TW200843847A - 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 substrate having mesopores and macropores, has (i) a total surface area between about 5 m<2>/g and 300 m<2>/g; and (ii) a predetermined isoelectric point (IEP) obtained in a pH range less than or equal to 14, preferably less than or equal to 7.8 and more preferably less than or equal to 6.0, but greater than 0. 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

200843847 IX. INSTRUCTIONS OF THE INVENTION: TECHNICAL FIELD 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 specifically, 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. 〇 [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. In the United States alone, the value of a product produced at a stage including a catalytic process is close to one trillion dollars (USD). Products produced using catalyst compositions include: : such as food, clothing, (4), household chemicals, xiao or fine chemicals, plastics, detergents, fuels and lubricants. Catalyst compositions are also available, &amp; treat emissions (eg, vehicle exhaust emissions, refinery emissions, public use, no construction plant emissions, etc.) and other process emissions streams to reduce potential for human health or The amount of harmful ingredients that cause negative effects. In terms of market sales, the sales of the solid-loaded catalyst in the heterogeneous catalytic reaction is about US$3 billion per year. The solid-carrying catalysts are generally classified into three types: petroleum refining catalysts, chemical processing catalysts, and emission control catalysts. The 126433.doc 200843847 three types of catalyst market sales are basically three-point world. For example, in the United States 181⁄4, the United States in the solid catalyst market, stone emission control catalysts accounted for 37%, 34% and 29% of the market. For example, in the petroleum refining catalyst market (10), which is about $100 million in the following year, the township revenue comes from the fluid-vehicle cracking (FCC) catalyst, while the 315%, 65%, and 45% revenues come from hydrotreating. Catalyst, hydrocracking catalyst and reforming catalyst.

C) As far as the mechanism is concerned, the catalyst can usually achieve a rate of equilibrium between the reactants and the product in a chemical reaction that does not substantially eliminate the U. Therefore, for any related reaction, the catalyst does not change the equilibrium state between the reactants and the product, but if properly designed and/or selected, the catalyst can accelerate the rate of the chemical reaction. ^ Catalysts are used for a wide range of commercial and practical processes for a variety of purposes, including improving process responsiveness, selectivity and energy efficiency, and other uses. For example, the reaction rate or reactivity of the high reactants can be reduced in the production of the desired product according to the specified process conditions to reduce the processing time for higher product throughput (eg, increase the volume or mass per unit hour). ). Thus, catalyst activity refers to the ability of the catalyst composition to effectively convert the reactants to the desired product in each of the early hours. Similarly, increasing the selectivity of the reaction increases the percent yield of the desired product in a set of possible reaction products. Among these possible reaction products, some products may not be required and require further processing to effect Remove or turn,. Thus &apos;catalyst selectivity is the ability of a catalyst composition to convert a portion of the reactants to a particular product under specified process conditions. In addition, the catalyst composition can be used to convert and reduce the amount of contaminants or undesired reactants in a process. Another use of snails to a ^ $ is the overall energy efficiency of the same day of the process of maintaining or improving the product's lunar color and / or reaction selectivity. The use of the media varies greatly. For example, but not limited to, a catalyst can be used to reduce the amount of contaminants such as hydrocarbons, carbon monoxide (CQ), nitrogen oxides (NQX), and sulfur oxides (SOx), which may be present in A series of processes (such as the exhaust gas engine of a vehicle or the combustion exhaust gas in a diesel engine, classified stone &amp; refining or coal burning process, etc.). Similarly, catalysts can be used in the process of k. 'This process is used for many different sources (such as straight-running oil cranes, recirculating oil, heavy oil, advancing green, leaf rock, natural gas - and g έ 可文) The hydrocarbon process stream of the other carbon species of the material that catalyzes the reaction 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 class of catalytic reactions in which the reactants and catalysts are mixed in a solution phase. Although gas phase catalytic reactions have been used in some cases, homogeneous catalysis is typically a liquid phase system. Therefore, the concentration gradient and the migration of the reactants to the catalyst will become an important factor in controlling the homogeneous catalytic reaction. In addition, 'in some cases, the solution phase' catalytic reaction can occur across the interface of two liquid phases, instead of forming a true solution, but forming an emulsified phase. Some general classes of homogeneous catalysis include acid-base catalysis, Organometallic catalysis, phase transfer catalysis, etc. On the other hand, heterogeneous catalysis describes a type of catalytic reaction in which the reactants in the gas phase or liquid phase are exposed to a substantially solid phase or half 126433.doc 200843847 In contrast, in heterogeneous catalytic processes, the catalyst and reactants produce a mixed solid-liquid phase or solid-gas phase reaction. Heterogeneous catalysis has many advantages over homogeneous catalysis, such as Solid catalysts are generally (a) less corrosive' and thus have lower safety and environmental risks than many homogeneous solution catalysts, and (b) provide a wide range of economically viable temperature and pressure conditions and (C) ) It is more capable of controlling more intense exothermic chemical reactions and endothermic chemical reactions.

On the other hand, solids can have mass transfer limitations that in turn significantly reduce the ultimate effectiveness of the catalyst. Typically, solid catalysts (sometimes referred to as catalyst particles) include one or more catalytic components on a porous material having a high internal surface area (eg, noble metals such as palladium (Pd), platinum (pt), ruthenium). (Ru), 铢 (Re), etc.) 'The internal surface area where the catalytic component is located, usually on the order of hundreds of square meters per a gram. Therefore, conventional catalyst compositions or catalyst particles comprise a particularly porous support having a large internal surface area on which the catalytic reaction takes place. However, such catalyst structures often produce mass transfer ties that reduce the effective performance of the catalyst particles with respect to catalyst activity and selectivity and cause other catalyst performance problems. In such a more representative catalyst structure, the reactants must diffuse through the network of pores to reach the interior region of the catalyst particles, and the product must diffuse back into the interior region of the catalyst particles. Because &, the porosity of the conventional catalyst composition depends, among other things, on the balance, that is, on the trade-off between the two characteristics of the conventional catalyst composition, namely the surface area of the catalyst and the transfer of the amount of the catalyst. The trade-off between capabilities. For example, many catalytic components are present in a carrier with a fine and complex pore structure in the general case (via 126433.doc 200843847 ¥ for U pores, ie &lt; 2 nm average maximum diameter) &amp; increase touch The surface area of the media particles. This higher surface area will in turn generally increase catalyst activity. 2. The increase in catalytic activity due to the higher surface area of the catalyst particles, 4 曰 causes the problem of resistance to the transfer of Berry (ie, prevents the movement of reactants and products, and the particles of the catalyst), especially the carrier includes This problem is more pronounced when the percentage of microporous structure is high. By increasing the percentage of larger pores such as 50 mm of nanopores in the carrier, the resistance to mass transfer (i.e., accelerated mass transfer) can be reduced. However, this solution tends to reduce the physical strength and durability of the catalyst particles. In other words, the robustness of the catalyst particles is reduced from the point of view of self-reliance. At the same time, if the reactants are subjected to significant mass transfer resistance in the pore structure of the catalyst particles, a concentration gradient will exist under the reaction conditions. Therefore, in the pore structure, 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 at the center of the :: particle than around 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 (9): reactivity, selectivity, life cycle between regeneration treatments, and anti-coking properties are also reduced accordingly. The purpose of developing a catalyst composition in the case of a crane is to improve the one or more processing targets as described above from the corner of the business. In some cases, one of the factors that affect the performance of the catalyst is its ability to promote rapid response between reactants. Therefore, touches and compositions with lower diffusion limits are often required. Then, in other cases, in order to obtain a better product, 126433.doc 200843847 may be more important for the selectivity of a particular product. By &amp;, additional processes and associated processing equipment for removing or converting undesired reaction products are eliminated. 〇 In 1976, γ·τ·shah et al. proposed the use of acid-impregnated aluminum shed rock powder fibers, specifically E-glass (more specifically, Ε_62ι) to produce a seed vehicle carrier. Compared with conventional catalysts, the catalyst carrier has a higher surface area to volume ratio, and the catalytic conversion of the vehicle exhaust system is reduced by K. (for example, ll 〇xidati〇n 〇jr(10)(10)

Gas Mixture by Fiber Catalysts, Ind. Eng. Chem.5 Prod. ReS· Dev·, PP· 29-35, V〇l· 15, No. 1, 1976). At the same time, Shah et al., are generally reactive gases (such as oxidized slaves, carbon dioxide, nitrogen oxides, methane, ethane, propane, ethylene, propylene, acetylene, benzene, toluene, etc.) that are produced in automotive exhaust mixtures. Contact with 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 m'g) compared to two conventional catalysts (platinum supported on alumina beads or platinum supported on silica beads) The performance of the glass-catalyst carrier is better than that of the catalyst with oxidized etch or cerium oxide as carrier (18 〇m2/g and 317 m2/g, respectively), and the average pore size of the E-type glass catalyst It is larger than the catalyst with oxidized imprint as carrier or the catalyst with cerium oxide as carrier. Although the person does not propose or suggest effective automotive exhaust oxidation as described herein, it 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 19&quot;, 126433.doc • 11 - 200843847 for use in The selective liquid phase hydrogenation of bismuth oxide glass fiber (SGF) for benzaldehyde is related to the formation of benzyl alcohol (using a platinum-based catalyst) or toluene (using a catalyst based on I bar) (see, for example, G7 (2W FAers Catalysts for Novel Multi-phase Reactor Design, Chem. Eng. Sci. pp. 4785-4790, Vol. 54, 1999). In this study, Kiwi-Minsker et al. found that SGF cannot be self-leached An increased surface area is obtained, so that the EGF sample (surface area is 15 m 2 /g and 75 (λ m 2 /g), respectively, relative to the catalytic component used to carry I bar as a catalyst composition based on ruthenium, The surface area of SGF is kept at a low level of 2 m2/g. However, Kiwi·

Minsker et al. noted that the SGF/catalyst has essentially the same effective surface area concentration as its EGF/palladium catalyst counterpart (ie, about 0.1 mmol/m2) (mole metal per square meter of moiré). However, the SGF/palladium catalyst composition showed a decrease in activity or reaction rate per gram of palladium compared to its EGF/palladium catalyst counterpart.

Kiwi-Minsker et al. suggest that the SGF/palladium catalyst has a reduced surface area due to reduced surface area and may be explained by the interaction of the active ingredient (ie, the catalyzed &quot;, in this case, palladium) with the SGF carrier. The effect is enhanced, not because of its small surface area (ie 2 m2/g). However, they failed to prove the following argument by using the following theory: EGF/palladium catalyst with a small surface area (ie, comparable to 2 m2/g of SGF/palladium), at least with a large surface area ( That is, the EGF/palladium catalyst samples of 15 m2/g and 75 m2/g, respectively, have the same catalytic activity. Therefore, Kiwi-Minsker et al. proposed the limitation of SGF/palladium activity (that is, the higher acidity of SGF compared with EGF, and the enhanced interaction between palladium and SGF), which is the main factor, not due to Substantially SGF/Pd Table 126433.doc -12- 200843847 is small in size and the reason is not clear. In any case, Kiwi_Minsker did not report that the 15 m2/g EGf/^ sample was enhanced in catalytic activity due to the increased diffusion rate relative to the 75 m2/g EGF/ sample. Otherwise, this may indicate a beneficial effect due to the smaller catalyst surface area. ^, and recently, in US 7,060,651 and EP 1 247 575 A1 (EP, 575),

Barelko et al. disclose the use of a cerium-rich carrier (including cerium oxide and an oxide comprising non-cerium oxide (eg, Al 2 〇 3, B 2 〇 3, Na 2 〇, MgO, CaO, etc.) as a catalyst carrier. The beneficial effect is that the cerium-enriched carrier has a pseudo-layered microporous structure in the lower surface of the carrier (see, for example, paragraphs 11, 13, 15, 17, 18, 23, 31 and 32 of EP, 575) In the case of a more complete description to the European Patent Office ("Ep"), in distinguishing the catalytic carrier (''Kiwi-Minsker carrier') disclosed by EP '575 and Kiwi-Minsker et al. Barelko et al. assert that the cerium-enriched carrier they claim has a pseudo-layered crater structure with a narrow interlayer space, while the Kiwi-Minsker carrier does not. This is more specific than a 'Barelko et al. In Kiwi-Minkser et al., there is no basis for assuming that (a) there is a pseudo-stratified microporous structure with a narrow interlayer space in the Kiwi-Minsker carrier; (b) the pseudo-separated space with pseudo-separation Layered microporous structure helps to enhance The support for the active metal (see e.g. EP, 575 and 32 of the first piece of content 13,17-18,23).

Barelko et al. further clarify the carrier of the cerium oxide-enriched carrier with the carrier proposed by Kiwi_Minsker et al. by explaining the following contents to the European Patent Office: because the catalytic component is highly active on the surface of the carrier. a dominant distribution of the 126433.doc -13· 200843847 catalytic components in the sub-surface layers of the support in a highly dispersed active statey\in Ling, X qi,

C

The cerium-rich carrier has a more active catalytic state, so the catalytic state of higher activity allows the catalytic component to withstand sintering, aggregation and self-carrier flaking and contact agents (see, for example, EP, 575, 11). segment). EP * 575 confirms that diffusion limitations may hinder the incorporation of cations into the interlayer space of the support and thus hinder the entry of cations into the support by chemisorption (see, for example, paragraph 17 of £?'575). In order to solve the problem of diffusion limitation, 6&1^1]&lt;:0 et al. propose (and claim) a carrier structure in which thin, layered helium-oxygen fragments are separated to form a narrow The interlayer space (ie, the pseudo-layered microporous structure), the narrow interlayer space contains, a large number of 〇H groups, the protons of which can be exchanged by cations. Barelk〇 et al. The thin &quot; 矽-oxygen fragment layer is unique for high Q3 to Q4 ratios, and they further declare that pseudo-layered microporous structures with a large number of 〇H groups sandwiched between narrow interlayer spaces have been 29Si NMR (nuclear magnetic resonance) and 汛 (infrared) light «曰里 measured combined with argon BET and titration surface area measurement confirmed. Like some of these glass catalyst compositions, many conventional catalysts attempt to solve to J A previously identified processing problem, but not performing well in other aspects of catalyst performance. Therefore, such conventional catalysts are often limited to a narrower range of process reactions and have a limited life cycle before regeneration or replacement is required. And/or need to be big Filling expensive catalytic components (such as precious metals such as platinum and palladium), thus significantly increasing the cost of catalyst production and catalytic processes. Therefore, there is a need for an improved catalyst composition that can be used in a variety of processing reactions while improving processes such as processes. Reactivity, selectivity and / or energy efficiency 126433.doc -14- 200843847, etc. The conjugate is preferably improved on the process conditions of the phase, while enhancing robustness and durability, and maintaining a relatively long period of time. The life cycle of the user has been found to be a kind of functional surface catalyst composition, pre: month b enough to meet the needs of the application of a wide range of catalytic reactions.

C. An aspect of the invention provides a process for the selective hydrogenation of a process stream for selectively hydrogenating at least a portion of a process stream using a catalyst composition comprising at least one species having at least one target chlorine The compound of the site, the catalyst composition comprises: - a substantially microporous matrix having mesopores, macropores, outer surfaces, open pore wall surfaces, surface regions and subsurface regions, - at least one catalytic component And at least one catalytically active region comprising the at least one catalytic component, wherein a) the substantially microporous matrix has i) when measured in a group selected from the group consisting of S·' S· and combinations thereof The total surface area measured between about 5 m2/g and 300 m2/g; Π) the predetermined isoelectric point (IEP) obtained over a pH range greater than 0 but less than or equal to 14; b The at least one catalytically active region may be continuous or discontinuous and have i) an average thickness of less than or equal to about 30 nanometers; and ii) a catalytically effective amount of at least one catalytic component, and c) the at least one catalytic activity Regional Substantially 126433.doc -15- 200843847 0 on the outer surface, ii) on the open pore wall surface, iii) in the surface area, iv) partially on the outer surface, partly on the open pore wall surface, and partly in the surface area And combinations thereof; &lt; v) (c) combinations of (i), (ii), (iii) and (iv). Based on the following embodiments and the accompanying claims and drawings, those skilled in the art will be able to clearly grasp other bears and samples of the present invention. [Embodiment] Definition The terms used herein have the meanings defined below. The π pore π represents a hole or channel having a depth greater than the width. , interconnecting pores, representing pores in communication with one or more other pores. ▼ 'Closed pores, indicating that there are no channels of pores on the outer surface of the material where the closed pores are located. "Open pores" means pores that have a direct path to the outer surface of the material in which the open pores are located, or that are connected via another pore or interconnected pores (i.e., pores that are not part of the closed pores). "Pore width," means the inner diameter of the pore or the distance between the opposing walls determined by the specified method. π pore clock product indicates that the total volume effect of all pores determined by the L疋 method is known, but does not include the volume of the closed pore. The effect ", porosity" means the ratio of the pore volume in a material to the total volume of the material. 126433.doc -16- 200843847 ''Microporosity τ' denotes pores having an internal width of less than 2 nanometers (nm). 'Intermediate pores'' means pores having an internal width of between 2 nm and 50 nm. The ''large pores'' indicate pores having an internal width of more than 5 Å. The 'outer surface' indicates a boundary or skin of a material (near thickness is zero), including a regular or irregular contour on the outer boundary or skin associated with the defect, if any. The surface of the wall refers to the inner boundary or the skin (thickness is close to zero), including any rules or irregularities on the inner or 表 ί, ' boundary or skin that are related to defects (if any). A shape having any open pores in the material of at least one or more types of pores. ''Surface'' generally means - the pore wall surface of the material (if any open pores are present), the outer surface of the material and its surface area. ''Surface area'' means that it can vary depending on the material and does not include any open pores from the material ( If there is any material region of the region defined by the open pores, but the surface region (4) is less than or equal to 30 nanometers below the outer surface of the material (preferably (four) nanometers, more preferably (four) nanometers); In any open gap, the surface area (b) is at the pore wall of the material at 30 nm (preferably &lt;20 too, A, and not y, more preferably 10 nm). For a material with a measurable surface elevation change, whether or not the change is regular, the average elevation of the outer boundary or the inner edge of the edge is used for 4 1 or the inner boundary or the skin; the average depth of the surface area is determined . "T-zone table can not be changed according to the material does not include any area defined by the material ^ two gaps (if there is any pores): domain 'but the subsurface area (4) on the outer surface of the material "below is greater than two i26433 .doc -17- 200843847 (preferably &gt; 20 nm, more preferably > 1 〇 nano wide in the gap 'the subsurface area (b) any open hole in the material surface (preferably 〉 M, more preferably &gt;1() nanometer "under 3 〇 奈 ', internal surface area" or "open surface wall surface area of all open pore walls in the material surface effect, method to determine, &quot; external surface area &quot;Table (four) shirt method shirt ^ material surface surface effect including the surface area effect of all the pore walls of the material towel. "Two surface area" means determined by the specified method: the sum of the surface area of the surface area of the material. The surface area of the sodium chemisorption, or SA- The surface area of the material determined by chemical adsorption of the sodium cation by chemisorption, (4) chemisorption method in GW Sears such as /. cw, 1956, ν〇ι 28, p lan MR. Iler, Chemistry of Silica, John Wiley &amp; Sons 1979, p. 203 and 35 Described in 3. "Sodium-chemical adsorption surface area change rate" or, sARC^,,, where sarc^=

At the beginning of Vyb/V, wherein (1)v is initially used to initially titrate a dilute NaOH titration solution of an aqueous slurry mixture, and at a temperature of about 25, a substantially water-insoluble material is included in the solution of 3·4 M NaCl, the solution The value of ρΗ is at zero time t. From the initial ΡΗ 4.0 to ΡΗ 9.0, and (ii) % to 15 means the total volume of the same concentration of NaOH titrant used to maintain the slurry mixture at pH 9 for 15 minutes, every 5 minutes (3 total) The 5 minute interval, h, ^ and ^5 respectively, the total volume is adjusted as needed as soon as possible. Therefore, V total refers to the NaOH used in the titration procedure described in more detail below. 126433.doc -18- 200843847 The total volume of the titrant, where V#"+V5 to i5=v total. Therefore, ^ to 15 can be expressed as the difference between v total and v initial, where % to 15 = ¥ total _v initial. For the purposes of this definition A 3?4 M NaCl solution was prepared by adding 30 grams of NaC1 (reagent grade) to 15 milliliters of water, and 1 beta 5 grams of sample material was added to the NaCl solution to produce an aqueous slurry mixture. The aqueous slurry mixture must first be adjusted to pH 4.0. In order to make this adjustment before titration, a small amount of dilute acid (such as HCl) or a dilute base (such as NaOH) can be used accordingly. In order to obtain the initial V, first use a dilute NaOH titration solution (for example, 〇el 1^ or 0 〇1 N)' Then use Vpm for SARC^ determination. For the purposes of this definition, 'Vs to is is the cumulative volume of NaOH titration solution used in , ^ and 5, where NaOH titration solution is used every 5 minutes (3 3 minute intervals) as soon as possible to titrate as needed . To the final time. The pH of the slurry mixture was adjusted to 9.0 within 15 minutes. For the purposes of this definition, it is treated with any alternative ion exchange (ΙΕχ), counter ion exchange (BIX) and/or electrostatic adsorption (ΕΑ) treatment to produce one or more Type 2 component precursors (described below) The S ARC^ of the sample material is determined prior to integration onto the surface of the substrate and/or in the surface of the substrate. 'Incipient wetness' means that for an aqueous slurry or paste mixture comprising a solid or semi-solid material, a point in time at which the isoelectric point ("IEp") of the material is being measured 'this time' is substantially covered by deionized water. The entire surface of the solid or semi-solid material, and to the extent that it can be filled with any water-permeable pore volume that the material may have, thereby allowing water to enter the aqueous slurry or paste mixture to provide contact of the glass electrode contact with its reference electrode The surface and the sufficient liquid contact between the two to determine the IEP of the material. 126433.doc •19· 200843847 “Isoelectric point” or IEP indicates the pH of a solid or semi-solid material with a zero 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 zer〇charge (PZC) on catalytically effective amount, and f is sufficient under appropriate processing conditions. Converting at least one reactant to at least one predetermined product of sufficient yield to support the amount of catalytic component of the pilot plant or commercial grade process. "Chalcogenide" e)" means that at least one element of group 16 (formerly Group VIA) derived from a group consisting of sulfur (S), sulphur (Se) and cerium (Te) and at least one positively charged stronger than its corresponding a compound of a group or element of a group 16 element. ''Precious metal, representing a group derived from rhodium (Rh), palladium (Pd), silver (Ag), iridium (Ir), platinum (Pt), and gold (Au). The transition metal, unless otherwise stated, is in a charged state in the form of a metal complex, metal salt, metal cation or metal anion, otherwise the transition metals are in a zero oxidation state (while in an unreacted state). ''Anti-corrosion matrix "" indicates a matrix that is capable of resisting substantial changes in the matrix composition of the subsurface region. The change in the composition is due to changes and/or loss of structural constituent elements and pore formation of the crucible due to the majority of acid or dilute alkali under standard temperature and pressure conditions. , pore size expansion, etc. However, the composition of the antiseptic matrix may be substantially high-intensity acid (eg, concentrated liver), high-intensity test (eg #浓他(10)) or other strong rot (four) reagents (whether alone or in combination with high temperature, high pressure and / Or a combination of high vibration frequency conditions), as defined by this definition, such matrices are still considered to be "corrosion resistant" substrates. 126433.doc • 20 - 200843847 ', surface activity '' indicates that the surface of a material is adequately loaded In the state of one or more charged components, the material containing one or more charged components is used to (1) promote catalytic reaction under steady state reaction conditions without further modification, or (ii) additionally, by reacting with one or more charged components The electrostatic interaction and/or ion exchange interaction between them is used for further modification, which in turn can be used as a catalytic component under steady state reaction conditions.

U ” matrix, means any solid or semi-solid material, including but not limited to glass and glass-like materials, IEP greater than 〇 but less than or equal to 14, surface active state can be in accordance with the matrix in the catalyst composition (catalytic effective amount of catalysis The intended use in the component is changed. "Integration, means interaction by electrons and/or physicochemical interactions (eg, ionic, electrostatic or covalent interactions including, but not limited to, hydrogen bonding, ionic bonding, electrostatic bonding) Vander Waals/Dipole Bonding, Affinity Bonding KJ Bonding, and combinations thereof combine the & ingredients with the matrix. MODES FOR CARRYING OUT THE INVENTION The notes underlying the present embodiments are set forth in the description of the scope of the patents that accompany the patent application and are therefore only used to facilitate the presentation of embodiments that may be of potential interest to the reader in a simplified wording. Some are out of shape. Therefore, 'the annotations of this embodiment should not be regarded as not limiting the scope of the invention appended to the application. IX. Samples relating to the catalyst composition, the average thickness of the catalytically active region of the surface active is less than or equal to about 3 〇. The meter, preferably &lt; about 2 〇 nanometer, and more preferably -1 〇 nanometer (&quot;catalyst composition"). 126433.doc -21- 200843847 of the invention is another aspect related to various manufacturing A method of the novel catalyst composition. Another aspect of the invention is to produce a composite form of the catalyst composition, with or without a forming medium. Yet another aspect of the invention relates to the use of a catalyst composition in various processes, Such processes are, for example, 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 enhance hydrocarbons, hydrocarbons and/or non-hydrocarbons. Reaction selectivity, reaction rate, yield yield and energy efficiency of hydrocarbon treatment, conversion, refining and/or emission control and treatment processes and other types of processes. Several factors should be considered in the production of catalyst compositions. Including but It is not limited to: (1) In view of the intended use, 'obtaining a substrate having a predetermined isoelectric point (,, ΙΕΡΠ)' obtained either as it is or after subsequent processing; (ii) the degree of corrosion resistance of the substrate for the intended use; (iii) in view of the intended use, in order to obtain the desired surface properties, the degree of porosity of the substrate, if any, and the associated elemental composition (particularly on the surface), (iv) depending on the intended use of the composition, as appropriate The substrate is chemically sensitive to the generation of a suitable electrical 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, which matrix can, but does not necessarily produce, a catalytically active region having an average thickness on and/or within the surface of the substrate of &lt; about 30 nm, preferably &lt; about 2 nanometers, more preferably about 10 nanometers; The chemical sensitivity of the substrate to a selective ion exchange (ΙΕχ), counter ion exchange 126433.doc -22- 200843847 (BIX) and/or electrostatic adsorption (EA) treatment methods, which are used to Various The two components are integrated onto and/or within the surface of the substrate having a second type of interaction with the matrix ions and/or electrostatics and thereby producing a catalytically active region on and/or within the surface of the substrate The average thickness is about 30 nm, preferably &lt; about 20 nm, more preferably about 10 nm; and (vi) depending on the intended use of the composition, the treated substrate is reacted as follows Chemical Sensitivity: Optional satin burning and / or reduction, oxidation or further chemically reacting the treated substrate with the first or second catalytic component prior to use of the catalyst composition. I. Matrix Description For many potential applications Preferably, the preferred embodiment and preferred range of IEp selections are preferred. The matrix used to produce the catalyst composition of the present invention is a glass composition. The surface activity is either received as received or treated to produce surface activity, and the 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, in an overview of the implementation). In view of the more detailed discussion below, those skilled in the art will be more aware of other factors associated with selecting an appropriate IEP. For example, for many processes of commercial interest, the glass (or glass-like) composition and its surface active product preferably have a enthalpy of greater than or equal to about 4. 5 but less than 14, and are expected to be greater than or equal to about 6 〇 but less than The glass of 14 and the preferred material of the crucible is more than or equal to about 7·8 but less than 14 glass 126433.doc -23- 200843847 The composition is the best. The absence of ", and" depends on the intended use of the catalyst composition and the extent and type of & f and tau pores in the matrix of the composition. The preferred IEP range may be affected. & 'Some catalytic processes are more sensitive to catalyst compositions that have surface activity at lower pH ranges. Therefore, in these cases, IEP is less than 7.8 (preferably t is preferably &lt;4·5) The matrix is likely to be more suitable for such processes. The household is $ ^ ^ α ^ ^ , so, again, when choosing the base negative within the appropriate range * only consider the intended use of the catalyst composition It is also necessary to combine the porosity of the substrate, the chemical composition and the processing procedure (if any), etc. Depending on the intended catalytic use, many glass types can be potential base f candidates, the appropriate degree of IEP and porosity. And class $, whether received or used as follows - or a variety of treatment methods. Typically, examples of such glass types include, but are not limited to, E-glass, boron-free glass, S-glass, R-glass 'AR type Glass, rare earth, bismuth silicate glass 钡 titanium-tannic acid Salt glass, nitride glass such as bismuth-aluminum_oxygen-nitrogen glass, A-glass, c-glass and CC-type glass. Then, the following is an example of glass that is generally expected for a range of catalytic applications and some possible treatments. Type bismuth leaching E-glass indicates that the substrate used to produce the catalyst composition of the present invention preferably comprises a glass composition substantially free of micropores, but at least some of the mesopores and macropores (&quot;no microporosity. The constituting glass material, and the IEp generally has a force of 7.8, preferably about 6, and more preferably &lt; about 4.5' but in any case is greater than 〇. For example, but not limited to, a certain money dip" E type "Glass is a wide range of &lt; glass combinations (whatever the surface active system receives or is treated as the main surface active 126433.doc -24- 200843847 state, the enthalpy is less than 4. 5 but greater than 0. Typically, such acid immersed bismuth glasses will include acidic or basic oxide type glass mesh modifiers including, for example, but not limited to, (Ζη), magnesium (Mg), calcium (Ca) , aluminum (Α1), boron (Β), titanium (Ti), iron (Fe), sodium (Na) and (K) an oxide of a specific element. If an organic network modifier is used, the amount included in the acid-impregnated E-glass tends to be &lt;5 wt.%, including strontium magnesium, calcium, The glass of aluminum, zinc, sodium and potassium is preferred. The catalyst composition of the present invention is preferably a microporous glass substrate, IEp, but &gt;〇, and the mesoporosity and macroporosity correspond to less than the total matrix. The surface area is about 95%, and the corresponding or external surface area ranges from about 5% to about 4% of the total surface area of the matrix. Porosity indicates that the porosity of the matrix produces another related aspect of the catalyst composition of the present invention. The matrix should be substantially free of microporosity, but there may actually be a number of mesopores and/or macropore volumes that do not adversely affect the intended use of the catalyst composition. Since the micropore volume in the material = is difficult to detect, it is described that two surface area measurements are used to determine whether the base 2 is substantially free of micropores' to the catalyst composition of the present invention. The first item surface area measurement data is determined by a thermal adsorption/desorption method suitable for accepting the measurement of the expected table ==, and the τ is used for (4) the degree of microporous pores and/or 2 large pores β, for example, For larger surface area two: eg &gt; about 3 mvg) Ν2 ΒΕΤ, according to astm 3, Γ (1AK) may be a preferred surface area measurement technique. However, ASTM is measured on a smaller surface area (for example, A) Kr BET, as described in the paragraph _95, (&quot;sa. coffee) may be better 126433.doc -25- 200843847 surface area measurement Techniques. Those skilled in the art of analyzing the surface area of solid and semi-solid materials will be aware of the best surface area measurement method for detecting microporosity, mesopores and/or macroporosity. The second measurement is sodium _ chemical adsorption surface area. (SAw) 'A certain type of analytical method can be used (R. Iler in &amp;·/—, John Wiley &amp; Sons (1979) on pages 203 and 353) to indicate the change in time versus time for NaOH titrant, and A more specific definition according to the SA-rate of change (''SARC-'). Thus, as defined herein, the matrix is substantially free of micropores, provided that the lamp or SAhwr of the substrate is between about 5 m2/g and about 300 m2/g, preferably from 5 m2/g to about 150. M2/g, and more preferably from 5 m2/g to about 75 m2/g; in any case, its sarC- is less than or equal to 〇·5. For example, the above is more than the ratio of the two volumes of the NaOH titration solution. The denominator is the volume of the initially used NaOH titration solution, which is initially used at zero time t. A matrix slurry mixture was titrated and the matrix slurry mixture contained 1.5 grams of substrate in a 4 M NaCl solution (pH 4 to pH 9) at about 25 °C. However, as mentioned above, before the initial NaOH titration is used for SARC^ determination, the aqueous slurry mixture must first be used with a small amount of acid.

(HC1) or base (NaOH) was adjusted to pH 4. In addition, as described above, the cumulative volume of the NaOH titrant (for three 5 minute intervals, maintaining the matrix slurry mixture at pH 9 within 5 minutes) is v^-V initial (ie, Vy 15), This is the numerator of the ratio SARCw. Therefore, if v--V is less than or equal to 〇·5 V at the beginning, the corresponding SARCw is less than or equal to 〇·5. Therefore, as defined herein, the matrix of 'SARCa^^O.5 is substantially free of microporosity (ie, mesopores and macropores), and uranium is extracted as a matrix. 8.8.#2』 lamp or sAhja is also about 5 M2/g to 126433.doc •26- 200843847 is between about 300 m2/g, preferably from 5 m2/g to about 150 m2/g, more preferably from about 5 m2/g to about 75 m2/g. If such surface area parameters are met, there may be insufficient concentration, distribution, and/or type of the matrix in any other type of pore volume&apos; which may adversely affect the desired performance of the catalyst composition for its intended use. The nano surface area (&quot;SAw") is an empirical titration procedure developed for substantially pure cerium oxide (Si〇2) in the form of granulated, powdered and suspended gels. sAw determination The measure of the reactivity and accessibility of the surface proton position (Glass-CTH-) corresponds to the Si-CrH+ position for pure cerium oxide. The bismuth silicate glass and crystalline bismuth silicate and pure cerium oxide (Si) 〇 2) There are significant differences in composition. For the stoichiometry of this titration procedure, the behavior of bismuth silicate glass and crystalline citrate cannot be determined from the absolute value of the Na〇H titrant determined in the SA·^ experiment. Or prediction. Therefore, the equations used by Sears and Iler to correlate the 〇A-experimental Na〇H volume with the N2_BET 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 G][ass_〇_H+ groups that can exist in different compositions of glass can include, for example, AWIT, Β_〇·Η+, Ti_〇-H+, Mg 〇_H+, and a single 矽Multiple si-o-ir parts of 2 positions combined more The same structure of the proton group (Q2 group). On the other hand, the total surface area of the 矽-like glass composition (such as acid immersion quartz) may be reliably determined using the SAW experiment, provided that the minimum pore size is in the standard gas phase. The bribe measurement can be reached because it consists mainly of the networked Si02 and Si_〇-H+ parts. However, the diffusion accessibility of the Giass_OH moiety to hydroxide ions and nanoions, and the relative percentage of pores, macropores, and/or substantially non-porous regions in the 126433.doc -27- 200843847 pores should be Detected according to the amount of NaOH (in the SAw experiment to maintain the final value of 9, must be added over time) (titrant). Therefore, in summary, the accessibility of the Glass-〇-H+ part to the oh- and Na+ contrast time, as determined by the above-mentioned SARCw experiment, can be used as a reasonable and reliable measure of the presence of micro-pores, including standard gas-phase BET measurements. And some kind of porosity. Again, the matrix is substantially free of micropores. However, if there is significant ion depletion and associated leaching on the matrix network, microporous regions are likely to be produced in the matrix. Therefore, as described above, SARC &amp; greater than about 〇 5 can be used as an indicator of the presence of a large amount of micropores on the substrate. 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 form such a dedicated matrix include, but are not limited to, woven composites, non-woven composites, mesh fabrics, extrudates, rings, saddles, cylinders, Films, spiral bonded films, filters, 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 (collectively "composite") with the catalytic substrate, including but not limited to soft water aluminum. Boehmite, hydrated titanium dioxide and Ti〇2, hydrated zirconia and 丫126433.doc 200843847 Alumina, alpha alumina, ceria, clay, natural and synthetic polymeric fibers, polymeric resins and solvents, and water soluble polymers Whether or not the matrix includes 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 catalytic composite, the resulting non-conceived The extent to which the internal composite material diffuses. Therefore, it should be understood that the proper distance for positioning a substantial portion of the catalytic substrate within and/or over the periphery of the composite will depend on the intended use of the catalytic composite, the overall size and shape of the catalytic composite, and the catalytic substrate. The overall size and shape. Thus, in various composite shapes and sizes, the average thickness of the perimeter of the composite (the catalytic substrate can be placed on and/or within the periphery of the composite) is typically between about 1 micrometer and about 4 micrometers. However, the average thickness of the periphery of the composite is preferably between about 1 meter and about 25 nanometers, more preferably between about 1 micrometer and about 15 micrometers. However, depending on the intended use of the composition, in some cases,

The average maximum size of the particles is typically between about 5 microns to less than or equal to 126433.doc -29 to 200843847 and about 150 microns, preferably about 2 microns to less than or equal to about 〇. More preferably between about 5 microns and about 5 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, beyond this range The matrix can still be effective, for example, in the continuous fiber form described above, without adversely affecting the desired properties of the catalyst composition. Those skilled in the art will appreciate that the compounding operation may have potential micropores and additional macropores and / or the mesopores are introduced into the finished composite. However, in a composite operation process, as described herein, this porosity does not introduce a functionalized surface component of the catalyst composition. π. Matrix surface activation is used to produce the catalyst of the present invention. The base f of the composition may be activated by - or a plurality of first components having a first type of ion and/or electrostatic interaction with the substrate (丨丨1形赤八乂 仏 n, t 1 1 into a knives drive). As described in more detail below, the type 1 precursor may be too material, the body has catalytic effect or can be further processed to produce catalytically active areas, The average thickness on and/or within the surface of the substrate is S about 30 nm. Preferably, the average thickness of S is about 2 nanometer nanometers, more preferably the average thickness of nanometer nanometers. For example, at some In some cases, depending on the intended use of the catalyst composition, if the matrix obtained has a suitable type and extent of pore structure (if any) and an isoelectric point (IEP) matrix in the range suitable for the intended use, It may have sufficient surface activity to effectively catalyze, although not necessarily, preferably, the substrate may be treated to further modify and/or entangle the eight surface activity. In addition, the substrate may also be treated to remove any expected interference. An organic coating or other possible stain of the properties of the composition 126433.doc &gt;30-200843847. Further, as discussed in more detail below, under "type 2 component precursor integration treatment", depending on the catalyst composition For intended use, better It may be possible to further treat the surface of the substrate by ion exchange (IEX), counter ion exchange (BIX) and/or electrostatic adsorption (EA) treatments which integrate one or more second components onto the surface of the substrate and/or Or internally, the surface of the substrate has a second type of ionic and/or electrostatic interaction with the substrate, and thus the catalytically active region 'average thickness on and/or within the surface of the substrate is 〇 nanometer' preferably &lt;20 Nano, more preferably &lt;1 〇 nanometer. Substrate contamination 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 and/or interference of the catalyst composition. Depending on the desired properties of the media composition for the intended use, a contaminant removal process may be selected. For example, typically, the AR-type glass is made using an organic coating (i.e., sized). The organic coating is used to facilitate processing, such as dispersion in aqueous formulations. However, the organic coating or sizing may interfere with the preparation of the catalyst composition, even if it does not interfere with most, if not all, of the catalytic properties of the intended use of the catalyst composition. Therefore, the organic coating should be removed. Calcination is a preferred method for removing such organic coatings. Because the primary goal of this treatment is to remove contaminants from the matrix, the conditions of such forging treatments are not particularly important for successful surface activation of the matrix. In some cases, depending on the nature of the contaminant to be removed from the substrate, solvents, surfactants, aqueous 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 gas 126433.doc • 31· 200843847 (e.g., in air or oxygen). In addition, it is important to select a high enough firing 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 50 lower than the softening point of the selected matrix material. Preferably, the calcination temperature should be at least about 1 Torr lower than the softening point of the selected matrix material. For example, when using AR-type glass, the calcination temperature at which most AR-type glasses can be removed to remove contaminants is Between about 300 ° C and about 700 ° C. Typically, the selected matrix material should be calcined for about 2 to 14 hours, preferably calcined for 4 to 8 hours. However, depending on the nature of the substrate obtained and desired The nature of the target contaminant removed by the matrix, the calcination time can vary outside of these time ranges. Surface activation by ion leaching treatment After any potential contaminants are substantially removed from the matrix, the matrix can be processed by Producing a surface active state and a desired isoelectric point (, ΙΕρπ), provided that the initial enthalpy obtained from the matrix is not within the desired range. However, in some cases the 'substrate received may have sufficient surface activity, requiring Further modification using one or more other treatments (described in more detail below) without using the first type of ion leaching (ΙΕΧ_υ treatment (this will be the first of the other treatments described in more detail below) In other words, the elemental composition of the matrix, especially on the outer surface or substantially close to the outer surface, may be sufficient to obtain the desired enthalpy. However, in many cases, the matrix composition of the matrix will require some modification. Varying the initial ΙΕρ and obtaining a suitable ΙΕΡ, and then obtaining a surface state that meets the requirements of the type and degree according to the intended use of the catalyst composition. Surface state, one or more first components having (1) first oxidation 126433.doc -32- 200843847 State and (ϋ) The first type of interaction with the ionic and/or electrostatic interaction of the substrate may be sufficient to produce a catalytically active region having an average thickness on and/or within the surface of the substrate. 30 nm, preferably &lt; about 2 〇 nanometers, more preferably &lt; about 1 〇 nanometer, and thus providing the desired properties of the catalyst composition to achieve the intended use, such as, but not limited to, on the surface of the substrate and/or Or within the Bronsted or Lewis acid sites and Brunsett or Lewis bases can effectively promote some hydrocarbons, hydrocarbons (such as oxygenated hydrocarbons) and non-hydrocarbons Process, conversion and/or refining process. 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) a second oxidation state which may be the same as or different from the first oxidation state, and (第二) a second type of interaction with the ions and/or electrostatics of the matrix, sufficient to produce a catalytically active region, on the surface of the substrate and/or within the average The thickness is about 30 nm, preferably &lt; about 20 nm, more preferably &lt; about 10 nm. ' Now the surface activation treatment, the surface activation treatment includes at least one ion leaching treatment to obtain The first type or hydrazine ion exchange (positive) matrix. However, it should be understood that if the substrate received has an IEP suitable for the intended use of the catalyst composition, then IEX_; [also prepared to illustrate the first class Matrix. Typically, the ion leaching process is performed by any suitable means, i.e., effective removal of the desired ionic species from the entire substrate surface in a substantially heterogeneous manner without significant erosion of the matrix network (eg, avoiding The surface area and/or the subsurface area produces any microporous structure). For example, but not limited to, most of the acids, whether inorganic or organic, and various chelating agents, 126433.doc -33-200843847 are suitable for ion leaching. Preferably, mineral acids such as, but not limited to, nitric acid, phosphoric acid, sulfuric acid, hydrochloric acid, acetic acid, perchloric acid, hydrobromic acid, chlorosulfonic acid, trifluoroacetic acid, and combinations thereof are used. Generally, the concentration of the acid solution used for the ion leaching treatment depends on the characteristics of the substrate (for example, the affinity of the ions to be removed from the glass network, the strength of the glass after removal of the network ions), the IEP of the substrate needs The extent of the change and the intended use of the catalyst composition. Preferably, the concentration of the acid solution used for the ion leaching treatment may be between about 〇5 wt.% to about 50 wt.%, more preferably between about 2.5 wt.% and about 25 wt.%. Preferably, it is between about 5 wt.% and about 1 〇wt 〇/〇. Chelating: It can also be used in ion leaching treatments such as, but not limited to, ethylenediaminetetraacetic acid (''EDTA'), crown ethers, oxalates, polyamines, polycarboxylic acids, and combinations thereof. The concentration of the treated chelating agent solution depends on the nature of the substrate (e.g., the affinity of the ions to be removed from the glass network, the strength of the glass after removal of the network ions) and the intended use of the catalyst composition. Preferably, the concentration of the chelating agent solution for ion leaching treatment may be between about 0.001 wt.% and saturation, more preferably between about 1 wt% and saturation. The type and concentration of the acid or chelating agent and the characteristics of the substrate, and the heat treatment conditions for the ion leaching treatment, such as the heating temperature, the heating time, and the mixing conditions, are selected. The range of the heating temperature depends on the concentration of the acid solution or the chelating agent solution. However, preferably, the heating temperature for the acid ion leaching treatment is 126433.doc -34 - 200843847 degrees between about 20 ° C and about 200 ° C, more preferably between about 40 ° C and about 95 ° Between C, preferably at about 60 ° C Between 9 and TC., the heating temperature suitable for the chelating agent ion leaching treatment is in the range of from about 20 ° C to about 200 ° C, more preferably in the range of from about 4 ° C to about 90 ° C. The heating time suitable for the ion secondary treatment may vary depending on the concentration of the chelating agent solution and the heating time. Preferably, the heating time for the ion leaching treatment is between about 15 minutes and about 48 hours, more preferably Between about 3 minutes and about 12 hours. f

Generally, depending on the type and concentration of the acid or chelating agent used and the characteristics of the substrate (for example, the affinity of the ions to be removed from the glass network, the strength of the glass after removal of the network ions, etc.) and heat treatment The duration, select 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 acid or chelating agent concentration, heat treatment conditions, and mixing conditions will be determined based on the degree of sufficient ion exchange between the acid or chelating agent and the target matrix ion to produce a suitable Electrostomosis: and the type and extent of surface electrical properties to achieve the surface active state required for the post-treatment of the base f or the intended use of the catalyst composition. Preferably, after completion of the secondary treatment, preferably any suitable The method separates the substrate subjected to ion leaching, including but not limited to "10,000", centrifugation, decantation, and combinations thereof. Washing the ion-leached scallops with one or more suitable cleaning solutions (such as deionized water and/or a suitable water-soluble organic solvent such as methanol, ethanol or propylene) and warming to about 110° in a chamber Dry at a temperature of c for about 20 to 24 hours. 126433.doc -35- 200843847 In the case of a b-exchange treatment, depending on the intended use of the catalyst composition, it may be possible to carry out counter-ion exchange or two-step 2-ion exchange treatment for the selected substrate compared to the L mode. (collectively referred to as processing in this article). The MX treatment is usually 'not limited to G' for counter ion exchange) because the ion-leached matrix I is mixed with a salt solution (eg, NaCl) of an ion that is initially removed, and is subjected to ion leaching treatment _ its @ ^ t ^ This type of ion (eg Na+) removed from the substrate will then

&quot; or 1 back to Kibe. It is unclear whether the ions removed from the matrix will return to the same position originally occupied in the matrix. However, regardless of whether the initially displaced ion completely or partially changes position due to BIX processing, and does not change position at all, it should be understood that the processing vessel described herein changes due to any such possible ionic site placement. All catalyst compositions produced. The type of salt solution used to treat the radical f of the ion leaching treatment depends on the type of ions that will undergo reverse ion exchange. Preferably, only one ion counter ion exchange is performed, but in some cases, counter ion exchange of two or more ions may be required. Any ion that is easily removed by the above ion leaching process can be subjected to t-t exchange. Some examples of such plasmas include, but are not limited to, Group 1 (in the immediate Group IA) alkali metal ions, such as lithium, sodium, and potassium ions, and soiled metal ions from Group 2 (former Group IIA), For example, wrinkles, magnesium, about ions, NH/ and amyl ammonium cations, and small organic polycations. Preferably, alkali metal ions and NH are preferred targets for hydrazine treatment, while Na+ and ΝΗ/ are preferred cesium ions, and Na+ is better for 126433.doc -36-200843847 ions. Typically, the concentration of the salt solution used for BIX treatment depends on the type of substrate to be treated by BIX via ion leaching • treatment and the relative affinity of the BIX ions used to return to the ion leaching matrix. Similarly, with yttrium ion return • matrix Site-independent in the network (eg, Na+ for phase versus H+ for matrix). For most types of glass substrates, such as, but not limited to, AR-type glass, A-glass or quartz glass, about 〇〇〇 Preferably, the BIX-salt solution is preferably at a concentration of $mol/L, and about 5 is f\1; the mol/L BIX-salt solution is more 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 hydrazine treatment using the BIX-salt solution may be between about 2 (TC to about 20 (TC), more preferably between about 3 (Γ(: to about 95 〇c). The heating time for the BDC treatment may vary depending on the concentration of the salt solution and the selected heating temperature. Preferably, the heating time of the Βιχ treatment is between about 5 minutes and about 24 hours, more preferably about Between 3 minutes and about 8' hours • . #, depending on the type and concentration of the solution used and the specificity of the substrate (for example, the affinity of the ions to be removed from the glass mesh, moving) In addition to, the strength of the glass after the bismuth ion, and the duration of the heat treatment, the S' combination condition is selected. For example, but not limited to 'the mixing condition may be continuous or intermittent, or may be mechanical mixing, fluidization, tumbling, Rolling or manual mixing. 126433.doc -37- 200843847 In summary 'BIX salt solution concentration, heat treatment conditions and combination of mixing conditions' are based on returning a sufficient amount and allocating a sufficient amount of separation, sub-back to the matrix to determine, And with ions in the matrix network The point is irrelevant. A sufficient amount of BIX-ion is returned and distributed to produce the desired surface charge type and extent to produce the surface active state desired for the intended use of the substrate or for the intended use of the catalyst composition. Adjusting the pH to adjust the surface charge of the substrate preferably requires the use of a negative surface charge on the substrate to support electrostatic interaction or affinity with positively charged components (e.g., cationic alkaline earth metals, cationic transition metal components, etc.). For some potential catalyst composition applications, it may be necessary to use a positive surface charge to support electrostatic interactions with negatively charged components such as anionic transition metal oxygen ions, sulfate anions, noble metal polydentate anions, etc. Affinity. Generally, the surface charge of the substrate can be changed to a net positive state by adjusting the pH I value of the ion/leaching substrate/IEX mixture to be lower or higher than the substrate isoelectric point (, IEP). Or net negative state. Please think back, IEp is also called zero point electricity (&quot;zpc"). So, in other words, IEP ( ZPC) can be regarded as having a pH of sheet material • net zero surface charge at the time of the beginning of the wet surface. Therefore, the group

• The pH of the mass/IEX water mixture is adjusted to be greater than the pH of the matrix IEP (or ZPC)

A value that produces a net negative surface charge on the substrate. In addition, adjusting the pH of the matrix/IEX water/heart composition 2 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 ARS glass is equal to 9.6, if the positive value of the AR-type glass treated by the ion 126433.doc •38-200843847 π is adjusted to a value of >9·6, it will be on the surface of the glass: Produces a net negative surface charge. Depending on the IEP profile of the AR-type glass, the pH may be adjusted to be greater than the IEp - or two or more pH units of the matrix to ensure that its 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. Generally, any dilute base can be used to adjust the surface charge of the substrate to the right of its IEp (ie, to produce a net negative surface charge), and any dilute acid can be used to adjust the surface charge of the substrate to the left of its IEP (ie, produce Net positive surface charge). The inorganic acid and the alkali or the organic acid and the base can be used in a dilute concentration, and the inorganic acid is preferably used. 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, electrostatic adsorption (EA) type integration mechanisms are likely to not occur. However, without being bound by theory, direct ion exchange (IEX) or reverse exchange (BIX) may occur at the exchangeable surface location, resulting in surface integration of the catalytic component or precursor, the 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 be provided for proper amount with the surface portion of the substrate 126433.doc -39 - 200843847 but A valid exchange location for IEX or BIX. For example, but not limited to, such moieties, such as the decyloxy (_si_crNa+) moiety, include Na+ which can be at least partially replaced by a positively charged catalytic metal or metal complex precursor (eg, but not _Pd(10)3), +). The ions, in turn, produce a matrix having a catalytically effective amount of catalytic component. The surface charge of the ruthenium treated substrate is controlled by adjusting the pH as in the case of IEX treatment or second treatment (&quot;ΙΕχ_2 treatment, as discussed below). For some BIX treatments, pH adjustment may be required, C, but not required. Similarly, depending on the type of BIX_ion that will be integrated into the surface and exchanged in the IEX-2 treatment, the degree of ipH adjustment required will often depend on the 1EP of the matrix, its IEP contrast surface charge distribution. Curves and: Types of Charges to be used. The type of solution used to carry out the pH adjustment will depend on the phase of the other reactants, the stability of the matrix in the relevant pH range, and the desired charge male and others. In general, any thin test 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 ( That is, a net positive surface charge is generated. The inorganic acid or organic acid or organic acid can be used in a dilute concentration. Usually, the concentration of the dilute acid solution or the rare solution will depend on the The type of the test, its dissociation constant, and the pH suitable for obtaining the type and density of the surface charge to be obtained. HI· Type 2 component precursor integration treatment. Whether the substrate surface active system is received as it is, or is subjected to ion leaching treatment (ie, Desin 1 treated substrate, or fine X treatment, preferably at (1) 126433.doc -40- 200843847 second ion exchange ("ΙΕΧ·2,,) treatment, (ii) electrostatic adsorption (EA) treatment or (丨(1) In some combinations of ΙΕΧ·2 and EA treatment, at least one second component precursor ("type 2 component precursor") is used to further process the substrate to integrate one or more second component precursors in a second On and/or within the surface of the substrate that interacts with the ions and/or static of the substrate. Next, certain Type 2 precursors can produce catalytically active regions without further treatment, or according to the intended use. Further processing produces a catalytically active region comprising one or more Type 2 components. However, regardless of whether the catalytically active region is comprised of a Type 2 component precursor, (b) is 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 and/or within the surface of the substrate is about 3 〇N, preferably < about 2 奈奈More preferably, S is about 10 nm. As mentioned above, in some cases, depending on the intended use of the catalyst composition, the substrate received as received or treated by ion leaching may have catalytic efficacy. 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 energies suitable for use in the process of using the catalyst composition of the present invention. Efficiency can be significantly improved by replacing at least a portion of the first component (, the quinoid component, and integrating the second component ("type 2 component") with the surface of the substrate. Without being bound by theory, direct or indirect ionic interactions are carried out by specific ion exchange sites on the surface of the substrate and/or in the opposite charge, by electrostatic adsorption to the surface of the oppositely charged substrate. Role, and some combinations of ionic and electrostatic adsorption interactions or some other type of precursor-charge-surface interaction to be understood 126433.doc -41 - 200843847 can be integrated with type 2 precursor ions . However, regardless of the nature of the interaction, the precursor of the type 2 precursor is produced in the case where the substrate received as received, the substrate treated with IEX-1 or the substrate treated with BIX produces a charge-surface interaction of the second precursor. The material may thus produce a catalytically active region having an average thickness on and/or within the surface of the substrate of from about 30 nanometers, preferably &lt; about 2 nanometers, more preferably &lt; about 1 nano. Meter. Just for the convenience of the following discussion, and is not intended to limit the present invention described herein.

(In the scope of J, this article uses ΙΕΧ·2 to collectively refer to the extensive interactions of precursor-charge-surface interactions or type 2 component precursor interactions commonly referred to as 2_type components. 'Generally, for the treatment of warp- 1 The type of salt solution of the treated or treated substrate will depend on the type of ion to be ion exchanged in the course of 2 treatments. Or an ion will be ion exchanged or, in some cases, two Exchange of more 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 is referred to herein as two Sub-ion exchange or two (four) treatment. Therefore, in the case of three different types of component precursor ions and matrix as a whole, 'IEX-2 treatment is called three-ion ion exchange or three-winning. &amp; type 2 composition and precursor Explain any salt solution of ΙΕΧ-2 ion, if it is received by ectopically, treated with ΙΕΧ-1 or treated with 3^-treated surface. The chemical is sensitive, or The charge affinity can be used to achieve electrostatic interaction with the surface of the substrate treated by the treatment or the BIX-treated 126433.doc -42-200843847. Therefore, the IEX-2 ion can be used as a precursor of the type 2 component. Said that the plasma ΙΕχ_2 precursor (ie, the type 2 component precursor) may have catalytic effect depending on its intended use, and if so, the plasma IEX-2 precursor can be like type 2 in a certain type of catalyst composition. The composition works in its precursor state, but the ions can also function as a precursor in the preparation of another type of catalyst composition process. However, in general, the ionic ΙΕΧ24 precursor ( It can be used to obtain the type 2 component integrated with the surface of the substrate, including but not limited to, Blenbuter or Lewis acid, Bruce (4) or Lewis, noble metal cerium ions and noble metal complex cations and anions, transition metal cations and transition metals Cation and anion, transition metal oxyanion, transition metal chalcogenide anion, main group oxygenate ion, tooth ion, rare earth ion, rare earth Cation and anion and: group

Similarly, depending on the intended use of the catalyst composition, certain ions are catalytically effective in the precursor state and can form a type 2 component when integrated with a suitable matrix. It is optional to have a catalytic 1 Γ-2 precursor without further processing, some examples including but not limited to. s Lewis acid, cloth tolerant (four) or Louis soil root ions, rare earth oxide ions and combinations thereof. : Certain precious metals as precursors of type 2 components and transitional metals, brothers 1b, Vb and Dichu), such as Syrian, Shi, Lu, 126433.doc -43- 200843847 copper, silver, gold, bismuth,铱, 钌, 铢, hungry, cobalt, iron, manganese, ionic salts and complex ion salts and combinations thereof. For the IEX-2 treatment, ionic salts of palladium, platinum, rhodium, ruthenium, osmium, iridium, copper, silver, gold and nickel are especially preferred. For convenience, the elements of these groups can be displayed by http://pearii.iani.gov/peri〇dic/default by using the element family number of the International Union of Theoretical and Applied Chemistry (IUPAC) nomenclature system. The chemical element of the periodic table (and shows the previously used family number) is queried.

Examples of certain transition metal oxyanions which may be used as precursors for the type 2 component, including but not limited to ionic salts of Groups 5 and 6 (formerly Groups vb and vib), such as V (V-, W〇) 42-, H2Wi2〇4q6-, M〇〇42., M〇70246_, Nb6〇196-, 〇4- and combinations thereof. For ΐΕχ_2 treatment, ionic salts of lanthanum, cerium, tungsten and vanadium are particularly preferred. Examples of certain transition metal chalcogenide anions as precursors of the type 2 component include, but are not limited to, ionic salts of Group 6 (formerly Group VIb), such as M〇S42-, Ws42-, and combinations thereof. Examples of certain main group oxygen anions of type component precursors, including but not limited to Group 16 (former Group VIa) ionic salts, such as S〇42·, Ρ〇Ά〇42·, and combinations thereof. For IEx_2 The ionic salt of the s?? can be used as a precursor of the type 2 component, and the ionic salt of the group II, including but not limited to the group 17 (formerly the νπ group), such as F, Cl ·, Br-, I and combinations thereof. For the ΙΕΧ_2 treatment, the ionic salts of f and C are especially preferred. As a type 2 component precursor or ion, Card-Rare Earth Ions and Rare Earth Miscellaneous Cationic Ions "Ion and (4) Element Ions 126433.doc -44- 200843847 Salts, such as La, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Th, U, and combinations thereof. Examples of transition metals that can be used to produce transition metal-carbides, transition metal-nitrides, transition metal-borides, and transition metal-phosphides as type 2 components. Including, but not limited to, ionic salts of chromium, molybdenum, tungsten, sharp, group, 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 matrix that is processed or BIX-treated and treated with IEX-2 and the relative affinity of the ΙΕχ-2 ion for interaction with and/or integration with the IEX_1 treated substrate. For most types of glass substrates (eg but Not limited to AR type, A type or soda (lima) glass, about wti wt·% to the balance of IEX·2 salt solution is preferred, and about 0.001 Wt·% to 5 wt·% IEX_2 salt The solution is better. However, it is considered necessary to achieve the intended use of the catalyst composition. Depending on the functional surface concentration of the chemical component, the positive _2 salt solution may be less than 〇. 〇〇1 Wt. %. If multiple ion types are exchanged with the matrix, either simultaneously or sequentially, the concentration of the salt solution will be The relative affinities required for the precursors of the various components on the substrate and the relative affinities of the matrix for one component precursor versus the other component precursor are adjusted, such as, but not limited to, two IEX-2 treatments (ie, two Used to precipitate various precursors of different catalytic components and integrated with i戋BIX-treated matrix or three times of IEX_2 treatment (ie, three different catalytic component precursors and warts) or ruthenium-treated substrates The concentration of the salt solution of the ions will depend on the target relative concentration of the constituent precursors that are suitable for integration with the 126433.doc -45-200843847 surface and the surface affinity for various ions. Typically, heat treatment conditions suitable for IEX-2 treatment, such as heating temperature, heating time and 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 between about 30 ° C and about 90. (: Between. Depending on the concentration of the IEX-2 salt solution and the selected heating temperature, the heating time for the f' and IEX-2 treatments may vary. Preferably, the heating time for the positive 12 treatment is about 5 Between minutes and about 48 hours, more preferably between about 30 minutes and about 5 hours. Usually, depending on the type and concentration of the IEX-2 salt solution used and the characteristics of the substrate (for example, from a glass mesh) The mixing conditions are selected for the affinity of the removed ions, the strength of the glass after removal of the network ions, and the duration of the heat treatment. For example, but not limited to, the mixing conditions may be continuous or discontinuous (continued or mechanically mixed). , fluidization, tumbling, rolling or manual mixing. In summary, the combination of IEX-2 salt solution concentration, heat treatment conditions and mixing conditions is essentially based on the integration of a sufficient amount of sigma-2 ions on and/or within the substrate. And the distribution of IEX_2 ions is determined irrespective of the nature of the physicochemical bonding of the surface of the substrate to produce the desired surface charge type and privacy to produce the surface activity required to achieve the intended use of the catalyst composition. Adjusting the surface charge of the substrate by adjusting the pH as described above, taking into account the type 2 component precursors that will be integrated with the surface 126433.doc •46-200843847 in the second ,(,,ΙΕχ2&quot;) treatment. The degree of pH adjustment required will generally depend on the IEP of the substrate, the IEp versus surface charge distribution curve of the substrate, and the type of electricity desired. For example, but not limited to, for substrates having an IEP equal to 8, preferably, basal negative / IEX- 2 The pH of the mixture is adjusted to 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. Properties, the stability of the matrix in the relevant pH range and the desired wide charge mobility and other factors. Generally, any dilute base can be used to adjust the surface charge of the substrate to the right of the IEP (ie, to produce a net negative surface charge). And any dilute acid can be used to adjust the surface charge of the substrate to the left side of its IEp (ie, to produce a net positive surface charge). The inorganic acid or base or organic acid or base can be used in a thick and concentrated manner. For organic testing. Usually, dilute acid is dissolved. Or the concentration of the dilute solution will depend on the type of acid or base used, its dissociation constant, and the pH appropriate to obtain the desired surface charge type and density. After the IEX-2 treatment is completed, preferably by ΙΕχ_2 treatment The substrate can be separated by any suitable means including, but not limited to, filtration, centrifugation, decantation, and combinations thereof. The substrate treated with ΙΕΧ_2 is then treated with one or more suitable cleaning solutions (e.g., distilled or deionized water). , dilute alkali or dilute acid and / or a suitable water-soluble organic solvent, such as methanol, ethanol or acetone, "wash" and dry at a temperature of about 11 ° C for about 20 to 24 hours. ϊ ν · post-precipitation treatment According to the description, after the matrix treated by hydrazine-2 is separated, it can be dried only, calcined, calcined under oxidizing conditions, then reduced or further oxidized, reduced without calcination or without smoldering. Oxidation. Transitional gold can be surface-precipitated in the gas or liquid phase using a suitable reducing, sulfurizing, carbonizing, nitriding, phosphating or boriding reagent (-IDING reagent) as required by 126433.doc -47- 200843847 The reaction of ions, oxyanions and/or sulfur anions to produce the corresponding catalytically effective metal sulfides/sulfur oxides, metal carbides/carbon oxides, metal nitrides/nitrogen oxides, metal borides or metal phosphorus Compound composition. Usually, but not limited to, the purpose of the post-precipitation calcination treatment is essentially to decompose the gold counterion or ligand and to more closely integrate the metal, metal oxide, metal chalcogenide, etc. with the surface of the substrate and remove any Residual water removed in the previous drying process. The calcination conditions for the IEX-2 treated substrate are not particularly important for the surface activation of the matrix. However, these conditions should only be sufficiently stringent to produce at least one precursor with a catalytically effective amount. Catalytic active region. 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 select a high temperature of C # high 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 also be sufficient. Low, can reasonably avoid the softening point of the matrix and the undesired - the decomposition of the precursor components of the Shendian. • For example, but not limited to, precipitated sulfates require calcination conditions to decompose the bound cations and immobilize the sulfate on the surface, but such conditions do not significantly decompose the sulfate into volatile sulfur oxides. Similarly, metal oxo • scorpion requires calcination conditions to decompose the combined cations and immobilize the anions on the surface, but the conditions must not be so strict that the metal oxides 126433.doc -48- 200843847 self-surface volatilization Or cause the metal oxide to dissolve into the matrix. Finally, precious metals and erroneous materials 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 metal is preferably returned directly without calcination. Generally, the calcination temperature should be at least about 100 ° C lower than the softening point of the selected substrate. The calcination temperature should be between about 8(8)^ and 7〇(rc, more preferably about 2〇(rc to 6〇〇C, optimally between about 30 (TC to 500°C). Typically, The substrate treated by IEX-2 is calcined to about 24 hours, preferably calcined for about 2 to about 12 hours. However, depending on the type 2 component integrated with the matrix, the calcination time can be in the ranges Typically, but not limited to, the post-precipitation reduction treatment aims to reduce, at least substantially, if not completely, the catalytic component precursor (eg, metal, metal oxide or metal cassava) to a lower oxidation state integrated with the surface of the substrate. Examples of suitable reducing agents include, but are not limited to, C0 and Hr®: preferred reducing agents, preferably having a flow rate of from about 001 L/hr to about 1 〇〇L/hr• per gram of matrix, more The flow rate is between 1 L/hr and 1 L/hr• per gram of matrix. Typically, the reduction temperature should be between 0 °C and 600 °C, provided that the temperature is selected by the household. It is at least 1 低 lower than the softening point of the matrix. 通常. Usually, the substrate treated with IEX-2 is subjected to about ι·ι hours. The reduction treatment of 48 hours is preferably carried out by a reduction treatment of about 1 hour to about 8 hours. Alternatively, the substrate treated by IEX-2 can be treated by solution phase treatment, also 126433.doc -49-200843847, the solution phase treatment The use of soluble reducing agents such as, but not limited to, hydrazine, sodium hydride, lithium aluminum hydride, and combinations thereof, is carried out in a suitable solvent, such as water or diethyl ether. Typically, but not limited to, after precipitation, the purpose of the IDING reaction treatment is to Reducing metal ions, metal oxyanions, and/or metal sulfide anions while reacting the reduced metal with a reagent containing a lower atomic weight-IDING element. In some cases, direct-IDING will occur without simultaneous metal oxide reduction. In the case of, for example, some vulcanization treatments. Typical gas phase-IDING reagents include, but are not limited to, hydrogen sulfide, methyl mercaptan and dimethyl sulfide (vulcanization reagent), ammonia (nitride reagent), methane, ethane and Other lucky materials, class k (1⁄4 reagent). These gas phase _iding reagents can react directly with IEX-2 treated substrate under ambient pressure or under pressure, or with inert gas. The gas mixed with hydrogen or hydrogen reacts with the substrate treated with ruthenium _2 to produce the corresponding sulfide, carbide or nitride. Part of the catalytic effect may be - IDED product (including sulfur oxides, carbon oxides and nitrogen) Oxide) can also be produced by: substantially as received/obtained substrate, IEX-2 treated integrated substrate, ruthenium-2 treated calcined substrate or IEX-2 treated reduced substrate Complete reaction. Metal phosphide can be produced by two ion exchange (two IEX-2 treatment) reduction treatments, one of which is one or more transition metal ions and the other is IEX-2 treatment system. Phosphate ion. Preferably, the two IEX-2 processes can be performed in sequence. Alternatively, the metal phosphide can be produced using a gas phase phosphating reagent such as, but not limited to, phosphine (PH3) to produce the desired metal phosphide. For example, a single ion exchanged substrate (a single IEX-2 treated substrate) with the desired transitional gold 126433.doc -50 - 200843847 in a suitable oxidation state can be further treated with PH3 to produce the desired metal phosphide. . Solution phase treatment can be used to produce metal sulfides, metal sinters, and metal filler catalytic components. Typical solution treatments for the production of metal sulfides include, but are not limited to, treatment of IEX-2 treated metal-ion-integrated matrices at an effective concentration of hexamethyl-sulfur-burned organic solution at temperatures 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 formation of boride include, but are not limited to, treatment with an aqueous solution of sodium borohydride or potassium borohydride over a period of effective time between room temperature and reflux temperature for an IEX-2 treated metal-ion-integrated substrate. Typical solution phase treatment of the formation of the composition comprises treatment of the IEX-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. The V · catalytically active region indicates that the catalytically active region resulting from any of the above substrate treatments will have an average thickness of (1) less than or equal to about 30 nanometers, preferably about 2 nanometers, more preferably about 10 Nano, and (ii) at least one catalytically effective amount of catalyzed. Preferably, XPS spectroscopy is used to determine the average thickness of the catalytic region. XPS optical edge learning uses a layered residual technique called a sputter depth profile (&gt; which will be described in more detail below in the analytical methods provided in the Examples below). However, other analytical techniques known to those skilled in the art can be used to determine the approximate location of the surface of the associated substrate associated with the catalytic component. Therefore, matrix catalysis 126433.doc -51· (

The average thickness of the region of 200843847 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 treatment or IEX-2 treatment (with or without hydrazine treatment), for any of the catalyst compositions of the present invention, the thickness of the catalytically active region is generally (4) ; will substantially pass through the surface area of the substrate or (b) will not exceed the surface of the substrate by 3 nanometers, preferably no more than about 2 nanometers thick, more preferably no more than the thickness of the rice. With regard to the localization of one or more catalytically active regions on the treated substrate and/or within the catalytically active region, it is also understood that the catalytically active region may: (4) be on the surface outside the substrate, and any pores present in the pore wall surface of the substrate; '(9) In the surface area of the matrix 'that is, below the outer surface of the substrate (4) Nano's car is about 2 nanometers below the outer surface of the substrate, more preferably about 10% below the outer surface of the substrate. When there are any pores, about 30 nm below the surface of the pore wall of the matrix is preferred. The surface of the pore wall of the matrix is about 20 nm below the armpit. It is better to be below the surface of the pore wall of the matrix (7) nanometer but below the surface of the substrate. Above; (C) in the surface region of the outer surface of the substrate or partially in the surface of the pore wall of the matrix, or (d) a combination of (a), (b) and (c). Above, when there are any pores, above or above, and partially located in the matrix, the amount of the catalytic component of either type 1 or type 2 can be between 0.0002 wt.% and about 5 wt.%. Preferably, it is between about 0.0002 wt.% and about 2 126433.doc -52- 200843847

Between Wt·%, more preferably between about wt5 wt% and about 1 wt%. Moreover, the catalytically active regions of the catalyst compositions of the present invention can be continuous or discontinuous. Without being bound by theory, it is believed that 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 active region covers the outer surface of the substrate can range from as low as 〇.〇〇〇1% 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 00001% and about. However, without being bound by theory, it is believed that the catalyst composition, particularly the catalyst composition having a lower catalytic component wt% loading, is likely to be more catalytically effective because of the treated substrate. The upper and/or inner catalytically active regions become more dispersed (i.e., more widely distributed and separated between the catalytically active regions). The catalytically active regions and other characteristics of the above-described catalyst compositions are based on the best available information from the inventors regarding the state of the catalyst composition prior to entering the steady state reaction conditions. The degree to which one or more of the described characteristics can vary is not certain and is largely unpredictable. Nevertheless, without being bound by theory, it is believed that the functional surface activity of the catalyst compositions described herein will permit the charge and/or charge of the catalytic component integrated with the matrix as the catalyst composition promotes its intended process reaction. Geometric positioning and other component characteristics vary significantly. Thus, it should be understood that the inventive subject matter described herein extends to all of the catalyst compositions produced by the claimed compositions under steady state reaction conditions. Application of VI·catalyst composition in selective argonization process 126433.doc -53- 200843847 - In general, the intraparticle diffusion resistance of the above-mentioned catalyst group makes the catalyst activity and selectivity two = reactant (that is, the diffusion limited process) is the most efficient process, the 寻μ into the finder combination, and 罟1 is used in processes that are not necessarily limited by diffusion. For example, the material can also be ambiguously only two |b/restricted, reminder: the catalyst composition provides a single-type: two-effect, to help reduce the reaction of a certain process (10), for example, to drive the process !=There is better thermodynamics and (4)❹), so commercial production is more cost effective. The selective hydrogenation process (i.e., SHP treatment) is a process for treating hydrocarbons, miscellaneous tobacco, and mixtures thereof. The hydrocarbon used herein refers to a group of compounds consisting only of a carbon atom (C) and a hydrogen atom (8), and the heterocarbon used herein means mainly composed of a carbon atom (c) and a hydrogen source = (H), 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 (N) A, or sulfur (s). In a SHP process, a process stream comprising hydrocarbons and/or heterohydrocarbons suitable for selective hydrogenation using a catalyst composition of the above type generally comprises having about 30 carbon atoms, but in some cases 3 Å. a hydrocarbon having more than one carbon atom and a bi- or more hetero atom (e.g., oxygen, nitrogen, etc.), sulfur, etc., wherein 'the smoke has at least one hydrogenatable site (ie, a target hydrogenatable site), Under suitable hydrogenation conditions (described in more detail below) of the desired product, yield and/or process efficiency, it is readily hydrogenated selectively. Process streams include, but are not limited to, feed streams, intermediate transfer streams, recycle streams, and/or discharge streams. As used herein, a target hydrogenatable site refers to an atomic position having at least one of 126,433.doc -54 - 200843,847 carbon atoms (c) or a hetero atom, but is generally a carbon-containing atomic position, and a hetero atom can be But not limited to) oxygen (〇), nitrogen (N) or sulfur (8). It is believed that the target hydrogenation sites have at least one degree of unsaturation, and that 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, polyalkynes, and cyclic olefins may have continuous (only continuous double-double bonds), conjugated or one or more double bonds and/or substituted carbons that are saturated and/or substituted for carbon. Of the hydrogenatable sites that may be present in the hydrocarbon of interest, one of them is preferentially saturated (at least partially) than the other hydrogenatable sites. The process stream suitable for SHP treatment may also be a mixture of olefins or multiolefins and aromatic hydrocarbons or light olefins for selective hydrogenation of olefins or multiolefins; or sulphur or eutectic L and alkyne or polyalkyne Mixture for the selective hydrogenation of alkynes or polyalkynes. For &lt;, for hydrocarbons and/or hetero hydrocarbon mixtures having at least one hydrogenatable site for at least two types of hydrocarbons or heterohydrocarbons, it is predetermined to use: a selectively hydrogenatable hydrogenatable site as a target hydrogenatable site (for example, a perylene hydrocarbon + olefin in which the olefin comprises a target hydrogenatable site, preferably hydrogenated relative to the aromatic hydrocarbon). Thus, hydrocarbons and hydrocarbons suitable for treatment with a catalyst composition of the type described above include, but are not limited to, olefins, diolefins, multiolefins, alkynes, acetylene k% olefins, aromatic hydrocarbons, unsaturated vegetable oils and It can be hydrogenated with an oxidizing agent. The deuterated oxygenates include, but are not limited to, aldehydes, hydroxy acids, brewed, and other heteroatoms having a heteroatom other than oxygen or sulfur such as nitrogen or sulfur. 0 126433.doc • 55- 200843847 Suitable for use A preferred class of hydrocarbons for SHP treatment of a type of catalyst composition is a normal chain olefin having from about 2 to 20 carbon atoms, a normal chain polyene and a 2 chain alkyne, and having from 6 to 2 (substituted or unsubstituted) carbons. Aromatic aromatic hydrocarbons. More preferred hydrocarbons are normal chain olefins having from 2 to 15 carbon atoms, normal chain polyenes, olefin-substituted aromatic hydrocarbons, normal chain alkynes, dilute alkanes and alkenyl ketones. The SHP treatment can be performed using various types of reactors having one or more hydrogenation zones such that the reaction hydrocarbon feed stream can be in sufficient contact with the catalyst composition in a selective hydrogenation zone maintained under selective chlorination conditions. (described in more detail below.) The contacting can be carried out in a fixed catalyst bed system, a moving catalyst bed system, a fluidized bed system, or in a batch operation using the various types of different catalyst composites described above. Generally speaking, it is better to use a fixed bed system. In the ^ bed system The flue feed stream is first preheated to the desired reaction temperature and then passed to a hydrogenation zone containing a bed of catalytic catalyst. The selective hydrogenation zone may itself comprise - or a plurality of separate reaction zones between There are heating means to ensure that the input end of each reaction zone maintains the desired reaction temperature. The hydrocarbon can contact the catalyst bed in an upward, downward or only dynamic manner. Preferably, the hydrocarbon flows radially through the catalyst bed. The smoke may be in a liquid phase, a gas-liquid mixed phase or a gas phase when contacting the catalyst, preferably a gas phase. The above-mentioned catalyst composition can be used in many selective hydrogenation conditions under which selective hydrogenation conditions are also determined. The desired product, yield and/or potential efficiency </ RTI> such hydrogenation conditions include (4) a temperature range generally from about 约 to about 约 '. and more preferably from 3 (TC to about 28 〇 c &gt;c; (8) pressure range Generally, it is from about (8) kPa to 9 kPa, and (4) hydrogen and mesh #hydrogenated oxime Mo Erfan 126433.doc -56- 200843847 is generally from about 0.1:1 to about 20:1, preferably about 〇·5: 1 to about 5:1, and more 、, , , spoon 0·8·1 to about 1 · 2:1, and (d) liquid space and time in the reactor The range of (lhsv) is generally from about 〇 1 hr-1 to about 20 hr-1. EXAMPLES The invention will now be described in more detail in connection with the following examples which illustrate or emulate various aspects relating to the practice of the invention. All changes within the spirit of the invention are intended to be protected, and therefore the invention is not to be construed as limited to the examples. Example 1 of a catalyst composition with an acid immersed E glass matrix E-06F glass fiber produced by Lauscha Fiber International with an average diameter of 500-600 nm. In the first step, the E_〇6F$ glass sample received as received and not calcined was subjected to acid leaching treatment. In this example, the acid solution used for the acid leaching treatment was presaturated with quartz glass. Specifically, 3 liters of 15 N nitric acid and 150 gram of quartz glass were placed in a 4 liter plastic wide-mouth container. Place the plastic barn in a 95C ventilated oven for 5 hours and shake it slightly with your hands every 3 minutes. After the presaturation treatment is completed, the sample is decanted to separate the presaturated sulphuric acid from the sarcophagus glass. Presaturated nitric acid is used in the following steps. Then, about 20 grams of E-06F glass and 3 liters of pre-saturated nitric acid were placed in a 4 liter plastic wide-mouth container. Place the plastic container at 95. 4 4 4 hours in a ventilated oven, shake it slightly with your hands every 30 minutes. After the acid leaching process is completed ‘Filtering with a Buchner funnel with Whatman 541 filter paper 126433.doc -57- 200843847

Samples were washed with approximately 7.6 mm of μμ, u, and A deionized water. Then, the acid immersed sample was dried for 22 hours at a temperature of 11 (TC). • In the second step, the acid-impregnated E. glass sample was subjected to ion exchange. Treatment In this example, dihydrogen-oxygen was used. The amine was prepared by using [Pd(NH3)4](〇H)2 to prepare 1.5 liters of 0·01 wt.% of the solution for ion exchange (,, ΐΕχ solution, )). In the ion exchange solution (&quot;glass/ion exchange of this compound). The value of the glass/ion exchange mixture was measured. About 29.8 Wt·% of ammonium hydroxide (ΝΗ4〇η) was added dropwise as needed, and the pH of the mixture was adjusted to be greater than 1 〇 (in the present example, the obtained value was about 10.8). Then, the glass/ion exchange mixture was transferred to a 4 liter beaker and heated at 50 ° C for two hours while mechanically stirring at a speed of 300 to 500 rpm using a stainless steel paddle mixer. After the ion exchange treatment was carried out, a Buchner funnel with Whatman 541 filter paper was used to pass the glass/ion exchange mixture and the ion exchange glass sample was collected, and then washed with a solution of about 7.6 liters of a diluted NH4 〇H solution. The dilute NHUOH solution was prepared by mixing 10 grams of a 29.8 wt.% concentrated NKUOH solution with about 3.8 liters of deionized water. Then, the ion exchange glass sample was dried at 11 °C for 22 hours. The result of analyzing the sample 'palladium concentration by inductively coupled plasma-atomic emission spectroscopy (ICP-AES) was about 1.00 wt.%. The E-06F glass was obtained from e-〇6F glass fiber produced by Lauscha Fiber International with an average diameter of 500-600 nm. 126433.doc -58- 200843847 Step 'For E-06F received as received, uncalcined The glass sample was subjected to I immersion treatment. In the present example, the acid solution used for the acid leaching treatment was pre-saturated with samarium glass. Specifically, 3 liters of 1.5 N nitric acid and 150 gram of quartz glass were each placed in 4 liters. In a plastic wide-mouth container, place the plastic container in a ventilated oven for 951 for 5 hours, and shake it slightly by hand every 3 minutes. After the pre-saturation treatment, the sample is decanted to separate the nitric acid from the quartz glass. One step, put about 15 grams of E-06F glass and 3 liters of 1.5N pre-saturated nitric acid into a 4 liter plastic wide-mouth container. Place the plastic container in a 95 ° C ventilated oven for 4 hours, every 3 hours. Minutes by hand Shake it. After the 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, at 110 C, the acid leached sample was taken. Drying for 22 hours. In the third step, the acid leached glass sample was subjected to ion exchange treatment. In this example, 1 liter of 0.003 wt· was prepared using palladium dihydrogen tetraamine [pd(NH3川(1)Η) 2 % palladium solution for ion exchange (&quot;ΙΕχsolution&quot;). Add about 14.22 grams of E-06F glass to the ion exchange solution ("glass/ion exchange mixture"). Measure the glass/ion exchange mixture? A value of about 29.8 wt.% ammonium hydroxide (ΝΗ4〇Η) was added dropwise as needed, and the pH of the mixture was adjusted to be greater than 10 (in the present example, the ?11 value was about 10.88). The glass/ion exchange mixture was transferred to a 4 liter plastic wide-mouth container. The plastic container was placed in a ventilated oven for 2 hours at f = 30 minutes with a slight shake. After the ion exchange treatment was completed, use W hatma η 5 41 filter Paper Buchner funnel filter broken glass / ion exchange mixing 126433.doc -59- 200843847 and collect ion exchange - glass sample, then use about 7 · 6 liters of diluted 〇Η 4 〇Η solution to clean. Dilute NEUOH solution is mixed 1 An ionic solution of 298 wt.% concentrated NH4 〇H was prepared with about 3.8 liters of deionized water. The ion exchange glass sample was then dried at a temperature of 11 〇c for 22 hours. In the fourth step, the ion exchange glass sample is subjected to a reduction treatment, wherein the ion exchange glass is reduced in a hydrogen atmosphere at a hydrogen (H2) flow rate of 2 L/hr and at a temperature of 30 (rc temperature for 4 hours. Sample analysis by ICP-AES) The result of the concentration was about 〇wt·%. The cross-section of the sample was examined by scanning transmission electron microscopy (STEM) as described in the example below (the following example), and the results showed that the particles (higher contrast points) were generally dispersed. In the range of less than or equal to about 30 nm from the surface of the pore wall (i.e., the perimeter of the darker shaded area relative to the material region of the substrate that is relatively brighter than the contrast). Example 3 E-Q6F glass Zhi Ming was awarded the E-〇6F glass fiber produced by Lauscha Fiber International with an average diameter of 500-600 nm. The first step was to carry out acid leaching treatment on the ^_0617 glass sample received as received and not calcined. In this example, the acid solution used for the acid leaching treatment is pre-saturated with quartz glass. Specifically, 3 liters of 1·5 N nitric acid and 150 g of quartz glass are placed in a 4 liter plastic wide mouth. Inside the container, the plastic container was placed in a ventilated oven at 95 ° C for 5 hours, and shaken by hand every 30 minutes. After the pre-saturation treatment, the sample was decanted to separate the pre-saturated nitric acid from the quartz glass. 126433.doc 200843847 In the second step, approximately 15 grams of E-06F glass and 3 liters of n presaturated nitric acid were placed in a 4 liter plastic wide-mouth container. The plastic container was placed in a 95 C ventilated oven for 4 hours. Shake it slightly by hand every 30 minutes. After the acid leaching process, the sample was filtered using a Buchner funnel with Whatman 541 filter paper and washed with about 7.6 liters of deionized water. Then, at a temperature of ii 〇 °c, The acid leached sample was dried for 22 hours. In the third step, the acid leached E-06F glass sample was subjected to ion exchange treatment. In this example, dioxetamine platinum [Pt(NH3)4] (cl) was used. 2) A platinum solution of 0.05 wt.% was prepared for ion exchange ("ΙΕχ solution,"). About 8.2 g of E-06F glass was added to the ion exchange solution ("glass/ion exchange mixture"). /positive value of ion exchange mixture As needed, about 40% of tetrapropylammonium hydroxide was added dropwise continuously, and the value of the mixture was adjusted to be greater than 10 (in the present example, the WpH value was about 1〇〇9). Then 'Ha 5 The glass/ion parent blend was transferred to a 4 liter beaker and heated at 50 ° C for two hours while mechanically stirring at 300 to 500 rpm using a stainless steel paddle mixer. After ion exchange treatment was completed, use The Buchner funnel was filtered with a Whatman 541 filter paper/ion exchange mixture and the ion exchange-glass samples were collected and then washed with a solution of about 7 6 liters of dilute NH4 〇H. The dilute NH4〇H solution was prepared by mixing 1 〇g of 29_8 wt·% concentrated NH4〇H solution with about 3.8 liters of deionized water. The ion exchange glass samples were then dried for 22 hours at iio °c. In the fourth step, the ion exchange glass sample is subjected to reduction treatment, wherein the ion exchange glass is reduced in hydrogen gas (hydrogen atmosphere with a HO flow rate of 2 L/hr and 25 〇t?c temperature 126433.doc 61 - 200843847 for 4 hours. -AES for sample analysis, the platinum concentration was approximately 5 99 wt.%. Example 4 E-06F glass was obtained from Euscha Fiber International and produced with E-06F glass fibers having an average diameter of 500-600 nm. In the first step, an acid treatment is performed on the E-06F glass sample which is received as it is and which is not calcined. In this example, the acid solution used for the acid leaching treatment is presaturated with quartz glass. Specifically, 3 liters is used. 15 N nitric acid and 150 g of quartz glass were placed in a 4 liter plastic wide-mouth container. Place the plastic container in 95. (: 5 hours in a ventilated oven, shake it slightly by hand every 30 minutes. Presaturation treatment After completion, the sample is decanted to separate the presaturated nitric acid from the quartz glass. In the second step, about 30.64 grams of E-06F glass and 3 liters of 丨5 N presaturated nitric acid are placed in a 4 liter plastic wide mouth. Inside the container The container was placed in a 95 C ventilated oven for 4 hours and shaken slightly by hand every 30 minutes. After the acid treatment was completed, the sample was filtered using a Buchner funnel with Whatman 54 丨 filter paper and rinsed with approximately 7.6 liters of deionized water. Then, the acid immersed sample was dried for 22 hours at a temperature of noc. In the third step, the acid leached 匕061? glass sample was subjected to ion exchange treatment. In the present example, tetrachlorotetramine platinum was used. [ρ^ΝΗ3)4]^^ Preparation of 'gong liters of 0.005 wt·% of platinum solution for ion exchange (,, ΙΕχ solution.. about 9. 5 1 gram E_06F glass plus human ion exchange solution (,, glass /ion exchange 126433.doc -62- 200843847 mixture"). Measure the pH of the glass / ion exchange mixture. Add about 40% of tetrapropylammonium hydroxide as needed, continuously adjust the pH of the mixture To be greater than ι (in this example, the positive value is about 10.85). The glass/ion exchange mixture is then transferred to a 4 liter glass beaker and heated at 50 ° C for two hours while Use a stainless steel paddle mixer Mechanical agitation at a speed of 3 to 500 rpm. After ion exchange treatment, use a Buchner funnel with whatman filter paper to pass the glass/ion exchange mixture and collect the ion exchange-glass sample' then use about 7.6 liters of thin The NHWH solution was cleaned. The diluted 1^^4〇11 solution was prepared by mixing 29 8 wt% concentrated stomach 4〇11 solution with about 3·8 liters of deionized water. Then, the ion exchange glass sample was dried at a temperature of 11 ° C for 22 hours. In the fourth step, the ion exchange glass sample is subjected to reduction treatment, wherein the ion exchange glass is reduced in hydrogen gas (hydrogen atmosphere at a flow rate of 2 L/hr and 3 Torr: temperature for 4 hours. Sample analysis is performed by ICP-AES, The result of platinum concentration is about wt56 wt%. Example 5 E-06F glass on the inscriptions · E-06F glass fiber produced by Lauscha Fiber International with an average weight of 500-600 nm. The un-calcined E-〇6F glass sample was subjected to acid leaching treatment as it is. In this example, the acid solution used for the acid leaching treatment was pre-saturated with quartz glass. Specifically, 3 liters of 15 n nitric acid was used. And 126433.doc -63- 200843847 100 grams of quartz glass were placed in a 4 liter plastic wide-mouth container. The plastic container was placed in a 95 °c ventilated oven for 5 hours, and was shaken slightly by hand every 30 minutes. After the pre-saturation treatment is completed, the sample is decanted to separate the pre-saturated nitric acid from the quartz glass. In the second step, about 50.21 g of E-06F glass and 3 liters of 1.5 N pre-saturated nitric acid are placed in 4 liters of plastic. Inside the wide mouth container. Will The plastic container was placed in a ventilated oven at 95 ° C for 4 hours and shaken slightly by hand every 3 minutes. After the acid leaching treatment, the sample was filtered using a Buchner funnel with Whatman 541 filter paper and used for about 7.6 liters. The ion-washed water is washed. Then, the acid-immersed sample is dried for 22 hours at a temperature of 110 c. In the third step, the acid-impregnated 匕0617 glass sample is subjected to ion exchange treatment. In this example, two are used. Gas tetraamine platinum i.e. 0.14 wt.% platinum solution for ion exchange ("ΙΕχ solution, about 33.68 grams of E-06F glass was added to the ion exchange solution (,, glass / ion exchange mixture"). / Ion exchange mixture 1) 11 value. As needed, about 40% of tetrapropylammonium hydroxide is added dropwise continuously, and the pH of the mixture is adjusted to be greater than 10 (in this example, the positive value obtained is about 10.94). Move the glass/ion exchange mixture into a 4 liter plastic wide-mouth container. Place the wide-mouth container in a 5 〇t ventilated oven for two days, shaking it slightly by hand every 3 〇 minutes.|Sub-exchange After processing is complete, use There is a Whatman 541 filter, paper Buchner funnel over the glass / ion exchange mixture and collect ion exchange · glass sample &amp;, then the material 7 6 liters of rare 〇h solution is cleaned. Rare nh: 4 〇 h solution system The ion exchange glass samples were dried for 22 hours at a temperature of = 126433.doc • 64-200843847 by mixing 1 gram of a 29 8 -% concentrated NH 4 〇H solution with about 3.8 liters of deionized water. In the fourth step, the ion-exchanged glass sample was subjected to a reduction treatment in which the ion-exchanged glass was reduced in a hydrogen atmosphere at a hydrogen (H2) flow rate of 2 L/hr and at a temperature of 300 ° C for 4 hours. Sample analysis by ICP-AES showed a platinum concentration of approximately 1.38 wt%. Example CH-1 analytical method re/XPS sputtering, SARCNa, isoelectric point (IEP) and SAN2-BET or SAKr-BET determination X-ray photoelectron spectroscopy (XPS) sputter depth distribution method uses a 1486.7 eV microfocus, monochromated Α1 Κα X-ray source ^ PHI Quantum 200 Scanning ESCA MicroprobeTM (Physical Electronics) to obtain XPS sputter depth distribution . 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: k - X-ray beam diameter 10-200 μηη - X-ray beam power 2-40 W . - Sample analysis area 10-200 | ΐιπι - Electron emission angle is 45° to the sample normal All XPS spectra and sputter depth profiles were recorded at room temperature without pretreatment of the sample, except when the sample was placed in a vacuum environment of the XPS instrument. The sputter depth profile was generated by alternately collecting the sample surface spectra for several cycles and then performing a 15 ksec 2 kv Ar+ sputtering on the surface of the sample every week at 126433.doc -65 - 200843847^ to remove the surface material. The thickness of the sputtering depth of the known thickness of the layer. Early

The peak area of the Pd and Si atomic concentration values is corrected for their respective atoms. The method is 'take Pd 3d3/2 and si sensitivity factor and the analyzer transmits 2p function.

Those skilled in the art of XPS analysis should understand that the measurement of the sputter depth parameter is affected by both human uncertainty and mechanical uncertainty. The combination of the two may be for each reporter using the XPS sputter depth distribution technique. The value causes an uncertainty of approximately 25%. Because of &amp;, the uncertainty is expressed in the depth: value. This inaccuracy is common throughout the XPS analysis technique, but for the average thickness and other material properties of the catalytically active regions disclosed herein, the inaccuracy is insufficient to prevent differentiation of the n compositions described herein. It also 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) sample detection uses a JEOL 3000F field emission scanning transmission electron microscope (stem) instrument operating at an acceleration voltage of 3 〇〇 !^¥. The instrument is equipped with Oxford Instruments (〇xf〇rd Instruments)

The Inca X-ray spectrometer system performs 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 8 inch thick slices using an ultramicrotome. The sections were collected on a thin 126433.doc-66-200843847 crucible carbon carrier and were not properly processed and properly positioned in the electron beam field of the above STEM instrument for detection and analysis. Those familiar with TEM analysis should understand that the location of the target analyte and the average thickness of the region of interest relative to the substrate surface using TEM analysis 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 cause uncertainty in the 20% 2 TEM vertical depth measurement (relative to a specific reference point) and a side position of about 5%. Measurement results (relative to a specific reference point) uncertainty. Therefore, the uncertainty is expressed in the distance of the measured catalytic component relative to the surface of the sample substrate, as shown in Figure 1. This inaccuracy is common throughout the TEM analysis process, but is not sufficient to prevent discrimination between the catalyst compositions. SARCNa determination, SARCNa empty sample and related statistical analysis For the reasons discussed above, the surface area change rate of sodium (nSARC^,) is reported as the ratio of the volume of NaOH titrant. According to the above SARCw program, the SARC^ of each sample given in the following examples was determined. An empty sample was prepared by formulating a 3.5 M NaCl solution (i.e., adding 30 grams of NaCl in 15 mL of deionized water), which contained no matrix sample. However, in order to resolve the statistical variability in the SAARC test procedure, four separate empty samples should be titrated and used to obtain the specified concentration used for initial and (ie, V-V initial) (in this example) The mean titer of the 〇〇1 N) titration was used to adjust (ie, correct) the volume of the titrant used for the determination of the SARC of each matrix sample. The pH of the empty sample was adjusted according to the same procedure as described above for the SARCy^ and the empty sample was titrated, but also contained no matrix. 126433.doc -67- 200843847 The statistical summary of the empty sample titer is reported in the empty sample and its respective mean and standard deviation (or V total σ) analysis test results table provided below. Similarly, the inherent statistical fluctuations corresponding to V5, V10 and vu in each titration caused by the respective V totals are also reported. From the statistical angle of use, the t-distribution is pre-calculated, and the value outside the specified confidence interval near the average value is not sinful because the degree of certainty of the inherent deviation of the experimental method is 95/〇. Therefore, the matrix sample within the confidence interval is near the average value of the empty sample. The V initial and Vt values measured by the mouth were considered to be statistically indistinguishable from the empty samples. Therefore, such samples do not calculate the SARC^ value. Isoelectric point (IEP) measurement The isoelectric point (, ΐΕρπ) of each sample given below was determined according to the following procedure. IEP measurements were performed using a Mettler T〇led〇 SevenMuhi watch with a pH mWORP module and a &amp; Mettler Toledo INLAB 413 pH composite electrode. Calibrate the meter with a standard pH buffer solution of pH 2, 4, 7 and 1 整个 over the entire IEP range of interest. The sample is wetted with a quantity of 16 Μ Ω deionized water (at about 25 t:) sufficient to bring the sample to its incipient state, and the IEP of each sample is determined, thereby producing a relatively dense slurry or paste mixture. 3 Incipient wetness can make a liquid contact between the glass electrode and its reference electrode contact surface and the liquid contacting the test solid sample (in this example, a slurry or paste mixture). Depending on the morphology of the sample (e.g., glass microfibers, granulated powder, chopped fibers, etc.) and its porosity (if any), the procedure requires a different amount of water. In all cases, however, the amount of water added should be sufficient to bring the sufficient liquid into contact with the glass electrode and the reference electrode. In other words, adding water to the sample should avoid as much as possible the sample is exposed to the initial humidity. In the case of 126433.doc -68- 200843847, the electrode tip is used, and the solid sample is mixed with deionized water (added for generating incipient wetness) by hand until the measured pH is stable, and then the pH is read from the meter. value. Ν2 BET or Kr BET surface area (S.A.) determination According to the ASTM procedure mentioned above, the S.A.N2-BET or S.A.Kr-BET assay 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 a preferred surface f-product measurement according to the method described in ASTM D3663-03. technology. For the lower surface area measurement (for example, &lt; about 3 11124), according to the method described in 8 8 ^ ^ 1 〇 4780-95 (''8. VIII. Heart _5 lamp)), 1^ BET It may be a better surface area measurement technique. SARCNa empty sample measurement and statistical analysis for correcting SARCNy^

Sample No. Dilute NaOH Titration Concentration (N) SAN2-BET (m2/g) In the initial value of NaOI adjusted to 3 pH 1 I titration, the pH is prepared from t0 (V initial) to 9.0, and at t5, 丨Hold the required titration solution at 9.0 时^ 4.0 at the beginning of ^5 to 1S) will taste (ml) V total = V initial + V5 to 15 V initial 0 minutes v5 5 minutes Vi 〇 10 minutes Vl5 15 minutes V5 ^ Is and the sample A 0.01 Not applicable 1.5 0.3 0.1 0.2 0.6 2.1 Empty sample B 0.01 Not applicable 2.2 0.1 0.1 0.2 0.4 2.6 Empty sample C 0.01 Not applicable 2.4 0.1 0.1 0.1 0.3 2.7 Empty sample D 0.01 Not applicable 2.2 0.1 0.2 0.1 0.4 2.6 Average value of empty sample 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 2.07-2.9T Example CH-2 E glass-SARCNa E-06F glass-like 126433.doc •69- 200843847 produced by Lauscha Fiber International is a glass fiber with an average diameter of 500 to 600 nanometers. The comparative sample Comp-A-1 was an e-glass sample received as it was, and Comp-A-2 was an e-glass which was received as it was by calcination but not prepared by acid leaching. For the comparative samples Comp-A-1 and Comp_A-2, the non-acid leached E glass sample was subjected to a calcination heat treatment. During this treatment, the non-acid leached glass was calcined for 4 hours at an air atmosphere having an air ML speed of 1 liter/hour and a temperature of 6 〇〇〇c. Sample B was prepared by subjecting non-calcined E glass received as it was to acid leaching. In this example, the acid solution used for the acid leaching treatment was presaturated with quartz glass. Specifically, 3 liters of 15 N nitric acid and 15 ounces of quartz glass were placed in a 4 liter plastic wide-mouth container. The plastic container was placed in a ventilated oven at 95 ° C for 5 hours and shaken slightly by hand every 3 minutes. After the presaturation treatment is completed, the sample is decanted to separate the presaturated Xiaoyu text from the quartz glass. Presaturated nitric acid will be used in the following steps. Then, 20 grams of E-06F glass and 3 liters of pre-saturated acid were placed in a 4 liter plastic wide-mouth container. Place the plastic container at 95. Shake it in your oven for 4 hours and shake it with your hands every 30 minutes. After the acid leaching treatment was completed, the sample was filtered using a Buchner funnel with Whatman 541 filter paper and washed with about 7.6 liters of deionized water. Then, the sample after acid leaching was dried at 11 (at a temperature of 22 ° for 22 hours. Using the above analytical method for measuring sARC, a for comparative samples c〇mp_ A-1, Comp-A-2, and sample B. The results are shown in the following table. 126433.doc -70- 200843847 Sample No. Sample Description Diluted NaOH The titration solution is concentrated in the NaOH titration to adjust the pH from the initial value of 4.0 at t〇 (V initial) to 9.0. And the actual volume (ml) of the titration required to maintain the pH at 9.0 at t5, 纟1〇 and 纟15 (¥5 幻5) (N) V first minute v5 5 minutes Vi 〇 10 minutes Vis! 15 minutes" V-V total-V initial sample empty sample 0.01 2.1 0.15 0.125 0.15 Ί Γ1.5 Not applicable Comp A-1 as it is E-06F 0.01 20.5 0.5 0.4 0.3 1 21.7 1.2 Comp A-2 烺E -06F 0.1 0.7 0 0.1 0 0.8 0.1 B Acid leaching E-06F 0.1 22.6 1.9 0.9 0.4 25.8 3.2 Sample number empty sample / Jr Sample description 3 sample average IEP ^ for SAN2-BET (m2/g) Not applicable in SAI Measure, determine the required volume of titration solution (swelling SARC chest (V--V-pre-V) / V at the beginning is not applicable V first 0 minutes 2.1 V5 5 minutes ~ αϊ?~ Vio ^〇Λ2Γ Vis 15 minutes V total 0.15 2.5| Corrected Comp-A«l P Jbr - as it is E-06F 8.9 2.7 18.4 0.35 0.25 0.15 19.2 0.04 Uncorrected Comp-A-9* Calcined E-06F 9.5 &lt;7 0.7 0 0.1 0 0.8 <~0.2 * He revised B* --- Acid leaching E-06F 4.1 161 22.6 1.9 0.9 ---. 0.4 25.8 〈~0.2* Because the empty sample correction value is obtained using 〇·〇1 N NaOH titrant concentration instead of The 样品·ι N Na〇H titration used in the special sample SARCw analysis is therefore not used to correct the sample titration. The above catalyst composition is described in more detail in conjunction with the following examples, which illustrate the above How the different types of catalyst compositions can be used in the selective hydrogenation process. All modifications and examples that are within the spirit of the invention are protected. Therefore, the following examples are not intended to be limited to the invention described and claimed herein. (SHP) Example In the following non-limiting examples, the selected catalyst composition was tested at the laboratory level. The general procedure is as follows. 126433.doc -71 - 200843847 百先' Load the catalyst sample into the 1/4&quot; inner diameter reactor. The catalyst was reduced in nitrogen at a flow rate of Wc/min for one hour. The soot feed consisting of 99.4 wt.% and 6 wt% of the block was then passed through the catalyst at 100 psig. The molar ratio of H2 to acetylene is about 1.2 and the liquid hourly space velocity is about / 63/hr. The temperature is roughly increased from 35 ° C to 5 (rc, valence, ah, valence, and then back to 65 ° C per hour). Example P-1 using acid leached E glass on the sjjp Example _, about 丨 gram prepared according to the procedure of Example 2 above, on the acid immersion E glass, 0·〇18 *% (4) into the reactor. The sputum was tested according to the above SHP example procedure. The following table lists the final The result of this test at a temperature of 65 °C.

EXAMPLE P-1 Acid Leached E Glass Starting at 0.6449 6 0.018 wt% Although in the foregoing embodiments, the invention has been described in accordance with certain preferred embodiments of the invention, and for purposes of illustration, Many of the details are apparent to those skilled in the art, and it is obvious that the present invention may 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 taken by a JEOL 3000F field emission transmission electron microscope at 3 〇〇 126 433.doc -72 - 200843847 volts accelerating voltage, the 眚 袅 has no microporosity, but has a medium porosity And scanning electron microscopy (STEivn fi # ^ , V image of the cross-section of the large-porosity glass matrix sample "you 丨 1 ', (for example, acid leached E glass), where the palladium particles are generally separated from the pore wall surface distance Less than or less than 次 in the range of about 30 nanometers.

C 126433.doc -73-

Claims (1)

200843847 X. Patent Application Scope: - A selective hydrogenation process for a process stream, wherein a selective hydrogenation of at least a portion of the process stream is carried out using a catalyst composition comprising at least one target hydrogenatable site having at least one target a compound, wherein the catalyst composition comprises: • a substantially microporous matrix having a mesoporous, macroporous, outer surface, open pore wall surface, surface region, and subsurface region, at least one catalytic component, and At least one catalytically active region comprising the at least one catalytic component, wherein (a) the substantially microporous matrix has i) when measured by a method selected from the group consisting of SAA^wr, SAhjw, and combinations thereof, The total surface area measured between about 5 m2/g and 300 m2/g; and 预定) the predetermined isoelectric point (IEP) obtained over a pH range greater than 0 but less than or equal to 14; The at least one catalytically active region may be continuous or discontinuous, and having i) an average thickness of less than or equal to about 30 nanometers; and Π) a catalytically effective amount of the at least one catalytic component; (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, iv) is partially on the outer surface, and partially The open pore wall surface 126433.doc 200843847 is partially in the surface region and combinations thereof; or v) (c) (combination of 〇, (ii), (iii) and (iv). 2. T request item i A selective hydrogenation process, wherein the at least one catalytic component is selected from the group consisting of: Browed or Lewis acid, Bruce, Stuart or Lewis, precious metal cations and precious metals Combined cations and anions, transition metal cations and transition metal miscible anodes and anions, metal oxide oxygenates, transition metal chalcogenide anions, main oxyanions, tellurides, rare earth ions, rare earth complex cations and anions, Precious metals, transition metals, transition metal oxides, transition metal sulfides, transition metal oxysulfides, transition metal carbides, transition metal nitrides, transition metallizations, transitions Is a phosphide, a rare earth hydroxide, a rare earth oxide and a combination thereof. The selective arrow #古, 土^ _ 扎1L method of claim 1 wherein the catalyst composition is in a steady state selective chlorine The at least one catalytic component is a ruthenium-based catalytic component having (a) a first pre-reactive oxidation state, and (8) a first pre-reaction with the substrate. The action is selected from the group consisting of ionic charge interactions, electrostatic charge interactions, and combinations thereof. 4. Selective method according to claim 3, the method of catalyzing columnization, wherein the first catalytic component is selected from the group consisting of acids and bases. a group of chalcogenides and combinations thereof. 5. The selective gasification method of claim 3, wherein at least a portion of the first catalytic component 126433.doc 200843847 is modified or replaced before the catalyst composition is subjected to a stable selective hydrogenation reaction condition Generating a second catalytic component having (a) a second pre-reactive oxidation state, and (b) a corresponding second pre-reaction interaction with the substrate; wherein 'the second pre-reactive oxidation state of the second catalytic component Less than, greater than or equal to the first pre-reactive oxidation state of the first catalytic component. 6. The selective hydrogenation process of claim 5, wherein the second catalytic component is selected from the group consisting of Pd, Pt, Rh, Ir, Ru, 0s, cu, Ag, Au, Ru, Re Λ Ni ' c〇, Fe a group of Mn, Cr, and combinations thereof. 7. The selective hydrogenation process of claim 1, wherein the substrate is a glass composition having a SARCNa of less than or equal to about 〇·5. 8. The selective hydrogenation process of claim 1, wherein at least 5% by weight of the at least one catalytically active region is substantially concentrated in a region having an average thickness of less than or equal to about 2 nanometers. 9. The selective hydrogenation method of claim 1, wherein the substantially microporous matrix is selected from the group consisting of AR glass, rare earth citrate glass, boroaluminosilicate glass, E glass, boron-free E glass, s glass, A group consisting of R glass, rare earth glass, bismuth salt glass, Ba-Ti-silicate glass, nitrided glass, a glass, C glass, and CC glass, and combinations thereof. 10. The selective hydrogenation process of claim 1, wherein the substantially non-microporous matrix obtains an IEp system of less than or equal to about 7.8, but greater than 〇 before or after the first leaching treatment. 126433.doc 200843847 VII. Designation of representatives: (1) The representative representative of the case is: (1). (2) A brief description of the symbol of the representative figure: (No description of the symbol of the component) 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: (none) 126433.doc