Molecular sieves and process for making molecular sieves

Abstract

To provide a process for preparing molecular sieves of framework structure MEI, TON, MRE, MWW, MFS, MOR, FAU, EMT, or MSE.SOLUTION: The process includes preparing a synthesis mixture for molecular sieves, wherein the synthesis mixture includes a morphology modifier L selected from the group consisting of cationic surfactants having a quaternary ammonium group comprising at least one hydrocarbyl group having at least 12 carbon atoms, nonionic surfactants, anionic surfactants, sugars and combinations thereof.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a novel process for preparing molecular sieve crystals, the molecular sieves prepared by this process, and their use as hydrocarbon conversion catalysts. [Background technology]

[0002] Molecular sieve materials, both natural and synthetic, have been demonstrated in the past to be useful as adsorbents and to have catalytic properties for various types of hydrocarbon conversion reactions. Certain molecular sieves are ordered and porous crystalline materials with a well-defined crystalline structure as determined by X-ray diffraction (XRD). Certain molecular sieves, such as MCM-41, are ordered and produce specific, definable X-ray diffraction patterns, but are not strictly crystalline. Within the molecular sieve material, there are numerous voids that may be interconnected by numerous channels or pores. These voids and pores are uniform in size within the particular molecular sieve material. Because the dimensions of these pores are such that they allow the adsorption of molecules of a certain size, but not molecules of a larger size, these materials are known as "molecular sieves" and are utilized in various industrial processes.

[0003] Such molecular sieves, both natural and synthetic, include a wide variety of positive ion-containing crystalline silicates. These silicates can be described as a three-dimensional framework of SiO4 and oxides of Group 13 elements of the periodic table (e.g., AlO4). The tetrahedra are typically corner-shared by oxygen atoms, and the valence of the tetrahedra containing Group 13 elements (e.g., aluminum, gallium, or boron) is charge-balanced by the inclusion of cations, such as protons, alkali metal, or alkaline earth metal cations.

[0004] Molecular sieves that have found application in catalysis include either naturally occurring or synthetic crystalline molecular sieves. Examples of these molecular sieves include large pore zeolites, medium pore size zeolites, and small pore zeolites. These zeolites and their isotypes are described in the online database of zeolite structures, http: / / www.iza-structure.org / databases / , incorporated herein by reference. Large pore zeolites generally have pore sizes of at least about 6.5-7 angstroms and include LTL, MAZ, FAU, OFF, *BEA, and MOR framework type 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 about 4.5 angstroms to less than about 7 angstroms, and include, for example, MFI, MEL, EUO, MTT, MFS, AEL, AFO, HEU, FER, MWW, and TON framework type 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 about 3 angstroms to less than about 5.0 angstroms, and include, for example, CHA, ERI, KFI, LEV, SOD, and LTA framework type 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 Summary of the Invention [Problem to be solved by the invention]

[0006] Although many molecular sieves, particularly zeolites, have been commercially established as adsorbents and catalysts, there is a need for improved molecular sieves, e.g., as catalysts with improved activity and / or selectivity. One aspect that has received much attention recently is the crystal size of the molecular sieve. Other things being equal, molecular sieves with smaller crystal sizes generally have larger external surface areas, which can lead to increased catalytic activity by increasing the rate of adsorption onto the surface of the molecular sieve crystals and / or by reducing the length of the diffusion path into the internal pores of the crystals. By reducing the crystal size of the molecular sieve catalyst, reactions that occur primarily on the external surface of the zeolite, e.g., reactions involving larger reactant molecules that diffuse slowly into the internal pores due to their size, can be promoted.

[0007] No. 7,482,300 describes the synthesis of ZSM-48 having a silica to aluminum ratio of 70:1 to 110:1, along with a method for using such ZSM-48 for catalytic dewaxing. The synthesis method is said to be suitable for forming ZSM-48 crystals with a reduced or minimized content of crystals having needle-like morphology. [Means for solving the problem]

[0008] The present invention relates to a process for the preparation of crystals of molecular sieves having a framework code selected from the group consisting of MEI, TON, MRE, MWW, MFS, MOR, FAU, EMT and MSE, comprising the steps of: combining at least a source of a tetravalent element X, a morphology modifier L, and water to form a synthesis mixture; heating the synthesis mixture under crystallization conditions for a time period between about 1 hour and 100 days to form crystals of molecular sieves having a framework code selected from the group consisting of MEI, TON, MRE, MWW, MFS, MOR, FAU, EMT, and MSE; recovering said crystals of molecular sieve from the synthesis mixture; wherein X=Si, and the morphology modifier L is selected from the group consisting of a cationic surfactant having a quaternary ammonium group containing at least one alkyl having at least 12 carbon atoms, a nonionic surfactant, an anionic surfactant, a sugar, and combinations thereof, and when a structure directing agent Q is present, L is different from the structure directing agent Q and is present in addition to the structure directing agent Q.

[0009] Optionally, the synthesis mixture also includes a source of hydroxide ions. Optionally, the synthesis mixture also includes a structure directing agent Q. Optionally, the synthesis mixture also includes a source of trivalent element Y. Optionally, the synthesis mixture also includes a source of pentavalent element Z. Optionally, the synthesis mixture also includes a source of halide ions W. - Optionally, the synthesis mixture also includes a source of alkali metal ions M + and / or a source of alkaline earth metal cation M 2+ Optionally, the synthetic mixture also includes one or more other components.

[0010] The inventors have found that by carrying out the synthesis of the molecular sieve in the presence of morphology modifier L, it is possible to affect the crystal growth such that the molecular sieve crystals have a modified crystal size and / or modified acidity compared to the crystals of the same molecular sieve prepared in the absence of morphology modifier L. This allows the production of molecular sieve crystals with new and desirable properties. The molecular sieve crystals produced by the process of the invention can be smaller than the crystals of the same molecular sieve prepared by the same process but in the absence of morphology modifier L. Without wishing to be bound by theory, the present invention believes that the presence of morphology modifier L can change the distribution of trivalent elements such as Al in the crystals and / or change the manner in which the crystals terminate such that access to the trivalent elements is enhanced. The molecular sieve crystals produced by the process of the invention may have increased surface area, particularly external surface area, compared to crystals of the same molecular sieve prepared by the same process but in the absence of morphology modifier L. The molecular sieve crystals produced by the process of the invention may have a higher external surface acidity, e.g., as measured by collidine adsorption, than crystals of the same molecular sieve prepared by the same process but in the absence of morphology modifier L. The reduced crystal size and / or increased external surface area and / or increased external acidity can lead to increased activity and / or increased selectivity of the molecular sieve when used as a component in a catalyst, e.g., in hydrocarbon conversion reactions.

[0011] The process of the present invention has been found to produce zeolites having crystals with increased external surface area and / or increased surface acidity compared to the same zeolites prepared under the same conditions except in the absence of morphology modifier L.

[0012] In another aspect, the present invention provides a molecular sieve having a framework code selected from the group consisting of MEI, TON, MRE, MWW, MFS, MOR, FAU, EMT and MSE, wherein the ratio of external surface area to internal surface area is 1.2 or greater and / or the ratio of external acidity, as measured by collidine adsorption, to internal acidity, as measured by ammonia adsorption, is greater than 1.5.

[0013] The present invention also provides the molecular sieve of the present invention in its as-prepared form. The present invention further provides the molecular sieve of the present invention in its calcined form.

[0014] The present invention further provides a catalyst comprising the molecular sieve of the present invention.

[0015] The present invention further provides a hydrocarbon conversion process comprising the step of contacting a hydrocarbon feedstock with the catalyst of the present invention. In one embodiment, the hydrocarbon conversion process is a dewaxing process. In another embodiment, the hydrocarbon conversion process is a process for aromatic alkylation. [Brief description of the drawings]

[0016] [Figure 1] FIG. 1 shows olefin yield versus amount of methanol exposure for various ZSM-48 catalysts. [Diagram 2] 1 shows paraffin yield versus amount of methanol exposure for various ZSM-48 catalysts. [Diagram 3] 1 shows the combined olefin and aromatic yield versus amount of methanol exposure for various ZSM-48 catalysts. [Figure 4] 1 shows the combined yield of olefins, aromatics and unknowns versus amount of methanol exposure for various ZSM-48 catalysts. [Diagram 5] FIG. 1 shows olefin yield versus amount of methanol exposure for ZSM-48 catalysts synthesized with various zeolite growth modifiers. [Figure 6]1 shows paraffin yield versus amount of methanol exposure for ZSM-48 catalysts synthesized with various zeolite growth modifiers. [Figure 7] FIG. 1 shows the combined olefin and aromatic yields versus amount of methanol exposure for ZSM-48 catalysts synthesized with various zeolite growth modifiers. [Figure 8] 1 shows the combined yield of olefins, aromatics, and unknowns versus amount of methanol exposure for ZSM-48 catalysts synthesized with various zeolite growth modifiers. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0017] The process for producing the molecular sieve according to the invention involves preparing a synthesis mixture according to the prior art, except that the synthesis mixture also contains a morphology modifier L. Without wishing to be bound by any theory, it is believed that the morphology modifier L may bind or otherwise interact with the growing surfaces of the crystallites in the synthesis mixture, thereby affecting the morphology, including size, aspect ratio and aggregation / agglomeration, of the final product crystals. Depending on the nature of the morphology modifier L and the concentration used, the product crystals may be smaller or larger than would otherwise be obtained using the same synthesis mixture without the morphology modifier L under the same conditions. The morphology modifier L may also affect the distribution of any trivalent elements present, and therefore the surface acidity of the molecular sieve.

[0018] synthetic mixture As mentioned above, the synthesis mixture can be prepared according to conventional methods. The morphology modifier L can be included in the synthesis mixture at any time during the crystallization process, but is preferably combined with the other components before the crystal nucleation or crystallization begins. Optionally, the morphology modifier L is combined with the other components of the synthesis mixture before the source of the tetravalent element X is added. For example, 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 components can also be combined in any order to form a mixture, and then a source of the tetravalent element is combined with the mixture.

[0019] In the molecular sieve of the present invention, the tetravalent element X is Si. Suitable sources of silicon (Si) that can be used to prepare the synthesis mixture include silica; colloidal suspensions of silica, such as Ludox®; precipitated silica; alkali metal silicates, such as potassium silicate and sodium silicate; tetraalkyl orthosilicates; and fumed silicas, such as Aerosil and Cabosil.

[0020] The synthesis mixture also optionally contains a source of hydroxide ions, for example the synthesis mixture may contain an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide. Hydroxide may also be present as the anion of any charged (organic) structure directing or modifying agent that may be present through the use of sodium aluminate or potassium aluminate as the source of Y or through the use of sodium silicate or potassium silicate as the source of X. Sodium or potassium salts of aluminic and silicic acids are preferably present as anions of alkali metals M + It can also be used as a source of

[0021] 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 synthesis mixture depend on the element Y selected (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 aluminas, such as boehmite, gibbsite, and pseudoboehmite, and mixtures thereof. Other sources of aluminum include, but are not limited to, other water-soluble aluminum salts, alkali metal aluminate solids or liquids, aluminum alkoxides, such as aluminum isopropoxide, or aluminum metal, such as aluminum in the form of chips or powder.

[0022] Besides or in addition to the above sources of Si and Al, sources containing both Si and Al elements can also be used as sources of Si and Al. Examples of suitable sources containing Si and Al elements include amorphous silica-alumina gel or dry silica-alumina powder, silica-alumina, clays such as kaolin, metakaolin and zeolites, especially aluminosilicates such as synthetic faujasites and ultrastable faujasites such as USY, beta, or other large 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, if present, is P. Suitable sources of phosphorus include one or more sources selected from the group consisting of phosphoric acid; organic phosphates such as triethyl phosphate, tetraethylammonium phosphate; aluminophosphates; phosphates such as alkali metal phosphates, dihydrogen phosphate, hydrogen phosphate and pyrophosphate, and mixtures thereof.

[0023] Optionally, a halide ion W - When present, is selected from the group consisting of chloride, bromide, fluoride and mixtures thereof. The source of halide ions may 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, such as metal halides, preferably where the metal is sodium, potassium, calcium, magnesium, strontium or barium. Suitable sources of fluoride ions (F-) include HF; ammonium fluoride or tetraalkylammonium fluoride, such as tetramethylammonium fluoride or tetraethylammonium fluoride; fluoride-containing salts, such as NaF and KF; compounds of fluoride with elements X, Y, such as AlF3 and SiF6 salts; and / or compounds where fluoride ions are present as counterions of the cationic structure directing agent (Q). If the synthesis mixture does not include a source of hydroxide ions, it preferably contains a source of fluoride ions, which can also act as a mineralizer. A convenient source of halide ions is HF.

[0024] Optionally, the synthesis mixture comprises an alkali metal cation M + and / or alkaline earth metal cation M 2+ If present, the alkali metal cation M + is preferably Li + , Na + , K + , Rb + and Cs + and mixtures thereof. + Suitable sources of K may include sodium salts such as NaCl, NaBr, NaF or NaNO3; sodium hydroxide, sodium aluminate and mixtures thereof. + Suitable sources of 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+ , B.A. 2+ and mixtures thereof.

[0025] Structure directing agents (Q) are compounds known to affect the crystallization of the molecular sieve framework to promote the formation of a particular desired molecular sieve. For example, tetrapropylammonium hydroxide or bromide is often used to produce ZSM-5. In contrast, the role of the morphology modifier (L) is to affect the crystallization to modify the crystal size, external surface area and / or external acidity of the molecular sieve, as described above, rather than affecting the identity of the molecular sieve. If the molecular sieve is one that requires the use of a structure directing agent Q, the synthesis mixture will also contain an effective concentration of the structure directing agent. In that case, the morphology modifier L will be different from and in addition to the structure directing agent Q. ZSM-18, ZSM-22, ZSM-48, MCM-49, ZSM-57, mordenite and MCM-68 require the use of a structure directing agent. The nature of the structure directing agent Q will depend on the desired framework type. Suitable structure directing agents are known to those skilled in the art. The structure directing agent Q may be present 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 will generally be 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 chains having more than 10 carbon atoms. For example, the structure directing agent Q may optionally be N,N,N-trimethyl-1-adamantammonium hydroxide (TMAdA) when it is desired to produce a zeolite of framework type CHA. Further structure directing agents Q and related zeolites are listed below: ZSM-48: Hexamethonium dichloride (Diquat-6-Cl2), Hexamethonium dihydroxide (Diquat-6-OH2), Pentamethonium dichloride (Diquat-5-Cl2), Pentamethonium dihydroxide (Diquat-5-OH2), Octylamine, 1,6-Diaminohexane, Pyrrolidine, Propylamine / Tetramethylammonium Hydroxide, Bis(N-methylpyridyl)ethylinium, Diethylenetriamine, Triethylenetetramine, Tetraethylenepentamine, 1,4,8,11-Tetra-aza-undecane, 1,5,9,13-Tetra-aza-undecane, 1,5,8,12-Tetra-aza-undecane, 1,3-Diaminopropane, Trimethylamine; ZSM-18: 2,3,4,5,6,7,8,9-octahydro-2,2,5,5,8,8-hexamethyl-1 1H-benzo[1,2-c:3,4-c':5,6-c"]tripyrrolium hydroxide and chloride, butamesonium hydroxide / tetramethylammonium hydroxide; ZSM-22: 1-aminobutane, diethylamine, ethylenediamine, 1,3-diaminopropane, 1,6-diaminohexane, 1,4,8,11-tetra-aza-undecane, 1,5,9,13-tetra-aza-undecane, 1,5,8,12-tetra-aza-undecane, N-ethylpyridinium; ZSM-57: hexaethyl-diquat-5 dichloride, hexaethyl-diquat-5 dihydroxide; Mordenite: Tetraethylammonium hydroxide, tetraethylammonium bromide, benzyltrimethylammonium chloride, benzyltrimethylammonium hydroxide, N-ethylpyridinium bromide, N-ethylpyridinium hydroxide, trioctylamine, alkylphenols / alkylsulfonates; MWW (including MCM-49, MCM-22, MCM-56): hexamethyleneimine, aniline, piperidine, diethyldimethylammonium hydroxide, ethyltrimethylammonium hydroxide, choline chloride, choline hydroxide, N-N,N',N'-tetramethyl-1,6-diaminohexane, triethylamine, hexamethonium dihydroxide, triethanolamine; Hexagonal faujasite (EMT): methyltriethylammonium hydroxide, tetraethylammonium hydroxide, 18-crown-6; Cubic faujasite (FAU): 15-crown-5; MCM-68: N,N,N',N'-tetraethylbicyclo[2.2.2]-oct-7-ene-2R,3S:5R,6S-dipyrrolidinium diiodide, N,N,N',N'-tetraethylbicyclo[2.2.2]-oct-7-ene-2R,3S:5R,6S-dipyrrolidinium dihydroxide, N,N-dimethyl-4-cyclohexylpiperazinium hydroxide, 1-butyl-1-methylpiperidinium hydroxide.

[0026] Those structure directing agents Q, if present in the synthesis mixture to promote the formation of the relevant molecular sieves, are not considered to be morphology modifiers L according to the present invention.

[0027] For embodiments related to the synthesis of ZSM-48 (or other MRE framework zeolites listed in the Zeolite Database maintained by the International Zeolite Association), any convenient structure directing agent suitable for use in the synthesis mixture for the formation of ZSM-48 can be used as the primary structure directing agent. One option can be to use a diquaternary alkyl ammonium salt (diquat-6) having a chain of six carbon atoms between the ammonium ions. Another option can be to use a diquaternary alkyl ammonium salt (diquat-5) having a chain of five carbon atoms between the ammonium ions. Both diquat-5 and diquat-6 are known to be suitable as structure directing agents for the formation of ZSM-48, but the resulting ZSM-48 crystals produced by diquat-5 and diquat-6 are typically different.

[0028] The synthesis mixture can have any composition that is suitable for preparing the desired zeolite framework. The following ranges are given as examples of desirable and preferred ranges for each pair of components in the synthesis mixture. Conveniently, the molar ratio of XO2:Y2O3 in the synthesis mixture can range from 2 to infinity (i.e. no Y), in particular from 5 to 500, preferably from 5 to 200. Optionally, in the synthesis mixture, the molar ratio of structure directing agent Q:(XO2+Y2O3+Z2O5) ranges from 0.01 to 1.0, preferably from 0.02 to 0.9, optionally from 0.04 to 0.5. Optionally, in the synthesis mixture, the molar ratio of H2O:(XO2+Y2O3+Z2O5) ranges from 5 to 100. Optionally, in the synthesis mixture, the molar ratio of 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 synthesis 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, in the synthesis mixture, a halide -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, for example, a composition expressed in molar ratios as shown in Table 1 below.

[0029] [Table 1]

[0030] Water may be added in any amount suitable to dissolve the components and prepare the desired molecular sieve. The synthesis mixture contains an aqueous liquid phase and may also contain some insoluble solid components as well as crystallized molecular sieves. The liquid present in the synthesis mixture is substantially single-phase, typically an aqueous solution, a gel phase, a slurry, a paste or a wet powder. The liquid present in the synthesis mixture typically contains less than 5% by weight, optionally less than 2% by weight, optionally 1% by weight of non-water-soluble liquid components. In particular, the liquid present in the synthesis mixture is not an emulsion or microemulsion. The synthesis may be carried out without or with the addition of nucleation seeds. If nucleation seeds are added to the synthesis mixture, the seeds are suitably present in an amount of about 0.01 to 10.0% by weight based on the synthesis mixture, for example, about 0.01 to 2.0% by weight of the synthesis mixture. The seeds can be any suitable zeolite, which can be, for example, a zeolite having the same or a different framework than the resulting zeolite.

[0031] Morphology Modifier L The morphology modifier L is selected from the group consisting of cationic surfactants having a quaternary ammonium group containing at least one hydrocarbyl, preferably alkyl group, having at least 12 carbon atoms, nonionic surfactants, anionic surfactants, sugars, and combinations thereof. The morphology modifier may be added to the synthesis mixture at any time before crystallization is complete. Optionally, the morphology modifier L is added to the other components of the synthesis mixture before crystal nucleation or crystallization begins. Mixtures of two or more morphology modifiers L may also be used, and such processes are within the scope of the present invention.

[0032] The morphology modifier may be a sugar. The sugar may be a monosaccharide or a disaccharide. Suitable monosaccharides include glucose, fructose and galactose, especially fructose. Suitable disaccharides include saccharose, maltose and lactose. The sugar may be a pentose. Alternatively, the sugar may be a hexose.

[0033] The morphology modifier L may be a cationic surfactant having a quaternary ammonium group containing at least one hydrocarbyl having at least 12 carbon atoms. The at least one hydrocarbyl 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 hydrocarbyl optionally has at least 14 carbon atoms, optionally at least 16 carbon atoms, optionally at least 18 carbon atoms. Optionally, the at least one hydrocarbyl has up to 30 carbon atoms. The alkyl may be saturated or unsaturated, preferably saturated. The cationic surfactant may contain two hydrocarbyls, 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 are optionally alkyls having 1 to 8, optionally 1 to 4 carbon atoms, such as alkyls having methyl groups. Each hydrocarbyl may optionally contain one or more heteroatoms selected from oxygen, sulfur, nitrogen and halides.

[0034] The morphology modifier L may be a cationic surfactant having a single quaternary ammonium group containing at least one alkyl having at least 12 carbon atoms. The at least one alkyl 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 optionally has at least 14 carbon atoms, optionally at least 16 carbon atoms, optionally at least 18 carbon atoms. Optionally, the at least one alkyl has up to 30 carbon atoms. The alkyl may be saturated or unsaturated, preferably saturated. The cationic surfactant may include two alkyls each having at least 12 carbon atoms bonded to the nitrogen atom of the quaternary ammonium group. The other substituent on the nitrogen atom of the quaternary ammonium group is optionally an alkyl having 1 to 8, optionally 1 to 4 carbon atoms, such as an alkyl having a methyl group.

[0035] A cationic surfactant may contain two or more such quaternary ammonium groups, or alternatively, a cationic surfactant may contain only a single (i.e., one or less) quaternary ammonium group.

[0036] The cationic surfactant may contain any suitable anion, such as hydroxide or halide, as a counterion. OH - , F - , Cl - and Br - is the preferred counterion.

[0037] The morphology modifier L optionally has the formula (1): (R 1 ) q (R 2 ) 4-q N + (X n- ) 1 / n (1) (Wherein, each R 1are independently C1-C6, optionally C1-C4 hydrocarbyl groups which may be linear or branched, saturated or unsaturated, preferably linear and saturated, and each hydrocarbyl may optionally contain one or more heteroatoms selected from oxygen, sulfur, nitrogen and halides; R 2 C may be 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 hydrocarbyls, and each hydrocarbyl may contain one or more aromatic or aliphatic cyclic groups and / or optionally one or more heteroatoms selected from oxygen, sulfur, nitrogen and halides; q is 1 or 2, preferably 1; X n- is an anion of valence n, n being preferably 1, and X n- is optionally a hydroxy anion or a halide anion, in particular a halide anion selected from fluoride, chloride or bromide, R 1 is optionally methyl).

[0038] Preferably, each R 1 are independently C1-C6, optionally C1-C4 alkyl groups which may be linear or branched, saturated or unsaturated, preferably linear and saturated. 2 C may be 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 a hydrocarbyl.

[0039] Optionally, the morphology modifier L is represented by formula (2): (R 3 )3R 4 N + A - (2) (In the formula, A - is an anion, preferably a hydroxide or halide, and is preferably OH - , Cl - and Br - Each R 3 is independently selected from hydrogen and C1-C4 alkyl, preferably methyl, and R 4 C may be branched or linear, saturated or unsaturated, optionally containing one or more cyclic groups, and is preferably saturated and linear. 12 ~C 30 Alkyl groups, preferably C 14 ~C 20 It is a cationic surfactant having an alkyl group.

[0040] Suitable cationic surfactants include dodecyltrimethylammonium chloride, dodecyltrimethylammonium bromide, hexadecyltrimethylammonium chloride, hexadecyltrimethylammonium bromide, octadecyltrimethylammonium chloride, octadecyltrimethylammonium bromide, hexadecylethyldimethylammonium chloride, and hexadecylethyldimethylammonium bromide.

[0041] The morphology modifier L may be a nonionic surfactant. Optionally, the nonionic surfactant is selected from the group consisting of alkyl ethoxylates, alkyl propoxylates, alkyl phenol ethoxylates, alkyl phenol 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 polyhydric compounds such as glycerol and sorbitan. For example, the morphology modifier L may be PEG-dodecyl ether or PEG oleyl ether. The morphology modifier L may be an anionic surfactant. The anionic surfactant comprises 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, the anionic surfactant is an alkyl sulfate, alkyl sulfonate, alkyl phosphate, or alkyl carboxylate. Optionally, the anionic surfactant is an alkyl sulfate, such as sodium lauryl sulfate.

[0042] The molar ratio L:X in the synthesis mixture is optionally in the range of 0.0001-0.10, optionally 0.0001-0.08, optionally 0.0001-0.05, optionally 0.0001-0.03, optionally 0.001-0.025. At lower ratios, the concentration of morphology modifier L is insufficient, which may cause a significant change in the crystal morphology, while at higher ratios, the concentration of morphology modifier is too high, which may hinder crystallization, significantly reducing the crystallization rate, or cause the formation of another molecular sieve framework instead of the desired one.

[0043] The morphology modifier L is optionally present in the synthesis mixture at a concentration in the range of 0.01 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 synthesis mixture.

[0044] Crystallization and Recovery Crystallization can be carried out under static or stirred conditions in suitable reactor vessels, such as, for example, polypropylene jars or Teflon bottles, acid digestion vessels, Teflon-coated or stainless steel autoclaves, plow shear mixers or reaction kettles. Crystallization is typically carried out at a temperature of about 80°C to about 250°C, optionally 100°C to about 200°C, optionally about 150°C to about 170°C, for a time sufficient for crystallization to occur at the temperature used, for example, about 1 day to about 100 days, particularly 1 to 50 days, for example, about 2 days to about 40 days. The synthesized crystals are then separated from the mother liquor by any convenient method, such as filtration or centrifugation, and recovered. The crystals are then dried, for example, under ambient conditions, washed with a low boiling solvent such as acetone, methanol, ethanol or propanol, or using microwave conditions, or oven dried at temperatures up to 150°C.

[0045] Firing The process optionally includes calcining the crystals recovered in step c) to obtain a calcined form of the molecular sieve. Calcination conditions will be selected to at least partially remove any remaining organic residues, such as residual morphology modifier L and / or structure directing agent Q (if present), that are typically trapped in the pores of the molecular sieve in its "as-produced" form.

[0046] The calcination step typically involves heating the zeolite at a temperature of at least about 200° C., preferably at least about 300° C., more preferably at least about 370° C., for at least 1 minute, generally no more than 20 hours. Although subatmospheric pressures can be utilized for the heat treatment, atmospheric pressure is usually desirable for reasons of convenience. The heat treatment can be carried out at a temperature up to about 925° C. For example, the heat treatment can be carried out in the presence of an oxygen-containing gas, e.g., in air, at a temperature of 400-600° C., e.g., 500-550° C.

[0047] The molecular sieve may be subjected to an ion exchange treatment with aqueous ammonium salts, such as ammonium nitrate, ammonium chloride and ammonium acetate, to remove residual alkali metal and / or alkaline earth metal cations and exchange them with protons, thereby producing the acid form of the molecular sieve. To the desired extent, the original cations of the as-synthesized material, such as alkali metal cations, may 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 tailor the catalytic activity to a particular hydrocarbon conversion reaction. These may 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 of the Elements. The ion exchange step may be carried out after drying the as-produced molecular sieve. The ion exchange step may be carried out before or after the calcination step.

[0048] The molecular sieve may be subjected to other treatments, such as steaming and / or washing with solvents, which are well known to those skilled in the art and are carried out to modify the properties of the molecular sieve as desired.

[0049] Molecular Sieves The molecular sieves of the present invention and those produced by the process of the present invention have a framework structure code selected from the group consisting of MEI, TON, MRE, MWW, MFS, MOR, FAU, EMT and MSE. Optionally, the molecular sieve is a zeolite selected from the group consisting of ZSM-18, ZSM-22, ZSM-48, MCM-49, ZSM-57, mordenite, cubic faujasite, hexagonal faujasite and MCM-68. Details of framework type and pore size are given in Table 2 below.

[0050] [Table 2]

[0051] Optionally, the molecular sieve is selected from the group consisting of ZSM-18, ZSM-22, ZSM-48, MCM-49, ZSM-57, cubic faujasite and hexagonal faujasite. Optionally, the molecular sieve is selected from the group consisting of ZSM-18 and ZSM-48. Optionally, the molecular sieve is selected from the group consisting of MCM-49, ZSM-57 and mordenite. Optionally, the molecular sieve is selected from the group consisting of cubic faujasite, hexagonal faujasite and MCM-68. ZSM-48 and MCM-49 are particularly preferred molecular sieves.

[0052] ZSM-12, ZSM-23, ZSM-50, zeolite beta, ZSM-10, chabazite and zeolite A are all further molecular sieves which may be produced according to the process of the present invention, and thus the molecular sieve of the present invention may in another embodiment be selected from the group consisting of ZSM-12, ZSM-18, ZSM-22, ZSM-48, MCM-49, ZSM-57, cubic faujasite, hexagonal faujasite, ZSM-23, ZSM-50, zeolite beta, ZSM-10, chabazite and zeolite A.

[0053] The molecular sieve produced by the process of the invention may have an increased surface area compared to the same molecular sieve produced in the absence of morphology modifier L. Optionally, the molecular sieve produced by the process of the invention has an external surface area that is at least 1.1 times, and optionally at least 1.2 times, the external surface area of ​​the same molecular sieve produced in the absence of morphology modifier L.

[0054] The molecular sieve produced by the process of the invention may have increased external acidity, as measured by collidine adsorption, compared to the same molecular sieve produced in the absence of morphology modifier L. Optionally, the molecular sieve produced by the process of the invention has an external acidity that is at least 1.1 times, optionally at least 1.2 times, the external acidity of the same molecular sieve produced in the absence of morphology modifier L.

[0055] Alternatively, the molecular sieve produced by the process of the present invention has a reduced external surface area and / or reduced external acidity compared to the same molecular sieve produced in the absence of morphology modifier L.

[0056] By selecting the appropriate morphology modifier L and the appropriate concentration of that morphology modifier, one skilled in the art can prepare molecular sieves having a range of external surface areas, external acidities and / or crystallite sizes.

[0057] In some embodiments, for molecular sieves with one-dimensional pore channel structure, such as MRE (ZSM-48), a small crystal size may be beneficial to improve catalyst life. Without being bound to any particular theory, it is believed that for one-dimensional pore channel molecular sieves, having a shorter crystal length in the direction of the pore channel can reduce or minimize the rate of coke formation. This allows for the processing of larger amounts of feed, such as larger amounts of oxygenate loss under oxygenate conversion conditions, while maintaining activity. As used herein, catalyst exposure life refers to the amount of oxygenate that a catalyst can process under oxygenate conversion conditions before the activity of the catalyst for conversion becomes substantially zero.

[0058] The molecular sieves of the present invention preferably have a ratio of external surface area to internal surface area greater than 1.20 and / or a ratio of external acidity, as measured by collidine adsorption, to internal acidity, as measured by ammonia adsorption, greater than 1.50.

[0059] In some embodiments, the molecular sieves produced by the processes described herein, either in calcined or as-produced form, can form agglomerates of small crystals that can have crystal sizes ranging from 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, which leads to a greater number of active catalytic sites for a given amount of catalyst.

[0060] Optionally, the zeolite contains Si and Al and has a SiO2:Al2O3 molar ratio of 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 framework structure provides acidic sites to the catalyst, but it is also associated with a decrease in the thermal stability of the zeolite. Many industrial organic feedstock conversion processes are carried out at temperatures that require the use of zeolite supports with SiO2:Al2O3 molar ratios greater than 6:1, or even greater than 10:1.

[0061] The molecular sieve has a crystallinity of at least 80%, optionally at least 90%, preferably at least 95%, and most preferably at least 98%. In one embodiment, the molecular sieve is an essentially pure crystalline material. The crystallinity can be calculated by X-ray diffraction (XRD).

[0062] In one embodiment, the molecular sieve is in its as-prepared form and optionally contains a structure directing agent Q within its pores.

[0063] In another embodiment, the molecular sieve does not include any structure directing agent Q. For example, the molecular sieve may be one that can be synthesized without any structure directing agent Q.

[0064] The molecular sieve may be in a calcined form. The 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.

[0065] The calcined acid form of the molecular sieve of the present invention preferably has 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 a molecular sieve produced using an equivalent process except that the synthesis mixture does not contain any morphology modifier. External acidity may be measured by collidine adsorption.

[0066] The calcined acid form of the molecular sieve of the present invention has an external surface area that is at least 1.10 times, more preferably at least 1.20 times, and in some cases at least 1.30 times, that of a molecular sieve produced using an equivalent process except that the synthesis mixture does not contain any morphology modifier. The external surface area may be measured by BET.

[0067] The molecular sieve of the present invention in its calcined form has a ratio of external surface area to internal surface area greater than 1.20 and / or a ratio of external acidity, as measured by collidine adsorption, to internal acidity, as measured by ammonia adsorption, greater than 1.50.

[0068] The molecular sieves of the present invention or those produced by the process of the present invention may be used as adsorbents or catalysts to catalyze a wide variety of organic compound conversion processes, including many of current commercial / industrial importance. Examples of preferred chemical conversion processes that can be effectively catalyzed by the zeolites of the present invention or those produced by the process of the present invention, alone or in combination with one or more other catalytically active materials, including other crystalline catalysts, include those that require catalysts with acid activity or hydrotreating activity. Examples of organic conversion processes that can be catalyzed by the zeolites of the present invention or those produced by the process of the present invention include cracking, hydrocracking, isomerization, polymerization, reforming, hydrogenation, dehydrogenation, dewaxing, hydrodesorption, adsorption, alkylation, transalkylation, dealkylation, hydrodecyclization, disproportionation, oligomerization, dehydrocyclization, and combinations thereof. The conversion of the hydrocarbon feedstock can be carried out in any convenient mode, for example, in a fluidized bed, ebullated bed, moving bed, or fixed bed reactor, depending on the type of process required.

[0069] Once the molecular sieve is synthesized, it can be formulated into a catalyst composition by combining it with other materials, such as binder and / or matrix materials, that provide additional hardness or catalytic activity to the finished catalyst. These other materials can be inert or catalytically active materials.

[0070] In particular, it may be desirable to incorporate the molecular sieve of the present invention or the molecular sieve produced by the process of the present invention with another material that is resistant to the temperatures and other conditions utilized in organic conversion processes. Such materials include synthetic or natural zeolites, as well as inorganic materials such as clays, silica and / or metal oxides such as alumina, yttria, zirconium oxide, gallium oxide, zinc oxide, and mixtures thereof. The metal oxides may be naturally occurring or in the form of gelatinous precipitates or gels that include mixtures of silica and metal oxides. Naturally occurring clays that may be used include the montmorillonite and kaolin families, including sub-bentonite, and kaolins commonly known as Dixie, McNamee, Georgia, and Florida clays, or others whose major mineral components are halloysite, kaolinite, dickite, nacrite, or anoxite. Such clays may be used in the raw state as originally mined, or after having been subjected to calcination, acid treatment, or chemical modification. These binder materials are resistant to temperature and other conditions, such as mechanical friction, encountered in various hydrocarbon conversion processes. Thus, 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 extrudates with a binder. They are typically bound by forming tablets, spheres or extrudates. The extrudates are usually formed by extruding the molecular sieves, optionally in the presence of a binder, and then drying and calcining the resulting extrudates. Further processing, such as steam treatment, addition of catalytic metals and / or ion exchange, may be carried out as required. The molecular sieves are optionally bonded to a matrix of at least 200 m 2 / g, optionally at least 300m 2 / g of surface area.

[0071] Binders may suitably function as diluents to control the amount of conversion in a given process so that products can be obtained in an economical and regular manner without utilizing other means to control the reaction rate. These materials may be incorporated into naturally occurring clays, such as bentonite and kaolin, to improve the crushing power of the catalyst under commercial operating conditions.

[0072] 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-thoria, silica-beryllia, silica-titania, and ternary compositions such as silica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesia, and silica-magnesia-zirconia.

[0073] The relative proportions of molecular sieve and inorganic oxide matrix can vary widely, with the molecular sieve content ranging from about 1 to about 100 weight percent, and more usually ranging from about 2 to about 95, optionally about 20 to about 90 weight percent of the composite, particularly when the composite is prepared in the form of an extrudate.

[0074] Additional Embodiments Additionally or alternatively, the present disclosure can include one or more of the following embodiments.

[0075] Embodiment 1. A process for the preparation of crystals of molecular sieves having a framework code selected from the group consisting of MEI, TON, MRE, MWW, MFS, MOR, FAU, EMT and MSE, comprising the steps of: a. a source of tetravalent element X, a morphological modifier L, water, optionally a source of hydroxide ions, optionally a structure directing agent Q, optionally a source of trivalent element Y, optionally a source of pentavalent element Z, optionally a halide ion W - and optionally a source of alkali metal ions M + and / or a source of alkaline earth metal cation M 2+and optionally one or more other components to form a synthetic mixture; b. heating the synthesis mixture under crystallization conditions for a time period between about 1 hour and 100 days to form molecular sieve crystals; c. recovering said crystals of molecular sieve from the synthesis mixture; wherein X=Si, and the morphology modifier L is selected from the group consisting of cationic surfactants having a quaternary ammonium group containing at least one hydrocarbyl group having at least 12 carbon atoms, nonionic surfactants, anionic surfactants, sugars, and combinations thereof, and when structure directing agent Q is present, L is different from structure directing agent Q and is present in addition to structure directing agent Q.

[0076] Embodiment 2. The process of embodiment 1, wherein the molar ratio of L:X in the synthesis mixture is in the range of 0.001 to 0.03.

[0077] Embodiment 3. The process of embodiment 1 or 2, wherein Y is present in the synthesis mixture, and Y is Al, and the ratio of XO2:Y2O3 is in the range of 5-500.

[0078] Embodiment 4. The process of any one of embodiments 1 to 3, wherein the ratio Q:(XO2+Y2O3+Z2O5) is in the range of 0.01 to 1.0.

[0079] Embodiment 5. The process of any one of embodiments 1 to 4, wherein the morphology modifier L is a cationic surfactant having a single quaternary ammonium group, and the single ammonium group comprises at least one C12 to C30 alkyl group bonded to the quaternary ammonium group.

[0080] Embodiment 6. The morphology modifier L is represented by the formula (1) (R 1 ) q (R 2 ) 4-q N + (X n- ) 1 / n (1) (Wherein, each R 1 are independently C1-C6, optionally C1-C4 hydrocarbyl groups which may be linear or branched, saturated or unsaturated, preferably linear and saturated, and each hydrocarbyl may optionally contain one or more heteroatoms selected from oxygen, sulfur, nitrogen and halides; R 2 C may be 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 are hydrocarbyl groups, and each hydrocarbyl may optionally contain one or more heteroatoms selected from oxygen, sulfur, nitrogen, and halides; q is 1 or 2, preferably 1; X n- The process of any one of embodiments 1 to 5, wherein the cationic surfactant has a valence of n.

[0081] Embodiment 7. The process of any one of embodiments 1 to 6, wherein the morphology modifier L is a monosaccharide.

[0082] Embodiment 8. The process of any one of embodiments 1 to 7, wherein the morphology modifier L is an anionic surfactant.

[0083] Embodiment 9. The process of any one of embodiments 1 to 8, wherein the morphology modifier L is a nonionic surfactant.

[0084] Embodiment 10. The process of any one of embodiments 1 to 9, wherein the synthesis mixture is substantially free of water-insoluble liquid components.

[0085] Embodiment 11. The process of any one of embodiments 1 to 10, comprising calcining the crystals recovered in step c) to obtain a calcined form of the molecular sieve.

[0086] Embodiment 12. The process of any one of embodiments 1 to 12, wherein the molecular sieve is a zeolite selected from the group consisting of ZSM-18, ZSM-22, ZSM-48, MCM-49, ZSM-57, mordenite, cubic faujasite, hexagonal faujasite, and MCM-68.

[0087] Embodiment 13. A molecular sieve having a framework code selected from the group consisting of MEI, TON, MRE, MWW, MFS, MOR, FAU, EMT and MSE, wherein the ratio of external surface area to internal surface area is greater than 1.2 and / or the ratio of external acidity as measured by collidine adsorption to internal acidity as measured by ammonia adsorption is greater than 1.5.

[0088] Embodiment 14. A molecular sieve having a framework code selected from the group consisting of MEI, TON, MRE, MWW, MFS, MOR, FAU, EMT and MSE, and having an external surface area at least 1.1 times that of the same molecular sieve produced using the same process except that the synthesis mixture does not contain any morphology modifier L, and / or an increased external acidity, as measured by collidine adsorption, compared to the same molecular sieve produced using the same process except that the synthesis mixture does not contain any morphology modifier L.

[0089] Embodiment 15. A molecular sieve according to embodiment 13 or 14, produced by the process of any one of embodiments 1 to 12.

[0090] Embodiment 16. The molecular sieve according to any one of embodiments 13 to 15, wherein the zeolite is selected from the group consisting of ZSM-18, ZSM-22, ZSM-48, MCM-49, ZSM-57, mordenite, cubic faujasite, hexagonal faujasite and MCM-68.

[0091] Embodiment 17. A catalyst comprising the molecular sieve of any one of embodiments 13 to 16, and optionally comprising a binder.

[0092] Embodiment 18. A process for converting hydrocarbons comprising contacting a hydrocarbon feedstock with the catalyst of embodiment 17.

[0093] Embodiment 19. The hydrocarbon conversion process of embodiment 18, which is a dewaxing process or an aromatic alkylation process. EXAMPLES

[0094] The synthesis of ZSM-48 was carried out according to the following procedure using hexamethonium dichloride (HMDC) as a structure directing agent and various morphology modifiers.

[0095] Example 1 (comparison). ZSM-48 reference, no morphology modifier, morphology modifier / SiO2 = 0.0, morphology modifier present at 0 wt% of total mixture. Dilute 1.26 g of 25% hexamethonium dichloride (HMDC) in 14.8 g of water. Stir to ensure homogenous solution. 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 seeds (17.2 wt. % seeds) 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 homogenous slurry. The approximate molgel composition for the mixture is as follows: SiO2 / Al2O3=100.0 OH - / SiO2=0.175 HMDC / SiO2=0.019 Modifier / SiO2=0.000 H2O / SiO2=18.7 Approximately 5100 ppm of seeds The autoclave is sealed and the mixture is kept stirred at 300 rpm using a U-shaped stirrer. The mixture is heated to 160°C (20°C / hr ramp rate) 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 shows the powder to be ZSM-48.

[0096] Transmission electron microscopy (TEM) revealed that the crystals typically had lengths in the range of 30-50 nm and widths in the range of 10-15 nm, with length:width aspect ratios of 3-5.

[0097] Example 2. ZSM-48, trimethyloctadecylammonium bromide morphology modifier, morphology modifier / SiO2=0.011, 1 wt% of total mixture Dilute 1.25g of 25% hexamethonium dichloride (HMDC) in 13.7g water. Stir to ensure homogenous solution. Add 0.61g of sodium aluminate solution (7.8% Na2O, 10.0% Al2O3, 82.8% water) to the structure directing agent solution. Stir to homogenize the solution. Add 3.6g of a 10% NaOH solution to the HMDC / aluminate solution. Stir to homogenize the mixture. Add 0.74g of colloidal beta seeds (17.2 wt% seeds) to the aluminate mixture. Add 1.28g of a 20 wt% solution of trimethyloctadecylammonium bromide (a cationic surfactant morphology modifier) ​​and stir the mixture to dissolve the morphology modifier. To this mixture is added 3.89 g of Ultrasil VN3 PM modified precipitated silica (92.4% SiO2). The mixture is stirred for 15 minutes to prepare a homogenous slurry. The approximate molgel composition for the mixture is as follows: SiO2 / Al2O3=89.3 OH - / SiO2=0.179 HMDC / SiO2=0.019 Modifier / SiO2=0.011 H2O / SiO2=17.9 Approximately 5200 ppm of seeds The autoclave is sealed and the mixture is kept stirred at 300 rpm using a U-shaped stirrer. The mixture is heated to 160°C (20°C / hr ramp rate) 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 shows the powder to be ZSM-48.

[0098] Example 3. ZSM-48, dodecyltrimethylammonium bromide morphology modifier, morphology modifier / SiO2=0.014, 1 wt% of total mixture Dilute 1.25g of 25% hexamethonium dichloride (HMDC) in 13.7g water. Stir to ensure homogenous solution. Add 0.61g of sodium aluminate solution (7.8% Na2O, 10.0% Al2O3, 82.8% water) to the structure directing agent solution. Stir to homogenize the solution. Add 3.6g of a 10% NaOH solution to the HMDC / aluminate solution. Stir to homogenize the mixture. Add 0.73g of colloidal beta seeds (17.2 wt% seeds) to the aluminate mixture. Add 1.26g of a 20 wt% solution of dodectyltrimethylammonium bromide (a cationic surfactant morphology modifier) ​​and stir the mixture to dissolve the morphology modifier. To this mixture is added 3.89 g of Ultrasil VN3 PM modified precipitated silica (92.4% SiO2). The mixture is stirred for 1 hour to prepare a homogenous slurry. The approximate molgel composition for the mixture is as follows: SiO2 / Al2O3=97.2 OH - / SiO2=0.176 HMDC / SiO2=0.019 Modifier / SiO2=0.014 H2O / SiO2=17.9 Approximately 5200 ppm of seeds The autoclave is sealed and the mixture is kept stirred at 300 rpm using a U-shaped stirrer. The mixture is heated to 160°C (20°C / hr ramp rate) 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 shows the powder to be ZSM-48.

[0099] Example 4. ZSM-48, ethylhexadecyldimethylammonium bromide morphology modifier, morphology modifier / SiO2=0.011, 1 wt% of total mixture Dilute 1.27g of 25% hexamethonium dichloride (HMDC) in 13.7g water. Stir to ensure homogenous solution. Add 0.62g of sodium aluminate solution (7.8% Na2O, 10.0% Al2O3, 82.8% water) to the structure directing agent solution. Stir to homogenize the solution. Add 3.6g of 10% NaOH solution to the HMDC / aluminate solution. Stir to homogenize the mixture. Add 0.73g of colloidal beta seeds (17.2 wt% seeds) to the aluminate mixture. Add 1.25g of a 20 wt% solution of ethylhexadecyldimethylammonium bromide (a cationic surfactant morphology modifier) ​​and stir the mixture to dissolve the morphology modifier. To this mixture is added 3.89 g of Ultrasil VN3 PM modified precipitated silica (92.4% SiO2). The mixture is stirred for 15 minutes to prepare a homogenous slurry. The approximate molgel composition for the mixture is as follows: SiO2 / Al2O3=98.2 OH - / SiO2=0.176 HMDC / SiO2=0.019 Modifier / SiO2=0.011 H2O / SiO2=17.9 Approximately 5100 ppm of seeds The autoclave is sealed and the mixture is kept stirred at 300 rpm using a U-shaped stirrer. The mixture is heated to 160°C (20°C / hr ramp rate) 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 shows the powder to be ZSM-48.

[0100] Example 5. ZSM-48, cetyltrimethylammonium bromide morphology modifier, morphology modifier / SiO2=0.023, 2% by weight of total mixture Dilute 1.24g of 25% hexamethonium dichloride (HMDC) in 12.5g water. Stir to ensure homogenous solution. Add 0.61g of sodium aluminate solution (7.8% Na2O, 10.0% Al2O3, 82.8% water) to the structure directing agent solution. Stir to homogenize the solution. Add 3.6g of a 10% NaOH solution to the HMDC / aluminate solution. Stir to homogenize the mixture. Add 0.73g of colloidal beta seeds (17.2 wt% seeds) to the aluminate mixture. Add 2.25g of a 20 wt% solution of cetyltrimethylammonium bromide (a cationic surfactant morphology modifier) ​​and stir the mixture to dissolve the morphology modifier. To this mixture is added 3.89 g of Ultrasil VN3 PM modified precipitated silica (92.4% SiO2). The mixture is stirred for 1 hour to prepare a homogenous slurry. The approximate molgel composition for the mixture is as follows: SiO2 / Al2O3=99.3 OH - / SiO2=0.174 HMDC / SiO2=0.019 Modifier / SiO2=0.023 H2O / SiO2=16.8 Approximately 5100 ppm of seeds The autoclave is sealed and the mixture is kept stirred at 300 rpm using a U-shaped stirrer. The mixture is heated to 160°C (20°C / hr ramp rate) 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 shows the powder to be ZSM-48.

[0101] Example 5B Additional ZSM-48 crystals were synthesized using the same reaction mixture as in Example 5, except that 1 wt% CTAB was used instead of 2 wt%. Transmission electron microscopy (TEM) revealed that the crystals had a median crystal length of about 53 nm and an aspect ratio of about 2.2.

[0102] Example 6. ZSM-48, Brij L4 morphology modifier, morphology modifier / SiO2=0.017, 1.6 wt% of total mixture Dilute 1.24g of 25% hexamethonium dichloride (HMDC) in 13.0g water. Stir to ensure homogenous solution. Add 0.59g 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 3.6g of a 10% NaOH solution to the HMDC / aluminate solution. Stir to homogenize the mixture. Add 0.75g of colloidal beta seeds (16.7 wt% seeds) to the aluminate mixture. Add 1.96g of a 19.2 wt% solution of Brij L493 (polyethylene glycol dodecyl ether as a nonionic surfactant morphology modifier) ​​and stir the mixture to dissolve the zeolite growth modifier. To this mixture is added 3.89 g of Ultrasil VN3 PM modified precipitated silica (92.4% SiO2). The mixture is stirred for 15 minutes to prepare a homogenous slurry. The approximate molgel composition for the mixture is as follows: SiO2 / Al2O3=100.0 OH - / SiO2=0.175 HMDC / SiO2=0.019 Modifier / SiO2=0.017 H2O / SiO2=18.7 Approximately 5200 ppm of seeds The autoclave is sealed and the mixture is kept stirred at 300 rpm using a U-shaped stirrer. The mixture is heated to 160°C (20°C / hr ramp rate) 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 shows the powder to be ZSM-48.

[0103] Example 7. ZSM-48, Brij 93 morphology modifier, morphology modifier / SiO2=0.018, 1.7 wt% of total mixture Dilute 1.27g of 25% hexamethonium dichloride (HMDC) in 12.9g water. Stir to ensure homogenous solution. Add 0.59g 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 3.6g of 10% NaOH solution to the HMDC / aluminate solution. Stir to homogenize the mixture. Add 0.75g of colloidal beta seeds (16.7 wt% seeds) to the aluminate mixture. Add 2.02g of an 18.54 wt% solution of Brij 93 (polyethylene glycol roleyl ether as a nonionic surfactant morphology modifier) ​​and stir the mixture to dissolve the zeolite growth modifier. To this mixture is added 3.89 g of Ultrasil VN3 PM modified precipitated silica (92.4% SiO2). The mixture is stirred for 15 minutes to prepare a homogenous slurry. The approximate molgel composition for the mixture is as follows: SiO2 / Al2O3=100.0 OH - / SiO2=0.175 HMDC / SiO2=0.019 Modifier / SiO2=0.018 H2O / SiO2=18.7 Approximately 5200 ppm of seeds The autoclave is sealed and the mixture is kept stirred at 300 rpm using a U-shaped stirrer. The mixture is heated to 160°C (20°C / hr ramp rate) 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 shows the powder to be ZSM-48.

[0104] Example 8. ZSM-48, sodium octyl sulfate morphology modifier, morphology modifier / SiO2=0.026, 1.5 wt% of total mixture Dilute 1.27g of 25% hexamethonium dichloride (HMDC) in 13.0g water. Stir to ensure uniform solution. Add 0.60g 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 3.6g of 10% NaOH solution to the HMDC / aluminate solution. Stir to homogenize the mixture. Add 0.75g of colloidal beta seeds (16.7% seeds by weight) to the aluminate mixture. Add 1.86g of a 20% solution by weight of sodium octyl sulfate and stir the mixture to dissolve the zeolite growth modifier. Add 3.89g of Ultrasil VN3 PM modified precipitated silica (92.4% SiO2) to the mixture. The mixture is stirred for 15 minutes to prepare a homogenous slurry. The approximate molgel composition for the mixture is as follows: SiO2 / Al2O3=100.0 OH - / SiO2=0.175 HMDC / SiO2=0.019 Modifier / SiO2=0.026 H2O / SiO2=18.7 Approximately 5200 ppm of seeds The autoclave is sealed and the mixture is kept stirred at 300 rpm using a U-shaped stirrer. The mixture is heated to 160°C (20°C / hr ramp rate) 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 shows the powder to be ZSM-48.

[0105] Example 9 (Comparative) ZSM-48, 1,2-hexanediol comparative modifier, comparative modifier / SiO2=0.053, 1.5% by weight of the total mixture Dilute 1.27g of 25% hexamethonium dichloride (HMDC) in 13.1g water. Stir to ensure uniform solution. Add 0.60g 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 3.6g of 10% NaOH solution to the HMDC / aluminate solution. Stir to homogenize the mixture. Add 0.75g of colloidal beta seeds (16.7% seeds by weight) to the aluminate mixture. Add 1.86g of a 20.1% solution by weight of 1,2-hexanediol and stir the mixture to dissolve the zeolite growth modifier. Add 3.89g of Ultrasil VN3 PM modified precipitated silica (92.4% SiO2) to the mixture. The mixture is stirred for 15 minutes to prepare a homogenous slurry. The approximate molgel composition for the mixture is as follows: SiO2 / Al2O3=100.0 OH - / SiO2=0.175 HMDC / SiO2=0.019 Modifier / SiO2=0.053 H2O / SiO2=18.7 Approximately 5200 ppm of seeds The autoclave is sealed and the mixture is kept stirred at 300 rpm using a U-shaped stirrer. The mixture is heated to 160°C (20°C / hr ramp rate) 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 shows the powder to be ZSM-48.

[0106] Example 10. ZSM-48, trimethyloctadecylammonium bromide morphology modifier, morphology modifier / SiO2=0.021, 2.0 wt% of total mixture Dilute 1.26 g of 25% hexamethonium dichloride (HMDC) in 12.5 g of water. Stir to ensure homogenous solution. 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 a 10% NaOH solution to the HMDC / aluminate solution. Stir to homogenize the mixture. Add 0.73 g of colloidal beta seeds (17.2 wt % seeds) to the aluminate mixture. Add 2.51 g of a 20 wt % solution of trimethyloctadecylammonium bromide (a cationic surfactant morphology modifier) ​​and stir the mixture to dissolve the morphology modifier. To this mixture is added 3.87 g of Ultrasil VN3 PM modified precipitated silica (92.4% SiO2). The mixture is stirred for 15 minutes to prepare a homogenous slurry. The approximate molgel composition for the mixture is as follows: SiO2 / Al2O3=100.0 OH - / SiO2=0.175 HMDC / SiO2=0.019 Modifier / SiO2=0.021 H2O / SiO2=18.7 Approximately 5100 ppm of seeds The autoclave is sealed and the mixture is kept stirred at 300 rpm using a U-shaped stirrer. The mixture is heated to 160°C (20°C / hr ramp rate) 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 shows the powder to be ZSM-48.

[0107] Example 11. ZSM-48, sodium lauryl sulfate morphology modifier, morphology modifier / SiO2=0.029, 2.0 wt% of total mixture Dilute 1.24g of 25% hexamethonium dichloride (HMDC) in 12.5g water. Stir to ensure uniform solution. Add 0.61g 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 3.6g of 10% NaOH solution to the HMDC / aluminate solution. Stir to homogenize the mixture. Add 0.73g of colloidal beta seeds (17.2% seeds by weight) to the aluminate mixture. Add 2.5g of a 20% solution by weight of sodium lauryl sulfate (anionic surfactant morphology modifier) ​​and stir the mixture to dissolve the morphology modifier. Add 3.90g of Ultrasil VN3 PM modified precipitated silica (92.4% SiO2) to the mixture. The mixture is stirred for 15 minutes to prepare a homogenous slurry. The approximate molgel composition for the mixture is as follows: SiO2 / Al2O3=100.2 OH - / SiO2=0.174 HMDC / SiO2=0.019 Modifier / SiO2=0.029 H2O / SiO2=18.6 Approximately 5100 ppm of seeds The autoclave is sealed and the mixture is kept stirred at 300 rpm using a U-shaped stirrer. The mixture is heated to 160°C (20°C / hr ramp rate) 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 shows the powder to be ZSM-48.

[0108] Example 11B Additional ZSM-48 crystals were synthesized using the same reaction mixture as in Example 11, except that 1 wt% SLS was used instead of 2 wt%. Transmission electron microscopy (TEM) revealed that the crystals had a median crystal length of about 41 nm and an aspect ratio of about 2.0.

[0109] Example 12. ZSM-48, sodium lauryl sulfate morphology modifier, morphology modifier / SiO2=0.075, 5.0 wt% of total mixture Dilute 1.2 g of 25% hexamethonium dichloride (HMDC) in 9.1 g of water. Stir to ensure uniform solution. Add 0.59 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 3.4 g of 10% NaOH solution to the HMDC / aluminate solution. Stir to homogenize the mixture. Add 0.73 g of colloidal beta seeds (17.2 wt % seeds) to the aluminate mixture. Add 6.3 g of a 20 wt % solution of sodium lauryl sulfate (anionic surfactant morphology modifier) ​​and stir the mixture to dissolve the morphology modifier. Add 3.78 g of Ultrasil VN3 PM modified precipitated silica (92.4% SiO2) to the mixture. The mixture is stirred for 15 minutes to prepare a homogenous slurry. The approximate molgel composition for the mixture is as follows: SiO2 / Al2O3=100.9 OH - / SiO2=0.174 HMDC / SiO2=0.019 Modifier / SiO2=0.075 H2O / SiO2=18.6 Approximately 5100 ppm of seeds The autoclave is sealed and the mixture is kept stirred at 300 rpm using a U-shaped stirrer. The mixture is heated to 160°C (20°C / hr ramp rate) 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 shows the powder to be ZSM-48.

[0110] Example 13. ZSM-48, benzylhexadecyldimethylammonium chloride morphology modifier, morphology modifier / SiO2=0.016, 1.5 wt% of total mixture Dilute 1.24g of 25% hexamethonium dichloride (HMDC) in 13.1g water. Stir to ensure homogenous solution. Add 0.61g 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 3.6g of a 10% NaOH solution to the HMDC / aluminate solution. Stir to homogenize the mixture. Add 0.73g of colloidal beta seeds (17.2 wt% seeds) to the aluminate mixture. Add 1.88g of a 20 wt% solution of benzyl hexadecyl dimethyl ammonium chloride (a cationic surfactant morphology modifier) ​​and stir the mixture to dissolve the morphology modifier. To this mixture is added 3.89 g of Ultrasil VN3 PM modified precipitated silica (92.4% SiO2). The mixture is stirred for 15 minutes to prepare a homogenous slurry. The approximate molgel composition for the mixture is as follows: SiO2 / Al2O3=100.0 OH - / SiO2=0.175 HMDC / SiO2=0.019 Modifier / SiO2=0.016 H2O / SiO2=18.7 Approximately 5100 ppm of seeds The autoclave is sealed and the mixture is kept stirred at 300 rpm using a U-shaped stirrer. The mixture is heated to 160°C (20°C / hr ramp rate) 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 shows the powder to be ZSM-48.

[0111] Example 14. ZSM-48, dihexadecyldimethylammonium bromide morphology modifier, morphology modifier / SiO2=0.012, 1.5 wt% of total mixture Dilute 1.24g of 25% hexamethonium dichloride (HMDC) in 13.1g water. Stir to ensure homogenous solution. Add 0.61g 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 3.6g of 10% NaOH solution to the HMDC / aluminate solution. Stir to homogenize the mixture. Add 0.73g of colloidal beta seeds (17.2 wt% seeds) to the aluminate mixture. Add 1.86g of a 20 wt% solution of dihexadecyldimethylammonium bromide (a cationic surfactant morphology modifier) ​​and stir the mixture to dissolve the morphology modifier. To this mixture is added 3.89 g of Ultrasil VN3 PM modified precipitated silica (92.4% SiO2). The mixture is stirred for 15 minutes to prepare a homogenous slurry. The approximate molgel composition for the mixture is as follows: SiO2 / Al2O3=100.0 OH - / SiO2=0.175 HMDC / SiO2=0.019 Modifier / SiO2=0.012 H2O / SiO2=18.7 Approximately 5100 ppm of seeds The autoclave is sealed and the mixture is kept stirred at 300 rpm using a U-shaped stirrer. The mixture is heated to 160°C (20°C / hr ramp rate) 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 shows the powder to be ZSM-48.

[0112] Example 15. ZSM-48, lithium dodecyl sulfate morphology modifier, morphology modifier / SiO2=0.023, 1.5 wt% of total mixture Dilute 1.24g of 25% hexamethonium dichloride (HMDC) in 13.1g water. Stir to ensure uniform solution. Add 0.61g 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 3.6g of 10% NaOH solution to the HMDC / aluminate solution. Stir to homogenize the mixture. Add 0.73g of colloidal beta seeds (17.2% seeds by weight) to the aluminate mixture. Add 1.86g of a 20% solution by weight of lithium dodecyl sulfate (anionic surfactant morphology modifier) ​​and stir the mixture to dissolve the morphology modifier. Add 3.89g of Ultrasil VN3 PM modified precipitated silica (92.4% SiO2) to the mixture. The mixture is stirred for 15 minutes to prepare a homogenous slurry. The approximate molgel composition for the mixture is as follows: SiO2 / Al2O3=100.0 OH - / SiO2=0.175 HMDC / SiO2=0.019 Modifier / SiO2=0.023 H2O / SiO2=18.7 Approximately 5100 ppm of seeds The autoclave is sealed and the mixture is kept stirred at 300 rpm using a U-shaped stirrer. The mixture is heated to 160°C (20°C / hr ramp rate) 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 shows the powder to be ZSM-48.

[0113] Transmission electron microscopy (TEM) revealed that the crystals generally had lengths in the range of 30-60 nm and widths in the range of approximately 30 nm, with length:width aspect ratios in the range of 1-2.

[0114] Example 16. ZSM-48, Pluronic EO-PO-EO morphology modifier, morphology modifier / SiO2=0.0007, 1.0 wt% of total mixture Dilute 1.25g of 25% hexamethonium dichloride (HMDC) in 13.7g water. Stir to ensure uniform solution. Add 0.61g 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 3.6g of a 10% NaOH solution to the HMDC / aluminate solution. Stir to homogenize the mixture. Add 0.73g of colloidal beta seeds (17.2 wt% seeds) to the aluminate mixture. Add 1.24g of a 20 wt% solution of Pluronic EO-PO-EO triblock copolymer (nonionic surfactant morphology modifier) ​​and stir the mixture to dissolve the morphology modifier. To this mixture is added 3.91 g of Ultrasil VN3 PM modified precipitated silica (92.4% SiO2). The mixture is stirred for 15 minutes to prepare a uniform slurry. The approximate molgel composition for the mixture is as follows: SiO2 / Al2O3=100.0 OH - / SiO2=0.175 HMDC / SiO2=0.019 Modifier / SiO2=0.0007 H2O / SiO2=18.7 Approximately 5100 ppm of seeds The autoclave is sealed and the mixture is kept stirred at 300 rpm using a U-shaped stirrer. The mixture is heated to 160°C (20°C / hr ramp rate) 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 shows the powder to be ZSM-48.

[0115] The synthesis of MCM-49 below was carried out using hexamethyleneimine (HMI) as a structure directing agent according to the following procedure.

[0116] Example 17. See MCM-49, no morphology modifier, morphology modifier / SiO2=0.000, 0 wt% of 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 a 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 aluminate 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 molgel composition for the mixture is as follows: SiO2 / Al2O3=25.0 OH - / SiO2=0.390 HMI / SiO2=0.350 Modifier / SiO2=0.000 H2O / SiO2=18.5 The autoclave is sealed and the mixture is kept stirred at 360 rpm using a U-shaped stirrer. The mixture is heated to 143°C (20°C / hr ramp rate) and held for 5 days. 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 shows that the powder is of MCM-49 / MCM-22 structure type.

[0117] Example 18. MCM-49, cetyltrimethylammonium bromide morphology modifier, morphology modifier / SiO2=0.013, 1 wt% of 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 aluminate solution. Stir the mixture until the slurry appears uniform. Add 1.85 g of hexamethyleneimine (HMI) to the slurry. Add 1.26 g of 20 wt% of cetyltrimethylammonium bromide (a cationic surfactant morphology modifier) ​​to the slurry. Stir the mixture for 10 minutes to prepare a uniform slurry. The approximate molgel composition for the mixture is as follows: SiO2 / Al2O3=25.0 OH - / SiO2=0.390 HMI / SiO2=0.350 Modifier / SiO2=0.013 H2O / SiO2=19.6 The autoclave is sealed and the mixture is kept stirred at 360 rpm using a U-shaped stirrer. The mixture is heated to 143°C (20°C / hr ramp rate) and held for 5 days. 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 shows that the powder is of MCM-49 / MCM-22 structure type.

[0118] Example 19. MCM-49, Sodium Lauryl Sulfate Morphology Modifier, Morphology Modifier / SiO2=0.016, 1 wt% of 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 aluminate solution. Stir the mixture until the slurry appears uniform. Add 1.85 g of hexamethyleneimine (HMI) to the slurry. Add 1.26 g of 20 wt% of sodium lauryl sulfate (anionic surfactant morphology modifier) ​​to the slurry. Stir the mixture for 10 minutes to prepare a uniform slurry. The approximate molgel composition for the mixture is as follows: SiO2 / Al2O3=25.0 OH - / SiO2=0.390 HMI / SiO2=0.350 Modifier / SiO2=0.016 H2O / SiO2=19.6 The autoclave is sealed and the mixture is kept stirred at 360 rpm using a U-shaped stirrer. The mixture is heated to 143°C (20°C / hr ramp rate) and held for 5 days. 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 shows that the powder is of MCM-49 / MCM-22 structure type.

[0119] Example 20. ZSM-48, fructose morphology modifier, modifier / SiO2=0.020, 1.0 wt% of total mixture Dilute 1.39g of 56% hexamethonium dichloride (HMDC) in 14.4g of water. Stir to ensure homogenous solution. Add 1.42g 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 2.6g of 10% NaOH solution to the HMDC / aluminate solution. Stir to homogenize the mixture. Add 0.03g of ZSM-48 seeds to the aluminate mixture. Add 0.63g of a 39.7% solution of fructose and stir to homogenize the mixture. Add 4.62g of Ultrasil VN3 PM modified precipitated silica (92.4% SiO2) to this mixture. Stir the mixture for 15 minutes to prepare a homogenous slurry. The approximate molgel composition for the mixture is as follows: SiO2 / Al2O3=99.9 OH - / SiO2=0.190 HMDC / SiO2=0.040 Modifier / SiO2=0.020 H2O / SiO2=14.9 Approximately 1000 ppm of seeds The autoclave is sealed and the mixture is kept stirred at 300 rpm using a U-shaped stirrer. The mixture is heated to 160°C (20°C / hr ramp rate) 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 shows the powder to be ZSM-48.

[0120] Post-synthesis processing and measurements The molecular sieve samples produced in Examples 1 to 20 above were subjected to the following treatments.

[0121] 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 for 2 hours at 550° C. to produce the acid form of the zeolite crystals.

[0122] The acid form of the crystals was then characterized using collidine adsorption to assess the acidity of the catalyst. Nitrogen BET techniques were used to determine the external and internal surface areas of the crystals, as well as the pore volume. This data was collected for the reference material and each of the modified materials of the present invention, and the ratio of the external surface area and collidine adsorption of each of the examples of the present invention to the reference example of the same zeolite is shown in Table 3, demonstrating the change in acidity and external surface area of ​​the modified crystals caused by the presence of the morphology modifier in the synthesis mixture.

[0123] BET analysis was performed as described in S.J. Gregg, K.S. Wising, “Adsorption, Surface Area and Porosity”, 1st ed., Academic Press, NY (1967) pp 30-31.

[0124] Ammonia and collidine 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).

[0125] [Table 3]

[0126] The results in Table 3 show that the use of 1,2-hexanediol, which is not a morphology modifier as described herein, shows no effect on collidine absorption or external surface area, as was the case for the reference ZSM-48 in Comparative Example 1.

[0127] For inventive examples 2-8, 10-16, 18 and 19, the presence of the morphology modifier had a significant effect on collidine adsorption and / or external SA compared to the synthesis of the reference material in the absence of the morphology modifier. In examples 11 and 12, the collidine adsorption and external SA values ​​recorded were lower than those for the reference synthesis of the same zeolite in the absence of the morphology modifier, but within 10%, which may be due to experimental error. For example 15, the collidine adsorption and external SA results 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 morphology 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, the one-dimensional channels of the framework run lengthwise of the crystal, and therefore the increase in the crystal width compared to the length may cause those channels to become more available to the incoming reactant molecules.

[0128] Examples 21-24 - Catalyst Life of Small Crystal Size One-Dimensional Zeolite Catalysts For catalysts based on one-dimensional zeolites, the catalyst exposure life can be improved by reducing the crystal size of the zeolite along the direction of the pore channels. This can be achieved by modifying the synthesis conditions for the preparation of the zeolite, by using zeolite growth modifiers (ZGMs) in the synthesis mixture, or by other methods that reduce or minimize the crystal size along the direction of the pore channels.

[0129] Small crystals of one-dimensional zeolites can correspond to a length of the crystal along the direction of the pore channel of 90 nm or less, or 70 nm or less, or 50 nm or less, or 45 nm or less, for example, down to 20 nm, or even less if possible. In such an embodiment, the crystal can have an aspect ratio, defined as the ratio of the length along the pore channel direction to the length along the perpendicular direction, of 4.0 or less, or 3.0 or less, or 2.5 or less, or 2.0 or less, for example, down to 1.0, or even less if possible. It is noted that the length of the crystal along the pore channel direction of some one-dimensional zeolites, such as ZSM-48, can typically correspond to the longest direction of the crystal.

[0130] Methanol conversion catalysts with increased catalyst exposure life can be beneficial in a variety of situations. For fixed bed systems (such as trickle bed reactors), increasing catalyst life can allow longer run lengths for a given thickness of catalyst bed and / or comparable run lengths with reduced amounts of catalyst. For systems capable of continuous catalyst regeneration, such as fluidized or moving bed reactors, increasing catalyst life can allow a reduction in the rate of catalyst removal from the system and a corresponding reduction in the addition of freshly made up catalyst. As used herein, catalyst exposure life refers to the amount of oxygenate that a catalyst can process under oxygenate conversion conditions before the activity of the catalyst for conversion becomes substantially zero.

[0131] To investigate the effect of crystal size, ZSM-48 catalysts were synthesized with two different silica:alumina ratios (about 70:1 and 90:1) and different lengths along the direction of the pore channels (about 60-70 nm or greater than 100 nm). More generally, the size effect demonstrated in this example is believed to be relevant for use with a variety of one-dimensional 10-ring zeolites at silica to alumina ratios of 30-100 and with hexane cracking activities of 15 and above (as defined in U.S. Pat. No. 3,354,078, incorporated herein by reference, for the limited purpose of hexane cracking activity testing).

[0132] The synthesis mixtures for preparing the catalysts are shown in Table 3. The catalyst mixtures are described based on the weight ratio of most of the components by weight in the mixture provided for the seeds. For each synthesis mixture, the silica to alumina ratio, the crystal length (along the pore channel direction) and the aspect ratio (AR) are listed.

[0133] [Table 4]

[0134] For the 90:1 ZSM-48 synthesis mixture, a mixture was prepared from water, hexamethonium chloride (56% solution), commercially available Ultrasil silica (available from Degussa), sodium aluminate solution (45%), TEAOH solution (35%), 50% sodium hydroxide solution, and seeds. The mixture was reacted at 320°F (160°C) with stirring at 250 RPM for 48 hours. The product was filtered, washed with deionized (DI) water, and dried at 250°F (120°C). The XRD pattern of the synthesized material showed a pure phase typical of ZSM-48 topology. SEM of the synthesized material shows that the material is composed of aggregates of crystals. For crystals with an aspect ratio of about 7, the crystals had a needle-like morphology, while crystals with an aspect ratio of about 3 had an irregular morphology.

[0135] For the 70:1 ZSM-48 synthesis mixture, a mixture was prepared from water, hexamethonium chloride (56% solution), commercially available Ultrasil silica, sodium aluminate solution (43%), TEAOH solution (35%), 50% sodium hydroxide solution, and seeds. The mixture was reacted at 340°F (about 170°C) with stirring at 250 RPM for 24 hours. The product was filtered, washed with deionized (DI) water, and dried at 250°F (120°C). The XRD pattern of the synthesized material showed a pure phase typical of ZSM-48 topology. SEM of the synthesized material shows that the material is composed of aggregates of crystals. For the crystals with an aspect ratio of about 7, the crystals had a needle-like morphology, while the crystals with an aspect ratio of about 3 had an irregular morphology.

[0136] After synthesis, the catalyst was blended with an alumina binder to produce catalyst particles having 80 wt% zeolite and 20 wt% binder.

[0137] For Catalyst A (90:1, length = 138 nm), the combined catalyst had an Alpha value of 90, a hexane cracking activity of about 56, a median pore size of 9.0 Å, and a pore size of 298 nm. 2 / g BET surface area (174 m 2 / g micropore surface area), aspect ratio of 7, and median crystal length of 138 nm.

[0138] For Catalyst B (90:1, length = 66 nm), the combined catalyst had an Alpha value of 100, a hexane cracking activity of about 55, a median pore size of 6.5 Å, and a pore size of 275 nm. 2 / g BET surface area (165 m 2 / g micropore surface area), aspect ratio of 3, and median crystal length of 66 nm.

[0139] For catalyst C (70:1, length = 110 nm), the combined catalyst had an Alpha value of 120, a hexane cracking activity of about 52, a median pore diameter of 20.3 Å, and a pore size of 323 m. 2 / g BET surface area (171 m 2 / g micropore surface area), aspect ratio of 7, and median crystal length of 110 nm.

[0140] For catalyst D (70:1, length = 61 nm), the combined catalyst had an Alpha value of 140, a hexane cracking activity of about 49, a median pore diameter of 14.4 Å, and a pore size of 324 nm. 2 / g BET surface area (169 m 2 / g micropore surface area), aspect ratio of 3, and median crystal length of 61 nm.

[0141] In addition to catalysts A-D, a fifth ZSM-48 catalyst was also synthesized having a silica to alumina ratio of about 70:1 and a median crystal length of less than 90 nm. This catalyst is designated as the "reference" ZSM-48 catalyst. This reference ZSM-48 catalyst is similar to the ZSM-48 catalyst described and used in U.S. Patent Application Publication No. 2018 / 0201843.

[0142] The catalyst was tested in an isothermal fixed bed reactor without recycle, but recycle is possible and may be desirable since it may further extend the catalyst cycle length or modify the overall yield. This reactor configuration is illustrative and should not be considered as limiting. Moving or fluidized bed operation may be preferred. In this example, pure methanol was used as the model feed, but co-feeds such as water, oxygenates (e.g., ethanol, DME), olefins, paraffins and aromatics are possible and may be desirable. Test conditions were 2h-1 WHSV (zeolite basis), temperature of 450°C and pressure of about 100 kPa-g.

[0143] Results from the methanol conversion tests are shown in Figures 1-4. Figure 1 shows the olefin yield (g MeOH / g catalyst) versus the amount of methanol exposed to the catalyst. Figure 2 shows the paraffin yield versus methanol exposure. Figure 3 shows the combined olefin and aromatics yield versus methanol exposure. Figure 4 shows the combined olefin, aromatic, and unknowns yield versus methanol exposure. The "unknowns" in Figure 4 are likely to correspond to iso-olefins containing 6 or more carbons. Thus, the "unknowns" likely correspond to compounds with relatively high octane numbers.

[0144] As shown in FIG. 1, changing the aspect ratio of the 90:1 ZSM-48 catalyst had a substantial effect on yield and catalyst life. This is due in part to the relatively low yield in either exposure for the 90:1 ZSM-48 with an aspect ratio of 7. However, the 90:1 ZSM-48 with an aspect ratio of 3 and a crystal length of less than 75 nm appeared to have a longer life than either of the 70:1 ZSM-48 catalysts. For the 70:1 catalyst, the lower aspect ratio catalyst had a somewhat higher peak yield of olefins, but the amount of catalyst exposure life increase was modest. The catalyst exposure life for the reference catalyst was similar to the 70:1 ZSM-48 catalyst with an aspect ratio of 3 and a crystal length of about 61 nm.

[0145] In terms of paraffin yield, Figure 2 shows that the 90:1 ZSM-48 with an aspect ratio of 3 had the highest paraffin yield at all exposures, but the 90:1 ZSM-48 crystals with an aspect ratio of 7 generally had lower activity. The paraffin yields of the 70:1 catalyst were roughly comparable, but the 70:1 ZSM-48 with an aspect ratio of 3 appeared to have a longer lifetime before the paraffin yield essentially dropped to zero. As shown in Figure 1, the catalytic exposure lifetime of the reference catalyst was similar to that of the 70:1 catalyst with an aspect ratio of 3 and a crystal length of about 61 nm.

[0146] Figure 3, showing the combined olefin and aromatic yields, also shows similar trends to those in Figure 1. Thus, Figure 3 shows that the 70:1 ZSM-48 with an aspect ratio of 3 provides only a modest increase in lifetime compared to the higher aspect ratio 70:1 ZSM-48, but a substantial increase in yield for the 90:1 ZSM-48 with an aspect ratio of 3. Figure 4, showing the combined olefin, aromatic and unknown yields, also shows similar trends to the data in Figures 1 and 3.

[0147] To further explore the benefit of small crystal size on the catalytic exposure life of unidimensional zeolites, catalysts from Example 5B (CTAB) and Example 11B (SLS) were exposed to methanol feedstock under the above reaction conditions and reactor configuration. Additionally, ZSM-48 crystals produced using a method similar to Example 5B or Example 11B, but using 1 wt% sodium sulfate as a crystal growth modifier, were also tested. Data from the reference catalysts from Figures 1-4 are also shown for comparison.

[0148] The catalyst prepared using sodium sulfate as a growth modifier had an Alpha value of 130 and an average molecular weight of 280m. 2 / g BET surface area (167 m 2 / g micropore surface area), an aspect ratio of 2.4, and a median crystal length of 49 nm. The catalyst prepared using CTAB as the growth modifier (Example 5B) had an Alpha value of 120, a pore size of 327 m 2 / g BET surface area (176 m 2 / g micropore surface area, aspect ratio of 2.2, and median crystal length of 53 nm. The catalyst prepared using SLS as a growth modifier (Example 11B) had an Alpha value of 120, a SiO2 value of 281 m 2 / g BET surface area (167 m 2 / g micropore surface area), an aspect ratio of 2.0, and a median crystal length of 41 nm.

[0149] Figures 5-8 show results from methanol conversion tests. Figure 5 shows the olefin yield (g MeOH / g catalyst) versus the amount of methanol exposed to the catalyst. Figure 6 shows the paraffin yield versus methanol exposure. Figure 7 shows the combined olefin and aromatics yield versus methanol exposure. Similar to Figure 4, Figure 8 shows the combined olefin, aromatics, and unknowns yield versus methanol exposure.

[0150] As shown in Figure 5, the addition of SLS as a modifier had a substantial effect on catalyst life, with olefin yields remaining above zero until well past 200 g / MeOH / g catalyst. Note that the SLS growth modifier produced the smallest median crystal length (41 nm) for the growth modifiers tested for methanol conversion. The addition of sodium sulfate or CTAB had a more modest effect, resulting in a similar overall life to the reference catalyst, but a higher production of olefins for the end of catalyst life of approximately 150 g MeOH / g catalyst.

[0151] The paraffin yields in Figure 6 are similar to the results shown in Figure 5, except that the addition of sodium sulfate resulted in some additional initial yield of paraffins. However, the lifetime trends for each growth modifier in Figure 6 are similar to those in Figure 5. Figure 7, showing the combined olefin and aromatic yields, and Figure 8, showing the combined olefin, aromatic and unknowns yields, also show trends similar to those in Figure 5. Thus, Figures 7 and 8 show an unexpected improvement in catalyst lifetime for the small crystal length ZSM-48 catalyst (synthesized using SLS).

Claims

1. A method for producing crystals of a molecular sieve having an MRE skeletal code, comprising: The method involves the following steps: a. combining at least a source of tetravalent element X, a source of trivalent element Y, structure directing agent Q, morphology modifier L, and water to form a synthesis mixture, wherein morphology modifier L is included in the synthesis mixture before nucleation or crystallization begins; b. heating the synthesis mixture under crystallization conditions for a time period between 1 hour and 100 days to form molecular sieve crystals; c. Recovering the molecular sieve crystals from the synthesis mixture; Including, X=Si and Y=Al, The morphology modifier L is At least one C bonded to a quaternary ammonium group １２ ~C ３０ cationic surfactants having a single quaternary ammonium group comprising an alkyl group; a nonionic surfactant selected from the group consisting of block copolymers of ethylene oxide and propylene oxide, block copolymers of ethylene oxide and butylene oxide, PEG dodecyl ether, and PEG oleyl ether; anionic surfactants selected from alkyl sulfates in which the alkyl group has at least 8 carbon atoms; a monosaccharide selected from glucose, fructose and galactose; and combinations thereof; A method of making wherein L is different from and is present in addition to structure directing agent Q.

2. In step a), a source of hydroxide ions, a source of pentavalent element Z, halide ions W － and a source of alkali metal ions M ＋ and / or a source of alkaline earth metal cation M ２＋ 10. The method of claim 1, wherein one or more additional components selected from the group consisting of sources of:

3. 10. The method of claim 1, wherein the molar ratio of L:X in the synthesis mixture ranges from 0.001 to 0.

03.

4. XO ２ :Y ２ O ３ The method of claim 1, wherein the ratio is in the range of 5 to 500.

5. Q: (XO ２ +Y ２ O ３ +Z ２ O ５ 3. The method of claim 2, wherein the ratio of

6. The morphology modifier L is a compound represented by the formula (1) (R １ ) ｑ (R ２ ) ４－ｑ N ＋ (X ｎ－ ) １／ｎ (1) (Wherein, each R １ are independently linear and saturated C １ ~C ４ R 2 is a C 14 -C 30 alkyl group that is straight-chain (linear) and saturated; q is 2; X ｎ－ is an anion of valence n.) The method of claim 1, wherein the cationic surfactant has the formula:

7. 10. The method of claim 1, wherein the amount of water-insoluble liquid components in the synthesis mixture is less than 5% by weight.

8. 10. The method of claim 1, comprising calcining the crystals recovered in step c) to provide a calcined form of the molecular sieve.

9. 2. The method of claim 1, wherein the molecular sieve is ZSM-48.

10. A process for converting hydrocarbons, comprising contacting a hydrocarbon feedstock with a catalyst comprising molecular sieve crystals produced by the process of any one of claims 1 to 9.

11. 11. The hydrocarbon conversion process of claim 10, which is a dewaxing process or an aromatic alkylation process.

12. 11. The hydrocarbon conversion process of claim 10, which is an oxygenate conversion process, a methanol conversion process, or a combination thereof.

13. The hydrocarbon conversion method of claim 12, wherein the molecular sieve comprises a median crystal length of 90 nm or less, an aspect ratio of 3 or less, or a combination thereof.

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