TW200902143A - Dehydrogenation processes using functional surface catalyst composition - Google Patents

Abstract

Dehydrogenation 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 m2/g and 50 m2/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

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a catalyst composition and a method of producing the same, which can be used in various chemical manufacturing methods and various emission control methods. More specifically, Q, 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 substrate and/or in the surface of the substrate, the catalyst composition being useful for various decoctions. Hydrogenation method application 0

[Prior Art] Catalyst compositions are used to promote chemical reactions that are generally described as catalytic or catalytic, and catalysis is critical for efficient operation of various chemical processes. = Partial industrial reactions and almost all biological reactions, if not catalytic, involve pre- or post-reaction treatments that are catalytic reactions. In the case of the United States alone, the value of a product produced at a stage including a catalytic process is close to - US$ (USD). Products produced using catalyst compositions include, for example, food, clothing, pharmaceuticals, pharmaceuticals, specialty or fine chemicals, plastics, detergents, fuels, and lubricants. Catalyst compositions can also be used to treat emissions (eg, vehicle exhaust emissions, refinery emissions, public I::: emissions, etc.) and other process emissions streams to reduce potential negative impacts on human health or the environment. The amount of harmful ingredients affected. The market/sales reduction and 5' sales of solid carrier catalysts for heterogeneous catalytic reactions in the full market are approximately $3 billion per year. The solid-loaded catalyst is usually divided into three parts: petroleum refining catalyst, chemical processing catalyst and emission control catalyst. ; 126435.doc 200902143 The market for three types of catalysts is basically three-thirds of the world. For example, i99吟 In the US$1.8 billion solid catalyst market, petroleum refining, chemical processing and emissions control catalysts accounted for 37%, 34% and 29% of the market. Take the petroleum refining catalyst market (about 100 million U.S. dollars in 1999) as an example. The proceeds are from the FCC catalyst, while the 31_5%, 6.5% and 45% revenues come from Hydrogen treatment catalyst, hydrocracking catalyst and reforming catalyst.

From a theoretical point of view, the catalyst can generally increase the rate at which the chemical reaction will reach a equilibrium state between the reactants and the product without substantially eliminating itself. Therefore, for any relevant reaction, the catalyst does not change the equilibrium state between the reactants and the product, but if properly designed and/or selected, the catalyst can accelerate the rate of the chemical reaction. Therefore, the use of catalysts for a wide range of commercial and practical processes for a variety of purposes includes improving process responsiveness, selectivity and energy efficiency, and other uses. For example, when the desired product is produced according to the specified process conditions, increasing the reaction rate or reactivity of the reactants can shorten the processing time and gain a greater product throughput (for example, increasing the volume of matter 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, increasing the selectivity of the reaction increases the percentage of yield of the desired product in a set of possible reaction products: some of the possible reaction products are not required and require further processing for the corresponding shift. In addition to or conversion, the 'catalyst selectivity' is the ability of the catalyst composition to convert a portion of the reactants to a particular product under specified process conditions. In addition, the catalyst combines the amount of product used to convert and reduce contaminants or undesired reactants in a process. 126435.doc 200902143 f. Alternatively, the overall energy efficiency of the reaction process is increased 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 level of contaminants such as smoke, carbon monoxide ((3)), nitrogen oxides (NOx), and sulfur oxides (S〇x), which may be present in one Series of processes (such as emissions from vehicles/air oil engines or diesel engines, classified petroleum refining or coal burning processes, etc.). Similarly, catalysts can be used in hydrocarbon processing processes that are used for many different sources (eg, Naoki's oil, sub-recycled petroleum, heavy oil, adventurous, rock, natural gas, and containable catalytic reactions). The hydrocarbon process stream of the other carbonaceous materials of the material is converted or upgraded. The catalytic reaction is usually divided into two different reaction types, namely homogeneous catalysis and heterogeneous catalysis. Homogeneous catalysis broadly describes a type of catalytic reaction in which the reactants and catalyst are mixed in a solution phase. Although gas phase catalytic reactions have been used in some cases, homogeneous catalysis is typically a liquid phase system. Therefore, concentration gradients and migration of reactants to the catalyst can become important factors in controlling homogeneous catalytic reactions. In addition, in some cases, the "solution phase" catalytic reaction can occur across the interface between the two liquid phases, rather than forming a true solution, but forming an emulsified phase. Some general classes of homogeneous catalysis include acid-base catalysis, organic Metal catalysis, phase transfer catalysis, etc. On the other hand, heterogeneous catalysis describes a type of catalytic reaction in which a reactant in a gas phase or a liquid phase is exposed to a substantially solid phase or half 126435.doc 200902143 solid phase Therefore, in the heterogeneous catalytic process, the catalyst and reactants produce a mixed solid-phase/liquid phase or solid-gas phase reaction. Compared with homogeneous catalysis, heterogeneous catalysis has many advantages. For example, solid catalysts (4) have lower rot, and the safety and environmental risks are relatively low compared to many homogeneous solution solutions. (b) Provide a wide range of economically viable temperatures and pressures 1 The burdock and (4) more ▲ control the exothermic chemical reaction and endothermic

The media solids can have mass transfer limitations' which in turn significantly reduce the contact and effectiveness. Typically, a solid catalyst (sometimes referred to as a catalyst = granule) includes one or more knives on a porous material having a high internal surface area (eg, precious metals, such as time sentences, beginnings (called, nails) (called, gossip), the internal surface area of the catalytic component, usually in the order of one kilogram per amp, conventional catalyst composition or catalyst particle package: a special porous carrier carrying a large internal surface area, The catalytic reaction occurs on the body: however, 'such catalyst structures often produce mass transfer: thereby reducing the effective activity of the catalyst particles with respect to catalyst activity and selectivity, and causing other catalyst performance problems. The more representative network of pore-penetrating pores is: in the medium, the structure, the reactant must diffuse through the inner region of the catalyst particles to the crucible (3), and the product must be =; the pores are out of the catalyst particles. _ domain. Therefore, the conventional catalyst group: the catalyst combination also depends on the balance, that is, the trade-off between the Xi Jin quality # #, 拴, that is, the trade-off between the catalyst surface area and the promotion ==: ability For example, many catalytic components are fine and complex in the code. In the carrier of the pore structure (by 126435.doc 200902143, the micro-porosity structure, ie, the average maximum diameter), to increase the catalyst enthalpy, the higher the surface area will generally increase the catalytic activity. ^The increase in catalyst activity due to the surface area of the catalyst particles of the 轶A, the problem of mass transfer resistance (ie, preventing the movement of the reactants and products μ from the catalyst particles), especially the carrier including a higher percentage In the case of a microporous structure, the problem is more pronounced. By increasing the percentage of the large pores of the larger size pores in the carrier, the mass and the resistance can be reduced (that is, the mass transfer is accelerated). The scheme tends to reduce the physical strength and durability of the catalyst particles. In other words, from the point of view of mechanics, the robustness of the t-catalyst particles is reduced. Field 5, if the reactants are exposed to the apparent mass in the pore structure of the catalyst particles The transfer resistance' will have a concentration gradient under steady state reaction conditions. Therefore, in the pore structure, the concentration of the reactants is the largest around the catalyst particles 'in the catalyst particles The heart is the smallest. On the other hand, the concentration of the reaction product is at the center of the touch: the particle is higher than the surrounding of the catalyst particles. These concentration gradients provide the driving force for mass transfer. The higher the concentration gradient becomes, the catalytic reaction The lower the rate, the more the performance of the catalyst particles (the selectivity of the reaction 14 and the life cycle and the anti-coking performance between the regeneration treatments) are correspondingly reduced. Normally, the catalyst composition is developed. The purpose is to improve one or more of the processing targets described above from the commercial point of view; in the case of ^^^ ^. In some cases, the effect of the catalyst is affected by Xin Yijing. Promote the ability of rapid reaction between reactants. Therefore, Dangdang I is a female soil, left hang * to have a lower diffusion limit of the catalyst composition. However, in the case of pots 衿隹 /, he It In order to obtain a better product, 126435.doc -10· 200902143 may be more important for the selectivity of a particular product. Thereby, additional processes and associated processing equipment for removing or converting undesired reaction products can be eliminated. For example, in 1976, Y_T. Shah et al. proposed the use of acid leaching demineral acid fibers, specifically E-glass (more specifically, E-621) to produce a catalyst carrier. Compared with conventional catalysts, the catalyst carrier has a high surface area to volume ratio, thereby reducing the K-inch of catalytic conversion benefits for automotive exhaust systems (eg, & 0xidati〇n 〇f(10)Aut〇m 〇bUe

Gas Mixture by Fiber Catalysts, Ind. Eng. Chem. 5 Pr〇d. Res· Dev_’ pp· 29_35, v〇1 15, N〇”, 1976). At the same time, et al. believe that reactive gases (such as carbon oxides, carbon dioxide, nitrogen oxides, methane, ethane, propane, ethylene, propylene, acetylene, benzene, toluene, etc.) are generally produced in automotive exhaust mixtures. Contact with the large surface area produced in acid leached E-glass.

Shah et al. showed a relatively small amount of fiber with a relatively small surface area (75 m2/g) compared to two conventional catalysts (platinum supported on alumina beads or platinum supported on silica beads). The performance of the glass-catalyst carrier is better than that of the catalyst supported by oxidized or supported by silica dioxide (180 m2/g and 317 m2/g, respectively). The average pore size of the E-type glass catalyst. Greater than the catalyst with emulsified aluminum as the carrier or the catalyst with cerium oxide as the carrier. However, Shah et al. did not propose or suggest that effective automotive exhaust oxidation can occur at a surface area 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 126435.doc 200902143 for selective solutions for benzaldehyde Phase-hydrogenated cerium oxide glass fiber (SGF) is associated with the formation of benzyl alcohol (using a platinum-based catalyst) or toluene (using a palladium-based catalyst) (see, for example, Qiaoly μ Catalysts for Novel Multi) -phase Reactor Design, Chem. Eng·Sd· PP· 4785-4790, Vol. 54, 1999). In this study, Kiwb Minsker et al. found that SGF does not achieve an increased surface area from acid leaching, so it is relative to an EGF sample used to carry palladium as a catalytic component of a palladium-based catalyst composition ( The surface area is 15 jaws 2/§ and m2/g, respectively, and the surface area of the SGF is kept at a low level of 2 jaws 2/§. However, Kiwi-Minsker et al. noted that the SGF/palladium catalyst palladium essentially has the same effective surface area concentration as its EGF/ruthenium catalyst counterpart (ie, about 01 mm〇1/m2) (mole metal/square The MGF/Palladium catalyst composition shows a decrease in activity or reaction rate per gram of palladium compared to its EGF/palladium catalyst counterpart.

Kiwi-Minsker et al. suggest that the SGF/palladium catalyst has a reduced surface area due to reduced surface area, which may be explained by the enhanced interaction of the active ingredient (ie, the catalytic component, in this case palladium) with the SGF carrier. Not because of its small surface area (ie 2 m2/g). However, they failed to verify this argument by proving the following arguments: a small surface area (ie, sgf/palladium phase with 2 m2/g)

The interaction is enhanced) Why is the main factor, GF / palladium activity limit! · Health 'palladium and SGF rather than essentially 126435.doc •12· 200902143 Anyway, Kiwi-/g EGF/palladium sample, and Enhanced catalytic activity. The beneficial effect of SG/Pd is small, and the reason is not clear. Minsker did not report that the diffusion rate is higher than the 75-15 m2/g EGF/palladium sample, which may indicate a smaller catalyst surface. Recently, in US 7,060,651 and EP 1 247 575 A1 (EP, 575),

Bareik. Et al. disclose the use of a carrier rich in dioxide dioxide (including cerium oxide and an oxide containing non-cerium oxide (for example, Αΐ2〇3, Β2〇3, ΝΑ〇, MgO, Ca0, etc.) as a catalyst carrier. The beneficial effect is that the cerium-enriched carrier has a pseudo-layered microporous structure in the lower surface of the carrier (see, for example, paragraphs U, 13, 15, 17, 18, 23, 31 and 32 of EP, 575). Content). As explained more fully to the European Patent Office ("EPO", in distinguishing the ugly? '575 with the ruler 1 丨->^1131^1' et al. "Kiwi-Minsker vector"), Barelk〇 et al. assert that their claimed ceria-rich carrier has a pseudo-stratified microporous structure with a narrow interlayer space, whereas the Kiwi-Minsker carrier does not. Structure. More specifically, 'Barelko et al.' believes that there is no basis in the paper by Kiwi_Minkser et al. (a) that there is a pseudo-layered microporous structure with a narrow interlayer space in the Kiwi_Minsker carrier; (b) Pseudo-stratified microporous junction with narrow mezzanine space It contributes to enhancing activity (see, e.g. EP '575 and 32 of the first piece of content 13,17-18,23) is applied to the metal support.

Barelko et al. further clarify the carrier of the cerium-enriched cerium and the carrier proposed by Kiwi-Minsker et al. by explaining the following contents to the European Patent Office, due to the fact that the catalytic component is highly dispersed in the active state in the carrier. 126435.doc -13- 200902143 Surface distribution of the catalytic components in the subsurface layers of the support a mountain jpeMed achve s^aie" (in the original line), rich in cerium oxide The carrier has a more active catalytic state, and thus the more active catalytic state allows the catalytic component to withstand sintering, collection and self-carrier flaking and contact agents (see, for example, paragraph η of EP '575). EP, 575 confirms that diffusion limitations may hinder the incorporation of cations into the intercalation space of 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, Bareik et al. propose (and advocate) a carrier structure in which the "thin" layer of bismuth-oxygen fragments are separated to form a narrow interlayer space (i.e., the number of pseudo-layers) Pore structure), the narrow interlayer space contains "a large number of |〇H groups, the protons of which can be exchanged by cations. Barelko et al. disclose a sufficiently "thin," 矽_oxygen fragment layer Unique for high Q3 to Q4 ratios, and they further stated that the pseudo-layered microporous structure with a large number of 〇H groups sandwiched between narrow interlayer spaces has been 29Si NMR (nuclear magnetic resonance) and汛 (infrared) spectrometry was confirmed in combination with argon BET and alkali titration surface area measurements. Many conventional catalyst tests

126435.doc Like some of the special glass catalyst compositions, the map solves at least one of the above identified processing problems, while others perform poorly. Therefore, these customary arguments -14- 200902143

Life cycle. Applicants have discovered that a field condition and demand for durability and a relatively long life functional surface catalyst composition are expected to meet the need for this broad range of catalytic reactions. SUMMARY OF THE INVENTION One aspect of the present invention provides a process for the dehydrogenation of a process stream, the portion of which is dehydrogenated, wherein at least one process stream of the process stream is at least one detachable with at least one process stream A hydrogenation site-containing compound, wherein the catalyst composition comprises: 'a substantially microporous/non-porous matrix having a large pore, an outer surface, an open pore wall surface, a surface region, and a subsurface region, - at least one catalytic component And at least one catalytically active region comprising the at least one catalytic component, wherein (a) the substantially microporous/non-porous matrix has i) when selected from the group consisting of SAwjfT·, s. Auh and combinations thereof When measured by the method of the group, the total surface area measured between about 1 m2/g and 50 m2/g is measured; and Η) is obtained in the range of pH values greater than 0 but less than or equal to 14. a predetermined isoelectric point (IEP); (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 126435.doc -15· 200902143 n) At least one effective amount of catalyzed a catalytic component; and (C) the position of the at least one catalytically active region is substantially i) on the outer surface, ii) on the open pore wall surface, iii) in the surface region, iv) partially on the open pore surface, partially Within the surface area and combinations thereof; or V) (c) a combination of (i), (ii), (iii) and (iv). Other aspects of the invention will be apparent to those skilled in the <RTIgt; [Embodiment] Definition The terms used herein have the meanings defined below. The aperture, 'represents a hole or channel having a depth greater than the width. &quot; Interconnecting pores&quot; means pores that communicate with - or a plurality of other pores. "Closed pores" means pores that have no channels with the outer surface of the material in which the closed pores are located. "Open pores" indicate the material with the open pores The outer surface has direct channels, or pores connected via another pore or interconnected pores (ie, pores that are not part of the closed pores). "Polar width," means the inner diameter of the pore or the relative wall determined by the specified method. the distance. "Pore volume, which represents the total volume effect of all pores according to the specified method 4" but does not include the volume effect of closed pores. 126435.doc -16- 200902143 M Porosity"矣-_ j. The ratio of the volume to the total volume of the material. "Microporosity" means pores having an internal width of less than 2 nanometers (nm). The pores of the intermediate pores having an internal width of between 2 nm and 50 nm: "two pores" means pores having an internal width greater than 5 Å. . "External surface" means—the outer boundary or skin of the material (near thickness is zero), the rule or irregular wheel on the boundary or skin that is associated with the defect (if any).

A pore wall surface, referred to as an inner boundary or skin (thickness near zero), including any regular or irregular contours associated with defects (if any) on the inner boundary or skin, substantially defined in at least one or more The shape of any open pores in the material of the type of pore. "Surface" generally means - the pore wall surface of the material (if any open pores are present), the outer surface of the material and its surface area. "Surface area" means 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 pores are present) but the surface area (4) is less than or equal to % below the outer surface of the material. Meter (more than W nano, better for Chennai); when the material has any (four) pores, the surface area (b) is less than or equal to 3 nanometers below the pore wall surface of the material (preferably M, more preferably (four) nano). For materials with detectable surface elevation changes, whether the changes are: 'Along the outer or inner boundary or skin, the outer or inner boundary or the average of the skin is used to determine the average deep sound of the surface area. "Subsurface area" means that it can be changed according to the material and does not include any open pores of the material I2635.doc •17· 200902143 (if there is any open pores jjb, the material of the area I 13 s, but the subsurface area ( a) Above the surface of material #, * Bu is greater than 3 0 umbrella (preferably &gt; 20 nm, more preferably &gt; no, pore, main not) 'When there is any opening in the material, The subsurface region (b) is elongated in the pores of the material, and is less than 30 m2 below the surface (preferably &gt; 20 nm, more preferably &gt; 1 〇 nanometer). ', 'internal surface area, or , the open pore wall surface area, the surface area effect of all open pore walls in the material determined by the specified method. The "external surface area" table specifies the method to determine the surface area of the material including the surface area effect of all the pore walls in the material. Effect ''Total surface area'' means the sum of the internal surface area of the material and its external surface area determined by subtraction. ''Sodium·Chemical adsorption surface area, or SA- means chemical adsorption by sodium cation by chemical adsorption method Indeed The surface area of the material, the (etc.) chemisorption method in GW Sears d«a/. 1956, v〇l. 28, ρ· 1981 and R. Iler, CT^w as r (?/NZ, j〇hn Wiley &amp; Sons 1979, P. 203 and 353. "Na·Chemical adsorption surface area change rate" or, SARCw", where SARCw -V5 to "/V initial" where (i)V is initially used for initial titration The initial volume of the dilute NaOH titration solution of the aqueous solution mixture is at about 25. (: temperature includes a material that is substantially insoluble in water in the solution of 3 · 4 Μ NaCl, the solution ρ Η value at zero time t〇 from the initial pH 4.0 reaches pH 9.0, and (n)V5i 15 refers to the total volume of the same concentration of NaOH titrant used to maintain the slurry mixture at pH 9 for a period of 15 minutes, every 5 minutes (3 5 minutes total) The intervals are t5, "and t! 5" respectively. The total volume is adjusted as needed as soon as possible. 126435.doc -18- 200902143 Therefore '^ refers to the NaOH titrant used in the titration procedure t described in more detail below. The total volume 'mV“V5”5 = v&quot; Therefore, 乂5 to 15 can be expressed as the difference between v and v at the beginning, where V5£im 〇 By definition, a 3.4 M NaCl solution is prepared by adding 3 gram grams of reagent (reagent grade) to (9) milliliters of water, and 1.5 grams of sample material is added to the NaCl mixture to produce an aqueous slurry mixture. The aqueous slurry mixture must first be adjusted. It is pH 4.0. In order to carry out this adjustment before titration, a small amount of dilute acid (for example, Ηα) or a dilute base (for example, Na〇H) can be used accordingly. The titration, in order to obtain the v initial, first use the dilute Na0H titration solution (for example, ι ι N), and then use Vsil5 for SARCW. In addition, for the purposes of this definition, Vp is 5 is the cumulative volume of Na〇H titration solution used in ts, ~ and ..., wherein the NaOH titration solution is titrated as soon as possible every 5 minutes (three 5 minute intervals). Take t as needed. To the final time. The pH of the slurry mixture was adjusted to 9.0 within 15 minutes. For the purposes of this definition, it is treated with any alternative ion exchange (ΙΕχ), counter ion exchange (BIX) and/or electrostatic adsorption (ΕΑ) treatment to produce one or more Type 2 component precursors (described below) The SARC&amp; of the sample material is determined prior to integration onto the surface of the substrate and/or in the surface of the substrate. "incipient wetness" means that for an aqueous slurry or paste mixture comprising a solid or semi-solid material, a point in time ("ΙΕριι") of the material is being measured, at which point the deionized water substantially covers the solid or The entire surface of the semi-solid material, and to the present extent, fills any water-permeable pore volume that the material may have, thereby allowing water to enter the aqueous slurry or paste mixture to provide contact between the glass electrode contact and its reference electrode and The liquid contact between the two is 126435.doc -19- 200902143, and then the material is measured. ''Isoelectric point, or IEP means that the solid surface charge of a solid or semi-solid material is zero at initial humidity. PH value. The IEp used herein may also be referred to as a zero P〇int charge (ZPC) or a zero charge point (p〇int 〇f "π charge, PZC). The catalytically effective amount,&apos;, represents at least a predetermined product sufficient to convert at least one of the reactants into sufficient yield under suitable processing conditions to support the amount of catalytic component of the test plant or commercial grade process.

Chalconide's table / ),, 丨, 〇何王 7 A group of 16 (formerly via) from a group consisting of sulfur (S), strontium (Se) and strontium (Te) An element and at least one compound that is more electropositive than the element or group of its corresponding Group 16 element. , precious metal, indicating transition metal from the group of 姥(10)), _, silver (Ag), silver (ir), Ming (Pt) and gold (AU), unless otherwise stated, metal complex, metal# The form of the metal cation or metal anion is in a charged state. Otherwise, the various transition metals are in a zero oxidation state (while in an unreacted state). "Anti-corrosion matrix, which means a matrix that is capable of resisting substantial changes in the matrix composition of the subsurface region". These changes are due to changes in structural elements caused by most acids or tests under standard temperature and pressure conditions and / = loss, new pore formation, pore size expansion, etc. ", the composition of the corrosion-resistant matrix may be substantially high-strength acid (such as concentration test (such as concentrated (four) H) or other strong rot (four) reagent (regardless of (four) and high temperature The combination of high pressure and/or high vibration frequency conditions, as defined by 126435.doc -20· 200902143, such matrices are still considered to be &quot;corrosion resistant substrates. :: Surface activity" means - material The surface is sufficiently filled with - or a plurality of charges:: the material that contains one or more charged components is used to (1) promote the catalytic reaction under the conditions of the stable reaction without further stepping, by Electrostatic interactions and/or ion exchange interactions between a variety of charged components and &quot; 11 electric phoenixes are used to further inductively react as a catalytic component under steady-state reaction conditions. ', means any solid or semi-solid ancestor X thousand U body 枓, including but not limited to glass and glass-like materials, (d) greater than 〇 but less than or equal to 14, surface active state can be in accordance with the matrix in the catalyst composition (with catalysis An effective amount of the catalyst is modified for its intended use. "Integration" means interaction by electrons and/or physicochemical interactions (eg, ionic, electrostatic or covalent interactions including, but not limited to, hydrogen bonding, ionic bonding, electrostatic bonding) The combination of van der Waals/dipole bonding, affinity bonding, covalent bonding, and combinations thereof, the chemical composition is combined with the matrix. 〇Implementation Overview The annotations in the overview of this embodiment are only used. The description is in a timely manner in relation to the selected aspect of the scope of the patent in question, and is therefore only used in a concise language to facilitate the presentation of certain aspects of the implementation that may be relevant to the potential interests of the reader. It should be considered as a limitation on the accompanying invention. One aspect of the present invention relates to a catalyst composition in which the average thickness of the surface active catalytically active region is less than Or equal to about 3 nanometers, preferably $126435, doc-21-200902143 4 20 nanometers, and more preferably about 1 nanometer nanometer (&quot;catalyst composition&quot;). Another aspect of the invention The present invention relates to various methods for producing novel catalyst compositions. The other aspect of the invention produces a composite form of the composition, whether or not the forming medium is present. The invention is further related to various processes. The use of catalyst compositions such as hydrocarbons, hydrocarbons and/or non-hydrocarbon treatment, conversion, refining and/or emission control and treatment processes and other types of processes. For example, 'new catalyst compositions can increase hydrocarbons , Hydrocarbon and/or non-hydrocarbon treatment, conversion, refining and/or emission control and treatment processes and other types of process selectivity, reaction rate 'finished yield and energy efficiency. There are several factors that should be considered in the production of the catalyst composition, including but not limited to: () in the intended use of 'substrate with a predetermined isoelectric point (&quot;ΐΕΡ&quot;), which is obtained as is or Obtained after subsequent processing; (^) the degree of corrosion resistance of the substrate in view of the intended use; (out) # in the intended use of 'in order to obtain the desired surface properties, the degree of porosity of the substrate (if any), and related elements Composition (particularly 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 - or a plurality of ions having the first species and the matrix and/or The first forming of the electrostatic interaction 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 within about 30 nanometers, preferably $20 nm' more preferably S about 10 nm; 126435.doc -22- 200902143 (V) matrix for an alternative ion exchange (ΙΕΧ), counter ion exchange (BIX) and/or electrostatic adsorption (ΕΑ )Approach Chemical sensitivities, which are used to integrate one or more second components onto the surface of the substrate and/or within the surface of the substrate having a second type of interaction with the matrix ions and/or electrostatics, and thereby producing a catalysis The active region 'the average thickness of the catalytically active region on and/or within the surface of the substrate is about 30 nm, preferably about 2 〇 nanometers, more preferably about 10 nanometers; and (vi) The intended use of the composition, the chemical sensitivity of the treated substrate to the following reactions: optional calcination and/or reduction, oxidation or further treatment of the treated substrate prior to use of the catalyst composition with the first or second catalyst The composition acts as a chemical reaction. I. Substrate Description IEp selection for the general and preferred description of many potential applications. Preferably, the substrate used to produce the catalyst composition of the present invention is a glass composition, whether the surface activity is received as received or processed. The state of surface activity 'IEP is greater than about 〇 but less than or equal to 14. The availability of a matrix with a suitable IEP (suitable to produce a catalyst composition for the intended use) depends on various factors, some of which have been outlined above (in the &quot;Embodiment Overview&quot;) 4 below Providing a more detailed discussion, those skilled in the art will have a clearer understanding of other factors associated with selecting an appropriate IEp. For example, for many commercially advantageous process 'glass (or glass-like) compositions and their surface active products preferably having greater than or equal to about 45 but less than 14, it is expected that IEp is greater than or equal to about 6q but less than Μ. Glass 126435.doc •23- 200902143 '° Good' and the glass composition with an IEP greater than or equal to about 7.8 but less than 14 is expected to be the most versatile. Sun, in particular, depends on the intended use of the catalyst composition and the extent and type of porosity of the composition Φ 炙 π + negative enthalpy of the composition, and the preferred range of IEP may be sizzling. Additionally, certain catalytic processes are more sensitive to catalyst compositions that are surface active at lower pH ranges. Therefore, in such cases, a matrix of ΙΕΡ/]' &amp; 7·8 (preferably $6' is preferably ^4.5) is likely to be more suitable for the table, so again, select within the appropriate range In the case of the substrate, it is not only necessary to consider the intended use of the catalyst composition, but also the porosity of the 纟α-containing matrix, the chemical composition and the treatment procedure (if any). In addition, depending on the intended catalytic use, many glass types can be potential matrix candidates to achieve the proper degree and type of enthalpy and porosity, whether received or used as one or more of the following treatments. Examples of glass types such as, but not limited to, bismuth-type glass, boron-free β-type glass, S-type glass, R-type glass, AR-type glass, rare earth-silicate powder, bismuth-titanium-tellurate glass Nitride glasses such as bismuth_aluminum_oxygen-nitrogen glass, type A glass, (: type glass and cc type glass. However, the following is an example of a glass type that is generally expected to be used for a range of catalytic applications and some possible treatments. The macroporous glass indicates that the substrate used to produce the catalyst composition of the present invention preferably comprises a glass combination which is substantially free of microporosity, has no mesoporosity, but has some large pores (&quot;no microporosity/no pores). The glass material of the material, whether it is originally surface-active or processed to form a surface active state, the IEP is generally greater than 78. 126435.doc -24- 200902143 Generally, the microporous/no-porous glass with an IEP greater than 7.8 The composition will include an acidic or basic oxide type glass mesh modifier, including, for example, but not limited to, zinc (Zn), magnesium (Mg), about (Ca), aluminum (A1), boron (B). , titanium (Ti), iron (Fe), nano (Na) and potassium (K) Oxide. If an alkaline mesh modifier is used, the amount included in the lower IEp glass tends to be &lt; 15 wt.%. Contains magnesium, calcium, aluminum, zinc, sodium and potassium. Preferably, the glass composition is better, and the glass composition containing more than or equal to about 7 〇wt.% of the cerium oxide is better. However, the macroporosity corresponds to less than about 98% of the total surface area, and the corresponding geometric outer surface A substantially microporous, void-free glass composition having a total surface area of from about 2% to about 5% by weight can also be used to produce the catalyst composition of the present invention' and that 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. Typically the 'matrix should be substantially non-microporous/no mesoporous, but may actually be quantitatively insignificant, for touch The microporosity and/or mesoporous volume 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 micropores/ No mesopores The catalyst composition of the present invention. The first surface area measurement is determined by a thermal adsorption/desorption method suitable for accepting the expected surface area range of the measurement, and can be used for detecting micropores, mesopores and/or macropores. For example, for larger surface area measurements (eg, > 3 m2/g) N2 BET, the square () according to ASTM D3663_〇3 may be a preferred surface area measurement technique. -25- 200902143 And, for smaller surface area spurs 1 / _ 里 里 (for example &lt; about 3 m2 / g) Kr BET, according to the method described in ASTM D4780.95, ("SA, m"), possible A preferred surface area measurement technique. Those skilled in the art of analyzing the surface area of solid and semi-solid materials will be well aware of the best surface area measurement methods for measuring microvoids, mesopores and/or macroporosity. The second measurement system for sodium-chemically adsorbed surface area (SA core) can be used in some type of analytical method (R_^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^ And description on page 353) is expressed as the change in time for the NaOH titrant and is more specifically defined in terms of the S An rate of change (&quot;SARC^". Thus, as defined herein, the matrix is substantially free of microporosity/nothing. The pores 'premise that the matrix S.An is here between about 〇1.m2/g to about 50 m2/g, and its SARC is less than or equal to 0.5. As discussed in more detail above, SARC is a NaOH titrant The ratio of the two volumes, the denominator is the volume of the initially used NaOH titration solution, ie initially used to titrate a matrix slurry mixture at 3.9 Μ NaCl solution (pH 4 to pH 9) at time zero. At about 25. (: contains 1.5 grams of matrix. But 'as mentioned above, before the initial NaOH titration is used for SARCw determination' the aqueous slurry mixture must first be adjusted accordingly with a small amount of acid (HC1) or alkali (NaOH) Is pH 4. In addition, still as described above, NaOH titration solution (for 3 5 minutes) The cumulative time at which the matrix slurry mixture is maintained at pH 9 for 15 minutes is V&amp;-V initial (ie, V5i 15), which is the numerator of the ratio SARCw. Therefore, if v total _v is less than or equal to At the beginning of V.5 V, the corresponding SARC&amp; is less than or equal to 〇.5 ^ Therefore, as defined herein, the matrix of SARC^^0.5 is substantially free of microporosity/no porosity (ie, macropores 126435.doc -26 - 200902143 gap), 刖 为 基质 基质 基质 基质 基质 基质 基质 基质 基质 基质 基质 基质 基质 基质 基质 基质 基质 基质 基质 基质 基质 基质 基质 基质 基质 基质 基质 基质 基质 基质 基质 基质 基质 基质 基质 基质 基质 基质 基质 基质 基质 基质 基质 基质 基质 基质 基质 基质Insufficient concentration, distribution, and/or type can adversely affect the desired performance of the catalyst composition for its intended use. Sodium surface area (&quot;SAw&quot;) is an empirical titration procedure that is granular Developed in the form of powdered and suspended gel form (suspended s〇l form) of substantially pure cerium oxide (Si〇2). S.A_cardiac determination of surface proton position (GlaSS-CTH+) reactivity and accessibility The measure of sex 'for pure ruthenium dioxide' corresponds to the Si-0_H+ position. Glass and crystalline niobate are significantly different in composition from pure niobium dioxide (Si〇2). For the stoichiometry of this titration procedure, the behavior of niobate glass and crystal niobate cannot be based on SA- The absolute value of the Na0H titration solution determined in the experiment was known or predicted. Therefore, the equations used by Sears and Iler to correlate the S.A_heart experiment&gt;^0^[volume with the N2_BET surface area of one of the oxidized stone materials of the nine researches are not suitable for reliable prediction of more complex tantalate combinations. The absolute surface area of the object. This is expected [because the Glass_〇.H+ group that can exist in different compositions of glass can include, for example, Al-0 H+, Β-ΟΉ+ ' Τί-ΟΉ+, Mg-CTH+, and more with a single stone eve position. The Si-CTH+ part combines with more differently structured proton groups (Q2 group). On the other hand, the total surface area of a "sampling" glass composition (such as acid immersion quartz) may be reliably determined using the SAw test, provided that the minimum pore size is within the range achievable by standard gas phase BET measurements because It is mainly composed of networked Si〇2 and Si-CrH+ parts. However, the accessibility of the Giass_ΟΉ+ moiety to hydroxide ions and sodium ions, and the relative percentage of macropores and/or substantially non-porous regions, 126435.doc -27-200902143 to:, 'According to Na〇_ f (in s Α · in the experiment to maintain the most value of 9 ' must be added compared to the time) (titrant) into (four) test. Therefore, 1 ancient, (7) part of the mine for the 0Η- and Na+ contrast time accessibility, as determined by the SARC heart experiment, can be used as a reasonable micro-porosity can be included in the standard gas phase tolerance test And some kind of porosity. Preferably, the surface area of the substrate will be substantially protected after its ion leaching process.

This is the same for most financial (, 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 performance of the catalyst composition to achieve the desired route. Since, if there is significant ion depletion and associated leaching on the matrix network, microporous regions are likely to be produced in the matrix. Therefore, as described above, when the SARC heart is larger than about 〇·5, it means that such a microporous structure exists. The matrix network showing these properties has produced sufficient microporous structure, particularly in the matrix region,

The microporous structure will adversely affect the ability of the substrate to maintain a surface active state, thus adversely affecting the desired properties of the catalyst composition for the intended use. The matrix shape, form and size are used to produce the tanning composition of the present invention. Matrix # has a variety of shapes and forms. Examples of suitable shapes include, but are not limited to, fibers, fibrillated fibers, cylindrical particles (eg, pellets), spherical particles (eg, spheres), elliptical particles (eg, ellipsoids), flat particles (eg, sheets), no Regular broken particles, spiral or helical particles, and combinations thereof. 126435.doc -28- 200902143 Examples of suitable shaped crucibles or composites that can form such I-shaped shapes include, but are not limited to, woven composites, non-woven composites, slabs, rings, saddles, cylinders , film, screw = film, filter, fiber, chopped fiber 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, with the catalytic matrix or composite (collectively &quot;composite", including but not limited to softwater crystal stones ( Boehmite), hydrated titanium dioxide and ^, hydrated zirconia and Zr〇2, bismuth oxide, alpha oxide, dioxo' clay, natural and synthetic polymeric fibers, polymeric resins and solvents, and water soluble polymers, whether or not the matrix includes a type 1 or type 2 catalytic component (described in more detail below). Preferably, the catalytic substrate should be at or substantially close to the outer surface of the composite (ie, located outside the composite). Without being bound by theory, It is believed that if a substantial portion of the catalytic substrate is placed on and/or within the periphery of the composite surrounding the outer region of the catalytic composite, the extent to which the undesirable internal composite diffusion effect is produced will be reduced. Therefore, it should be understood that the proper distance for positioning a substantial portion of the catalytic substrate within and/or over the periphery of the composite will depend on the intended use of the catalytic composite, the overall size and shape of the catalytic composite, and the catalytic substrate. The overall size and shape R. The average thickness of the periphery of the composite (the catalytic substrate can be placed on and/or within the periphery of the composite) is typically from about 4 microns to about 4 microns in various composite shapes and sizes. between. However, the average thickness of the periphery of the composite is preferably between about 丨 microns and about microns, more preferably between about 1 μm and about i 5 〇 microns. 126435.doc • 29· 200902143 2. Depending on the intended use of the catalyst composition, in some cases it may be necessary to substantially distribute the matrix over the entire forming medium. For example, but not limited to, 'in a process that requires extensive exposure of the reactants and/or reaction intermediates', preferably a composite matrix (whether type or type 2 catalytically active matrix) over the entire forming medium, with a controlled pore size distribution though Better but not necessary. The minimum size of the I material used to produce the shaped or composite material (i.e., the average maximum size of the matrix particles) is typically between about 5 mils to less than or about 150 microns, preferably at about 2 micrometers. Between less than or equal to about (10) microns, more preferably between about 0.2 microns and about 5 microns, depending on the intended use of the composition and other process variables that may be affected by the shape and form of the combination of catalysts, Substrates outside this range are still effective, for example in the continuous fiber form described above, without adversely affecting the desired properties of the catalyst composition. Those skilled in the art will appreciate that the composite operation can and/or microporosity be incorporated into the finished composite. However, this porosity does not introduce the functionalized surface component of the catalyst composition during the complex process as described herein. π. Matrix Surface Activation The base f used to produce the catalyst composition of the present invention can be surface activated by - or a plurality of first components - the first component has a first-type ion and/or electrostatic interaction with the substrate (" Type component precursor"). As described in more detail below, the Type 1 component precursor may itself have catalytic potency or may be further processed to produce a catalytically active region 'average thickness on and/or within the surface of the substrate 126435.doc • 30 - 200902143 degrees 仏An average thickness of about 30 nm, preferably about 10 nm. The average thickness of Example 220 is not more than that of the medium composition, and in some cases, depending on the extent to which the contact is obtained, the appropriate type of substrate is suitable for the intended use (just, The substrate may be::::structure (if any) and isoelectrically spotted. Although not necessary, preferably: surface activity 'is effectively promoted to improve its surface activity. In addition, further modifications and / or

It may be dry (4) ( (4) I (4) In addition to any pre-existing materials, such as organic paint or other possible contamination. In addition, as described in more detail below, the Μ Μ Τ Τ ύ ύ ύ ύ 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在The treatment side, H, and the electrostatic adsorption (EA) treatment method further processes the surface of the matrix in the main A, and the treatment method integrates the first component into the surface of the substrate; ¢ / 十女一冲 buying on the surface and / or inside, the surface of the substrate has a class of ions and / 戋 static, long / and electrostatic interactions with the matrix, and thus a catalytically active region, at the base, The average thickness on and/or within the surface is 30 nm, preferably S 20 nm, more preferably $ 1 nm. The non-matrix contaminant removal treatment β is typically determined by the composition of the material found on the surface of the substrate and whether the material is expected to interfere with the preparation of the catalyst composition and/or interfere with the desired properties of the intended use of the catalyst composition. , optional for removal of contaminants. For example, typically, the AR-type glass is made using an organic coating (i.e., sized). The organic coating is used to facilitate processing, such as dispersion in aqueous formulations. However, the organic coating or sizing may interfere with the preparation of the catalyst composition, even if it does not interfere with most, if not all, of the catalytic properties of the intended use of the catalyst composition. Therefore, the organic coating should be removed. A general firing system is a preferred method for removing such organic coatings. Because the primary goal of this treatment is to remove contaminants from the substrate, the conditions of such a segmentation process are not particularly important for successful surface activation of the matrix. In some cases, depending on the nature of the contaminant to be removed from the substrate, solvents, surfactants, aqueous cleaning or other suitable methods can be used to remove contaminants for satisfactory results. However, depending on the degree of calcination used, the substrate is preferably calcined in an oxidizing atmosphere (e.g., in air or oxygen). It is also important to select the southern calcination temperature to remove the target contaminant, but the calcination temperature is low enough to avoid the softening point of the material. Generally, the calcination temperature should be at least about 5 (rc lower than the softening point of the selected matrix material. Preferably, the calcination temperature should be at least about 1 〇〇〇 C lower than the softening point of the selected matrix material. For example, in the use of the AR type In the case of glass, the calcination temperature of most AR type glass acceptable for removing contaminants is between about 300 t and about 70 (TC. Typically, the selected matrix material should be calcined for about 2 to 14 hours, preferably calcined 4 to 8 Hour. However, depending on the nature of the substrate obtained and the nature of the target contaminant to be removed from the substrate, the calcination time can vary outside of these time ranges. Surface activation is achieved by ion leaching in any potential contamination After the substance is substantially removed from the substrate, the substrate can be treated to produce a surface active state and a desired isoelectric point (, ΙΕρ,), provided that the initial IEP obtained from the substrate is not within the desired range. In some cases, the substrate received may be sufficiently surface active and needs to be further modified using one or more other treatments (described in more detail below), 126435.doc •32· 200902143 without using One type of ion leaching (IEX-1) treatment (which will be discussed first in other treatments described in more detail below). In other words, the elemental composition of the matrix 'in particular on the outer surface or substantially close to the outer surface, may be sufficient to obtain The desired IEP. However, in many cases, the elemental composition of the matrix will require some modification to change the original IEP and obtain a suitable IEP, followed by the type and extent of compliance with the intended use of the catalyst composition. Surface active state.

The surface active state, in the case where one or more of the first components have (1) a first oxidation state and (11) a first type of ion and/or electrostatic interaction with the matrix, may be sufficient to produce a catalytically active region on the surface of the substrate And/or the inner thickness is about 3 〇 nanometers, preferably about 2 〇 nanometers, more preferably ^, the spoon 10 is not rice, and thus provides the desired properties of the catalyst composition to achieve the intended use. For example, but not limited to, Bronsted or Lewis acid sites on the surface of and/or in the matrix can be effectively promoted by some hydrocarbon hydrocarbons (eg, Oxygenated smoke) and non-smoke treatment, conversion and/or refining processes. / and 'in other cases' based on the intended use of the catalyst composition, mr-type system - or a variety of ion exchange methods as described below to enter a = = shell to achieve (1) can be the same as the first oxidation state Or an average of different interactions, Γg, and (11) the second and the ion and/or electrostatic phase of the base f: to produce a catalytically active region on the surface of the substrate and/or within about 3 mm. 2 heart, more preferably ^ is now transferred to the surface activation treatment surface activation treatment including at least one ion 126435.doc -33- 200902143 leaching treatment, using (iv) to obtain the first type or type 1 ion exchange (de(1) matrix. However 'should understand If the substrate to be received has a suitable foot for the intended use of the catalyst composition, it is also intended to be used to describe the first type of substrate. Generally, the ion leaching treatment is performed by any suitable method, that is, in essence. Heterogeneous means effectively remove the desired ionic species from the entire substrate surface without significantly eroding the matrix network (eg, avoiding the creation of any microporous structures in the surface region and/or subsurface regions), such as but not limited to large Partial acid The substance 'whether inorganic or organic acid, and various sounding agents, is suitable for ion leaching treatment. Preferably 'inorganic acid, such as but not (d) succinic acid, phosphoric acid, sulfuric acid, hydrochloric acid, acetic acid, perchloric acid, Tannic acid, chlorosulfonic acid, trifluoroacetic acid, and combinations thereof. Generally, the concentration of the acid solution used for ion leaching depends on the properties of the substrate (eg, the affinity of the ions to be removed from the glass mesh, removed) The strength of the glass after the ionization of the network), the enthalpy of the substrate, and the intended use of the catalyst composition. Preferably, the concentration of the acid solution used for the ion leaching treatment may be about 〇.5 wt.%. Between about 5 G wt%, more preferably between about 2.5 wt.% and about 25 wt.%, most preferably between about 5 red % and about ι 。. The chelating agent can also be used for ion leaching, for example 'But not limited to ethylenediaminetetraacetic acid (&quot;EDTA&quot;), crown bismuth, oxalate, polyamine, polycysteine, and combinations thereof. Generally, the concentration of the integrator solution treated with silk 9 depends on Characteristics of the matrix (eg '9 pro-ion removed from the glass mesh The force, the strength of the glass after removal of the network ions) and the predetermined composition of the catalyst composition 126435.doc -34. 200902143. Preferably, the concentration of the chelating agent solution for ion leaching treatment may be about 〇 〇〇1 wt.% to saturation, more preferably between about wti wt% to saturation. Usually, depending on the type and concentration of the acid or chelating agent used and the characteristics of the substrate, The heat treatment conditions for the ion leaching treatment, such as the heating temperature, the heating time, and the mixing conditions. The heating temperature varies widely depending on the concentration of the acid solution or the chelating agent solution. However, it is preferably applied to the acid ion leaching treatment. The heating temperature is between -20 C and about 200 C, more preferably about 4 Torr. 〇 between about %, preferably between about 6 (TC to about 9 〇t. Preferably, the heating temperature suitable for the chelating agent ion leaching treatment is in the range of about 2 〇t to about 2 ,, More preferably, it is about 40. 〇 to about 9 〇. (: range. Depending on the concentration of the acid solution or the chelating agent solution and the heating time, the heating time suitable for the ion leaching treatment may be changed. Preferably, for the ion The leaching treatment is heated for a period of time between about 15 minutes and about 48 hours, more preferably between about 3 minutes and about 12 hours. Depending on the type and concentration of the acid or chelating agent used and the matrix Characteristics (eg, 'affinity of ions to be removed from the glass mesh, strength of the glass after removal of the network ions, etc.) and duration of heat treatment, the mixing conditions are selected. For example, but not limited to, the mixing conditions may be continuous Or intermittent, mechanical mixing, fluidization, tumbling, rolling or manual mixing. The combination of human ~ 'tannin or chelating agent concentration, heat treatment conditions and mixing conditions' will be based on the acid or chelating agent and the target matrix ion Achieve enough ion father to change The degree of &quot;ΙΕχ&quot;) is determined to produce the appropriate isoelectric point 126435.doc -35- 200902143 and the type and extent of surface charge to achieve the surface required for the post-treatment of the substrate or the intended use of the catalyst composition. Active state. After the ion leaching treatment is completed, preferably the appropriate method is used to separate the substrate subjected to ion leaching, including but not limited to filtration, centrifugation, decantation, and combinations thereof. Then, one or more appropriate Cleaning solution (9) such as deionized water and / or a suitable water-soluble organic solvent such as methanol, ethanol or acetone, the ion-leached substrate is washed and dried at a temperature of about 11 ° C from about 20 ° C to about 24 ° C. The anti-ion exchange treatment may in some cases be 'depending on the predetermined composition of the compositing composition, which may be preferred: counter-ion exchange (&quot;Βιχ") or two-step ion-parent treatment for the selected substrate ( In this context, collectively referred to as ΒΙχ treatment. Βιχ treatment is commonly referred to as (but not limited to) &quot;anti-ion" exchange because the ion-leached substrate is included with the initial removal - mixing of a salt solution of an ion (eg, blue), which is removed from the substrate by ion/removal treatment (eg, subsequent return or return to the substrate. It is not clear whether the ions removed from the matrix,疋 will return to the same position originally occupied in the matrix. But 'whether or not the originally replaced ion will change position completely or partially because of BIX treatment, it should be understood that the Βΐχ treatment described in this article covers any The composition of the catalyst produced by the change of the possible ionic sites. The type of salt solution used to treat the substrate subjected to ion leaching treatment depends on the type of ions that will be subjected to counter ion exchange. Preferably, only counter-ion exchange of ions is performed'. However, in some cases, counter-ion exchange of two 126435.doc-36-200902143 or more ions may be required. - Any ion that is easily removed by the above method of ion leaching can be replaced by a counter anti-ion parent. Some examples of such plasmas include, but are not limited to, Group 1 (former Group IA) alkali metal ions, such as lithium, sodium and potassium ions, and alkaline earth metal ions from Group 2 (former Group IIA), for example Antimony, magnesium, mionic, NH/ and calcined cations, and small organic polycations. Preferably, the alkali metal ion &amp; NH4+ system is preferred for BIX treatment.

Na+ and NH/ are preferred ruthenium ions, and Na+ is a better ion. Generally, the concentration of the salt solution used for the BIX treatment depends on the type of the substrate to be treated by the BIX by the ion leaching treatment and the relative affinity of the ruthenium ions for returning to the ion leaching treatment group I, as well as the ruthenium ion return matrix. The site in the mesh is independent (eg, the relative affinity of Na+ for the matrix versus Η+). For most types of glass substrates, such as, but not limited to, AR-type glass, enamel-type glass, or quartz glass, a BIX-salt solution having a concentration of about 〇〇.〇im〇1/L to $mol/L is preferred, and about 〇〇 5 m〇1/L to 3 mol/LBIX-salt solution is more preferred. Typically, the heat treatment conditions for the BIX treatment, such as the heating temperature, the heating time, and the mixing conditions, are selected depending on the type and concentration of the ΒΙΧ salt solution used and the characteristics of the substrate. Preferably, the heating temperature for the hydrazine treatment using the BIX-salt solution may be between about 20 ° C and about 200 ° C, more preferably between about 3 Torr and about 95. Between. Depending on the concentration of the BIX salt solution and the heating temperature chosen, the heating time for the BIX treatment can be varied for 126435.doc •37· 200902143 BIX. Preferably, the heating time of the Βιχ treatment is between about 5 minutes and about 24 hours' more preferably between about % minutes and about 8 hours. 'Generally, depending on the type and concentration of BIX solution used and the characteristics of the substrate (eg 'affinity of ions to be removed from the glass network, strong glass after removing the network ions, etc.) and heat treatment Hold and renew the day (five) and choose the mixing conditions. For example, without limitation, the mixing conditions can be continuous or intermittent, or mechanical mixing, fluidization, tumbling, rolling, or manual mixing. In short, the concentration of BIX salt solution, heat treatment conditions and mixing conditions. In essence, it is determined based on the return of a sufficient amount and the distribution of a sufficient amount of Βιχ_ ions back to the substrate, irrespective of the location of ions in the matrix network. A sufficient amount of Βιχ_ion is used to produce the desired surface charge type and extent&apos; to produce a surface active state desired for the intended use of the post-treatment or catalyst composition to achieve base f. By adjusting the pH to adjust the surface charge of the substrate, it is preferable to use a negative surface charge on the substrate to support electrostatic interaction with a positively charged tool such as a cationic alkaline earth metal, a cationic transition metal component, or Affinity. However, for some potential touch, '', sputum applications, it may be necessary to use a positive surface charge to support the components with negative charge (such as anionic transition metal oxygen ions, sulfate anions, noble metal polyhalide anions, etc.) Electrostatic interaction or affinity. Generally, the surface energy of the substrate can be changed to 126435.doc -38· 200902143 by adjusting the pH of the substrate/IEX mixture 2 treated by ion leaching to be lower or higher than the isoelectric point of the substrate, ΙΕΡ"). Positive or net negative state. Think back, ιΕρ is also called zero charge (&quot;ZPC&quot;). Therefore, in other words, IEP (or ZPC) can be regarded as the pH of the material with a net zero surface charge on the surface at initial humidity. Therefore, adjusting the pH of the matrix/IEX water mixture to be greater than the pH of the matrix IEp (or 21&gt;(:) produces a net negative surface charge on the substrate. In addition, the pH of the matrix/hydrazine mixture The value is adjusted to be less than the positive value of the matrix ι (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-reformed AR type is processed Adjusting the pH of the glass to a pH of &gt; 9,6 will result in a net negative surface charge on the glass surface. Depending on the IEp distribution of the AR glass, the preferred way may be to adjust the pH to be greater than Substrate IEp one or two or more pH units to protect It is proved that the surface charge is fully supported. The type of solution used to carry out the pH adjustment will depend on compatibility with other reactants, glass stability and desired charge density, and other factors. Usually 'any dilute alkali It can be used to adjust the surface charge of the substrate to the right of its IEp (ie, to produce a net negative surface charge), and any dilute acid can be used to adjust the surface charge of the substrate to the left of its IEP (ie, to produce a net positive surface charge). Inorganic acids and bases or organic acids and bases can be used in dilute concentrations, and are generally preferably inorganic acids. 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 To obtain 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. 126435.doc •39 - 200902143. Under these conditions, electrostatic adsorption (EA) type integration mechanisms may not occur. However, without being bound by theory, in exchangeable Direct ion exchange (IEX) 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 position for IEX or BIX, such as, but not limited to, such moieties, such as decyloxy (-Si-o-Na, partially including at least partially a positively charged catalytic metal or metal complex precursor The Na+ ion displaced by a substance such as, but not limited to, I^NH3 42), thereby producing a substrate having an effective amount of a catalytic component. Controlling the surface charge of the BlX treated substrate by adjusting the pH is as in the case of IEX treatment or second treatment (&quot;ΙΕχ_2 treatment, as discussed below), for some BIX treatments, pH adjustment may be required, But not required. Similarly, depending on the type of BIX-ion that will be integrated into the surface = second component and exchange in the IEX-2 treatment, the degree of ipH adjustment required will generally depend on the ratio of the matrix, its IEP versus surface charge distribution curve, and The type of charge required. The type of solution used to effect the pH adjustment will depend on compatibility with other reactants, the inertness of the matrix within the relevant pH range, and the desired charge = degree and other factors. Any rarity 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), while 126435.doc •40-200902143 can be used to adjust the surface charge of the substrate to its The left side of the IEP (that is, the net positive surface charge). The inorganic acid or organic acid or organic acid can be used in a dilute concentration. Usually, the concentration of the dilute acid solution or the rare test solution will depend on The type of acid or base used, its dissociation constant, and the pH at which it is suitable for obtaining the type and density of the surface charge. III. Pre-integration treatment of type 2 precursors Whether the surface surfactant of the substrate is received as it is, or is subjected to ion leaching ( That is, the substrate treated by IEX-1, or treated by BIX, preferably, in (1) second ion exchange ΓΙΕΧ-2"), (Π) electrostatic adsorption (EA) treatment or (out) certain IEX- 2 in combination with the EA treatment, using at least one second component precursor (type 2 component precursor '') to further treat the substrate so that one or more

Alternatively, certain Type 2 component precursors may produce catalytically active regions without further treatment or may be further processed to produce catalytically active regions comprising one or more Type 2 components. However, regardless of the catalytically active region

About 20 nm, more preferably about 1 〇 nano.

126435.doc 200902143 The reaction rate and energy efficiency of the process using the catalyst composition of the present invention can be carried out by k. / / and / or the first component - "component 1" and A component ("type 2 component") is significantly increased in integration with the surface of the substrate. - In the case of a theoretical constraint, the ion is directly connected to a specific ion exchange site on the surface of the substrate and/or in the inner I. The combination of your surface and the surface of the substrate with the opposite charge and some interactions between electrostatic interactions or some other types of precursor charge-surface interactions to be understood 'Form 2 component precursor ions can be integrated. However, regardless of the nature of the interaction, the substrate is treated as received, the substrate treated with hydrazine, or the mx-treated substrate produces a second precursor charge-surface In the case of a second interaction, the precursor of the type 2 component may thus produce a catalytically active region having an average thickness on the surface of the substrate and/or within the range of -3, and not more than about 2, preferably about 2 Nano, more preferably about 丨〇 nanometer. For the convenience of the following discussion, and is not intended to limit the scope of the invention described herein, ΙΕχ_2 is used herein to collectively refer to the charge-surface interactions of precursors commonly referred to as type 2_types. Extensive interaction of interactions or precursor interactions of type 2. In general, the type of salt solution used to treat a substrate treated with IEX-1 or treated with hydrazine will depend on the ion exchange to be carried out in the ΙΕχ_2 treatment. Class 1 or sputum ions will undergo ion exchange or, in some cases, exchange of two or more ions, or simultaneous ion exchange' or ion exchange in sequence. In two different types Integration of Component Precursor Ions with Matrix 126435.doc -42- 200902143 In the following article, "Hui ΙΕΧ 2 treatment is called two ion exchanges or two ΐΕχ_2 treatments. Therefore, the precursor ions are integrated with the matrix in three different types of components. In the case of ΙΕΧ-2 treatment, avoiding it is called two-human ion exchange or three times IEX-2 treatment. Type 2 components and pre-mediation instructions serve - 2 ions (four) dissolve If the (4)-like receiving, group-purchasing, or BIX-treated substrate surface replacement ions are chemically sensitive, or have charge affinity to achieve electrostatic interaction with the surface of the substrate treated by the treatment or by Βιχ_, ie, It can be used. Therefore, 'ΙΕΧ-2 ion can be used as a precursor of type 2 component. As described above, according to eight intended uses, the plasma ΙΕχ_2 precursor (ie, type 2) may have catalytic efficiency, and if so, the ionicity The ΙΕΧ-2 precursor can be used in the same manner as the type component in a certain type of catalyst composition, but the ion can also be used in the preparation of another type of catalyst composition. ΙΕΧ-2 precursor works. However, in general, 'ionic ΙΕΧ_2 precursors (which can be used to obtain type 2 components integrated with the surface of the substrate) include, but are not limited to, Blenzel or Lewis acid, Blenz or Lewis, f metal strontium ions and precious metals Mismatched cations and anions, transition metal cations and transition metal complex cations and anions, transition metal oxyanions, transition metal chalcogenide anions, main oxyanions, halides, rare earth ions, rare earth cations and anions, and combinations thereof . Also, depending on the intended use of the catalyst composition, certain ΐΕχ2 ions themselves have a catalytic effect in the prodenial state, and a type 2 component can be produced when integrated with a suitable matrix. It can be selected to have catalysis without further treatment. 126435.doc 43 200902143 文文力的 Ionic I ρ γ 1 ^X-2 then, some examples include but not limited to Sterling or Lewis acid, Bronx Special or Lewis test, noble metal cation Γ 2 metal cations, transition metal oxyanions, main oxygen anions, South, rare earth hydroxide ions, rare earth oxide ions and combinations thereof. Certain precious metals and transition metals that can be used as precursors to type 2 components, including but not limited to Groups 7 through (10) (formerly _, 瓜, 纪, 州, Vb, and 契) For example, New Zealand, Bissil Silver, Gold m, Chain, Iron, Cobalt, Iron, -, Word: Ionic Salts and Mixed Ion Salts, and combinations thereof. For the 2 treatments, the ionic salts of the faces, the faces, the 7-square bismuth, the bismuth, the bismuth, the copper, the silver, the gold and the nickel are particularly preferably linked: the elements of the groups can be used by using international theories and applications: 2 t ( The IUPAC) naming system is queried in the P. peam.lanKgGV/peHQdie/defauh ht t periodic table "showing the previously used family number". u can be used as a precursor to the type 2 component of some transition metal oxygen yin, including but not limited to the 5th family 筮 ^ real fantasy,

Salts of the ion, the first and the sixth (formerly the % and VIb), such as V043·, W〇-H2W., Mg(VM〇7〇24, Nb6〇i/·, ReCV and Combination. The ionic salts of bismuth, molybdenum, tungsten and vanadium are particularly preferred for f 'X-2 treatment, as some of the transition metal chalcogenides of the precursor of the type II component such as a ~ and its = (... pseudo-family)... For example, some of the main groups of the precursors of the type 2 component are anodic, but not limited to, the ionic salts of the group 16 (formerly vj example, including the group), such as S〇42-, 126435. Doc -44- 200902143 ',SeCU2· and combinations thereof. For ΙΕχ_2 treatment, the ionic salt of scu2_ is especially good. Some examples of _ ions that can be used as precursors of type 2 components, including but not limited to group 17 (formerly An ionic salt of the group 113, for example, F-, C1-, Br., I, and combinations thereof. For the IEX_2 treatment, an ionic salt of F· and Cl· is particularly preferred. Some rare earths can be used as a precursor of the type 2 component. Examples of ion and rare earth misidentified cations or ions, including but not limited to lanthanides and ionic salts of lanthanides such as La, pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy , Ho, Er, Tm, Yb, Lu, Th, U and combinations thereof. It can be used to produce transition metal-carbides, transition metal-nitrides, transition metal-borides and transition metal-phosphides as type 2 components. Some examples of transition metals include, but are not limited to, ionic salts of chromium, molybdenum, tungsten, rhenium, knobs, iron, cobalt, nickel, and combinations thereof.

The concentration of the salt solution used for IEX-2 treatment depends on the type of substrate treated by ΙΕχ_丨 treatment or BIX-treatment and treated by ΙΕΧ_2 and for interaction and/or integration with the substrate treated with ΙΕΧ-1. The relative affinity of the 圧 and _2 ions. For most types of glass substrates (such as, but not limited to, AR type, A type, or soda_lime glass), an IEX-2 salt solution of about 1% to saturated is preferred, and about 〇〇 〇1 wt% to 5 wt% ΐΕχ_2 salt solution is better. However, the ΙΕχ_2 salt solution may be less than 0.00 1 wt.0/ depending on the functional surface concentration of the catalytic component necessary to achieve the intended use of the catalyst composition. . If multiple ion types are exchanged with the substrate, either simultaneously or in sequence 126435.doc -45· 200902143, the concentration of the salt solution will be on a daily basis for the relative loading of the various component precursors on the substrate and the matrix,八^ _ is used to compare the relative affinity of a component precursor to another component of the precursor _ 琨仃 整. For example, but not limited to, two EX-2 treatments (ie, two non-1J catalytic component precursors are integrated with a ΙΕχ_i. BIX-treated substrate) or =^X-- into an IEX-2 treatment (ie, three In the case of different catalytic components, the ruthenium drive is integrated with the substrate of 戎γγ 丄驭 丄驭·························································· The compositional precursors that are integrated with the surface of the substrate are initially in relative concentration and surface affinity for various ions. Typically, heat treatment conditions suitable for the ΙΕχ_2 treatment, such as heating temperature, heating time, and mixing conditions, are selected depending on the type and concentration of the ΙΕχ2 salt solution used and the characteristics of the substrate. Preferably, the heating temperature suitable for the hydrazine 2 treatment using an acid may be between about 2 (TC to about 200 ° C, more preferably between about 30 ° C and about 9 (Γ between: depending on IEX-2) The concentration of the salt solution and the selected heating temperature may vary depending on the heating time of the IEX-2 treatment. Preferably, the heating time for the pressure parent treatment is between about 5 minutes and about 48 hours, more preferably Between about 3 minutes and about 5 hours. Usually 'depends on the type and concentration of the IEX-2 salt solution used and the characteristics of the substrate (eg 'affinity of the ions to be removed from the glass mesh, remove the net The mixing time of the strength of the glass after the ion and the duration of the heat treatment, for example, but not limited to, the mixing condition may be continuous chopping, mechanical mixing, fluidization, tumbling, rolling or manual mixing. The combination of IEX-2 salt solution concentration, heat treatment state and mixing conditions 126435.doc -46- 200902143 is essentially based on the integration of a sufficient amount of IEX-2 ions and IEX-2 ions on and/or in the matrix. Distribution is determined, and physical and chemical bonding with the surface of the substrate Irrespective of nature, to produce the desired surface and extent to produce the desired surface activity for the intended use of the catalyst composition. / Adjust the surface charge of the substrate by adjusting the pH as described above. The degree of {)^1 adjustment required for the type 2 component precursor to be integrated with the surface in the second (&quot;ΙΕχ_2&quot;) treatment will generally depend on the IEP of the matrix, the IEP versus surface charge distribution curve of the matrix, and The desired type of charge, such as, but not limited to, for a substrate having an IEp equal to 8, preferably, the pH of the kebab/IEX-2 mixture is adjusted to between about 8 and about 12, more preferably between about 9 and about 11. The type of solution used to effect the pH adjustment will depend on compatibility with other reactants, stability of the matrix over the relevant pH range, and the desired electrical conductivity and other factors. Rare tests can be used to adjust the surface charge of the substrate to the right of its IEP (ie, to produce a net negative surface charge), and any dilute acid can be used to adjust the surface charge of the substrate to the left of its IEp (ie, to produce a net positive surface). Charge) inorganic acid or alkali The organic acid or base can be used in a dilute concentration, and is usually preferably an organic base. Usually, the concentration of the dilute acid solution or the dilute alkali solution will depend on the type of acid or base used, its dissociation constant, and the desired surface. pH of charge type and density. After completion of the 1EX_2 treatment, preferably, the IEX-2 treated substrate can be isolated using any suitable method including, but not limited to, filtration, centrifugation, decantation, and combinations thereof. The substrate treated with ΙΕΧ_2 uses one or more 126435.doc •47- 200902143 suitable cleaning solutions (such as distilled water or deionized water, dilute alkali or dilute acid and / or D suitable water-soluble organic solvent, such as indanol, It is washed with ethanol or acetone and dried at a temperature of about 110 ° C for about 2 to 24 hours. JV. Post-deep treatment description As needed, after the substrate treated by IEX_2 is separated, it can be dried only by melon, simmered under oxidizing conditions, then reduced or further oxidized, reduced without calcination or not calcined. Oxidation in case. The surface metal precipitated transition metal ions, oxyanions and/or may be subjected to surface precipitation in a gas phase or a liquid phase by a suitable reduction, sulfurization, carbonization, nitridation, phosphating or boronating agent (-IDING reagent). The reaction of a sulfur anion produces a corresponding catalytically effective metal sulfide/sulfur oxide, metal carbide/carbon oxide, metal nitride/nitrogen oxide, metal boride or metal phosphide component. Typically, but not limited to, the purpose of the post-precipitation calcination treatment is essentially to decompose the metal counterion or ligand and to more closely integrate the metal, metal oxide, metal chalcogenide, etc. with the surface of the substrate and remove any Residual water removed in the previous drying process. The calcination conditions for the IEX-2 treated substrate are not particularly important for successful surface activation of the substrate, however, these conditions should only be sufficiently stringent to produce at least one precursor with precipitated components in a catalytically effective amount. Active area. However, in the case of calcination, the substrate is first calcined in an oxidizing atmosphere (e.g., in air or oxygen). In addition, the important system is to choose a high calcination temperature to ensure that the precursor of the type 2 component of interest is oxidized and any residual water is removed (if any residual water is still present), but forging 126435.doc -48- 200902143 The burning temperature should also be low enough to decompose the precipitated precursors reasonably to avoid the softening point of the matrix and undesired. For example, but not limited to the 'salt of the sulphate salt, the cation is required to decompose the bound cation and fix the sulfate. The surface is flawed, but these 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, provided that the conditions are such that the metal oxides volatilize from the surface or cause the metal oxides to dissolve into the matrix. Finally, precious metals and complexes should be calcined under the following conditions: decomposition of the ligands and anions present, but not so strict that the precious metals accumulate on the surface. For this reason, as explained in more detail below, the noble metal is preferably directly reduced without calcination. Typically, the calcination temperature should be at least about 10 ° C lower than the softening point of the selected substrate. The calcination temperature should be between about 100 ° C and 700 ° C, more preferably about 2 Torr. 〇 Between 600 ° C, preferably between about 300 ° C and 500. (Between: Typically, the substrate treated with IEX-2 is calcined for about i to about 24 hours, preferably calcined for about 2 to about 12 hours. However, depending on the type 2 component of the matrix integration, The calcination time can vary outside of these ranges. Typically, but not limited to, the post-precipitation reduction treatment aims to reduce, at least substantially, if not completely, the catalytic component precursor (eg, metal, metal oxide or metal sulfide) to A lower oxidation state integrated with the surface of the substrate. Examples of suitable reducing agents include, but are not limited to, CO and H2. H2 is a preferred reducing agent, preferably having a flow rate of from about 0.01 L/hr to about 100 126435 per gram of substrate. Doc -49- 200902143 L / hr 'better flow rate between each gram of matrix 〇 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 It is at least 1 〇〇t lower than the softening point of the substrate. 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 1 hour to about 8 hours. , the substrate treated by IEX-2 can be dissolved by The phase treatment is carried out for reduction, and the solution phase treatment is carried out using a soluble reducing agent such as, but not limited to, hydrazine, sodium hydride, lithium aluminum hydride or a combination thereof in a suitable solvent such as water or diethyl ether. Usually, but not limited to, precipitation The purpose of the post-IDING reaction treatment is to 'reducing metal ions, metal oxyanions and/or metal sulfide anions while reacting the reduced metal with a reagent containing a lower atomic amount of _IDING element. In some cases, 'direct- IDING can occur without simultaneous metal oxide reduction, such as certain sulfurization treatments. Typical gas phase-IDING reagents include, but are not limited to, hydrogen sulfide, methyl mercaptan and dimethyl sulfide (vulcanization reagent), ammonia ( Nitriding reagent), methyl ketone, e-sinter and other light hydrocarbons (carbonizing agents). These gas-IDING reagents can be directly reacted with IEX-2 treated substrates under ambient pressure or under pressure, or It is reacted with a substrate treated with IEX-2 in a gas mixed with an inert gas or hydrogen to produce a corresponding sulfide, carbide or nitride. It may have catalytic effect. Part of the force - IDED products (including sulfur oxides, carbon oxides and nitrogen oxides) can also be produced by: substantially as received/obtained matrix, IEX-2 treated integrated matrix, via IEX -2 treated calcined substrate or IEX-2 treated reducing substrate for incomplete reaction. 126435.doc •50- 200902143 Metal phosphide can be produced by two ion exchange (two IEX_2 treatment) substrate reduction treatment, One of the IEX_2 treatments is one or more transition metal ions, and the other IEX-2 treatment is a phosphate ion. Preferably, the two IEX-2 treatments can be performed sequentially. Alternatively, the metal phosphide can be produced by using a gas phase phosphating reagent such as, but not limited to, phosphine (pH 3) to produce the desired metal phosphide. For example, a substrate that is subjected to a single ion exchange with a desired transition metal in a suitable oxidation state (a substrate treated with a single Master 2) can be further treated with PH3 to produce the desired metal phosphide. Solution phase treatment can be used to produce metal Sulfide, metal boride and metal phosphide catalytic components. Typical solution treatments for metal sulfides include, but are not limited to, in the range of to / ΒΠ to reflux temperature, with an effective concentration of hexamethyl-sulfonane organic The solution treats the metal-ion-integrated bismuth treated with ΙΕΧ_2 for a time sufficient to produce a catalytically effective amount of the catalytic component on and/or within the surface of the substrate. Typical solution phase treatments that produce borides include, but are not limited to, for warp -2 treated metal-ion_integrating substrate, treated with sodium borohydride or potassium borohydride solution at room temperature to reflux temperature over a period of time effective. Typical solution phase treatment for phosphating includes room temperature to reflux Internally, the metal-ion-integrated matrix treated with hydrazine-2 is treated with an aqueous solution of sodium hypophosphite for a sufficient period of time. A catalytically effective amount of a catalytic component is produced on and/or in the surface of the V. The catalytically active region indicates that the catalytically active region resulting from any of the above substrate treatments will have an average thickness of (1) less than or equal to about 30 nm, preferably $ about 2 nanometers, 126435.doc • 51. 200902143 more preferably about 10 nanometers, and (ii) a catalytically effective amount of at least one catalytic component. Preferably, XPS spectroscopy is used to determine the average thickness of the catalytic region. XPS spectroscopy uses a layered etching technique called sputter depth distribution (described in more detail in the analytical methods provided below). However, other analytical techniques known to those skilled in the art can also be used to determine catalysis. The composition is compared to the approximate location of the surface of the associated substrate. Therefore, the average thickness of the matrix catalytic region can be determined using, for example, but not limited to, transmission electron microscopy (TEM) or scanning TEM (STEM, also described in more detail below). Those skilled in the art have a thorough understanding of the XPS or TEM procedures. It should be understood that in the extreme case, regardless of the catalytically active region, Or IEX-2 treatment (with or without BIX treatment), for any of the catalyst compositions of the present invention, the thickness of the catalytically active region is generally (4) not substantially passing through the & surface region or (8) Not f exceeding the surface of the substrate by a thickness of about 30 nm, preferably not more than about 2 () nanometer thickness, more preferably not more than 1 nanometer thickness. About one or more on the treated substrate and/or within Catalysis: The enthalpy of the f-region, it should also be understood that the catalytically active region may: (a) be on the outer surface of the matrix, and in the presence of any pores, on the pore wall surface of the matrix; W in the surface region of the matrix 'is also The outer surface of the base f is below (4) nanometer, preferably about 2 nanometers below the outer surface of the matrix, more preferably about 1G nanometer under the outer surface of the matrix; when there is any pore, about 3 below the surface of the porous pore wall It is about 20 nm below the surface of the soil, preferably about 100 nm below the surface of the pore wall of the matrix, but above the surface of the surface of the substrate; 126435.doc -52. 200902143 (4) Part of the pore wall of the matrix on the outer surface of the matrix Any pores, the main "on the surface or above" Yi points located on the surface area of the substance, or in, the soil shell (d) (a), (b) (and combinations of the square. Usually, the amount of the catalytic component may be about 0.0002 wt.% j.^5 wt 〇/-, whether it is a type 1 component or a type 2 component, summer! Between the main, W wt. / 0, preferably between about 2 2 2 wt.%, more preferably from about to about 旯 在, ,, spoon 0.0005 Wt.% to about! The initial catalytically active region of the wt% of the catalyst composition of the present invention may be continuous or discontinuous. Without being bound by theory, it is believed that a catalyst composition covered with a discontinuous catalytically active region is at least as effective as a catalytic component substantially covered with a continuous or more extensive continuous catalytically active region, And in some cases it is more effective. The extent to which the catalytically effective region covers the outer surface of the substrate can range from as low as 〇〇〇〇1% coverage to as high as ι〇〇% coverage. Preferably, the extent of surface coverage outside the catalytically active region is between about 0.0001% and about 10%, more preferably between about 1% and about 1%. However, without being bound by theory, it is believed that the T-I composition, especially a catalyst composition having a lower catalytic component wt.% loading, is likely to be more catalytically effective because of the treated substrate. The upper and/or inner catalytically active regions become more dispersed (i.e., more widely distributed and separated between the catalytically active regions). The catalytically active regions and other characteristics of the above-described catalyst compositions are based on the best available information from the inventors regarding the state of the catalyst composition prior to entering the steady state reaction conditions. The degree to which one or more of the described characteristics can be changed is not certain, and is 126435.doc -53· 200902143 large. The score is unpredictable. Nevertheless, without being bound by theory, it is believed that the functional surface activity of the catalyst compositions described herein will permit the charge and/or charge of the catalytic component integrated with the matrix as the catalyst composition promotes its intended process reaction. Geometric positioning and other component characteristics vary significantly. Thus, it is to be understood that the scope of the invention described herein extends to all of the catalyst compositions produced by the claimed compositions under steady state reaction conditions. VI. Use of Catalyst Compositions in Dehydrogenation Processes - Generally, catalyst compositions of the above type have processes that limit catalyst activity and selectivity due to intraparticle diffusion resistance of the product or reactants (also That is, the diffusion is limited.) It is most advantageous. However, such catalyst compositions can also be used in processes that are not necessarily limited by diffusion. For example, if not limited, some processes require only a single type of catalytic composition of the type described above to provide a single type of catalytic interaction&apos; to help reduce the activation energy of a process reaction. As a result, lower activation energy allows the process to have better thermodynamic properties (e.g., less energy is required to drive the process), so commercial production is also more cost effective. The dehydrogenation process is a process of the above-described catalyst composition which can be advantageously used to treat hydrocarbons, heterohydrocarbons and mixtures thereof. The hydrocarbon used herein refers to a group of compounds composed only of a carbon atom (C) and a hydrogen atom (H), and the term "honey" as used herein refers mainly to a carbon atom (C) and a hydrogen atom (H). However, it also contains a group of compounds other than carbon and hydrogen, such as, but not limited to, oxygen (〇(^) and/or sulfur (S)). The dehydrocyclization method can also use the above types. The catalyst composition is advantageously carried out. In the dehydrogenation or deuteration cyclization process, it is suitable to use the catalyst of the above type 126435.doc -54· 200902143 The composition is subjected to dehydrogenation and/or dehydrocyclization of hydrocarbons and/or Or the process stream of a heterohydrocarbon generally comprises a hydrocarbon having from i to about 30 carbon atoms, but in some cases may exceed 30 carbon atoms 'where the hydrocarbon has at least one dehydrogenation site or dehydrodecyclable site Preferably, the dehydrogenation or dehydrocyclization is readily carried out under suitable dehydrogenation or dehydrocyclization conditions (described in more detail below) for the desired product, yield and/or process efficiency. Process streams include, but are not limited to, feed streams , intermediate transfer streams, recycle streams and/or discharge streams. The dehydrogenation site refers to an atomic position having at least one carbon atom (C) or one hetero atom, but is generally a carbon-containing atomic position, and the hetero atom may be, but not limited to, oxygen (9), nitrogen (n) Or sulfur (8). However, in any case, the dehydrogenation site has at least one degree of saturation, and under appropriate reaction conditions, at least partial unsaturation is readily achieved with the participation of the catalyst composition. Dehydrogenation as used herein. A cyclization site refers to an atomic position having to a slave atom (C) or a hetero atom, but is generally a carbon-containing atomic position, and the hetero atom may be, but is not limited to, oxygen (9), nitrogen (N), or Sulfur (8). However, 'in any case, the dehydrocyclization site has at least one saturation' and under appropriate reaction conditions, when the catalyst composition is involved, it is easy to achieve at least partial unsaturation, and at least One other dehydrocyclization site forms a covalent bond, and a ring having at least three or more atoms is formed therein containing at least two carbon atoms. j it is degassed using a catalyst composition of the above type Smoke and / or miscellaneous k I includes (but is not limited to) soot, iso-chain hydrocarbon, alkyl aromatic, cycloalkane and alkenyl. When using a catalyst composition of the above type, a preferred L class suitable for dehydrogenation is from 2 to about a normal paraffin having 3 carbon atoms. More preferably 126435.doc -55- 200902143 The chain hydrocarbon is a carbon atom having 2 to 15 carbon atoms. For example, it is suitable for cyclization using a catalyst composition of the above type (10). (d) and / or heterohydrocarbons include (but are limited to) regular and semi-chain hydrocarbons (often converted to the corresponding aromatic product (eg, n-octane to ethylbenzene or xylene) or other desired ring or Heterocyclic olefin products. When using a catalyst composition of the above type, preferred hydrocarbons suitable for dehydrocyclization are positive chain hydrocarbons having from 3 to about 30 carbon atoms, more preferably from 3 to atoms. Normal chain burning hydrocarbon. The amine Γί is subjected to a dehydrogenation or hydration process using various reactors having one or more chlorination zones to enable the 'reaction tobacco feed stream to be combined with the catalyst in the dehydrogenation zone maintained under the dechlorination zone. The material is in full contact (hereinafter, the contact can be carried out in the fixed catalyst m to move the catalyst bed system, in the smelting bed system), and the different types of catalyst composites described above can also be used in batch operations. Preferably, a fixed bed system is preferred. In a fixed bed system, the hydrocarbon stream is first preheated to the desired reaction temperature and then passed to a dehydrogenation (four) containing a solid catalyst complex bed. Separate reaction zones 'heating between them to ensure that the reaction is maintained at the input end. The hydrocarbons can be in the upward, downward or catalytic bed. Preferably, the hydrocarbons flow radially through the catalyst. Bed 2: The medium can be a liquid phase, a gas-liquid mixed phase or a gas phase, preferably a gas dehydrogenation or dehydrogenation ring. Many chlorination methods are also determined by the desired product, yield and : 126435.doc -56- 200902143 Efficiency, such dehydrogenation or dehydrocyclization conditions Including (a) the temperature range is generally from about 200 ° C to about 1, 〇〇 (TC, and preferably from about 35 〇 0 C to about 9 〇〇 ° C, and the pressure range is generally from about 40 kPa to about 1 〇, 342 kPa, and preferably from about 50 kPa to about 2,75 8 kPa, (c) a diluent gas (such as hydrogen, which reduces the coking rate of the catalyst composition) and a dehydrogenated or dehydrogenatable cyclized hydrocarbon The ratio of liquid hourly space velocity (LHSV) in the reactor is generally from about 1:1 to about 40:1, and preferably from about i: 丨 to about 丨〇: 丨, and (d) About 10 Torr, and preferably about 0.5 hr·1 to about 40 hr·1. The effluent stream of the deuteration zone usually contains unconverted dehydrogenated hydrocarbons, gas and dehydrogenation reaction products. The effluent stream is usually cooled. It is sent to the hydrogen separation zone to separate the hydrogen-rich phase from the smoky liquid phase. In general, the hydrocarbon-rich liquid phase is prepared by a suitable selective adsorbent, selective solvent, selective reaction or by suitable fractionation. The scheme is further separated. The unconverted dehydrogenated hydrocarbon is recovered and can be recycled to the dehydrogenation zone. The dehydrogenation reaction product will be recovered as a final product or as a preparation for otherization. An intermediate of the compound. The dehydrogenated hydrocarbon may be mixed with a diluent before, during or after the inflow of the dehydrogenation zone. The diluent may be a gas such as hydrogen, steam, methane, ethane, carbon dioxide, nitrogen, argon or the like. The mixture 'hydrogen is the preferred diluent. Generally, when hydrogen is used as a diluent, the amount should be sufficient to ensure that the molar ratio of gas to hydrocarbon is from about 1:1 to about 4:1, of which molar ratio The result is preferably from about 10:1. The dilute hydrogen stream fed to the dehydrogenation zone is typically a recirculating hydrogen separated from the dehydrogenation zone discharge stream in the hydrogen separation zone. Adding water to the dehydrogenation zone or a substance such as alcohol, aldehyde, shouting 126435.doc -57- 200902143 ketone which can be decomposed to form water under dehydrogenation conditions, the amount of addition is calculated by the equivalent amount of water, and accounts for about the hydrocarbon feed stream by weight. About 1卯111 to about 2〇, 00〇1){)111. When the alkane having 2 to 30 or more carbon atoms is subjected to dehydrogenation, from about 1 ppm to about 10 by weight, 〇〇〇ρριη or a water additive is most effective. EXAMPLES The invention will now be described in more detail in connection with the following examples which illustrate or emulate various aspects of the practice of the invention. It is to be understood that all changes that come within the spirit of the invention are intended to be protected, and therefore the invention is not to be construed as limited only. Catalyst Composition with Large Porous Glass Substrate Example 1 Macroporous Glass A large pore foamed soda lime glass sample produced by Dennert Poraver was obtained, i.e., glass beads having an average diameter of about 40 to 125 microns. In the first step, the macroporous glass sample received as it is and not calcined is subjected to acid leaching. Place approximately 25 grams of macroporous glass and 3 liters of 5.5 wt.% nitric acid in a 4 liter plastic wide-mouth container. Place the plastic container in a 30C ventilated oven for 30 minutes. Shake the manuscript slightly every 10 minutes. . After the acid leaching treatment was completed, the sample was filtered using a Buchner funnel with Whatman 541 crepe paper and washed with about 7-6 liters of deionized water. Then, at. The acid immersed sample was dried at a temperature of C110 ° C for 22 hours. The second step is an ion exchange (IEX) treatment of the acid immersed macroporous glass. In this example 'Using dihydrogenated tetraamine palladium 126435.doc -58- 200902143 [Pd(NH3)4](OH)2 to prepare 8 〇ml.] wt% of the solution for ion exchange ("mx solution &quot;). Add 4 grams of macroporous glass to the ion exchange solution (''glass/ion exchange mixture&quot;). Measure the pH of the glass/ion exchange mixture and measure about 10.3. Then, transfer the mixture to 15〇. The plastic of the milliliter is wide-mouthed. When the plastic container is placed in a 5 〇t ventilated oven, shake it by hand every 30 minutes. After the ion exchange treatment, filter it with a Buchner funnel with Whatman 541 filter paper. The glass/ion exchange mixture was washed with about 3.8 liters of deionized water. Then, the ion exchange glass sample was dried for 22 hours at a temperature of 11 ° C. The third step was to reduce the ion exchange glass, where the ion exchange The glass is firstly air-conditioned at an air flow rate of 2 L/hr and at 30 (calculated at a temperature of rc for 2 hours) and then at a hydrogen (Η) flow rate of 2 L/hr of hydrogen (Η) atmosphere and 300 ° C Reduction at temperature for 4 hours. Inductive coupling The results of plasma-atomic emission spectroscopy (ICP_AES) analysis of the sample 'palladium concentration were about 0.098 wt.%. Example 2 The large pore glass was obtained on a large-pore glass to obtain a sample of macroporous foamed soda lime glass produced by Dennert Poraver, ie, an average diameter of about It is a glass bead of 4 to 125 microns. The first step is to carry out acid leaching treatment on the macroporous glass sample which is received as received and not calcined. About 25 grams of macroporous glass and 3 liters of 5.5 wt.% of nitric acid are placed separately. Into a 4 liter plastic wide-mouth container, place the plastic container in a ventilated oven at 30 °C for 30 minutes, shake it slightly by hand every 10 minutes. After acid leaching, use the paper with Whatman 54 1 The cloth 126435.doc -59- 200902143 funnel filter sample, and use about 7,,. 'A liter of deionized water to clean. Then 'at 110 c temperature, will 酴,, * 咕一红红后The sample was dried for 22 hours. In the first step, the acid-impregnated &lt;large-porosity glass was subjected to ion exchange (IEX) treatment. In this example, 'the use of monochlorotetramine palladium [Pd(NH3)4] ( Cl)2 Preparation of 80 ml of 〇_i wt.% palladium solution for cold night Sub-exchange ("ΙΕχsolution"). Add 4 grams of large-porosity glass to the ion-exchanger's solution (&quot;glass/ion exchange mixture&quot;). Measure the glass/ion exchange and change the pH of the compound. The value was measured to be about 8 · 1. Then 'move the mixture into a 15 inch plastic wide-mouthed container. Place the plastic container in a ventilated bait 50 恧 烘 烘 50 2 2 2 2 2 2 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 After the ion exchange process is completed, use

Whatman 5411 paper Brine funnel passes the glass/ion exchange mixture, and uses about 38 liters to separate from the early a, main, and soil, and V is separated from the water. Then, the ion exchange glass sample was dried at 11 (TC temperature for 22 hours. In the third step, the ion exchange glass was subjected to reduction treatment, wherein the ion exchange glass was first placed in an air atmosphere having an air flow rate of 2 L/hr and 3 Torr. It was calcined at a temperature of 〇c for 2 hours and then reduced under a hydrogen (h2) flow rate of 2 to a chlorine gas (8) atmosphere and at a temperature of 3 〇0 C for 4 hours. Sample analysis was performed using ICP-AES, and the palladium concentration was about wt45 wt.%. Example 3 Treatment of Large Porous Glass on Reverse Ion Exchange A large pore foamed soda lime glass sample produced by Dennert P〇raver was obtained, i.e., glass beads having an average diameter of about 4 to 125 microns. In the first step, the macroporous glass sample 126435.doc •60-200902143 received as received and uncalcined 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 stainless steel violet mixer at a speed of 300 to 500 rpm at 90. (: Mechanically transfer for 2 hours. After acid leaching is completed, use a Buchner funnel with Whatman 54 1 paper to filter the sample and wash it with about 7.6 liters of deionized water. Then 'at. Cll 〇 °C At the temperature, the acid leached sample was dried for 22 hours. The second step was to subject the acid leached macroporous glass to Na+_ counter ion exchange ("Na-BIXn" treatment. The process obtained in the first step The acid leached sample was mixed with 4 liters of 3 mol/L sodium chloride (NaCl) solution ("glass/gasified sodium mixture"). Measure the pH of the glass/NaCl mixture. Add about 40 drops as needed. The wt%% tetrapropylammonium hydroxide is adjusted to a positive value of the glass/NaCi mixture to greater than 10 (in this example, the resulting pH is about ι〇5). Then the glass/NaCl mixture is transferred to 4 In a liter glass beaker and heated at 50 °C for 4 hours while stirring at 300 to 500 rpm using a stainless steel paddle mixer. After Na-BIX treatment, filter with a Buchner funnel with Whatman 541 filter paper. Glass/gasified sodium mixture and collected Na-BIX/glass Then, use about 7.6 liters of deionized water to clean. Then, dry the Na-BIX/glass sample for 22 hours at a temperature of 11 (TC). The third step is to perform a second ion on the Na-BIX/large pore glass sample. Exchange (&quot;IEX·2") treatment. In this example, 3 liters of wt1 wt.% palladium solution was prepared for ion exchange using palladium chloride dichloride [pd(NH3)4](cl)2. (,, ΐΕχ_2 solution,,). Add 35 grams of macroporous glass to the ΙΕχ_2 solution ("glass/ΙΕχ_2 mixture"). Measure the {11 value of the glass/ion exchange mixture and measure about 81. Then, 126435.doc -61- 200902143 The far mixture is transferred into a 2 liter glass beaker and is used at 5 (heating 4 J at TC temperature) while using a stainless steel violet blender at 300 to 5 G0 rpm. After the parental treatment was completed, the glass/ion exchange mixture was filtered using a Buchner funnel with whMman 541 filter paper and rinsed with about a liter of deionized water. The ion exchange glass samples were then dried for 22 hours at i thief temperature. #Step 4, the IEX_2 glass sample is subjected to reduction treatment, and the sample is sampled. The product was reduced in a hydrogen atmosphere at a flow rate of 2 L/hr of mouse gas (H2) and at a temperature of 3 Torr for a period of time. Sample analysis by ICP-AES showed a palladium concentration of about 21 wt.%. 4 Macroporous glass was obtained from a large pore foamed soda lime glass sample produced by Dennert P〇raver, a glass bead 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 treatment. Approximately 20 grams of macroporous glass and 4 liters of 55 wt% nitric acid were placed in a 4 liter glass beaker. Mechanical agitation was carried out at 901 for 2 hours at a speed of 300 to 500 rpm using a stainless steel paddle 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 at a temperature of 110 C for 22 hours. In the second step, the acid-impregnated macroporous glass sample is subjected to ion exchange treatment. In this example, 3 126435.doc -62 - 200902143 liters 0.01 wt.% of the solution was prepared for ion exchange (&quot;IEX solution" using dioxetamine palladium [pd(NH3)4](cl)2. Approximately 18 grams of acid leached macroporous glass is added to the glass/ion exchange mixture in the ion exchange solution"). The pH of the glass/ion exchange mixture was measured. The pH of the mixture was adjusted to more than 1 Torr (in this example, the ρη value was about 1 0.8) by continuously adding about 29.8 wt.% of ammonium hydroxide (NH4OH) as needed. Then, the glass/ion exchange mixture was transferred into a *liter glass beaker&apos; and heated at 50 C for two hours while stirring at 300 to 500 rpm using a stainless steel paddle mixer. After the ion exchange treatment was completed, the glass/ion exchange mixture was filtered using a Buchner funnel with Whatman 541 filter paper and washed with about 76 liters of deionized water. The ion exchange glass samples were then dried for 22 hours at ιιοί. In the third step, the ion-exchanged glass sample was subjected to reduction treatment, wherein the sample was reduced in a hydrogen atmosphere at a hydrogen (Hz) flow rate of 2 L/hr and at a temperature of 30 (rc) for 4 hours. Sample analysis by ICP-AES, palladium concentration The result was about wt47 wt.%. Example 5 A large-porosity foamed soda lime glass sample produced by Dennert P〇raver was obtained on a large-porous glass, that is, glass beads having an average diameter of about 4 to 125 μm. Step, ion exchange treatment of the macroporous glass sample received as it is, without calcination and without acid leaching. In this example, [PcHNHOAOH) 2 was used to prepare Μ 0.001 wt% palladium using dihydrogen oxytetramine. Solution 126435.doc -63- 200902143 for ion exchange (·, hydrazine solution). Add about 8 grams of macroporous glass to the ion exchange solution (, glass / ion exchange mixture &quot;). Measure glass / ion exchange The pH of the mixture. As needed, about 29.8% by weight of ammonium hydroxide (NH4〇H) is added dropwise, and the pH of the mixture is adjusted to be greater than 1 〇 (in this example, the pH obtained is about 10.5). Glass / away Transfer the sub-exchange mixture into a 2 liter plastic wide-mouth container. Place the plastic container at 5 〇. 通风 ventilate the box for 2 hours, shake it slightly by hand every 3 〇 minutes. After the ion exchange treatment is completed, use Whatman 541 filter paper Buchner funnel filter glass / ion exchange mixture and collect ion exchange _ glass sample, then use about 7.6 liters of diluted NH4 〇 H solution. Dilute NH4OH solution is mixed with 10 gram of 29.8 wt.% concentrated NH4 〇 The H solution was prepared with about 3.8 liters of deionized water. The ion exchange glass sample was then dried for 22 hours at a temperature of 丨丨〇 ° C. In the second step, the ion exchange glass sample was subjected to a reduction treatment in which the ion exchange sample was The hydrogen (H2) flow rate was 2 L/hr of hydrogen atmosphere and the temperature was reduced at 300 ° C for 4 hours. The sample analysis by ICP-AES showed that the palladium concentration was about i3 i wt.%. Glass on the glass obtained a sample of macroporous foamed soda lime glass produced by Siscor, a glass bead with an average diameter of about 45 to 75 microns. Step by step, for macropores that were received as received and not calcined The glass sample was subjected to acid leaching treatment. Approximately 49.61 grams of macroporous glass and 4 liters of 5.5 126435.doc -64 - 200902143 wt.% of nitric acid were placed in a wide-mouth container. The plastic was ventilated. After 2 hours in the phase, shake it slightly by hand every 30 minutes. After the treatment was completed, the sample was passed through a Buchner funnel with Whatman 541 filter paper, and (4) 76 liters of deionized water was removed. Then, the acid immersed sample was dried at a temperature of U 〇t for 22 hours. In the second step, the acid leached macroporous glass sample was subjected to ion exchange treatment. In this example, it was prepared using dichlorotetramine [Pt(NH3)4](Ci)2! A 0.16 wt.% platinum solution is used for ion exchange (&quot;ΐΕχ solution will be about 15.86 grams of acid-impregnated macroporous glass added to the ion exchange solution., glass/ion exchange mixture"). Measurement of glass/ion exchange mixture The pH value is adjusted according to the need of about 4% by weight of tetrapropylammonium hydroxide. The tetrapropylammonium hydroxide is continuously added to adjust the pH to more than 1 〇 (in this example, the obtained pH) The value is approximately U.83. The glass/ion exchange mixture is transferred to a 4 liter plastic wide-mouth container. The plastic container is placed in a 5 〇 ventilated oven for 2 hours and shaken slightly by hand every 30 minutes. After the exchange process was completed, 'Using a Buchner funnel transition glass/ion exchange mixture with Whatman 541 filter paper' and washing with about 7.6 liters of deionized water. Then, the ion exchange glass sample was dried for 22 hours at a temperature of 〇 ° ° C. The sample analysis by ICP-AES showed that the platinum concentration was about wt41 wt.%. Example 7 The large pore glass of the large pore glass was obtained from Siscor, which is an average of 126435.doc - 65 - 200902143 Glass beads β with a diameter of about 45 to 75 μm. The first step is to carry out acid leaching of large pore glass samples that are received as received and not calcined. About 50·37 grams of macroporous glass and 4 liters of 55

Wt.% nitric acid was placed in 4 liters ^. J glue wide mouth mouth inside the device. Place the plastic container in a ventilated oven at 90 °C for 2 small odors, and shake it once with a hand for 30 minutes. After the acid leaching treatment, the two liquids were separated, and then the solid matter was washed with about 7 liters of deionized water. Jude, ..., 佼' The acid immersed sample was dried for 22 hours at a temperature of 11 〇 c.

In the first step, the acid-impregnated macroporous glass sample was subjected to ion exchange treatment. In this example, 'using dichlorotetramine material pt(NH3)4](6))2 to prepare j liters of 0.18 wt.% platinum solution for ion exchange (&quot; ΙΕχ solution. About 41.79 gram by acid leaching Pore glass is added to the glass/ion parent exchange mixture '') in the ion exchange solution. The pH value of the glass/ion exchange mixture was measured to be 6.8. In this example, the pH was not adjusted. The glass/ion exchange mixture was transferred to a 4 liter plastic wide mouth container. The plastic container was placed in a 9 〇〇 ventilated oven for 4 hours and shaken slightly by hand every 30 minutes. After the ion exchange treatment was 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 at a temperature of 1 l〇t for 22 hours. Sample analysis by ICP-AES showed a platinum concentration of about 0.13 wt.%. Example 8 A large-porosity glass sample obtained from S i s c 〇 r was obtained, i.e., an average of 126435.doc -66-200902143 glass beads having a diameter of about 45 to 75 microns. In the first step, the macroporous glass sample received as it is and not calcined is subjected to acid leaching. Approximately 20 grams of macroporous glass and 4 liters of 5·5 wt% acid were placed in a 4 liter glass beaker. Mechanical agitation was carried out at 90 ° C 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 crepe paper and washed with about 76 liters of deionized water. The acid immersed sample was then dried at a temperature of 11 0 C for 22 hours. The second step is an ion exchange treatment of the acid immersed macroporous glass sample. In this example, 3 liters of a 0.01 wt.% palladium solution was prepared for ion exchange (, hydrazine solution) using palladium chloride tetrachloride [pd(NH3)4KC1h). About 18 g of acid leached macropores were used. Glass is added to the glass/ion exchange mixture in the ion exchange solution"). The pH of the glass/ion exchange mixture was measured. About 29.8 wt.% ammonium hydroxide (nh4〇h) was added dropwise as needed.

The pH of the mixture was adjusted to greater than 10 (in this example, the resulting pH was about 10.78). The glass/ion exchange mixture was then transferred to a 4 liter glass beaker at 50. Heat at 〇 for two hours while stirring at 300 to 5 rpm using a stainless steel paddle mixer. After the ion parent treatment was completed, the glass/ion exchange mixture was filtered using a Buchner funnel with Whatman 541 filter paper, and washed with about 7.6 liters of deionized water β, and then ion exchanged glass samples were taken at 11 〇C. Dry for 22 hours. In the third step, the ion-exchanged glass sample is subjected to a reduction treatment, wherein the sample is reduced in a hydrogen atmosphere at a flow rate of 2 L/hr of hydrogen (Η2) and at a temperature of 3 Torr (126435.doc •67-200902143 for 4 hours. Sample analysis was performed by ICP-AES, and the concentration was about 〇θα wt.%. Example 9 A large-porosity foamed soda lime glass sample produced by Siscor was obtained on a large-pore glass, that is, an average diameter of about 45 to 75 μm. Glass beads. The first step is to carry out acid leaching of the macroporous glass samples received as they are, without calcination. About 49.61 grams of macroporous glass and 4 liters of $5 wt% of nitric acid are placed in 4 liters of plastic. Inside the wide-mouth container, place the plastic barn in a ventilated oven at 90 °C for 2 hours, shake it slightly by hand every 30 minutes. After the acid leaching treatment, filter it with a Buchner funnel with Whatman 541 paper. The sample was washed with about 7.6 liters of deionized water. Then the sample after acid leaching was dried for 22 hours at a temperature of 11 ° C. The second step was to ion exchange the acid leached macroporous glass sample. Processing In this example, 1 liter of 0.0003 wt.% solution was prepared using dihydrooxytetramine palladium [pd(NH3)4](〇H)2 for ion exchange ("ΐΕχ solution"). It will be about 1 5.06 g. The acid-impregnated macroporous glass is added to the ion exchange solution (glass/ion exchange mixture &quot;). Measure the pH of the glass/ion exchange mixture. Add about 29-8 wt% of hydrogen hydroxide as needed. Νί^ΟΗ) 'The pH of the mixture was adjusted to be greater than in the present example, and the pH obtained was about 1 〇 2). The glass/ion exchange mixture was transferred to a 4 liter plastic wide-mouth container. Placed in 5 (rc ventilated oven 126435.doc -68- 200902143 / mother 3G minutes with a slight shake - under. Ion exchange treatment finished ^ 'Use Buchner funnel filter with Whatman 5411 paper:: use About 7.6 liters of diluted NH solution is cleaned. The dilute NH4 〇H solution is prepared by using this mouth 10 gram of 29 8 wt% thick bribe 4 〇 11 solution with about 38 liters of deionized water. 'Then, (1) The ion-exchanged glass sample was dried for 22 hours at a temperature of C. Knowing the sample by ICP-AES The result of the concentration is about 〇〇165 gas%°. The scanning-transmission electron microscope (STEM) analysis as described in Example (5) below (5) is used to detect the part of the sample. The result shows that the neoparticle (the contrast is brighter) Disperse in the range of less than or equal to about 30 nm from the surface of the pore wall (that is, on the perimeter of the material area around the substrate with relatively dark contrast) The town obtained a sample of macroporous foamed soda lime glass produced by Sisc〇r, a glass bead having an average diameter of about 45 to 75 microns. The first step is to carry out acid leaching treatment on the macroporous glass sample which is connected to the original as it is not calcined. Approximately 20 grams of macroporous glass and 4 liters of 5.5% by weight of nitric acid were placed in a 4 liter glass beaker. Mechanical stirring was carried out at a speed of 300 to 500 rpm at 9 Torr for 2 hours using a stainless steel music 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 iio °c. ... The second step is the ion exchange of the acid leached macroporous glass sample. 126435.doc •69· 200902143 Treatment. In this example, '3 liters of 〇_〇5 Wt.% 鶊 solution was prepared for ion exchange ("ΐΕχ solution") with ~Herbic acid (10) 4) 6H2Wl2 〇 4Q · nH2 。. About 18 grams of acid leaching The big money side adds people to the ion exchange (four) liquid, for the mixture "). Measuring the glass/ion exchange mixture ρ Η value glass = as needed, about 29.8 wt% of ammonium hydroxide (and gamma) was added dropwise continuously, and the pH of the mixture was adjusted to be greater than 8. Then, the glass/ion exchange mixture was transferred into a 4 liter glass beaker and heated at a temperature of (10) while stirring at a rate of 3 Torr to 5 Torr using a stainless steel paddle mixer. After the ion exchange treatment was completed, the glass/ion exchange mixture was filtered using a Buchner funnel with a number of 541 filter papers and washed with about 5 liters of deionized water. The ion exchange glass samples were then dried for 22 hours at a temperature of 11 Torr. In the third step, the ion-exchanged glass sample was calcined, wherein the sample was at an air flow rate of 2 L/hr of air and 500. (: calcination at a temperature of 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, isoelectric point (IEP) and SAN2-bet or SAKr-BET determination X-ray photoelectron spectroscopy (XPS) sputter depth distribution method using a PHI Quantum 200 Scanning ESCA MicroprobeTM (Physical) with a 1486.7 eV microfocus monochromator Α1 Κα X-ray source Electronics) obtained XPS sputter depth profile. The instrument has dual neutralization capability 'in the spectrum acquisition process, using low energy electrons and cations to provide 126435.doc -70- 200902143 charge compensation. XPS spectrum is usually measured under the following conditions: - X-ray beam diameter 10 - 200 μιη - X-ray beam power 2 - 40 W - Sample analysis area 1 〇 - 2 〇〇 _ electron emission angle is 45 with the sample normal. All XPS spectra and _ depth distribution are in the chamber Record under temperature, do not pre-process the sample 'but the sample is placed in the xps instrument vacuum environment: by alternating several cycles of sample surface spectrum acquisition, then 15 to 3 seconds on the sample surface in each cycle 2 Kv Ar+ sputtering removes 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 ^ and 邛 and correcting their respective atomic sensitivity factors and analyzer transfer functions. Those familiar with XPS analysis should understand that the measurement of the sputter depth parameter is affected by both human uncertainty and mechanical uncertainty. The combination of the two may be reported for each sputter depth measured by the XPS sputter depth profile technique. The value causes an uncertainty of approximately 25%. Therefore, the uncertainty is expressed in the depth value shown in Figure 2. This inaccuracy is common throughout the XPS analysis technique. 'However, for the average thickness and other material properties of the catalytically active regions disclosed herein, this inaccuracy is not sufficient 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 in this 126435.doc 71 200902143. Violation electron microscopy (HPLC) analysis Transmission electron microscopy (TEM) sample detection is performed using a 3 〇〇 kv accelerating voltage _〇L 3_F field emission scanning transmission electron microscope (STEM) instrument. The instrument is equipped with Oxford Instruments (〇xfQrd Inst)

The Inca X-ray spectrometer system performs local chemical analysis using an energy dispersive spectrometer. Preparation of the sample The sample material is first silvered into a standard epoxy package known to those skilled in the art. After curing, use an ultra-thin microtome to sample the epoxy. The remaining cut of the mouth is about 8 〇 nanometer thick slices. The knife is collected on a thin film porous carbon carrier and does not require advance processing to be properly positioned in the electron beam field of the above STEM instrument for detection and analysis. Those familiar with TEM analysis should understand that the location of the target analyte and the average thickness of the region of interest relative to the surface of the substrate using TEM analysis are both subject to human uncertainty and mechanical uncertainty, depending on the sample. Factors such as image resolution, physicochemical properties of the target analyte, and sample morphology may result in an uncertainty of about ±2〇% of the TEM vertical depth measurement (relative to a specific reference point) and about ±5% The lateral 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 determination, SARCNa empty sample and related statistical analysis For the reasons discussed above, the surface area change rate of sodium (nSARC^,) is reported as 126435.doc -72- 200902143 as the ratio of NaOH titrant volume. According to the above SARC#a program, the SARC* of each sample given in the following example is determined. An empty sample was prepared by formulating a 3.5 M NaC1 solution (i.e., adding 30 grams of NaC1 in 15 mL of deionized water), which contained no matrix-like mouth to solve the statistical variability in the SARCiva experimental procedure. Four separate empty samples should be titrated and adjusted (ie corrected) for each matrix sample SARCW using the initial and I&quot; (ie, the specified concentration used (the sample towel is 〇〇1 N). The volume of the titrant used is determined. The pH of the empty sample is adjusted and titrated according to the same procedure as described above for the SARC^, but the matrix is also absent. The empty samples provided below and their respective mean and standard deviations ( Or the statistical analysis of the empty sample enthalpy in each of the V total σ) analysis test results. Similarly, the intrinsic statistics corresponding to each titer V initial, vs, ν10 &amp; νπ are also reported due to their respective... Fluctuation. From a statistical point of view, using the statistical t-distribution, near the average value, the value outside the specified confidence interval is reliable 'not derived from the inherent degree of the experimental method's inherent deviation of 95 / .. The initial V and Vt values measured for the matrix samples in the confidence interval near the mean of the empty samples were considered to be statistically indistinguishable from the empty samples. Therefore, 'such samples are not calculated. The isoelectric point (1EP) is determined according to the following The program determines the isoelectric point of each sample given below (&quot;iEp&quot;). Use the MetUer T〇led〇SevenMum meter with pH mv/ORP module with Mettler Toledo INLAB 413 pH composite electrode for IEp measurement. Within the entire IEP range, use the standard values of pH 2, 4, 7 and i〇 126435.doc • 73 · 200902143 PH value buffer solution calibration &quot; use a sufficient amount of time to reach the initial wetness of a certain amount of 16 deionized Water (in the wet test of the (four) sample, determine the IEP of each sample, "匕 can produce a relatively dense package or paste mixture. And the initial wet state can make the glass electrode and its reference electrode contact and contact measured Liquid contact between the liquid of the solid sample (in this example a slurry or paste mixture) depending on the morphology of the sample (eg glass microfibers, granules at the end, chopped fibers, etc.) and its porosity (if any) )degree, The program requires a small amount of water, but in all cases the amount of water added should be only sufficient to bring enough liquid into contact with the glass electrode and the reference electrode. In other words, adding water to the sample to be tested should avoid making the sample more than possible. Wet state. In all cases, use the electrode tip 'by hand to mix the solid sample with deionized water (added for generating incipient wetness), first pull, *g丨丨MU / Shi Li $ + until the measured pH is stable The resulting pH is then read from the meter. ABET or Kr BET Surface Area (S, A) Determination $ The SAN2-BET or sAKrBET assay is performed on each sample given below according to the ASTM procedure mentioned above. As discussed more fully above, for higher surface area measurements (eg, from about 3 to 6, N2BET is likely to be a preferred surface area measurement technique as described in ASTM D3663.03. For lower surface areas) The measured value (for example, &lt; about 3 m2/g), h BET may be a preferred surface area measurement technique according to the method described in ASTM D478〇_95 (&quot;SA Heart &quot;). 126435.doc • 74- 200902143 SARCNa Empty Sample Measurement and Statistical Analysis for Correcting SARCNa Titration Sample No. Dilute NaOH Titration Concentration (N) SAN2-BET (m2/g) In NaOH titration, pH is adjusted from te(V) *) When the initial value of 4.0 is adjusted to 9.0, and the pH of the titrant required to maintain the pH at 9.0 at ts, t10, and t15 (Vs*15) (ml) V = V initial + vsiis V first 0 minutes V5 5 minutes V10 10 minutes V15 15 minutes V5il5 sum and sample A 0.01 Not applicable 1.5 0.3 0.1 0.2 0.6 2.1 Empty sample B 0.01 Not applicable 2.2 0.1 0.1 0.2 0.4 2.6 Empty sample C 0.01 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 Sample standard deviation 0.01 NA NA 0.3947 0.1 0.2708 0.05 0.0577 95% CI empty sample 1.45-2.70 2.07-2.93

EXAMPLE CH-2 Macroporous Glass Matrix - SARCNa A macroporous foamed nanoglass sample produced by Dennert Poraver, a glass bead having an average diameter of about 40 to 125 microns, was obtained. Sample A is a macroporous glass bead that is received as it is. Sample A was analyzed by the above-described analytical method for measuring S ARC^. The results are shown in the table below. Sample No. Sample Description Dilute NaOH Titration Concentration (4) In the titration, adjust the initial value of 4.0 from pH* to 9.0, and maintain the pH at 9.0 at ts, tlfl and tls (V5il5). The actual volume of the titration solution (ml) V first 0 minutes V5 5 minutes V10 10 minutes V15 15 minutes V suspect v*-v The average value of the initial empty sample 0.01 2,1 0.15 0.125 0.15 2.5 Not applicable A Original porous glass beads 0.01 5.2 0.8 0.4 0.1 6.5 1.3 B Acid-impregnated porous glass beads not determined Not determined -75- 126435.doc 200902143 Sample No. Sample Description IEP SAN2.bet (m2/g) Corrected titration volume (ml) used in SARQv determination SARCyva (V*iV initial)/V initial V first 0 minutes V5 5 minutes V10 10 minutes V15 15 minutes Vi* empty sample average value not applicable Not applicable 2.1 0.15 0.125 0.15 2.5 Not applicable Corrected A Original porous glass beads 10.2 0.4 3.1 0.65 0.275 -0.05 3.97 0.28 Modified B Acid-Immersed Porous Glass Beads 8.9 6.0 Not Determined Not Determined The above-described catalyst composition is described in more detail in connection with the following examples, which illustrate that the different types of catalyst compositions described above may be used. It dehydrogenation method. All modifications and embodiments that conform to the spirit of the invention are protected. Therefore, the following examples are not intended to be limited to the invention described and claimed herein. Dehydrogenation (DeHYD) Process Example In the following non-limiting examples, the selected catalyst composition was tested for dehydrogenation activity by laboratory grade equipment. The general procedure is as follows. First, a suitable mass of the catalyst sample as described in the table below was loaded into a reaction tube of 7.3 mm internal diameter. The catalyst was reduced using hydrogen at a flow rate of 500 cc/min for about 30 minutes at a temperature of 350 °C. Next, methylcyclohexane (MCH) and hydrogen were passed through the catalyst at a WHSV of 16 at a pressure of about 3 psig. The molar ratio of hydrogen to feedstock is about 62. The conversion of methylcyclohexane to form toluene was determined. Example P-1 De-argonization using platinum on macroporous glass In this example, about 125 mg of the melt prepared from the method of Example 6 above was placed in a reactor at 0.41 wt.% on a large-pore glass bead. The 126435.doc-76-200902143 medium was tested at a temperature of 325 ° C according to the example procedure of the dehydrogenation method described above. The results are shown in the following table. Example P-1 0.41 wt.% of the catalyst mass on the macroporous glass ^ MCH conversion (mg) mol-% 125 53.34 ----- ' ' 1-, Na Jin, Guan W &lt; show strong pregnancy father implementation

The invention of the invention has been described, and for the purpose of illustration, it is obvious that those skilled in the art will appreciate that the invention is susceptible to other embodiments and without departing from the invention. Based on the principles, some of the details described herein may vary considerably. [Simple description of the diagram] Figure 1 shows a glass matrix sample with virtually no microporosity/no mesoporosity but large pores, photographed by a JEOL 3000F field emission transmission electron microscope under a 3 volt kilovolt accelerating ink. A scanning transmission electron microscope (STEM) image of a cross-sectional portion of (for example, acid-dip soda-lime glass) in which the particles are generally dispersed within a range of less than or equal to (four) nai (iv) from the surface of the pore wall. 126435.doc -77-

Claims (1)

200902143 X. Patent Application Range: 1 · A process flow dehydrogenation process which utilizes a catalyst composition to dehydrogenate at least a portion of the process &quot;IL, the process stream containing at least one having at least one dehydrogenation site a compound of a point, wherein the catalyst composition comprises: - a substantially microporous/non-porous matrix having a large pore, an outer surface, an open pore wall surface, a surface region, and a subsurface region, - at least one catalytic component, And r,, - at least one catalytically active region comprising the at least one catalytic component, wherein (a) the substantially microporous/non-porous matrix has 1) when selected from the group consisting of SAw-sh, sAhdw, and combinations thereof When measured by a method of grouping, the total surface area measured between about 1 ^^ to 50 m 2 /g is measured; and η) is obtained in a pH range greater than 0 but less than or equal to 14. Predetermined, the isoelectric point (IEP); (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 H) a catalytically effective amount At least one reminder a component; and '(c) s at least one catalytically active region is substantially i) on the outer surface, ii) on the open pore wall surface, iii) in the surface region, iv) is in the On the outer surface, a portion is on the open pore wall surface 126435.doc 200902143, partially in the surface region and combinations thereof; or v) a combination of (c) (1), (ii), (iii) and (iv). 2. 3. 4. 5. The dehydrogenation process of claim 1, Αs, wherein the at least one catalytic component is selected from the group consisting of Brünsted or LeWls acid , Brunsett or Louise test, noble metal cations and noble metal complex cations and anions, transition metal cations and transition metal complex cations and anions, transition metal ruthenium anions, transition metal hydride anions, main oxyanions, I, rare earth ions, rare earth complex cations and anions, noble metals, transition metals, transition metal oxygen, transition metal sulfides, transition metal oxysulfides, transition metal transition metal nitrides, transition metal compounds, transition metal ruthenium Compounds, rare earth hydroxides, rare earth oxides, and combinations thereof. And a dehydrogenation process, wherein the at least one catalytic component is a first catalytic component having (a) a first pre-reactive oxidation state, and (8) and 4, before the catalyst composition is in a steady-state deweathering reaction condition The first pre-reaction interaction between the matrices is selected from the group consisting of ionic charge interactions, electrostatic charge interactions, and combinations thereof. A method of dehydrogenation according to claim 3, wherein the first catalytic component is selected from the group consisting of ruthenium: a base, a chalcogenide, and combinations thereof. a dehydrogenation process of m 1 ', wherein at least a portion of the first catalytic component is modified or substituted to form a second catalytic component having 126435 before the catalyst composition is subjected to a steady 'SI> reaction condition .doc 200902143 (a) a second pre-reactive oxidation state, and (7) a corresponding second pre-reaction interaction with the substrate; "the second pre-reactive 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. 6. The dehydrogenation process according to claim 5, wherein the second catalytic component is selected from the group consisting of pd, Pt, Rh, ir, ru, 〇s, Cu, Ag a group consisting of Au, Ru, Re, Nl 'Co, Fe, Mn, Cr, and combinations thereof. 7. The method of dehydrogenation of claim 1, wherein the substrate is a glass composition having a SARC of less than or equal to about 0.5. 8. The dehydrogenation process of claim 1, wherein the at least one catalytically active region is substantially concentrated in a region having an average thickness of less than or equal to about 2 nanometers. 9. The method of claim 1, wherein the Substantially no microporous/no mesoporous matrix selected from A R glass, rare earth citrate glass, borosilicate glass, E glass, boron-free E glass, S glass, R glass, rare earth glass, silicate glass, Ba-Ti-silicate glass, nitrided glass a group consisting of a glass, C glass, and CC glass, and combinations thereof. 10. The dehydrogenation method of claim 1 wherein the substantially microporous/non-porous matrix is before or after the first leaching treatment The obtained IEP is greater than or equal to about 6.0, but less than 14. 126435.doc 200902143 VII. Designated representative map: (1) The representative representative of the case is: (1). ' (2) The symbol of the representative figure is simple Explanation: (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) 126435.doc