Method for manufacturing molecular sieves

Abstract

A process for preparing a molecular sieve for use as a catalyst is provided, which comprises preparing a synthesis mixture for the molecular sieve containing a morphology modifier that may be selected from a cationic surfactant having a single quaternary ammonium group containing at least one hydrocarbyl group having at least 12 carbon atoms, a nonionic surfactant, an anionic surfactant, a sugar, and combinations thereof.

Description

[Technical Field]

[0001] This invention relates to a novel method for producing molecular sieve crystals, molecular sieves produced by this method, and their use as adsorbents and / or hydrocarbon conversion catalysts. [Background technology]

[0002] Molecular sieve materials, both natural and synthetic, have been demonstrated to be useful as adsorbents and to possess catalytic properties for various types of hydrocarbon conversion reactions. Certain molecular sieves are regular, porous crystalline materials with a distinct crystalline structure determined by X-ray diffraction (XRD). Certain molecular sieves, such as MCM-41, are regular and produce a specific, definable X-ray diffraction pattern, but are not strictly crystalline. Molecular sieve materials contain numerous vacancies that can be interconnected by numerous channels or pores. These vacancies and pores are uniform in size within certain molecular sieve materials. Because the dimensions of these pores allow for the adsorption of molecules of a certain size but prevent the adsorption of larger molecules, these materials are known as "molecular sieves" and are used in various industrial processes.

[0003] Such molecular sieves, both natural and synthetic, comprise crystalline silicates containing a wide variety of positive ions. These silicates can be described as three-dimensional skeletons of SiO4 and oxides of Group 13 elements of the periodic table (e.g., AlO4). This tetrahedron typically shares corners with oxygen atoms, and the valence of the tetrahedron containing a Group 13 element (e.g., aluminum, gallium, or boron) is balanced by the inclusion of cations, such as protons, alkali metals, or alkaline earth metal cations.

[0004] Molecular sieves for which catalytic applications have been found include both naturally occurring and synthetic crystalline molecular sieves. Examples of these molecular sieves include large-pore zeolites, medium-pore zeolites, and small-pore zeolites. These zeolites and their isotypes are described in Non-Patent Literature 1, incorporated herein by reference, and in the online database of zeolite structures, http: / / www.iza-structure.org / databases / . Large-pore zeolites generally have a pore size of at least about 6.5 to 7 angstroms and include LTL, MAZ, FAU, OFF, *BEA, and MOR skeleton zeolites (IUPAC Commission of Zeolite Nomenclature). Examples of large-pore zeolites include mazzite, offretite, zeolite L, zeolite Y, zeolite X, omega, and beta. Medium-pore size zeolites generally have a pore size of approximately 4.5 angstroms to less than approximately 7 angstroms and include, for example, MFI, MEL, EUO, MTT, MFS, AEL, AFO, HEU, FER, MWW, and TON skeleton zeolites (IUPAC Commission of Zeolite Nomenclature). Examples of medium-pore size zeolites include ZSM-5, ZSM-11, ZSM-22, MCM-22, SilicaLite 1, and SilicaLite 2. Small-pore size zeolites have a pore size of approximately 3 angstroms to less than approximately 5.0 angstroms and include, for example, CHA, ERI, KFI, LEV, SOD, and LTA skeleton zeolites (IUPAC Commission of Zeolite Nomenclature). Examples of small-pore zeolites include ZK-4, SAPO-34, SAPO-35, ZK-14, SAPO-42, ZK-21, ZK-22, ZK-5, ZK-20, Zeolite A, Chabazite, Zeolite T, and ALPO-17. [Prior art documents] [Non-patent literature]

[0005] [Non-Patent Document 1] "Atlas of Zeolite Framework Types", edited by Ch.Baerlocher, LBMcCusker, DHOlson, Elsevier, Sixth Revised Edition, 2007 [Overview of the Initiative] [Problems that the invention aims to solve]

[0006] Many molecular sieves, particularly zeolites, have been commercially established as adsorbents and catalysts, but there is a need for improved molecular sieves, for example, as catalysts with improved activity and / or selectivity. One aspect that has recently attracted considerable attention is the crystal size of molecular sieves. All other things being equal, molecular sieves with smaller crystal sizes generally have a larger external surface area, which can lead to increased catalytic activity by increasing the adsorption rate onto the surface of the molecular sieve crystal and / or decreasing the length of the diffusion pathway into the internal pores of the crystal. By reducing the crystal size of molecular sieve catalysts, reactions that mainly occur on the external surface of zeolites, such as reactions involving larger reactant molecules whose diffusion into the internal pores is slow due to their size, can be promoted. [Means for solving the problem]

[0007] The present invention relates to a process for preparing molecular sieve crystals, comprising the following steps: The steps include: combining a source of at least a tetravalent element X, a morphological modifier L, and water to form a synthetic mixture; The process involves heating the synthetic mixture under crystallization conditions for approximately 1 hour to 100 days to form molecular sieve crystals; The steps include recovering the molecular sieve crystals from the synthetic mixture and The morphological modifier L is selected from the group consisting of cationic surfactants, nonionic surfactants, anionic surfactants, sugars, and combinations thereof, having a single quaternary ammonium group containing at least one C12 or more hydrocarbyl group, and is present in the synthetic mixture before crystal nucleation or crystallization begins; The present invention provides a preparation process in which, if the molecular sieve requires a structure-directing agent Q, the morphology modifier L is distinct from and present in addition to the structure-directing agent Q; the molar ratio L:X in the synthetic mixture is in the range of 0.0001 to 0.03; and the synthetic mixture is a liquid or a mixture of solid and liquid, with the liquid being substantially single-phase.

[0008] Optionally, the synthetic mixture may also include a source of hydroxide ions. Optionally, the synthetic mixture may also include a structure-directing agent Q. Optionally, the synthetic mixture may also include a source of trivalent element Y. Optionally, the synthetic mixture may also include a source of pentavalent element Z. Optionally, the synthetic mixture may also include halide ions W. - This also includes the source of the alkali metal ions M. Optionally, the synthetic mixture contains alkali metal ions M. + and / or alkaline earth metal cation M 2+ This also includes the source of the substance. Optionally, the synthetic mixture may also include one or more other components.

[0009] The expression "the liquid is substantially single-phase" should be understood to mean that the liquid phase contains less than 5% by weight of a water-insoluble liquid component. In particular, the liquid phase is not an emulsion or microemulsion.

[0010] The inventors have found that by synthesizing molecular sieves in the presence of a morphological modifier L, it is possible to influence crystal growth so that the molecular sieve crystals have a modified crystal size and / or modified acidity compared to crystals of the same molecular sieve prepared in the absence of the morphological modifier L. This makes it possible to produce molecular sieve crystals with novel and desirable properties. Molecular sieve crystals produced by the process of the present invention may be smaller than crystals of the same molecular sieve prepared by the same process but in the absence of the morphological modifier L. While not wishing to be bound by theory, the present invention considers that the presence of a morphological modifier L can alter the distribution of trivalent elements such as Al in the crystal, and / or alter the way the crystal terminates so that its approach to trivalent elements such as Al is enhanced. Molecular sieve crystals produced by the process of the present invention may have an increased surface area, particularly the external surface area, compared to crystals of the same molecular sieve prepared by the same process but in the absence of the morphological modifier L. Molecular sieve crystals produced by the process of the present invention may have a higher external surface acidity, measured, for example, by colidine adsorption, compared to crystals of the same molecular sieve prepared by the same process but in the absence of the morphological modifier L. The reduced crystal size and / or increased external surface area and / or increased external acidity can lead to increased activity and / or selectivity of the molecular sieve when used, for example, as a component in a catalyst in a hydrocarbon conversion reaction.

[0011] This process is generally applicable to molecular sieves and is not limited to any particular molecular sieve or subgroup of molecular sieves. As used herein, the term “molecular sieve” should be understood to include materials such as MCM-41 that have a regular and definable X-ray diffraction pattern but are not strictly crystalline. Preferably, the molecular sieve has a crystalline framework structure.

[0012] The present invention also provides molecular sieves prepared by the process of the present invention in their as-manufactured form. Furthermore, the present invention provides molecular sieves prepared by the process of the present invention in their calcined form.

[0013] Furthermore, the present invention provides a catalyst comprising the molecular sieve of the present invention.

[0014] Furthermore, the present invention provides a hydrocarbon conversion process comprising the step of contacting a hydrocarbon raw material with the catalyst of the present invention. [Modes for carrying out the invention]

[0015] The molecular sieve manufacturing process according to the present invention involves preparing a synthetic mixture according to the prior art, except that the synthetic mixture also contains a morphology modifier L. While we do not wish to be bound by any particular theory, it is conceivable that the morphology modifier L may bond to or otherwise interact with the crystallite growth surface in the synthetic mixture, thereby affecting the morphology, including the size, aspect ratio, and aggregation / aggregation of the final product crystals. Depending on the properties of the morphology modifier L and the concentration used, the product crystals may be smaller or larger than those obtained in other ways using the same synthetic mixture without the morphology modifier L under the same conditions.

[0016] synthetic mixture As described above, the synthetic mixture can be prepared according to conventional methods. The morphological modifier L may be included in the synthetic mixture at any time before crystal nucleation or crystallization begins. Optionally, the morphological modifier L is combined with other components of the synthetic mixture before the source of the tetravalent element X is added. For example, to form the mixture, water, a source of hydroxide ions (if present), a structure directing agent (if present), a source of the trivalent element Y (if present), a seed (if present), and any other component may be combined in any order, and then the source of the tetravalent element is combined with the mixture.

[0017] Optionally, molecular sieves have a skeleton containing one or more elements selected from the group consisting of Si, Al, P, As, Ti, Ge, Sn, Fe, B, Ga, Be, and Zn, and mixtures thereof. The tetravalent element X is optionally selected from the group consisting of Si, Ge, Sn, and Ti, and mixtures thereof. Preferably, the tetravalent element X is Si. When X=Si, suitable sources of silicon (Si) that can be used to prepare the synthetic mixture include silica; colloidal suspensions of silica, e.g., Ludox®; precipitated silica; alkali metal silicates such as potassium silicate and sodium silicate; tetraalkyl orthosilicates; and fumed silica such as Aerosil and Cabosil.

[0018] The synthetic mixture also contains a source of hydroxide ions, for example, the synthetic mixture may contain alkali metal hydroxides such as sodium hydroxide or potassium hydroxide. The hydroxide can also exist as anion of a charged (organic) structure directing agent or morphology modifier, which may be present by the use of sodium aluminate or potassium aluminate as a source of Y, or by the use of sodium silicate or potassium silicate as a source of X. The sodium or potassium salts of aluminic acid and silicate are alkali metal M + It can also be used as a source of supply.

[0019] Optionally, the trivalent element Y is selected from the group consisting of Al, B, Fe, and Ga, and mixtures thereof. Optionally, Y is selected from B, Ga, or Al, or mixtures thereof. Preferably, the trivalent element Y is Al. Suitable sources of the trivalent element Y that can be used to prepare the synthetic mixture depend on the selected element Y (e.g., boron, aluminum, iron, and gallium). In embodiments where Y is boron, sources of boron include boric acid, borax, and potassium tetraborate. Optionally, the trivalent element Y is aluminum, and sources of aluminum include aluminum sulfate, aluminum nitrate, aluminum hydroxide, hydrated alumina, e.g., boehmite, gibbsite, and pseudoboehmite, and mixtures thereof. Other sources of aluminum include, but are not limited to, other water-soluble aluminum salts, alkali metal aluminates in solid or liquid form, aluminum alkoxides, e.g., aluminum isopropoxide, or aluminum metal, e.g., aluminum in the form of chips or powder.

[0020] In addition to the aforementioned sources of Si and Al, sources containing both Si and Al elements may also be used as sources of Si and Al. Examples of suitable sources containing Si and Al elements include amorphous silica-alumina gel or dried silica-alumina powder, silica-alumina, clay, e.g., kaolin, meta-kaolin and zeolites, especially aluminosilicates, e.g., synthetic hojasite and ultrastable hojasite, e.g., USY, beta, or other large-pore to medium-pore zeolites. Optionally, the pentavalent element Z (if present) is selected from the group consisting of P and As and mixtures thereof. Preferably, Z is P if present. Suitable sources of phosphorus include one or more sources selected from the group consisting of phosphoric acid; organic phosphate esters such as triethyl phosphate and tetraethylammonium phosphate; aluminophosphates; phosphates such as alkali metal phosphates, dihydrogen phosphate, hydrogen phosphate and pyrophosphate, and mixtures thereof.

[0021] Optionally, halide ion W - when present, is selected from the group consisting of chloride, bromide, fluoride and mixtures thereof. The source of halide ions can be any compound capable of releasing halide ions in the molecular sieve synthesis mixture. Non-limiting examples of sources of halide ions include salts containing one or more halide ions, for example, preferably metal halides where the metal is sodium, potassium, calcium, magnesium, strontium or barium. Suitable sources of fluoride ions (F-) include HF; ammonium fluoride or tetraalkylammonium fluoride, for example, tetramethylammonium fluoride or tetraethylammonium fluoride; fluoride-containing salts, such as NaF and KF; fluoride compounds having elements X, Y such as AlF3 and SiF6 salts; and / or compounds in which fluoride ions are present as counterions of the cationic structure directing agent (Q). When the synthesis mixture does not contain a source of hydroxide ions, the synthesis mixture preferably contains a source of fluoride ions which can also act as a mineralizing agent. A convenient source of halide ions is HF.

[0022] Optionally, the synthesis mixture also contains a source of alkali metal cation M + and / or alkaline earth metal cation M 2+ . When present, the alkali metal cation M + is preferably selected from the group consisting of Li + , Na + , K + , Rb + and Cs + and mixtures thereof. Suitable sources of Na + can include sodium salts such as NaCl, NaBr, NaF or NaNO3; sodium hydroxide, sodium aluminate and mixtures thereof. Suitable sources of K + include potassium hydroxide, potassium halides such as KCl, KF or NaBr, potassium nitrate and mixtures thereof. When present, the alkaline earth metal cation is preferably Mg2+ Ca 2+ Sr 2+ Ba 2+ and mixtures thereof are selected.

[0023] A structure-directing agent (Q) is a compound known to influence the crystallization of the molecular sieve skeleton to promote the formation of a particular, desirable molecular sieve. For example, tetrapropylammonium hydroxide or bromide is often used to produce ZSM-5. In contrast, the role of a morphology modifier (L), as described above, is to influence crystallization in such a way as to change the crystal size, external surface area, and / or external acidity of the molecular sieve, rather than affecting the identity of the molecular sieve. If the molecular sieve requires the use of a structure-directing agent Q, the synthetic mixture will also contain an effective concentration of the structure-directing agent. In that case, the morphology modifier L will be present separately from and in addition to the structure-directing agent Q. The properties of the structure-directing agent Q will depend on the desired skeleton type. Many such structure-directing agents are known to those skilled in the art. The structure-directing agent Q may exist in any suitable form, for example, as a halide such as a chloride or bromide, or as a hydroxide, or as a nitrate. For example, the structure-directing agent Q is generally an organic structure-directing agent, such as an amine, such as propylamine, pyrrolidine, or pyridine, or a nitrogen-containing cation, such as a quaternary ammonium cation. Optionally, the ammonium cation does not contain any alkyl chain having more than 10 carbon atoms. For example, if it is desirable to produce a zeolite with a skeletal CHA structure, the structure-directing agent Q may optionally be N,N,N-trimethyl-1-adamantammonium hydroxide (TMAdA).

[0024] The synthetic mixture can have any composition suitable for preparing the desired molecular sieve skeleton. The following ranges are given as examples of desirable and preferred ranges for each pair of components in the synthetic mixture. Conveniently, the molar ratio of XO2:Y2O3 in the synthetic mixture may be in the range of 2 to infinity (i.e., no Y), particularly 5 to 500, preferably 5 to 200. Optionally, in the synthetic mixture, the molar ratio of the structure directing agent Q:(XO2+Y2O3+Z2O5) is in the range of 0.01 to 1.0, preferably 0.02 to 0.9. Optionally, in the synthetic mixture, the molar ratio of H2O:(XO2+Y2O3+Z2O5) is in the range of 5 to 100. Optionally, in the synthetic mixture, M + The molar ratio of (XO2 + Y2O3 + Z2O5) is in the range of 0 to 1.2, preferably 0 to 1.0. Optionally, in the synthetic mixture, OH - The molar ratio of (XO2 + Y2O3 + Z2O5) is in the range of 0.05 to 1.1, preferably 0.10 to 1.0. Optionally, halides are added to the synthetic mixture. - The molar ratio of (XO2 + Y2O3 + Z2O5) is in the range of 0 to 1, preferably 0 to 0.5. The reaction mixture may have a composition expressed in molar ratios, for example, as shown in the table below.

[0025] [Table 1]

[0026] Water may be added in any amount appropriate for dissolving the components and preparing the desired molecular sieves. The synthetic mixture includes an aqueous liquid phase and may also include several insoluble solid components and crystallized molecular sieves. The liquid present in the synthetic mixture is substantially single-phase, typically aqueous, gel, slurry, paste, or wet powder. The liquid present in the synthetic mixture typically contains less than 5% by weight, optionally less than 2% by weight, and optionally 1% by weight of water-insoluble liquid components. In particular, the liquid present in the synthetic mixture is not an emulsion or microemulsion. The synthesis may be carried out with or without the addition of nucleating species. If nucleating species are added to the synthetic mixture, the species are appropriately present in an amount of about 0.01 to 10.0% by weight, based on the synthetic mixture, for example, about 0.01 to 2.0% by weight of the synthetic mixture. The species can be any suitable zeolite, for example, a zeolite having the same or different skeleton as the resulting zeolite.

[0027] Morphological denaturing agent L The morphological modifier L is selected from the group consisting of cationic surfactants, nonionic surfactants, anionic surfactants, sugars, and combinations thereof, having a single quaternary ammonium group containing at least one hydrocarbyl, preferably alkyl, or a group having at least 12 carbon atoms, and is added to the other components of the synthetic mixture before crystal nucleation or crystallization begins. A mixture of two or more morphological modifiers L may also be used, and such a process is within the scope of the present invention.

[0028] Morphological denaturants can be sugars. Sugars can be monosaccharides or disaccharides. Suitable monosaccharides include glucose, fructose, and galactose, particularly fructose. Suitable disaccharides include saccharose, maltose, and lactose. Sugars can be pentoses, or hexoses.

[0029] The morphology modifier L may be a cationic surfactant having a single quaternary ammonium group comprising at least one hydrocarbil having at least 12 carbon atoms. The at least one hydrocarbil having at least 12 carbon atoms is covalently bonded to the nitrogen atom of the quaternary ammonium and may be branched or linear, preferably linear. The at least one hydrocarbil may optionally have at least 14 carbon atoms, optionally at least 16 carbon atoms, or optionally at least 18 carbon atoms. Optionally, the at least one hydrocarbil may have 30 or fewer carbon atoms. The hydrocarbil may contain an aromatic group such as phenyl. The hydrocarbil may be saturated or unsaturated, preferably saturated. Each cationic surfactant may contain two hydrocarbils having at least 12 carbon atoms bonded to the nitrogen atom of the quaternary ammonium group. The other substituents on the nitrogen atom of the quaternary ammonium group may optionally be alkyls having 1 to 8 carbon atoms, optionally 1 to 4 carbon atoms, such as alkyls having a methyl group. Each hydrocarbyl may contain one or more heteroatoms optionally selected from oxygen, sulfur, nitrogen, and halides.

[0030] The morphological modifier L may be a cationic surfactant having a single quaternary ammonium group comprising at least one alkyl group having at least 12 carbon atoms. The at least one alkyl group having at least 12 carbon atoms is covalently bonded to the nitrogen atom of the quaternary ammonium and may be branched or linear, preferably linear. The at least one alkyl group may optionally have at least 14 carbon atoms, at least 16 carbon atoms, or at least 18 carbon atoms. Optionally, the at least one alkyl group may have 30 or fewer carbon atoms. The alkyl group may be saturated or unsaturated, preferably saturated. Each cationic surfactant may comprise two alkyl groups, each having at least 12 carbon atoms bonded to the nitrogen atom of the quaternary ammonium group. The other substituents on the nitrogen atom of the quaternary ammonium group may optionally be alkyl groups having 1 to 8 carbon atoms, or optionally 1 to 4 carbon atoms, such as alkyl groups having a methyl group.

[0031] Cationic surfactants contain only one (i.e., one or fewer) quaternary ammonium groups.

[0032] Cationic surfactants may contain a suitable anion as a counterion, such as a hydroxide or halide. - F - Cl - and Br - This is a preferred counterion.

[0033] The morphological denaturing agent L is optionally determined by formula (1) (R 1 ) q (R 2 ) 4-q N + (X n- ) 1 / n (1) (In the formula, each R 1R is independently a linear or branched, saturated or unsaturated, preferably linear and saturated C1-C6, optionally C1-C4 hydrocarbyl group, and each hydrocarbyl may contain one or more heteroatoms optionally selected from oxygen, sulfur, nitrogen and halides; 2 C is branched or linear, saturated or unsaturated, preferably linear and saturated. 12 ~C 30 , optionally C 14 ~C 30 , optionally C 16 ~C 30 , optionally C 18 ~C 30 A hydrocarbil, and each hydrocarbil may contain one or more aromatic or aliphatic cyclic groups and / or one or more heteroatoms optionally selected from oxygen, sulfur, nitrogen and halides; q is 1 or 2, preferably 1; X n- X is an anion with valence n where n is preferably 1, and n- R is a halogen anion that is optionally selected from hydroxy anions or halide anions, particularly fluorides, chlorides, or bromides. 1 It is a cationic surfactant having (optionally methyl).

[0034] Preferably, each R 1 R is independently a linear or branched, saturated or unsaturated C1-C6 alkyl group, preferably linear and saturated, and optionally a C1-C4 alkyl group. Preferably, 2 C is branched or linear, saturated or unsaturated, preferably linear and saturated. 12 ~C 30 , optionally C 14 ~C 30 , optionally C 16 ~C 30 , optionally C 18 ~C 30 It is hydrocarbil.

[0035] Optionally, the morphological denaturant L is given by equation (2) (R 3 )3R 4 N + A - (2) (In the formula, A - is an anion, preferably a hydroxide or halide, and preferably OH - Cl - and Br - Selected from, each R 3 These are independently selected from hydrogen and C1-C4 alkyl, preferably methyl, and R 4 C is branched or linear, and can be saturated or unsaturated, optionally containing one or more cyclic groups, and preferably saturated and linear. 12 ~C 30 Alkyl alkyl group, preferably C 14 ~C 20 It is a cationic surfactant having an alkyl group.

[0036] Suitable cationic surfactants include dodecyltrimethylammonium chloride, dodecyltrimethylammonium bromide, hexadecyltrimethylammonium chloride, hexadecyltrimethylammonium bromide, octadecyltrimethylammonium chloride, octadecyltrimethylammonium bromide, hexadecylethyldimethylammonium chloride, and hexadecylethyldimethylammonium bromide.

[0037] Cationic surfactants have only a single quaternary ammonium group, and compounds having two quaternary ammonium groups (so-called "diquaternary ammonium") or more quaternary ammonium groups, as defined herein, are not morphological modifiers.

[0038] The morphology modifier L may be a nonionic surfactant. Optionally, the nonionic surfactant is selected from the group consisting of alkyl ethoxylates, alkyl propoxylates, alkylphenol ethoxylates, alkylphenol propoxylates, fatty acid ethoxylates, fatty acid propoxylates, ethoxylated amines, propoxylated amines, ethoxylated amides, propoxylated amides, block copolymers of ethylene oxide and propylene oxide, block copolymers of ethylene oxide and butylene oxide, and fatty acid esters of polyvalent compounds such as glycerol and sorbitan. For example, the morphology modifier L may be PEG-dodecyl ether or PEG-oleyl ether. The morphology modifier may be a block copolymer, such as an EO-PO-EO block copolymer containing ethylene oxide blocks and propylene oxide blocks. The morphology modifier L may be an anionic surfactant. Anionic surfactants include an anionic group such as a sulfate, sulfonate, phosphate, or carboxylate group, and an alkyl group having at least 8 carbon atoms, optionally at least 10 carbon atoms, optionally at least 12 carbon atoms, for example, 14 to 30 carbon atoms. Optionally, anionic surfactants are alkyl sulfates, alkyl sulfonates, alkyl phosphates, or alkyl carboxylates. Optionally, anionic surfactants are C8-C30 alkyl sulfates, such as alkyl sulfates like sodium lauryl sulfate.

[0039] The molar ratio L:X in the synthetic mixture is in the range of 0.0001 to 0.03, and optionally 0.001 to 0.025. A lower ratio results in an insufficient concentration of the morphology modifier L, which can cause significant changes in the crystal's morphology. A higher ratio, however, results in an excessively high concentration of the morphology modifier, which can hinder crystallization, significantly reduce the crystallization rate, or lead to the formation of a different molecular sieve framework instead of the desired one.

[0040] The morphological modifier L is optionally present in the synthetic mixture at concentrations ranging from 0.1 to 10% by weight, optionally 0.1% to 5% by weight, optionally 0.2% to 3% by weight, preferably 0.5% to 2% by weight, based on the weight of the synthetic mixture.

[0041] Crystallization and recovery Crystallization can be carried out under static or agitated conditions in a suitable reaction vessel, such as a polypropylene jar or Teflon® bottle, an acid digester, a Teflon® processed or stainless steel autoclave, a plow shear mixer, or a reaction kettle. Crystallization is typically carried out at temperatures of about 80°C to about 250°C, optionally 100°C to about 200°C, or optionally about 150°C to about 170°C, for a sufficient amount of time for crystallization to occur at the temperature used, for example, about 1 day to about 100 days, especially 1 to 50 days, for example, about 2 days to about 40 days. The synthesized crystals are then separated from the mother liquor and recovered by any convenient method, such as filtration or centrifugation. The crystals are then dried, for example, under atmospheric conditions, washed with a low-boiling point solvent such as acetone, methanol, ethanol, or propanol, or microwaved, or oven-dried at temperatures up to 150°C.

[0042] firing The process optionally includes the step of calcining the crystals recovered in step c) to obtain a calcined form of molecular sieves. The calcination conditions would be selected to at least partially remove any residual organic residues, such as residual morphology modifiers L and / or structure directing agents Q (if present), which are typically trapped in the pores of the molecular sieves in their "as-manufactured" form.

[0043] The firing step typically involves heating the zeolite at a temperature of at least about 200°C, preferably at least about 300°C, and more preferably at least about 370°C, for at least 1 minute, and generally no more than 20 hours. Lower pressures than atmospheric pressure can be used for the heat treatment, but atmospheric pressure is usually preferred for convenience. The heat treatment can be carried out at temperatures up to about 925°C. For example, the heat treatment can be carried out at temperatures of 400-600°C, for example, 500-550°C, in the presence of an oxygen-containing gas, for example, in air.

[0044] To remove residual alkali metal cations and / or alkaline earth metal cations, and to exchange them with protons, thereby producing the acidic form of the molecular sieve, the molecular sieve may be subjected to ion exchange treatment with aqueous ammonium salts such as ammonium nitrate, ammonium chloride, and ammonium acetate. To a desired extent, the initial cation of the as-synthesized material, such as alkali metal cations, can be exchanged by ion exchange with other cations. Preferred exchange cations may include metal ions, hydrogen ions, hydrogen precursors, such as ammonium ions and mixtures thereof. Particularly preferred cations may be those that adjust the catalytic activity to suit a particular hydrocarbon conversion reaction. These include hydrogen, rare earth elements and metals of groups IIA, IIIA, IVA, VA, IB, IIB, IIIB, IVB, VB, VIB, VIIB, and VIII of the periodic table. The ion exchange step may be performed after drying the as-produced molecular sieve. The ion exchange step may be performed before or after the calcination step.

[0045] Molecular sieves may be subjected to other treatments, such as steam treatment and / or washing with a solvent. Such treatments are well known to those skilled in the art and are performed to modify the properties of the molecular sieves as desired.

[0046] Molecular sieves The molecular sieve of the present invention may be of any type. The molecular sieve may be selected from the group consisting of silicates, aluminosilicates, borosilicates, gallosilicates, titanosilicates, germanosilicates, zincosilicates, aluminophosphates (ALPO), silicoaluminophosphates (SAPO), and mixed oxide frameworks (MOFs); preferably silicates, aluminosilicates, aluminophosphates (ALPO), and silicoaluminophosphates (SAPO); more preferably silicates and aluminosilicates.

[0047] The molecular sieves of the present invention may optionally be crystalline aluminophosphate or silicoaluminophosphate. Aluminophosphate molecular sieves are porous skeletons containing alternating aluminum and phosphorus tetrahedral atoms linked by bridging oxygen atoms. In the case of silicoaluminophosphate molecular sieves, some phosphorus or aluminum-phosphorus atom pairs can be substituted with tetrahedral silicon atoms. These materials, under anhydrous conditions, can be expressed as follows: mSDA:(Si x Al y P z )O2 (In the formula, m is (Si x Al y P z ) is the number of moles of SDA per mole of O2, and m has a value of 0.01 to 0.5, preferably 0.04 to 0.35, in the as-synthesized form; x, y, and z represent the mole fractions of Si, Al, and P as tetrahedral oxides, respectively, where x + y + z = 1, and y and z are 0.25 or greater. Preferably, in the case of silicoaluminophosphate molecular sieves, x is greater than 0, and optionally x is in the range of 0 to about 0.31. The range of y is 0.25 to 0.5, and z is in the range of 0.25 to 0.5, preferably y and z are in the range of 0.4 to 0.5.

[0048] Preferably, the molecular sieve is a zeolite. The zeolite may be a small-pore size zeolite. The zeolite may be a medium-pore size zeolite. The zeolite may be a large-pore size zeolite. The molecular sieve may be a molecular sieve having a skeletal code selected from the group consisting of MRE, MWW, MTW, FAU, EMT, MFS, MEI, BEA and their polymorphs, TON and MTT. The molecular sieve may be a zeolite selected from the group consisting of ZSM-48, a zeolite having an MWW skeleton, ZSM-12, cubic hojasite, hexagonal hojasite, ZSM-57, ZSM-18, beta, ZSM-22 and ZSM-23. The molecular sieve is a zeolite selected from the group consisting of ZSM-48, MCM-49, ZSM-12, cubic hojasite, hexagonal hojasite, ZSM-57, ZSM-18, beta, ZSM-22, and ZSM-23.

[0049] Molecular sieves produced by the process of the present invention may have an increased surface area compared to identical molecular sieves produced in the absence of the morphological modifier L. Optionally, molecular sieves produced by the process of the present invention may have an external surface area at least 1.1 times, and optionally at least 1.2 times, that of identical molecular sieves produced in the absence of the morphological modifier L.

[0050] Molecular sieves produced by the process of the present invention may have increased external acidity, as measured by colidine adsorption, compared to the same molecular sieves produced in the absence of the morphological modifier L. Optionally, molecular sieves produced by the process of the present invention may have an external acidity at least 1.1 times, and optionally at least 1.2 times, that of the same molecular sieves produced in the absence of the morphological modifier L.

[0051] Alternatively, molecular sieves produced by the process of the present invention have a reduced external surface area and / or reduced external acidity compared to the same molecular sieves produced in the absence of the morphological modifier L.

[0052] By selecting an appropriate morphological modifier L and an appropriate concentration thereof, a person skilled in the art can prepare molecular sieves having a range of external surface area, external acidity, and / or crystal size.

[0053] The molecular sieve of the present invention preferably has a ratio of external surface area to internal surface area of ​​1.20 or higher, and / or a ratio of external acidity measured by colidine adsorption to internal acidity measured by ammonia adsorption of 1.50 or higher.

[0054] In some embodiments, molecular sieves produced by the processes described herein, either in a calcined or as-produced form, can form aggregates of small crystals having a crystal size in the range of 0.01 to 1 μm. These small crystals can be desirable because they generally lead to higher activity. Small crystals can mean a larger surface area that leads to a greater number of active catalytic sites for a given amount of catalyst.

[0055] Optionally, zeolites contain Si and Al and have an SiO2:Al2O3 molar ratio greater than 2:1, optionally greater than 5:1, optionally greater than 10:1, optionally greater than 30:1, optionally greater than 100:1, and optionally greater than 150:1. The SiO2:Al2O3 molar ratio is optionally less than 500, optionally less than 300, or optionally less than 200. The presence of aluminum in the skeletal structure provides acidic sites to the catalyst, which also contributes to a decrease in the thermal stability of the zeolite. Many industrial organic raw material conversion processes are performed at temperatures that require the use of zeolite supports with an SiO2:Al2O3 molar ratio greater than 6:1, or even greater than 10:1.

[0056] The molecular sieve has a crystallinity of at least 50%, at least 80%, at least 90%, preferably at least 95%, and most preferably at least 98%. In one embodiment, the molecular sieve is essentially a pure crystalline material. The crystallinity can be calculated by X-ray diffraction (XRD).

[0057] In one embodiment, the molecular sieve is in its as-manufactured form and optionally contains a structure-directing agent Q within its pores.

[0058] In another embodiment, the molecular sieve does not contain a structure-directing agent Q. For example, the molecular sieve may be synthesized without containing any structure-directing agent Q.

[0059] Molecular sieves may be in a calcined form. Molecular sieve crystals may be "as-synthesized" crystals still containing the organic template, or the crystals may be calcined crystals such as K-type molecular sieve crystals or Na-type molecular sieve crystals, or the crystals may be calcined and ion-exchanged crystals such as H-type molecular sieve crystals.

[0060] The calcined acidic molecular sieves of the present invention preferably have an external acidity at least 1.10 times, more preferably at least 1.30 times, and in some cases at least 1.50 times, that of molecular sieves produced using an equivalent process, except that the synthetic mixture does not contain any morphological modifiers. The external acidity can be measured by colidine adsorption.

[0061] The calcined acid-type molecular sieves of the present invention have an external surface area at least 1.10 times, more preferably at least 1.20 times, and in some cases at least 1.30 times, that of molecular sieves produced using an equivalent process, except that the synthetic mixture does not contain any morphological modifiers. The external surface area can be measured by BET.

[0062] The calcined molecular sieves of the present invention have an external surface area ratio greater than 1.20 for internal surface area and / or an external acidity ratio greater than 1.50 for internal acidity as measured by ammonia adsorption to internal acidity as measured by ammonia adsorption.

[0063] The molecular sieves of the present invention or molecular sieves produced by the processes of the present invention can be used as adsorbents or catalysts to catalytically act on a wide variety of organic compound transformation processes, many of which are currently of commercial / industrial importance. Examples of preferred chemical transformation processes that can be effectively catalytically acted on by the zeolites of the present invention or zeolites produced by the processes of the present invention, either alone or in combination with one or more other catalytically active substances, including other crystalline catalysts, include those requiring catalysts having acid activity or hydrogenation activity. Examples of organic transformation processes that can be catalytically acted on by the zeolites of the present invention or zeolites produced by the processes of the present invention include decomposition, hydrocracking, isomerization, polymerization, modification, hydrogenation, dehydrogenation, dewaxing, hydro-deleaching, adsorption, alkylation, alkyl exchange, dealkylation, hydro-decyclization, disproportionation, oligomerization, dehydrocyclization, and combinations thereof. The transformation of hydrocarbon raw materials can be carried out in any convenient mode, depending on the type of process required, for example, in a fluidized bed, boiling bed, moving bed, or fixed bed reactor.

[0064] Once molecular sieves are synthesized, they can be incorporated into a catalyst composition by combining them with other materials, such as binders and / or matrix materials, to impart additional hardness or catalytic activity to the finished catalyst. These other materials can be inert or catalytically active.

[0065] In particular, it may be desirable to combine the molecular sieves of the present invention or molecular sieves produced by the process of the present invention with other materials that are resistant to the temperature and other conditions used in the organic conversion process. Such materials include synthetic or natural zeolites, as well as inorganic materials, such as clay, silica and / or metal oxides, such as alumina, yttria, zirconium oxide, gallium oxide, zinc oxide and mixtures thereof. The metal oxides may be of natural origin or may be in the form of gelatinous precipitates or gels containing mixtures of silica and metal oxides. Naturally derived clays that can be used include subbentonite, as well as kaolin, commonly known as Dixie, McNamee, Georgia and Florida clays, or the montmorillonite and kaolin families, including others whose main mineral component is halloysite, kaolinite, dickite, nacrite or anoxite. Such clays can be used in their raw material state as initially mined, or after being calcined, acid-treated or chemically modified. These binder materials are resistant to temperature and other conditions, such as mechanical friction arising in various hydrocarbon conversion processes. Therefore, the molecular sieves of the present invention or molecular sieves produced by the process of the present invention may be used in the form of extruded products with the binder. They are typically bound together by forming tablets, spheres, or extruded products. The extruded products are optionally formed by extruding the molecular sieves, usually in the presence of the binder, and then dried, and the resulting extruded products are calcined. Further treatments such as steam treatment, addition of catalytic metals, and / or ion exchange may be performed as needed. The molecular sieves are optionally made at least 200 m 2 / g, optionally at least 300m 2They may be bonded by a binder having a surface area of ​​ / g.

[0066] The binder can function appropriately as a diluent for controlling the amount of conversion in a given process, so that the product can be obtained in an economical and regular manner without the use of other means to control the reaction rate. These materials may be incorporated into naturally derived clays, such as bentonite and kaolin, to improve the pulverizing power of the catalyst under commercial operating conditions.

[0067] In addition to the materials mentioned above, the molecular sieves of the present invention can be composited with porous matrix materials such as silica-alumina, silica-magnesia, silica-zirconia, silica-tria, silica-beryllium, silica-titania, and ternary compositions such as silica-alumina-tria, silica-alumina-zirconia, silica-alumina-magnesia, and silica-magnesia-zirconia.

[0068] The relative proportions of molecular sieves and inorganic oxide matrix can be very wide, with molecular sieve content ranging from about 1% to about 100% by weight, and more commonly, particularly when the composite is prepared in the form of an extruded product, the composite content ranging from about 2% to about 95%, and optionally from about 20% to about 90% by weight.

[0069] Additional embodiments In addition, or instead, this disclosure may include one or more of the following embodiments:

[0070] Embodiment 1. A process for preparing molecular sieve crystals, a. Source of tetravalent element X, morphology modifier L, water, optionally source of hydroxide ions, optionally source of structure directing agent Q, optionally source of trivalent element Y, optionally source of pentavalent element Z, optionally source of halide ions W - The source of the alkali metal ions M + and / or alkaline earth metal cation M 2+A source of [unspecified], and a step of combining one or more other components as optional to form a synthetic mixture; b. The step of heating the synthetic mixture under crystallization conditions for approximately 1 hour to 100 days to form molecular sieve crystals; c. A step of recovering the molecular sieve crystals from the synthetic mixture. The morphological modifier L is selected from the group consisting of cationic surfactants, nonionic surfactants, anionic surfactants, sugars, and combinations thereof, having a single quaternary ammonium group containing at least one hydrocarbyl group having at least 12 carbon atoms, and is present in the synthetic mixture before crystal nucleation or crystallization begins; If a molecular sieve requires a structure-directing agent Q, then the morphological modifier L is different from the structure-directing agent Q and is present in addition to the structure-directing agent Q; The molar ratio L:X in the synthetic mixture is in the range of 0.0001 to 0.03; and A synthetic mixture is a liquid or a mixture of solids and liquids, where the liquid is substantially single-phase; a preparation process.

[0071] Embodiment 2. The process of Embodiment 1, wherein the molecular sieve is a zeolite, X is selected from Si, Ge and mixtures thereof, and Y is selected from Al, B, Ga, Zn and mixtures thereof.

[0072] Embodiment 3. The process of Embodiment 2, wherein X=Si and Y=Al.

[0073] Embodiment 4. Any one of the above embodiments, wherein the molecular sieve has a skeletal structure selected from the group consisting of MRE, MWW, MTW, FAU, EMT, MFS, MEI, BEA and their polymorphs, TON and MTT.

[0074] Embodiment 5. Any one of the above embodiments, wherein the molar ratio of L:X in the synthetic mixture is in the range of 0.001 to 0.025.

[0075] Embodiment 6. The morphology modifier L is a cationic surfactant having a single quaternary ammonium group and at least one C 12 ~C 30 alkyl group, according to any one of the above embodiments.

[0076] Embodiment 7. The morphology modifier L is of formula (1) (R 1 ) q (R 2 ) 4-q N + (X n- ) 1 / n (1) (where each R 1 is independently a C1-C6, optionally C1-C4 alkyl group which can be linear or branched, saturated or unsaturated, preferably linear and saturated; R 2 is a C 12 ~C 30 , optionally C 14 ~C 30 , optionally C 16 ~C 30 , optionally C 18 ~C 30 alkyl; q is 1 or 2, preferably 1; X - is an anion of valence n, and X - is an optionally hydroxyanion or halide anion, particularly a halide anion selected from fluoride, chloride or bromide), according to any one of the above embodiments.

[0077] Embodiment 8. The morphology modifier L is a monosaccharide, according to any one of Embodiments 1-5. B

[0078] Embodiment 9. The morphology modifier L is an anionic surfactant, according to any one of Embodiments 1-5.

[0079] Embodiment 10. Any one of Embodiments 1 to 5, wherein the morphology modifier L is a nonionic surfactant.

[0080] Embodiment 11. A process from any one of Embodiments 1 to 10, comprising the step of calcining the crystals recovered in step c) to obtain a calcined form of molecular sieve.

[0081] Embodiment 12. A molecular sieve, prepared by any one of the processes of the above embodiments, in its as-manufactured or calcined form.

[0082] Embodiment 13. A molecular sieve of Embodiment 12, having an external acidity at least 1.10 times that of a molecular sieve produced using an equivalent process, except that the synthetic mixture does not contain any morphological modifier L.

[0083] Embodiment 14. A molecular sieve of Embodiment 12 or 13, having an external surface area at least 1.10 times that of a molecular sieve produced using an equivalent process, except that the synthetic mixture does not contain any morphological modifier L.

[0084] Embodiment 15. A catalyst comprising any one molecular sieve from Embodiments 12 to 14, and optionally comprising a binder.

[0085] Embodiment 16. A hydrocarbon conversion process comprising the step of contacting a hydrocarbon raw material with the catalyst of Embodiment 15.

[0086] Embodiment 17. The hydrocarbon conversion process of Embodiment 16, which is a dewaxing, oligomerization, alkylation, isomerization, or decomposition process. [Examples]

[0087] ZSM-48 was synthesized using hexamethonium dichloride (HMDC) as a structure-directing agent and various morphology modifiers according to the following procedure.

[0088] Example 1 (Comparative). See ZSM-48, no morphological modifier, modifier / SiO2 = 0.0, morphological modifier present at 0% by weight of the total mixture. Dilute 1.26 g of 25% hexamethonium dichloride (HMDC) in 14.8 g of water. Stir to ensure the solution is homogenized. Add 0.62 g of sodium aluminate solution (7.8% Na2O, 10.0% Al2O3, 82.2% water) to the structure-directing agent solution. Stir to homogenize the solution. Add 3.6 g of 10% NaOH solution to the HMDC / aluminate solution. Stir to homogenize the mixture. Add 0.73 g of colloidal beta species (17.2 wt% species) to the aluminate mixture. Add 3.95 g of Ultrasil VN3 PM-modified precipitated silica (92.4% SiO2) to this mixture. Stir the mixture for 15 minutes to prepare a homogeneous slurry. The approximate molar gel composition of the mixture is as follows: SiO2 / Al2O3 = 100.0 OH - / SiO2=0.175 HMDC / SiO2 = 0.019 Denaturant / SiO2 = 0.000 H2O / SiO2 = 18.7 Seeds at approximately 5100 ppm

[0089] The autoclave is sealed, and the mixture is continuously stirred at 300 rpm using a U-type stirrer. The mixture is heated to 160°C (ramp rate of 20°C / hour) and held for 28 hours. The solid is isolated by vacuum filtration and washed with three volumes of water. The material is dried in an oven at 120°C. X-ray diffraction indicates that the powder is ZSM-48.

[0090] Transmission electron microscopy (TEM) revealed that the crystals generally have a length in the range of 30–50 nm and a width in the range of 10–15 nm, with a length-to-width aspect ratio of 3–5.

[0091] Example 2. ZSM-48, Brij L4 morphological modifier, morphological modifier / SiO2 = 0.017, 1.5% by weight of the total mixture. Dilute 1.27 g of 25% hexamethonium dichloride (HMDC) in 13.0 g of water. Stir to ensure the solution is homogenized. Add 0.59 g of sodium aluminate solution (7.5% Na2O, 10.2% Al2O3, 82.3% water) to the structure-directing agent solution. Stir to homogenize the solution. Add 3.6 g of 10% NaOH solution to the HMDC / aluminate solution. Stir to homogenize the mixture. Add 0.75 g of colloidal beta species (16.7 wt% species) to the aluminate mixture. Add 1.96 g of 19.2 wt% Brij L4 (polyethylene glycol dodecyl ether as a nonionic surfactant morphology modifier) ​​solution, and stir the mixture to dissolve the zeolite growth modifier. Add 3.89 g of Ultrasil VN3 PM-modified precipitated silica (92.4% SiO2) to this mixture. Stir the mixture for 15 minutes to prepare a homogeneous slurry. The approximate molar-gel composition of the mixture is as follows: SiO2 / Al2O3 = 100.0 OH - / SiO2=0.175 HMDC / SiO2 = 0.019 Denaturant / SiO2 = 0.018 H2O / SiO2 = 18.7 Seeds at approximately 5200 ppm

[0092] The autoclave is sealed, and the mixture is continuously stirred at 300 rpm using a U-type stirrer. The mixture is heated to 160°C (ramp rate of 20°C / hour) and held for 28 hours. The solid is isolated by vacuum filtration and washed with three volumes of water. The material is dried in an oven at 120°C. X-ray diffraction indicates that the powder is ZSM-48.

[0093] Example 3. ZSM-48, Brij 93 morphological modifier, morphological modifier / SiO2 = 0.018, 1.5% by weight of the total mixture. Dilute 1.27 g of 25% hexamethonium dichloride (HMDC) in 12.9 g of water. Stir to ensure the solution is homogenized. Add 0.59 g of sodium aluminate solution (7.5% Na2O, 10.2% Al2O3, 82.3% water) to the structure-directing agent solution. Stir to homogenize the solution. Add 3.6 g of 10% NaOH solution to the HMDC / aluminate solution. Stir to homogenize the mixture. Add 0.75 g of colloidal beta species (16.7 wt% species) to the aluminate mixture. Add 2.02 g of an 18.5 wt% solution of Brij 93 (polyethylene glycol loryl ether as a nonionic surfactant morphology modifier), and stir the mixture to dissolve the zeolite growth modifier. Add 3.89 g of Ultrasil VN3 PM-modified precipitated silica (92.4% SiO2) to this mixture. Stir the mixture for 15 minutes to prepare a homogeneous slurry. The approximate molar-gel composition of the mixture is as follows: SiO2 / Al2O3 = 100.0 OH - / SiO2=0.175 HMDC / SiO2 = 0.019 Denaturant / SiO2 = 0.018 H2O / SiO2 = 18.7 Seeds at approximately 5200 ppm

[0094] The autoclave is sealed, and the mixture is continuously stirred at 300 rpm using a U-type stirrer. The mixture is heated to 160°C (ramp rate of 20°C / hour) and held for 28 hours. The solid is isolated by vacuum filtration and washed with three volumes of water. The material is dried in an oven at 120°C. X-ray diffraction indicates that the powder is ZSM-48.

[0095] Example 4. ZSM-48, sodium octyl sulfate morphological modifier, morphological modifier / SiO2 = 0.027, 1.5% by weight of the total mixture. Dilute 1.27 g of 25% hexamethonium dichloride (HMDC) in 13.0 g of water. Stir to ensure the solution is homogenized. Add 0.60 g of sodium aluminate solution (7.5% Na2O, 10.2% Al2O3, 82.3% water) to the structure-directing agent solution. Stir to homogenize the solution. Add 3.6 g of 10% NaOH solution to the HMDC / aluminate solution. Stir to homogenize the mixture. Add 0.75 g of colloidal beta species (16.7 wt% species) to the aluminate mixture. Add 1.86 g of 20 wt% sodium octyl sulfate solution, and stir the mixture to dissolve the zeolite growth modifier. Add 3.89 g of Ultrasil VN3 PM modified precipitated silica (92.4% SiO2) to this mixture. Stir the mixture for 15 minutes to prepare a uniform slurry. The approximate molar-gel composition of the mixture is as follows: SiO2 / Al2O3 = 100.0 OH - / SiO2=0.175 HMDC / SiO2 = 0.019 Denaturant / SiO2 = 0.027 H2O / SiO2 = 18.7 Seeds at approximately 5200 ppm

[0096] The autoclave is sealed, and the mixture is continuously stirred at 300 rpm using a U-type stirrer. The mixture is heated to 160°C (ramp rate of 20°C / hour) and held for 28 hours. The solid is isolated by vacuum filtration and washed with three volumes of water. The material is dried in an oven at 120°C. X-ray diffraction indicates that the powder is ZSM-48.

[0097] Example 5 (Comparative): ZSM-48, 1,2-Hexanediol comparative modifier, comparative modifier / SiO2 = 0.053, 1.5% by weight of the total mixture. Dilute 1.27 g of 25% hexamethonium dichloride (HMDC) in 13.1 g of water. Stir to ensure the solution is homogenized. Add 0.60 g of sodium aluminate solution (7.5% Na2O, 10.2% Al2O3, 82.3% water) to the structure-directing agent solution. Stir to homogenize the solution. Add 3.6 g of 10% NaOH solution to the HMDC / aluminate solution. Stir to homogenize the mixture. Add 0.75 g of colloidal beta species (16.7 wt% species) to the aluminate mixture. Add 1.86 g of 20.1 wt% solution of 1,2-hexanediol, and stir the mixture to dissolve the zeolite growth modifier. Add 3.89 g of Ultrasil VN3 PM modified precipitated silica (92.4% SiO2) to this mixture. Stir the mixture for 15 minutes to prepare a uniform slurry. The approximate molar-gel composition of the mixture is as follows: SiO2 / Al2O3 = 100.0 OH - / SiO2=0.175 HMDC / SiO2 = 0.019 Denaturant / SiO2 = 0.053 H2O / SiO2 = 18.7 Seeds at approximately 5200 ppm

[0098] The autoclave is sealed, and the mixture is continuously stirred at 300 rpm using a U-type stirrer. The mixture is heated to 160°C (ramp rate of 20°C / hour) and held for 28 hours. The solid is isolated by vacuum filtration and washed with three volumes of water. The material is dried in an oven at 120°C. X-ray diffraction indicates that the powder is ZSM-48.

[0099] Example 6. ZSM-48, trimethyloctadecylammonium bromide morphological modifier, morphological modifier / SiO2 = 0.021, 2.0% by weight of the total mixture. Dilute 1.26 g of 25% hexamethonium dichloride (HMDC) in 12.5 g of water. Stir to ensure the solution is homogenized. Add 0.61 g of sodium aluminate solution (7.8% Na2O, 10.0% Al2O3, 82.2% water) to the structure-directing agent solution. Stir to homogenize the solution. Add 3.6 g of 10% NaOH solution to the HMDC / aluminate solution. Stir to homogenize the mixture. Add 0.73 g of colloidal beta species (17.2 wt% species) to the aluminate mixture. Add 2.51 g of 20 wt% trimethyloctadecylammonium bromide (cationic surfactant morphology modifier) ​​solution, and stir the mixture to dissolve the morphology modifier. Add 3.87 g of Ultrasil VN3 PM-modified precipitated silica (92.4% SiO2) to this mixture. Stir the mixture for 15 minutes to prepare a homogeneous slurry. The approximate molar-gel composition of the mixture is as follows: SiO2 / Al2O3 = 100.0 OH - / SiO2=0.175 HMDC / SiO2 = 0.019 Denaturant / SiO2 = 0.021 H2O / SiO2 = 18.7 Seeds at approximately 5100 ppm

[0100] The autoclave is sealed, and the mixture is continuously stirred at 300 rpm using a U-type stirrer. The mixture is heated to 160°C (ramp rate of 20°C / hour) and held for 28 hours. The solid is isolated by vacuum filtration and washed with three volumes of water. The material is dried in an oven at 120°C. X-ray diffraction indicates that the powder is ZSM-48.

[0101] Example 7. ZSM-48, sodium lauryl sulfate morphological modifier, morphological modifier / SiO2 = 0.028, 2.0% by weight of the total mixture. Dilute 1.24 g of 25% hexamethonium dichloride (HMDC) in 12.5 g of water. Stir to ensure the solution is homogenized. Add 0.61 g of sodium aluminate solution (7.8% Na2O, 10.0% Al2O3, 82.2% water) to the structure-directing agent solution. Stir to homogenize the solution. Add 3.6 g of 10% NaOH solution to the HMDC / aluminate solution. Stir to homogenize the mixture. Add 0.73 g of colloidal beta species (17.2 wt% species) to the aluminate mixture. Add 2.5 g of 20 wt% sodium lauryl sulfate solution (anionic surfactant morphology modifier), and stir the mixture to dissolve the morphology modifier. Add 3.90 g of Ultrasil VN3 PM-modified precipitated silica (92.4% SiO2) to this mixture. Stir the mixture for 15 minutes to prepare a uniform slurry. The approximate molar-gel composition of the mixture is as follows: SiO2 / Al2O3 = 100.2 OH - / SiO2=0.174 HMDC / SiO2 = 0.019 Denaturant / SiO2 = 0.028 H2O / SiO2 = 18.6 Seeds at approximately 5100 ppm

[0102] The autoclave is sealed, and the mixture is continuously stirred at 300 rpm using a U-type stirrer. The mixture is heated to 160°C (ramp rate of 20°C / hour) and held for 28 hours. The solid is isolated by vacuum filtration and washed with three volumes of water. The material is dried in an oven at 120°C. X-ray diffraction indicates that the powder is ZSM-48.

[0103] Example 8. ZSM-48, benzylhexadecyldimethylammonium chloride morphological modifier, morphological modifier / SiO2 = 0.016, 1.5% by weight of the total mixture Dilute 1.24 g of 25% hexamethonium dichloride (HMDC) in 13.1 g of water. Stir to ensure the solution is homogenized. Add 0.61 g of sodium aluminate solution (7.8% Na2O, 10.0% Al2O3, 82.2% water) to the structure-directing agent solution. Stir to homogenize the solution. Add 3.6 g of 10% NaOH solution to the HMDC / aluminate solution. Stir to homogenize the mixture. Add 0.73 g of colloidal beta species (17.2 wt% species) to the aluminate mixture. Add 1.88 g of 20 wt% solution of benzylhexadecyldimethylammonium chloride (cationic surfactant morphology modifier), and stir the mixture to dissolve the morphology modifier. Add 3.89 g of Ultrasil VN3 PM-modified precipitated silica (92.4% SiO2) to this mixture. Stir the mixture for 15 minutes to prepare a homogeneous slurry. The approximate molar-gel composition of the mixture is as follows: SiO2 / Al2O3 = 100.0 OH - / SiO2=0.175 HMDC / SiO2 = 0.019 Denaturant / SiO2 = 0.016 H2O / SiO2 = 18.7 Seeds at approximately 5100 ppm

[0104] The autoclave is sealed, and the mixture is continuously stirred at 300 rpm using a U-type stirrer. The mixture is heated to 160°C (ramp rate of 20°C / hour) and held for 28 hours. The solid is isolated by vacuum filtration and washed with three volumes of water. The material is dried in an oven at 120°C. X-ray diffraction indicates that the powder is ZSM-48.

[0105] Example 9. ZSM-48, dihexadecyldimethylammonium bromide morphological modifier, morphological modifier / SiO2 = 0.012, 1.5% by weight of the total mixture Dilute 1.24 g of 25% hexamethonium dichloride (HMDC) in 13.1 g of water. Stir to ensure the solution is homogenized. Add 0.61 g of sodium aluminate solution (7.8% Na2O, 10.0% Al2O3, 82.2% water) to the structure-directing agent solution. Stir to homogenize the solution. Add 3.6 g of 10% NaOH solution to the HMDC / aluminate solution. Stir to homogenize the mixture. Add 0.73 g of colloidal beta species (17.2 wt% species) to the aluminate mixture. Add 1.86 g of 20 wt% dihexadecyldimethylammonium bromide (cationic surfactant morphology modifier) ​​solution, and stir the mixture to dissolve the morphology modifier. Add 3.89 g of Ultrasil VN3 PM-modified precipitated silica (92.4% SiO2) to this mixture. Stir the mixture for 15 minutes to prepare a homogeneous slurry. The approximate molar-gel composition of the mixture is as follows: SiO2 / Al2O3 = 100.0 OH - / SiO2=0.175 HMDC / SiO2 = 0.019 Denaturant / SiO2 = 0.012 H2O / SiO2 = 18.7 Seeds at approximately 5100 ppm

[0106] The autoclave is sealed, and the mixture is continuously stirred at 300 rpm using a U-type stirrer. The mixture is heated to 160°C (ramp rate of 20°C / hour) and held for 28 hours. The solid is isolated by vacuum filtration and washed with three volumes of water. The material is dried in an oven at 120°C. X-ray diffraction indicates that the powder is ZSM-48.

[0107] Example 10. ZSM-48, lithium dodecyl sulfate morphological modifier, morphological modifier / SiO2 = 0.023, 1.5% by weight of the total mixture Dilute 1.24 g of 25% hexamethonium dichloride (HMDC) in 13.1 g of water. Stir to ensure the solution is homogenized. Add 0.61 g of sodium aluminate solution (7.8% Na2O, 10.0% Al2O3, 82.2% water) to the structure-directing agent solution. Stir to homogenize the solution. Add 3.6 g of 10% NaOH solution to the HMDC / aluminate solution. Stir to homogenize the mixture. Add 0.73 g of colloidal beta species (17.2 wt% species) to the aluminate mixture. Add 1.86 g of 20 wt% lithium dodecyl sulfate solution (anionic surfactant morphology modifier), and stir the mixture to dissolve the morphology modifier. Add 3.89 g of Ultrasil VN3 PM-modified precipitated silica (92.4% SiO2) to this mixture. Stir the mixture for 15 minutes to prepare a uniform slurry. The approximate molar-gel composition of the mixture is as follows: SiO2 / Al2O3 = 100.0 OH - / SiO2=0.175 HMDC / SiO2 = 0.019 Denaturant / SiO2 = 0.023 H2O / SiO2 = 18.7 Seeds at approximately 5100 ppm

[0108] The autoclave is sealed, and the mixture is continuously stirred at 300 rpm using a U-type stirrer. The mixture is heated to 160°C (ramp rate of 20°C / hour) and held for 28 hours. The solid is isolated by vacuum filtration and washed with three volumes of water. The material is dried in an oven at 120°C. X-ray diffraction indicates that the powder is ZSM-48.

[0109] Transmission electron microscopy (TEM) revealed that the crystals generally have a length in the range of 30–60 nm and a width in the range of approximately 30 nm, with a length-to-width aspect ratio in the range of 1–2.

[0110] Example 11. ZSM-48, Pluronic EO-PO-EO morphological modifier, morphological modifier / SiO2 = 0.002, 1.0% by weight of the total mixture. Dilute 1.25 g of 25% hexamethonium dichloride (HMDC) in 13.7 g of water. Stir to ensure the solution is homogenized. Add 0.61 g of sodium aluminate solution (7.8% Na2O, 10.0% Al2O3, 82.2% water) to the structure-directing agent solution. Stir to homogenize the solution. Add 3.6 g of 10% NaOH solution to the HMDC / aluminate solution. Stir to homogenize the mixture. Add 0.73 g of colloidal beta species (17.2 wt% species) to the aluminate mixture. Add 1.24 g of 20 wt% solution of Pluronic EO-PO-EO triblock copolymer (nonionic surfactant morphology modifier), and stir the mixture to dissolve the morphology modifier. Add 3.91 g of Ultrasil VN3 PM-modified precipitated silica (92.4% SiO2) to this mixture. Stir the mixture for 15 minutes to prepare a homogeneous slurry. The approximate molar-gel composition of the mixture is as follows: SiO2 / Al2O3 = 100.0 OH - / SiO2=0.175 HMDC / SiO2 = 0.019 Denaturant / SiO2 = 0.0007 H2O / SiO2 = 18.7 Seeds at approximately 5100 ppm

[0111] The autoclave is sealed, and the mixture is continuously stirred at 300 rpm using a U-type stirrer. The mixture is heated to 160°C (ramp rate of 20°C / hour) and held for 28 hours. The solid is isolated by vacuum filtration and washed with three volumes of water. The material is dried in an oven at 120°C. X-ray diffraction indicates that the powder is ZSM-48.

[0112] The following synthesis of MCM-49 was carried out using hexamethyleneimine (HMI) as a structure-directing agent, following the procedure below.

[0113] Example 12. See MCM-49, no morphological modifier, morphological modifier / SiO2 = 0.000, 0% by weight of the total mixture. Dilute 3.54 g of a 40 wt% solution of aluminum sulfate octahydrate in 12.0 g of water. Add 4.1 g of 20% NaOH solution to the aluminum sulfate solution. Stir to homogenize the mixture. Add 3.46 g of Ultrasil VN3 PM modified precipitated silica (92.4% SiO2) to the sodium aluminumate solution. Stir the mixture until the slurry appears uniform. Add 1.86 g of hexamethyleneimine (HMI) to the slurry. Stir the mixture for 10 minutes to prepare a uniform slurry. The approximate molar gel composition of the mixture is as follows: SiO2 / Al2O3 = 25.0 OH - / SiO2 = 0.390 HMI / SiO2 = 0.350 Denaturant / SiO2 = 0.000 H2O / SiO2 = 18.5

[0114] The autoclave is sealed, and the mixture is continuously stirred at 360 rpm using a U-type stirrer. The mixture is heated to 143°C (ramp rate of 20°C / hour) and held for 125 hours. The solid is isolated by vacuum filtration and washed with three volumes of water. The material is dried in an oven at 120°C. X-ray diffraction indicates that the powder has an MCM-49 / MCM-22 structure.

[0115] Example 13. MCM-49, cetyltrimethylammonium bromide morphological modifier, morphological modifier / SiO2 = 0.013, 1% by weight of the total mixture. Dilute 3.51 g of a 40 wt% solution of aluminum sulfate octahydrate in 10.9 g of water. Add 4.1 g of a 20% NaOH solution to the aluminum sulfate solution. Stir to homogenize the mixture. Add 3.42 g of Ultrasil VN3 PM-modified precipitated silica (92.4% SiO2) to the sodium aluminumate solution. Stir the mixture until the slurry appears uniform. Add 1.85 g of hexamethyleneimine (HMI) to the slurry. Add 1.26 g of a 20 wt% solution of cetyltrimethylammonium bromide (cationic surfactant morphology modifier) ​​to the slurry. Stir the mixture for 10 minutes to prepare a uniform slurry. The approximate mol / gel composition of the mixture is as follows: SiO2 / Al2O3 = 25.0 OH - / SiO2 = 0.390 HMI / SiO2 = 0.350 Denaturant / SiO2 = 0.013 H2O / SiO2 = 19.6

[0116] The autoclave is sealed, and the mixture is continuously stirred at 360 rpm using a U-type stirrer. The mixture is heated to 143°C (ramp rate of 20°C / hour) and held for 125 hours. The solid is isolated by vacuum filtration and washed with three volumes of water. The material is dried in an oven at 120°C. X-ray diffraction indicates that the powder has an MCM-49 / MCM-22 structure.

[0117] Example 14. MCM-49, sodium lauryl sulfate morphological modifier, morphological modifier / SiO2 = 0.016, 1% by weight of the total mixture Dilute 3.51 g of a 40 wt% solution of aluminum sulfate octahydrate in 10.9 g of water. Add 4.1 g of a 20% NaOH solution to the aluminum sulfate solution. Stir to homogenize the mixture. Add 3.42 g of Ultrasil VN3 PM-modified precipitated silica (92.4% SiO2) to the sodium aluminumate solution. Stir the mixture until the slurry appears uniform. Add 1.85 g of hexamethyleneimine (HMI) to the slurry. Add 1.26 g of a 20 wt% solution of sodium lauryl sulfate (anionic surfactant morphology modifier) ​​to the slurry. Stir the mixture for 10 minutes to prepare a uniform slurry. The approximate mol / gel composition of the mixture is as follows: SiO2 / Al2O3 = 25.0 OH - / SiO2 = 0.390 HMI / SiO2 = 0.350 Denaturant / SiO2 = 0.016 H2O / SiO2 = 19.6

[0118] The autoclave is sealed, and the mixture is continuously stirred at 360 rpm using a U-type stirrer. The mixture is heated to 143°C (ramp rate of 20°C / hour) and held for 125 hours. The solid is isolated by vacuum filtration and washed with three volumes of water. The material is dried in an oven at 120°C. X-ray diffraction indicates that the powder has an MCM-49 / MCM-22 structure.

[0119] Example 15. ZSM-48, fructose morphology modifier, modifier / SiO2 = 0.020, 1.0% by weight of the total mixture Dilute 1.39 g of 56% hexamethonium dichloride (HMDC) in 14.4 g of water. Stir to ensure the solution is homogenized. Add 1.42 g of sodium aluminate solution (20% NaOH, 7.8% Al(OH)3, 72.2% water) to the structure-directing agent solution. Stir to homogenize the solution. Add 2.6 g of 10% NaOH solution to the HMDC / aluminate solution. Stir to homogenize the mixture. Add 0.03 g of ZSM-48 to the aluminate mixture. Add 0.63 g of 39.7% fructose solution and stir to homogenize the mixture. Add 4.62 g of Ultrasil VN3 PM-modified precipitated silica (92.4% SiO2) to this mixture. Stir the mixture for 15 minutes to prepare a homogeneous slurry. The approximate molar-gel composition of the mixture is as follows: SiO2 / Al2O3 = 99.9 OH - / SiO2 = 0.190 HMDC / SiO2 = 0.040 Denaturant / SiO2 = 0.020 H2O / SiO2 = 14.9 Seeds at approximately 1000 ppm

[0120] The autoclave is sealed, and the mixture is continuously stirred at 300 rpm using a U-type stirrer. The mixture is heated to 157°C (ramp rate of 60°C / hour) and held for 30 hours. The solid is isolated by vacuum filtration and washed with three volumes of water. The material is dried in an oven at 120°C. X-ray diffraction indicates that the powder is ZSM-48.

[0121] Post-synthesis processing and measurement The molecular sieve samples prepared according to Examples 1 to 15 above were subjected to the following treatments.

[0122] After crystallization is complete and the material is determined to be crystalline by XRD, the crystals are ion-exchanged twice with NH4NO3, washed with water, and dried in an oven at 120°C. The ammonium form of the powder is then calcined in air at 550°C for 2 hours to produce the acid form of the zeolite crystals.

[0123] Next, to evaluate the acidity of the catalyst, the acidity type of the crystal was characterized using colidine adsorption. The external and internal surface area and pore volume of the crystal were determined using nitrogen BET technique. This data was collected for the reference material and each modified material of the present invention, and the ratio of the external surface area and colidine adsorption of each example of the present invention to the reference example of the same zeolite is shown in Table 1 to demonstrate the changes in acidity and external surface area of ​​the modified crystal caused by the presence of the morphological modifier in the synthetic mixture.

[0124] The BET analysis was performed as described in SJ Gregg, KWSing, "Adsorption, Surface Area and Porosity," 1st ed., Academic Press, NY (1967), pp. 30-31.

[0125] Ammonia and colidine absorption tests were generally performed as described in J.Phys.Chem.B, 2002, 106(2), pp395-400 (note that in some cases the apparatus differed slightly, but in all cases the measurements were performed on a thermogravimetric balance).

[0126] [Table 2]

[0127] The results in Table 1 show that when 1,2-hexanediol, which is not a morphological modifier described herein, is used, no effect on colidine absorption or external surface area is observed. This was similar to the case of reference ZSM-48 in Comparative Example 1.

[0128] In Examples 2-4, 6, 8-11, and 13-15 of the present invention, the presence of a morphological modifier had a significant effect on colidine adsorption and / or external SA compared to the synthesis of a reference material without a morphological modifier. In Example 7, the recorded colidine absorption and external SA values ​​were lower than those for the reference synthesis of the same zeolite without a morphological modifier, but within 10%, which may be due to experimental error. In Example 10, the results for colidine absorption and external SA were lower than those for the reference material. In this case, TEM results showed that the aspect ratio of the crystals produced in the presence of lithium dodecyl sulfate as a morphological modifier was significantly reduced compared to the reference ZSM-48, mainly due to the increased crystal width compared to the reference material. In ZSM-48, one-dimensional channels in the framework run longitudinally through the crystal; therefore, an increase in crystal width compared to length can make those channels available to incoming reactant molecules.

Claims

1. A method for preparing molecular sieve crystals, a. The step of forming a synthetic mixture by combining a source of at least a tetravalent element X, a morphology modifier L, a structure-directing agent Q, and water; b. The step of heating the synthetic mixture under crystallization conditions for a period of time from 1 hour to 100 days to form the crystals of the molecular sieve; c. A step of recovering the crystals of the molecular sieve from the synthetic mixture. The morphology modifier L is a cationic surfactant containing a single quaternary ammonium group, comprising one or two C12-C30 alkyl groups bonded to a single quaternary ammonium group, wherein the other substituent on the nitrogen atom of the single quaternary ammonium group is a C1-C4 alkyl group, and is present in the synthetic mixture before the nucleation or crystallization of the crystal begins; Unlike the morphological modifier L, the structure-directing agent Q is: The molar ratio L:X in the aforementioned synthetic mixture is in the range of 0.0001 to 0.03; The synthetic mixture is a liquid or a mixture of solids and liquids, wherein the liquid is substantially single-phase; X is Si, and the synthetic mixture also includes a source of the trivalent element Y, where Y is Al; The molecular sieve has the skeletal structure of an MRE; The morphological modifier L is present in the synthetic mixture at a concentration of 0.1% to 10% by weight, based on the weight of the synthetic mixture; and A method for preparing the molecular sieve, wherein the molecular sieve has an external surface area at least 1.10 times that of a molecular sieve produced using an equivalent method, except that the synthetic mixture does not contain any morphological modifier L.

2. In step a), a source of hydroxide ions, a source of pentavalent element Z, and halide ions W － Sources of, and alkali metal ions M ＋ and / or alkaline earth metal cation M ２＋ The method according to claim 1, wherein one or more further components selected from the group consisting of sources are also combined in the synthetic mixture.

3. The method according to claim 1, wherein the molar ratio of L:X in the synthetic mixture is in the range of 0.001 to 0.

025.

4. The method according to claim 1, further comprising the step of calcining the crystals recovered in step c) to obtain a calcined form of the molecular sieve.

5. The method according to claim 1, wherein the molecular sieve has an external acidity at least 1.10 times that of a molecular sieve produced using an equivalent method, except that the synthetic mixture does not contain any morphological modifier L.

6. A hydrocarbon conversion method comprising the step of contacting a hydrocarbon raw material with a catalyst comprising crystals of molecular sieves prepared by the method of any one of Claims 1 to 5.

7. The hydrocarbon conversion method according to claim 6, comprising a dewaxing process, an oligomerization process, an alkylation process, an isomerization process, or a decomposition process.

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