TW426640B - Synthetic porous crystalline material, process for synthesizing it and processes of using it - Google Patents

Abstract

This invention relates to a new synthetic porous crystalline material, designated MCM-61, a method for its preparation using specific crown ethers and use thereof as a sorbent or in catalytic conversion of organic or inorganic compounds. The new crystalline material exhibits a distinctive X-ray diffraction pattern.

Description

426640 A7 B7 V. Description of the invention (1. Yin Changfa, a consumer cooperative of the Central Procurement Bureau of the Ministry of Economic Affairs, is a kind of synthetic porous crystalline materials, its preparation ^ and its catalytic properties as absorption or for organic or inorganic compounds Utilization in transformation. In the past, sludge materials (both natural and synthetic) have been proven to be used for all types of smoke! They have catalytic properties, specific zeolite materials are arranged, and porous crystals have a clear crystal structure when they are shot. Among them, there are a large number of smaller pores, which can be connected by many smaller ditches or pores. The dimensions of these channels and pores in a specific stagnant stone material are all β, because the size of these pores can accept a specific size These materials are known to be used as molecular sieves, and they are used in various ways to obtain the advantages of these properties. This type of molecular sieve (both natural and synthetic) Contains a variety of positive ion-containing bismuth salts. These silicates can describe compounds such as hi and compounds of the πα group of the periodic table, such as the hard three-dimensional structure of dove 4, where four sides are intersected by common atoms. Therefore, the ratio of all 4MILA group elements, such as chain-cutting atoms to oxygen, is 1: 2. The price of tetrahedrons containing elements of Group VIII, such as Ming, is balanced by the inclusion of cations in the crystal, such as alkali metals or alkaline earth. Metal cations. This can be expressed by the ratio of the number of IIIA elements, such as aluminum to various cations, such as Ca〆2, Sr / 2, Na, K, or Li. The cations can be traditionally used by ion exchange technology. The species are exchanged in whole or in part. By this cation exchange, through the winter season, the choice of cations may change the properties of a given salt. The first four dehydrations: the space is filled with water molecules. The result of technology is the formation of various synthetic stagnant stones. The company · Xi Juxi Xie Ziyou selects these (please read the precautions on the back before filling this page), and this paper is applicable to China National Standards (CNS) } a4 size (210X29 * 7mm) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 4 2 6 6 4-0 A7-__B7_____ __ V. Description of the invention (2) Zeolite is expressed in words or other convenient symbols, such as Zeolite A (US Patent No. 2,882,243); Zeolite X (US Patent No. 2,882,244); Zeolite Y (US Patent No. 3,130,007); Zeolite ZK-5 (US Patent No. 3,247,195); Zeolite B (US Patent No. 3,314,752); Zeolite ZSM-5 (US Patent No. 3,702,886); Zeolite ZSM-11 (US Patent No. 3,709,979); Zeolite ZSM-12 (US Patent No. 3 832,449): Zeolite ZSM-20 (US Patent No. 3,972,983); ZSM-35 (US Patent No. 4,016,245); zeolite ZSM-23 (US Patent No. 4,076,842); zeolite MCM-22 (US Patent No. 4,954,325); and zeolite MCM-35 (US Patent No. 4,981,663) indicate . 'The Si02 / Al2 03 ratio of a given zeolite is often variable. For example, zeolite X can be synthesized at a Si02 / A2 / 03 ratio of 2 to 3; zeolite γ, from 3 to about 6. In some zeolites, the limit of Si02 / AI2 03 is not limited. z S Μ-5 is one of the examples, where the Si02 / Al2 03 ratio is at least 5, and reaches the limit of this analytical measurement technology. U.S. Patent No. 3,941,871 (Re. 29,948) discloses a porous crystalline salt that is made from a reaction mixture that does not contain a planned addition of alumina and exhibits the characteristics of the X-ray diffraction pattern of ZSM-5 . U.S. Patent Nos. 4,061,724, 4,073,865, and 4,104,294 describe crystalline silicates with different alumina and metal components. In one of the objectives, the present invention belongs to a porous crystalline material, called MCM-61, and its X-ray diffraction pattern characteristics include substantially as listed in Table I below. ’. In another object, the present invention belongs to a manifestation inclusion list! The characteristics of the ^ -maximum interval shown in the synthesis of porous crystalline material with X-ray diffraction pattern shown in the figure ____ -5- ^ Paper size is applicable to China National Standard (CNS) M specification (2) 0 × 297 mm)- -(Please read the notes on the back before filling this page) -Order

A 4 2 6 6 Λ ο Α7 * _____B7 V. Description of the invention (3) Method 'includes (i) preparing a mixture capable of forming the material, the mixture including a potassium source (M), a trivalent oxide (X), Tetravalent element halide (γ), water, and a guide agent including a puzzle (selected from 15-crown-5, 18-crown-6, and mixtures thereof) (R), and having a composition in the following range ( Moore ratio): γ〇2 / χ2〇3 15 to 200 η2ο / υο2 5 to 200 οη · / υο2 0 to 3.0 μ / υο2 0 to 3.0 r / yo2 0.02 to 1'0 (ii) Make d / Kunhe The substance is maintained at a temperature of 80 ° C. to 250 ° C. until crystals of the substance are formed; and (iii) the crystalline substance is recovered from step (ii) *. The crystalline MCM-61 substance of the present invention exhibits a single crystalline phase. It can be prepared in pure form with essentially little or no measurable crystalline phase and has an X-ray diffraction pattern in the calcined form, which is synthesized with other known or The heat-treated crystalline material has different patterns: Table (please read the precautions on the back before filling in this page) 〇 Packing. Order 00 rooms d- between the flatness S strong antiphase printed by the Central Standards Bureau of the Ministry of Economic Affairs and Consumer Cooperatives 9 2 4 4 0 6 * ο ···· 34 1 * 8. 6 * 6 · 5 ± Toast's Tutu's 5 3 0 112 0 · 0 · 0 ·

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w W Applicable Standards and Standards for Primary Schools and Middle Schools One Scale Ruler One Iron Paper I Centimeter 7 9 2 42664 0 A7 B7 V. Description of Invention (4 4.85 soil 0.10 4.31 ± 0.12 3.92 soil 0.15 3.79 ± 0.08 3.69 soil 0.08 3.37 soil 0.08 3.26 ± 0.10 3.16 ± 0.06 2.850 ± 0.06 2.806 ± 0.05 2.680 ± 0.05 2.617 ± 0.05 2.491 ± 0.08 2.380 ± 0.06 2.318 ± 0.06 2.276 ± 0.08 2.042 ± 0.05 1.913 ± 0.06 1.895 ± 0.06

WW VS wm WW wm vw WW WW ww WW / ww v \ v (Please read the precautions on the back before filling in this page) The X-ray diffraction data printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs is fixed by the device germanium _ State detector, collected using a copper K-α light-emitting Scintag diffraction system. Diffraction data is recorded in green at a step-scan of 0.05 degrees two-Θ, where Θ is the Bragg angle, and the calculation time for each step is 1 second. The interval between the planes, d's is calculated in Egyptian units (A), and straight -7 This paper size applies to Chinese national standards (CNS > A4 specification (210X297 mm) 42664 〇 Printed by the Central Standards Bureau of the Ministry of Economic Affairs and Consumer Cooperatives Α7 ____B7 V. Description of the invention (5) The relative strength of the line, I / Io is one percent of the strongest straight line strength on the background, and is derived using a suitable path on the side (or the second derivative algorithm). The strength is not targeted at Lorentz And polarization correction. The sign of relative intensity is vs-very strong (80-100)., S = strong (60-80), m = medium (40-60), w = weak (20-40), And vw = very weak (0 · 20). It should be understood that the diffraction data listed for this sample as a single straight line may contain multiple repeated straight lines (which are under certain conditions), such as differences in crystalline changes, which may appear as analysis or Partial analysis of straight lines. Generally 'changes in crystallization include minor changes in unit cell parameters and / or changes in crystalline symmetry' without changing the structure ^ These minor changes (including changes in relative strength) can also be Cation content, structural bonds, properties Differences in the degree of pore filling, heat, and / or hydrothermal history occur as a result. The crystalline material of the present invention has a composition containing a Mohr relationship: X203: (n) Y〇2, where X is a trivalent element such as aluminum Boron, iron, willow, and / or aluminum, preferably aluminum; europium is a tetravalent element such as silicon, tin, and / or germanium, preferably silicon: and η is from 15 to 200, usually from 30 Up to about 90. In a synthetic form, the substance has the following formula on an anhydrous basis and the number of oxide moles per mole of mol: mol: 2 (0.5-5 · 0) M2O: (0.5-3.0 ) R: X203: nY02 where M includes potassium and R is an organic part. The μ and R components are combined with the substance, resulting in the existence of the crystallization process, and can be easily removed by the crystallization method after a more specific description thereafter. The crystalline material is thermally stable and shows obvious __- 8- _ nine scales are applicable to the Chinese National Cricket (CNS) Α4 specification (210 × 297 mm) '(谙 Please read the precautions on the back before filling (This page)

Printed by the Consumers' Cooperative of the Central Government Bureau of the Ministry of Economic Affairs 426640 A7-__________B7 V. Description of the Invention (6) k Absorption iil Force "For the purpose intended, for example, the original potassium cations of synthetic substances can be based on techniques known in the art, Replaced at least in part by ion exchange with other cations. Preferable substituted cations include metal ions, hydrogen ions, rhenium precursors, for example, ammonium ions and mixtures thereof. The best cations are catalytic activities suitable for certain fe conversion reactions. Β These include hydrogen, rare earth metals' And metals of the Periodic Table of the Group IIA, IIIA, IVA, IB, IIIB ', IIIB, IVB and VIII. When used as a catalyst ', the crystalline material of the present invention may be treated to remove some or all of the organic components. This can be easily achieved by heat treatment, one of which is performed at a temperature of at least 3 70 C for at least 1 minute, and generally does not exceed 20 hours. Although sub-atmospheric pressure may be used for the heat treatment, atmospheric pressure may be used for reasons of convenience. Heat treatment can reach 925. ": At the temperature. The heat treatment products, especially their metal, hydrogen and ammonia products, are particularly useful for catalyzing the conversion of certain organic materials such as hydrocarbons. The crystalline material can also be used as a catalyst in close combination with hydrogenation components, such as tungsten, vanadium, molybdenum, baht, nickel, cobalt, chromium, manganese, or precious metals such as platinum or palladium, among which hydrogenation-dehydrogenation is required. This component can be co-crystallized in the composition, allowing the composition to be exchanged for a group IIIA element, such as aluminum, which is in the structure, inserted into it, or physically premixed intimately with it. Such ingredients, such as platinum, can be added to or by treating silicates with a solution containing platinum-containing metal ions. Therefore, suitable platinum compounds for this purpose include aeroplatinic acid, vaporized platinum, and various compounds containing a platinum amine complex. When the crystalline substance of the present invention is used as an absorbent or catalyst in the conversion process of organic compounds, it should be at least partially dehydrated. This can be done in the case of gas such as air-9-this paper size applies Chinese National Standards (CNS) Α4 specifications (2 〖〇 × 297mm) ---- ^-Γ --- α pack-(please first Min, please note on the back, please fill in this page) Order Α7 Β7 V. Description of the invention (in nitrogen, etc., 'heated to 20 at atmospheric pressure, subatmospheric or super atmospheric pressure (TC to 3 70 ° C for 30 minutes to It can be carried out for 48 hours. It can also be dehydrated by placing MCM-61 in the air at near room temperature, but it takes a long time to obtain a sufficient amount of tax water. This crystalline substance can be composed of potassium source (M) cations, trivalent Element X such as an oxide of aluminum and / or boron, tetravalent element europium, such as an oxide of silicon, a directing agent (R) 'and a reaction mixture of water, the composition of the reaction mixture (by the molar ratio of the oxide ) The range is as follows: The use of reactants is preferably / 02 / χ2 〇3 15 to 200 * 30 to 90 η2 〇 / 2〇2 5 to 200 20 to 100 OH. / Υ02 0 to 3.0 * 0.10 to 0.50 m / y〇2 0 To 3.0 0.10 to 2.0 r / yo2 0.02 to 1.0 0.10 to 0.50 The preferred source of 'Y〇2 in this synthesis method mainly includes solid γ〇2, such as Approximately 30 wt% of solid γ〇2. When γ〇2 is silicon oxide, use the consumer cooperation of the Central Standards Bureau of the Ministry of Economic Affairs to print the example (please read the note on the back before filling this page) At least Silicon oxide source of about 30 wt% solid oxide, such as Ultrasil (—precipitation, spray-dried oxygen containing about 90 wt% silicon oxide: containing about one, oxidized, one free h20 and two 4 bound, and particle size Precipitation hydration of about 0.02 microns "〇2) is better for the formation of the above-mentioned mixtures. Therefore, fortunately γ (such as oxidized) source contains at least about 3G wt% solids, such as oxygen And the most -10- paper size specifications (210X297 mm) '--42664 〇 A7 B7 V. Description of the invention () At least about 40 wt% solid Y 〇2, such as silicon oxide. The organic directing agent used is a crown ether selected from the group consisting of 15-crown "5, 18-crown-6 and combinations thereof. These compounds can be represented as follows: O CL ·

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iS-Crnwn'-S lS-Crovm- < The Central Bureau of Standards, Ministry of Economic Affairs, X. Consumer cooperation. The crystals of this crystalline substance can be printed in appropriate reactor tanks, such as polypropylene bottles or Teflon-lined or In a stainless steel autoclave, it is carried out under static or sanding conditions. Crystallization is usually carried out at a temperature between 80 ° C and 250 ° C *, and usually takes 12 hours to 100 days. Subsequently, crystals were separated from the liquid and recovered. It should be understood that the components of the reaction mixture may be provided from more than one source. The reaction mixture may be manufactured batch-wise or continuously. The crystallization scale of the new crystalline substance-and the crystallization time will vary depending on the nature of the reaction mixture used and the crystallization conditions. The synthesis of the new crystal can be achieved by the presence of at least 0.01%, preferably 0 10% and better 1 Percent seed crystals of the crystalline product (based on total weight) assist 0 The crystalline material of the present invention can be used to catalyze a variety of chemical conversion processes that include many existing commercial / industrial issues. Examples of chemical conversion processes that can be effectively catalyzed by the crystalline material of the present invention (which can be catalyzed by itself or in combination with one or more other catalytically active materials containing other catalysts) include those requiring a catalyst with acidic activity, special Examples include: " 11- The paper size is applicable to Chinese National Standard (CNS) A4 ^ TT ^ 7297 mm (please read the precautions on the back before filling this page) Printed A7 B7 V. Description of the invention (9) (1) Toluene disproportionation, reaction conditions include temperature of 200 X: to 760 ° C, pressure of 100 to 6000 kPa (1 to 60 atmospheric pressure), hourly space velocity (WHSV) is 0.1 hr · 1 to 20 hr · 1, and the hydrogen / hydrocarbon mole ratio is from 0 (non-hydrogenated) to about 50, and a disproportionation product is obtained, including p-dimethylbenzyl; (2) an aromatic compound at Trans-alkylation in gas or liquid phase, the reaction conditions include a temperature of 100 ° C to 500 X: 'pressure is 100 to 20000 kPa (1 to 20 atmospheric pressure)' and WHSV is 1 hr · 1 to i〇, 〇 〇〇hr_1; (3) Alkanes react with aromatics to form alkyl aromatics And light gases, the reaction conditions include a temperature of 260 ° C to 375 ° C, a pressure of 100 to 7000 kPa (0 to 1000 psig), a WHSV of 0.5 hr · 1 to 10 hr · 1, and a hydrogen / hydrocarbon mole ratio of 0 (unhydrogenated) to 10; (4) isomerization of the alkane to obtain a branched alkane, the reaction conditions include a temperature of 200. Ό to 315eC 'a pressure of 800 to 7 Ϊ 300 kPa (100 to 1000 psig), WHSV is 0.5 hr * 1 to 10hr · 1, and the hydrogen / hydrocarbon mole ratio is 0.5 to 10; and (5) the aromatic is alkylated with olefin, and the reaction conditions include a temperature of 2000 to 5000 ° C 'pressure is 100 to 3550 kPa (0 to 500 psig), total WHSV is 0.5 hr—1 to 50 hi-1, and hydrogen / hydrocarbon mole ratio is 0 (non-hydrogenated) to 10, and aromatic The molar ratio of the group / olefin is from 1 to 50. The crystalline material of the present invention can also be used as an absorbent or as an absorbent that separates substances from a mixture thereof. For example, it can be obtained from a mixture of vapors or liquid phases different from the adsorption characteristics of MCM-61 absorbent, By contacting the mixture containing the ingredients with the MCM-61 absorbent, selective absorption from the mixture and absorption of at least one component of the mixture onto the absorbent, separation of at least -12- This paper Le / 1 degree applies Chinese national standards (CNS) A4 size (210X297 mm) (Please read the notes on the back before filling out this page.) Printed by the Consumer Cooperatives of the Central Government Bureau of the Ministry of Economic Affairs 4 2664 〇Α7-____— _Β7 ι〇 ---- ------ V. Description of the invention ()-Ingredients, so that at least one absorbing component is selectively separated from other at least one non-absorbing component of the mixture. In the process of selective adsorption, the mixture may include water and at least one hydrocarbon component, and at least one hydrocarbon component of the mixture is preferentially and selectively adsorbed on the MCM-61 absorbent than the water in the mixture. The adsorption process may include a mixture of 'at least two hydrocarbon components, at least one of which is preferentially and selectively adsorbed on the MCM-61 absorbent over at least one other hydrocarbon component of the Zhan compound. The adsorptive separation of the present invention may include at least one smoke component of a mixture ' mixture comprising an alcohol and at least one hydrocarbon component is preferentially absorbed onto the MCM-61 absorbent over the alcohol in the mixture. When the MCM-61 of the present invention is used as a catalyst, other substances need to be added to resist the temperature and other conditions used in the organic matter conversion process. Such materials include activated and unactivated materials, and fluorinated or naturally occurring zeolites, as well as inorganic materials such as limestone, silicon oxide, and / or metal oxides such as aluminum halide. The latter can be in the form of naturally occurring or gel-struck products, or gels containing a mixture of oxidized ash metal oxides. The use of substances in combination with new crystals, that is, to combine them with the crystals of the present invention during the synthesis of new crystals, is activated to protect the conversion and / or selectivity of the catalyst in the specific organic substance conversion process. Inactive materials are suitable as diluents to control the amount of conversion in a customized process. Therefore, products can be produced economically and sequentially without the use of other equipment to control the reaction rate. These materials can be added to naturally occurring graystone , Such as t * soil and kaolin, to improve the crushing frontier of the catalyst under commercial conditions. The substance, ie, limestone, oxide, etc., can be used as a binding agent for the catalyst. Because in commercial applications, it is necessary to prevent the catalyst from breaking into a powdery substance, so -13- the standard of this paper is applicable to the Chinese National Standard (CNS) VIII (210X297 mm) ---- ^ ----- -------- ΐτ ------ (Please read the precautions on the back 苒 Fill this page first) r- 4 266 4 0 A 7-B7 V. Description of the invention (11) Need to provide good crushing Strength catalysts. These limestones and / or oxide binders are generally only used to improve the crushing strength of catalysts. Naturally produced limestones that can be compounded with new crystals include the montmorillonite and kaolin groups, which include · Hydratite, and kaolins generally known as Dixie, McNamee, Georgia, and Florida limestone, or the main mineral constituents are polykaolin, kaolin, geocline, pearl clay, or snail clay. Such limestone can be based on the original Minerals are used in the main state, or they are first calcined, acid treated or chemically modified. The binder used for compounding with this crystal also contains inorganic oxides, such as silicon oxide, zirconium halide, titanium halide, magnesium oxide, Beryllium oxide, alumina and mixtures thereof. In addition to the foregoing, new crystals can interact with plutonium. Porous matrix material composites such as silica-alumina, silica-magnesia, silica-zirconia, silica-hafnium oxide, silica-beryllium oxide, oxygen beta silica-titanium oxide and ternary compositions such as Silica-alumina-rhenium oxide, silica-alumina-oxidized junction, silica-alumina-magnesium oxide and silica-magnesia and hafnium oxide. The relative proportions of finely crystalline substances and organic oxide substrates vary widely and crystallize The content range is from 1 to 90 weight percent of the compound, and most often from 2 to 80 weight percent. Printed by the Consumers Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page). It will be described in more detail with reference to the examples and the accompanying drawings, which show the X-ray diffraction pattern of the calcined product of Example 3. In the examples, the adsorption data for comparing the adsorption capacities of cyclohexane and water are listed, which are the following measurements The equilibrium absorption of plutonium. The weighed sample of the calcined absorbent is contacted with the pure absorbent required in the adsorption chamber, evacuated to less than 1 mm, and is in contact with cyclohexane 5.3 kPa (40 Torr). Paper size applicable to China Standard (CNS) A4 size UlO'X297 mm) Five employees of the Central Bureau of Standards of the Ministry of Economic Affairs of the People's Republic of China printed A7 B7, invention description (12) ~ steam or l'6kPa (12 Torr) water contact, the pressure at room temperature Below the gas-liquid equilibrium pressure of each absorbent. During the adsorption period (not more than about 8 hours), the pressure is maintained by adding absorber vapor controlled by a pressure regulator (in the range of about 0.5 milligrams). When When new crystals of the absorbent are absorbed, the pressure drop causes the pressure regulator to open, allowing more absorbent vapor to enter the chamber to maintain the above-mentioned control pressure. When the pressure change is insufficient to make the pressure regulator move, the adsorption is completed . Calculate the increase in weight as the adsorption capacity of the milligram sample per gram of calcined absorbent. When measuring α 値, it should be noted that α 约 is a rough indication of the catalytic cleavage activity of the catalyst compared with the standard catalyst, and it provides a relative rate constant (n-hexane conversion per unit time per volume of catalyst, rate ). It is based on silicon oxide _ oxidation chain cleavage catalyst as β as the main i (rate constant 〇16 se (rl). The general test is described in US Patent No. \ 354, 〇78; J〇urnal 〇f

Catalysis 4, 527 ¢ 1965); 6, 278 (1966); and 61, 395 (1980). The experimental conditions of the test used here include a constant temperature of 538 ° C and a variable flow rate, as detailed in Journal of Catalysis. 61,395. Examples 1-1 1 An experiment was performed to synthesize the crystalline MCM-61 substance of the present invention. In these experiments, 'A12 (S04) 3. 18Η20 and KΗ or NaOH particles were dissolved in deionized water. 15-crown-5 (15-C-5), or 18-crown-6 (18-C-6) crown acid was dissolved in the resulting solution and the colloidal silica sol (30% of 5% 〖〇2） Mixed in the solution, and the mixture was stirred for 2 minutes to make a homogeneous' fluid hydrogel whose respective compositions are listed in Table η, in which Wei is a crown ether directing agent. The molar ratio of each reaction mixture composition is 2 〇 / Si02 Moore ratio is maintained at 40/1, each mixed -15- This paper size applies Chinese National Standard (CNS) A4 specification (nOXW? Mm) ----- 〆 --- J pack-'/ V (please read the note ^^ on the back before filling in this page) Order 42664 〇 Α7 Β7 13 V. Description of the invention (the molar ratio of 0H- / Si02 of the compound is 0, 30. The hydrogel of each experiment was transferred to a 300-ml stainless steel autoclave equipped with a stirrer. The autoclave was capped and sealed; and an inert gas of 2860 kPa (400 psig) was introduced into the high pressure dad. Immediately start stirring and Heating. The crystallization was performed under stirring for 7 days under i 70. The crystal product was recovered, filtered, washed with deionized water, and dried on an oven in an air stream under an infrared lamp. The dried crystalline powder product For X-ray diffraction and chemical analysis. 'Table. II Example R Mixture composition Γ 苴 二十, Sj〇2 / K + / Na +' T ~~~ 2 'Ai? O ^ Si〇? &Quot; sinr ——. R / Si〇 ?, product 1 15-C-5 30 0.57 · 0.40 MCM-61 2 18-C-6 30 --- 0.33 0.32 Mordenite 3 18-C-6 60 0.43 0.30 MCM- 61 4 18-C ~ 6 60 0.43 ___ 0.32 MCM-61 5 18-C-6 60 0.43 ___ 0.50 MCM-61 6 7 18-C-6 15-C-5 60 60 0.43 0.43 ___ 0.30 0.40 MCM-61 MCM-61 s 18-0-6 60 0.33 0.35 Mordenite _L 9 18-C-6 90 — 0.32 0.35 Quartz ZSM-5 10 11 I8, C-6 18-C-6 180 〇〇 + 0.34 0.30 Sale__ 0.35 0.35 Decade-quartz-cristobalite λτ -Quartz-16 This paper size applies to Chinese national standards (CNS > A4 size (2 丨 0 · 〆297mm) ---- r--r --- 0 # ^-(Please read the note on the back first Please fill in this page for further information.) · Printed by the Consumers 'Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 i' Description of the Invention (14) The chain source was not added to the reaction mixture a For the calcination of Example 3 (50% in air) X-ray diffraction data of the product for 15 hours) are listed in Table 111. The x-ray diffraction pattern of the calcined product of Example 3 is shown in FIG. 1. The d-spacing between planes of the printed work table III by the Central Bureau of Standards of the Ministry of Economic Affairs (Α, 1 ^ 0 11.70 50 8.03 25 6.92 * 1 3 6.35 8 5.85 '< 1 5.39 14 5.11 6 4.84 23 4.30 100 3 '92 25 3.79 10 3.70 26 3.65 5 3.37 7 3.34 27 * 3.25 16 -17- This paper size is applicable to China National Shaker (CMS) Α4 specification (210X297 mm > --------- Q Pack- -(Please read the precautions on the back before filling out this page)-Order 4 2664 Ο Α7 -Β7 V. Description of the invention (15) 3.16 11 2.98 1 2.945 1 2.898 2 2.845 12 2.805 6 2.684 6 2.652 1 2.616 · 4 2.576 2 2.550 1 2.484 9 2.458 1 * 2.376 1 2.315 2 2.281 2 1.193 2 1.900 1 (Please read the precautions on the back before filling out this page) Order printed by the Central Ministry of Economic Affairs, Central Bureau of Work, Consumer Cooperatives * Quartz Impurity Example 1, The chemical analysis results of synthetic products such as 3, 4 '5, 6, and 7 are listed in Table IV. -18- This paper size applies to China National Standard (CNS) Α4 specification (210 X 297 mm) 4 2 6 6 4 〇A7-B7 V. Description of the invention (16 4_ IV Example Mohr H / Molar C per Molar Al 2 〇3 Ear R: K ^ O * Si〇2 Composition (1) Al / K + 100 Td 100 Td R / 100 Td 1 2.70 0.72 1.31 24.2 7.5 10.0 2.7 3 2.39 0.83 0.73 25.1 7.4 5.4 3.1 4 2.63 2.01 1.97 39.8 4.8 9.4 4.8 5 2.59 1.23 1.61 42.6 4.5 7.2 2.7 6 2.72 1.53 1.95 49.6 3.9 7.6 3.0 7 2.44 2.28 4.34 57.8 '~. 3.3 14.0 3.8 (1) Calculated based on 100 (Si02 + AI02) tetrahedron (please read the note on the back first) Please fill in this page again) For the content of the bell in the product Si 2 / A. 3 Mobbi range display is not clearly corrected 'but it is shown in the MCM-61 framework on average about 100 per tetrahedron 3 coronary acids, showing the activity of the coronary chain. Examples 1 2-1 3 The MCM-61 products of Examples 4 and 5 were weighed into a quartz boat-shaped vessel, placed in a Heviduty® tube furnace, and sealed with nitrogen flowing through the tube. The furnace was heated from room temperature at 2 X: / min to 538 ° C. When the furnace reached the maximum temperature, the flowing gas was released into the air, and the zeolite was calcined for 15 hours before stopping. The air calcined samples were exchanged with 1M NH4N 0 3 ammonium for 6 hours at 80 ° C. After the ammonium exchange, the stagnant stone was filtered, the strip was washed with deionized water, and dried in an air stream on a filter furnace under an infrared heating lamp. Repeat the calcination step of the ammonium exchange material in the tube furnace in the same way as above. -19- This paper size is applicable to China National Standard (CNS) A4 specification UlOX29 :! mm. Ordered by the Shell Standard Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. Loading 4 4 0 Α7 Β7 — 17 V. Description of the invention () But at this time, the sample was maintained at 538 aC for 8 hours to make it into HMCM-61. The products of Examples 12 and 13 are the HMCM-61 material from the products of Examples 4 and 5, respectively. Example I 4 The sample of the HMCM-6I product of Example 13 was tested for acid catalytic activity in the alpha test, and its or was found to be 10. ^ 1. —N---ί-! Ί-I. II--* 1τ c-^ < Please read the notes on the back before filling out this page) Packing • 20- This paper size applies to China National Standard (CNS) Α4 size (2! 0 × 297 mm)

Claims (1)

426640 No. 86Ι00〗 7δ Patent Application Amendment to Patent Scope (July 88) r C8 / D8 Patent Scope 'I. 1. I_ _____ A synthetic porous crystalline substance' which has a composition including the following Moire relationship: χ2 〇3: (η) Υ〇2 > wherein η is 15 to 200 'X. It is selected from the group consisting of iron, fine, copper, and combinations thereof; and the system is selected from silicon, tin, germanium, and combinations thereof, It is characterized in that it uses an X-ray diffraction pattern 4__L with a value as listed in Table I. The d-interval (A) between the soil bearing is 100 j. For strong grinding, ϊ / ΐη γ ms vw-w Ministry of Economic Affairs Central Standards Bureau—Industrial and Consumer Cooperatives Printing 11.69 soil 0.50 8.02 soil 0.15 6.94 soil 0.13 6.34 soil 0.20 5.40 soil 0.12 5.11 soil 0.10 4.85 soil 0.10 4,31 soil 0.12 3.92 soil 0.15 3.79 soil 0.08 3.69 soil 0.08 3.37 soil 0.08 3.26 soil 0.10 3.16 soil 0.06 2.850 soil 0.06 2.806 person 0.05 vs -w _w The paper size is Zhonggu Guohong; ^ sitting ^ milk) person 4 specifications 1 ^ 210 father 297 male) (Please read the precautions on the back before filling in this page) A2664 0 A8 B8 C8 D8, patent application range 2.680 soil 0.05 2.617 soil 0.05 2.491 soil 0.08 2.380 soil 0.06 2.318 soil 0.06 2.276 soil 0.08 2.042 soil 0.05 1.913 soil 0.06 1.895 soil 0.06 --------- Q-1 ( Please read the notes on the back before filling in this page) Printed by the Ministry of Economic Affairs and the Central Bureau of Associate Bureau Consumer Consumption Cooperative 2'Crystalline substance according to Item 丨 of the patent application park, its composition is based on an anhydrous basis and Y per mole. The oxide molar number of 2 is based on the following formula: (° -5-5.0) M2O: (0.5-3.0) R: X2O3: nY02 where M includes potassium and the ruler is an organic part. 3. The crystalline substance according to item 2 of the scope of the patent application, wherein r is selected from crown ethers containing 15-crown-5 '18-crown-6, and mixtures thereof. 4. A catalyst composition 'comprising 1 to 90% by weight of a crystalline substance and a matrix according to item 1 of the patent application park. 5. The composition according to item 4 of Shenjing's patent scope, wherein the substrate comprises oxidized silicon oxide, zirconia, titanium oxide, magnesium oxide, beryllium oxide, or a combination thereof. 6. —A method for synthesizing a porous crystalline substance, which exhibits a characteristic X-ray diffraction pattern containing the maximum value of d-interval as shown in Table I-2-This paper scale applies Chinese National Standard (CNS) A4 Specification (210X297 mm)-Order 'Λ266Λ Ο Α8 Β8 C8 D8 Patent Application Fanyuan Table Ministry of Economic Affairs Central Standards Bureau Staff Consumer Cooperative Printed d-space between printed planes (A) 100 11.69 soil 0.50 8.02 soil 0.15 6.94 soil 0.13 6.34 ± 0.20 5.40 ± 0.12 5.11 0.10 4.85 ± 0.10 4.31 ± 0.12 3.92 ± 0.15 3.79 ± 0.08 3.69 ± 0.08 3.37 ± 0.08 3.26 ± 0.10 3.16 ± 0.06 2.850 ± 0.06 2.806 ± 0.05 2.680 ± 0.05 2.617 ± 0.05 2.491 ± 0.08 2.380 0.06 2.318 soil 0.06 2.276 soil 0.08 relative strength, I / Io X m's vw-w / -w / -w ww vs wm ww wm vw ww " W (Please read the precautions on the back before filling this page) -3- This paper size is in accordance with Chinese National Standard (CNS) A4 specification (210X297 mm) A8 A? SSAQ m 6. Application scope of patent 2.042 soil 0.05 1.913 ± 0.06 1.895 + 0.06 This method includes (i) preparing the substance which can be formed A mixture comprising bell source (M) 'oxide of trivalent element (X), oxide of tetravalent element (γ)' water and comprising a member selected from 15-crown-5 '18-crown-6 and The directing agent (R) of the crown ether of the mixture is in the following range in terms of the molar ratio: Υ〇2 / χ2〇3 15 to 2〇〇2〇 / Υ02 5 to 200 OR- / Y〇2 0 To 3.0 M / Υ0 0 to 3.0 K / Υ〇2 0.02 to 1.0 (ii) maintaining the mixture at a temperature of 80 ° C to 250 eC until crystals of the substance are formed; and (iii) from Step (ii) recovers the crystalline material. Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs-^^^ 1 ^^^ 1 ^^^ 1 ^^^ 1 I ^^^ 1.--Ί— I Hi —I— i) ^-1- (Please read the notes on the reverse side before filling out this page) 7. —A method for converting a raw material including organic compounds into a conversion product, which includes crystallization of the raw material with Catalyst contact with a substance or an activated form of a composition according to item 4 or 5 of the scope of patent application. S. —A method for separating at least one component from a mixture of components in a gas or liquid phase having different adsorption characteristics for an absorbent comprising a crystalline substance according to any of claims 1 to 3 This method _ _ 4 _ This paper size adopts Chinese National Standard (CNS) 8 4 (210X297 gong) 0 8888 ABCD 6. The scope of patent application includes contacting the mixture containing the ingredients with the absorbent to Selective absorption of the mixture 'and at least one component of the mixture is absorbed on the absorbent, thereby selectively separating at least one absorbing component from the remaining at least one unabsorbed component of the mixture. * (Please read the notes on the back before filling out this page) Printed by the Employees' Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs This paper size is in accordance with China National Standards (CNS) Α4 grid (210 × 297 mm)