TW200843848A - Hydrogenation processes using functional surface catalyst composition - Google Patents

Abstract

Hydrogenation processes using a catalyst composition which, preferably comprises a glass substrate, with one or more functional surface active constituents integrated on and/or in the substrate surface. A substantially nonmicroporous/nonmesoporous substrate having macropores has (i) a total surface area between about 0.1 m<SP>2</SP>/g and 50 m<SP>2</SP>/g: and (ii) a predetermined isoelectric point (IEP) obtained in a pH range greater than 0, preferably greater than or equal to 4.5, or more preferably greater than or equal to 6.0, but less than or equal to 14. At least one catalytically-active region may be contiguous or discontiguous and has a mean thickness less than or equal to about 30 nm, preferably less than or equal to 20 nm and more preferably less than or equal to 10 nm. Preferably, the substrate is a glass composition having a SARCNa less than or equal to about 0.5.

Description

200843848 IX. INSTRUCTIONS: [Technical field to which the invention pertains] The present invention relates to a catalyst composition and a preparation method thereof, and the catalyst group is not applicable to various chemical production methods and various emission control methods. More specifically, the present invention relates to a catalyst composition preferably comprising a glass substrate and incorporating one or more functional surface active ingredients on the surface of the base and/or the surface of the substrate, the catalyst composition being useful for various hydrogenation Method application.

Ο [Prior Art] The catalyst composition is used to promote a chemical reaction that is described as a catalytic reaction or a catalytic reaction, and catalytic limitation is essential for effective chemical processes. : Some industrial reactions and almost all biological reactions, if not catalyzed, involve pre- or post-reaction treatments that are catalytic reactions. For products that are only produced in the United States and at a certain stage including catalytic processes, the value of the product is close to one trillion US dollars (USD). You are using the catalyst composition to produce products including, for example, food. , clothing, Chinese, ', 曰 use to mouth, special or fine chemicals, plastics, detergents, 1 J 枓 and lubricants. The catalyst composition can also be used to treat emissions (such as squid car exhaust emissions, refinery sputum emissions, utility effluent emissions, etc.) to reduce the potential for human Wei or the environment. The amount of harmful components affected. In terms of sales, the sales of solid carrier catalysts for heterogeneous catalytic reactions in the global market are about 备 , , 一 一 一 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 Refining, L ^ i catalyst, chemical processing catalyst and emission control catalyst. The 126426.doc 200843848 second-class catalyst market sales are basically three-point world. For example, 1 9 9 years, in the United States 1 In the $800 million solid catalyst market, petroleum refining, chemical processing and emission control catalysts accounted for 37%, 34% and 29% of the market. The market for petroleum refining catalysts (about $100 million in 1990) For example, 56% of the revenue comes from fluid-cracking (FCC) catalysts, while 31.5%, 6.5%, and 4.5% of the revenue comes from hydrotreating catalysts, hydrocracking catalysts, and reforming catalysts.

From a chemical mechanism point of view, the catalyst generally increases the rate at which the chemical reaction is brought to equilibrium between the reactants and the product without substantially eliminating itself. Therefore, for any relevant reaction, although the catalyst cannot change the equilibrium state between the reactants and the product, the catalyst can accelerate the rate of the chemical reaction if properly set and/or selected. Thus, catalysts are used for a wide variety of commercially useful processes for a variety of purposes including improved process responsiveness, selectivity and energy efficiency, and other uses. For example, the desired product % can be produced according to the specified process conditions, and the reaction rate or reactivity of the reactant can be shortened to achieve higher product throughput (for example, increasing the volume per unit hour). Or quality). Thus, catalyst activity refers to the ability of the catalyst composition to effectively convert the reactants to the desired product, per unit time. Similarly, the selectivity of the reaction can increase the percentage of yield of the desired product in a set of possible reaction products: among the possible reaction products, some products are undesired and f is required. Process for corresponding removal or conversion. Thus &apos;catalyst selectivity is the ability of a catalyst composition to convert a portion of the reactants to a particular product under regulatory conditions. In addition, the catalyst is combined to convert and reduce the amount of contaminants or undesired reactants in a process. The additional use is to increase the overall energy efficiency of the reaction process while maintaining or improving product production capacity and/or reaction selectivity. The range of use of the catalyst varies greatly. For example, but not limited to, a catalyst can be used to reduce the content of contaminants such as hydrocarbons, carbon monoxide ((3)), nitrogen oxides (10) X), and sulfur oxides (sox), which may exist in the contaminated temples/woods. In a series of processes (such as the gasoline engine type of the vehicle, the combustion exhaust gas in her 木 wood/甴 machine, the classified petroleum refining or coal burning process, etc.). Similarly, the catalyst can be used in a hydrocarbon treatment process, which is used for different sources of π-pairs (such as straight-run petroleum fractions, recycled petroleum fractions, heavy-knife/yield, asphalt, porphyry, natural gas, and A hydrocarbon process stream comprising other carbon species that can be subjected to a catalytic reaction material is converted or upgraded. The catalytic reaction is usually divided into two different types of reactions, namely homogeneous catalysis and heterogeneous catalysis. Homogeneous catalysis broadly describes a class of hydrazine and deuteration reactions in which reactants and catalysts are &amp; in a solution phase. In some cases, &amp; some cases use a gas phase catalytic reaction, but homogeneous catalysis is a liquid phase system under the typical situation. Therefore, the concentration gradient-object migration to the catalyst will become an important factor in controlling the homogeneous catalytic reaction. In addition, in some cases, the "solution phase" catalyzes the reaction at the interface of the liquid phase, forming a true solution. It is the formation of a servant. Homogeneous catalysis includes general acid-base catalysis, organometallic catalysis, phase transfer catalysis, and the like. /, the phase catalytic catalyzes a type of catalytic reaction as follows: The reactant in the gas phase or the liquid phase is exposed to a catalyst which is substantially solid phase or a solid phase or 126426.doc 200843848 solid phase. Therefore, in the heterogeneous catalytic process, the catalyst and reactants produce a mixed solid-liquid phase or solid phase-gas phase reaction. Heterogeneous catalysis has many advantages over homogeneous catalysis. For example, solid catalysts are generally less corrosive (13) and are more compatible with many Xiaojing solutions. Safety and environmental risks are relatively low, (b) A wide range of economically viable temperature and pressure conditions 'and (4) can control more intense exothermic chemical reactions and endothermic chemical reactions. On the other hand, solids can have mass transfer limitations that in turn significantly reduce the ultimate effectiveness of the catalyst. Typically, solid catalysts (sometimes referred to as catalyst particles) include one or more catalytic components on a porous material having a high internal surface area (eg, precious metals such as (Pd), turn (Pt), 钌(Ru), 铢 (Re), etc., the internal surface area of the catalytic component, usually on the order of hundreds of square meters per gram. Therefore, the conventional catalyst composition or catalyst particles have a large internal surface area. In the porous support, the catalytic reaction occurs on the carrier. However, such a catalyst structure often produces a mass transfer which reduces the effectiveness of the catalyst particles with respect to the activity and selectivity of the catalyst, and causes other Catalyst performance problems. ^^/, representative catalyst structure, the reactants must diffuse through the 罔 罔 to reach the inner region of the catalyst particles, and the product must be expanded 2 times to exit the interior of the catalyst particles Therefore, the compatibility of the conventional catalyst group depends on the balance, among other factors, depending on the trade-off between the two characteristics of the conventional catalyst composition, ie, the catalyst. Surface area plate promotes quality #夕处丄' The trade-off between this power. For example, many catalytic components are stored under the code of the brothers. The grazing has a fine and complex pore structure in the carrier (via 126426.doc 200843848 For microporous gentleman granules ... ie &lt; 2 nm average maximum diameter) to increase the catalyst, θ, product. This higher surface area will usually increase the catalytic activity. However, due to the black eve to w ^ ^ The catalyst activity increases due to the surface area of the particles, I: the problem of the resistance of the amount of transmission (ie, the reaction of the reactants and the microporous structure of the product..." The carcass includes the southerly percentage. The problem is more obvious. By increasing the size of the pores (for example, &gt; 50 nm

Percentage in the carrier reduces the resistance to mass transfer (ie, speed, rib, and berry transfer). However, this solution tends to be low: the physical strength and durability of the media particles. In other words, the self-mechanical concept &lt;:, and p, the robustness of the catalyst particles is reduced. ^ The right reactant is subjected to significant mass transfer resistance in the pore structure of the catalyst particles', and a concentration gradient will exist under steady state 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 touch: particle than around the catalyst particles. These concentration gradients provide the driving force for the Berry transfer. The greater the concentration gradient becomes, the lower the rate of the catalytic reaction. In this way, the effectiveness of the catalyst particles, the female response H, the long-term selectivity, the life cycle between the regeneration treatments, and the anti-coking properties are also reduced accordingly. In general, the purpose of developing a catalyst composition is to improve one or more of the processing objectives described above from a commercial perspective. In some cases, one of the factors affecting the performance of the catalyst is its ability to promote rapid and efficient reaction between reactants. Therefore, it is often desirable to have a catalyst composition having a lower diffusion limit. However, in other cases, in order to obtain a better product, 126426.doc 200843848 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. For example, in 1976, γ·τ·Shah et al. proposed the use of acid leaching on a lycopene fiber, specifically an E-glass (more specifically, Ε_62ι) to produce a catalyst carrier. Compared with the conventional catalyst, the catalyst carrier has a high surface area-volume ratio and is used for the catalytic conversion of the automobile row (for example, t参xidation 吋 an Aut〇m〇biie (10) μ

Gas Mixture by Fiber Catalysts, Ind. Eng. Chem. 5 Prod Res. Dev., pp. 29_35, v〇 1.15, N〇1, 1976). At the same time, he believes that reactive gases (such as carbon monoxide, carbon dioxide, nitrogen oxides, methane, ethane, propane, ethylene propylene acetylene, stupid and stupid), which are generally produced in automobile exhaust mixtures, are easily accessible. The large surface area produced in acid leached E-glass.

Shah et al. showed that a relatively small amount of fiber 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 should be better than that of alumina as the carrier or cerium oxide as the carrier (180 m2/g and 317 m2/g, respectively), wherein the average pore diameter of the E-type glass catalyst is greater than The ruthenium oxide is a catalyst for the carrier or a catalyst for the carrier of the oxidized stone. Despite this, Shah et al. did not propose or suggest that effective vehicle exhaust oxidation can occur at surface areas of less than 75 m2/g. Nearly 25 years later, Kiwi-Minsker et al. studied the reduction of surface area in another acid-impregnated aluminum borosilicate type E glass fiber (EGF) in 1999. Phase 126426.doc -11 - 200843848 The selective liquid phase hydrogenation of cerium oxide glass fiber (SGF) of A-plate is related to the effect of producing benzyl alcohol (using a platinum-based catalyst) or toluene (using a catalyst for the main one) (see, for example, j)

Catalysts for Novel Multi-phase Reactor Design, Chem.

Eng·Sci· PP· 4785-4790, Vol· 54, 1999). In this study, Kiwi-Minsker et al. found that SGF does not obtain an increased surface area from acid leaching, so it is relative to the egf sample used to carry palladium as a catalytic component of palladium-based catalyst combination v. (The surface area is 15 mVg and 75 m2/g, respectively), and the surface area of SGF is kept at a low level of 2 or less. However, Kiwi-Minsker et al. noted that the SGF/palladium catalyst palladium essentially has the same effective surface area concentration as its EGF/palladium catalyst counterpart (ie, about (M mm〇1/m2) (mole metal/ The SGF/palladium catalyst composition shows a decrease in activity or reaction rate per gram of palladium compared to its EGF/palladium catalyst counterpart.

Kiwi-Minsker et al. suggest that the SGF/palladium catalyst has a reduced surface area due to a decrease in U and may be explained by the enhanced interaction of the active ingredient (ie, the catalytic component 'palladium in this case) with the SGF carrier. , not because of its small surface area (ie 2 m2/g). However, they failed to verify this argument by proving the following argument: EGF/palladium catalysts with a small surface area (ie, comparable to 2 m2/gi sgf/palladium), at least with a larger surface area (ie, The iGF/palladium catalyst samples of i5 and 75 m2/g) have the same catalytic activity. Therefore, Kiwi-Minsker et al. proposed a limitation on the activity of SGF/palladium (ie, because SGF has a higher acidity than EGF, and the interaction between palladium and SGF is enhanced), which is a major factor, not a SGF/pd Table 126426.doc •12- 200843848 Faces are small, the reason is not clear. In any case, Kiwi_Minsker did not report σ Xiongming, compared with the 75 m2/g EGF/I bar sample, the 15 m2/g EGF/|ba sample mouthwash has an increased diffusion rate and enhanced catalytic activity. Otherwise, this may have the beneficial effect of the surface of the moon due to the small catalyst surface area. Recently, in US 7, 〇 6〇, 651 and EP 1 247 575 A1 (EP, 575),

Barelko et al. disclose the beneficial effects of using a cerium oxide-rich carrier, including cerium oxide and an oxide comprising non-cerium oxide (e.g., Al2?3, B203, Na20, ζg Ca?) as a catalyst carrier? Wherein the cerium-enriched support has a pseudo-layered microporous structure in the underlying layer of the support (see, for example, paragraphs 11, 13, 15, 17, 18, 23, 31 and 32 of EP '575) As a more complete description of the European Patent Office ("Ep"), in distinguishing the catalytic carrier (''Kiwi-Minsker carrier') disclosed in EP '5 75 and Kiwi-Minsker et al. Barelko et al. assert that the cerium-enriched carrier they claim has a pseudo-layered microporous structure with a narrow interlayer space, while the Kiwi-Minsker carrier does not. This is more specific than a 'Barelko et al. In the paper by Kiwi-Minkser et al., it is assumed that (a) there is a pseudo-stratified microporous structure with a narrow interlayer space in the Kiwi-Minsker carrier; (b) the narrow sandwich space Pseudo-layered microporous structure helps to enhance The activity of the metal applied to the carrier (see, for example, paragraphs 13, 17-18, 23 and 32 of EP '575).

Barelko et al. further clarified the carrier containing the oxidized sulphur oxides and the carrier proposed by Kiwi-Mins ker et al. by explaining to the European Patent Office that the catalytic component is in a highly dispersed active state. The surface of the carrier t is the distribution of the potential of the pred〇minanf distribution of the 126426.d〇i -13 - 200843848 catalytic components in the subsurface layers of the support in a highly dispersed active state)', (in the increase, Ai meal), rich The carrier containing the dioxide dioxide has a more active catalytic state, so the catalytic activity of the higher activity is such that the catalytic component can withstand the effects of sintering, aggregation and self-carrier stripping and rescue agents (see, for example, EP). 'Paragraph 11 of 5 7 5). EP, 5 7 5 confirms that diffusion limitations may hinder the intercalation of cations into the support and thus hinder the entry of cations into the support by chemisorption (see, for example, paragraph 17 of Ep, 575). In order to solve this diffusion limitation problem, Barelk et al. propose (and advocate) a carrier structure in which thin, layered helium-oxygen fragments are separated to form a narrow interlayer space (ie, a large number of pseudo-layers) Microporous structure), the narrow interlayer space contains "mass" 〇H groups, and the protons of the 〇h groups can be exchanged by cations. Barelk〇f reveals that the full, thin, and slick _ oxygen shard layers are unique for high Q3 to Q4 ratios, and they further state that there are a large number of (10) groups of pseudo-segments sandwiched between narrow interlayer spaces. The layered microporous structure has been confirmed by 29Si NMR (nuclear magnetic resonance) and by (infrared) spectrometry combined with argon BET and alkali titration surface area measurements. Like some of these glass catalyst compositions, many conventional catalysts attempt to solve the above-mentioned confirmed processing problems, but perform poorly in other aspects of catalyst performance. Therefore, such conventional catalysts are often limited to a narrower range of process reactions, have limited useful life before regeneration or replacement is required, and/or require large amounts of expensive catalytic components (such as precious metals such as platinum and palladium). Significantly increase the cost of catalyst production and catalytic processes. □ This is an improved touch I composition that can be used in a variety of processing reactions with % improvement such as process reactivity, selectivity and/or energy efficiency 126426.doc 14 200843848 et al. The catalyst composition is preferably tailored to a wide range of process conditions and requirements while enhancing robustness and durability while maintaining a relatively long life: cycle. A functional surface catalyst composition has been found to meet the needs of this broad range of catalytic reactions. SUMMARY OF THE INVENTION One aspect of the present invention provides a method of hydrogenating a process stream, the basin utilizing a catalyst composition to hydrogenate at least a portion of a process stream, the process

t catching from 3 to V compounds having at least one hydrogenatable site, wherein the 'catalyst composition comprises: substantially void-free, outer surface, open pore wall surface, surface region, and subsurface region substantially free of microporosity/ a mesoporous matrix, - at least one catalytic component, and - at least one catalytically active region comprising the at least one catalytic component, wherein the substantially microporous/non-porous matrix has a ... ▲ L from 8 · Α · The total surface area measured between ΛΤ2_β£Γ, S· and its combined group is measured to be between about 0.1 m2/g and 50 m2/g; and η) is greater than 0 but less than or equal to a predetermined isoelectric point (IEP) obtained within a pH range of 14; b) 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 nm; and ii) catalysis An effective amount of at least one catalytic component; and c) a position of the at least one catalytically active region is substantially 126426.doc 15 200843848 i) on the outer surface, π) on the open pore wall surface, iii) in the surface region, N) portion Opening wall surface , Shu knife in the surface region, and combinations thereof; or v) (c) (i), (ii), (iii) and (iv) the combination. Based on the following embodiments and the accompanying drawings and drawings, it will be apparent to those skilled in the art that the present invention can be clearly understood. ..., [Embodiment] I''° Definitions The terms used herein have the meanings defined below. , "pores" means holes or channels having a depth greater than the width. ''Interconnected pores'" means pores that communicate with one or more other pores. "Closed pores" means pores that do not have any passages to the outer surface of the material in which the closed pores are located. ί, , ▼Open pores π means that there is a direct channel with the open pores*, the outer surface of the material where the gap exists, or via another pore or interconnected pores; the pores connected to the pores (ie, not closed pores) The pores). "Pore width" means the distance between the inner diameter of the pores or the opposite wall of the pores of the pores according to the specified method. "Pore volume" means the total volume effect of all pores in accordance with the specified method, and does not include the volume effect of the closed pores. "Porosity" means the ratio of the pore volume in the material to the total volume of the material. I26426.doc 16 200843848 ''Microporosity'' denotes pores having an internal width of less than 2 nanometers (nm). The 'intermediate pores'' represent pores '' macropores having an internal width between 2 nm and 5 Å, representing pores having an internal width greater than 5 Å. The outer surface '' denotes a boundary or skin of a material (thickness near zero), including a regular or irregular contour on the outer boundary or skin associated with the defect (if any). 0 '▼Porous wall surface' means the inner boundary or skin (thickness near zero), including any regular or irregular contours on the inner boundary or skin associated with defects, if any, defined on any open porosity in a material having at least one or more types of pores. Shape. "Surface" overall representation - 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 a material area that may vary depending on the material and does not include any area defined by the open pores of the material (if any open σ pores are present), but the δH surface area (4) is less than or equal to the outer surface of the material. Capturing rice (better than nano, more preferably _&lt;1〇N); when the material has any open pores, the surface area (b) is less than or equal to 30 nm below the pore wall surface of the material ( Preferably, the illusion nano, more preferably ^1 〇 nanometer. For materials with detectable surface elevation changes, whether the changes are regular, external or internal boundaries or skin, external or internal Boundary or skin: The average range is used to determine the average depth of the surface area. ''Under surface area' means the material that can be changed depending on the material, excluding the area where the open pores (if any open pores are present) , but the subsurface region (4) is greater than % nanometer 126426.doc -17- 200843848 (preferably &gt; 20 nm, more preferably > 1 nanometer) below the outer surface of the material; Lower area (8) In the pore wall of the material = what is the opening pore meter (preferably (10) nanometer, more preferably > 1Q nai... Table ^ is greater than 3 〇: internal surface area" or, open pore wall surface area" means designated The surface area effect of all open pore walls in the material. ^ Surface area, ' indicates the surface area effect determined by the specified method that does not include the surface area effect of all pores in the material. , Total surface area, Table W specified method The sum of the surface area of the material (IV) and its external surface area. ''Nano-Chemical Adsorption Surface Area' or SA·Qin Table# The surface area of the material determined by chemical adsorption of sodium cations by chemisorption, the chemical adsorption method GW· Sears ^/. C/2 Rat, 1956, V〇l. 28, P. 1981 and R. Iler, C/z(10) outside/meaning&quot;ca,j〇hn Wiley &amp; Sons 1979, ρ· 203 And 353. ''Na-Chemical adsorption surface area change rate' or 'SARCiVa', where SARCA^=V5q5/v initial, where (i) V is initially used to initially titrate an aqueous slurry mixture of dilute NaOH titration solution Initial volume, at about 25 °C at 3·4 M Na The Cl solution comprises a material that is substantially insoluble in water, the pH of the solution is at zero time t. From the initial pH 4.0 to pH 9.0, and (ii) 乂5 to 15 means that the slurry mixture is used for a period of 15 minutes. Maintain the total volume of the same concentration of NaOH titrant at pH 9 every 5 minutes (a total of 3 5 minute intervals 't5, t1G and t15 respectively). The total volume is adjusted as needed as soon as possible. Therefore, V, total Refers to the total volume of NaOH titrant used in 126426.doc -18- 200843848, which is used in the titration procedure described in more detail below, where v initial + Vp15 = v total. Therefore, 乂5 to 15 can be expressed as V. The difference between the total and V initial, where Vy15=V total.V initial. For the purposes of this definition, 1.5 grams of sample material is added to the NaCl solution by adding 3 gram grams of NaCl (reagent grade) to 150 liters of water to produce an aqueous slurry mixture. The aqueous slurry mixture must first be adjusted to pH 4.0. To make this adjustment prior to titration, a small amount of dilute acid (e.g., HCl) or a dilute base (e.g., NaOH) may be used accordingly. Titration, in order to obtain the V initial, first use a dilute Na〇H titration solution (for example, 〇1 n or 0.01 N) ’ and then use Vy υ for the SARCa^ measurement. In addition, for the purposes of this definition, 曰 'V" μ is the cumulative volume of the Na〇H titration solution used in ts, ~ and y, wherein the NaOH titration solution is titrated as soon as possible every 5 minutes (3 intervals of 5 minutes). Adjust the pH of the slurry mixture to 9.0 within 15 minutes from t to the final time of 4. As far as this is concerned, 'with any optional ion exchange (ΙΕχ), counter ion exchange (BIX) and / or electrostatic adsorption (ΕΑ) treatment method to determine the SARC heart of the sample material prior to integration of one or more 2-component precursors (described below) onto the surface of the substrate and prior to "goth surface." "Incipient wetness" means an aqueous slurry comprising a solid or semi-solid material or a moon-like shape. The time at which the isoelectric point (i, iEp, ) of the material is being measured, the deionized water is overlaid on the entire surface of the solid or semi-solid material and is filled to the present extent. The material may have any water-permeable pore volume, which in turn allows water to enter the human aqueous slurry or paste mixture' to provide sufficient liquid contact between the glass electrode contact surface and its reference electrode contact surface, and thereby determine the material's ΙΕρ . 126426.doc -19- 200843848 ''Electrical point,' or IEP means the pH at which the net surface charge of a solid or semi-solid material is zero at initial humidity. The ιΕρ used herein may also be referred to as a zero point charge (ZPC) or a p〇int of zero charge (PZC) 〇 '▼ catalytically effective amount '' indicating sufficient processing conditions The at least one reactant is converted to at least one predetermined product of sufficient yield to support the amount of catalytic component of the pilot plant or commercial grade process. "Cha丨conide" means a group of at least one group of 16 (formerly Group VIA) derived from a group consisting of sulfur (S), sulphur (Se) and cerium (Te) and at least one positive A compound that is more electrically stronger than the element or group of its corresponding Group 16 element. , a noble metal, representing a transition metal from the group of rhodium (Rh), palladium (Pd), silver (Ag), iridium (Ir), platinum (Pt), and gold (Au), unless otherwise stated The form of the substance, metal ruthenium, metal cation or metal anion is in a state of charge, otherwise the various transition metals are in a zero oxidation state (at the same time in an unreacted state). ''Anti-corrosion #matrix' means a substrate that is capable of resisting substantial changes in the matrix's electrical structure under the subsurface region'. These changes are due to changes in structural elements due to most acids or tests under standard temperature and pressure conditions. And / or loss, new pore formation, pore size expansion, etc. However, the composition of the corrosion-resistant matrix may be substantially high-strength acid (such as thick stiffness test (such as concentrated Η) or other strong rot (four) reagents (regardless of In combination with high temperature, high pressure and/or high vibration frequency conditions, the matrix is still considered to be "corrosion resistant, matrix." 疋126426.doc -20- 200843848 , '' "Surface activity" means that the surface of a material is sufficiently filled with one or more charged materials, and 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 electrostatic interaction and/or ion exchange interaction with - or a plurality of charged components, for further modification, and subsequently under steady state reaction conditions Is a catalytic component. ', matrix' means any solid or semi-solid material 'including but not limited to glass and glass-like materials, IEP greater than G but less than or equal to 14, surface active state can be "matrix in the catalyst composition (with catalytic effective The intended use of the quantity is changed. "Integration" in the "knife" means mutual, electrostatic or covalent interaction by electron and/or physicochemical, including but not limited to gas bonding, ionic bonding 2: electrical bonding, Vas / dipole bonding, affinity, covalent bonding and combinations thereof. Combining chemical composition with the base. Can be = two complaints and factors 'so only used for a brief wording convenience: some aspects of the implementation of the second reader's potential benefits. System. This poor mode of application should not be considered as an accompanying application invention Scope limit: The sample is related to the type of catalyst composition, the surface activity =: the area of the flat: _ less than or equal to _ nanometer, preferably _ &lt; butyl ... card 'and more preferably - < about 】0 nm (,, catalyst composition) . Another aspect of the invention is the production of a composite form of a catalyst composition, regardless of the presence or absence of a medium, with respect to various other aspects of the manufacture of the novel catalyst composition. A further aspect of the invention relates to the use of catalyst compositions in various processes such as hydrocarbon, hetero/er and/or non-hydrocarbon treatment, conversion, refining and/or emission control and treatment processes and other types. Dream journey. For example, new catalyst compositions can enhance hydrocarbon, miscellaneous and/or non-hydrocarbon treatment, conversion: refining and/or emission control and treatment processes and other types of processes. Reaction selectivity, reaction rate, yield, and energy efficiency. . Several factors should be considered in the production of the catalyst composition, including but not limited to: μ (1) = obtaining a substrate having a predetermined isoelectric point ("ΐΕρ") for the intended use, either as it is or as a follow-up Obtained after treatment; (Π) the degree of corrosion resistance of the substrate in view of the intended use; (iv) in view of the intended use 'in order to obtain the desired surface properties, the degree of porosity of the substrate (if any), and related elemental composition (special (on the surface), (d) depending on the intended use of the composition, where appropriate, the chemical sensitivity of the substrate to the generation of the appropriate isoelectric point, and by one or more of the first and the substrate ions and/or electrostatic interactions a component which imparts surface activity to the substrate which can, but does not, produce a catalytically active region having an average thickness on the surface of the substrate and/or a spoon of &lt; about 3 nanometers, preferably about 2 〇 nano, more preferably s about 10 奈; (7) matrix for - selective ion exchange (IEX), counter ion exchange 126426.doc -22- 200843848 (BIX) and / or electrostatic adsorption (EA) treatment Chemical sensitivity of the method for integrating one or more second components onto and/or within the surface of the substrate having a second type of interaction with the matrix ions and/or electrostatic interactions, and thereby producing a 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 20 nm, more preferably about 1 〇N•m; and Vi) depending on the intended use of the composition, the chemical sensitivity of the treated substrate to the following f, reaction: optional calcination and/or reduction, oxidation or further treatment of the treated substrate prior to use of the catalyst composition The first or second catalytic component acts as a chemical reaction. I. Substrate Description The preferred and preferred range of 1Ep options for many potential applications. Preferably, the matrix used to produce the catalyst composition of the present invention is a glass composition that is either received as received or processed by surface activity. Surface activity (sorry, 1 is greater than about 0 but less than or equal to 14. Whether to obtain a matrix with suitable IEP (suitable for producing a catalyst composition for the intended use) depends on various factors, some of which are factors It has been outlined above (in the "Overview of Implementation"). As discussed in more detail below, those skilled in the art will be more aware of other factors associated with selecting an appropriate IEP. For example, for many businesses For the benefit process, the glass (or glass-like) composition and its surface active product preferably have a weight greater than or equal to about 4. 5 but less than 14, and a glass composition having a ΙΕΡ greater than or equal to about 6 〇 but less than 14 is more preferred. Preferably, the composition is preferably greater than or equal to about 7. 8 but less than 14 126426.doc -23 - 200843848 Preferably, the composition is preferred. However, depending on the intended use of the catalyst composition The preferred extent of IEP may be plasticized in the extent and type of porosity in the base of the mouthpiece.: a ^ ' Bu, some catalytic processes are more sensitive to the Table® _' composition at lower pH ranges Therefore, in these cases, the matrix of J; 8 (軚佳为,更优选为4·5) is likely to be more suitable for such processes. α α . α ^ /Τ 乂' It is stated that when selecting the base in the appropriate range, it is necessary to consider not only the factor of the intended use of the catalyst composition, but also the porosity of the substrate, the chemical composition and the treatment procedure (if any), etc. For expected catalytic use 'many glass types can be potential matrix candidates to obtain the appropriate degree and type of enthalpy and porosity, whether received or used as one or more of the following treatment methods. Examples include, but are not limited to, bismuth-type glass, boron-free glass, S-glass, sizing glass, AR-type glass, rare earth silicate glass, strontium-titanium-silicate glass, nitride glass such as 矽Aluminum_Oxygen-nitrogen glass, A-glass, C-glass Cc-type glass. However, the following is a exemplification of the type of glass that is generally expected for a range of catalytic applications and some possible treatments. Large-pore glass indicates that the substrate used to produce the catalyst composition of the present invention is preferably substantially Porous, non-medium pores, but some glass materials composed of large pores ("no microporosity / no mesoporosity,"), whether originally had a surface, tongue, or treated to form a surface active state, IEp is generally greater than 7 8. Typically, a microporous/non-porous glass-filling composition having an IEP greater than 7.8 will include an acidic or basic oxide type glass mesh modifier, 6 w 匕祜 (for example) but 126426. Doc -24- 200843848

Not limited to oxidation of elements such as zinc (Zn), magnesium (Mg), calcium (Ca), aluminum (Al), boron (B), titanium (Ti), iron (Fe), sodium (Na), and potassium (K) Things. If an alkali network modifier is used, the amount included in the lower IEp glass tends to be &lt;15 wt.%. A glass composition containing magnesium, calcium, aluminum, zinc, sodium, and potassium is preferred, and a glass composition containing greater than or equal to about 7 〇 wt% of cerium oxide is more preferred. However, the macroporosity corresponds to a substantially microporous, void-free glass composition having a total surface area of less than about 98% and a corresponding geometric outer surface ranging from about 2% to about 5% by total surface area. The catalyst composition, and the IEP of the composition is typically greater than 7.8 but less than or equal to 14. Porosity indicates that the porosity of the matrix produces another relevant aspect of the catalyst composition of the present invention. The basis weight should be substantially free of microporosity/no pores, but may actually be quantitatively insignificant. The microporosity and/or mesoporous volume of the intended use of the media composition is not adversely affected. Since the micropore volume in the material is often difficult to detect, the present description uses two surface area measurements to determine if the matrix is substantially free of microporosity/no porosity to distinguish the catalyst composition of the present invention. And for smaller surface area measurements (eg, the method described in ASTM D4780-95, the first-surface area measurement is determined by a thermal adsorption/desorption method suitable for accepting the expected surface area range of the measurement, τ is used for Debt measurement of micropores, mesopores and/or macropores (IV). Example %, for larger surface area measurements (eg > 3 m2/g) 贿2 bribe 'according to the method described in ASTM m663_〇3' (" S_A.❿朦&quot;)' may be a preferred surface area measurement technique. However, &lt; about 3 m2/g) Kr BET, according to (, may be better than 126426.doc -25-200843848 surface area measurement technique. Those skilled in the art of analyzing the surface area of solid and semi-solid materials will be aware of the optimal surface area measurement method for detecting microporosity, mesopores and/or macroporosity. The second measurement is the sodium-chemical adsorption surface area (, 'SA·^,,), can be expressed as a change in the ratio of NaOH titrant to time using a certain type of analytical method (R·Ilei • described in on Silica, John Wiley &amp; Sons (1979) pp. 203 and 353), and According to s · a - rate of change (&quot;SARCw") more specific definition. Thus, as defined herein, the matrix has substantially no microporosity / no mesoporosity 'k is a matrix of SAa^^et or SA gauges between about 0.1 m2/g to about 50 m / g, and s ARCw is less than or equal to 0 · 5. As discussed in more detail above, the ratio of the two volumes of SARCNa NaOH titrant, the denominator is the volume of the initially used NaOH titration solution, ie initially used for titration at zero time t◦ a matrix slurry mixture comprising 1.5 grams of substrate in a solution of 34 μ NaCl (pH 4 to pH 9) at about 25 ° C. But 'as described above' is used for SARCw at the initial NaOH titration Before the determination, the 'aqueous slurry mixture must first be adjusted accordingly to a pH of 4 with a small amount of acid (HCi) or base (NaOH). In addition, as described above, Na〇H titration solution (for three 5 minute intervals, at The cumulative volume of the matrix slurry mixture maintained at pH 9 for 5 minutes is initial (ie vy15), which is the molecular ratio of the SARCw. Therefore, if the % total initial is less than or equal to 〇5¥, the corresponding SARC· Less than or equal to 〇·5. Therefore, as defined herein, the basis of SARCa^S0.5 Substantially no microporosity / no mesoporosity (ie, macropores) 'the river is also a matrix between about 仏 to about 50 m2 / g. If these surface area parameters are met, the matrix has any 126,426.doc -26 - 200843848 Other types of pore volumes may have insufficient concentrations, distributions, and/or types, and thus may adversely affect the desired performance of the catalyst composition for its intended use. The sodium surface area (''SAa^'') is an empirical titration procedure for essentially pure cerium oxide (Si〇2) in the form of granulated, powdered and suspended gels (suspended s〇1 f〇rm). Developed. s. Α·heart measurement of surface proton position • Measure of reactivity and accessibility for pure oxidizing (' 矽, equivalent to 8 〇-〇·Η+ position. Tellurite glass and crystal citrate Pure cerium oxide (Si〇2) is significantly different in composition. For the stoichiometry of this titration procedure, the behavior of bismuth silicate glass and crystalline citrate cannot be determined according to the Na〇H titration determined in the SAW experiment. The absolute value of the liquid is known or predicted. Therefore, the equations used by Sears and Iler to correlate the volume of the SA·^ experiment with the N2_bet surface area of the ceria material studied are not suitable for reliable prediction. The absolute surface area of the citrate composition. This is expected because the t groups that can be present in the different compositions of the glass can include, for example, Α1-〇-Η+, Β_〇Ή, Ti_〇_H+, Mg-〇. · Minerals and proton groups (Q2 groups) with more different structures combined with multiple Si-〇-H+ parts at a single 矽2 position. On the other hand, 矽-like glass compositions (such as acid immersion quartz) The total surface area may be reliably determined using the SA·heart test, provided that The minimum pore size is within the range achievable by standard gas phase BET measurements,

It consists mainly of Si连2 and Si-OlT parts connected by the network. However, the diffusion accessibility of the Glass_ 〇_H + moiety to hydroxide ions and sodium ions, and the relative percentage of pores: macropores and/or substantially non-porous regions in microporous contrast should be based on NaOH The amount (in the SA·* experiment to maintain the final pH 126426.doc -27- 200843848 value 9, must be added in time) (titrant) for detection. Therefore, in general, the accessibility of the 'Glass-〇-H+ part for the contrast time of 〇H- and Na+, as determined by the above SAR~a experiment, can be used as a reasonable guilty degree of existence of microporosity, including standard gas. A certain type of porosity that is not comparable to the phase BET measurement. Preferably, the surface area of the substrate will remain substantially unchanged after its ion leaching process, which is a common occurrence for most alkali resistant (&quot;AR&quot;) glasses. However, in some cases, some of the ions consumed from the matrix network do not significantly affect the microporous structure of the substrate, if any, thereby avoiding adverse effects on the desired properties of the catalyst composition for the intended use. However, if there is significant ion depletion and associated leaching on the matrix network, it is likely that a microporous region will be produced in the matrix. Thus, as noted above, sar (^ is greater than about ♦ indicates that there is such a multiplicity; ^ pore structure. The matrix network showing these properties has produced sufficient microporous structure, especially in the matrix region, such The microporous structure will adversely affect the ability of the substrate to maintain a surface active state, thereby achieving the desired performance impact on the intended use of the catalyst composition. 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 seven particles (eg, pellets), spherical particles (eg, spheres), elliptical particles (eg, ellipsoids), flat particles ( For example, flakes, irregularly fractured particles, spiral or spiral particles, and combinations thereof. Examples of suitable shaped bodies or composites that can form such matrix shapes include, but are not limited to, woven composites, non-woven composites, webs Eye woven 126426.doc -28- 200843848 objects, extrudates, rings, saddles, cylinders, membranes, spiral bonded membranes, filters, Weft, chopped fibers, and combinations thereof. In some cases, depending on the intended use of the catalyst composition, any suitable material may be used as the forming medium to form a shaped body or composite with the catalytic substrate (collectively, Composite materials"), including but not limited to boehmite, hydrated titanium dioxide and 11〇2, hydrated zirconia and Zr〇2, yttrium alumina, oc alumina, ceria, clay, natural and synthetic polymeric fibers , polymeric resins and solvents and water soluble polymers, whether or not the matrix comprises a type 1 or type 2 catalytic component (described in more detail below). Preferably, the catalytic substrate should be at or substantially adjacent to the outer surface of the composite (ie, in the composite) Outside the periphery. 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 extent to which the unwanted internal composite diffusion effect is produced. Therefore, it should be understood that the substantial portion of the catalytic substrate is positioned within the perimeter of the composite and/or The appropriate distance or distance will depend on the intended use of the catalytic composite, the overall size and shape of the catalytic composite, and the overall size and shape of the catalytic substrate. Therefore, in the shape and size of the composite, the composite periphery The average thickness (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 perimeter of the composite is preferably between about 10 microns. About 25 〇 from between meters is more preferably between about 1 micrometer and about 150 micrometers. However, depending on the intended use of the catalyst composition, in some cases it may be necessary to substantially distribute the matrix to On the entire forming medium, for example, but not i26426.doc -29- 200843848 is limited to 'in the process of expanding the exposure of reactants and / or reaction intermediates', preferably on the entire forming medium (whether type 1 or type 2) The catalytically active matrix), with a controlled pore size distribution, is preferred but not necessary. The minimum size of the matrix used to produce the shaped body or composite (i.e., the average largest dimension of the matrix particles) is typically between greater than about 0.05 microns and less than or equal to about 150 microns, preferably from about 2 microns to less than or equal to. Between about 15 〇 micro f meters, more preferably between about 2 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, matrices outside of this range may still be effective, for example, in the continuous fiber form described above, without the combination of catalysts. The expected performance of the object has an adverse effect. Those skilled in the art will appreciate that the composite operation may introduce potential mesopores and/or microporosity into the finished composite. However, in a composite process, the functionalization of the porous unintroduced catalyst composition is as described herein.

Surface composition.基质·Matrix surface activation, the matrix used to produce the catalyst composition of the present invention can be activated by one or more first surfaces. The first component has a first type of ion and/or electrostatic interaction with the matrix (" Type 1 ingredients in the previous month J horses). As described in more detail below, a type 1 component such as a flooding may itself have catalytic effect on the right or may be further processed to produce a catalytically active region having an average thickness of about 30 on and/or within the surface of the rolled shell. The nanometer preferably has an average thickness of about 1 and a spoon 20, more preferably an average thickness of 幺, 、, spoon 1 〇 nanometer. For example, in some cases, depending on the intended use of the composition of the catalyst 126426.doc -30. 200843848, the substrate of the powder is suitable for the predetermined circumference and has the appropriate type of cutter and life, The target (iEP), n Wang's pore structure (if any) and isoelectric point: although it may have sufficient surface activity, can be effectively catalyzed. Although it is not necessary, it can be treated to further improve the surface activity of the bismuth/heart. Additionally/modifications and/or possible secondary _ organic coatings or other possible contaminants that may be removed by treatment to remove the performance of any pre-drying catalyst composition. In addition, as described in more detail below, in the case where Type 2 becomes a W-driver integration, depending on the catalyst composition, it is better to use #子父换 (IEX), reverse, ^ _ square Φ, # ^ ^ change (βΙΧ) and/or electrostatic adsorption (EA) 4 the surface of the ribbed shell, these treatment methods integrate the second component of the species into the surface of the US, on the surface of the base and/or inside, The surface of the substrate has an average thickness of the second and the base of the fish, and the interaction between the active and the active regions, on the surface of the base, and/or within the base. For illusion nano, it is preferably $20 nm, more preferably $1 〇 nanometer. The matrix contaminant removal treatment is dependent upon the composition of the material typically found on the surface of the base f and whether the material is expected to interfere with the preparation of the catalyst composition and/or interfere with the desired performance of the catalyst composition for the intended use, Optional contaminant removal. For example, 'typically' 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 126426.doc -31 - 200843848 The primary goal of this treatment is to remove contaminants from the matrix, the conditions of such arduous treatment are not particularly important for successful surface activation of the matrix. ‘In some cases, depending on the nature of the contaminant to be removed from the substrate, the solvent interface, lingual agent, aqueous solution cleaning or other suitable methods can be used to remove contaminants for satisfactory results. However, depending on the degree of calcination used, the substrate is preferably calcined in an oxidizing atmosphere (9) such as in air or oxygen. In addition, it is important to select the calcination temperature to remove the target contaminant, but the satin temperature is also low to avoid the softening point of the material. Generally, the calcination temperature should be at least about 5 ° C lower than the softening point of the selected matrix material. Preferably, the calcination temperature is at least about 1 〇〇t: lower than the softening point of the selected matrix material. For example, when using a type of glass, most of the cannons that are acceptable for removing contaminants from the glazing are 300 C to about 700. . between. Typically, the selected substrate material should be calcined for about 2 to 14 hours and is preferably calcined for 4 to 8 hours. Nonetheless, the calcination time may vary outside of the time range depending on the nature of the substrate obtained and the nature of the target contaminant to be removed from the substrate. Surface activation by ion leaching treatment After any potential contaminants are substantially removed from the substrate, the substrate can be used to generate the surface active state and the desired isoelectric point (&quot;IEP", provided that the substrate is The initial IEP obtained is not within the desired range. However, the substrate received at a certain time may have sufficient surface activity and needs to be further modified (other than described in more detail below) without using the first type. Ion leaching (IEX-1) treatment (this will be discussed first in the other treatments of the following more detailed months). In other words, the matrix element group 126426.doc -32- 200843848, especially on the outer surface or substantially close to the outer surface The composition of the elements may be sufficient to obtain the desired IEP. However, in the case of multiple reports, the 70-prime composition of the matrix will require some modification to change the original IE P and obtain a suitable I. Then follow the catalyst composition. For the intended use, obtain a surface active state that meets the requirements of type and degree. ' = surface active state, in - or a plurality of _ components have (1) first oxidation The interaction between L and (11) of the first type and 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 of W3G nanometers, preferably s. 2() nanometers, more preferably $about nanometers' and thus provide the desired properties of the catalyst composition for the intended use, such as, but not limited to, ^formed or Louise on and/or within the surface of the substrate. 'Lewis' acid position and Buchen, Ster or Lewis position can effectively promote some hydrocarbons, hydrocarbons (such as oxygenated hydrocarbons) and non-hydrocarbon treatment, conversion and / or refining processes. ',, &lt; In other cases, based on the intended use of the catalyst composition, it may be preferred to use one or more ion exchange methods as described below to further treat the surface of the substrate to achieve (1) the same state as the first oxidation state. Or a different second oxidation state, and (ii) a second type of ion and/or electrostatic interaction with the substrate sufficient to produce a catalytically active region having an average thickness on the surface of the substrate and/or within the substrate. It is preferably U0 nanometer, more preferably illusion 0 meters. To the surface activation treatment, the surface activation treatment includes at least one ion/removal treatment to obtain a first or a class 1 ion exchange (IEX-1) matrix. "And it should be understood that if the substrate is suitable for the catalyst The composition reaches 126426.doc -33 - 200843848 For the intended use of IEP, Satoshi is also prepared to explain the first type of substrate, ie: 2:: The sub-leaching treatment is performed by any suitable method. The entire surface of the substrate effectively removes the desired ion species without significantly invading the matrix network (e.g., the LJg T7 / brother's clothing area and/or subsurface area produces any microporous structure). For example, but not limited to, some of the acid substances' are inorganic acid or organic acid, and various are suitable for ion leaching treatment. Preferably, a mineral acid is used, for example: not = nitric acid, phosphoric acid, sulfuric acid, hydrochloric acid, acetic acid, perchloric acid, hydrochloric acid, chlorosulfonic acid, trifluoroacetic acid, and combinations thereof. - usually the concentration of the acid solution used for ion leaching depends on the properties of the substrate (for example, the affinity of the ions removed from the glass network, the strength of the glass after removal of the network ions), the matrix The extent to which the IEP needs to be altered and the intended use of the catalyst composition. Preferably, the concentration of the acid solution used for the ion leaching treatment may be between about 0.5 wt.% and about 5 wt%, more preferably between about 2.5 wt.% and about 25 wt.%, most preferably About 5 wt% to about w%

Between C. The mouth cut can also be used for ion leaching treatment, such as, but not limited to, ethylenediamine oxime (EDTA), yoke, oxalate, polyamine, polyacid, and combinations thereof. The concentration of the chelating agent solution depends on the characteristics of the kebab (for example, the affinity of the ions that are missing from the glass network, the strength of the glass after removal of the network), and the intended use of the catalyst composition. . Preferably, the concentration of the chelating agent solution used for the ion leaching treatment may range from about 0. 001 wt.% to saturation, more preferably from about 〇.〇1 wt.% to saturation 126426.doc • 34· Between 200843848. Usually, depending on the type and concentration of the acid or chelating agent used and the characteristics of the substrate, (d) the heat treatment conditions for the ion leaching treatment, such as heating temperature, heating time and mixing conditions. Depending on the concentration of the acid solution or the integrator solution, the heating temperature varies widely. Preferably, however, the heating temperature suitable for the acid ion leaching treatment is between about 20 C and about 200 ° C, more preferably between about 4 ° C and about 95, and most preferably between about 6 (TC to Preferably, the heating temperature for the chelating agent ion leaching treatment is in the range of from about 2 (rc to about 2 〇〇t &gt; c, more preferably from about 40 ° C to about 90 ° C. The heating time suitable for the ion π-out treatment may vary depending on the concentration of the acid solution or the chelating agent solution and the heating time. Preferably, the heating time for the ion leaching treatment is from about 15 minutes to about 48 hours. More preferably, between about 3 minutes and about 12 hours. Typically, depending on the type and concentration of the acid or chelating agent used and the nature of the substrate (eg, ions to be removed from the glass network) Affinity, the strength of the glass after removing the mesh ions, etc.) and the duration of the heat treatment, depending on the mixing conditions, such as, but not limited to, the mixing conditions may be continuous or broken, and the shell may be mechanically mixed or fluidized. , tumbling, rolling or manual mixing. ,, 'acid or chelating agent concentration, heat The set of conditions and mixing conditions will be determined according to the degree of sufficient ion exchange ("ΙΕχ,") between the acid or chelating agent and the target matrix ion to produce a suitable isoelectric point. Type and extent 'to achieve the surface activity state required for the post-treatment of the substrate or the intended use of the catalyst composition. 126426.doc -35- 200843848 After the ion leaching treatment is completed, the separation is preferably carried out by any suitable method. Substrates for ion leaching, including but not limited to, transition mode, centrifugation, decantation, and combinations thereof. Then 'use one or more suitable cleaning solutions (eg, deionized water and/or a suitable water soluble organic solvent such as methanol, The substrate subjected to ion leaching treatment is washed with ethanol or acetone and dried at a temperature of about room temperature to 110 C for about 20 to 24 hours. The reverse ion exchange treatment may in some cases depend on the use of the catalyst composition, possibly The method of scooping is to carry out reverse ion exchange ("Βιχ") or two-step, sub-twisting treatment on the remotely determined substrate (collectively referred to herein as "ΒΙΧ treatment"). Usually referred to as (but not limited to) ', counter ion &quot; exchange, because the ion leached matrix is mixed with a salt solution (such as NaCl) including the initially removed ions, and is processed again and removed from the base. In addition to this ion (such as the heart +) will then be returned or returned to the base. It is not clear whether the ions removed from the matrix will return to the phase that originally occupied the T ^ image in the matrix.冋 position. However, regardless of whether the originally replaced ion is m or not, the mouth is completely or partially changed position or the position is not changed at all, it should be understood that the BIX treatment of Ichimachi + Azumi is covered by any The possible ion-catalyst compositions are all of the types of salt solutions used to treat the substrate subjected to ion leaching, and the type of ions that will be used for the reverse ion exchange. Preferably, only the counter ion exchange of the ions is carried out. In the case of the case, it may be necessary to carry out the counter ion exchange of the two or more ions. Any one of the above-mentioned early, jubilant steps The ions removed by the π-out process can be subjected to counter ion exchange in I26426.doc -36- 200843848. Some examples of the plasma include, but are not limited to, Group 1 (former Group IA) alkali metal ions such as lithium and sodium. And potassium ions, and alkaline earth metal ions from Group 2 (formerly iia), such as barium, magnesium, calcium ions, NH4 + and silk ammonium cations, and small organic polycations. Preferably, metal ions and NH/ is the preferred target ion for hydrazine treatment, while Na+ and ΝΗ/ are preferred cesium ions, and Na+ is better for strontium ions. Generally, the concentration of salt solution used for BIX treatment depends on the ion. The type of matrix to be treated by BIX for leaching and the relative affinity of the BIX ions for returning to the ion leaching matrix are also independent of the sites in the 负ιχ ion back: basal negative network (eg, Na+ for matrix comparison) Mine phase Affinity. For most types of glass substrates, such as, but not limited to, AR-type glass, bismuth-type glass or quartz glass, ΒΙΧ-salt solution of 〇················· Preferably, about 〇〇5 coffee 1 to 3 mο 1 /L Β IX-salt solution is better. Typically, it will be selected according to the type and concentration of the BIX_salt solution used and the characteristics of the substrate. The heat treatment conditions of the BIX treatment, for example, 2 heat temperature, heating time, and mixing conditions. Preferably, the heating temperature for the hydrazine treatment using the fresh salt solution can be between about 2 (TC to about 2 Torr (TC), more Preferably, the heating time of the treatment may vary depending on the concentration of the solution and the selected heating temperature. Preferably, the addition of the mx treatment is between about 5 minutes and about 24 hours. More preferably, between about 30 minutes and about 8 hours _ 126426.doc 200843848, depending on the type and concentration of the BIX solution used and the matrix properties (eg 'the affinity of the ions to be removed from the glass mesh, The strength of the glass after moving the mesh ions, etc.) and the duration of the heat treatment, the heart Bonding conditions such as, but not limited to 'mixing conditions may be continuous or intermittent, but also may be a mechanical mixture, fluidizing, tumbling, rolling, or manual mixing.

U In summary, the concentration of BIX salt solution, the heat treatment conditions and the mixing conditions are also substantially determined based on the return of a sufficient amount and the distribution of a sufficient amount of meth-ion back to the matrix, and the position of the ion in the matrix network ^ turn off. A sufficient amount of BIX_ionic system is returned and distributed to produce the desired: what type and extent of surface electricity&apos; to produce a surface active state desired for the intended use of the post-treatment or catalyst composition of the substrate. By adjusting the pH to adjust the surface charge of the substrate to a lesser extent, the negative surface charge on the substrate is used to support electrostatic interaction or affinity with positively charged components (eg, cationic alkaline earth metals, cationic transition metal components, etc.). . However, for some potential catalysts, and for oral applications, it may be necessary to use positive surface charges to support negatively charged components (eg, anionic transition metal oxygen ions, sulfate anions, noble metal polyhalide anions, etc.) Electrostatic interaction or affinity. By changing the value of the matrix/ruthenium mixture subjected to ion leaching to a level lower or higher than the isoelectric point of the matrix (, IEp", the surface of the substrate is changed to a net positive state or a net state. Negative state. Think back, IEP is also known as zero charge (''ZPC,'). Therefore, in other words, IEP (or ZPC) can be regarded as material 126426.doc -38· 200843848 material has a net zero on the surface at initial humidity The _ value of the surface charge. Therefore, adjusting the pH of the matrix/IEX water mixture to be greater than the value of the matrix iEp (or W) can produce a net negative surface charge on the substrate. In addition, the matrix/ΐΕχ The pH of the water mixture is adjusted to be less than the ρΗ value of the matrix ΙΕρ (or zpc) to produce a net positive surface charge on the substrate. For example, but not limited to, if the IEP of the AR-type glass is equal to 9.6, if the ion leaching is performed The ρΗ value of the treated AR-type glass is adjusted to the value of 1)11 of 9.6, which will produce a net negative surface charge on the surface of the glass. Depending on the iEp distribution of the Bahan-type glass, the preferred way may be The pH is adjusted to be greater than one or two or more pH units of the IEp of the substrate to ensure The surface charge is fully supported. The type of solution used to effect the pH adjustment will depend on compatibility with other reactants, glass stability and desired charge density, among other factors. Generally, any dilute base can be used. To adjust the surface charge of the substrate to the right side of its IEp (ie, to produce a net negative surface charge), and any dilute acid can be used to adjust the surface charge of the substrate to the left side of its IEP (ie, to produce a net positive surface charge). Acids and bases or organic acids and bases can be used in dilute concentrations, and inorganic acids are usually preferred. Generally, the concentration of the dilute acid solution or the dilute alkali solution will depend on the type of acid or base used, its dissociation constant and Obtaining the pH of the desired surface charge type and density. In some cases, it may be necessary 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 the electrostatic adsorption (EA) type of integration mechanism is likely to not occur. However, in the case of not being bound by theory, in the exchange of 126426.doc -39- 200843848 table Direct ion exchange (ΙΕΧ) or reverse exchange (BIX) may occur at the surface location resulting in surface integration of the catalytic component or precursor, which may be physically and/or chemically different from electrostatic adsorption ( EA) the same components integrated under the mechanism. For example, some 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 surface portion of the substrate. An appropriate but effective exchange site of ruthenium or osmium, such as, but not limited to, a ruthenium moiety, such as a decyloxy (-Si-0-Na+) moiety, including at least a portion of a positively charged catalytic metal or metal complex precursor. (For example, but not, Pd (NH3 〇 substituted Na+ ion, which in turn produces a matrix with a catalytically effective amount of catalytic component. By adjusting the pH to control the surface charge of the substrate treated with ruthenium, as in the case of IEX treatment or second treatment (&quot;iex_2 treatment, as discussed below), adjustments may be required for certain treatments. Value, but not required. Similarly, depending on the type of bismuth ion that is to be integrated into the surface during the ΙΕΧ-2 treatment and the type of ΒΙΧ·ion exchanged, the degree of pH adjustment required depends on the IE p,# Τ ϋ p of the matrix. Jfcl IL * -r- ^ Tube 曰 IEP contrast surface charge distribution curve and the type of charge required. The type of solution used to carry out the ρΗ value adjustment will depend on the compatibility with other anti-objects and the matrix. Stability within the range of ρΗ and the desired electrical η mountain and other factors f. Generally, any thin test can be used to adjust the surface charge of the substrate to the right side of its IEP (ie, to produce a net negative surface charge). : Sparse fee can be used to adjust the surface charge of the substrate to the left side of the money (that is, to produce &quot; surface charge). The inorganic acid or base or organic acid or base can be used at a concentration of 126426.doc -40-200843848 degrees. Usually, dilute Concentration of the solution or dilute alkali solution, will depend on the type of acid or base used, its dissociation constant and the pH suitable for obtaining the desired type and density of surface charge. ΠΙ · Type 2 precursor component integration processing

Whether the substrate surface active is received as is, or is subjected to ion leaching (ie, IEX-1 treated substrate), or via Βιχ, preferably, in (1) second ion exchange (ΠΙΕΧ-2Π) treatment, ( Ii) electrostatic adsorption (ΕΑ) treatment or (out) the use of at least one second component precursor ("type 2 component precursor") in combination with certain ΙΕΧ-2 and hydrazine treatments to further treat the substrate so that one or more A component precursor is integrated on and/or within the surface of the substrate having a second ion and/or electrostatic interaction with the substrate. Next, according to the intended use, certain Type 2 component precursors can produce catalytically active regions without further processing, or can be further processed to produce catalytically active regions comprising one or more Type 2 components. However, whether the catalytically active region consists of a U) type 2 component precursor, (b) consists of a type 2 f component resulting from a type 2 component precursor, or (4) consists of a combination of (4) and (b), catalyzed. The average thickness of the area on and/or within the surface of the substrate is "about 3 〇 nanometers, and the car is preferably &lt; about 2 〇 nanometers, more preferably about 1 〇 nanometer. As mentioned above, in some In this case, the substrate that is received as received or ion leached may have catalytic potency depending on the intended use of the catalyst composition. = 1 For many potential applications, a better way is to select the IBE for the selected base. 2 and/or EA treatment, such as, but not limited to, a plurality of reactions (4), «sexuality and/or efficiency" suitable for the process of the catalyst composition of the present invention, by replacing at least a portion of the first component ("type component" ;) and 126426.doc •41 · 200843848 The two components of the brother ("type 2 ingredient") are significantly improved by integration with the surface of the substrate.

C*, without being bound by theory, undergoes direct or indirect ionic interactions by specific ion exchange sites on the surface of the substrate and/or on the opposite side of the internal charge. H is electrostatically charged from the surface of the oppositely charged substrate. Adsorption interactions' and combinations of certain ionic and electrostatic adsorption interactions or some other type of precursor to be understood_charge-surface interactions': type component precursor ions can be integrated. However, irrespective of the nature of the interaction, the substrate received as received, the substrate treated with IEX-1, or the substrate treated with BI:-produces the second precursor charge-surface interaction, 2 The type component precursor may thus produce a catalytically active region or an average thickness of the catalytically active region on and/or within the surface of the substrate of &lt; about 3 nanometers, preferably about 20 nanometers, more preferably &lt; About 10 nm. Only in order to facilitate the following discussion's and is not intended to limit the scope of the invention described herein, ΙΕχ_2 is used herein to collectively refer to the broad range of charge-surface interactions or type 2 precursor interactions commonly referred to as type 2 precursor precursors. Interaction. A〆 In general, the type of salt solution used to treat the IEXq-treated or ΒΙχ-treated substrate will depend on the type of ion to be ion-exchanged in the ΙΕΧ-2 treatment. Alternatively, the ions will be ion exchanged or, in some cases, two more "Ion's money, 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 4 ΙΕχ-2 treatment herein is referred to as two ion exchanges or two positive and two treatments. Therefore, in the case of three different types of component precursor ions and matrix integration 126426.doc -42- 200843848, the ΙΕΧ-2 treatment is called three-ion ion exchange or three ΐΕχ·2 treatment. Type 2 Ingredients and Precursor Description Any salt solution of ΙΕΧ 2 ions, if it is chemically sensitive to the surface-replacement ions received, treated or BIX-treated as received, or has a charge affinity to achieve The electrostatic interaction of the treated or treated substrate surface can be used. Γ Therefore, ΙΕΧ-2 ion can be used as a precursor to the type 2 component. As described above, the precursor of the plasma ΐΕχ_2 (i.e., the precursor of the type 2 component) may have catalytic effect according to its predetermined use. If so, the plasma IE X-2 precursor can be combined with a certain type of catalyst. The type 2 component is the same as its ruthenium drive' but the ion can also function as a trace 2 precursor in the preparation of another type of catalyst composition process. However, in general, ionic IEX-2 precursors (which can be used to obtain a type 2 component that is integral with the surface of the substrate) include, but are not limited to, Blenzel or Lewis acid, Bruce: or Lewis base, noble metal cations and Precious metal complex cations and anions, transition metal cations and transition metal complex cations and anions, transitional oxyanions, transition metal chalcogenide anions, main oxygen anion ions, rare earth ions, rare earth complex cations and anions ^ Combination. Similarly, depending on the intended use of the catalyst composition, some of the ΐΕχ_ itself has a catalytic effect in the precursor state' in combination with a suitable matrix to produce a Type 2 component. Optional ionic ΙΕΧ-2 precursors with no efficiencies, some examples include but not limited to stell or Lewis acid, Blenz or Lewis, precious metal cations 126426.doc -43 - 200843848 Main group of oxygen anions, halogens and combinations thereof. Transition metal cations, transition metal oxyanions, ions, rare earth hydroxide ions, rare earth oxides can be used as examples of certain noble metals and transition metals of type 2 precursors, including but not limited to the first to the fourth group (formerly Articles _, Di, Vb, VIb, Vb, and Dichu), such as turning, turning, recording, money, silver, nails, chains, copper, rebellion, winter, and nickel Ionic salts are especially preferred. For the sake of convenience, the elements of these families are exaggerated, and the use of the International Union of Theoretical and Applied Chemistry (IUPAC) is named after the continuation of the #α 7卩a system of the 兀 族 family number in PP arll.lanl. Query in the chemical element periodic table (and display the previously used family number) shown in gov/pen〇dlc/default htm. Copper, silver, gold, ruthenium, osmium, iridium, chain, moth, Ming, iron, fierce, ionic salt and complex ion salt and combinations thereof. For ΙΕχ_2 treatment, palladium, platinum,

ί can be used as an example of some transition metal oxyanions of type 2 precursors, &lt;not limited to ionic salts of Group 5 and Group 6 (formerly Groups and Groups), such as VCV·, W(V· , H2Wi2〇4q6_, Μ.#, M〇70246, Nb6〇196·, Re (V and combinations thereof. For IEX-2 treatment, ionic salts of bismuth, molybdenum, tungsten and vanadium are especially preferred. Certain transition metal chalcogenide anion shells H of the constituent precursors 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 the precursor include ionic salts limited to the 16th private (ie, vu group of hydrazine), such as s〇42_, Ρ Ο +4-4, and combinations thereof. For IEX-2 treatment, S042 The ionic salt is especially preferred. 126426.doc -44- 200843848 can be used as a precursor to a type 2 component - an example of a card II ion, including but not limited to the group 17 (formerly Group VII) _ your 'ion Salts such as F·, Cl·, Br·, Ι· and combinations thereof. It is especially preferred for the treatment of ionic salts of t and ci with ΙΕΧ-2. Examples of certain rare earth ions and rare earth complex cations or ions of the precursor, including but not limited to lanthanide and (iv) element ionic salts such as La, Pr, Nd, Pm, q - (4), Sm, Ell, Gd, Tb , Dy, H〇, Er, Tm, Yb, Lu, Th, U, and combinations thereof.

Examples of certain transition metals that can be used to produce transition metal-carbides, transition metal-tellurides, transition metal-borides, and transition metal-phosphides as type 2 components, including but not limited to chromium, molybdenum, tungsten, rhenium, Button, iron, ionic salts of nickel, and combinations thereof. IEX_2 Treatment Description Typically, the concentration of the salt solution used for IEX-2 treatment depends on the type of substrate that is treated or BIX-treated and treated by IEXj and used to interact with the substrate treated with IEX-1 and/or Or the relative affinity of the integrated positive 乂_2 ion. For most types of glass substrates (such as, but not limited to, ar type, A type, or soda-iime glass), about 1 wt.% to saturated IEX-2 salt solution is preferred. The salt solution of about 1 wt.% to 5 wt.% ΙΕχ_2 is more preferred. However, depending on the functional surface concentration of the catalytic component necessary to achieve the intended use of the catalyst composition, the ΙΕΧ-2 salt solution may have a monthly b of less than 〇 〇 〇 1 wt.%. If multiple ion types are exchanged with the substrate, either simultaneously or sequentially, the concentration of the salt solution will be based on the relative loading of the precursors of the various components on the substrate and the matrix is applied to one component precursor versus the other. 126426.doc -45- 200843848 The relative affinity of the precursor is 敕 θ positive. For example, it is not limited to IEX-2 treatment (that is, two different, matrix integration in two treatments) or - knife precursor and call or or one-human IEX-2 treatment (ie, three-catalyzed The composition precursor and the IEX] or postal treatment group species (4) solution (four) degree will depend on the target relative concentration of the component precursors suitable for T integration and the surface affinity for various separations.

Typically, heat treatment conditions suitable for τργ 丄 and 辰 -2 treatments, such as heating, are selected according to the type of 'state' and χ-2 salt solution and the characteristics of the bismuth and matrix. Temperature, heating time and mixing conditions. Preferably, the heating temperature suitable for the ΙΕΧ_2 treatment using an acid may be between about 2 Torr and about 2 (K) t, more preferably between about 3 and about (4). The heating time for the IEX-2 treatment can vary depending on the concentration of the IEX-2 salt solution and the selected heating temperature. Preferably, the heating time suitable for the ΐΕχ_2 treatment is between about 5 minutes and about 48 hours, more preferably between about 3 minutes and about 5 hours. The system will be based on the type and concentration of the ΙΕΧ-2 salt solution used and the specificity of the matrix|± (for example, the affinity of the ions to be removed from the glass mesh, after the annihilation, Strength, etc.) and the duration of the heat treatment, depending on the mixing conditions. For example, without limitation, the mixing conditions can be continuous or broken, or mechanical mixing, fluidization, tumbling, rolling, or manual mixing.衾· ^ 丫' σ ' IEX-2 salt solution concentration, heat treatment state and combination of mixing conditions 5 each, only on the shell based on the integration of a sufficient amount of ΙΕΧ-2 ion and ΙΕχ-2 on the substrate and / or The distribution of ions is determined irrespective of the nature of the physico-chemical bonding of the surface of the substrate 126426.doc • 46-200843848 to produce the desired type and extent of surface charge to produce the desired use for the intended use of the catalyst composition. Surface, tongue state. Adjusting the surface charge of the substrate by adjusting the pH As mentioned above, considering the 2蜇 component precursor that will be integrated with the surface in the second IEX ("IEX-2") treatment, the degree of pH adjustment required will usually depend on ' The IEP of the matrix, the IEP of the matrix, the surface charge distribution curve and the desired charge type. For example, but not limited to, for a substrate having an IEP equal to 8, preferably, the pH of the matrix/IEX-2 mixture is adjusted to be between about 8 and about 12, more preferably between about 9 and about 11. The type of solution used to effect the pH adjustment will depend on compatibility with other reactants, stability of the matrix over the relevant pH range, and desired 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 side of its IEp (ie, to produce ϋ 'The positive surface charge of the battle.' The inorganic acid or base or the organic acid or base can be both concentrated and used, and is generally preferably an organic test. 35, often, the trace of a dilute acid solution or a dilute solution will depend on the type of acid or test used, its dissociation constant, and the pH at which the desired surface charge type and density are obtained. Preferably, after the 1EX-2 treatment is completed, the matrix treated with the core 2 can be separated by any suitable method including, but not limited to, over-twisting, centrifugation, decantation, and combinations thereof. Then, the substrate treated with ΙΕχ_2 is cleaned with one or more a human, suitable cleaning solutions (such as distilled water or deionized water, dilute alkali or dilute acid and / or a suitable water-soluble organic solvent such as methanol, ethanol or acetone). 126426.doc -47- 200843848 Wash, sub-dry at a temperature of about no c for about 2 to 24 hours. IV. Post-deep treatment description As a matter of course, the substrate treated by IEX.2 can be separated|can be dried only, calcined, calcined under oxidizing conditions, then reduced or further oxidized, • (d) reduced or in the case of drama Oxidation without calcination. The transition gold (Λ 35 ion, oxyanion and cations) of the surface deposition chamber can be carried out in the gas phase or liquid phase according to 'supremely, with suitable reduction, sulfurization, carbonization, nitridation, filling or chemical reagents (-(1)(4) reagent). / or a reaction of a sulfur anion to produce a corresponding catalytically effective metal sulfide / sulfur oxide, metal carbide / carbon oxide, metal nitride / nitrogen oxide, metal boride or metal phosphide component. Without limitation, the purpose of post-precipitation calcination treatment is essentially to decompose metal counterions or ligands, and to integrate metals, metal oxides, metal chalcogenides, etc. more closely with the surface of the substrate, and to remove any prior drying. Residual water removed during treatment. c Calcination conditions for substrates treated with IEX-2 are not particularly important for successful surface activation of the substrate. However, such conditions should only be sufficiently stringent to produce at least a catalytically effective amount. a catalytically active region of a precursor having a precipitated component. However, in the case of calcination, the substrate is first in an oxidizing atmosphere (for example, in air or oxygen). Calcination. In addition, the important system is to choose a high enough satin temperature to ensure that the precursor of the type 2 component of interest is oxidized and any residual water is removed (if any residual water remains), but the satin temperature should also be Low enough to reasonably avoid the softening point of the matrix and the decomposition of the undesired precipitated precursors. 126426.doc -48 - 200843848 For example, but not limited to, the precipitated sulfate requires calcination conditions to decompose the bound cations and fix the sulfate &amp; surface i, but #, etc. conditions must not significantly decompose the sulfate into volatile sulfur oxides. Similarly, metal oxyanions require calcination conditions to decompose the bound cations and immobilize the anions as oxides on the surface, However, the conditions shall not be so strict that the metal oxide volatilizes from the surface or causes the metal oxide to dissolve into the matrix. Finally, the precious metal and the complex compound should be calcined under the following conditions: decomposition of the ligand and anion present, but not strictly to concentrate the precious metal On the surface. For this reason, as explained in more detail below, the noble metal is preferably directly returned without calcination. Typically, 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, more preferably between about 2 Torr and 600 ° C, optimally at about 300. (: Between 5(10) and c. Typically, the IEX-2 treated substrate is calcined for about 24 hours, preferably calcined for about 2 to about 12 hours. Nevertheless, the matrix-integrated type 2 component As such, the calcination time can vary outside of these ranges. Typically, but not limited to, the post-precipitation reduction treatment is intended to at least substantially (if not a king) catalyze the catalyzed component (eg, metal, metal oxide or metal sulfide) Reducing to a lower oxidation state integrated with the surface of the substrate. Suitable reducing agent is not limited to ccmH" h2 is a preferred reducing agent, and its flow rate is preferably about 001 L / hr per gram of substrate to Approximately 100 [/ between ''s better flow rate between 0.1 L/hl1 L/hr per gram of substrate. Typically, the reduction temperature should be between generations (four generations), provided that the temperature chosen is 126426.doc -49- 200843848 and the temperature selected is at least 1 &£&gt;c lower than the softening point of the matrix. Typically, the substrate treated with IEX-2 is subjected to a reduction treatment of from about 1 hour to about 48 hours, preferably from about W to about 8 hours. Alternatively, the ruthenium-2 treated substrate can be treated by solution phase treatment. Originally, the solution phase treatment uses a soluble reducing agent (such as, but not limited to, hydrazine, sodium hydride, hydrogenation, and combinations thereof) in a suitable solvent ( For example, water or B (6) • is carried out. f ^ but not limited to, after the temple is very, the purpose of the reaction treatment is to reduce the metal ions and metal oxygen while additionally reacting the reduced metal with a reagent containing a lower atomic amount of _lmNG element. Anion and/or metal sulphide anion In some 6 cases, direct-IDING will occur without simultaneous reduction of the metal oxidation state, such as certain sulfidation treatments. Typical gas phase-IDING reagents include, but are not limited to, hydrogen sulfide , methyl mercaptan and dimethyl sulfide (sulfiding reagent), ammonia (nitriding reagent), methane, ethane and other light hydrocarbons (carbonizing agents). These gas-IDING reagents can be at ambient pressure V or Directly reacting with IEX-2 treated substrate under pressure, or reacting with IXX_2 treated substrate in a gas mixed with inert gas or hydrogen to produce the corresponding sulfide, carbon Compounds or nitrides. Potentially catalytically active parts - IDED products (including sulfur oxides, carbon oxides and nitrogen oxides) can also be produced by: receiving and obtaining the substrate substantially as it is, via IEX- 2 treated integrated matrix, IEX-2 treated satin scallop or IEX-2 treated reducing matrix for incomplete reaction. Metal can be produced by two ion exchange (twice ΙΕχ_2 treatment) reduction treatment of the substrate A phosphide, wherein one ΙΕΧ_2 treatment is one or more transitions 126426.doc -50-200843848 metal ions, and the other -1EX_2 treatment is a lyon ion. Preferably, the two IEX-2 treatments can be performed sequentially. Alternatively, the metal dish can be used to produce the desired metal phosphide by using a vapor phase fill reagent such as, but not limited to, hydrogen (pH). For example, a single ion can be carried out with the desired transitional genus in a suitable oxidation state. The exchanged substrate (matrix treated with a single m) can be further treated with PH3 to produce the desired metal phosphide. The solution phase treatment can be used to produce metal sulfides, metal deletions and metal compounds. Forming a knife. Typical solution treatment for producing metal sulfides includes, but is not limited to, treatment of IEX_2 treated metal·ion-integration groups at an effective concentration of hexamethyldisulfanesulfane organic solution at room temperature to reflux temperature. The catalyzed 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 that produce cleavage include, but are not limited to, for IEX-2 treated metal-ion-integrated substrates, The sodium borohydride or potassium borohydride aqueous solution is treated at room temperature to reflux temperature over a period of time effective. Typical solution phase treatment for the formation of telluride includes in the range from room temperature to reflux 'for IEX-2 treated metal - The ion-integrating substrate is treated with an aqueous solution of sodium hypophosphite for a time sufficient to produce a catalytically effective amount of a catalytic component on and/or within the surface of the substrate. V. Catalytic active region indicates that the catalytically active region resulting from any of the above substrate treatments will have (1) an average thickness of less than or equal to about 30 nm, preferably S of about 20 nm, more preferably S of about 10 nm. And (ii) catalyzing an effective amount of at least one catalytic component. Preferably, XPS spectroscopy is used to determine the average thickness of the catalytic region, 126426.doc -51 - 200843848 x P s spectroscopy uses a layered residual technique called the stencil depth distribution (the analysis method will be provided in the examples below) More detailed below). However, other analytical techniques known to those skilled in the art can be used to determine the general location of the substrate surface associated with the catalytic component contrast component. Therefore, the average thickness of the I-catalyzed region can be determined using, for example, but not limited to, transmission electron microscopy (TEM) or scanning TEM (STEM, also described in more detail below). Those skilled in the art have a thorough understanding of XPS or TEM procedures. It should be understood that in the extreme case, regardless of whether the catalytically active region is produced by IEX] treatment or IEX-2 treatment (with or without hydrazine treatment), for the catalyst composition of the present invention, the thickness of the catalytically active region Generally, (4) does not pass over the surface area of the matrix of the kappa shell or does not exceed the surface of the substrate by about 3 nm, preferably not more than about 2 nm, more preferably not more than the thickness of the nanometer. 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: (a) be on the outer surface of the base g, and in the presence of any pores, in the pore walls of the matrix (b) in the surface region of the substrate, that is, about % nanometer below the outer surface of the substrate, preferably about 2 nanometers below the outer surface of the substrate, more preferably about 10 nanometers below the outer surface of the substrate; In the presence of any pores, about 30 nm below the surface of the pore wall of the matrix, preferably about 20 nm below the surface of the pore wall of the matrix, more preferably about 1 nm below the surface of the pore wall of the base f, but below the surface of the substrate surface. Above (C) above or above the outer surface of the substrate, t is partially on or above the surface of the pore wall of the substrate, and partially in the surface area of the substrate 126426.doc •52·200843848, or (d) A combination of (a), (b) and (c). Generally, the amount of the catalytic component may range from about 0.0002 wt.% to about 5 wt.%, preferably from about 〇·〇〇〇2 _% to about 2 wt.°, whether it is a type 1 component or a type 2 component. /. More preferably, it is between about 0.0005 wt.% and about 1 wt.%. Moreover, the catalytically active regions of the catalyst compositions of the present invention may be continuous or discontinuous. In the case of no 5: rational constraints, 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 by a continuous or broader continuous catalytically active region. And in some cases more effective. The extent to which the catalytically effective region covers the outer surface of the substrate can range from as low as 0.0001% coverage to as high as 1% coverage. Preferably, the extent of surface coverage outside the catalytically active region is between about 0.0001% and about 10%, more preferably between about 00001% and about 1%. However, without being bound by theory, it is believed that the catalyst composition, especially the J system / the catalyst composition with a lower catalytic component wt.% loading, may promote I It is stronger because the catalytically active regions on and/or within the treated substrate 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 possible information for the developer to state 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 large. The sickle is unpredictable. Nevertheless, without being bound by theory, it is believed that the functional surface activity of the catalyst compositions described herein will allow for the integration of the catalytic component with the matrix 126426.doc-53 as the catalyst composition promotes its intended process reaction. - 200843848 The charge and / or geometric positioning and other composition characteristics vary significantly. Thus, it is to be understood that the scope of the invention described herein extends to all of the catalyst compositions produced by the claimed compositions under steady state reaction conditions. Application of νι·catalyst composition in hydrogenation process..................................................................................................................................................................................................................................................................................................................................................................... Diffusion is limited by the limit). However, such catalyst compositions can also be used in processes that are not limited by diffusion. For example, if not limited, some processes require only a single type of catalytic composition to provide a single type of catalytic interaction to help reduce the activation energy of a process reaction. Therefore, the lower activation energy allows the process to have better thermodynamic properties (for example, driving the 曰i column of the 裎 柱 而 而 ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ' ' ' ' ' ' ' ' ' ' ' ' ' Cost-effectiveness. Non-selective hydrogenation (or simply "hydrogen gim") The above-mentioned catalyst composition can be advantageously used for the treatment of hydrocarbons, hydrocarbons and 1 field - dip. Refers to a group of compounds consisting only of carbon atoms # M ', (C) and helium atoms (H), and the term "miscellane" as used herein refers mainly to carbon = \ _, but also contains carbon and hydrogen. : to the sub-children (such as but not limited to oxygen (〇), nitrogen (N) and / /" in the hydrogenation process, suitable for the use of the above type: contact: compound. Contains hydrocarbons and / or (d) Μ, touch The medium composition is hydroquinone y, and the I-flow is generally included and ancient 4 «from 1 carbon atom and possibly - /, there are about 1 to 30 hetero atoms (such as oxygen, but in some cases Shovel, &amp;, etc., J J 匕 more than 3 屌 carbon 屌 early t hydrogenation sites, in the atom, hydrocarbons have at least one desired product, yield and / or process efficiency of I26426. Doc -54- 200843848 Easily hydrogenated under suitable hydrogenation conditions (described in more detail below) Process streams include, but are not limited to, feed streams, medium A transfer stream, a recycle stream, and/or a discharge stream. As used herein, a hydrogenatable site refers to an atomic position having at least one carbon atom (c) or a hetero atom, but is generally a carbon-containing atomic position, and a hetero atom For (but not limited to) oxygen (〇), nitrogen (N) or sulfur (8). 'How to make it, the chemical sites have at least one degree of unsaturation, and

Under the reaction conditions, at least partial Z saturation is easily achieved when the catalyst composition is involved.

Ο In addition, the extent and type of unsaturation in the smoke may vary. Therefore, there may be continuous (only continuous double-double bonds), common or interval- or multiple double bonds of saturated and/or substituted carbon and/or: bond sites. The process stream suitable for hydrogenation may also have an olefin or multiolefin, an aromatic furnace or a cyclic olefin, an alkyne or a mixture of hydrocarbons and/or have at least one which may be suitable for use with a catalyst composition of the above type. Hydrogenated hydrocarbons and/or heterohydrocarbons include, but are not limited to, olefinic, di- and dilute hydrocarbons, poly-saturated hydrocarbons, cyclic olefins, aromatic hydrocarbons, private, unsaturated vegetable oils, and hydrogenatable oxygenates. Chlorinated oxygenates include, but are not limited to, hydrazine, light, acid, and other miscellaneous gases having one or more heteroatoms other than oxygen or sulfur. A preferred class of hydrocarbons suitable for hydrogenation using a contact group of the above-described type of strontium manganes is a normal chain hydrocarbon having from 2 to 20 carbon atoms, a normal chain polybasic hydrocarbon, and a normal chain; 6 to 12 (substituted or unsubstituted) aromatic hydrocarbons of carbon atoms. More preferably; n-hydrocarbons having from 2 to 15 carbon atoms, normal chain polyterpenes, alkene (tetra) scent, positive-chain chunks, olefinic acids and dilute hydrocarbons and having 6 to 8 carbons 126426.doc - 55- 200843848 Aromatic aromatic hydrocarbons. A hydrogenation zone having one or more reactors of the various types is used; ^ should = the stream can be maintained under chlorination conditions). The contact compound is in full contact (hereinafter detailed in the bed system:: the bed system, the mobile batch operation is carried out.... The various catalyst complexes in the original bed system, the fixed bed _, - -... The required reaction temperature is then flowed into the chlorination zone containing the solid catalyst hard bed. The chlorination zone itself may include one or more: a separate reaction zone 'with heating means between them' to ensure each reaction The zone input maintains the desired reaction temperature. The hydrocarbon can contact the catalyst bed in an upward, downward or radial flow. Preferably, the hydrocarbon flows radially through the catalyst bed. The contact catalyst can be liquid or gas. a liquid mixed phase or a gas phase, preferably a gas phase. Under which hydrogenation conditions, the above-mentioned contact sites can be used in many gasification processes 'also depending on the desired product' yield and/or process efficiency, The hydrogenation conditions include (a) a temperature range generally from about 538 to about 538. (b) a pressure range of from about 1 〇 1 kPa to about 13,789 kPa, and (4) a molar ratio of hydrogen to a chlorinated hydrocarbon is generally about 〇.1:1 to about 20:1, (4) The liquid hourly space velocity (LHSV) in the reactor is generally in the range of约·〇 hr·1 to about 20 hr1. Examples The present 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. It is understood that all within the spirit of the invention The changes are intended to be protected, and therefore it is not considered that the present invention is limited to such examples. Catalyst Compositions with Large Porous Glass Substrate Example 1 Large Porous Glass was obtained from Dennart Poraver. A macroporous foamed soda lime glass sample, i.e., glass beads having an average diameter of about 4 to 125 microns.

u In the first step, the macroporous glass sample received as it is and not calcined is subjected to acid leaching. Approximately 25 grams of macroporous glass and 3 liters of 5·5 wt% of nitric acid were placed in a 4 liter plastic wide-mouth container. The plastic container was placed in a ventilated oven at 30 ° C for 30 minutes and shaken slightly by hand every 1 minute. After the acid treatment was completed, the sample was filtered using a Buchner funnel with Whatman 541 filter paper and washed with about 7.6 liters of deionized water. Then, the acid immersed sample was dried for 22 hours at a temperature of 11 (rc). In the second step, the acid leached macroporous glass was subjected to ion exchange (IEX) treatment. In this example, 'dihydrogen oxygen was used. Tetraamine palladium [Pd(NH3)4](OH)2 was prepared in 80 ml of hydrazine, 1 wt% palladium solution for ion exchange (&quot;IEX solution&quot;). 4 g of macroporous glass was added to the ion exchange solution ( ''Glass/ion exchange mixture'). Measure the pH of the glass/ion exchange mixture and measure about 1 ()·3. For &amp;, transfer the mixture to a 15 〇 ml plastic wide-mouth container. Place the plastic container in a 5 (arc selected box at 2^', shaking it by hand every 3G minutes. After the ion exchange process is completed, use a Buchner funnel with Whatman 541 filter paper to pass the glass/ion exchange mixture. And use about 3.8 liters of deionized water to clean. Then, at 126426.doc -57-200843848 1HTC, the ion exchange glass sample is dried for 22 hours. The second step is to reduce the ion exchange glass, where the ion exchange glass First in an air atmosphere with an air flow rate of 2 L/hr The mixture was calcined at a temperature of 3 ° ° C for 2 hours, and then reduced under a hydrogen gas flow rate of 2 L / hr of hydrogen gas at a temperature of 300 ° C for 4 hours. Inductively coupled plasma-atomic emission spectroscopy The method (ICp_AES) analyzes the result of the mouth-freeness of about 0.098 wt.% 〇jr, example 2 \ 4 on the large-porosity glass, the large-porosity foamed soda-lime glass sample produced by Dennert Poraver Glass beads with an average diameter of about 40 to 125 microns. In the first step, the macroporous glass sample received as received and not calcined is subjected to acid leaching treatment. About 25 grams of macroporous glass and 3 liters of 5·5 wt% The nitrates are placed in a 4 liter plastic wide-mouth container. Place the plastic container in a 30 C ventilated oven for 30 minutes, and shake it with a hand for 1 〇 minutes. The sample was filtered using a Buchner funnel with Whatman 541 filter paper and rinsed with about 7.6 liters of deionized water. The acid immersed sample was then dried for 22 hours at a temperature of 110 ° C. The second step, The acid-impregnated macroporous glass is subjected to ion exchange treatment. In this example, difluorotetramine palladium [pd(NH3) small ο) was used: 80 ml of a palladium solution of 〇·ΐ wt.% was prepared for ion exchange (, ΙΕχ solution). 4 g of macroporous glass was added. Ion exchange solution (,, glass/ion exchange mixture). Measure the value of the glass/ion exchange mixture to a value of about 8.1. Then, transfer the mixture into a 15 liter plastic wide-mouth container. 126426. Doc -58- 200843848 The plastic container is placed in a 5 ° ° °, s, air oven for 2 hours, shaking slightly by hand every 30 minutes. After the ion is replaced and the process is completed, use

Whatman 54 1 filter paper is celebrated, Chongshi leak + filter glass / ion exchange mixture, and use about 3 · 8 liters to wash the Heyi u ^ t water. The ion exchange glass samples were then dried for 22 hours at a temperature of 110 °C. First, the glass is subjected to a reduction treatment for each of the scorpions, wherein the ion exchange glass is first placed in an air atmosphere having an air flow rate of 2 L/hr. The steel was calcined at a temperature of c for 2 hours, and then reduced under hydrogen atmosphere at a hydrogen (η) atmosphere of 6 L/hr and at a temperature of 300 ° C for 4 hours. Revealed by ICP_AES. Eight private X Λ sample mouth knife analysis, the concentration of the result is about 0.045 wt·% 〇 Example 3 reverse ion exchange on the large pore glass to get by Dennert Poraver peak priest a rr small ^, raver house A macroporous foamed soda lime glass sample, i.e., glass beads having an average diameter of about 40 to 125 microns. In the first step, the macroporous glass sample received as it is and not calcined is subjected to acid leaching. Approximately 50 grams of macroporous glass and 4 liters of 5.5 wt% nitric acid were placed in a 4 liter glass beaker. Use a _ stand-free iron-type steel mixer to mechanically mix at 9 (rc) at a speed of 300 to 500 rpm. After the acid leaching process, use a Buchner funnel with Whatman 541 filter paper to pass through the sample' And use about 7.6 liters of deionized water to clean. Then, the acid immersed sample is dried for 22 hours at a temperature of 110 ° C. The second step is to carry out Na' counter ion exchange on the acid leached macroporous glass. (&quot;Na-BIX") treatment. Mix the acid leached sample obtained in the first step with 126426.doc -59-200843848 4 liters of 3 mol/L sodium chloride (NaCl) solution ("glass/chlorine Sodium mixture ',). Measure the pH of the glass/NaCl mixture. Add about 40 wt.% tetrapropylammonium hydroxide as needed, and adjust the pH of the glass/NaCl mixture to more than 1 〇. (In this example, the pH obtained is about 1 〇·5.) Then, the glass/NaCl mixture was transferred into a 4 liter glass beaker' and heated at 50 °C for 4 hours while using one The stainless steel purple mixer is stirred at a speed of 300 to 500 rpm. After the Na-BIX treatment is completed, use Filter the glass/sodium chloride mixture with a Buchner funnel with Whatman 541 filter paper and collect the Na-BIX/glass sample, then rinse with about 7.6 liters of deionized water. Then, at a temperature of 11 (TC, Na_BIX/glass sample) Dry for 22 hours. The third step is to perform a second ion exchange (&quot;IEX-2" treatment on the Na-BIX/macroporous glass sample. In this example, [Pd(NH3)4 is used using dioxetane. (Cl) 2 Prepare 3 liters of a 0.01 wt.% palladium solution for ion exchange (IEX-2 solution ''). Add 35 grams of macroporous glass to the ΙΕχ 2 solution ("glass / IEX-2 mixture"). The value of the glass/ion exchange mixture was measured and found to be about 8.1. Then, the mixture was transferred into a 2 liter glass beaker' and heated at 50 ° C for 4 hours while using a stainless steel violet mixer to 300 Stir at a speed of 500 rpm. After the ion exchange treatment is completed, the glass ion exchange mixture is filtered using a Buchner funnel with Whatman 54 丨 filter paper and washed with about 7.6 liters of deionized water. Then, at ii 〇 °c temperature Next, dry the ion exchange glass sample 22 Time. w, the fourth step, the IEX-2 glass sample is reduced, wherein the sample is reduced in hydrogen (HO gas flow rate of 2 L / hr hydrogen atmosphere and 3 〇〇〇 c temperature 4 j 126426.doc -60 - 200843848. Sample analysis by ICP-AES, the palladium concentration result is about ι2ι Wt·% 〇 Example 4 on the large-porosity glass, the large-porosity foamed sodium-calcium granule sample produced by Dennert Poraver is obtained. Glass beads having a diameter of about 40 to 125 microns. In the first step, the macroporous glass sample received as it is and not calcined is subjected to acid leaching. Approximately 20 grams of macroporous glass and 4 liters of 5·5 nitric acid were placed in a 4 liter glass beaker. Mechanical stirring was carried out for 2 hours at a speed of 300 to 500 rpm using a stainless steel violet mixer. After the acid leaching treatment was completed, the sample was filtered using a Buchner funnel with Whatman 541 filter paper and washed with about 7.6 liters of deionized water. The acid immersed sample was then dried for 22 hours at a temperature of 11 〇 c. In the second step, the acid-impregnated macroporous glass sample is subjected to ion exchange treatment. In the present example, 3 liters of a 0.01 wt.% palladium solution was prepared for ion exchange (, hydrazine solution &quot;) using dioxetamine palladium [pd(NH3)4]Cl2. About 18 grams of acid immersed macroporous glass was added to the ion exchange solution ("glass/ion exchange mixture"). Measure the 1) value of the glass/ion exchange mixture. About 29.8 wt% of ammonium hydroxide (ΝΗ4〇Η) was added dropwise as needed, and the pH of the mixture was adjusted to be greater than 1 Torr (in this example, the value obtained was about 10.8). The glass/ion exchange mixture was then transferred to a 4 liter glass beaker and heated at 50 C for 2 hours while stirring at 300 to 500 rpm using a stainless steel paddle mixer. Ion exchange 126426.doc -61- 200843848 After the completion of the treatment, use a Buchner funnel with Whatman 541 filter, paper filter glass / ion exchange mixture, and use about 7. 6 liters of deionized water to clean, then at 110 c temperature The ion exchange glass samples were dried for 22 hours. In the next step, the ion parent glass-changed sample was subjected to reduction treatment, in which the sample was reduced in a hydrogen atmosphere at a hydrogen (Η2) flow rate of 2 L/hr and at a temperature of 3 ° C for 4 hours. Sample analysis by ICP-AES showed a palladium concentration of approximately W47 Wt·%. Example 5 A large-porosity glass sample obtained from Dennart Poraver was obtained as a glass bead having an average diameter of about 4 to 125 μm. In the first step, ion exchange treatment is performed on a large pore glass sample which is received as it is, which is not calcined and which has not been acid leached. In the present example, 1.5 liters of a 0.001 wt.% palladium solution was prepared for ion exchange (&quot;IEX solution" using palladium dichlorooxytetramine [??1(&gt;^3)4](011)2. Add about 8 grams of macroporous glass to the glass/ion exchange mixture in the ion exchange solution ''). Measure the pH of the glass/ion exchange mixture. Add about 29.8 wt.% ammonium hydroxide (NH4) as needed. 〇H), adjust the pH of the mixture to more than 1 〇 (in this example, the pH obtained is about 10.5). Move the glass/ion exchange mixture into a 2 liter plastic wide-mouth container. Shake it by hand for 5 hours in a ventilated oven at 5 (rc). After the ion exchange treatment was completed, filter the glass/ion exchange mixture using a Buchner funnel with Whatman 541 filter paper 126426.doc -62- 200843848 The ion exchange-glass sample was collected and then washed with a solution of about 7-6 liters of dilute NH4〇H. The diluted nh4〇h solution was mixed with 10 grams of 29 8 wt 0/df NH 4 〇H solution and about 3.8 liters of deionized water. Preparation of m11Gt: ion exchange glass samples at temperature Drying for 22 hours. In the first step, the ion-exchanged glass sample was subjected to reduction treatment, in which the ion exchange sample was purged with hydrogen gas atmosphere at a flow rate of 2 L/hr for 4 hours. μ Grab the sample with ICP-AES Analysis, the result of palladium concentration is about

Wt.%. Example 6 On the large-porosity glass U-cells were made from a large-pore foam produced by Siscor, a glass bead with an average diameter of about 45 to 75 microns. In the first step, the macroporous glass sample t received as it is, which has not been calcined, is subjected to acid leaching treatment. About 49.61 grams of macroporous glass and 4 liters of 5.5 wt% of nitric acid were placed in a 4 liter plastic wide mouth container. Place the plastic container in a ventilated oven at 9 °C for 2 hours with a slight shake 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 acid immersed sample was dried at a temperature of 1 io ° C for 22 hours. In the second step, the acid-impregnated macroporous glass sample is subjected to ion exchange treatment. In this example, a platinum solution of 0_16 wt.% was prepared using platinum tetrachloride tetrachloride [PKNHjdCU for ion exchange ("ΙΕχ solution. Will be approximately 126426.doc -63 - 200843848

15.86 grams of acid immersed macroporous glass is added to the ion exchange solution ("glass/ion exchange mixture"). The pH of the glass/ion exchange mixture was measured. The pH was adjusted as needed with about 4% of tetrapropylammonium hydroxide. The tetrapropylammonium hydroxide was continuously added to adjust the pH to more than 1 Torr (the pH obtained in this example was about u.83). The glass/ion exchange mixture was transferred to a 4 liter plastic wide mouth container. Place the plastic container in the ventilated box for 2 hours, and shake it with your hands every 30 minutes. After the ion exchange treatment was completed, the glass/ion exchange mixture was filtered using a Buchner funnel with Whatman 54&quot; paper and washed with about 7.6 liters of deionized water. After the absence, the ion exchange glass samples were dried for 22 hours at 1HTC temperature. ... ICP-AES for sample analysis, the result of platinum concentration is about 〇·4ι

Wt.0/〇. Example 7 On the large-porosity glass A sample of a large-pore foamed soda lime glass produced by Siscor, that is, a glass bead having an average diameter of about 45 to 75 μm was obtained. In the first step, the macroporous glass sample received as it is and not calcined is subjected to acid leaching. About 50.37 grams of macroporous glass and 4 liters of 5·5 wt% of nitric acid were placed in a 4 liter plastic wide-mouth container. The plastic container was placed in a 9 CTC ventilated oven for 2 hours and shaken slightly by hand every 30 minutes. After the acid leaching treatment was completed, the solution was decanted, and then the solid matter was washed with about 7.6 liters of deionized water. Then, the acid immersed sample was dried at a temperature of u 〇 °c for 22 hours. In the second step, the acid-impregnated macroporous glass sample is subjected to ion exchange 126426.doc -64-200843848. In the present example, a platinum solution of 0.18 wt% was prepared using tetrachlorotetramine platinum [Pt(NH3)4]ci2 for ion exchange (, ΙΕχ solution π). Approximately 41.79 grams of acid immersed macroporous glass was added to the ion exchange solution (, glass/ion exchange mixture). The value of the glass/ion exchange mixture was determined to be 6.8. In this example, the value of ρΗ was not Adjust. Move the glass/ion exchange mixture into a 4 liter plastic wide-mouth container. Place the plastic container in a 9 〇 通风 ventilated oven for 4 hours, shake it slightly by hand every 30 minutes. After the ion exchange treatment is completed, The solution was decanted, and then the solid was washed with about 7.6 liters of deionized water. Then, the ion-exchanged glass sample was dried for 22 hours at ll〇t: temperature. Sample analysis by ICP-AES, the result of platinum concentration was about 〇13 wt·0/. Example 8 On a large-pore glass, a large-pore foamed soda lime glass sample produced by Siscor, that is, a glass bead having an average diameter of about 45 to 75 μm, was obtained. The macroporous glass sample received and not satin-fired was subjected to acid leaching treatment. About 20 grams of macroporous glass and 4 liters of 55-% nitric acid were placed in a 4 liter glass beaker. A stainless steel was used. The machine was mechanically searched at a speed of 300 to 500 rpm for 2 hours at 90 ° C. After the acid leaching process was completed, the sample was filtered using a Buchner funnel with Whatman 541 filter paper and used for about 7.6 liters. Ion water cleaning. The sample after acid leaching was dried for 22 hours at a temperature of 110 ° C. In the second step, the acid leached macroporous glass sample was subjected to ion exchange 126426.doc -65 - 200843848 treatment. In the present example, 3 liters of a 0.01 wt.% palladium solution was prepared for ion exchange (&quot;IEX solution" using dichlorotetramine palladium [Pd(NH3)4]ci2. Approximately 18 grams of acid leached macroporous glass is added to the ion exchange solution ("glass/ion exchange mixture"). The pH of the glass/ion exchange mixture is measured. As needed, 'continuously add about 29.8 The wt%% hydrogen hydroxide (nh4〇h), the pH of the mixture is adjusted to greater than 1 〇 (in this example, the resulting pH is about 10.78). Then, the glass/ion exchange mixture is transferred to 4 In a glass beaker of liters and heated at 50 °C for two hours while using a stainless steel paddle crucible; the mixer is mixed at a speed of 300 to 500 rpm. After the ion exchange treatment is completed, 'Use with Whatman 541 filter paper The Buchner funnel was passed through the glass/ion exchange mixture and washed with about 7.6 liters of deionized water. The ion exchange glass sample was then dried for 22 hours at ll 〇 ° C. The third step was to ion exchange glass. The sample was subjected to a reduction treatment in which the sample was reduced in a hydrogen atmosphere at a hydrogen (H2) flow rate of 2 L/hr and at a temperature of 30 Torr. The sample was analyzed by ICP-AES, and the concentration was approximately 〇〇47. Wt· % 〇 Example 9 On the large-porosity glass, a large-porosity foamed soda-calcium glass sample produced by Siscor, that is, a glass bead having an average diameter of about 45 to 75 μm was obtained. The first step was received as received without being burnt. The macroporous glass sample is subjected to acid leaching treatment. Will be about 49.61 grams of macroporous glass and 4 liters 5.5 126426.doc -66 - 200843848

Wt·% nitric acid is placed in a 4 liter plastic wide-mouth container. Place the plastic container at 90. (: 2 hours in a ventilated oven, shake the hand slightly every 30 minutes, after the text is processed, 'Filter the sample with a Buchner funnel with Whatman 54 1 filter paper and wash it with about 6 liters of deionized water. The acid leached sample was then dried for 22 hours at the temperature of litre.

In the second step, the acid-impregnated macroporous glass sample is subjected to ion exchange treatment. In the present example, 1 liter of a 0.0003 wt.% palladium solution was prepared using palladium dihydrooxytetraamine [pd(NH3)(〇H) 2 for ion exchange (,, ΙΕχ solution. About 15.06 gram of acid leaching The macroporous glass is added to the ion exchange solution (glass/ion exchange mixture). The pH of the glass/ion exchange mixture is measured. If necessary, about 29.8 ammonium hydroxide (ΝΗβΗ) is continuously added dropwise, The pH of the mixture was adjusted to greater than 1 〇 (in this example 'the pH obtained was approximately 10.2.) The glass/ion exchange mixture was transferred to a 4 liter plastic wide-mouth device. The plastic container was placed in a ventilated flood. The box was shaken for 2 hours every 30 minutes. After ion exchange treatment: After that, the sample was filtered using a Buchner funnel with Whatman 541 filter paper and washed with a solution of about 7.6 liters of dilute NH4〇h. The solution was prepared by mixing 1 () g of 29·δ wt % concentrated Wei solution with about 3.8 liters of deionized water. Then, the ion exchange glass sample was dried at (10) for 22 hours. ICP-AES was used. Sample analysis About (6) %. Using a scanning transmission electron microscope (STEM) analysis as described in the example below (C), a portion of the sample was examined, and the mouth of the sample showed that the palladium particles (the point where the contrast was brighter) were scattered. The distance from the surface of the pore wall is less than or equal to 126426.doc -67-200843848 in the range of about 30 nanometers (i.e., the perimeter of the darker contrasted shadow region relative to the material region around the substrate where the contrast is relatively bright). Example 10 Tungsten on Large Porous Glass - Obtained a sample of macroporous foamed soda lime glass produced by siscor, a glass bead having an average diameter of about 45 to 75 microns. • The first step, for receiving as received, without smoldering Large pore glass sample

c Perform acid leaching. Approximately gram of macroporous glass and 4 liters of 5.5 wt. Z of nitric acid were placed in a 4 liter glass beaker. Mechanical stirring was carried out at 9 Torr for 2 hours using a stainless steel paddle mixer at 300 to 500 rpm. After the acid leaching treatment was completed, the sample was filtered using a Buchner funnel with Whatman 541 filter paper and washed with about 7.6 liters of deionized water. The acid immersed sample was then dried for 22 hours at a temperature of 11 〇 c. In the second step, the acid-impregnated macroporous glass sample is subjected to ion exchange treatment. In this example, 3 I is prepared with ammonium metatungstate, and a 0.05 wt.% tungsten solution is used for ion exchange (&quot;IEX solution). About 18 g of acid-impregnated macroporous glass is added to the ion. Exchange the solution (,, glass/ion exchange mixture &quot;). Measure the pH of the glass/ion exchange mixture. Add about 29.8 wt% ammonium hydroxide (NH4〇h) continuously as needed. The pH of the mixture was adjusted to be greater than δ. The glass/ion exchange mixture was then transferred to a 4 liter glass beaker and heated at 5 (rc temperature for two hours while using a stainless steel paddle mixer to 3 (10) Stir at a speed of 5 Torr (5). After completion of the ion exchange treatment, the glass/ion exchange mixture was filtered using a Buchner funnel with Whatman 541 filter paper and rinsed with about 126426.doc -68 - 200843848 5 liters of deionized water. Then, the ion-exchanged glass sample was dried for 22 hours at 丨丨〇t: temperature. In the third step, the ion-exchanged glass sample was subjected to a calcination treatment in which the sample was air at a flow rate of 2 L/hr and 500 (: Temperature Squeeze for 4 hours. Sample analysis by ICP-AES, the result of tungsten concentration is expected to be about 0·01 wt·%. Example CH-1 Analysis method re/XPS sputtering, SARCNa, special point (IEP) and SAN2- BET or SAKr-BET measurement X-ray photoelectron spectroscopy (XPS) sputter depth distribution method using PHI Quantum 200 Scanning ESCA MicroprobeTM (Physical Electronics) with 1486·7 eV microfocus monochromator Α1 Κα X-ray source The xps sputter depth profile is obtained. The instrument has dual neutralization force, which provides charge compensation using low-energy electrons and cations during spectral acquisition. XPS spectra are usually measured under the following conditions: - X-ray beam diameter 1〇_2 〇〇μχη -X-ray beam power 2-40 W • Sample analysis area 10-200 μπι • The electron emission angle is 45 with the sample normal. All XPS spectra and sputter depth distributions are recorded at room temperature without pre-preparing the sample. Dispose of, except when the sample is placed in a vacuum environment of the xps instrument. The surface of the sample is collected by alternating several cycles, and then the surface of the sample is subjected to 15 to 30 seconds per week 126426.doc -69 - 200843848 2 kv Ar+ sputtering is used to remove the surface material to create a sputter depth profile. The sputter depth rate is calibrated using a thin film of known thickness.

The Pd and Si atomic concentration values are obtained by taking the peak areas of pd 3d3/2 and Si 2 并 and correcting their respective atomic sensitivity factors and analyzer transfer functions. 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 used to determine the sputter depth of the wood using the XPS sputter depth distribution technique. The reported values cause an uncertainty of approximately 25%. Therefore, the uncertainty is expressed in the depth values of Figures and 2. 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, this inaccuracy is insufficient to hinder the performance of the catalyst compositions described herein. The distinction 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 was performed using a JEOL 3000F field emission scanning transmission electron microscope (stem) instrument operating at 3 〇〇 kv accelerating voltage. The instrument is equipped with Oxford Instruments (〇xf〇rd Price (4) (10)^

The Inca X-ray spectrometer system performs local chemical analysis using an energy dispersive spectrometer. Preparation of the sample The sample material is first embedded in a standard epoxy embedding agent known to those skilled in the art of fTEM analysis. After curing, the epoxy-embedded sample material was cut into approximately 80 nm thick sections using an ultramicrotome. The sections were collected on a thin film 126426.doc -70-200843848 membrane-porous carbon support 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 use of TEM analysis to determine the position of the target analyte and the average thickness of the region of interest relative to the surface of the substrate are both subject to human uncertainty and mechanical uncertainty, depending on the sample. Factors such as image resolution, physicochemical properties of the target analyte, and sample morphology may result in an uncertainty of about ±20% of the TEM vertical depth measurement (relative to a specific reference point) and about 5% of the side The measurement results (relative to a specific reference point) uncertainty. Therefore, the uncertainty is expressed in the distance of the measured catalytic component relative to the surface of the sample substrate. This inaccuracy is common throughout the TEM analysis but is not sufficient to prevent discrimination between the catalyst compositions. SARCNa test, SARCNa empty sample and related statistical analysis. Due to the original g] discussed above, the surface area change rate of nanometer ("sarc〇 is reported as the ratio of NaOH titrant volume. According to the above SARC cardiac program, each of the given examples is determined. A sample of SAIU^ was prepared by preparing a 3.5 MNaC1 solution (that is, adding 3 gram of NaC1 in ... ml of deionized water) to prepare a J-cut 1 sample, which contained no matrix sample. However, in order to solve SAR' The statistical variability in the experimental procedure should be titrated with four independent empty samples' and adjusted using the mean values of V and V...5 (also used in the specified concentration (〇〇1 N in this example). (ie, correct) the volume of the sputum used in the determination of each substrate σ - negative mouth SARCW. The pH of the empty sample was adjusted according to the same procedure as the above SARQ 并 and the empty sample was titrated, but also contained no matrix. 126426.doc 200843848 A statistical analysis 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 below. Similarly, the respective V total is also reported. corresponding The inherent statistical fluctuations of Vw V5 Vio and V]5 in each titration. From the statistical angle _ I纟t distribution, near the average value, the value of the specified confidence interval X is sinful, not from the experiment. The degree of certainty of the inherent deviation of the method reaches 95 / 〇. Therefore, the V initial and vt values measured for the matrix sample in the confidence interval near the average of the empty sample are considered to be statistically different from the empty sample. Therefore, this class The sample does not calculate the SarCw value. The isoelectric point (1EP) measurement determines the isoelectric point (, ΐΕρπ) of each sample given below according to the following formula: Using the Meuler T〇led〇SevenMulti meter with the pH mV/0RP module, iEp measurement with a Mettler Toledo INLAB 413 pH composite electrode. Align the meter with a standard pH buffer solution at pH 2, 4, 7 and 1 整个 over the entire IEP range of interest. Use enough to bring the sample to incipient wetness State of C, a quantity of 16 ΜΩ* ionized water (wet the sample at about 25 (under), determine the enthalpy of each sample, thereby producing a denser poly- or paste-like mixture. Wet state can make glass electrode and The liquid contact between the reference electrode contact surface and the liquid contacting the solid sample to be tested (in this example, a slurry or paste mixture) depends on the morphology of the sample (eg, glass microfibers, granular powder, chopped fibers, etc.) ) and its porosity (if any), the procedure requires a different amount of water, but in all cases, the amount of water added should be sufficient to bring enough liquid into contact with the glass electrode and the reference electrode. In other words, The sample should be added with water as much as possible to avoid exceeding the initial humidity. In the case of 126426.doc -72- 200843848, the electrode tip is used by hand, and the solid sample is mixed with deionized water (adding force for generating the initial humidity) by hand until the measured pH value is stable, and then from the instrument 1 Read the resulting pH. N2 BET or Kr BET surface area (S.A.) determination According to the A S TM procedure mentioned above, the S.A.N2-BET or S.A.Kb BET determination is performed for each sample given below. As discussed above, for higher surface area measurements (e.g., about 3 to 6 m2/a, W, % BET is likely to be preferred) according to the method described in ASTM D3663-03. Measurement technique. For lower surface area measurements (eg, &lt; approx. 3 m2/g), ^ 'Kr BET may be compared as described in ASTM D4780-95 (,, SApir&quot;) Good surface area measurement technology. Sample number dilute NaOH titration solution SAN2-BET (m2/g) In the NaOH titration, adjust the pH value from the initial value of 4·〇 to 9.0 at tc (V initial), and at the time The volume of the titration required to maintain the pH at 9.0 (ml) Concentration (N) V initial 0 minutes v5 5 minutes v10 10 minutes V15 15 minutes V5i15 and V initial ~ ls empty sample A 0.01 Not applicable 1.5 0.3 0.1 0.2 0.6 2.1 Empty sample B 0.01 Not applicable 2.2 0.1 0.1 0.2 0.4 2.6 Empty sample C 0.01 Not applicable 2.4 0.1 0.1 0.1 0.3 2.7 Empty sample D 0.01 Not applicable 2.2 0.1 0.2 0.1 0.4 2.6 ----- Average value of empty sample 0.01 Not applicable 2.075 0.15 0.125 0.15 0.325 ----- 2.5 Standard deviation of empty sample 0.01 Not applicable 0.3947 0.1 0.05 0.0577 Not applicable Empty sample 95% Trust interval 1.45-2.70 2.07-2.93

U 126426.doc -73 - 200843848 EXAMPLE CH-2 Macroporous Glass Matrix - SARCNa A macroporous soda lime calcium glass sample produced by Dennen Poraver, a glass bead having an average diameter of about 40 to 125 microns, was obtained. Sample A is a macroporous glass bead that is received as it is. Sample A was analyzed using the above analytical method for determining SARC^. The results are shown in the table below. Sample No. Sample Description Dilute NaOH Titration Concentration (N) ==================== 0.01 In the titration, the pH value is adjusted from the initial value of 4.0 at the beginning of UV) To 9.0, and to maintain the pH at 9.0 at t5, tio and ti5 (V5M5), the actual volume of titrant required (ml) V first 0 minutes a 2.1 v5 5 minutes v10 10 minutes v15 I 15 minutes V total V« rV initial • one empty sample ----- average value of empty sample 0.15 0.125 0.15 2.5 not applicable A original porous glass beads 0.01 5.2 0.8 0.4 0.1 6.5 1.3 B acid immersion porous glass beads ----------- Measurement not determined -----

Sample No. Sample Description Empty Sample Average Corrected A Original Porous Glass Bead Corrected B Acid-Immersed Porous Glass Bead IEP Volume of Modified Titration Used in SARCw Measurement ^ Am2-BET (ml) SARC/να (m2/ g) V initial V5 v10 v15 V螅〇 minutes 5 minutes 10 minutes 15 minutes - —== _ Not applicable 2.1 0.15 0.125 0.15 2.5 Not applicable _^一—' 0.4 3.1 0.65 0.275 -0.05 3.97 0.28 6.0 Not determined not determined The above method is illustrated in conjunction with the following example examples. The above described catalyst compositions are described in more detail in accordance with the present invention. All modifications and examples of how the different types of catalyst compositions can be used in the hydrogenation spirit are protected. 126426.doc -74- 200843848, the following examples are not intended to be limited to the invention described and claimed herein. Hydrogenation (HYD) Process Example In a non-limiting example of an underarm, a selected catalyst composition test is conducted for nitriding activities in laboratory scale work waste. The general procedure is as follows. &quot;Firstly load the catalyst into a 7/8” inner diameter reactor with a 3/16', outer diameter thermowell. The catalyst is used at 3 sails with a flow rate of 75q ee/mh^ nitrogen reduction of about 16 Next, a hydrocarbon feedstock consisting of 8 〇Wt.% cyclohexane and 2 〇wt·% benzene flows through the catalyst at a rate of 72 cc/hr at a pressure of 400 psig. The molar ratio is about h4 to 1. The temperature ranges from 9G ° C to 210 ° C to achieve the desired conversion of benzene to cyclohexane. Example P-1 Utilization of platinum hydrogenation on macroporous glass in this example In the macroporous glass beads prepared according to the method of the above Example 6, about 5 g (7.5 cc) of i.4i wt.% was charged into the reactor. At the temperature of hydrazine, according to the hydrogenation method example procedure described above The catalyst was tested. The results are shown in the following table. 0.41 wt·% of the catalyst on the macroporous glass—the conversion rate (°/〇) 5.00 g 7.5 cc ----- 100 ---- -- Sample Description Example P-1 describes the invention, and for the description of ^ (3), 逖 puts forward a lot of details. However, it is obvious that the present invention is likely to have other implementations. And without departing from the basic principles of the present invention, some of the details described herein may be quite different. [Simplified Schematic] Figure 1 is a JEOL 3〇 〇〇F field emission transmission electron microscope photographed at an acceleration voltage of 3 〇〇 kV, substantially without microporosity / no mesoporosity, but with a 2-gap glass matrix sample (eg, acid immersion glass) cross section 2 A transmission electron microscope (STEM) image in which the distance from the surface of the pore wall is less than or equal to the nanometer

126426.doc 76-

Claims (1)

200843848 X. Patent Application Range: 1 . A method of hydrogenating a process stream, wherein at least a portion of the process stream is hydrogenated using a catalyst composition comprising at least one compound having at least one hydrogenatable site, wherein The catalyst composition comprises: ^ _ a substrate having a large pore, an outer surface, an open pore wall surface, a surface region, and a subsurface-free region having substantially no microporosity/no porosity, at least one catalytic component, and _ at least one catalytically active region comprising the at least one catalytic component, wherein (a) the substantially microporous/non-porous matrix has 1) a method of measurement selected from the group consisting of: s. Ajmm and combinations thereof Is the total surface area measured between about 1 m2/g and 50 m2/g measured; and η) greater than 〇 but less than or equal to 14? a predetermined isoelectric point (IEP) obtained within a range of 11 values; (b) the at least one catalytically active region may be continuous or discontinuous, and having an average thickness of 1) less than or equal to about 30 nm; and 'ii) Catalyzing an effective amount of the at least one catalytic component; and (c) the at least one catalytically active region is positioned substantially i) on the outer surface, ii) on the open pore wall surface, iii) within the surface region, Iv) partially on the outer surface, partially on the open pore wall surface 126426.doc 200843848, partially in the surface region and combinations thereof; or V) (c) (i), (ii), (out) and a combination of (iv). 2. The hydrogenation process of claim 2, wherein the at least one catalytic component is selected from the group consisting of: B_ted or Lewis, or Lewis, precious metal cations, and precious metals. Complex cations and anions, transition metal cations and transition metal complex cations and anions, transition metal oxyanions, transition metal sulfonium anions, main oxyanions, _ compounds, rare earth ions, rare earth cations and anions, Precious metals, transition metals, transition metal oxides, transition metal sulfides, transition metal oxysulfides, transition to slaves, transition metal nitrides, transition metal side compounds, transition metal plates, rare earth hydroxides, rare earth oxides And their combinations. '3· ^ May hydrogenation method of claim 1, wherein the at least one catalytic component is a first catalytic component having i) before the catalyst composition is under steady state hydrogenation reaction conditions (hook first pre-reaction) An oxidation state, and (b) a first pre-reaction interaction with the substrate, selected from the group consisting of: an ionic charge interaction, an electrostatic charge interaction, and combinations thereof. 4. Request No. 3 The hydrogenation method, wherein the first catalytic component is selected from the group consisting of an acid, a base, a chalcogenide, and a combination thereof. 5. The hydrogenation method of claim 3, wherein the catalyst composition is in a steady state deuteration reaction Prior to the condition, at least a portion of the first catalytic component is ruthenium modified or substituted to form a second catalytic component having a second pre-reactive oxidation state, and (b) Corresponding second pre-reaction interaction; wherein the second pre-reaction oxidation state of the second catalytic component is less than, greater than or equal to the first pre-reaction oxidation state of the first catalytic component. Hydrogenation method, The second catalytic component is selected from the group consisting of Pd, Pt, Rh, Ir, RU, 0s, Cu, Ag, Au, Ru, Re, Ni, Co, Fe, Mn, Cr, and combinations thereof. The method of hydrogenation of claim 1, wherein the substrate is a glass composition having a SARCN^h of or equal to about 0.5. 8. The hydrogenation method of claim 1, wherein the at least one catalytically active region is substantially concentrated on the average The region having a thickness of less than or equal to about 2 nanometers. 9. The hydrogenation method of claim 1, wherein the substantially microporous/no-porous matrix is selected from the group consisting of AR glass, rare earth silicate glass, and the like Lushi silicate glass, E glass, boron-free E glass, S glass, R glass, rare earth glass, silicate glass, Ba-Ti-silicate glass, nitrided glass, a glass, C glass and CC A group of glass and a combination thereof. The hydrogenation method of claim 1, wherein the IEp system obtained by the substantially microporous/non-porous matrix is greater than or equal to about before or after the first leaching treatment. 6.0, but less than 14. 126426.doc 200843848 VII. Designated representative map: (1) The picture is: (1) Figure (2) The symbolic symbol of the representative figure is simple: (No component symbol description) 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: (none) 126426. Doc