TW309515B - - Google Patents

Description

3〇85l5 Λ7 B7 5. Description of the invention (1) (please read the notes on the back before filling in this page) The present invention provides an acidic solid, which contains a group IVB metal oxide modified by an oxide anion of a group VIB metal . The acidic solid further contains an oxide of Mn and / or Fe. The modified solid oxide can be used as a catalyst, for example, isomerizing C 4 to C 8 alkanes. The modified solid oxide is prepared by co-precipitating the Group IVB metal oxide with the Group VIB metal oxidizing anion. This catalyst, especially the oxidation catalyst modified by tungstate, can be used in many hydrocarbon conversion methods, such as alkane isomerization, ring opening of cyclic compounds, naphthalene alkylation, hydrocracking, etc. . The preparation of these catalysts consists of a complex impregnation process of several steps, which includes the precipitation of zirconia precursor, reflux, secondary filtration / cleaning, and then the impregnation of cranes in the pulp step, and finally Huai burn effect. In a preferred method, the complex procedure is reduced to only three steps: co-precipitation of tungsten and zirconia precursors, filtration, and sintering. This co-precipitation method produces a better catalyst at a lower manufacturing cost (fewer steps) and is more resilient to possible environmental considerations. Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. The solid substance described in this patent specification contains an oxide of a group IVB metal, such as an oxide hammer or titanium dioxide. The Group IVB metal oxide is modified by the Group VIB metal oxide anion, such as tungsten oxide anion, such as tungstate. The group VIB metal oxide anion is used to modify the group IVB metal oxide to impart acid functionality to the substance. Oxidation of anions with Group VIB metals, especially tungstate modified Group VB metal oxides, especially zirconia is described in US Patent No. 5,113,034; Kokai Patent Application No. Hei 1 [1989]- No. 288339: and Proceedings Qth -4- This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) Printed by the Ministry of Economic Affairs Central Bureau of Customs, Beigong Consumer Cooperative 309515 A7 B7 V. Description of invention (2) International Congress on Catalysis, Volume 4, pages 1727-1735 (1988) in the literature of K. Arata and M. Hino. According to these documents, tungstate is impregnated onto the pre-formed solid zirconia material. For the purpose of the present invention, a group IVB metal oxide modified by an oxide anion of a group VIB metal means a substance containing a group IVB metal, a group VIB metal, and oxygen, and a separately formed IVB metal oxide after elemental analysis Compared with simple mixtures that individually form VIB metal oxides or oxidized anions, they contain higher acidity. The group IVB metal of the present invention is modified with a group VIB metal, such as tungsten oxide anion, such as a cone oxide, Xianxin is a chemistry between the source of group IVB metal oxide and the source of group VIB metal oxide or oxide anion Interaction. Such chemical interactions are discussed in the aforementioned Proceedings 9th International Congress on Catalysis, Volume 4, pages 1727-1735 (1988) in the literature of K. Arata and M. Hino. In this document, it is suggested that when a sulfate reacts with a certain metal, such as a hydroxide or oxide of Zr, a solid excess acid is formed. These excess acids are said to contain a two-coordinate sulfate ion structure coordinated with a metal, such as Zr. In this document, it is further suggested that an excess acid can also be formed when tungstate reacts with the hydroxide or oxide of Zr. The resulting tungstate-modified oxidized substance has the same structure as the aforementioned excess acid containing sulfate and zirconium, in which the tungsten atom replaces the sulfur atom in the diligand structure. Although Xianxin's catalysts of the present invention may contain the two ligand structures suggested in the aforementioned Arata and Hino literatures, in the Group IV B metal oxides modified by the oxidation anions of Group VIB metals of the present invention, the catalytically active sites are unique. -5-_ This paper uses the Chinese National Standard (CNS) Α4ΛΙ grid (210X297mm) '~~: ---------- Γ 丨 | (Please read the precautions on the back before filling in this Page) The Central Ministry of Economic Affairs of the Ministry of Economic Affairs®; A7 B7 printed by the Industrial and Consumer Cooperatives V. Description of the invention (3) The special structure has not been determined, but it does not mean that the catalyst component should be limited to any special structure. The present invention provides an acidic solid comprising a group IVB metal oxide modified with an oxide anion of a group VIB metal. The acidic solid further comprises at least one oxide selected from metals including iron and manganese. The present invention also provides a method for preparing an acidic solid, the acidic solid containing a group IVB metal oxide anion modified ivb group metal oxide, the method includes the source of the group IVB metal oxide, the source of the group VIB metal oxide anion, Co-precipitate with an oxide source selected from metals including Fe and Mn. The invention also provides a method for preparing an acidic solid, the acidic solid comprising zirconia-modified zirconia, the method includes several steps: (a) making the first liquid solution and the second liquid solution and the third liquid solution Merging 'the first liquid solution contains a source of oxidized hammer dissolved in water, the second solution contains a source of tungstate dissolved in water, and the third solution contains at least one source selected from oxides including iron and shovel (B) maintaining the combined solution in step (a) under conditions sufficient to form a solid co-precipitate, the co-precipitate comprising tungstate-modified oxide cones and at least one containing Fe and / or Mn The compound; (c) the solid co-precipitate of step (b) is recovered by filtration; and (d) the recovered co-precipitate of the burning step (c). The present invention also provides a method for converting an organic compound, the method comprising contacting the organic compound with a catalyst under conditions sufficient for conversion, wherein the catalyst comprises an acidic solid which comprises a Use the Chinese National Sample Rate (CNS) A4 specification (210X297 public daughter) (please read the notes on the back before filling this page) Order the A7 printed by Beigong Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs -------- -—---— B7 ____ 5. Description of the invention (4) Group IVB metal oxides modified by the oxidation anions of Group VIB metals' The acidic solid further contains at least one oxide selected from metals including iron and manganese. 0 Also provided is a method for isomerizing hydrocarbons, the method comprising contacting a feedstock comprising C 4 to C 8 hydrocarbons with an isomerization catalyst under conditions sufficient to effect isomerization, the isomerization catalyst comprising ( i) a precious metal and (ii) an acidic solid comprising a group IVB metal oxide modified with an oxidized anion of a group VIB metal, the acidic solid further comprising at least one selected Metals including iron oxide and chains. Suitable sources of Group IVB metal oxides for the preparation of the catalysts of the present invention include compounds capable of producing such oxides, such as oxygenates, oxides, nitrates, oxidized nitrates, etc., especially 鲒 or 鈥. The pit oxygen compounds of these metals can also be used as precursors or sources of ϊ V Group B metal oxides. Examples of such alkoxy compounds include n-propanol cone and iso-propanol titanium. The sources of these Group IVB metal oxides, especially zirconium oxide, can form germanium hydroxide, that is, Zr (OH) 4, or hydrated zirconium oxide, which is precipitated from an aqueous medium in the absence of tungstate reaction source Intermediate species. The term hydrated zirconium oxide means a substance containing zirconium atoms covalently linked to other zirconium atoms via bridge oxygen atoms' meaning Zr-0-Zr, which further contains available surface hydroxyl groups. Under sufficient conditions, when the hydrated zirconia is impregnated with a suitable source of tungstate, these available surface hydroxyl groups react with the source of tungstate to form an acidic catalyst. As mentioned in the Proceedings 9th International Congress on Catalysis, Volume 4, pages 1727-1735 (1988), as suggested by the literature of K. Arata and M. Hino, at the temperature of about the paper scale, the Chinese National Standard (cns & A4) is applicable ( 210x297 gong mai) ----------- {II (please read the notes on the back before filling in this page) Order 30S515 A7 B7 V. Description of the invention (δ) 100 C to about 400 ° C Calcining Zr (OH) 4 can produce a species, which is beneficial to interact with tungstate when leached with it. This pre-burning action causes the condensation of ZrOH groups and surface hydroxyl groups to form a polymerized oxidation This polymerizable species is specified in this patent specification as a form of hydrated zirconia. Group VIB metals 'especially suitable sources of oxidized anions of molybdenum or tungsten include' but are not limited to ammonium metatungstate or metamolybdic acid Ammonium, tungsten chloride, or vaporized molybdenum, tungsten carbonyl or molybdenum carbonyl, tungstic acid or molybdic acid, and sodium tungstate or sodium molybdate. The preparation of the modified oxide of the present invention oxidizes metals containing Group VB The first liquid solution from the source, and containing group VIB metals The second liquid solution from the source of oxidized anions is combined. The combination of the two solutions occurs under conditions sufficient to co-precipitate the modified oxide from the liquid medium into a solid. Alternatively, the source of Group IVB metal oxides and Group VIB metals The sources of oxidized anions can be combined in a single liquid solution. This solution can then be subjected to conditions sufficient to cause co-precipitation of the solid modified by the oxide substance, such as adding a precipitant to the solution. The preferred solvent is water. The temperature of the liquid medium during co-precipitation is maintained slightly below about 200 ° C, such as from about 0 ° C to about 200 °. This liquid medium can be maintained at ambient temperature (meaning room temperature ), Or the liquid can be cooled or heated. The special range of these temperatures is about 50 ° C to about 100 ° C. The liquid medium from which the catalyst component of the present invention co-precipitates may optionally contain a solid support, in In this case, the catalyst of the present invention can be directly co-precipitated onto a solid support. Examples of such supports include a substance named M41S, -8- This paper size is applicable to China Home Standard (CNS) A4 Specification (210X297mm) ---------- (------ 1T (Please read the precautions on the back before filling in this page) Ministry of Economic Affairs Central Bureau of ec Industrial and Consumer Cooperatives Printing and Printing A7 ____B7_ printed by the Ministry of Economic Affairs, Central Bureau of Accreditation of the Ministry of Economy V. Description of the invention (6) It is described in US Patent No. 5,102,643. A special example of this M41S substance is named MCM-41 It is described in US Patent No. 5,098,684. The support and / or co-catalyst material may also be co-precipitated from the liquid medium together with the group IVB metal oxide and the group VIB metal oxide anion if desired. An example of a cocatalyst substance is a hydrogenation / dehydrogenation component. According to the solid substance described in this patent specification as needed for modification, the hydrogenation / dehydrogenation component is combined with the substance. When the organic substance is in contact with the modified substance under conditions sufficient for hydrogenation or dehydrogenation, the hydrogenation / dehydrogenation component gives the substance the ability to catalytically add hydrogen to or dehydrogenate the organic substance, The organic substance is, for example, a hydrocarbon substituted with one or more heteroatoms as needed, such as oxygen, nitrogen, metal or sulfur. Examples of hydrogenation / dehydrogenation components include Group VIII metals (ie, Pt, Pd, Ir, Rh, Os, Ru, Ni in the form of oxide hydroxides or free-state metals (meaning zero valence) , Co and Fe), Group IVA metals (meaning 'Sn and Pb), Group VB metals (meaning Sb and Bi) and Group VIIB metals (meaning' Mn, Tc and Re). The catalyst of the present invention may comprise one or more precious metals in one or more catalytic forms (i.e., Pt, pd, ir, Rh, Os, or Ru). Combinations of these precious metals or non-noble metals in catalytic form can be used, such as the combination of Pt and Sn. The metal valence of the hydrogenation / dehydrogenation component may be a reducing valence state, for example, when the component is in the form of an oxide or hydroxide. During the reaction, when a reducing agent such as hydrogen is included in the raw material to react, the reducing valence of this metal can be achieved in situ. Other elements, such as 狯 (Group IA) or alkaline earth (Group Π) compounds can be added as needed. -9 ------ ^ --I (Please read the precautions on the back before filling out this page) Order 309515

5. Description of the invention (Add to or co-precipitate with the catalyst of the present invention to change the catalytic properties. Adding these alkaline compounds or alkaline earth compounds to the catalyst of the present invention can improve the catalytic properties of its components, such as Pt or W, Its ability to act as a hydrogenation / dehydrogenation component or acid component. The IVB metal (ie, Ti, Zr4Hf) and VIB group metal (ie, Cr, Mo, or W) species of the catalyst of the present invention are not limited to this Any special valence state of other species. These species can exist in this catalyst with any possible positive oxidation number of these species. For example, when the catalyst contains tungsten, the catalyst is subjected to reducing conditions, such as Xianxin enough to reduce the price of tungsten It can improve the overall catalytic ability of the catalyst to catalyze specific reactions, such as the isomerization of n-hexane. Printed by Beigong Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs ---------- f (please read first (Note f on the back and then fill in this page) Order-Modified acidic oxides can be contacted with hydrogen at elevated temperatures. These elevated temperatures are 100 ° C or higher, such as 250 ° C or higher , For example about 300 ° C. The duration of this contact can be as short as 1 hour or even 10 hours. However, the contact can also be extended. This extended contact can be conducted for 6 hours or more, for example about 18 hours. When the oxidized hammer is modified with tungstate, then It is found to increase catalytic activity when contacted with hydrogen at elevated temperatures, such as the isomerization of alkanes. The modified acidic oxides can be contacted with gas in the presence or absence of co-added hydrocarbons. For example, at high temperatures When hydrocarbons and hydrogen pass through the catalyst at temperature, the activity of the catalyst can be increased in situ during the reaction, such as argon cracking. The hydrogenation / dehydrogenation component of this catalyst can be derived from Group VIII metals, such as platinum 'Iridium, starvation, palladium, germanium, ruthenium, nickel, cobalt iron and their mixtures of two or more. The components of the catalyst of the present invention can be used alone or mixed with the above hydrogenation / dehydrogenation components, -10- This paper scale is applicable to the «National Kneading Rate (CNS) A4 specification (210X297 mm) Α7 Β7 Printed by the Beigong Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy V. Description of invention (8 is derived from IVA group metals) In particular, sn, and / or components derived from Group VIIB metals, especially baht and manganese. These components can be added to the catalyst according to methods known in the art, such as ion exchange, impregnation, or physical blending. For example, under conditions sufficient to combine the components, the salt solution of these metals can be contacted with the rest of the catalyst components. The salt-containing metal may be water-soluble. Examples of such M include hydrogen platinum acid and platinum tetraamine Composites, tetra-vaporized platinum, tin sulfate and vaporized tin. The components as needed can also be co-precipitated with other components of the modified oxide. The tungstate · modified zirconia catalyst of the present invention is impregnated with platinum When it breaks down, a catalyst particularly suitable for catalyzing the isomerization of alkanes is formed. It has been found that it is satisfactory that about 1% by weight of F e or M η co-sink together with the solid precipitated from the aqueous mixture. The aqueous mixture contains a source of zirconia and a source of tungstate. Suitable iron salts that can be included in this aqueous mixture include Fe (N03) 3 and Fe2 (S04) 3. The modified oxide of the present invention can be recovered from the liquid medium by filtration and then dried. The scorching effect of the generated material can be more particularly in an oxidizing environment. The temperature is about 500 ° C to about 900 ° C, especially about 700 ° C to about 850 ° C, and more particularly about 75 ° C to about 825 °. The burn-in time can be as long as about 48 hours, especially about 0.1 to 24 hours, and more particularly about 丨 〇_ 丨 〇 hours. In an important specific embodiment, the burn-in effect is about 8〇 〇. (: For about 1 to about 3 hours. The components of the catalyst (such as vnj group metal, VIIB group metal, etc.) can be added according to the known techniques in the art, such as impregnation, co-impregnation Action, co-precipitation, physical blending, etc., are added before or after the burning step. Components added as needed, such as hydrogenation -11-This paper scale is applicable to the Chinese National Standard (CNS > A4 specification (210X297 Mm) ______ I ---- f II (please read the precautions on the back before filling in this page) Order ^ 309515 Α7 Β7 V. Description of the invention (9) The use / dehydrogenation component can also be combined with other catalyst components Before or after the binder or parent material described below in this patent specification , Combined with the rest of these catalyst components. In the catalyst of the present invention, zirconia is very important in the group IVB oxide; tungstate is very important in the group VIB anion; hydrogenation / dehydration as needed Among the hydrogenation components, platinum and / or platinum / tin are very important. Printed by the Beigong Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (Jing first read the note $ item on the back and then fill in this page) Qualitatively, the acidity of the invention Elemental analysis of solids shows the presence of Group IVB metals, Group VIB metals, and oxygen. The amount of oxygen measured in these analyses depends on several factors, such as the valence of Group IVB metals and Group VIB metals, as needed. The form of hydrogenation / dehydrogenation components, moisture content, etc. According to this, it is best not to limit any specific amount of oxygen when characterizing the composition of the catalyst of the present invention. In terms of function, Group VIB oxidation in the catalyst of the present invention The amount of anions can be expressed as the amount of increase in the acidity of the group IVB oxide. This amount is specified as the amount of acidity increase in this patent specification. Elemental analysis of the catalyst of the present invention can be used to determine the group IVB metal in the catalyst Relative amounts of Group VIB metals. From these amounts, the molar ratio in the form of X〇2 / Y03 can be calculated, where X is the Group IVB metal, assuming it is in the form of χ〇2, and Y is the Group VIB metal 'assumption It is in the form of Υ〇3. However, it is fortunate that these forms of oxides' means that X〇2 and Υ〇3 do not actually exist, and are only specified for calculating the relative amount of X and Υ in the catalyst of the present invention. In this patent specification, the catalyst of the present invention has a calculated molar ratio of up to 1000, such as up to 300, such as from 2 to 100, such as from 4 to 30, which is calculated by X〇2 / γ〇3 In form, where X is at least one group IVB metal (meaning Ti, Zr, and Hf) and γ _ -12- This paper uses the Chinese National Standard (CNS) Α4 specification (210X297 mm) A7 B7 economy Printed by the Beigong Consumer Cooperative of the Central Prototype Bureau of the Ministry 5. The description of the invention (10) is at least one group VIB metal (meaning cr, Mo, or W). The amount of iron and / or manganese incorporated into the acidic solid of the present invention can also be expressed as the calculated molar ratio of the oxide, which is based on elemental analysis of the solid Group IVB metal, X, and Mn and Fe. More specifically, the present acidic solid may have a calculated molar ratio expressed in the form of χ〇2 / (Mn02 + Fe203), for example, 10 to 500. Fortunately, Mn is not necessarily in the form of Mn02, and Fe is not necessarily in the form of Fe203. More specifically, at least a part of these components are in the form of free metals, or other forms that are not a combined form of Mn〇2 or Fe2〇3, such as salts of elements other than oxygen, X, Mn, or Fe. Valence. Accordingly, Xian understands that the term X02 / (Mn02 + Fe203) is only used to express the calculated amounts of X, Mn, and Fe, and is not intended to limit the positive forms of these elements in the acidic solid material of the present invention. The amount of the hydrogenation / dehydrogenation component selected as required is to provide or increase the overall hydrogenation or dehydrogenation of the hydrogenable or dehydrogenable organic compound under conditions sufficient for hydrogenation or dehydrogenation The amount of catalytic activity of a substance. This amount is designated as the catalytic amount in this patent specification. Quantitatively speaking, the catalyst of the present invention may contain, for example, about 0.001 to about 5 weight ° / 〇, for example, about 0.1 to about 2% by weight of the hydrogenation / dehydrogenation component optionally added, especially when When this component is a precious metal. In particular, when the catalyst of the present invention contains a platinum hydrogenation / dehydrogenation component, the catalyst may also contain up to about 5 weight percent Fe and / or Mn when measured by elemental analysis of the catalyst. The catalyst of the present invention is acidic and has been found to be extremely acidic, even to the point of becoming excessive acid. Excess acid is an acidic substance_a known classification-13- This paper scale is applicable to the Chinese National Standard (CNS> Α4 specifications (2 丨 0X297mm) (please read the precautions on the back before filling this page) Μ, I. Order A7 B7 V. Description of the invention (11) 'This substance has an acidity exceeding 100% h2 s 〇4. For this degree of acidity determination, any suitable method can be used, including the use of appropriate indicators and the measurement of specific chemicals The ability to protonate, and / or measure its ability to stabilize specific cations, especially to stabilize specific carbon ions or carbenium ions. For example, whether the component is selected as required (eg, argonation / dehydrogenation group) Parts) and / or in the presence or absence of a binder substance, the catalyst is measured with the color change of an appropriate indicator, such as a Hammett indicator, and all have an acid strength of excess acid. More specifically, The strength of the catalyst of the present invention has a value below -1 3, which means " acid strength " is greater than 1 13. The measurement of the acidity of solid excess acid using Hanmot indicator is discussed in Soled et al_US No. 5,157,199. This Soled et al. Patent also describes the sulphuric acid strength of the excess acid of the transition metal transition metal sulfated. The catalyst described in this patent specification can be used as a catalyst for the isomerization of C 4 to C 8 fumes. Appropriate feedstocks contain normal mass and / or mono-branched low-carbon octane C4 to C8 hydrocarbons. The feedstock may also contain small amounts of C6 and C7 cyclic hydrocarbons that can undergo ring-opening reactions. Printed by a consumer cooperative (please read note f on the back before filling in this page)

1T The heterogeneous method of the present invention is carried out at a temperature below 5001, especially below 3 50 C, especially below 300 ° C, in a pressure range of i to 200 atm, especially at 1 to 100 atm, more particularly The hydrocarbon feedstock, whether in the liquid or oxygen phase, is brought into contact with the solid catalyst at 5 to 5 () atmospheric pressure. The isomerization process can be carried out in the presence or absence of hydrogen, especially in the presence of hydrogen. The molar ratio of hydrogen to hydrocarbon is in particular in the range of 〇i: 1 to 1: 1. The catalyst of the present invention can satisfactorily incorporate other substances that can improve its characteristics. These substances include active or inactive substances, synthetic and naturally occurring -14- 3C? 5l5 A7 B7 5. Description of the invention (12) Zeolite zeolite and inorganic substances such as clay, silica, and / or metal oxides. The latter may be natural or in the form of gelled precipitates, gum solutions, or gels, including mixtures of crushed earth and metal oxides. Xian noted that the catalyst of the present invention does not need to contain any sulfate ion (US Patent No. 4,918,041). Xianxin's catalysts of the present invention are compared with sulfated catalysts, such as the excessive acid sulfated catalysts mentioned in the literature of K. Arata and M. Hino in Proceedings 9th International Congress on Catalysis. Volume 4, pages 1727-1735 (1988) , More stable and easier to regenerate. In the isomerization method of the present invention, the n-chain alkyl and mono-methyl branched alkane components are isomerized to a higher carbon branched alkane, which is generally the preferred octane expander. The importance of these reactions can be explained by reviewing P.H. Emmett, ed., Catalysis, Vol. VI (1958) under the table of pure hydrocarbon octane. The number of octanes of pure hydrocarbons M. Blending research octane value (clear) ---------- (-I (please read the notes on the back before filling in this page) Beigong Consumer Cooperative printed n-heptane 0 2-methylhexane 4 1 3-methylhexane 56 2,2-dimethylpentane 89 2,3-dimethylpentane 87 2,2, 3-Trimethylbutane 113 -15- This paper scale is applicable to China ’s Standards for the Poor (CNS) (210X297mm) A7 B7 Printed by the Employee Consumer Cooperative of the Central Bureau of Samples of the Ministry of Economy V. Description of the invention (13) The method of the invention The raw material contains a large amount of c, normal and / or slightly branched alkanes. In addition, the raw material may contain monocyclic aromatic compounds and / or cyclic alkanes such as cyclohexane. The raw material has 6 or fewer carbon atoms Among the hydrocarbons, at least 1% by weight, such as at least 5% by weight, such as at least 10% by weight, such as at least 20% by weight, such as at least 30% by weight, such hydrocarbons are cyclic hydrocarbons, such as aromatic compounds or cyclic Pit hydrocarbons. The catalyst of the present invention can be used to isomerize C 4-C 8 alkanes, whether pure compounds or mixtures. During the refining process, alkanes are usually present In the mixture, in addition to the C4_C8 substance, and may contain hydrocarbons boiling outside this range; there may also be naphthenic smoke and aromatic compounds. Therefore, the raw materials will contain c4_c8 alkanes such as butane, pentane, hexane, and These substances can be present in the refining stream, such as the residual liquid from the solvent extraction unit, the gasoline octane increase furnace feedstock from the ethylidene milling roller or the pyrolysis gasoline. The feedstock can also contain ring smoke, such as C6 + In the form of naphtha; the cyclic material in this raw material can undergo a ring-opening reaction to form an alkane in the presence of the catalyst and the metal component used together, which is then subjected to isomerization to become an iso-alkane, which is extinct after recycling Fractional distillation of cyclic compounds, iso-alkanes can be separated from cyclic compounds. In addition to pure alkane raw materials (c 4-C 8), mixed alkane-hydrocarbon raw materials containing large amounts of olefins can also be used. Isomerization is carried out at In the presence of a catalyst, especially in the presence of hydrogen. The appropriate reaction temperature range is 200 ° to 800T (93. to 425. 〇, but can also be used outside this range of temperature, although less typical. 300. to 700T The temperature of (149 ° to 370 ° C) is typical. The pressure is usually as high as 1000 psig (7,000 kPa abs.), Although there is no reason not to use a paper that is more than 16 Rate (CNS) A4 specification (210X297mm) ---------- ^ (please read the notes on the back first #fill in the text). Printed by the Ministry of Economic Affairs Central Bureau of Quotations Consumer Cooperatives 309515 A7 B7 V. Description of the invention (14) High pressure. Lower pressures in the range of 50 to 600 psig (445 to 790 kPa abs.) Are easier to use, and in order to use low-pressure devices, it is generally preferred to use those in this range Relatively low pressure. Isomerization is usually carried out in the presence of hydrogen, and its molar ratio relative to the raw material is typically 0.01 to 10: 1, and often 0.5 · 1 to 2: 1. The space velocity is typically 0.1 to 10 LHSV, and usually 0.5 to 5 LHSV. When other acidic substances (Lewis acid or Bronsted acid) are included in the catalyst, a lower operating temperature may be used to facilitate heteromorphism beyond the less desirable cracking reaction. The precious metal component added as needed in the catalyst of the present invention provides a catalyst hydrogenation / dehydrogenation component to the catalyst. Metals with enhanced hydrogenation function are preferred, especially platinum and other precious metals such as palladium, rhodium, and lack of 'chain' although other metals that can be used as hydrogenation components, such as nickel, tungsten or other Group VIII metals can also be used , Whether alone, in a mixture or in combination with other metals. The amount of the precious metal component occupies the total catalyst in the range of 〇〇〇 to 5 weight 0 / 〇, for example, 0.1 to 2% by weight. A slightly larger amount of alkali metal hydrogenation components can be added. The hydrogenation component can be exchanged onto the support, impregnated into it or physically blended with it. For example, if the metal is impregnated into it or the parent is replaced on the support, it can be achieved by treating the support with platinum metal ions. Suitable platinum compounds include hydrogen platinum acid, vaporized platinum, and various compounds containing platinum amine compounds. The metal compound may be a compound in which the metal is present in the cation 4 of the compound or a compound in the anion of the compound, and both compounds may be used. Platinum compounds in the form of cation complexes of metals, such as cations of Pt (NH3) 4Cl2, are particularly useful, as are anionic complexes such as vanadate and metatungstate ions. Due to delivery -------------- (please read the precautions on the back before filling in this page) Order -17- Printed by the Central Squash Bureau of the Ministry of Economic Affairs Beigong Consumer Cooperative Α7 Β7 5. Description of the invention (15) The cationic form of other metals is also useful for changing to or being impregnated into the support. Under conventional conditions, the catalyst undergoes final calcination to dehydrate the catalyst 'and provide the required mechanical strength on the catalyst. The catalyst can be pre-sulfurized before use. When a source of hydrogenation metal, such as H2PtCl6, is used as the source of the hydrogenation / dehydrogenation component in the catalyst of the present invention, it is desirable to subject the catalyst of the present invention to extended reduction conditions, for example to more than 4 hours. The inclusion of other substances with Lewis acid or Bronsted acid activity in the catalyst can provide higher isomerization activity, especially when the catalyst contains porous binding substances. For this purpose, either liquid or solid acid substances can be used. Examples of suitable other acidic substances include complexes of aluminum trioxide, trifluoride and boron trifluoride with, for example, water, lower alcohols or esters. The maximum addition amount can be determined by the ability of the support, especially the binding substance, to adsorb the added component. The maximum addition amount can be easily determined experimentally. The catalyst of the present invention can be used as the only isomerization catalyst in a single or double catalyst bed, or it can be used in combination with other isomerization catalysts. For example, the feedstock can be first contacted with a catalyst bed containing the catalyst of the present invention, and then contacted with a different catalyst, such as "mordenite" described in US Patent Nos. 4,783,575 and 4,834,866, "pt on zeolite cold or a gasified The platinum · aluminum catalyst is in contact with the second catalyst bed. The temperature of the first catalyst bed is higher than that of the second catalyst bed. When the catalyst of the present invention is used to promote large-scale ring-opening, especially in the primary catalyst bed -18- This paper scale is suitable for China National Standard (CNS> A4 secret (21〇χ297mm (please read the precautions on the back before filling this page) -Λ;! Order A7

Printed by the Beigong Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs, relatively high temperatures can be used, such as up to 50 ° C, and / or relatively high pressures, such as up to 200 atmospheric pressure. The catalyst of the present invention can be made into a wide fan size The shape. In general, the particles can be in the form of powder, granules or molded products, such as extrudates with a particle size sufficient to pass through a 2 mesh (Taylor) sieve, but kept on a 400 mesh (Taylor) sieve In the case where the catalyst is molded, if it is extruded, the catalyst is dried or partially dried before extrusion, and then extruded. The catalyst of the present invention can be composed of a matrix material to form the final form of the catalyst. For this purpose, general matrix materials such as alumina, silica-alumina and alumina are suitable, and silica is preferred when a non-acidic binder is required. Other bonding materials such as titania, zirconia and other metals Oxides or clays can also be used. The composition of the active catalyst and the substrate can be 80: 2 0 to 20: 80 by weight, such as 80: 2 0 to 50: 50. Active catalyst: substrate. This can be accomplished by conventional methods, including grinding the material together, and then extruding the pellets into the desired final catalyst particles. The catalyst can be treated by conventional pre-sulfurization, such as heating in the presence of hydrogen sulfide to oxidize the metal components The form of the compound is converted into its corresponding sulfide. Although the use of the catalyst of the present invention in the isomerization reaction has been emphasized in the foregoing of this patent specification, it is fortunate that the catalyst can be used for the conversion of various organic compounds, such as hydrocarbon compounds In the process, when the catalyst of the present invention contains a hydrogenation / dehydrogenation component, it can be used for reactions that require the use of dual-function (1) acidic and (2) hydrogenation / dehydrogenation catalysts. These conversion methods Including, as a non-limiting example, including the temperature of 100 -19-This paper standard uses the Chinese National Standard (CNS) A4 specification (210X297mm> (Please read the note $ item on the back and fill in this page)- Order 308515 A7 B7 V. Description of the invention (17). (: To 700 ° C, pressure 0.1 atmospheric pressure (bar) (10Kpa) to 30 atmospheric pressure (3040 Kpa), weight Space-time velocity of 0.1 to 20, and hydrogen / hydrocarbon molar ratio of 0 to 20, hydrocracking of hydrocarbons; including temperature 300 ° C to 700 ° C, pressure 0.1 atmospheric pressure (10 Kpa) to 10 atmospheres Force (1〇13 Kpa), dehydrogenation of hydrocarbon compounds under reaction conditions with a weight hourly space velocity of 0.1 to 20; at a temperature including 100 ° C to 700 ° C, a pressure of 0.1 atmospheric pressure (1〇Kpa) to 60 atmospheres Force (6080 Kpa), weight hourly space velocity 0.5 to 400 and hydrogen / hydrocarbon molar ratio of 0 to 20 under the reaction conditions, the conversion of alkanes to aromatic compounds; including the temperature of 100 ° C to 700 ° C, pressure 〇. 1 Atmospheric pressure (10 Kpa) to 60 Atmospheric pressure (6080 Kpa), weight hourly space velocity ο "to 400 and hydrogen / hydrocarbon molar ratio 〇 to 20 under the reaction conditions, the conversion of olefins into aromatic compounds, such as benzene , Toluene and xylene; in the presence of multi-pit aromatic hydrocarbons, including temperature 100 ° C to 500 ° C, pressure from atmospheric pressure (ιοί Kpa) to 200 atmospheric pressure (20265 Kpa), weight hour space velocity 10 To 1000 and aromatic hydrocarbon / polyalkyl aromatic hydrocarbon molar ratio 〇3 / 1 to 2〇 / 1, and / Hydrocarbon mole ratio of 0 to 20 under reaction conditions to effect conversion of alkyl aromatic hydrocarbons; at a temperature comprised · 2 5 X: to 400. (: For example 75. (: To 200 ° C, the pressure is lower than atmospheric pressure (101 Kpa) to 5000psig (34566 Kpa) 'For example, atmospheric pressure to 100psig (6994 Kpa), total alkane Molar ratio to total olefins 1: 2 to 500: 1 ', for example, 5: 1 to 100 ....; weight hourly space velocity in terms of hydrocarbons, 0.01 to 100, for example, 〇〇5 to 5. Under the reaction conditions, the hydrogen is transferred from the burned hydrocarbon to the associated hydrocarbon. The catalyst of the present invention can also be used in the isoalkane / hydrocarbon alkylation process. The isofluorescent smoke is isobutane-1, and the olefin smoke is ethylene, propylene and / or Or Ding Xi, for example, 2_ -20- This paper is A81 (green CNS) A4 «l # > (210X297mm) (Please read the note $ item on the back and then fill in this page) Order the Central Sample Bureau of the Ministry of Economic Affairs Printed by Beigong Consumer Cooperatives Printed by the Central Bureau of Standards of the Ministry of Economics Printed by Aigong Consumer Cooperatives A7 ________B7_ V. Description of invention (18) Butene. The isoalkyl / associated hydrocarbon alkylation reaction occurs in the hydrogenation / dehydrogenation component In the presence or absence, in the presence or absence of co-added argon 'temperature -25 to 400 ° C, and 75 ° C is the more usable upper limit, willing to lower Atmospheric pressure (101 Kpa) to 5000 (34566 Kpa), weight hourly space velocity of 0.01 to 100 hours in terms of associative hydrocarbons, and total molar ratio of different burned smoke to total hydrocarbons from 1: 2 to 500: 1 hour. The inventive catalyst can also be used in various argon processing reactions, such as the removal of metals, nitrogen, and / or sulfur from raw materials, such as including these elements, especially the resids in the form of heteroatoms. Such hydrogen processing reactions include Hydrogen and the catalyst of the present invention are contacted under conditions sufficient to remove metals, nitrogen, and / or sulfur. Example 1 This example describes the preparation of tungstate-modified zirconia (W〇x / Zr02). 500 g ZrOC〗 2 · 8H20 Dissolve in 7.0 liters of distilled water with stirring. A solution containing 263 ml of concentrated NH4OH, 500 ml of distilled water, and 54 g (NH4) 6H2W12O40.xH2〇 is added dropwise over a period of 30-45 minutes. Additional drops are added Adjust the pH of the solution to about 9 (if necessary). The slurry is then placed in a steam box for 72 hours. The product formed is recovered by filtration, washed with excess water, and heated at 85 ° C. Dry overnight. The material is then dried in air Burned to 825 ° C for 3 hours. Example 2 This example describes the preparation of tungstate-modified oxide cones containing 0.6% by weight Pt (〇6% by weight Pt / W〇x / Zr〇2) .12 Grams of WOx / Zr〇2 made according to Example 1 contain 0.019217 grams of 112? 1 (: 16.6H20, via ___- 21-this paper scale is used in China National Standard (CNS) A4 specifications (210x297 PCT) ---------- 11 — (Please read the notes on the back before filling this page)

• Printed by Beigong Consumer Cooperative of the Central Bureau of Industry and Information Technology of the Ministry of IT A7 _B7 V. Description of the invention (19) The initial moisture is dissolved in a solution of 20 ml of distilled deionized water. The catalyst produced by drying was then calcined in dry air at 300 ° C for 2 hours. Example 3 This example describes the preparation of 0.3 wt% Pt / W0x / Zr02. 12 grams of WOx / Zr〇2 made according to Example 1 were impregnated with a solution containing 0.096 grams of H2PtCl6.6H20 dissolved in 20 ml of steamed deionized water through initial moisture. The resulting catalyst was dried, and then burned in dry air at 300 ° C for 2 hours. Example 4 This example describes the preparation of 0.5 wt% Pt / Si02-W0x / Zr02. 12 grams of wox / Zr02 prepared according to Example 1 were mechanically mixed with 7 grams of 0.5% by weight Pt / Si〇2 catalyst. The 0.5% by weight Pt / SiO2 catalyst was prepared by ion exchange. At a pH of 9 under alkaline conditions, the silica gel (Davison Chemical, grade 12) was exchanged with an aqueous solution containing Pt (NH3) 4 + +. The resulting material was dried at 120 ° C for 16 hours, and then burned under air at 3501: 4 hours. After 0.5 wt% Pt / Si〇2 catalyst was cooled to room temperature, it was reduced at 45 ° C in flowing hydrogen for 30 minutes. Example 5 This example describes the preparation of Fe / Mn / W0x / Zr02. 500 g of ZrOCl2. 8H20 was stirred Dissolve in 6.5 liters of distilled water. Dissolve a solution containing 46 grams of MnS04.H20 and 7.6 grams of FeS04.7H20 in 500 milliliters of distilled water and then add to the oxygen-containing solution. Contain 263 milliliters of concentrated NH4OH, 500 Milliliters of distilled water and 54 grams of (NH4) 6H2W12O40. The third solution of X h20 in a period of 30-45 minutes -22- This paper is new and 8 BI household materials (CNS) A4 specifications (210X297 mm) I ----- ---- ί ------ IT (Please read the precautions on the back before filling in this page) Printed by the Central Standards Bureau of the Ministry of Economic Affairs, printed by the Consumer Cooperative Cooperative 3〇95l5 at January (20) One ~ drop by drop Add to the iron / ϋ / zirconium mixture. Add additional concentrated NH40Η dropwise to adjust the pH of the solution to about 9 (if necessary). The slurry is then placed in a steam box for 72 hours. The resulting product is steamed off Recycle, wash with excess water and dry overnight at 85 ° C. The material is then burned to 825 ° C in dry air for 3 hours Example 6 12 grams of Fe / Mn / W0x / Zr02 prepared according to Example 5 were impregnated with a solution containing 0.19217 grams of H2PtCl6.6H20 dissolved in 20 ml of distilled deionized water via initial moisture. The resulting catalyst was dried, followed by It was calcined in dry air at 30 ° C for 2 hours. Example 7 This example describes the preparation of Fe / WOx / Zr〇2. 500g of Zr〇cl2. 8H2〇 was dissolved in 6.5 liters of distilled water with stirring. Contains 7 "G?"% 7H2〇 solution was dissolved in 500 ml of distilled water, and then added to the solution containing oxygen cone base. Contains 263 ml of concentrated Nh4〇h, 500 ml of distilled water and 54 g (NH4) 6H2Wi2O40. The third solution of Xh2〇 was added dropwise to the iron / zirconium mixture during 3045 minutes. Additional concentrated NH4OH was added dropwise to adjust the pH of the solution to about 9 (if necessary). The slurry The material was then placed in a steam box for 72 hours. The formed product was recovered by steaming, washed with excess water and dried overnight at 85X. The material was then burned to 825 ° C in dry air for 3 hours. Example 8 This example describes Preparation containing PttFe / w〇x / Zr〇2. 36 g prepared according to Example 7 The Fe / W〇x / Zr〇2 contains 0.58 g ^ (please read the precautions on the back before filling out this page) Λ 訂 -23- Printed by the Ministry of Economic Affairs Central Standard Falcon Bureau Employee Consumer Cooperative A7 B7 V. Description of the invention (21) 6H2O is impregnated by a solution of initial moisture dissolved in 60 ml of distilled deionized water. The resulting catalyst was dried, and then burned in dry air at 300 ° C for 2 hours. Example 9 This example describes the preparation of Mn / WOx / Zr〇2. 500 grams of Zr〇ci 2. 8112〇 was dissolved in 6.5 liters of distilled water while being evacuated. A solution containing 4.6 g ^ 1180.7H2〇 was dissolved in 500 ml of distilled water and then added to the solution containing zirconium oxyzirconium. A third solution containing 263 ml of concentrated NH 4 OH, 500 ml of distilled copper water and 54 g (NH 4) 6H 2 W 2 040. X H 2 0 was added dropwise to the basin / zirconium mixture during 30-45 minutes. Add additional concentrate dropwise to adjust the pH of the solution to about 9 (if necessary). The slurry was then placed in a steam box for 72 hours. The formed product was recovered by steaming and filling, washed with excess water and dried overnight at 85 ° C. The material was then burned to 825 ° C for 3 hours in dry air. Example 1 0 This example describes the preparation of Mn / W0x / Zr02 containing Pt. Twelve grams of Mn / WOx / Zr02 prepared according to Example 9 were impregnated with a solution containing 0.1926 grams of H2Ptcl6 · 6Η2〇 dissolved in 20 ml of distilled deionized water via incipient wetness. The resulting catalyst was dried, and then burned in dry air at 300 ° C for 2 hours. Examples 1 1 -1 4 These examples illustrate the negative effect of Pt on WOx / Zr02 activity in pentane isomerization. In a fixed-bed downflow reactor, 21 (TC, 350 psig, 2 mol H2 / mol n-C5, and 2 LHSV (cc n-C5 feed / cc catalyst-24-This paper size applies to China National Standards (CNS ) A4 specification (210X297mm) (please read the notes on the back before filling in this page) * The Ministry of Economic Affairs Central Sample Bureau employee consumption cooperation Du Yinju A7 _ B7 V. Invention description (22) / hour) Test Example 1-4 The activity of the catalyst for the isomerization of valpro. The catalyst was burned at 300 ° C for 1 hour in flowing nitrogen before the catalytic test. The results are shown in Table i. When pt does not contain W〇x / The catalytic activity of Zr〇2 line 1 'is compared with the catalytic activity of W Ο χ / Z r Ο 2 containing P t. When rows 2 to 4 are compared, the negative effect of Pt on the catalytic activity of Chen 0, / 21 * 02 Obviously. The activity of catalysts containing P t is weaker than those without P t. Examples 1 5-1 8 These examples show the effect of Pt on Fe / Mn / WOx / Z r〇2 catalysts for pentane isomerization Positive effect of activity and selectivity. Test Example 5 _ 丨 〇 catalyst for pentane isomerization under conditions similar to those described in Examples 1 1-14. Activity. The results are shown in Table 2, line 1 and 2 represents the free p t

Fe / Mn / W0x / Zr02, the results observed at 200 ° C and 210 ° C at different temperatures. The results of Fe / Mn / W0x / Zr02 containing Pt at 200C and 210 ° C are shown in lines 3 and 4, respectively. Adding Fe / Mn, the catalyst containing Pt maintains high activity. Examples 1 9-2 0 These examples illustrate the activity of Pt / Fe / W0x / Zr02 and Pt / Mn / WOx / Zr02 for pentane isomerization. The activity of the catalysts of Examples 8 and 10 was tested for the isomerization of pentane under conditions similar to those described in Examples 1 1 ~ 4. The results are shown in Table 3. When comparing the second to fourth rows of Table 1 with the first and second rows of Table 3, in order to maintain the high activity of the wox / Zr02 catalyst, the positive effect of adding Fe and Mn on the addition of pt is very obvious. Example 2 1-2 2 These examples describe Fe / W0x / Zr02 without Pt and Fe -25 with Pt- The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X 297mm) (please read the back Please pay attention to this page and then fill out this page) Xu No. 34112573 Patent Application Case Chinese Patent Correction Page (86a 异 e |) V. Description of the invention (23

/ W〇x / Zr〇2 on n-hexane isomerization. At ^ 仞 ^, 450 psig '2 mol h2 / mol n-c6, and 2 JLHSV (cc n_c5 feed / cc catalyst / hour), test examples 7 and 8 catalysts for n-hexane isomerization Influence "Results are shown in Table 4. Adding Pt to Fe / WOx / Zr〇2 significantly improves n-hexane isomerization activity and selectivity to the desired high-octane dimethylbutane. Please read the precautions before reading-Table 1 fill this page. Printed by the Central Bureau of Economic Affairs of the Ministry of Economy '• Beigong Consumer Cooperative Printed Example 1 1 · 1 4 Zheng-7¾ Data Example of Pit Isomerization 11 * 12 13 14 Catalyst W0x / Zr02 Pt / WOx / Zr02 Pt / WOx / • Zr02 Pt / Si02 / WOx / ZrO: Preparation of catalyst in the example 1 2 3 4 Product distribution weight% Cj + 〇2 0.4 0.1 0.1 0.2 c3 0.4 0.1 0.2 0.2 i-C4 2.7 0.1 ---- 0.3 n-C4 0.2 0.1 0.1 0.1 i-C5 69.1 52.4 46.9 40.4 n-C5 26.5 47.1 52.7 58.6 C6 + 0.6 0.2 0.05 0.9 11- (: 5 conversion., Wt.% 73.5 52.9 47.3 41.4 i-C5 / total C5,% 72.3 52.7 • 47.1 40.8 -26 The size of the linear paper is applicable to China National Standards (CNS) Α4 specifications (2! 〇 < 297mm) 309515 (twenty four

Employee's Cooperative of the Central Bureau of Standards, Ministry of Economic Affairs, Employee Cooperative Table 2 Examples of 15-18 n-pentane isomerization data 15 16 17 18 Catalyst Fe / Mn / Fe / Mn / Pt / Fe / Mn / Pt / Fe / Mn W0x / Zr02 W0x / Zr02 W0x / Zr02 WOx / ZrO; Preparation of the catalyst in the example 5 5 6. 6 Operating temperature. C 200 210 200 210 Product distribution weight% 0.7 1.0 0.4 0.5 c3 0.5 0.8 0.4 0.5 i-c4 1.3 2.5 0.2 0.3 n-C4 0.2 0.3 0.3 0.5 i-C5 64.6 68.6 '70 .8 70.9 n-C5 32.7 26.6 27.5 26.7 * · *-0.2 0.3 0.5 n-C5 conversion., Wt.% 67.3 73.4 72.5 73.3 i-C5 / total C5,% 66.4 72.0 72.0 72.6, 27 (please read the notes on the back and fill in this page)

T The standard of the paper method is applicable to the Chinese National Standard (CNS) A4 specification (2 丨 0 X 297 male thin) A7 B7 printed by the Employee Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of invention (25) Table 3 Positive examples 19 and 20 -Data Example of Pentane Isomerization 19 20 Pt / Fe / Pt / Mn Catalyst WOx / Zr02 WOx / Zr02 Preparation of Catalyst in Examples 8 10 Product Distribution Weight% C! + C2 0.7 0.1 C3 0.8 0.3 i-C4 0.7 0.2 II-C4 0.9 0.2 i-C5 69.3 69.4 n-C5 26.8 29.3 c6 + 0.8 0.4 n-C5 conversion, weight% 73.2 70.7 i-C5 / total C5,% 72.1 70.3 (Please read the notes on the back before filling in This page) Λ 、-= β -28- This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) A7 A7 Printed B7 by the employee consumer cooperative of the Central Bureau of Standards of the Ministry of Economy V. Description of invention (26) Table 4 Example 21 and 22 Data of hexane isomerization Example 21 22 Fe / Pt / Fe catalyst W0X / Zr02 WOx / Zr02 Preparation of catalyst in the example 7 8 Product distribution, weight% Cj + c2 0.03 0.6 C3 1.3 1.2 i-C4 9.3 0.9 n-C4 0.9 0.9 i-C5 5.6 1.0 n-C5 0.9 0.4 2 , 2-dimethylbutane 5.3 24.4 2,3-dimethylbutane 9.0 9.1 2-methylpentane 30.0 29.6 3_methylpentane 18.6 18.2 η-hexane burn 18.4 13.4 Cj + tr tr η-hexane Alkane conversion, weight% 81.6 86.6 dimethylbutane production, weight% 14.3 33.5 (please read the precautions on the back before filling this page) Λ,-° -29- This paper size applies to China National Standard (CNS) A4 Specifications (21〇297297mm)

Claims (1)

Patent No. 1 573, please abandon and reapply »The original version of the patent template (86 months without a month) A8- B8 C8 D8 Please read the notes before applying for the scope of the patent I " fill in this page 1--acidic solid skeleton combination Which includes a group IVB metal oxide modified with an oxide anion of a group VIB metal, wherein the group VIB metal is selected from a group containing molybdenum and tungsten and the group IVB metal oxide is selected from a group containing titanium and zirconium, the The acidic solid still contains at least one oxide selected from metals including iron and lithium. The calculated molar ratio of X〇2 / γ〇3 is as high as 300, where X is the group IVB metal, assuming X02 Form, and γ is the group VIB metal, assuming the form of Y03, and the calculated X〇2 / (Mn〇2 + Fe2〇3) molar ratio is 10 to 500, of which manganese and iron are respectively It is assumed that it is in the form of ^ 〇2 and Fe2〇3 "2. The acidic solid composition according to item 1 of the patent application scope, which still contains a precious metal" 3. The acidic solid composition according to item 2 of the patent application scope, where The precious metal is Ming 9-Ministry of Economic Affairs Cooperative India 4 · A method for preparing an acidic solid composition as claimed in item 1 of the patent application, the acidic solid comprising a group IVB metal oxide modified with an oxidized anion of a group VIB metal, the method comprising using a group IVB metal oxide The source, the source of oxide anions of Group VIB metals, and a source selected from oxides including Fe and Mn are co-precipitated. 5. The method according to item 4 of the patent application scope, wherein the source of the oxidized anion of the group VIB metal is selected from ammonium metatungstate, ammonium metamolybdate, tungsten fluoride, vaporized molybdenum, tungsten carbonyl, carbonylation "Molybdenum, Tungstic Acid, Sodium Tungstate, and Sodium Molybdate" 6. The method according to item 4 of the patent application scope, wherein the group IVB metal is Zr 'and wherein the group νίΒ metal is W. The paper scale is applicable to China National Standard (CNS) A4 (210X297mm) A kind of equipment, such as the method of applying the acidic solid composition of the i-th patent scope, the acidic solid contains tungstate-modified oxidized complex, the method includes the following steps: (a) making the first liquid solution and the second liquid solution Combined with a third liquid solution, the first solution contains a source of germanium oxide dissolved in water, the second solution contains a tungstate dissolved in water to tick, and the third solution contains at least one selected from the group consisting of iron and shovel Source of oxides; (b) maintaining the combined solution of step (a) under conditions sufficient to form a solid co-deposit, which solid oxide contains tungstate modified oxidized junctions and at least one contains Fe and And / or Mn compounds; (c) recover the solid co-precipitate from step (b) through peroxidation; and (d) calcine the co-precipitate recovered from step (c). 8. The method according to item 7 of the patent application scope, wherein the source of zirconia is ZrOCl2 and the source of tungstate is ammonium metatungstate. 9. A method of converting an organic compound, the method comprising contacting the organic compound with a catalyst under conditions sufficient for sufficient conversion, wherein the catalyst comprises an acidic solid snake composition as claimed in item 1 of the patent application. Printed by the Cooperative Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 51 10. A method for isomerizing hydrocarbons. This method involves the isomerization of raw materials containing C4 to C8 hydrocarbons and isomerization under conditions sufficient for isomerization. When the catalyst is contacted, the isomerization catalyst contains (i) a precious metal and (ii) an acidic solid composition as described in the patent application. II. The method according to item 10 of the patent application scope, in which the precious metal contains foreign metals. This paper scale is applicable to China National Standards (CNS) eight 4 wash grid (210X 297 mm) ¢ 09¾ ^ ^ year supplement 86. Ι, ι, patent application scope A & B8 C8 Dt 12 · According to the patent application scope No. 1 The method of item 〇, wherein the precious metal comprises platinum in the form of an oxide, hydroxide, or free metal, the group IVB metal oxide is zirconia, and the group VIB metal oxide anion is tungstate. 13. The acidic solid composition according to item 1 of the patent application scope, wherein the group metal is ζΓ and the group viB metal is W. Please read the notes on the back and fill in this page. Threads are printed by the Ministry of Economic Affairs, China National Standards Service, Beigong Consumer Cooperative. The paper size is applicable to the Chinese National Standard (CNS) A4 regulation (210X 297mm)