CN108238610B

CN108238610B - Molecular sieve, and preparation method and application thereof

Info

Publication number: CN108238610B
Application number: CN201710282847.7A
Authority: CN
Inventors: 孙明毅; 王永睿; 慕旭宏; 舒兴田
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2016-12-23
Filing date: 2017-04-26
Publication date: 2020-02-28
Anticipated expiration: 2037-04-26
Also published as: CN108238610A; CN108238611B; CN108238611A

Abstract

The invention relates to a molecular sieve, in particular to a super macroporous molecular sieve. The invention also relates to a method for producing said molecular sieve and to the use thereof as an adsorbent or catalyst. The molecular sieve has a unique X-ray diffraction pattern (XRD) and has a unique primary crystal morphology ranging from flat prism to flat cylinder. The molecular sieve is capable of adsorbing more/larger molecules, thereby exhibiting excellent adsorption/catalytic properties.

Description

Molecular sieve, and preparation method and application thereof

Technical Field

The invention relates to a molecular sieve, in particular to a super macroporous molecular sieve. The invention also relates to a method for producing said molecular sieve and to the use thereof as an adsorbent or catalyst.

Background

The molecular sieve has wide application, and different applications often put different requirements on the framework pore structure of the molecular sieve. The molecular sieve has four framework pore structure types of small pore, medium pore, large pore and super large pore: the small pore molecular sieve has a molecular weight distribution of from

To

Pore sizes such as CHA, LEV, SOD, LTA, ERI, KFI; the mesoporous molecular sieve has a molecular weight distribution of from

To

Pore sizes such as MFI, MEL, EUO, MWW, TON, MTT, MFS, AEL, AFO, HEU, FER; the macroporous molecular sieve has

Pore sizes such as FAU, BEA, MOR, LTL, VFI, MAZ; the ultra-large pore molecular sieve has a molecular weight greater than

The pore diameter of (a). Among the molecular sieves with different framework pore structure types, the ultra-large pore molecular sieve breaks through the pore channel limitation of the molecular sieve, has a plurality of advantages in the aspects of improving the macromolecular reaction activity, prolonging the service life of the molecular sieve, improving the product selectivity and the like, and is expected to be well applied to heavy oil processing and organic chemical raw material production.

In the framework pore structure of the current 232 molecular sieves, the ultra-large pore molecular sieve only accounts for more than 10 types, and mainly comprises three types: a phosphoaluminum/gallium molecular sieve, such as AlPO-8(AET,14-ring,

)、VPI-5(VFI,18-ring,

)、Cloverite(-CLO,20-ring,

) JDF-20(20-ring) and ND-1(24-ring,

) (ii) a A silicon-germanium/gallium molecular sieve is used,such as OSB-1(OSO,14-ring, Si/Be ═ 2,

) ECR-34(ETR,18-ring,10.5A, Si/Ga ═ 3), ITQ-37(30-ring), ITQ-43(28-ring), ITQ-33(18-ring), ITQ-44(18-ring), ITQ-40(16-ring) SSZ-53(14-ring), and SSZ-59 (14-ring); and silicon aluminum molecular sieves, such as UTD-1(DON,14-ring, Si/Al)₂＝∞,

) And CIT-5(CFI,14-ring,

Si/Al₂＝190)。

in view of its good performance and application prospects, there is still a need in the art to develop a wider variety of ultra-large pore molecular sieves.

Disclosure of Invention

The present inventors have assiduously studied on the basis of the prior art and have found that a novel ultra-large pore molecular sieve and a novel method for producing the molecular sieve are provided, thereby satisfying the aforementioned requirements of the prior art.

In particular, the present invention relates to the following aspects:

1. a molecular sieve having a crystal morphology ranging from prismoid to oblate, preferably having one or both of its profile lines of the upper end face in longitudinal section with a convex shape and having an X-ray diffraction pattern substantially as shown in the following Table,

2. a molecular sieve according to any preceding claim wherein said X-ray diffraction pattern further comprises X-ray diffraction peaks substantially as shown in the Table,

3. a molecular sieve according to any preceding claim wherein said X-ray diffraction pattern further comprises X-ray diffraction peaks substantially as shown in the Table,

4. a molecular sieve according to any preceding claim wherein the dimensions of said crystal morphology comprise: an effective diameter of from 100nm to 1000nm, preferably from 100nm to 500nm, a height of from 100nm to 1000nm, preferably from 150nm to 300nm, and an aspect ratio of from 0.1 to 0.9, preferably from 0.4 to 0.7.

5. A molecular sieve according to any one of the preceding claims, wherein the total specific surface area of the molecular sieve is from 400m²G to 600m²G, preferably from 450m²G to 580m²A pore volume of from 0.3 to 0.5ml/g, preferably from 0.30 to 0.40 ml/g.

6. A molecular sieve according to any one of the preceding claims, having a schematic chemical composition represented by the formula "first oxide second oxide" or by the formula "first oxide second oxide organic template water", wherein the molar ratio of said first oxide to said second oxide is from 40 to 200, preferably from 40 to 150; the first oxide is selected from at least one of silicon dioxide, germanium dioxide, tin dioxide, titanium dioxide and zirconium dioxide, preferably silicon dioxide or a combination of silicon dioxide and germanium dioxide, and the second oxide is selected from at least one of aluminum oxide, boron oxide, iron oxide, gallium oxide, rare earth oxide, indium oxide and vanadium oxide, preferably aluminum oxide; the molar ratio of water to said first oxide is from 5 to 50, preferably from 5 to 15; the molar ratio of the organic templating agent to the first oxide is from 0.02 to 0.5, preferably from 0.05 to 0.5, from 0.08 to 0.5, or from 0.3 to 0.5.

7. A method for producing a molecular sieve, comprising a step of contacting a first oxide source, a second oxide source, optionally an alkali source, an organic template, and water under crystallization conditions to obtain a molecular sieve, and optionally, a step of calcining the obtained molecular sieve, wherein the organic template comprises a compound represented by the following formula (I),

wherein the radical R₁And R₂Are the same or different from each other and are each independently selected from C_3-12Straight or branched alkylene, preferably each independently selected from C_3-12Straight chain alkylene, particularly preferably one selected from C_3-12Linear alkylene and the other is selected from C_4-6A linear alkylene group; a plurality of radicals R, equal to or different from each other, each independently selected from C_1-4A linear or branched alkyl group, preferably each independently selected from methyl and ethyl, more preferably both methyl; x is OH.

8. The production method according to any one of the preceding claims, wherein the first oxide source is selected from at least one of a silica source, a germanium dioxide source, a tin dioxide source, a titanium dioxide source, and a zirconium dioxide source, preferably a silica source or a combination of a silica source and a germanium dioxide source, and the second oxide source is selected from at least one of an alumina source, a boron oxide source, an iron oxide source, a gallium oxide source, a rare earth oxide source, an indium oxide source, and a vanadium oxide source, preferably an alumina source.

9. The production method according to any one of the preceding claims, wherein the crystallization conditions include: a crystallization temperature of from 80 ℃ to 120 ℃, preferably from 120 ℃ to 170 ℃ or from 120 ℃ to 200 ℃, a crystallization time of at least 1 day, preferably at least 2 days, preferably from 3 days to 8 days, from 5 days to 8 days or from 4 days to 6 days, and the calcination conditions comprise: the calcination temperature is from 300 ℃ to 750 ℃, preferably from 400 ℃ to 600 ℃, and the calcination time is from 1 hour to 10 hours, preferably from 3 hours to 6 hours.

10. The production method according to any one of the preceding claims, wherein the molar ratio of the first oxide source (based on the first oxide) to the second oxide source (based on the second oxide) is from 40 to 200, preferably from 40 to 150; water with the first mentionedThe molar ratio of the source of monoxide (based on the first oxide) is from 5 to 50, preferably from 5 to 15; the molar ratio of the organic templating agent to the first oxide source (based on the first oxide) is from 0.02 to 0.5, preferably from 0.05 to 0.5, from 0.08 to 0.5, or from 0.3 to 0.5; the alkali source (in OH)^-In terms of the first oxide) to the first oxide source (in terms of the first oxide) is from 0 to 1, preferably from 0.04 to 1, from 0.1 to 1, from 0.2 to 1, from 0.3 to 0.7 or from 0.45 to 0.7.

11. A molecular sieve composition comprising the molecular sieve of any preceding claim or obtained according to the method of manufacture of any preceding claim, and a binder.

12. A process for the conversion of hydrocarbons comprising the step of subjecting hydrocarbons to a conversion reaction in the presence of a catalyst, wherein the catalyst comprises or is produced from the molecular sieve of any preceding claim, the molecular sieve obtained by the production process of any preceding claim, or the molecular sieve composition of any preceding claim.

13. The conversion process according to any one of the preceding claims, wherein the conversion reaction is selected from the group consisting of catalytic cracking, hydrocracking, disproportionation, alkylation, oligomerization, and isomerization.

Technical effects

The molecular sieve according to the invention has a framework pore structure with extra large pores, which is at least reflected by its higher pore volume data.

The molecular sieve according to the invention has good thermal/hydrothermal stability and has larger pore volume. As a result, the molecular sieve of the present invention is capable of adsorbing more/larger molecules, thereby exhibiting excellent adsorption/catalytic performance.

The molecular sieve according to the present invention has a unique X-ray diffraction pattern (XRD) together with a unique primary crystal morphology, such as from prismoid to prismoid. This is a molecular sieve that has not been produced in the prior art.

The molecular sieve according to the invention has a strong acidity, in particular a high number of L acid centers. This is a molecular sieve that has not been produced in the prior art. As a result, the molecular sieves of the present invention have superior performance characteristics, particularly in acid catalyzed reactions.

According to the method for manufacturing the molecular sieve, the organic template agent with a specific chemical structure is used, so that the characteristics of simple process conditions and easy synthesis of the molecular sieve product are shown.

Drawings

FIG. VI-1 is a scanning electron micrograph of the molecular sieve made in example VI-3.

Figure VI-2 is an XRD pattern of the molecular sieve made in example VI-3.

FIG. VI-3 is the NH of the molecular sieve made in example VI-3₃-TPD map.

FIG. VI-4 is an infrared spectrum of the molecular sieve made in example VI-3.

FIG. VI-5 is a scanning electron micrograph of the molecular sieve made in example VI-4.

Figure VI-6 is an XRD pattern of the molecular sieve made in example VI-4.

FIG. VI-7 is a scanning electron micrograph of the molecular sieve made in example VI-5.

FIG. VI-8 is a scanning electron micrograph of the molecular sieve made in example VI-6.

FIG. VI-9 is a scanning electron micrograph of the molecular sieve made in example VI-7.

FIGS. VI-10 are scanning electron micrographs of the molecular sieves made in example VI-8.

Figure VI-11 is an XRD pattern of the molecular sieve made in example VI-9.

Figure VI-12 is an XRD pattern of the molecular sieve made in example VI-10.

Figure VI-13 is an XRD pattern of the molecular sieve made in example VI-11.

Fig. VI-14(a) is a schematic view showing that the end face contour line of the molecular sieve of the present invention has one convex shape, fig. VI-14(b) is a schematic view showing that the end face contour line of the molecular sieve of the present invention has another convex shape, and fig. VI-14(c) is a schematic view showing that the end face contour line of the molecular sieve of the present invention does not have a convex shape but has a flat shape.

Detailed Description

The following detailed description of the embodiments of the present invention is provided, but it should be noted that the scope of the present invention is not limited by the embodiments, but is defined by the appended claims.

All publications, patent applications, patents, and other references mentioned in this specification are herein incorporated by reference in their entirety. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In case of conflict, the present specification, including definitions, will control.

When the specification concludes with claims with the heading "known to those skilled in the art", "prior art", or the like, to derive materials, substances, methods, procedures, devices, or components, etc., it is intended that the subject matter derived from the heading encompass those conventionally used in the art at the time of filing this application, but also include those that are not currently in use, but would become known in the art to be suitable for a similar purpose.

In the context of this specification, the symbol "/" is generally understood to mean "and/or", such as the meaning of the expression "more/larger" is "more and/or larger", unless the understanding is not in line with the conventional knowledge of a person skilled in the art.

In the context of the present specification, the term organic templating agent is sometimes referred to in the art as a structure directing agent or an organic directing agent.

In the context of the present specification as C_1-4Examples of the linear or branched alkyl group include a methyl group, an ethyl group, and a propyl group.

In the context of the present invention, the term "linear or branched oxaalkylene" refers to a divalent radical obtained by interrupting the carbon chain structure of a linear or branched alkylene group by one or more (for example 1 to 3, 1 to 2 or 1) hetero groups-O-. It is preferable from the viewpoint of structural stability that, when plural, any two of the hetero groups are not directly bonded to each other. It is evident that by interrupted is meant that said hetero-group is not in said linear or branched alkylene group or said linear or branched oxa-groupAny one terminal of the alkylene group. For example, C₄Straight chain alkylene (-CH)₂-CH₂-CH₂-CH₂-) can be interrupted by a hetero-group-O-to obtain-CH₂-O-CH₂-CH₂-CH₂-or-CH₂-CH₂-O-CH₂-CH₂-equal C₄The linear oxaheteroalkylene radical, interrupted by two hetero radicals-O-, giving-CH₂-O-CH₂-O-CH₂-CH₂-or-CH₂-O-CH₂-CH₂-O-CH₂-equal C₄Straight-chain dioxaalkylene interrupted by three hetero radicals-O-to give-CH₂-O-CH₂-O-CH₂-O-CH₂-equal C₄Straight chain trioxaalkylene. Or, specifically for example, C₄Branched alkylene (-CH)₂(CH₃)-CH₂-CH₂-) can be interrupted by a hetero-group-O-to obtain-CH₂(CH₃)-O-CH₂-CH₂-、-CH₂(CH₃)-CH₂-O-CH₂-or-CH₂(-O-CH₃)-CH₂-CH₂-equal C₄The branched monooxyheteroalkylene, interrupted by two hetero groups-O-, giving-CH₂(CH₃)-O-CH₂-O-CH₂-、-CH₂(-O-CH₃)-O-CH₂-CH₂-or-CH₂(-O-CH₃)-CH₂-O-CH₂-equal C₄Branched dioxaalkylene interrupted by three hetero radicals-O-to give-CH₂(-O-CH₃)-O-CH₂-O-CH₂-equal C₄A branched trioxalkylene group.

In the context of the present specification, the total specific surface area refers to the total area of the molecular sieve per unit mass, including the internal and external surface areas. Non-porous materials have only an external surface area, such as portland cement, some clay mineral particles, etc., while porous materials have an external surface area and an internal surface area, such as asbestos fibers, diatomaceous earth, molecular sieves, etc.

In the context of the present specification, the term pore volume, also known as pore volume, refers to the volume of pores per unit mass of a molecular sieve. The micropore volume means the volume of all micropores (i.e., pores having a pore diameter of less than 2 nm) per unit mass of the molecular sieve.

In the context of this specification, in the XRD data of molecular sieves, w, m, s, vs represent diffraction peak intensities, w is weak, m is medium, s is strong, vs is very strong, as is well known to those skilled in the art. Generally, w is less than 20; m is 20 to 40; s is 40-70; vs is greater than 70.

Unless otherwise expressly indicated, all percentages, parts, ratios, etc. mentioned in this specification are by weight unless otherwise not in accordance with the conventional knowledge of those skilled in the art.

In the context of this specification, any two or more aspects of the present invention may be combined in any combination, and the resulting solution is part of the original disclosure of this specification, and is intended to be within the scope of the present invention.

The present invention relates to the following embodiments.

According to one aspect of the present invention, there is provided a molecular sieve having an X-ray diffraction pattern substantially as shown in the table below.

According to one aspect of the present invention, in the X-ray diffraction pattern of the molecular sieve, preferably still further comprises X-ray diffraction peaks substantially as shown in the following table.

According to one aspect of the invention, the molecular sieve (referred to as a single crystal) has a crystal morphology ranging from prismoid to oblate, and in particular has a primary crystal morphology ranging from prismoid to oblate, when observed using a Scanning Electron Microscope (SEM). Here, the crystal morphology refers to the (overall) external shape that a single molecular sieve crystal exhibits in the observation field of view of the scanning electron microscope. Virgin refers to the morphology that the molecular sieve objectively appears directly after manufacture, and not to the morphology that the molecular sieve appears after manufacture by human handling. By prism is meant convex prism and generally refers to both straight prisms and regular polygonal prisms (such as regular hexagonal prisms). It is to be noted in particular that, since the crystals of the molecular sieve may be disturbed by various factors during growth, the actual crystal morphology may deviate to some extent, such as 30%, 20% or 5%, from the geometrical (true) right prisms, (true) regular polygonal prisms or (true) cylinders, resulting in the obtaining of oblique prisms, irregular polygonal (even curved sided polygonal) prisms or elliptic cylinders, but the invention is not intended to specifically specify the extent of the deviation. Moreover, any greater or lesser deviation may be made without departing from the scope of the invention. By "flat" it is meant that the ratio of height to width (or diameter) (such as the ratio of height to diameter described below) is less than 1. By "flat prism shape to flat cylinder shape", it is meant that the crystal morphology of the molecular sieve may be flat prism shape, flat cylinder shape, or any shape transitioning from flat prism shape to flat cylinder shape. Specific examples of the transition shape include a shape obtained by rounding one or more edges of the flat prism. It is evident that by rounding all the edges of the flat prism it is possible to obtain the flat cylinder.

According to a variant embodiment of the invention, as previously described, the molecular sieve has a columnar crystal morphology when observed with a Scanning Electron Microscope (SEM). When a longitudinal section is taken along the center line of the column, a longitudinal section of the column can be obtained. The longitudinal section has end surface contour lines on the upper and lower sides (the range surrounded by the two broken lines) and side surface contour lines on the left and right sides (the range surrounded by the two broken lines). The molecular sieve of this variant embodiment is unique in that one or both of the end contour lines have an outwardly convex shape, i.e. a radius of curvature which is positive. The present invention is not intended to limit the specific range of values of the radius of curvature as long as it is a positive value. Alternatively, the molecular sieve of the present modified embodiment may be said to have an outer shape obtained by rounding or chamfering the edge of one end face or both end faces of the column. This can be understood, for example, with reference to fig. VI-14(a) and VI-14 (b). Here, the drawings VI to 14(a) and VI to 14(b) are only for explaining the present invention, and are not intended to limit the present invention. In addition, fig. VI-14(c) exemplify the case where the end face contour line does not have a convex shape but a flat shape.

The inventors of the present invention have earnestly investigated and found that the prior art has not produced a molecular sieve having both the aforementioned specific X-ray diffraction pattern and the aforementioned specific (as-grown) crystal morphology.

According to one aspect of the invention, the molecular sieve (single crystals) generally has an effective diameter of from 100nm to 1000nm, preferably from 100nm to 500nm, when viewed using a Scanning Electron Microscope (SEM). Here, the effective diameter means that two points are arbitrarily selected along the profile (edge) of the cross section of the molecular sieve (single crystal) on the cross section, and the straight-line distance between the two points is measured, with the largest straight-line distance as the effective diameter. If the cross-sectional profile of the molecular sieve is in the form of a polygon, such as a hexagon, the effective diameter generally refers to the linear distance (diagonal distance) between the two vertices of the polygon that are farthest apart. In simple terms, the effective diameter substantially corresponds to the diameter of a circle circumscribing the polygon represented by the outline of the cross-section. Alternatively, if the cross-sectional profile of the molecular sieve is presented as a circle, the effective diameter refers to the diameter of the circle.

According to one aspect of the invention, the height of the molecular sieve (single crystals) is generally from 100nm to 1000nm, preferably from 150nm to 300nm, when viewed using a Scanning Electron Microscope (SEM). Here, the height refers to a straight line distance between the centers of both end faces of the pillars in a single crystal (columnar crystal) of the molecular sieve.

According to one aspect of the present invention, the aspect ratio of the molecular sieve (single crystals) is generally from 0.1 to 0.9, preferably from 0.4 to 0.7, when observed using a Scanning Electron Microscope (SEM). Here, the aspect ratio refers to a ratio of the height to the effective diameter. The prior art has not produced a molecular sieve having both the specific X-ray diffraction pattern and the specific aspect ratio. For example, the crystal morphology of the molecular sieve at this point is similar to that of an oral tablet.

According to one aspect of the invention, the total specific surface area of the molecular sieve is generally from 400m²G to 600m²G, preferably from 450m²G to 580m²(ii) in terms of/g. Here, the total specific surface area is calculated by a BET model by a liquid nitrogen adsorption method.

According to one aspect of the invention, the molecular sieve has a pore volume generally from 0.3 to 0.5ml/g, preferably from 0.30 to 0.40 ml/g. The molecular sieve of the present invention has a very high pore volume, which indicates that it is an ultra-large pore molecular sieve. Here, the pore volume was calculated by a BET model through low-temperature nitrogen adsorption.

According to one aspect of the present invention, the molecular sieve may have a schematic chemical composition represented by the formula "first oxide — second oxide". It is known that molecular sieves sometimes contain some amount of moisture, particularly immediately after synthesis, but it is not considered necessary to specify this amount of moisture in the present invention because the presence or absence of this moisture does not substantially affect the XRD spectrum of the molecular sieve. In view of this, the schematic chemical composition represents, in effect, the anhydrous chemical composition of the molecular sieve. Moreover, it is apparent that the schematic chemical composition represents the framework chemical composition of the molecular sieve.

In accordance with one aspect of the present invention, the molecular sieve may further generally contain in its composition, immediately after synthesis, an organic templating agent, water, and the like, such as those filled in its channels. Thus, the molecular sieve may sometimes have a schematic chemical composition represented by the formula "first oxide, second oxide, organic template, water". Here, the molecular sieve having the schematic chemical composition represented by the formula "first oxide/second oxide/organic template/water" can be obtained by calcining the molecular sieve having the schematic chemical composition represented by the formula "first oxide/second oxide/organic template/water" so as to remove any organic template, water, and the like present in the pore channels thereof. In addition, the calcination may be carried out in any manner conventionally known in the art, for example, the calcination temperature is generally from 300 ℃ to 750 ℃, preferably from 400 ℃ to 600 ℃, and the calcination time is generally from 1 hour to 10 hours, preferably from 3 hours to 6 hours. In addition, the calcination is generally carried out in an oxygen-containing atmosphere, such as air or oxygen.

According to an aspect of the present invention, in the foregoing schematic chemical composition, the first oxide is generally a tetravalent oxide, and for example, at least one selected from the group consisting of silicon dioxide, germanium dioxide, tin dioxide, titanium dioxide and zirconium dioxide may be cited, and silicon dioxide (SiO) is preferable₂) Or a combination of silicon dioxide and germanium dioxide. These first oxides may be used singly or in combination in any ratio. When a plurality of kinds are used in combination, the molar ratio between any two first oxides is, for example, from 20: 200 to 35: 100. examples of the combination include a combination of silica and germanium dioxide, in which case the molar ratio of silica to germanium dioxide is, for example, from 20: 200 to 35: 100.

according to an aspect of the present invention, in the foregoing schematic chemical composition, the second oxide is generally a trivalent oxide, and for example, at least one selected from the group consisting of aluminum oxide, boron oxide, iron oxide, gallium oxide, rare earth oxide, indium oxide and vanadium oxide may be cited, and aluminum oxide (Al) is preferable₂O₃). These second oxygenThese compounds may be used singly or in combination in any ratio. When a plurality of kinds are used in combination, the molar ratio between any two second oxides is, for example, from 30: 200 to 60: 150.

according to an aspect of the present invention, in the foregoing schematic chemical composition, for example, any organic templating agent used in the production of the molecular sieve, and particularly, the organic templating agent used in the production of the molecular sieve according to the present embodiment, may be cited as the organic templating agent (see the detailed description below). These organic templates may be used singly or in combination in any ratio. Specifically, specific examples of the organic template include compounds represented by the following formula (I).

According to one aspect of the invention, in formula (I), the radical R₁And R₂Are the same or different from each other and are each independently selected from C_3-12A linear or branched alkylene group, a plurality of groups R, equal to or different from each other, each independently selected from C_1-4Straight or branched chain alkyl, and X is OH.

According to one aspect of the invention, in the foregoing exemplary chemical composition, the molar ratio of the first oxide to the second oxide (e.g., SiO)₂With Al₂O₃In a molar ratio) is generally from 40 to 200, preferably from 40 to 150.

According to one aspect of the present invention, in the aforementioned schematic chemical composition, the molar ratio of water to the first oxide is generally from 5 to 50, preferably from 5 to 15.

According to one aspect of the present invention, in the foregoing schematic chemical composition, the molar ratio of the organic templating agent to the first oxide is generally from 0.02 to 0.5, preferably from 0.05 to 0.5, from 0.15 to 0.5, or from 0.3 to 0.5.

According to one aspect of the present invention, the molecular sieve may further contain, in its composition (typically filled in its pores), metal cations such as alkali metal and/or alkaline earth metal cations as a constituent component depending on the starting materials used in its manufacturing process. As the content of the metal cation at this time, for example, the mass ratio of the metal cation to the first oxide is generally from 0 to 0.02, preferably from 0.0002 to 0.006, but is not limited thereto in some cases.

According to one aspect of the invention, the molecular sieve may be manufactured by the following manufacturing method. Here, the production method includes a step of contacting a first oxide source, a second oxide source, an optional alkali source, an organic template, and water under crystallization conditions to obtain a molecular sieve (hereinafter referred to as a contacting step).

In the method for manufacturing the molecular sieve according to an aspect of the present invention, the contacting step may be performed in any manner conventionally known in the art, such as a method of mixing the first oxide source, the second oxide source, the optional alkali source, the organic template, and water, and crystallizing the mixture under the crystallization condition.

According to an aspect of the present invention, in the contacting step, the organic template includes at least a compound represented by the following formula (I). Here, the compounds represented by the formula (I) may be used singly or in combination in any ratio.

According to one aspect of the invention, in said formula (I), the radical R₁And R₂Are the same or different from each other and are each independently selected from C_3-12Straight or branched chain alkylene.

According to a variant embodiment of the invention, in said formula (I), the radical R is₁And R₂Are identical or different from each other, one of them being selected from C_3-12Linear alkylene and the other is selected from C_4-6A linear alkylene group.

According to an aspect of the present invention, as said C_3-12Straight-chain or branched alkylene, for example, C_3-12Specific examples of the linear alkylene group include a n-propylene group, an isopropylene group, a n-butylene group, an isobutylene group, a tert-butylene group, a n-pentylene group, an isopentylene group, a neopentylene group, a n-hexylene group, an isohexylene group, a n-octylene group, an isooctylene group, a neooctylene group, a nonylene group (or its isomer), a decylene group (or its isomer), an undecylene group (or its isomer) or a dodecylene group (or its isomer), and a n-propylene group, a n-butylene group, a n-pentylene group, a n-hexylene group, a n-heptylene group, a n-octylene group, a n-nonylene group, a n-decylene group, a n-undecylene.

According to an aspect of the present invention, as said C_4-6Examples of the linear alkylene group include n-butylene group, n-pentylene group and n-hexylene group.

According to one aspect of the invention, in said formula (I), a plurality of radicals R, equal to or different from each other, are each independently selected from C_1-4The linear or branched alkyl groups are preferably each independently selected from methyl and ethyl, more preferably both methyl.

According to one aspect of the invention, in said formula (I), X is OH.

According to one aspect of the present invention, in the contacting step, the molar ratio of the organic templating agent to the first oxide source (based on the first oxide) is generally from 0.02 to 0.5, preferably from 0.05 to 0.5, from 0.15 to 0.5, or from 0.3 to 0.5.

According to an aspect of the present invention, in the contacting step, other organic templating agents conventionally used in the art for producing molecular sieves may be further used in addition to the compound represented by the formula (I) as the organic templating agent. Preferably, in the contacting step, only the compound represented by the formula (I) is used as the organic templating agent. Here, the compounds represented by the formula (I) may be used singly or in combination in any ratio.

According to one aspect of the invention, in the contacting step, the first oxide source is generally fourThe source of the oxide of valence includes, for example, at least one selected from the group consisting of a source of silica, a source of germanium dioxide, a source of tin dioxide, a source of titanium dioxide and a source of zirconium dioxide, and preferably Silica (SiO)₂) A source or a combination of a silica source and a germanium dioxide source. These first oxide sources may be used singly or in combination of plural kinds in an arbitrary ratio. When a plurality of kinds are used in combination, the molar ratio between any two first oxide sources is, for example, from 30: 200 to 60: 150. examples of the combination include a combination of a silica source and a germanium dioxide source, and in this case, the molar ratio of the silica source to the germanium dioxide source is, for example, from 20: 200 to 35: 100.

according to an aspect of the present invention, in the contacting step, as the first oxide source, any corresponding oxide source conventionally used in the art for this purpose may be used, including, but not limited to, oxides, hydroxides, alkoxides, metal oxyacids, acetates, oxalates, ammonium salts, sulfates, halides, nitrates, and the like of the corresponding metal in the first oxide. For example, when the first oxide is silica, examples of the source of the first oxide include silica sol, coarse silica gel, tetraethoxysilane, water glass, white carbon, silicic acid, silica gel, potassium silicate, and the like. When the first oxide is germanium dioxide, examples of the source of the first oxide include tetraalkoxygermanium, germanium oxide, and germanium nitrate. When the first oxide is a tin dioxide source, examples of the first oxide source include tin chloride, tin sulfate, and tin nitrate. When the first oxide is titanium oxide, examples of the source of the first oxide include titanium tetraalkoxide, titanium dioxide, and titanium nitrate. When the first oxide is zirconium dioxide, examples of the source of the first oxide include zirconium chloride, zirconium sulfate, and zirconium nitrate. These first oxide sources may be used singly or in combination of plural kinds in a desired ratio.

According to one aspect of the invention, in the contacting step, the second oxide source is generally a trivalent oxide source, such asAt least one selected from the group consisting of an alumina source, a boron oxide source, an iron oxide source, a gallium oxide source, a rare earth oxide source, an indium oxide source and a vanadium oxide source, preferably alumina (Al)₂O₃) A source. These second oxide sources may be used singly or in combination of plural kinds in an arbitrary ratio. When a plurality of species are used in combination, the molar ratio between any two second oxide sources is, for example, from 20: 200 to 35: 100.

according to an aspect of the present invention, in the contacting step, as the second oxide source, any corresponding oxide source conventionally used in the art for this purpose may be used, including but not limited to oxides, hydroxides, alkoxides, metal oxyacids, acetates, oxalates, ammonium salts, sulfates, halides, nitrates, and the like of the corresponding metal in the second oxide. For example, when the second oxide is alumina, examples of the second oxide source include aluminum chloride, aluminum sulfate, hydrated alumina, sodium metaaluminate, alumina sol, and aluminum hydroxide. When the second oxide is boron oxide, examples of the second oxide source include boric acid, borate, borax, diboron trioxide, and the like. When the second oxide is iron oxide, examples of the second oxide source include iron nitrate, iron chloride, and iron oxide. When the second oxide is gallium oxide, examples of the source of the second oxide include gallium nitrate, gallium sulfate, gallium oxide, and the like. When the second oxide is a rare earth oxide, examples of the second oxide source include lanthanum oxide, neodymium oxide, yttrium oxide, cerium oxide, lanthanum nitrate, neodymium nitrate, yttrium nitrate, and ammonium ceric sulfate. When the second oxide is indium oxide, examples of the second oxide source include indium chloride, indium nitrate, and indium oxide. When the second oxide is vanadium oxide, examples of the second oxide source include vanadium chloride, ammonium metavanadate, sodium vanadate, vanadium dioxide, vanadyl sulfate, and the like. These second oxide sources may be used singly or in combination of plural kinds in a desired ratio.

According to an aspect of the invention, in saidIn the contacting step, the first oxide source (based on the first oxide, such as SiO)₂) With said second oxide source (based on said second oxide, such as Al)₂O₃) Is generally from 40 to 200, preferably from 40 to 150.

According to one aspect of the invention, in the contacting step, the molar ratio of water to the first oxide source (based on the first oxide) is generally from 5 to 50, preferably from 5 to 15.

According to an aspect of the present invention, in the contacting step, an alkali source may or may not be used. The group X contained in the compound represented by the formula (I) can be used to provide the OH group required therein without the intentional use of an alkali source^-. Here, as the alkali source, any alkali source conventionally used in the art for this purpose may be used, including but not limited to inorganic bases having an alkali metal or an alkaline earth metal as a cation, particularly sodium hydroxide, potassium hydroxide and the like. These alkali sources may be used singly or in combination of two or more in an arbitrary ratio.

According to one aspect of the invention, in the contacting step, the source of alkalinity (in OH)^-In terms of the first oxide) to the first oxide source (in terms of the first oxide) is generally from 0 to 1, preferably from 0.04 to 1, from 0.1 to 1, from 0.2 to 1, from 0.3 to 0.7 or from 0.45 to 0.7.

According to an aspect of the present invention, in the contacting step, as the crystallization condition, the crystallization temperature is generally from 80 ℃ to 120 ℃, preferably from 120 ℃ to 170 ℃ or from 120 ℃ to 200 ℃.

According to an aspect of the present invention, in the contacting step, as the crystallization condition, the crystallization time is generally at least 1 day, preferably at least 2 days, preferably from 3 days to 8 days, from 5 days to 8 days, or from 4 days to 6 days.

According to an aspect of the present invention, in the method for producing a molecular sieve, after the contacting step is completed, the molecular sieve may be separated from the obtained reaction mixture as a product by any separation means conventionally known. Herein, the molecular sieve product comprises the molecular sieve of the present invention. In addition, as the separation method, for example, a method of filtering, washing and drying the obtained reaction mixture may be mentioned.

According to an aspect of the present invention, in the method for manufacturing the molecular sieve, the filtering, washing and drying may be performed in any manner conventionally known in the art. Specifically, for example, the reaction mixture obtained may be simply filtered by suction. As the washing, for example, washing with deionized water until the filtrate has a pH of 7 to 9, preferably 8 to 9, can be mentioned. The drying temperature is, for example, 40 to 250 ℃ and preferably 60 to 150 ℃, and the drying time is, for example, 8 to 30 hours and preferably 10 to 20 hours. The drying may be carried out under normal pressure or under reduced pressure.

According to an aspect of the present invention, the method for producing the molecular sieve may further include a step of subjecting the obtained molecular sieve to calcination (hereinafter, referred to as calcination step) as necessary to remove the organic template and moisture and the like that may be present, thereby obtaining a calcined molecular sieve. In the context of the present specification, the molecular sieves before and after calcination are also collectively referred to as the molecular sieve of the invention or the molecular sieve according to the invention.

According to one aspect of the present invention, in the method for manufacturing a molecular sieve, the calcination may be carried out in any manner conventionally known in the art, such as calcination temperature is generally from 300 ℃ to 750 ℃, preferably from 400 ℃ to 600 ℃, and calcination time is generally from 1 hour to 10 hours, preferably from 3 hours to 6 hours. In addition, the calcination is generally carried out in an oxygen-containing atmosphere, such as air or oxygen.

According to one aspect of the invention, the molecular sieve of the invention or any molecular sieve produced according to the method of producing a molecular sieve of the invention (in the context of the present specification, both are also collectively referred to as the molecular sieve of the invention or the molecular sieve according to the invention), may, if desired, also be subjected to ion exchange by any means conventionally known in the artFor example, the metal cations (such as Na ions or K ions, depending on the specific production method thereof) contained in the composition thereof may be replaced in whole or in part with other cations by an ion exchange method or a solution impregnation method (see, for example, U.S. Pat. nos. 3140249 and 3140253). Examples of the other cation include a hydrogen ion, other alkali metal ion (including K ion, Rb ion, etc.), and ammonium ion (including NH)₄Ions, quaternary ammonium ions such as tetramethylammonium ion and tetraethylammonium ion, etc.), alkaline earth metal ions (including Mg ion, Ca ion), Mn ion, Zn ion, Cd ion, noble metal ions (including Pt ion, Pd ion, Rh ion, etc.), Ni ion, Co ion, Ti ion, Sn ion, Fe ion, and/or rare earth metal ion, etc.

The molecular sieve according to the present invention may be further treated with a dilute acid solution or the like as necessary to increase the silica-alumina ratio, or treated with water vapor to increase the acid-erosion resistance of the molecular sieve crystals.

The molecular sieves according to the invention have a stronger acidity, in particular the L acid (the number of centres is higher, which is a molecular sieve not produced in the prior art).

The molecular sieve according to the invention may be in any physical form, such as a powder, granules or molded article (e.g. a strip, a trilobe, etc.). These physical forms can be obtained in any manner conventionally known in the art and are not particularly limited.

The molecular sieve according to the invention may be used in combination with other materials, thereby obtaining a molecular sieve composition. Examples of the other materials include active materials and inactive materials. Examples of the active material include synthetic zeolite and natural zeolite, and examples of the inactive material (generally referred to as a binder) include clay, silica gel, and alumina. These other materials may be used singly or in combination in any ratio. As the amount of the other materials, those conventionally used in the art can be directly referred to, and there is no particular limitation.

The molecular sieves or molecular sieve compositions according to the invention are particularly suitable for use as adsorbents, for example for separating at least one component from a mixture of components in the gas or liquid phase.

The molecular sieve or molecular sieve composition according to the invention is particularly suitable for use as a catalyst in hydrocarbon conversion reactions. Examples of the hydrocarbon conversion reaction include catalytic cracking, hydrocracking, disproportionation, alkylation, oligomerization, and isomerization.

The molecular sieve or molecular sieve composition according to the invention is particularly suitable for use as a support or support component for a catalyst and has supported thereon an active component in any manner conventionally known in the art, such as by solution impregnation. These active components include, but are not limited to, active metal components (including Ni, Co, Mo, W, or Cu, etc.), active inorganic aids (such as F, P, etc.), and organic compounds (such as organic acids, organic amines, etc.), among others. These active ingredients may be used singly or in combination in any ratio. As the amount of the active ingredient, the amount conventionally used in the art can be directly referred to, and is not particularly limited.

Examples

The present invention will be described in further detail with reference to examples, but the present invention is not limited to these examples.

In the context of the present description, including the examples and comparative examples below, an Autochem ii 2920 temperature programmed desorption instrument from mack, usa was used. And (3) testing conditions are as follows: weighing 0.2g of 20-40 mesh molecular sieve, placing in a sample tube, placing in a heating furnace, taking He gas as carrier gas (25mL/min), heating to 600 deg.C at 20 deg.C/min, and purging for 60min to remove impurities adsorbed on the surface of the molecular sieve. Then cooling to 100 ℃, keeping the temperature for 10min, and switching to NH₃-He mixed gas(10％NH₃+ 90% He) for 30min, and then continuing to sweep with He gas for 90min until the baseline plateaus to desorb the physisorbed NH 3. And (4) carrying out desorption by heating to 600 ℃ at the heating rate of 10 ℃/min in a programmed manner, keeping for 30min, and finishing the desorption. And detecting the change of gas components by adopting a TCD detector, and automatically integrating by an instrument to obtain the acid amount distribution.

In the context of the present specification, including in the following examples and comparative examples, XRD testing was carried out using a Netherland, PANALYTICAL Corporation apparatus test conditions of Cu target, K α radiation, Ni filter, tube voltage 40kV, tube current 40mA, and scanning range 2-50 deg..

In the context of the present description, the following examples and comparative examples are included, using TECNAIG from FEI USA²Model F20(200kv) scanning electron microscope. And (3) testing conditions are as follows: a suspension method is adopted for sample preparation, and 0.01g of molecular sieve sample is put into a 2mL glass bottle. Dispersing with anhydrous ethanol, shaking, dropping with a dropper onto a sample net with diameter of 3mm, drying, placing in a sample injector, and observing with an electron microscope. The observation may use a magnification of 1 ten thousand times or a magnification of 5 ten thousand times. In addition, the molecular sieve is observed under the magnification of 5 ten thousand times, an observation field is randomly selected, and the average value of the sum of the effective diameters and the average value of the sum of the heights of all the molecular sieve crystals in the observation field are calculated. This operation was repeated a total of 10 times. The effective diameter and height were determined as the average of the sum of the average values of 10 times.

In the context of the present specification, including the examples and comparative examples below, the U.S. Varian is used^UNITYINOVA 500MHz NMR spectrometer. And (3) testing conditions are as follows: using a solid dual-resonance probe, 4mm phi ZrO₂And a rotor. Experimental parameters: the test temperature is room temperature, the number of scanning times nt is 5000, the pulse width pw is 3.9 mus, the spectrum width sw is 31300Hz, the resonance frequency Sfrq of the observed nucleus is 125.64MHz, the sampling time at is 0.5s, and the chemical shift calibration delta _TMS0, delay time d1 is 4.0s, decoupling mode dm is nny (anti-gated decoupling), deuterated chloroform lock field.

In the context of the present specification, the following implementations are includedIn examples and comparative examples, a 3013 type X-ray fluorescence spectrometer, manufactured by Nippon Denshi Motor Co., Ltd, was used. And (3) testing conditions are as follows: tungsten target, excitation voltage 40kV, excitation current 50 mA. The experimental process comprises the following steps: the sample is pressed into a sheet and then arranged on an X-ray fluorescence spectrometer, and the sample emits fluorescence under the irradiation of X-rays, wherein the following relationship exists between the fluorescence wavelength lambda and the atomic number Z of the element: k (Z-S)^-2K is a constant, and as long as the wavelength λ of fluorescence is measured, the element can be identified. And measuring the intensity of each element characteristic spectral line by using a scintillation counter and a proportional counter, and carrying out element quantitative or semi-quantitative analysis.

In the context of the present description, including the examples and comparative examples below, a Fourier Infrared spectrometer model FTS3O00 from BIO-RAD, USA was used. And (3) testing conditions are as follows: vacuum pumping is carried out at 350 ℃ to 10-3Pa, and the wave number range is 1300-^-1. And (3) tabletting the sample, and then placing the sample in an in-situ cell of an infrared spectrometer for sealing. Vacuum pumping is carried out at 350 ℃ to 10^-3Pa, keeping for 1h to enable gas molecules on the surface of the sample to be desorbed completely, and cooling to room temperature. Introducing pyridine/2, 4, 6-trimethylpyridine with pressure of 2.67Pa into the in-situ tank, carrying out equilibrium adsorption for 30min, heating to 200 ℃, and vacuumizing again to 10 DEG C^-3Pa, maintaining for 30min, cooling to room temperature at 1300-3900cm^-1Scanning in wave number range, and recording the infrared absorption spectrum of pyridine/2, 4, 6-trimethyl pyridine at 200 ℃. Then the sample in the infrared absorption cell is moved to a heat treatment area, the temperature is raised to 350 ℃, and the vacuum is pumped to 10 DEG^-3Pa, keeping for 30min, cooling to room temperature, and recording the infrared spectrogram of pyridine adsorption at 350 ℃.

In the context of this specification, including the examples and comparative examples below, all medicaments and starting materials are either commercially available or can be manufactured according to established knowledge.

In the context of the present embodiment, including in the examples and comparative examples below, the total specific surface area, pore volume and pore diameter of the molecular sieve are measured according to the following analytical methods.

Equipment: micromeritic ASAP2010 static nitrogen adsorption instrument

Measurement conditions were as follows: placing the sample in a sample processing system, and pumping at 350 deg.CVacuum to 1.33X 10^-2Pa, keeping the temperature and the pressure for 15h, and purifying the sample. And measuring the adsorption quantity and the desorption quantity of the purified sample on nitrogen under different specific pressures of P/P0 at the liquid nitrogen temperature of-196 ℃ to obtain an adsorption-desorption isothermal curve. And then calculating the total specific surface area by using a two-parameter BET formula, taking the adsorption capacity below a specific pressure P/P0 which is approximately equal to 0.98 as the pore volume of the sample, and calculating the pore size distribution according to a BJH model.

Example VI-1

Preparation of template agent A:

adding 15g (0.087mol) of tetramethylhexamethylenediamine into a 500ml three-necked bottle, adding 250ml of isopropanol, dropwise adding 18.8g (0.087mol) of 1, 4-dibromobutane at room temperature, after 15min, heating to reflux, gradually changing the solution from colorless transparency to white turbidity, tracking the reaction of the raw materials by High Performance Liquid Chromatography (HPLC), adding 200ml of ethyl acetate into the reaction solution, refluxing for 1h, cooling, performing suction filtration, washing the obtained solid by ethyl acetate and diethyl ether in sequence to obtain 30g of a white solid product, namely 1,1,6, 6-tetramethyl-1, 6-diaza-dodecacyclo-1, 6-dibromo salt (a compound with n being 4, m being 6, R being methyl and X being Br), the relative molecular weight of 388.2, the melting point of 273.7 ℃, and the chemical shift of 1HNMR (300MHz, CDCl)₃)δ1.50(t,4H),1.90(t,8H),3.14(s,12H),3.40(t,8H)。

Preparation of template B: replacing Br in the template agent A with OH by adopting an ion exchange method; the ion exchange resin is strong-base styrene anion exchange resin, the working solution is a 15 m% template agent A aqueous solution, the operation temperature is 25 ℃, and the mass ratio of the working solution to the ion exchange resin is 1: 3; the flow rate was 3 drops/second; and (3) removing water from the exchanged solution by using a rotary evaporator to obtain a product, wherein the product is a compound in which n is 4, m is 6, R is methyl and X is OH in the formula (I), the relative molecular weight is 262.2, the purity is 99.21 percent, and the bromine content is 0.79m percent.

Example VI-2

Preparation of template C

Adding 10g (0.058mol) of tetramethylhexanediamine into a 500ml three-necked bottle, adding 250ml of isopropanol, dropwise adding 16.6g (0.058mol) of 1, 9-dibromononane at room temperature, after 15min, heating to reflux, gradually changing the solution from colorless transparency to white turbidity, tracking the raw materials by High Performance Liquid Chromatography (HPLC), adding 200ml of ethyl acetate into the reaction solution after the reaction is completed, refluxing for 1H, cooling, performing suction filtration, washing the obtained solid with ethyl acetate and diethyl ether in sequence to obtain 25g of a white solid product (a compound with the relative molecular weight of 458.4, the chemical shift of 1 MR spectrogram (300MHz, CDCl3) delta 1.51(t,14H),1.92(t,8H),3.16(s,12H),3.40(t, 8H).

Preparation of template D: replacing Br in the template agent C with OH by adopting an ion exchange method; the ion exchange resin is strongly basic styrene anion exchange resin, the working solution is a 15 m% template agent C aqueous solution, the operating temperature is 25 ℃, and the mass ratio of the working solution to the ion exchange resin is 1: 3; the flow rate was 3 drops/second; and (3) removing water from the exchanged solution by using a rotary evaporator to obtain a product, wherein the product is a compound in which n is 9, m is 6, R is methyl and X is OH in the formula (I), the relative molecular weight is 332.4, the purity is 99.8 percent, and the bromine content is 0.2m percent.

Example VI-3

0.132g of sodium metaaluminate is charged into a 45mL Teflon container, 8.024g of template B is added, and then 3g of coarse silica gel (Qingdao ocean chemical Co., Ltd., Industrial product, SiO) is added₂The content is 98.05 percent), standing and aging for 1 hour, and fully mixing, wherein the molar ratio of each component is as follows: SiO 2₂/Al₂O₃＝60、H₂O/SiO₂7.8, template B/SiO₂＝0.15。

The above mixture was charged into a 45mL steel autoclave with a Teflon liner, which was covered and sealed, and the autoclave was placed in a rotary convection oven set at 20rpm, reacted at 120 ℃ for 1 day, and then heated to 150 ℃ for 5 days. Taking out the autoclave and rapidly cooling the autoclave to room temperature, separating the mixture on a high-speed centrifuge with 5000rpm, collecting the solid, fully washing the solid with deionized water, and drying the solid for 5 hours at 100 ℃ to obtain the product.

The product is shown in figure VI-1 by scanning electron microscope, in which it is evident that the molecular sieve has flat prism or flat cylindrical crystal morphology, effective diameter of 600nm, and height300nm and an aspect ratio of 0.5. The total specific surface area of the molecular sieve was measured to be 518m²The pore volume was 0.351 ml/g. XRF analysis results showed Si/Al₂63. The XRD pattern of the product is shown in FIG. VI-2. NH (NH)₃The results for TPD show (FIG. VI-3) that the molecular sieve has a pronounced acidity. The result of the infrared spectrum shows (figure VI-4), the acid content of the B acid of the molecular sieve is low, and the acid content of the L acid is high.

Example VI to 4

0.735g of sodium metaaluminate is charged into a 45mL Teflon container, 8.024g of template B is added, and then 3g of coarse silica gel (Qingdao ocean chemical Co., Ltd., Industrial product, SiO) is added₂The content is 98.05 percent), standing and aging for 1 hour, and fully mixing, wherein the molar ratio of each component is as follows: SiO 2₂/Al₂O₃＝80、H₂O/SiO₂7.5, template B/SiO₂0.15. The above mixture was charged into a 45mL steel autoclave with a Teflon liner, which was covered and sealed, and the autoclave was placed in a rotary convection oven set at 20rpm, reacted at 120 ℃ for 1 day and then heated to 150 ℃ for 5 days. Taking out the autoclave and rapidly cooling the autoclave to room temperature, separating the mixture on a high-speed centrifuge with 5000rpm, collecting the solid, fully washing the solid with deionized water, and drying the solid for 5 hours at 100 ℃ to obtain the product.

The scanning electron micrograph of the product is shown in figure VI-5, which obviously shows that the molecular sieve has the flat prism or flat cylindrical crystal morphology, the effective diameter is 300nm, the height is 200nm, and the height-diameter ratio is 0.67. The total specific surface area of the molecular sieve was measured to be 482m²The pore volume is 0.346 ml/g. XRF analysis results showed Si/Al₂84. The XRD pattern of the product is shown in figure VI-6.

Examples VI to 5

0.132g of sodium metaaluminate is charged into a 45mL Teflon container, 8.731g of template D is added, and then 3g of coarse silica gel (Qingdao ocean chemical Co., Ltd., Industrial product, SiO) is added₂The content is 98.05 percent), standing and aging for 1 hour, and fully mixing, wherein the molar ratio of each component is as follows: SiO 2₂/Al₂O₃＝60、H₂O/SiO₂8 as template agent D/SiO₂0.15. The above mixture was charged into a 45mL steel autoclave with a Teflon liner, which was covered and sealed, and the autoclave was placed in a rotary convection oven set at 20rpm, reacted at 120 ℃ for 1 day, and then heated to 150 ℃ for 4 days. Taking out the autoclave and rapidly cooling the autoclave to room temperature, separating the mixture on a high-speed centrifuge with 5000rpm, collecting the solid, fully washing the solid with deionized water, and drying the solid for 5 hours at 100 ℃ to obtain the product.

The scanning electron micrograph of the product is shown in figure VI-7, which obviously shows that the molecular sieve has the flat prism or flat cylindrical crystal morphology, the effective diameter is 300nm, the height is 200nm, and the height-diameter ratio is 0.67. The total specific surface area of the molecular sieve was measured to be 452m²The pore volume is 0.385 ml/g. XRF analysis results showed Si/Al₂＝62。

Examples VI to 6

Adding 0.132g of sodium metaaluminate into a 45mL Teflon container, adding 4.1g of template D, stirring for 30 minutes until uniform, and adding 3g of coarse silica gel (Qingdao ocean chemical Co., Ltd., Industrial product, SiO)₂The content is 98.05 percent), standing and aging for 1 hour, and fully mixing, wherein the molar ratio of each component is as follows: SiO 2₂/Al₂O₃＝60、H₂O/SiO₂7 as template agent D/SiO₂＝0.32。

The scanning electron microscope image of the product is shown in figure VI-8, which obviously shows that the molecular sieve has flat prism or flat cylindrical crystal morphology, the effective diameter is 600nm, the height is 400nm, and the height-diameter ratio is 0.67. The total specific surface area of the molecular sieve is measured to be 487m²The pore volume was 0.387 ml/g. XRF analysis results showed Si/Al₂＝63。

Examples VI to 7

0.132g of sodium metaaluminate is charged into a 45mL Teflon container, 6.0g of template C is added, and then 4g of coarse silica gel (Qingdao ocean chemical Co., Ltd., Industrial product, SiO) is added₂The content is 98.05 percent), standing and aging for 1 hour, and fully mixing, wherein the molar ratio of each component is as follows: SiO 2₂/Al₂O₃＝80、H₂O/SiO₂(5) template agent C/SiO₂0.2. The above mixture was charged into a 45mL steel autoclave with a Teflon liner, which was covered and sealed, and the autoclave was placed in a rotary convection oven set at 20rpm, reacted at 110 ℃ for 1 day, and then heated to 150 ℃ for 5 days. Taking out the autoclave and rapidly cooling the autoclave to room temperature, separating the mixture on a high-speed centrifuge with 5000rpm, collecting the solid, fully washing the solid with deionized water, and drying the solid for 5 hours at 100 ℃ to obtain the product.

The scanning electron microscope image of the product is shown in figure VI-9, which obviously shows that the molecular sieve has flat prism or flat cylindrical crystal morphology, the effective diameter is 400nm, the height is 200nm, and the height-diameter ratio is 0.5. The total specific surface area of the molecular sieve was measured to be 412m²The pore volume is 0.372 ml/g. XRF analysis results showed Si/Al₂＝83。

Examples VI to 8

0.132g of sodium metaaluminate is charged into a 45mL Teflon container, 4g of template A is added, and then 3g of coarse silica gel (Qingdao ocean chemical Co., Ltd., Industrial product, SiO) is added₂The content is 98.05 percent), standing and aging for 1 hour, and fully mixing, wherein the molar ratio of each component is as follows: SiO 2₂/Al₂O₃＝60、H₂O/SiO₂(5) template agent C/SiO₂0.2. The above mixture was charged into a 45mL steel autoclave with a Teflon liner, which was covered and sealed, and the autoclave was placed in a rotary convection oven set at 20rpm, reacted at 120 ℃ for 1 day, and then heated to 150 ℃ for 5 days. Taking out the autoclave and rapidly cooling the autoclave to room temperature, separating the mixture on a high-speed centrifuge with 5000rpm, collecting the solid, fully washing the solid with deionized water, and drying the solid for 5 hours at 100 ℃ to obtain the product.

The scanning electron micrograph of the product is shown in figure VI-10, which obviously shows that the molecular sieve has the flat prism-shaped or flat cylindrical crystal morphology, the effective diameter is 400nm, the height is 250nm, and the height-diameter ratio is 0.625. The total specific surface area of the molecular sieve is measured to be 427m²The pore volume was 0.418 ml/g. XRF analysis results showed Si/Al₂＝58。

Examples VI to 9

0.588g of sodium metaaluminate are placed in a 45mL Teflon container, 8.024g of template B are added, and 3g of coarse silica gel (Qingdao ocean chemical Co., Ltd., Industrial product, SiO) are added₂The content is 98.05 percent), standing and aging for 1 hour, and fully mixing, wherein the molar ratio of each component is as follows: SiO 2₂/Al₂O₃＝100、H₂O/SiO₂7.6, template B/SiO₂＝0.15。

The XRD pattern of the product is shown in figure VI-11.

Examples VI to 10

0.49g of sodium metaaluminate is charged into a 45mL Teflon container, 8.024g of template B is added, and then 3g of coarse silica gel (Qingdao ocean chemical Co., Ltd., Industrial product, SiO) is added₂The content is 98.05 percent), standing and aging for 1 hour, and fully mixing, wherein the molar ratio of each component is as follows: SiO 2₂/Al₂O₃＝120、H₂O/SiO₂7.5, template B/SiO₂＝0.15。

The above mixture was charged into a 45mL steel autoclave with a Teflon liner, which was covered and sealed, and the autoclave was placed in a rotary convection oven set at 20rpm, reacted at 120 ℃ for 1 day, and then heated to 150 ℃ for 5 days. Taking out the autoclave and rapidly cooling the autoclave to room temperature, separating the mixture on a high-speed centrifuge with 5000rpm, collecting the solid, fully washing the solid with deionized water, and drying the solid for 5 hours at 100 ℃ to obtain the product. The XRD pattern of the product is shown in figure VI-12.

Examples VI to 11

0.392g of sodium metaaluminate are placed in a 45mL Teflon container, 8.024g of template B are added and then 3g of coarse silica gel (Qingdao ocean chemical Co., Ltd., Industrial product, SiO)₂The content is 98.05 percent), standing and aging for 1 hour, and fully mixing, wherein the molar ratio of each component is as follows: SiO 2₂/Al₂O₃＝150、H₂O/SiO₂7.3, template B/SiO₂＝0.15。

The above mixture was charged into a 45mL steel autoclave with a Teflon liner, which was covered and sealed, and the autoclave was placed in a rotary convection oven set at 20rpm, reacted at 120 ℃ for 1 day, and then heated to 150 ℃ for 5 days. Taking out the autoclave and rapidly cooling the autoclave to room temperature, separating the mixture on a high-speed centrifuge with 5000rpm, collecting the solid, fully washing the solid with deionized water, and drying the solid for 5 hours at 100 ℃ to obtain the product. The XRD pattern of the product is shown in FIGS. VI-13.

Although the embodiments of the present invention have been described in detail with reference to the examples and the accompanying drawings, it should be noted that the scope of the present invention is not limited by the embodiments, but is defined by the appended claims. Those skilled in the art can appropriately modify the embodiments without departing from the technical spirit and scope of the present invention, and the modified embodiments are also clearly included in the scope of the present invention.

Claims

1. A molecular sieve having a crystal morphology ranging from prismoid to oblate and having an X-ray diffraction pattern as shown in the following Table,

wherein the molecular sieve has a schematic chemical composition represented by the formula "first oxide-second oxide" or the formula "first oxide-second oxide-organic template-water", wherein the molar ratio of the first oxide to the second oxide is from 40 to 200; the first oxide is silicon dioxide, and the second oxide is aluminum oxide; the molar ratio of water to the first oxide is from 5 to 50; the molar ratio of the organic templating agent to the first oxide is from 0.02 to 0.5.

2. A molecular sieve according to claim 1 wherein one or both of the end profile lines on a longitudinal section of the crystals of the molecular sieve have a convex shape.

3. A molecular sieve according to claim 1 wherein said X-ray diffraction pattern further comprises X-ray diffraction peaks as shown in the following table,

4. a molecular sieve according to claim 1 wherein said X-ray diffraction pattern further comprises X-ray diffraction peaks as shown in the following table,

5. the molecular sieve of claim 1 wherein the dimensions of the crystal morphology comprise: an effective diameter of from 100nm to 1000nm, a height of from 100nm to 1000nm, and an aspect ratio of from 0.1 to 0.9.

6. The molecular sieve of claim 5 wherein the dimensions of said crystal morphology comprise: an effective diameter of from 100nm to 500nm, a height of from 150nm to 300nm, and an aspect ratio of from 0.4 to 0.7.

7. Push buttonThe molecular sieve of claim 1, wherein the total specific surface area of the molecular sieve is from 400m²G to 600m²(ii) a pore volume of from 0.3mL/g to 0.5 mL/g.

8. The molecular sieve of claim 7 wherein the total specific surface area of the molecular sieve is from 450m²G to 580m²(ii) a pore volume of from 0.30mL/g to 0.40 mL/g.

9. The molecular sieve of claim 1 wherein the molar ratio of the first oxide to the second oxide is from 40 to 150; the molar ratio of water to the first oxide is from 5 to 15; the molar ratio of the organic templating agent to the first oxide is from 0.05 to 0.5.

10. The molecular sieve of claim 9 wherein the molar ratio of the organic template to the first oxide is from 0.08 to 0.5.

11. The molecular sieve of claim 10 wherein the molar ratio of the organic template to the first oxide is from 0.3 to 0.5.

12. A method for producing the molecular sieve of claim 1, comprising a step of contacting a first oxide source, a second oxide source, optionally an alkali source, an organic template, and water under crystallization conditions to obtain a molecular sieve, and optionally, a step of calcining the obtained molecular sieve, wherein the organic template comprises a compound represented by the following formula (I),

wherein the radical R₁And R₂Are the same or different from each other and are each independently selected from C_3-12A linear or branched alkylene group; a plurality of radicals R, equal to or different from each other, each independently selected from C_1-4A linear or branched alkyl group; x is OH.

13. The process according to claim 12, wherein the group R₁And R₂Are the same or different from each other and are each independently selected from C_3-12A linear alkylene group; the plurality of groups R, equal to or different from each other, are each independently selected from methyl and ethyl.

14. The process according to claim 13, wherein the group R₁And R₂One is selected from C_3-12Linear alkylene and the other is selected from C_4-6A linear alkylene group; a plurality of radicals R are each methyl.

15. The manufacturing method according to claim 12, wherein the crystallization conditions include: a crystallization temperature of from 80 ℃ to 120 ℃ or from 120 ℃ to 200 ℃, a crystallization time of at least 1 day, and the firing conditions comprise: the roasting temperature is from 300 ℃ to 750 ℃, and the roasting time is from 1 hour to 10 hours.

16. The manufacturing method according to claim 15, wherein the crystallization conditions include: the crystallization temperature is from 120 ℃ to 170 ℃, the crystallization time is from 3 days to 8 days, and the calcination conditions include: the roasting temperature is from 400 ℃ to 600 ℃, and the roasting time is from 3 hours to 6 hours.

17. The production method according to claim 12, wherein a molar ratio of the first oxide source to the second oxide source is from 40 to 200, based on the first oxide and the second oxide, respectively; a molar ratio of water to the first oxide source, based on the first oxide, is from 5 to 50; the molar ratio of the organic template to the first oxide source, based on the first oxide, is from 0.02 to 0.5; the alkali source is OH^-For the first oxide source, the molar ratio of the alkali source to the first oxide source is from 0 to 1 based on the first oxide.

18. According toThe production method as claimed in claim 17, wherein the molar ratio of the first oxide source to the second oxide source is from 40 to 150, based on the first oxide and the second oxide, respectively; the molar ratio of water to the first oxide source is from 5 to 15, based on the first oxide; the molar ratio of the organic templating agent to the first oxide source, based on the first oxide, is from 0.3 to 0.5; the alkali source is OH^-The first oxide source is calculated based on the first oxide, and the molar ratio of the alkali source to the first oxide source is from 0.45 to 0.7.

19. A molecular sieve composition comprising the molecular sieve of any one of claims 1 to 11, and a binder.

20. A process for converting hydrocarbons comprising the step of subjecting hydrocarbons to a conversion reaction in the presence of a catalyst, wherein the catalyst comprises the molecular sieve of any one of claims 1 to 11, or the molecular sieve composition of claim 19.

21. The conversion process of claim 20 wherein said conversion reaction is selected from the group consisting of catalytic cracking, hydrocracking, disproportionation, alkylation, oligomerization, and isomerization.