was washed with about 7.6 liters of deionized water. Then, the ion exchange glass sample was dried for 22 hours at a temperature of 11 ° C. In the fourth step, the IEX-2 glass sample was subjected to reduction treatment, in which the sample was The hydrogen (H2) flow rate was 2 L/hr of hydrogen atmosphere and the temperature was reduced for 4 hours at 300. The sample analysis by ICP-AES showed that the concentration of Ba was about 〇wt·%. Example 4 On the large-porosity glass Obtained a macroporous foamed soda lime glass sample produced by Dennert Poraver, a glass bead with an average diameter of about 40 to 125 microns. The first step is for macropores that are received as received and not calcined. The glass samples were subjected to acid leaching. Approximately 20 grams of macroporous glass and 4 liters of 55 wt% nitric acid were placed in a 4 liter glass beaker using a stainless steel paddle mixer at a speed of 300 to 500 rpm at 9 ( Mechanical stirring was carried out for 2 hours under rc. After the acid leaching treatment was completed, the sample was filtered using a Buchblad funnel with Whatman 541 filter paper 126432.doc -61·200836831 and washed with about 7.6 liters of deionized water. At the temperature, the acid leached sample was dried for 22 hours. The second step was to perform ion exchange treatment on the (four) treated macroporous glass sample. In this example, tetrachlorotetramine (tetra) cholesteric] (6)) 2 was prepared. 3 liters of 0.01 wt.% palladium solution for ion exchange (&quot; ΙΕχ solution will be similar to the large (four) glass plus human ion exchange solution ("glass / ion exchange mixture"). The value of the ion exchange mixture is 11. If necessary, about 29.8 wt.% of ammonium cerium oxide (ΝΗ4〇η) is continuously added dropwise, and the pH of the mixture is adjusted to be greater than 1 〇 (the ρ 得到 value obtained in this example) About 10.8). Then, will The glass/ion exchange mixture was transferred to a 4 liter glass beaker and heated at 5 (TC temperature for two hours while stirring at 300 to 500 rpm using a stainless steel paddle mixer. After the ion exchange treatment was completed, the belt was used. The Buchner funnel filter glass/ion exchange mixture with Whatman 541 filter paper was washed with about 7.6 liters of deionized water and the ion exchange glass samples were dried for 22 hours at 11 〇C. In the third step, the ion-exchanged glass sample was subjected to a reduction treatment in which the sample was reduced in a hydrogen atmosphere at a helium (Hi) flow rate of 2 L/hr and at a temperature of 300 ° C for 4 hours. Sample analysis by ICP-AES was performed with a concentration of approximately 〇 047 wt·%. Example 5 Palladium on Large Porosity Glass A large pore foamed sodium bismuth glass material produced by Dennert Poraver was obtained. 126432.doc • 62- 200836831 The product was a glass bead having an average diameter of about 40 to 125 microns. In the first step, ion exchange treatment is performed on a large pore glass sample which is received as it is, which is not calcined and which has not been acid leached. In the present example, 1 · 5 liters of 〇·〇〇 1 wt· was prepared using palladium hydroxide (Pd(NH3)4](OH)2. /. The palladium solution is used for ion exchange (&quot;IEX solution&quot;). Approximately 8 grams of macroporous glass was added to the ion exchange glass/ion exchange mixture in the ion exchange solution,&apos;). Measuring glass/ion exchange • pH of the mixture. About 29 8 wt% of ammonium hydroxide (NH 4 〇 H) was continuously added dropwise as needed, and the pH of the mixture was adjusted to be greater than 1 Torr (a pH obtained in the present example was about 10.5). Transfer the glass/ion exchange mixture into a 2 liter plastic wide mouth container. Place the plastic container in a ventilated oven for 2 hours and shake it slightly by hand every 30 minutes. After the ion exchange treatment was completed, the glass/ion exchange mixture was filtered using a Buchner funnel with Whatman 541 filter paper and the ion exchange glass sample was collected, and then washed with a solution of about 7-6 liters of a dilute NH4 〇H solution. The dilute nh4〇H solution was prepared by mixing 10 g of a 29.8 wt·% concentrated NHWH solution with about 3·8 liters of de-ionized ion water. The ion exchange glass samples were then dried for 22 hours at a temperature of 110 °C. In the second step, the ion-exchanged glass sample was subjected to a reduction treatment in which the ion parent was exchanged for 4 hours under a hydrogen atmosphere of hydrogen (H2) flow rate of 2 L/hr and 3 〇q, w β degree. Sample analysis was performed using ICP-AES, and the palladium concentration was about 〇 1 wt.%. Example 6 Platinum on Macroporous Glass 126432.doc -63 - 200836831 A sample of macroporous foamed soda lime glass produced by Siscor, a glass bead having an average diameter of about 45 to 75 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 49.61 grams of macroporous glass and 4 liters of 5 5 wt.% nitric acid were placed in a 4 liter plastic wide mouth container. Place the plastic container at 90. Shake it in your ventilated oven for 2 hours every 3 minutes. After the acid leaching treatment was completed, the sample was filtered using a Buchner funnel with Whatman 541 filter paper and washed with about 7.6 liters of deionized water. Then, the acid immersed sample was dried at a temperature of 11 ° C for 22 hours. In the second step, the acid-impregnated macroporous glass sample is subjected to ion exchange treatment. In this example, a solution of platinum (16 wt. %) in platinum (Pt(NH3)4)(ci) 2 was prepared for ion exchange ("ΙΕχ solution,"). It will be about 15.86 g. The acid immersed macroporous glass is added to the ion exchange solution (&quot;glass/ion exchange mixture"). The pH value of the glass/ion exchange mixture was measured. The pH was adjusted as needed with about 40% tetrapropylammonium hydroxide. The tetrapropyl hydrazine hydroxide was continuously added to adjust the pH to be greater than ι (in the present example, the pH obtained was about 11.83). Move the glass/ion exchange mixture into the plastic wide-mouth container of Douglas. Place the plastic container at 5 inches. The ventilated oven was simmered for 2 hours and shaken slightly by hand every 30 minutes. After the ion exchange treatment was completed, the glass/ion exchange mixture was filtered using a Buchner funnel with Whatman 541 paper and washed with about 7.6 liters of deionized water. The ion exchange glass sample was then dried for 22 hours at 11 Torr: temperature. ... Sample analysis by ICP-AES, the result in white concentration is about... wt.%. -64- 126432.doc / 200836831 Example 7 Macroporous Glass Glass A large pore foamed soda lime glass sample produced by Siscor, a glass bead having an average diameter of about 45 to 75 microns, was obtained. In the first step, the macroporous glass sample received as it is and not calcined is subjected to acid leaching. Approximately 50.37 grams of macroporous glass and 4 liters of 5.5 wt.% nitric acid were placed in a 4 liter plastic wide mouth container. The plastic container was placed in a 90 C ventilated oven for 2 hours, and shaken slightly by hand every 3 minutes. After the acid leaching treatment was completed, the solution was decanted, and then the solid matter was washed with about 7.6 liters of deionized water. Then, at! The acid immersed sample was dried for 22 hours at a temperature of 1 〇〇c. In the second step, the acid-impregnated macroporous glass sample is subjected to ion exchange treatment. In this example, 1 liter of a 0.18 wt.% platinum solution was prepared for the ion exchange ("ΙΕχ solution" using tetrachlorotetramine platinum [Pt(NH3)4](Cl)2. About 41.79 grams was acid leached. Large pore glass is added to the glass/ion parent exchange mixture in the ion exchange solution"). The 1) 11 value of the glass/ion exchange mixture was measured to be 6.8 ′. In this μ case, 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 4 4 hours in a ventilated oven, shake it slightly with your hands every 3 minutes. After the ion exchange treatment is completed, the solution is decanted, and then the solid obscurant is washed with about 7.6 liters of deionized water. The ion exchange glass sample was then dried for 22 hours at a temperature of u〇〇c. Sample analysis by ICP-AES, the platinum concentration was about wt13 wt·% 〇126432.doc -65 - 200836831 Example 8 Palladium on macroporous glass obtained a large pore foamed sodium I bow 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. Approximately 20 grams of macroporous glass and 4 liters of 5.5 wt.0/〇 of nitric acid were placed in a 4 liter glass beaker. Mechanical agitation at 90 °C for 2 hours using a stainless steel paddle stirrer at 300 to 500 rpm. After the acid leaching treatment was completed, the sample was filtered using a Buchner funnel with Whatman 541 filter, paper, and washed with about 7.6 liters of deionized water. Then, the acid immersed sample was dried at a temperature of 110 ° C for 22 hours. In the second step, the acid-impregnated macroporous glass sample is subjected to ion exchange treatment. In the present example, 3 liters of a 0.011 wt% palladium solution was prepared for ion exchange ("Im solution") using dioxetamine palladium [Pd(NH3)4](Cl)2. About 18 grams of acid immersed macroporous glass was added to the ion exchange solution ("glass/ion exchange mixture"). The pH of the glass/ion exchange mixture was measured. About 29.8 wt% of hydrogen 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 obtained pH was about 10.78). The glass/ion exchange mixture was then transferred to a 4 liter glass beaker and heated at 5 (TC temperature for two hours while using a stainless steel paddle stirrer to scramble at a speed of 3 to 500 rpm. After the ion parent treatment was completed, the glass/ion exchange mixture was filtered using a Buchner funnel with Whatman 541 filter paper and washed with about 7.6 liters of deionized water. Then, the ion exchange glass sample was dried at 1HTC temperature. 126432.doc -66- 200836831 22 hours. The third step is to reduce the ion-exchanged glass sample, wherein the sample is reduced in hydrogen gas (hydrogen atmosphere with a flow rate of 2 L/hr and a temperature of 3 〇 0 ° C for 4 hours). Sample analysis by ICP-AES, the palladium concentration results in about wt47 wt.%. Example 9 Palladium on macroporous glass obtained a large pore foamed soda lime glass sample produced by Siscor, ie an average diameter of about 45 to 75 micron glass beads. In the first step, the macroporous glass sample received as received and not calcined is subjected to acid leaching treatment. About 49.61 grams of macroporous glass and 4 liters of 5·5 wt% of nitric acid are placed separately. 4 liters of plastic wide-mouth container. Place the plastic container in a ventilated oven at 90 ° C for 2 hours, shake it slightly by hand every 30 minutes. After acid leaching, 'Use Brinell with Whatman 54 1 filter paper The funnel filters the sample' and rinses with about 7.6 liters of deionized water. Then, the acid immersed sample is dried for 22 hours at a temperature of 110 ° C. The second step is to treat the acid leached macroporous glass sample. Ion exchange treatment was carried out. In this example, 1 liter of 0.0003 wt% of a solution was prepared for ion exchange using dihydrooxytetramine|bar [Pd(NH3)4](〇H)2 (&quot;IEX solution&quot ;). Add about 15.06 grams of acid-impregnated macroporous glass to the ion exchange solution (&quot;glass/ion exchange mixture). Measure the pH of the glass/ion exchange mixture. Add about 29 drops as needed. 8 wt.% ammonium hydroxide (ΝΙί4ΟΙ·Ι), the pH of the mixture was adjusted to be greater than 1 () (in this example 126432.doc -67-200836831, the pH obtained is about 10.2). The glass/ion exchange mixture was transferred to a 4 liter plastic wide-mouth container. The plastic container was placed in a 5 (TC ventilated oven for 2 hours and shaken slightly by hand every 30 minutes. After the ion exchange treatment was completed, the sample was filtered using a Buchner funnel with Whatman 541 filter paper, and approximately 7.6 liters of dilute NH4 was used. 〇H solution cleaning. Dilute NH4〇H solution • Prepared by mixing 10 g of 29.8 wt·% concentrated ΝΗβΗ solution with about 3.8 liters • deionized water. Then, the ion-exchanged glass sample was dried at a temperature of 110 ° C for 22 hours. _ Sample analysis by ICP-AES, the result of palladium concentration is about 〇〇165 wt.%. A portion of the sample was examined by scanning transmission electron microscopy (STEM) analysis as described in Example (j) below, and the results showed that the palladium particles (higher contrast points) were generally spread at a distance of less than or equal to about 30 from the surface of the pore wall. Within the range of nanometers (i.e., the perimeter of the shaded area with a darker contrast relative to the region of the material surrounding the relatively bright contrast). Example 10 Φ Tungsten 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 to perform acid leaching on large pore glass samples that are received as received and that have not been calcined. Approximately 20 grams of macroporous glass and 4 liters of 5.5 wt% nitric acid were placed in a 4 liter glass beaker. Use a stainless steel paddle mixer at 90 to 500 rpm. (: Mechanical agitation 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 deionized water. After 126432.doc -68-200836831, The acid immersed sample was dried for 22 hours at a temperature of 110 ° C. In the second step, the acid leached macroporous glass sample was subjected to ion exchange treatment. In this example, ammonium metatungstate (NH 4 ) was used. 6H2W12O40 · ηΗ20 Prepare 3 liters of 0.05 wt.% tungsten solution for ion exchange (&quot;IEX solution). Add about 18 grams of acid-impregnated macroporous glass to the ion exchange solution ("glass/iso-β-exchange mixture &quot;). Measure the pH of the glass/ion exchange mixture. Root. Add about 29.8 wt% ammonium hydroxide (NH4OH) continuously as needed, and adjust the pH of the mixture to more than 8. Then, The glass/ion exchange mixture was transferred to a 4 liter glass beaker and heated at 50 ° C for two hours while using a stainless steel paddle mixer to scramble at 300 to 500 rpm. Ion exchange was completed. After making The Buchner funnel filter glass/ion exchange mixture with Whatman 541 filter paper was washed with about 5 liters of deionized water. Then, the ion exchange glass sample was dried at 110 ° C for 22 hours. The glass sample was exchanged for calcination, wherein the sample _ was calcined for 4 hours at an air flow rate of 2 L/hr of air and at a temperature of 500 ° C. Sample analysis by ICP-AES, the result of tungsten concentration is expected to be about 0.01 wt·% 〇Example CH-1 Analytical method re/XPS sputtering, SARCNa, isoelectric point (IEP) and SAN2 -BET or SAKi*_BET Determination of X-ray photoelectron spectroscopy (XPS) sputtering depth distribution method with one 1486.7 eV microfocus monochromator Α1 Κα X-ray source of PHI Quantum 200 Scanning ESCA MicroprobeTM (Physical 126432.doc -69- 200836831

Electronics) obtained the xps sputtering depth profile. The instrument has a dual neutralization capability that provides charge compensation using low-energy electrons and cations during spectral acquisition. The XPS spectrum is usually measured under the following conditions:

- X-ray beam diameter 10-200 μπι - X-ray beam power 2-40 W, - Sample analysis area 10-200 μπι - The electron emission angle is 45 with the sample normal. _ All XPS spectra and sputter depth profiles were recorded at room temperature without pre-treatment of the sample, except when the sample was placed in a vacuum environment of the XPS instrument. The carbon intensity distribution is generated by alternately collecting the sample surface spectra for several cycles and then subjecting the sample surface to 2 kV Ar+ sputtering for 15 to 30 seconds per cycle to remove the surface material. The sputter depth rate is calibrated using a layer of known thickness of the stone. The _Pd&amp;Si atomic concentration value is obtained by taking the peak areas of Pd 3d3/2 and Si 2p and correcting their respective atomic sensitivity factors and analyzer transfer functions. * Those familiar with XPS analysis should understand that the measurement of the sputter depth parameter is affected by both the inaccuracy and the mechanical uncertainty. The combination of the two may be the sputtering depth measured by the XPS sputtering depth profile technique. Each reported value caused an uncertainty of approximately 25%. Therefore, the uncertainty is expressed in the depth value shown in the figure. This inaccuracy is common throughout the xps analysis technique 'but' for the average thickness of the catalytically active regions disclosed herein and for other material properties of 126432.doc •70-200836831, this inaccuracy is not sufficient to hinder this article. The differentiation of the described catalyst compositions does not affect the differentiation of such compositions from other compositions not described and claimed herein. Transmission Electron Microscopy (TEM) Analysis Transmission electron microscopy (TEM) samples were measured using a JEOL 3000F field emission scanning transmission electron microscope (STEM) instrument operating at 300 kV accelerating voltage. The instrument is equipped with an Oxford Instruments Inca X-ray spectrometer system that performs a local chemical analysis using an energy dispersive spectrometer. Sample Preparation The sample material is first embedded in a standard epoxy embedding agent known to those skilled in TEM analysis. After curing, the epoxy-embedded sample material was cut into approximately 80 nm thick sections using an ultramicrotome. The sections were collected on a thin film porous carbon support and were not properly processed and properly positioned in the electron beam field of the above STEM apparatus for detection and analysis. Those familiar with TEM analysis should understand that the use of TEM analysis to determine the position of the target analyte and the average thickness of the region of interest relative to the surface of the substrate are both subject to human uncertainty and mechanical uncertainty, depending on the sample. Factors such as image resolution, physicochemical properties of the target analyte, and sample morphology may result in an uncertainty of about ±20% of the TEM vertical depth measurement (relative to a specific reference point) and about ±5% of the side The measurement results (relative to a specific reference point) uncertainty. Thus, as seen in Figure 1, the uncertainty is expressed in terms of the measured distance of the catalytic component relative to the surface of the sample substrate. This inaccuracy is common throughout the TEM analysis process, but is not sufficient to interfere with the differentiation between the catalyst compositions. 126432.doc -71- 200836831 SARC^ Determination, SAm and related statistical analysis For the reasons discussed above, the surface area change rate of the surface sodium (&quot;SARC heart) is reported as the ratio of the volume of the NaOH titrant. Procedure, the SAR of each sample given in the following examples was determined by preparing a 3·5 M Naa solution (i.e., adding 30 g of NaC1 in (9) ml of deionized water) to prepare a blank sample, 1 containing no matrix sample. However, in order to solve the statistical soil variability in the SA heart test procedure, four independent empty samples should be titrated, and the specified concentration used to obtain V initial and ~15 (ie, H) is used (in this example 〇〇ι n) The average value of the titer is adjusted (that is, corrected) for a long time. #, l) The volume of the titration solution used for the determination of the SARc sample of each of the base samples is based on the sincerity of the plate; AR Γ , 日 j像, The same procedure was used to adjust the pH of the empty sample and titrate the empty sample, but also did not contain the matrix. The empty sample and its respective mean and standard deviation (or v total σ) analysis test are provided below. The statistical analysis of the μ sample titer in the results table is also the same. The inherent statistical fluctuations corresponding to the initial V, V5, V10 and Vl5 of each titer due to the respective V totals are also reported. From a statistical point of view, the statistical t distribution is used, near the mean, specified The reliability of the value outside the confidence interval is not due to the fact that the inherent deviation of the experimental method itself is 95%. Therefore, the V initial and Vt values measured for the matrix sample in the confidence interval near the average of the empty sample are regarded as statistical. There is no difference between the upper and the empty samples. Therefore, the sample does not calculate the SARC value. The isoelectric point (IEP) determines the isoelectric point (&quot;IE?&quot;) of each sample given below according to the following private method. Mettler T〇led〇SevenMuhi watch with pH mv/0RP module, with 126432.doc -72· 200836831 and Mettler Toledo INLAB 413 pH composite electrode for IEP measurement. Use pH value for the entire range of enthalpy of interest Standard pH buffer solution calibration instruments for 2, 4, 7 and 10. Wet samples with a quantity of 16 Μ Ω deionized water (at approximately 25 ° C) sufficient to bring the sample to its incipient state, and determine the IEP for each sample. , which can be produced A denser slurry or paste mixture, and the incipient wet state allows liquid contact between the glass electrode and its reference electrode contact surface and the liquid (in this example, a slurry or paste mixture) that contacts the solid sample under test. Depending on the morphology of the sample (eg glass microfibers, granulated powder, chopped fibers, etc.) and its porosity (if any), the procedure requires a different amount of water. However, in all cases, the amount of water added should only be sufficient to The liquid is in contact with the glass electrode and the reference electrode. In other words, adding water to the sample to be tested should avoid making the sample exceed the initial humidity as much as possible. In all cases, the electrode tip was used and the solid sample was mixed by hand with deionized water (added for generating incipient wetness) until the measured pH was stable, and the resulting pH was read from the meter. N2 BET or Kr BET surface area (S.A·) determination According to the ASTM procedure mentioned above, the S _ A . N2-BET or S · Α · Κ Ι Ι ΒΕΤ measurement is suitably performed for each of the samples given below. As discussed more fully above, for higher surface area measurements (eg, about 3 to 6 m2/g), N2 BET is likely to be the preferred surface area measurement technique according to the method described in ASTM D3 663-03. . For lower surface area measurements (e.g., &lt; about 3 m2/g), Kr BET may be a preferred surface area measurement technique as described in ASTM D4780-95 ("SAum&quot;). .doc -73- 200836831 SARCNa empty sample measurement and statistical analysis for the correction of SARCNp^ sample number Dilute NaOH titrant SAN2.BET (m2/g) In NaOH titration, the pH value is from t0 (V initial When the initial value of 4·0 is adjusted to 9.0, and the pH of the titrant required to maintain the pH at 9.0 at ts, t10, and tls (V^ls) (ml) V flag = V phase + V5 to 15 concentration (N) V 〇 minute v5 5 minutes Vio 10 minutes v15 15 minutes Vs^is sum and 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 No 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 Macroporous Glass Matrix - SARCNa A large pore foam sodium dance glass sample produced by Dennert Poraver, a glass bead having an average diameter of about 40 to 125 microns, was obtained. 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^. The results are shown in the table below. Sample No. Sample Description 豨 NaOH Titration Concentration (N) In the titration, the pH is adjusted from the initial value of 4:00 to 9.0, and the pH is maintained at 9·0 at ts, t1G and tls (VSMS). The actual volume of the required titration solution (ml) V initial 0 minutes v5 5 minutes v10 10 minutes v15 15 minutes V suspect v^v initial empty sample flat one 0.01 2.1 0.15 0.125 0.15 2.5 ~ not applicable A original porous glass beads _ 0.01 5.2 0.8 0.4 0.1 6.5 1.3 B Acid-immersed porous glass beads _ one unmeasured 1 not determined 126432.doc -74- 200836831 sample number sample description IEP saN2. BET (m2/g) modified titration solution used in SARQva_ Volume (ml) SARC^fl (WV)/V-phase V first 0 minutes v5 5 minutes v10 10 minutes v15 15 minutes V-air sample empty sample mean not applicable 2.1 0.15 0.125 0.15 2.5 Not applicable Correction A Porous Glass Beads 10.2 0.4 I 3.1 0.65 0.275 -0.05 3.97 0.28 Modified B Acid-Immersed Porous Glass Beads 8.9 6.0 Not Determined Undetermined Binding The above catalyst compositions are described in more detail in the following examples, which illustrate the different types described above. Catalyst composition It selective hydrogenation methods. All modifications and embodiments that conform to the spirit of the invention are protected. Therefore, the following examples are not intended to be limited to the invention described and claimed herein. Examples of Selective Hydrogenation Process (SHP) In the following non-limiting examples, selected catalyst compositions were tested on laboratory grade equipment. The general procedure is as follows. First, the catalyst sample was loaded into a 1/4" inner diameter reactor. The catalyst was reduced for one hour at 80 ° C using 33% H 2 at a flow rate of 125 cc / min. Next, by 99.4 wt A hydrocarbon feed of .% ethylene and 0.6 wt.% acetylene flows through the catalyst at a pressure of 100 psig. The molar ratio of H2 to acetylene is about 1.2 to 1, and the liquid hourly space velocity is about 0.63/hr. It is steadily increased from 35 ° C to 50 ° C, to 65 ° C, to 80 ° C, to 95 ° C every 1 hour, and then back to 65 ° C. Example P-1

SHP using palladium on macroporous glass In this example, about 1 gram of palladium on the macroporous glass beads prepared according to the procedure of Example 3 above was loaded into the reactor at 0.021 wt.% palladium. The catalyst is tested according to the above SHP example program 126432.doc -75- 200836831. The table below lists the results of this test at a final temperature of 651. Example P-2

SHP using palladium on macroporous glass In this example, about 1 gram of palladium 0.031 wt% palladium on macroporous glass prepared according to the procedure of Example 5 above was loaded into the reactor. The catalyst is tested according to the SHP example program described above. The table below lists the results of this test at a final temperature of 65 °C. Sample Description Catalyst Catalyst Loading (g) Conversion Rate (%) Selectivity (%) Example P-1 0.021 wt% on large pore glass 1.004 44 12 Example P-2 0.031 wt% on macroporous glass 1.005 32 54 Although in the foregoing embodiments, the invention has been described in terms of certain preferred embodiments thereof, and at the same time, numerous details are set forth for the purpose of illustration, The invention is likely to have other embodiments, and some of the 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 taken by a JEOL 3000F field emission transmission electron microscope at an acceleration voltage of 3 〇〇 kV, which is substantially free of microporosity/no pores but has large pores. For example, a scanning transmission electron microscope (STEM) image of a cross-sectional portion of an acid immersion soda lime glass, wherein the palladium particles are generally dispersed within a range of less than or equal to about 3 nanometers from the surface of the pore walls. 126432.doc • 76 -

Claims (1)

200836831 X. Patent Application Range: 1. A selective hydrogenation process for a process stream, wherein a selective hydrogenation of at least a portion of the masher is carried out using a catalyst composition comprising at least one hydrogenate having at least one target a compound of a site, wherein 'the catalyst composition comprises ··' has a macroporous, outer surface, open pore wall surface, surface region, and a substantially microporous/non-porous matrix of the subsurface region, - at least a catalytic component, and - at least one catalytically active region comprising the at least one catalytic component, wherein (a) the substantially microporous/non-porous matrix has i) rich in selected from the group consisting of S.' S·Α· ^&gt;·ϋ and its combination of methods for measuring the total surface area measured between about 1 m2/g and 50 m2/g; and U) at greater than 0 but less than or a predetermined isoelectric point (IEP) obtained within a pH range equal to 14; (b) the at least one catalytically active region may be continuous or discontinuous, and having an average thickness of 4 i) less than or equal to about 30 nm; H) Catalysis An effective amount of the at least one catalytic component; and (c) the position of the at least one catalytically active region is substantially i) on the outer surface, ii) on the open pore wall surface, iii) in the surface region, 126432 .doc 200836831 iv) partially on the outer surface, partially on the surface of the open pore wall 'partially in the surface area and combinations thereof; or V) (c)(i), (ii), (iii) and Iv) combination. 2. The selective hydrogenation process according to claim 1, wherein the at least one catalytic component is selected from the group consisting of Bronsted or Lewis acid, Blenzide or Lewisine. , noble metal cations and noble metal complex cations and anions, transition metal cations and transition metal complex cations and anions, transition metal oxyanions, transition metal chalcogenide anions, main oxyanions, _ compounds, rare earth ions, rare earths Combined cations and anions, noble metals, transition metals, transition to genus oxides, transition metal sulphide, transition metal oxysulfides, transition metal carbides, transition metal nitrides, transition metal borides, transitional phosphides, rare earth hydrogens Oxide, rare earth oxide, and combinations thereof. 3. 3. A selective hydrogenation process as claimed, wherein the at least one catalytic component is first catalyzed prior to the catalyst composition being stabilized under selective hydrogenation conditions. a composition having (a) a first pre-reactive oxidation state, and a first pre-reverse between '(8) and the substrate Should interact, it is selected from the group consisting of, _ sub-electron interaction, electrostatic charge interaction and their combination. 4. The selective hydrogenation side of the claim 3, the soil # „ 虱 方 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , a gasification process wherein at least a portion of the first catalytic component is modified or displaced to form a second catalytic component prior to the steady-state selective hydrogenation reaction conditions at the catalyst composition 126432.doc 200836831, It has (a) a second pre-reaction oxidation state, and ( )/, a corresponding second pre-reaction interaction between the substrates; =^, the second pre-reaction oxidation state of the second catalytic component is less than, greater than or equal to a first pre-reaction oxidation state of the first catalytic component. 6. The selective hydrogenation process according to claim 5, wherein the second catalytic component is k free Pd, Pt, Rh, Ir, Ru, 〇s, Cu, Ag a group consisting of Au, Ru, Re'Ni' c〇, Fe, Mn, Cr, and combinations thereof. 7. A method for selectively hydrogenating a substrate, wherein the substrate is a glass of less than or equal to about 〇·5 8. The selective hydrogenation method of claim 1, wherein the at least one reminder The living 14 region is concentrated only in a region having an average thickness of less than or equal to about nanometer. 9. The selective hydrogenation method of claim 1, wherein the substantially microporous/non-porous matrix is selected from the group consisting of AR glass, Rare earth strontium silicate glass, boroaluminosilicate glass, E glass, boron-free e-glass, S-glass, R-glass, rare earth glass, 夕 ®® salt glass, Ba-Ti-lithite glass, nitrided glass, a group consisting of glass, C glass, and CC glass, and combinations thereof. 1) The selective hydrogenation method of claim 1, wherein, after or after the first leaching treatment, the material is substantially free of micropores/no pores The lanthanide obtained by the matrix is greater than or equal to about 6 〇, but less than 14. 126432.doc 200836831 VII. Designated representative map: (1) The representative representative of the case is: (1). (2) The components of the representative figure Brief description of the symbol: (No component symbol description) φ VIII. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: (none) 126432.doc