Porous molecular sieve material, method of preparation thereof, and applications

Abstract

The present invention discloses a porous molecular sieve material having at least three concave arcs and at least two, preferably two, adsorption-desorption hysteresis loops in its low-temperature nitrogen adsorption isotherm. The porous molecular sieve material is prepared by mixing a molecular sieve containing silicon as the first skeletal element with a polymeric quaternary ammonium base, water, and optionally a low molecular weight nitrogen-containing basic compound, treating the mixture at 100-200°C for 1-72 hours, separating at least a portion of the solid product from the treated mixture, and drying and calcining the solid product.

Description

[Technical Field]

[0001] This invention relates to inorganic materials, methods for preparing the same, and applications, and more specifically to molecular sieve materials, methods for preparing the same, and applications. [Background technology]

[0002] Porous materials are highly suitable for processes such as the transformation and adsorption of specific substrate molecules due to their abundant pore channel structure and the advantage of being able to control the pore channel size and the location and state of active sites. Inorganic porous materials, whose main structure consists of inorganic elements, are widely studied due to their structural stability, resistance to strong acid and strong alkali environments, and wide range of application possibilities. In terms of structural classification, inorganic porous materials are divided into amorphous and crystalline structural materials. Molecular sieve materials, which belong to the crystalline structural material category, are widely used in processes such as chemical catalysis and adsorption separation.

[0003] Molecular sieves are a type of inorganic material formed by the interconnection of TO4 tetrahedra, possessing a unique pore structure and active sites. Here, T represents the skeletal element in trivalent, tetravalent, pentavalent, or other valence states, such as Si, B, Al, Ga, C, Ge, Sn, Pb, Ti, V, Zr, Hf, and P. When some of the T elements are substituted with elements other than Si, the material can be called a heteroatom-substituted molecular sieve material. By introducing stabilized heteroatoms into the molecular sieve framework, excellent physical and chemical properties can be obtained.

[0004] Molecular sieves have a regular pore structure based on the linked configuration of TO4 tetrahedra. Based on the size of the pore channels, they can be classified into small pores (pore openings composed of 8-membered ring T atoms), medium pores (pore openings composed of 10-membered ring T atoms), large pores (pore openings composed of 12-membered ring T atoms), and super-large pores. According to the classification rules recommended by IUPAC, pore structures can also be classified by size into micropores (pore channel size less than 2 nm), mesopores (pore channel size between 2 nm and 50 nm), and macropores (pore channel size greater than 50 nm). Generally, the parent materials of industrial molecular sieves have pore sizes mainly distributed in the micropore range. To obtain larger openings and good diffusion performance, they can be further subjected to pore expansion treatment.

[0005] CN1301599A discloses a method for producing titanium-silicon molecular sieves with cavities within the crystal by treating TS-1 molecular sieves with a solution containing an organic base. However, these cavities exhibit a closed structure and still impose significant diffusion resistance on substrate molecules. Furthermore, the preparation method involves complex processing steps, a long workflow, and high production costs.

[0006] Pore ​​expansion using inorganic base solutions such as sodium hydroxide is more difficult than treatment with organic bases. This is because inorganic bases have low structure-inducing ability and tend to disrupt the molecular sieve structure during treatment.

[0007] Silylation pore expansion is a recently developed technique that uses silylation reagents as synthetic pore expanders to achieve efficient pore expansion. CN108726528A, CN106145147A, CN106145148A, and CN106145149A all disclose the preparation of titanium-silicon molecular sieves with a hierarchical pore structure and larger mesopore volume using an improved silylation method. However, titanium-silicon molecular sieves prepared by this method exhibit increased structural disorder and poor stability, making them suitable for activating organic peroxides but performing poorly in reactions using hydrogen peroxide as an oxidizing agent.

[0008] In summary, porous molecular sieve inorganic materials prepared using conventional pore expansion methods suffer from problems such as monotonous pore structure, low structural stability, complex preparation processes, high cost, and limited range of applications. [Overview of the project]

[0009] The first object of the present invention is to provide a porous molecular sieve material that is structurally stable and has pore distribution characteristics different from those of the prior art.

[0010] A second object of the present invention is to provide a simple and low-cost method for preparing a structurally stable porous molecular sieve material having pore distribution characteristics different from those of the prior art.

[0011] A third object of the present invention is to provide applications of the porous molecular sieve material of the present invention as a catalyst material that improves, for example, reaction conversion rate and product selectivity.

[0012] To achieve the first objective of the present invention, the present invention provides a porous molecular sieve material characterized in that its low-temperature nitrogen adsorption isotherm has at least three concave arcs and at least two, preferably two, adsorption-desorption hysteresis loops.

[0013] To achieve a second objective of the present invention, the present invention provides a process for preparing a porous molecular sieve material. This process is characterized by mixing a molecular sieve containing silicon as the first skeletal element with a polymeric quaternary ammonium base, water, and optionally a low molecular weight nitrogen-containing basic compound; treating the mixture at a temperature of 100 to 200°C for 1 to 72 hours; separating at least a portion of the solid product from the treated mixture; and drying and calcining the solid product.

[0014] To achieve the third object of the present invention, the present invention provides a method for applying the porous molecular sieve material. The characteristics are that the porous molecular sieve material or the porous molecular sieve material prepared by the method is applied to the adsorption process, catalytic reaction, catalyst preparation or used as a carrier.

[0015] The porous molecular sieve material provided by the present invention has physicochemical properties different from those of the prior art. Mainly, its low-temperature nitrogen adsorption isotherm has at least three concave arcs and at least two, preferably two, adsorption-desorption hysteresis loops.

[0016] The preparation method of the porous molecular sieve material provided by the present invention is simple in procedure, easy to implement, and low in cost. Thereby, a porous molecular sieve material having physicochemical properties different from those of the prior art can be produced, and problems such as the monotonous pore structure, low structural stability, and narrow application range in the existing preparation methods are solved.

[0017] Since the porous molecular sieve material according to the present invention has physicochemical properties different from those of the prior art, it shows good effects in processes such as catalytic reaction and adsorption-desorption separation. For example, when used as a catalyst material, the reaction conversion rate and product selectivity are improved.

Brief Description of the Drawings

[0018] [Figure 1] SEM image of the hollow titanium-silicon molecular sieve HTS sample prepared in Comparative Example 1. [Figure 2] TEM image of the hollow titanium-silicon molecular sieve HTS sample prepared in Comparative Example 1. [Figure 3] Low-temperature nitrogen adsorption-desorption curve of the hollow titanium-silicon molecular sieve HTS sample prepared in Comparative Example 1. [Figure 4] SEM image of the Ti-Si molecular sieve comparative sample STS-D prepared in Comparative Example 2. [Figure 5]TEM image of the Ti-Si molecular sieve comparative sample STS-D prepared in Comparative Example 2. [Figure 6] Low-temperature nitrogen adsorption-desorption isotherm of the Ti-Si molecular sieve comparative sample STS-D prepared in Comparative Example 2. [Figure 7] XRD spectrum of the porous molecular sieve material TS-1-1 prepared in Example 1. [Figure 8] SEM image of the porous molecular sieve material TS-1-1 prepared in Example 1. [Figure 9] TEM image of the porous molecular sieve material TS-1-1 prepared in Example 1. [Figure 10] Low-temperature nitrogen adsorption-desorption isotherm of the porous molecular sieve material TS-1-1 prepared in Example 1. [Figure 11] SEM image of the all-silicon molecular sieve comparative sample S-1-D prepared in Comparative Example 3. [Figure 12] TEM image of the all-silicon molecular sieve comparative sample S-1-D prepared in Comparative Example 3. [Figure 13] Low-temperature nitrogen adsorption-desorption isotherm of the all-silicon molecular sieve comparative sample S-1-D prepared in Comparative Example 3. [Figure 14] SEM image of the porous all-silicon molecular sieve material S-1-1 prepared in Example 7. [Figure 15] Low-temperature nitrogen adsorption-desorption isotherm of the porous all-silicon molecular sieve material S-1-1 prepared in Example 7. [Figure 16] SEM image of the tin-silicon molecular sieve comparative sample Sn-MEL-D prepared in Comparative Example 4. [Figure 17] Low-temperature nitrogen adsorption-desorption isotherm of the tin-silicon molecular sieve comparative sample Sn-MEL-D prepared in Comparative Example 4. [Figure 18] SEM image of the porous molecular sieve material Sn-MEL prepared in Example 10. [Figure 19]This is the low-temperature nitrogen adsorption-desorption curve of the porous molecular sieve material Sn-MEL prepared in Example 10. [Figure 20] This is an SEM image of the Zr-MFI-D zirconium-silicon molecular sieve comparison sample prepared in Comparative Example 5. [Figure 21] This is the low-temperature nitrogen adsorption-desorption curve of the Zr-MFI-D zirconium-silicon molecular sieve comparative sample prepared in Comparative Example 5. [Figure 22] This is an SEM image of the porous molecular sieve material Zr-MFI prepared in Example 11. [Figure 23] This is the low-temperature nitrogen adsorption-desorption curve of the porous molecular sieve material Zr-MFI prepared in Example 11. [Modes for carrying out the invention]

[0019] The present invention provides a porous molecular sieve material having a low-temperature nitrogen adsorption isotherm with at least three concave arcs and at least two, preferably two, adsorption-desorption hysteresis loops.

[0020] Low-temperature nitrogen adsorption-desorption isotherms are obtained by measuring the adsorption-desorption performance of nitrogen at liquid nitrogen temperature (e.g., 77K). Based on the shape of the low-temperature nitrogen adsorption-desorption isotherm, the surface structure and pore properties of the material can be determined. IUPAC (International Union of Pure and Applied Chemistry) classifies adsorption isotherms into six types based on their shape. Furthermore, adsorption-desorption isotherms where the adsorption and desorption branches do not coincide and form a hysteresis loop are also classified into six types, roughly distinguishing the characteristics of surface and pore structures with different structures.

[0021] The porous molecular sieve material of the present invention has at least three concave arcs in the low-temperature nitrogen adsorption isotherm. A concave arc is an arc formed by the curve being concave in one direction. Conventional porous materials typically have only two or one concave arcs in the nitrogen adsorption curve. According to the porous molecular sieve material of the present invention, at least two concave arcs are located at positions where the relative pressure (i.e., the ratio of the nitrogen adsorption pressure p to the nitrogen saturated vapor pressure P0 at the same temperature, p / p0) is less than 0.3, and one concave arc is located at a position where the relative pressure exceeds 0.7. The presence of three or more concave arcs indicates the rich surface and pore structure of the porous molecular sieve material of the present invention.

[0022] Hysteresis loops appearing in the low-temperature nitrogen adsorption-desorption isotherm curves of porous molecular sieve materials are usually closely related to the presence of mesopores in the material. A hysteresis loop refers to a loop-shaped feature formed when adsorption branching and desorption branching do not coincide. The presence of at least two, preferably two, hysteresis loops in the adsorption-desorption isotherm curve of the porous molecular sieve material of the present invention indicates the presence of specific pore structure characteristics. On the other hand, conventional porous materials have at most one hysteresis loop.

[0023] Furthermore, according to the porous molecular sieve material of the present invention, at least two concave arcs, namely a first hysteresis loop and a second hysteresis loop, exist in the low-temperature nitrogen adsorption-desorption isotherm curve. Here, the first hysteresis loop is located in the range where the relative pressure p / p0 is less than 0.3, and the second hysteresis loop is located in the range where the relative pressure p / p0 is greater than 0.45. Due to the change in the surface properties of the material, the porous molecular sieve material of the present invention has a weakened ability to adsorb nitrogen gas in the low-pressure region, resulting in the formation of two adsorption platforms, including a first adsorption platform and a second adsorption platform. Normally, the hysteresis loop of mesoporous materials begins at a relative pressure of about 0.45 in the high-pressure region, but the porous molecular sieve material of the present invention exhibits a hysteresis loop even in the range where the relative pressure is less than 0.3.

[0024] The porous molecular sieve material of the present invention contains silicon as the first skeletal element of the molecular sieve. For example, it may exist as a total silicon molecular sieve containing only silicon and oxygen. Alternatively, it may further contain other skeletal elements other than silicon and oxygen, for example, by selecting one or more from C, Ge, Sn, Pb, Ti, Zr, Hf, B, Al, and Ga as the second skeletal element, and exist as a heteroatom molecular sieve (e.g., TS-1, TS-2, tin-titanium-silicon molecular sieve, etc.). A skeletal element means an element that exists in the topological structure of the molecular sieve skeleton, is bonded to four neighboring atoms, and exists in a tetrahedral coordination structure with other skeletal elements. For example, the porous molecular sieve material may contain SiO2 in its skeletal structure, or SiO2 and GeO2, SnO2, PbO2, TiO2, ZrO2, HfO 2、 It may contain one or more of C, B2O3, Al2O3, and Ga2O3. Preferably, the second skeleton element is one or more of Ti, Sn, and Zr. For example, the porous molecular sieve material may contain SiO2 and one or more of SnO2, TiO2, and ZrO2. The molar ratio of the first skeleton element to the second skeleton element is preferably 1:(0.0001~1), more preferably 1:(0.001~0.4), even more preferably 1:(0.005~0.1), and most preferably 1:(0.01~0.06).

[0025] A further feature of the porous molecular sieve material of the present invention is that, when observed with a scanning electron microscope (SEM), it has at least one surface pore on its surface, the maximum dimension of which (i.e., the maximum straight-line distance between any two points on the edge of the surface pore opening in the SEM image, also referred to herein as the "maximum radial dimension") is 5 nm or more and 200 nm or less. This surface pore extends into the interior of the porous molecular sieve material to form an open pore chamber. Preferably, the maximum radial dimension is 10 nm or more, more preferably 20 nm or more. When observed with a transmission electron microscope (TEM), an open pore chamber formed by the surface pore extending into the interior of the particles of the porous molecular sieve material can be observed. The pore size of this open pore chamber is 10 nm or more, preferably 20 nm or more, more preferably 40 nm or more, and 200 nm or less. Because the porous molecular sieve material of the present invention has a surface open pore chamber, it effectively shortens the diffusion pathway of substrate molecules and promotes rapid diffusion of substrate molecules to the active site.

[0026] According to the present invention, the pore diameter of an open pore chamber increases substantially first and then decreases as it extends inward from the opening of the surface pore. In the direction of extension inward from the opening of the surface pore, the equivalent diameter of the cross section with the largest area among all cross sections perpendicular to the direction of extension is defined as the pore size of the open pore chamber of the present invention. The equivalent diameter of a cross section is the diameter of the largest circle inscribed in that cross section. The direction of extension can be determined as follows: in the case of an open pore chamber with an axis, the direction of extension is the direction of that axis. Alternatively, the open pore chamber can be differentiated in some way, each differentiated open pore chamber can be given an axis, and all axes can be connected to form the direction of extension.

[0027] The equivalent diameter (d) of a particle in a porous molecular sieve material is defined as the diameter of the smallest sphere that can accommodate the particle, and the center point of this smallest sphere is called point (O). The open pore chambers of the porous molecular sieve material particles extend inward from the particle surface. Among the endpoints of this extension, the point closest to point O is called the extension endpoint (A). The ratio of the length of line segment OA to the equivalent diameter is defined as the degree of extension of the open pore chambers of the porous molecular sieve material particles. The porous molecular sieve material is observed with a transmission electron microscope (TEM), and the degree of extension of the open pore chambers is determined for each particle of the porous molecular sieve material in the image. The average value of the degree of extension of the open pore chambers of 100 particles is then taken as the degree of extension of the open pore chambers of the porous molecular sieve material. The degree of extension of the open pore chambers of the porous molecular sieve material of the present invention is 0 to 0.2, preferably 0 to 0.1.

[0028] Optionally, the porous molecular sieve material of the present invention may have, in addition to the open pore chambers described above, at least one isolated intracrystalline hollow structure with a pore size of 5 to 100 nm. The pore size of the intracrystalline hollow structure is the maximum straight-line distance between any two points on the boundary curve of the intracrystalline pores observed in the TEM image. An isolated intracrystalline hollow structure means that, in the TEM image, this hollow structure is not connected to other intracrystalline hollow structures via channels having a size of 5 nm or more. The porous molecular sieve material of the present invention has various forms of mesopores, macropores, and open pore structures, which promote the diffusion of substrate molecules and improve their application performance.

[0029] The structure of the porous molecular sieve material of the present invention can be determined by X-ray diffraction (XRD). The structure is an amorphous structure having a disordered atomic arrangement, an amorphous structure having short-range order and long-range disorder, or a crystalline structure having regularly arranged atoms, and is not particularly limited in the present invention. Preferably, the porous molecular sieve material of the present invention has a crystalline structure. Its unit cell atomic arrangement can be a crystal system selected from cubic, trigonal, tetragonal, hexagonal, orthorhombic, monoclinic, and triclinic systems. Preferably, the porous molecular sieve structure is one or more of the structural codes approved by the International Zeolite Association (IZA), such as ABW, ACO, AEI, AEL, AEN, AET, AFG, AFI, AFN, AFO, AFR, AFS, AFT, AFV, AFX, AFY, AHT, ANA, ANO, APC, APD, AST, ASV, ATN, ATO, ATS, ATT, ATV, AVE, AVL, AWO, AWW, BCT, BEC , BIK, BOF, BOG, BOZ, BPH, BRE, BSV, CAN, CAS, CDO, CFI, CGF, CGS, CHA, -CHI, -CLO, CON, CSV, CZP, DAC, DDR, DFO, DFT, DO H, DON, EAB, EDI, EEI, EMT, EON, EPI, ERI, ESV, ETL, ETR, ETV, EUO, EWO, EWS, -EWT, EZT, FAR, FAU, FER, FRA, GIS, GIU, GM E, GON, GOO, HEU, IFO, IFR, -IFT, -IFU, IFW, IFY, IHW, IMF, IRN, IRR, -IRY, ISV, ITE, ITG, ITH, ITR, ITT, -ITV, ITW, IWR , IWS, IWV, IWW, JBW, JNT, JOZ, JRY, JSN, JSR, JST, JSW, KFI, LAU, LEV, LIO, -LIT, LOS, LOV, LTA, LTF, LTJ, LTL, LTN, MAR , MAZ, MEI, MEL, MEP, MER, MFI, MFS, MON, MOR, MOZ, MRT, MSE, MSO, MTF, MTN, MTT, MTW, MVY, MWF, MWW, NAB, NAT, NES, NON, NPO, NPT, NSI, OBW, OFF, OKO, OSI, OSO, OWE, -PAR, PAU, PCR, PHI, PON, POR, POS, PSI, PTO, PTT, PTY, PUN, PWN, PWO, PWW,It is of the RHO, -RON, RRO, RSN, RTE, RTH, RUT, RWR, RWY, SAF, SAO, SAS, SAT, SAV, SBE, SBN, SBS, SBT, SEW, SFE, SFF, SFG, SFH, SFN, SFO, SFS, SFW, SGT, SIV, SOD, SOF, SOR, SOS, SOV, SSF, -SSO, SSY, STF, STI, STT, STW, -SVR, SVV, SWY, -SYT, SZR, TER, THO, TOL, TON, TSC, TUN, UEI, UFI, UOS, UOV, UOZ, USI, UTL, UWY, VET, VFI, VNI, VSV, WEI, -WEN, YFI, YUG, and ZON types of topology. Preferably, the porous molecular sieve material of the present invention has a crystal structure selected from the MFI, MEL, MWW, BEA, and SVR types of topology. More preferably, it has a crystal structure of the MFI type of topology.,

[0030] The porous molecular sieve material of the present invention has a distribution of micropores, mesopores, macropores, and surface open pores. There are no particular restrictions on the specific surface area and pore volume distribution of various pore structures. Optionally, the porous molecular sieve material characterized by low-temperature nitrogen adsorption - desorption has a BET specific surface area of 350 - 460 m 2 / g, preferably 370 - 430 m 2 / g, more preferably 380 - 420 m 2 / g. The micropore volume is 0.15 - 0.19 cm 3 / g, preferably 0.16 - 0.18 cm 3 / g. Also, the mesopore volume is 0.1 - 。15 cm 3 / g or 0.12 - 0.15 cm 3 / g, preferably 0.11 - 0.14 cm 3 / g, more preferably 0.12 - 0.13 cm 3 / g.

[0031] The present invention also provides a process for preparing porous molecular sieve material. This process involves mixing a molecular sieve containing silicon as the primary backbone element with a polymeric quaternary ammonium base, water, and optionally a low molecular weight nitrogen-containing basic compound; treating the mixture at 100-200°C, preferably 130-180°C, more preferably 150-170°C for 1-72 hours, preferably 6-48 hours, more preferably 12-24 hours; separating at least a portion of the solid product from the treated mixture; and drying and calcining the solid product to produce a porous molecular sieve material.

[0032] In the preparation method according to the present invention, preferably, the polymer-based quaternary ammonium base is a quaternary ammonium base polymer having an average degree of polymerization of 10 to 100,000, preferably 100 to 50,000, more preferably 500 to 10,000, and most preferably 1,000 to 5,000. The average degree of polymerization refers to the average number of repeating units contained in the polymer chain.

[0033] For example, the polymer-based quaternary ammonium base of the present invention comprises a polymer polymer chain portion and one or more quaternary ammonium base portions. 、 The sum of the molecular weights of one or more quaternary ammonium bases (R1, R2, R 3、 The ratio of the molecular weight of the N atom and the hydroxide radical (the sum of the molecular weights of the hydroxide radical, or the sum of the molecular weights of the cyclic structure portion and the hydroxide radical) to the molecular weight of the polymeric quaternary ammonium base is (0.01~0.4):1, preferably (0.1~0.38):1, and more preferably (0.2~0.35):1.

[0034] The above quaternary ammonium base substructure may have the following branched structure: [ka] Here, in each occurrence, R1, R2, and R3 are independently C1-C 12Alkyl and unsaturated groups (such as aromatic and alkenyl groups) are independently selected; these groups may optionally be substituted, and the substituents may be halogen, hydroxyl, nitro, cyano, alkyl, alkenyl, alkynyl, or alkoxy; and these groups may optionally be oxidized; Alternatively, it could have the following ring structure: [ka] Here, the cyclic portion comprises 2 to 13 ring atoms in addition to the indicated quaternary nitrogen atom, the ring atoms being selected from C, O, S, and N, the cyclic portion may be monocyclic or polycyclic (spiro ring, fused ring, bridging ring), and the cyclic portion may be aromatic, unsaturated, or saturated; the cyclic portion may optionally be substituted, and the substituents may be halogen, hydroxyl, nitro, cyano, alkyl (e.g., C1-C) 12 ), alkenyl (e.g., C2-C 12 ), alkynyl (e.g., C2-C 12 ), alkoxy (e.g., C1-C 12 ) may be; the aforementioned cyclic portion may be optionally oxidized; [ka] These indicate the bonding points between each quaternary ammonium base moiety and the polymer chain moiety.

[0035] Polymeric quaternary ammonium bases are preferably prepared by treating at least one of the following polymeric quaternary ammonium salts by hydroxide radical exchange: Polyquaternium-2, CAS number: 68555-36-2, has the following structural formula: [ka] Polyquaternium-6, CAS number: 26062-79-3, poly(diallyldimethylammonium chloride), has the following structural formula: [ka] Polyquaternium-7, CAS number: 26590-05-6, poly(acrylamide-co-diallyldimethylammonium chloride), has the following structural formula: [ka] Polyquaternium-10, CAS number: 68610-92-4, chloro-2-hydroxy-3-(trimethylamino)propyl poly(ethylene oxide)cellulose ether, has the following structural formula: [ka] Polyquaternium-22, CAS number: 53694-17-0, diallyldimethylammonium acrylate copolymer, polymerized from the following structural units: [ka] Polyquaternium-32, CAS number: 35429-19-7, ethanium, N,N,N-trimethyl-2-[(2-methyl-1-oxo-2-propenyl)oxy]-, chloride, copolymer with 2-propenamide, having the following structural formula: [ka] Polyquaternium-37, CAS number: 26161-33-1, N,N,N-trimethyl-2-[(2-methyl-1-oxo-2-propenyl)oxy]ethanium chloride homopolymer, having the following structural formula: [ka] Polyquaternium-39, CAS number: 25136-75-8, diallyldimethylammonium chloride-acrylamide-acrylic acid copolymer, polymerized from the following structural units: [ka] Polyquaternium-44, CAS number: 150599-70-5, poly[[3-methyl-1-vinylimidazolium methylsulfate]-co-[1-vinylpyrrolidone]], has the following structural formula: [ka] Polyquaternium-47, CAS number: 197969-51-0, a copolymer of N,N,N-trimethyl-3-[(2-methyl-1-oxo-2-propenyl)amino]-1-propananium chloride polymer with methyl 2-propenoate and 2-propenoic acid, polymerized from the following structural units: [ka] Polyquaternium-51, CAS number: 125275-25-4, poly(2-methacryloyloxyethyl phosphorylcholine-co-n-butyl methacrylate), polymerized from the following structural units: [ka]

[0036] In the present invention, the polymer-based quaternary ammonium salts are commercially available products, and the present invention does not impose any particular limitations on them as long as they satisfy the requirements for the degree of polymerization.

[0037] The inventors unexpectedly discovered that porous molecular sieve materials prepared using polymer-based quaternary ammonium salts generate novel pore structures. Among polymer-based quaternary ammonium bases, polymer-based quaternary ammonium salts obtained by subjecting polyquaternium-2, polyquaternium-6, polyquaternium-7, polyquaternium-22, polyquaternium-32, polyquaternium-37, polyquaternium-39, or polyquaternium-47 to hydroxide radical exchange are preferred, with those obtained by subjecting polyquaternium-32, polyquaternium-37, or polyquaternium-47 to hydroxide radical exchange being most preferred. The operation of subjecting the polymer-based quaternary ammonium salt to hydroxide radical exchange can be carried out by forcing the polymer-based quaternary ammonium salt through a membrane material such as a semipermeable membrane, or by immersing it in a stationary or flowing solution containing hydroxide radicals. The solution containing hydroxide radicals can have a hydroxide radical concentration of 0.001 to 5 mol OH- / L, more preferably 0.05 to 2 mol OH- / L, and even more preferably 0.1 to 1 mol OH- / L. The exchange time should be sufficient to achieve an exchange rate of 30% or more, preferably 50% or more, more preferably 70% or more, more preferably 90% or more, and most preferably 98% or more. The exchange rate refers to the molar percentage of anions substituted with hydroxide radicals relative to the total anions in the polymer-based quaternary ammonium salt.

[0038] In the preparation method according to the present invention, the low molecular weight nitrogen-containing basic compound contains one or more organic ammonium salts and inorganic ammonium salts having 15 or fewer carbon atoms.

[0039] The organic ammonium salts include linear ammonium carboxylates, cyclic ammonium carboxylates, and aromatic ammonium carboxylates having 15 or fewer carbon atoms, preferably 12 or fewer, and more preferably 6 or fewer carbon atoms; for example, the organic ammonium salt may be one or more of ammonium formate, ammonium acetate, ammonium propionate, ammonium butyrate, ammonium valerate, ammonium cyclopentanecarboxylate, ammonium hexanoate, and ammonium hexenoate.

[0040] The inorganic ammonium salt may be one or more of ammonium nitrate, ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium sulfate, ammonium bisulfite, ammonium bisulfite, ammonium chloride, ammonium bromide, ammonium fluoride, ammonium carbonate, and ammonium bicarbonate, and a preferred inorganic ammonium salt is one or more of ammonium nitrate, ammonium bicarbonate, ammonium carbonate, and ammonium chloride.

[0041] In the preparation method according to the present invention, the ratio of molecular sieve containing silicon as the first skeletal element (silica equivalent, molar ratio), polymer-based quaternary ammonium base (weight ratio), water (molar ratio), and any small molecule nitrogen-containing basic compound (molar ratio) is 1:(0.001~0.5):(5~100):(0~0.3), preferably 1:(0.005~0.2):(10~50):(0~0.15), and more preferably 1:(0.01~0.1):(15~30):(0.02~0.08).

[0042] In the preparation method according to the present invention, the preparation method may be performed once or repeated multiple times. For example, it may be repeated 1 to 10 times, and the technical effects of the present invention can be achieved.

[0043] In the preparation method according to the present invention, the molecular sieve containing silicon as the first framework element does not contain any other four-coordinate framework elements, and the molecular sieve containing silicon as the first framework element is prepared in the following steps: a silicon source, a quaternary ammonium base, and water are mixed to produce a first mixture; the mixture is aged at a temperature of 5 to 120°C for 0.5 to 24 hours (preferably 20 to 100°C for 2 to 18 hours, more preferably 40 to 90°C for 4 to 12 hours, and even more preferably 60 to 80°C for 5 to 10 hours) to obtain a sol; this sol is then crystallized at a temperature of 100 to 200°C for 2 to 168 hours (preferably 130 to 180°C for 12 to 96 hours, more preferably 150 to 170°C for 24 to 72 hours); at least a portion of the product is separated therefrom; and the product is then dried and calcined to produce at least a portion of the molecular sieve.

[0044] In the preparation method according to the present invention, the molecular sieve containing silicon as the first skeleton element may further contain a second skeleton element, the second skeleton element being selected from C, Ge, Sn, Pb, Ti, Zr, Hf, B, Al, and Ga, preferably one or more of Sn, Ti, and Zr, and the molar ratio of silicon to the second skeleton element being 1:(0.001~1), preferably 1:(0.005~0.3), more preferably 1:(0.01~0.1), even more preferably 1:(0.015~0.06), and most preferably 1:(0.02~0.04). The molecular sieve containing silicon as the first skeletal element is prepared by the following steps: mixing a silicon source, a second skeletal element source, a quaternary ammonium base, and water to produce a first mixture; aging the mixture at 5 to 120°C for 0.5 to 24 hours (preferably 20 to 100°C for 2 to 18 hours, more preferably 40 to 90°C for 4 to 12 hours, and even more preferably 60 to 80°C for 5 to 10 hours) to obtain a sol; then crystallizing this sol at 100 to 200°C for 2 to 168 hours (preferably 130 to 180°C for 12 to 96 hours, more preferably 150 to 170°C for 24 to 72 hours); separating at least a portion from the product; and then drying and calcining the product to produce at least a portion of the molecular sieve.

[0045] In the preparation method according to the present invention, there are no special requirements for the silicon source used in the preparation of molecular sieves containing silicon as the first skeletal element. A general silicon source well known to those skilled in the art can be used as the silicon source of the present invention. Silicon sources are further classified into monodisperse silicon sources and aggregated silicon sources based on the degree of interbonding of silicon atoms. A monodisperse silicon source refers to a silicon source in which silicon atoms are not bonded to other silicon atoms via Si-O-Si bonds, while an aggregated silicon source refers to a silicon source in which at least some of the silicon atoms are bonded to other silicon atoms via Si-O-Si bonds.

[0046] The silicon source may be a monodisperse silicon source and / or an agglomerated silicon source. It is preferable to use both a monodisperse silicon source and an agglomerated silicon source as the silicon source. The monodisperse silicon source contains tetraalkoxysilane, specifically one or more of tetramethyl orthosilicate, tetraethyl orthosilicate, and tetrabutyl orthosilicate. The agglomerated silicon source includes silica white, silica gel, and silica sol. The molar ratio (silica equivalent) of the monodisperse silicon source to the agglomerated silicon source is preferably 1:0.1 to 10, more preferably 1:0.5 to 7, even more preferably 1:1 to 5, and most preferably 1:2 to 4. A silicon source having a silica equivalent silicon content (by weight) of 80%, 90%, 95%, or more than 99% on a dry basis can be used as the silicon source of the present invention. Preferably, the silica content (by weight) on a dry basis exceeds 95%, more preferably exceeding 99%. Dry silica content (or silica equivalent silicon content) refers to the silica content (by weight) in the chemical composition of a silicon source obtained after drying to remove moisture and calcining at 880°C for 3 hours, and is measured by XRF.

[0047] According to the method for preparing molecular sieves containing silicon as the first framework element, when the second framework element is C, the source of the second framework element has the structure A1A2A3Si-A4Si-A5A6A7, where A1, A2, A3, A5, A6, and A7 are each independently and optionally substituted C1-C 10A4 is a C1-C3 alkyl group, and A4 is an alkoxy group or halogen group; preferably A1, A2, A3, A5, A6, and A7 are each independently a C1-C8 alkoxy group or halogen, and A4 is a C1-C2 alkyl group; more preferably A1, A2, A3, A5, A6, and A7 are each independently a C1-C3 alkoxy group or halogen, and A4 is a C1 alkyl group. For example, if the second skeletal element is C, the source of the second skeletal element is one or more of bis(trimethoxysilyl)methane, bis(triethoxysilyl)methane, bis(tripropoxysilyl)methane, bis(trichloromethylsilyl)methane, and bis(diethoxychlorosilyl)methane.

[0048] According to the method for preparing molecular sieves containing silicon as the first skeleton element, when the second skeleton element is Ge, the source of the second skeleton element may be a general germanium source well known to those skilled in the art. For example, when the second skeleton element is Ge, the source of the second skeleton element may be selected from one or more germanium oxides, salts, or organometallic salts, specifically germanium monoxide, germanium dioxide, germanium tetrafluoride, germanium tetrachloride, germanium tetrabromide, germanium tetraiodide, germanium sulfide, tetramethylgermane, tetraethylgermane, tetrapropylgermane, tetrabutylgermane, methylgermane, ethylgermane, propylgermane, and butylgermane.

[0049] According to the method for preparing molecular sieves containing silicon as the first skeleton element, if the second skeleton element is Sn, the source of the second skeleton element can be a common tin source well known to those skilled in the art. For example, if the second skeleton element is Sn, the source of the second skeleton element can be selected from one or more of tin oxides, salts, organometallic salts, specifically tin dioxide, stannous oxide, stannous chloride, stannous trichloride, stannous tetrachloride, potassium stannate, sodium stannate, metastannic acid, stannic acid, tetramethyltin, tetraethyltin, tetrapropyltin, and tetrabutyltin.

[0050] According to the method for preparing molecular sieves containing silicon as the first structural element, if the second structural element is Pb, the source of the second structural element can be a general lead source well known to those skilled in the art. For example, if the second structural element is Pb, the source of the second structural element can be selected from one or more lead oxides, salts, organometallic salts, specifically lead oxide, lead chloride, lead nitrate, lead sulfate, and lead acetate.

[0051] According to the method for preparing the molecular sieve containing silicon as the first skeleton element, when the second skeleton element is titanium, the source of the second skeleton element may be a general titanium source well known to those skilled in the art, such as titanium salts and organometallic salts; specifically, it may be one or more of tetraalkoxy titanium, titanium tetrachloride, titanium trichloride, titanium sulfate, hexafluorotitanium acid, bis(cyclopentadienyl)titanium(IV) dichloride, and titanium nitrate, preferably one or more of tetraalkoxy titanium and titanium tetrachloride, more preferably one or more of tetraethyl titanate, tetrapropyl titanate, and tetrabutyl titanate.

[0052] According to the method for preparing the molecular sieve containing silicon as the first framework element, when the second framework element is Zr, the source of the second framework element may be one or more of the common zirconium sources known to those skilled in the art, such as zirconium salts and organometallic salts, specifically zirconium tetrachloride, zirconium trichloride, zirconium oxychloride, zirconium oxysulfate, zirconium nitrate, zirconium acetate, and tetraalkoxyzirconium.

[0053] According to the method for preparing molecular sieves containing silicon as the first framework element, when the second framework element is Hf, the source of the second framework element may be one or more of the common hafnium sources known to those skilled in the art, such as hafnium oxides, salts, and organometallic salts, specifically hafnium oxide, hafnium tetrachloride, hafnium hydroxide, hafnium carbide, and hafnium boride.

[0054] According to the method for preparing molecular sieves containing silicon as the first framework element, when the second framework element is V, the source of the second framework element may be one or more of the common vanadium sources known to those skilled in the art, such as vanadium oxides, salts, and organometallic salts, specifically vanadium trioxide (V2O3), vanadium pentoxide (V2O5), vanadium trichloride (VCl3), and ammonium metavanadate (NH4VO3).

[0055] According to the method for preparing the molecular sieve containing silicon as the first skeleton element, when the second skeleton element is B, the source of the second skeleton element may be one or more of the common boron sources known to those skilled in the art, such as boron oxides, salts, or organoboro salts, specifically boron oxide, boric acid, borax, alkylboron compounds, and alkoxyboron compounds.

[0056] According to the method for preparing molecular sieves containing silicon as the first skeleton element, when the second skeleton element is Al, the source of the second skeleton element may be one or more of the common aluminum sources known to those skilled in the art, such as aluminum oxides, salts, and organoaluminum compounds, specifically aluminum oxide, aluminum chloride, aluminum sulfate, aluminum nitrate, aluminum phosphate, sodium aluminate, aluminum acetate, alkylaluminum compounds, and alkoxyaluminum compounds.

[0057] According to the method for preparing the molecular sieve containing silicon as the first skeletal element, when the second skeletal element is Ga, the source of the second skeletal element may be one or more of the common gallium sources known to those skilled in the art, such as oxides, salts, and organogallium compounds of gallium, specifically gallium oxide, gallium chloride, gallium sulfate, gallium nitrate, gallium phosphate, sodium gallate, gallium acetate, alkylgallium compounds, and alkoxygallium compounds.

[0058] According to the method for preparing the molecular sieve containing silicon as the first skeletal element, the quaternary ammonium base is R1R2R3R4N + OH -The structure is as follows: where R1, R2, R3, and R4 are each independently a linear or branched alkyl or alkenyl group having 2 to 5 carbon atoms, or a linear or branched alkyl or alkenyl group having 2 to 5 carbon atoms substituted with a halogen (fluorine, chlorine, bromine, iodine), nitro, amino, hydroxyl, carboxyl, carbonyl, aldehyde, ketone, ether, ester, sulfonic acid, cyano, amide, or acylhalide group, such as ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, 1,1-dimethylpropyl, vinyl, propenyl, allyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl Nyl, 1,1-dimethylvinyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 3-methyl-1-butenyl, 3-methyl-2-butenyl, 3-methyl-3-butenyl, 2,2-dimethyl-1-propenyl, 2,2-dimethyl-2-propenyl, 1-methyl-1-butenyl, 1-methyl-2-butenyl, 1-methyl-3-butenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl, 1,2-dimethyl-1-propenyl, 1, Preferably, it is one of 2-dimethyl-2-propenyl, 1,1-dimethyl-1-propenyl, 1,1-dimethyl-2-propenyl, chloroethyl, chloropropyl, 2,3-dichloropropyl, chlorobutyl, chloropentyl, 1-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 2-chloro-3-hydroxypropyl, 2-hydroxy-3-chloropropyl, 2-aminopropyl, and 3-aminopropyl. 、R1, R2, R3, and R4 are each independently a linear or branched alkyl or alkenyl group having three carbon atoms, or a linear or branched alkyl or alkenyl group having three carbon atoms substituted with a halogen (fluorine, chlorine, bromine, iodine), nitro, amino, hydroxyl, carboxyl, carbonyl, aldehyde, ketone, ether, ester, sulfonic acid, cyano, amide, or acylhalide group, for example, one of n-propyl, isopropyl, chloropropyl, 2,3-dichloropropyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 2-chloro-3-hydroxypropyl, 2-hydroxy-3-chloropropyl, 2-aminopropyl, or 3-aminopropyl.

[0059] According to the method for preparing molecular sieves containing silicon as the first skeletal element, quaternary ammonium bases may exist in the form of hydroxide radicals, or in a state where hydroxide radicals coexist with other anions (e.g., fluoride, chloride, bromide, iodide, nitrate radicals, sulfate radicals, phosphate radicals, etc.). The molar percentage of quaternary ammonium bases existing in the form of hydroxide radicals relative to the total number of moles of quaternary ammonium bases may be >5%, preferably >20%, more preferably >50%, still more preferably >80%, more preferably >90%, and most preferably >99%.

[0060] According to the method for preparing the molecular sieve containing silicon as the first skeletal element, the molar composition of the silicon source, quaternary ammonium base, and water in the supply materials is preferably 1:(0.05~0.3):(5~60), preferably 1:(0.08~0.25):(10~50), and more preferably 1:(0.12~0.2):(15~30).

[0061] In the method for preparing molecular sieves containing silicon as the first skeletal element, a material having a crystalline structure can optionally be added before the crystallization treatment. The weight ratio of the crystalline material to the silicon source (in terms of SiO2) is (0.001~2):1, preferably (0.005~1):1, more preferably (0.01~0.7):1, and even more preferably (0.03~0.3):1. The crystalline material preferably has an MFI structure. The crystalline material contains Si and O, or Si, O and one or more elements from C, Ge, Sn, Pb, Ti, Zr, Hf, V, B, Al, and Ga. For example, it may be at least one of all-silicon molecular sieves, silicon-aluminum molecular sieves, silicon-boron molecular sieves, titanium-silicon molecular sieves, tin-silicon molecular sieves, zirconium-silicon molecular sieves, vanadium-silicon molecular sieves, silicon-gallium molecular sieves, silicon-lead molecular sieves, or silicon-hafnium molecular sieves. Preferably, the crystalline material is at least one of all-silicon molecular sieves, titanium-silicon molecular sieves, zirconium-silicon molecular sieves, tin-silicon molecular sieves, or boron-silicon molecular sieves.

[0062] In the preparation method according to the present invention, the operation of separating at least a portion of the solid product from the processing mixture includes any method capable of achieving solid-liquid separation, such as filtration, sedimentation, evaporation, membrane separation, and adsorption separation, and is not particularly limited in the present invention. Drying can be carried out in an inert gas atmosphere or an oxygen-containing gas atmosphere under conditions from room temperature to 200°C, preferably 50 to 160°C, more preferably 80 to 140°C. The drying time should be sufficient to reduce the moisture content (by weight) of the solid product to less than 30%, preferably less than 10%, and more preferably less than 5%. For example, the drying time can be 0.5 to 24 hours. Calcination can be carried out in an inert gas atmosphere or an oxygen-containing gas atmosphere under conditions from 300 to 800°C, preferably 400 to 700°C, more preferably 500 to 600°C. The calcination time should be sufficient to reduce the organic content (by weight) of the solid product to less than 5%, preferably less than 1%, and more preferably less than 0.1%. For example, the calcination time is 0.5 to 24 hours.

[0063] The present invention also provides a porous molecular sieve material obtained by the preparation process described above.

[0064] The present invention further provides a method for applying the aforementioned porous molecular sieve material.

[0065] The porous molecular sieve material described above of the present invention can be used in adsorption processes, catalyst preparation, catalytic reactions, or as a carrier.

[0066] In adsorption processes, the porous molecular sieve material of the present invention can be used as an adsorbent and applied to adsorption and separation processes for hydrocarbons, gases, inorganic substances, and the like.

[0067] The preparation of the catalyst may include methods using the porous molecular sieve catalyst material of the present invention as a catalytically active component, methods utilizing its unique skeletal elements, or methods using it as a support to further load active centers, or methods of mixing it with other catalysts, co-catalysts, structure enhancers, electron enhancers, binders, inert supports, etc., or methods of preparing the catalyst using mechanical mixing, kneading and molding, tablet compression, extrusion molding, spray drying, ball rolling and molding, oil droplet granulation, etc.

[0068] The catalytic reaction may include a method of directly using the porous molecular sieve catalyst material of the present invention as a catalyst, a method of further processing it to form a catalyst, and a method of using the catalyst in a catalytic reaction. Catalytic reactions include, but are not limited to, oxidation reactions (preparation of aldehydes, ketones, acids, epoxides, and vicinal diols by olefin oxidation / epoxidation; preparation of alcohols, aldehydes, and acids by alkane oxidation; preparation of ketones and acids by alcohol oxidation; preparation of acids by aldehyde oxidation; preparation of phenols by aromatic oxidation; preparation of sulfoxides and sulfones by sulfide oxidation), reduction reactions, oxidation reactions (preparation of amides and lactams by aldehyde / ketone amoximation), aldol condensation reactions, substitution / halogenation reactions, elimination reactions, transesterification reactions, dehydration reactions, etherification reactions, esterification reactions, double / triple bond addition reactions, Diels-Alder reactions, Beckmann rearrangement reactions (production of caprolactam by gas-phase rearrangement of ring hexanone oxime), and hydrogen transfer reactions.

[0069] Applications as a support material may include using the porous molecular sieve catalyst material of the present invention as a support for other active ingredients.

[0070] According to the application method of porous molecular sieve material of the present invention, the porous molecular sieve catalyst material can be used in powder form or in molded forms such as spherical, strip, tablet, or granular shapes, and can also be used as a mixture with other catalysts. Applications can be carried out in various reactors such as tank reactors, slurry bed reactors, fixed bed reactors, fluidized bed reactors, moving bed reactors, and microchannel reactors. The reaction raw materials and catalysts may be added all at once, intermittently, or continuously, and are not limited to the present invention.

[0071] Those skilled in the art will understand that in the application process of the porous molecular sieve material of the present invention, separation of the product and catalyst can be achieved by various methods. For example, when using powdered molecular sieves as a catalyst, the product can be separated and the catalyst recovered and reused by sedimentation, filtration, centrifugation, evaporation, membrane separation, etc. Alternatively, the catalyst can be molded and packed into a fixed-bed reactor, and the catalyst can be recovered after the reaction. Various methods for catalyst separation and recovery are described in detail in existing literature and will not be described in detail here.

[0072] The present invention will be further illustrated by the following embodiments, but will not be limited thereto. [Examples]

[0073] In the following examples and comparative examples: The phase structure and relative crystallinity of the molecular sieves were determined by XRD analysis. The instrument used for characterization was a Philips Panalytic Empire X-ray diffractometer. The test conditions were as follows: Cu target, Kα radiation, Ni filter, tube voltage 40kV, tube current 40mA, scintillation counter, step size 0.0131°, scanning range 5°~35°. The relative crystallinity of the molecular sieves was calculated based on the peak area of ​​the "five-fingered peak" in the 2θ = 22°~26° range. The chemical composition and elemental ratio of heteroatoms to silicon of the molecular sieves were determined by XRF analysis. The instrument used for characterization was a Rigaku Corporation (Japan) Model 3013 X-ray fluorescence analyzer. The test conditions were a tungsten target, excitation voltage 40kV, and excitation current 250mA. After compressing the sample into a pellet, fluorescence was emitted under X-ray irradiation. The relationship between fluorescence wavelength (λ) and the atomic number (Z) of an element is given by λ = K(ZS) - 2, where K is a constant. By measuring the fluorescence wavelength, the type of element could be identified. The intensity of the characteristic spectral lines of each element was measured using a scintillation counter and proportional counter, and semi-quantitative analysis was performed.

[0074] The specific surface area of ​​the micropores was measured by the low-temperature nitrogen adsorption-desorption method and calculated using the BET method. Pore volume and pore distribution were determined according to the method described in RIPP 151-90 of "Analytical Methods in the Petrochemical Industry" edited by Yang Cui-ding et al. (Science Press, September 1990, 1st edition).

[0075] The morphology of the molecular sieves was determined by SEM. The instrument used for the analysis was a Hitachi S4800 high-resolution cold cathode scanning electron microscope with an acceleration voltage of 20 kV.

[0076] The internal hollow morphology of the molecular sieves was determined by TEM. The instrument used for the analysis was a Tecnai G2F20S-TWIN transmission electron microscope manufactured by FEI. The analytical method included dispersing the sample in an ethanol solution, placing it on a sample grid, drying it, and then measuring it. The acceleration voltage was 200kV.

[0077] Unless otherwise specified, all raw materials used in the examples and comparative examples were analytical reagents.

[0078] The composition of the catalytic reaction product was analyzed by gas chromatography, and the results were quantified using an external standard method. The chromatographic analysis conditions included an Agilent-6890 chromatograph, HP-5 capillary column, injection volume of 0.5 μL, injection port temperature of 280°C, column temperature: held at 100°C for 2 minutes, then increased to 250°C at a rate of 15°C / min and held for 10 minutes; FID detector, detector temperature of 300°C.

[0079] In the examples and comparative examples: Ti-Si molecular sieves were evaluated using cyclohexanone amoximation under the following reaction conditions: Cyclohexanone oxime was produced by amoximation reaction of cyclohexanone, hydrogen peroxide, and aqueous ammonia under the action of a catalyst. Cyclohexanone, hydrogen peroxide (30% by weight), aqueous ammonia, and tert-butanol were added to a three-necked flask in a molar ratio of 1:1.1:2:10, followed by the addition of catalyst in an amount equivalent to 5% of the weight of cyclohexanone. The reaction was carried out at 80°C under reflux at a stirring speed of 400 rpm for 1 hour, after which the product was cooled, the liquid phase was separated, and chromatographic analysis was performed.

[0080] Evaluation metrics: Cyclohexanone conversion rate (%) = (Number of moles of cyclohexanone in raw material - Number of moles of cyclohexanone in product) / Number of moles of cyclohexanone in raw material × 100% Cyclohexanone oxime selectivity (%) = Number of moles of cyclohexanone oxime in the product / (Number of moles of cyclohexanone in the raw material - Number of moles of cyclohexanone in the product) × 100% Total silicon molecular sieves were evaluated using the formation of caprolactams by gas-phase rearrangement of cyclohexanone oxime under the following reaction conditions: Cyclohexanone oxime underwent a gas-phase Beckmann rearrangement reaction catalyzed by a total silicon molecular sieve to produce caprolactam. 5 g of molecular sieve was pulverized and sieved to 40-60 mesh, then packed into a fixed-bed reactor. Cyclohexanone oxime was mixed with methanol solvent in a molar ratio of 1:20. The cyclohexanone oxime solution was introduced into the fixed-bed reactor at a space velocity of 10 h⁻¹ and the reaction was carried out at 380°C. After condensation of the product, it was subjected to chromatographic analysis.

[0081] Evaluation metrics: Cyclohexanone oxime conversion rate (%) = (Amount of cyclohexanone oxime in raw material per unit time - Amount of cyclohexanone oxime in product per unit time) / Amount of cyclohexanone oxime in raw material per unit time × 100% Caprolactam selectivity (%) = Moles of caprolactam produced in the product / Moles of cyclohexanone oxime consumed by the total product × 100% Tin-silicon molecular sieves were evaluated using the cyclohexanone Baeyer-Villiger (BV) oxidation reaction under the following reaction conditions: Cyclohexanone and hydrogen peroxide were reacted under the catalytic action of a tin-silicon molecular sieve to produce ε-caprolactone. Cyclohexanone and hydrogen peroxide were added to a three-necked flask in a molar ratio of 1:2. The amount of catalyst added was 5% of the weight of cyclohexanone, and 1,4-dioxane was used as the solvent, with a solvent:cyclohexanone molar ratio of 20:1. The mixture was reacted at 80°C under circulation at a stirring speed of 400 rpm for 8 hours. The products were cooled and separated, and the obtained liquid products were analyzed by gas chromatography.

[0082] Evaluation metrics: Cyclohexanone conversion rate (%) = (Number of moles of cyclohexanone in raw material - Number of moles of cyclohexanone in product) / Number of moles of cyclohexanone in raw material × 100% ε-Caprolactone Selectivity (%) = Number of Moles of ε-Caprolactone in the Product / (Number of Moles of Cyclohexanone in the Starting Material - Number of Moles of Cyclohexanone in the Product) × 100% Zirconium-silicon molecular sieves were evaluated using the reduction of levulinic acid with isopropanol via the Meerwein-Ponndorf-Verley (MPV) reaction, followed by esterification to produce γ-valerolactone. The reaction process is summarized below: [ka]

[0083] Here, step (1) was a catalytic reaction under zirconium-silicon molecular sieves, and step (2) could be carried out under non-catalytic conditions (e.g., heating). The weight ratio of zirconium-silicon molecular sieves to levulinic acid was 0.05:1, the molar ratio of isopropanol to levulinic acid was 1:20, the reaction temperature was 80°C, and the reaction time was 8 hours. After the reaction, the liquid phase product was separated and analyzed by chromatography.

[0084] Evaluation metrics: Levulinic acid conversion rate (%) = (Moles of levulinic acid in raw material - Moles of levulinic acid in product) / Moles of levulinic acid in raw material × 100% γ-Valerolactone yield (%) = Moles of γ-Valerolactone in the product / Moles of levulinic acid in the raw materials × 100%

[0085] Preparation Example 1 This preparation example demonstrates the preparation of a polymer-based quaternary ammonium salt compound.

[0086] 10 g of commercially available polyquaternium-2 with a degree of polymerization of 4500 was placed in a semipermeable membrane and immersed in a 0.5 mol / L caustic soda solution. Hydroxide radical exchange was performed under stirring, with each exchange lasting 24 hours. After each exchange was completed, the caustic soda solution was replaced and the exchange was repeated. A total of four exchanges were performed. Based on ion concentration detection and calculations, the degree of exchange reached 99%. The obtained product was dehydrated, named polymeric quaternary ammonium base-2, and made available for use. Its pKa was measured to be approximately 12.8.

[0087] Polyquaternium-6, polyquaternium-7, polyquaternium-22, polyquaternium-32, polyquaternium-37, and polyquaternium-47 were treated similarly to prepare polymer-based quaternary ammonium bases-6, 7, 22, 32, 37, and 47, respectively. These are ready for use.

[0088] Preparation Example 2 This preparation example demonstrates the preparation of titanium-silicon MFI type molecular sieve TS-1-A.

[0089] A silicon source (tetraethyl orthosilicate and silica white, SiO2 equivalent), tetrabutyl titanate, a solution of tetrapropylammonium hydroxide (25% by weight, hydroxide purity 99.5% or higher), and water were mixed in a molar ratio of 1 (tetraethyl orthosilicate:silica white = 1:2):0.04:0.15:25 and aged at 80°C for 6 hours to obtain a sol. Next, this sol was crystallized at 170°C for 48 hours. Finally, the obtained slurry was filtered, dried at 120°C for 6 hours, and calcined at 550°C for 6 hours to obtain a solid product. This yielded TS-1-A molecular sieve.

[0090] Preparation Example 3 This preparation example shows the preparation of all-silicon-based MFI type molecular sieve S-1.

[0091] A silicon source (tetraethyl orthosilicate and silica white, SiO2 equivalent), a tetrapropylammonium hydroxide solution (25% by weight, hydroxide purity 99.5% or higher), and water were mixed in a molar ratio of 1 (tetraethyl orthosilicate:silica white = 1:4):0.2:30 and aged at 60°C for 10 hours to obtain a sol. Next, this sol was crystallized at 170°C for 72 hours. Finally, the obtained slurry was filtered, dried at 120°C for 6 hours, and calcined at 550°C for 6 hours to obtain a solid product. This yielded S-1 molecular sieves.

[0092] Preparation Example 4 This preparation example demonstrates the preparation of tin-silicon MEL type molecular sieve, Sn-MEL.

[0093] A silicon source (tetraethyl orthosilicate and silica white, SiO2 equivalent), stannous chloride, tetrabutylammonium hydroxide (25% by weight, hydroxide purity 99.5% or higher) solution, and water were mixed in a molar ratio of 1 (tetraethyl orthosilicate:silica white = 1:2):0.02:0.2:30 and aged at 70°C for 5 hours to obtain a sol. Next, this sol was crystallized at 170°C for 24 hours. Finally, the obtained slurry was filtered, dried at 120°C for 6 hours, and calcined at 550°C for 6 hours to obtain Sn-MEL molecular sieves.

[0094] Preparation Example 5 This preparation example demonstrates the preparation of a zirconium-silicon MFI type molecular sieve, Zr-MFI.

[0095] A silicon source (tetraethyl orthosilicate and silica white, SiO2 equivalent), zirconium propoxide, a solution of tetrapropylammonium hydroxide (25% by weight, hydroxide purity 99.5% or higher), and water were mixed in a molar ratio of 1 (tetraethyl orthosilicate:silica white = 1:2):0.02:0.2:30 and aged at 80°C for 5 hours to obtain a sol. Next, this sol was crystallized at 170°C for 72 hours. Finally, the obtained slurry was filtered, dried at 120°C for 6 hours, and calcined at 550°C for 6 hours to obtain a solid product. This yielded a Zr-MFI molecular sieve.

[0096] Preparation Example 6 This preparation example demonstrates the preparation of titanium-silicon MFI type molecular sieve TS-1-B.

[0097] A silicon source (tetraethyl orthosilicate, SiO2 equivalent), tetrabutyl titanate, a solution of tetrapropylammonium hydroxide (25% by weight, hydroxide purity 99.5% or higher), and water were mixed in a molar ratio of 1:0.04:0.15:25. The mixture was aged at 80°C for 6 hours to obtain a sol. This sol was then crystallized at 170°C for 48 hours. Finally, the resulting slurry was filtered, dried at 120°C for 6 hours, and calcined at 550°C for 6 hours to obtain a solid product. This yielded TS-1-B molecular sieves.

[0098] Comparative Example 1 This comparative example demonstrates the preparation, characterization, and evaluation of hollow Ti-Si molecular sieves (HTS).

[0099] The TS-1-B molecular sieve obtained in Preparation Example 6, sulfuric acid, and water were uniformly mixed in a ratio of molecular sieve (g): sulfuric acid (mol): water (mol) = 100:0.15:150, reacted at 90°C for 5.0 hours, and then filtered, washed, and dried by conventional methods to obtain acid-treated TS-1-B molecular sieve.

[0100] The above-mentioned acid-treated TS-1-B molecular sieves, triethanolamine, tetrapropylammonium hydroxide, and water (moles) were uniformly mixed in a ratio of molecular sieves (g):triethanolamine (moles):tetrapropylammonium hydroxide (moles):water of 100:0.20:0.15:180. This mixture was placed in a sealed stainless steel reactor and maintained at 190°C for 0.5 days under self-generated pressure. After cooling and depressurization, the product was filtered, washed, dried by conventional methods, and calcined at 550°C for 3 hours under an air atmosphere to obtain hollow Ti-Si molecular sieves HTS.

[0101] We performed a characterization of hollow Ti-Si molecular sieves (HTS).

[0102] XRD analysis revealed that the HTS molecular sieve possesses an MFI structure.

[0103] The SEM results (Figure 1) show that the hollow Ti-Si molecular sieve HTS exhibits an aggregation and growth morphology of microcrystalline grains, and that there are no open pore chambers on the molecular sieve surface.

[0104] The TEM results (Figure 2) showed that the hollow Ti-Si molecular sieve HTS has a hollow structure within the crystal and does not have open mesopores.

[0105] The nitrogen adsorption-desorption characteristics evaluation results (Figure 3) showed that there are two concave arcs in the nitrogen adsorption curve of the hollow Ti-Si molecular sieve HTS. One is located at p / p0 < 0.3, and the other is located at p / p0 > 0.7. A hysteresis loop exists from p / p0 > 0.45 onwards.

[0106] Table 1 shows the results of the characterization of chemical composition, specific surface area, and pore volume.

[0107] Table 1 shows the results of evaluating hollow Ti-Si molecular sieves (HTS) using the cyclohexanone amoximation reaction.

[0108] Comparative Example 2 This comparative example shows the preparation, characterization, and evaluation of Ti-Si molecular sieve STS-D prepared by the silylation method.

[0109] Tetraethyl orthosilicate, tetrabutyl titanate, tetrapropylammonium hydroxide, and water were mixed and treated at 30°C for 12 hours to obtain a silicon-titanium gel with a molar composition of SiO2:TiO2:tetrapropylammonium hydroxide:water = 1:0.04:0.15:25. The silicon-titanium gel was treated at 90°C for 12 hours. Next, the treatment product (SiO2) and the silylation reagent N-phenyl-3-aminopropyltrimethoxysilane were mixed in a molar ratio of 1:0.1 and crystallized at 170°C for 48 hours. The crystallized product was filtered and washed, dried at 120°C for 6 hours, and then calcined at 550°C for 6 hours to obtain a Ti-Si molecular sieve comparative sample STS-D, which was expanded with the silylation reagent.

[0110] The Ti-Si molecular sieve comparative sample STS-D was expanded with a silylation reagent.

[0111] XRD analysis revealed that STS-D molecular sieves possess an MFI structure.

[0112] SEM results (Figure 4) showed that the STS-D molecular sieve exhibited a morphology in which microcrystalline grains accumulated and grew, and that there were no open pore chambers on the molecular sieve surface.

[0113] TEM results (Figure 5) showed that STS-D has a "sponge-like" morphology in which fine particles are loosely deposited, and neither open mesopores nor hollow structures were observed.

[0114] The nitrogen adsorption-desorption characteristic evaluation results (Figure 6) showed that the nitrogen adsorption curve of STS-D exhibited concave arcs at two points, p / p0 < 0.3 and p / p0 > 0.7, as well as a hysteresis loop from p / p0 > 0.45 onwards.

[0115] Table 1 shows the results of the characterization of chemical composition, specific surface area, and pore volume.

[0116] Table 1 shows the results of evaluating the Ti-Si molecular sieve comparison sample STS-D, which was expanded with a silylation reagent, by cyclohexanone amoximation.

[0117] Example 1 This example demonstrates the preparation, characterization, and evaluation of the porous molecular sieve material TS-1-1 of the present invention.

[0118] The Ti-Si molecular sieve obtained in Preparation Example 2 was mixed with polymer-based quaternary ammonium base-47, water, and ammonium bicarbonate in a ratio of molecular sieve (moles): polymer-based quaternary ammonium base (weight): water (moles): nitrogen-containing basic compound (moles) = 1:0.1:20:0.05 to obtain a mixture with a pH of approximately 10.8. This mixture was treated at 150°C for 18 hours, and the treated mixture was filtered to obtain a solid product. It was further dried at 120°C for 6 hours and calcined at 550°C for 6 hours to obtain porous molecular sieve material TS-1-1.

[0119] The porous molecular sieve material TS-1-1 was characterized.

[0120] XRD analysis revealed that the TS-1-1 molecular sieve possesses an MFI structure (Figure 7).

[0121] SEM results (Figure 8) showed that open pore chambers with a pore size of 20 nm or more exist on the surface of the TS-1-1 molecular sieve.

[0122] TEM results (Figure 9) showed that the TS-1-1 molecular sieve has open pore chambers with a pore diameter of 20 nm or more, while it was observed that approximately 50% of the molecular sieve grains have an isolated hollow structure.

[0123] The nitrogen adsorption-desorption characteristics evaluation results (Figure 10) showed that the nitrogen adsorption curve of the TS-1-1 molecular sieve had four concave arcs (three with p / p0 < 0.3 and one with p / p0 > 0.7) and two hysteresis loops (the first hysteresis loop was located in the range where the relative pressure p / p0 was less than 0.3, and the second hysteresis loop was located in the range where the relative pressure p / p0 was greater than 0.45).

[0124] Table 1 shows the results of the characterization evaluation regarding chemical composition, specific surface area, and pore volume.

[0125] Table 1 shows the results of evaluating the porous molecular sieve material TS-1-1 using the cyclohexanone amoximation reaction.

[0126] The open pore chambers of the molecular sieves had an elongation degree in the range of 0 to 0.1.

[0127] Example 2 This example demonstrates the preparation, characterization, and evaluation of the porous molecular sieve material TS-1-2 of the present invention.

[0128] The Ti-Si molecular sieve obtained in Preparation Example 2 was mixed with polymer-based quaternary ammonium base-32, water, and ammonium nitrate in the ratio molecular sieve (moles): polymer-based quaternary ammonium base (weight): water (moles): nitrogen-containing basic compound (moles) = 1:0.05:15:0.02. The resulting mixture was treated at 160°C for 24 hours, and then filtered to obtain a solid product. It was further dried at 120°C for 6 hours and calcined at 550°C for 6 hours to obtain porous molecular sieve material TS-1-2.

[0129] We evaluated the properties of the porous molecular sieve material TS-1-2.

[0130] XRD analysis revealed that TS-1-2 molecular sieves possess an MFI structure.

[0131] SEM results showed that the surface of the TS-1-2 molecular sieve contains open pore chambers with a pore diameter of 30 nm or more.

[0132] TEM results showed that TS-1-2 molecular sieves have open pore chambers of 40 nm or more, while it was observed that approximately 40% of the molecular sieve grains have an isolated hollow structure.

[0133] The results of the nitrogen adsorption-desorption characteristic evaluation showed that the nitrogen adsorption curve of the TS-1-2 molecular sieve had three concave arcs (two with p / p0 < 0.3 and one with p / p0 > 0.7) and two hysteresis loops (the first hysteresis loop was located in the range where the relative pressure p / p0 was less than 0.3, and the second hysteresis loop was located in the range where the relative pressure p / p0 was greater than 0.45).

[0134] Table 1 shows the results of the characterization evaluation regarding chemical composition, specific surface area, and pore volume.

[0135] Table 1 shows the results of evaluating the porous molecular sieve material TS-1-2 using the cyclohexanone amoximation reaction.

[0136] The open pore chambers of the molecular sieves had an elongation degree in the range of 0 to 0.1.

[0137] Example 3 This example demonstrates the preparation, characterization, and evaluation of the porous molecular sieve material TS-1-3 of the present invention.

[0138] The Ti-Si molecular sieve obtained in Preparation Example 2 was mixed with polymer-based quaternary ammonium base-37, water, and ammonium carbonate in a ratio of molecular sieve (moles): polymer-based quaternary ammonium base (weight): water (moles): nitrogen-containing basic compound (moles) = 1:0.01:30:0.08. The resulting mixture was treated at 170°C for 12 hours, then filtered to recover the solid product, which was further dried at 120°C for 6 hours and calcined at 550°C for 6 hours. The above preparation process was repeated two more times to obtain porous molecular sieve material TS-1-3.

[0139] We evaluated the properties of the porous molecular sieve material TS-1-3.

[0140] XRD analysis revealed that TS-1-3 molecular sieves possess an MFI structure.

[0141] SEM results showed that the surface of the TS-1-3 molecular sieve contains open pore chambers with a pore size of 40 nm or larger.

[0142] TEM results showed that TS-1-3 molecular sieves have open pore chambers of 40 nm or more, while it was observed that approximately 60% of the molecular sieve grains have an isolated hollow structure.

[0143] The results of the nitrogen adsorption-desorption characteristic evaluation showed that the nitrogen adsorption curve of the TS-1-3 molecular sieve had three concave arcs (two with p / p0 < 0.3 and one with p / p0 > 0.7) and two hysteresis loops (the first hysteresis loop was located in the range where the relative pressure p / p0 was less than 0.3, and the second hysteresis loop was located in the range where the relative pressure p / p0 was greater than 0.45).

[0144] Table 1 shows the results of the characterization evaluation regarding chemical composition, specific surface area, and pore volume.

[0145] Table 1 shows the results of evaluating the porous molecular sieve material TS-1-3 using the cyclohexanone amoximation reaction.

[0146] The open pore chambers of the molecular sieves had an elongation degree in the range of 0 to 0.1.

[0147] Example 4 This example demonstrates the preparation, characterization, and evaluation of the porous molecular sieve material TS-1-4 of the present invention.

[0148] The Ti-Si molecular sieve obtained in Preparation Example 2 was mixed with polymer-based quaternary ammonium base-6 and water in a ratio of molecular sieve (moles): polymer-based quaternary ammonium base (weight): water (moles) = 1:0.008:20. The resulting mixture was treated at 170°C for 6 hours, then filtered to recover the solid product, which was further dried at 120°C for 6 hours and calcined at 550°C for 6 hours to obtain porous molecular sieve material TS-1-4.

[0149] We evaluated the properties of the porous molecular sieve material TS-1-4.

[0150] XRD analysis revealed that TS-1-4 molecular sieves possess an MFI structure.

[0151] SEM results showed that the surface of the TS-1-4 molecular sieve contains open pore chambers with a pore size of 15 nm or larger.

[0152] TEM results showed that TS-1-4 molecular sieves have open pore chambers of 20 nm or more, while no isolated hollow structures were observed within the molecular sieve grains.

[0153] The results of the nitrogen adsorption-desorption characteristic evaluation showed that the nitrogen adsorption curve of the TS-1-4 molecular sieve had three concave arcs (two with p / p0 < 0.3 and one with p / p0 > 0.7) and two hysteresis loops (the first hysteresis loop was located in the range where the relative pressure p / p0 was less than 0.3, and the second hysteresis loop was located in the range where the relative pressure p / p0 was greater than 0.45).

[0154] Table 1 shows the results of the characterization evaluation regarding chemical composition, specific surface area, and pore volume.

[0155] Table 1 shows the results of evaluating the porous molecular sieve material TS-1-4 using the cyclohexanone amoximation reaction.

[0156] The open pore chambers of the molecular sieves had an elongation degree in the range of 0 to 0.1.

[0157] Example 5 This example demonstrates the preparation, characterization, and evaluation of the porous molecular sieve material TS-1-5 of the present invention.

[0158] The Ti-Si molecular sieve obtained in Preparation Example 2 was mixed with polymer-based quaternary ammonium base-22 and water in a ratio of molecular sieve (moles): polymer-based quaternary ammonium base (weight): water (moles) = 1:0.12:30. The resulting mixture was treated at 150°C for 36 hours, then filtered to recover the solid product, which was further dried at 120°C for 6 hours and calcined at 550°C for 6 hours to obtain porous molecular sieve material TS-1-5.

[0159] We evaluated the properties of the porous molecular sieve material TS-1-5.

[0160] XRD analysis revealed that TS-1-5 molecular sieves possess an MFI structure.

[0161] SEM results showed that the surface of the TS-1-5 molecular sieve contains open pore chambers with a pore size of 15 nm or larger.

[0162] TEM results showed that TS-1-5 molecular sieves have open pore chambers of 30 nm or more, while no isolated hollow structures were observed within the molecular sieve grains.

[0163] The results of the nitrogen adsorption-desorption characteristic evaluation showed that the nitrogen adsorption curve of the TS-1-5 molecular sieve had three concave arcs (two with p / p0 < 0.3 and one with p / p0 > 0.7) and two hysteresis loops (the first hysteresis loop was located in the range of relative pressure p / p0 < 0.3, and the second hysteresis loop was located in the range of relative pressure p / p0 > 0.45).

[0164] Table 1 shows the results of the characterization evaluation regarding chemical composition, specific surface area, and pore volume.

[0165] Table 1 shows the results of evaluating the porous molecular sieve material TS-1-5 using the cyclohexanone amoximation reaction.

[0166] The open pore chambers of the molecular sieves had an elongation degree in the range of 0 to 0.1.

[0167] Example 6 This example demonstrates the preparation, characterization, and evaluation of the porous molecular sieve material TS-1-6 of the present invention.

[0168] The Ti-Si molecular sieve obtained in Preparation Example 2 was mixed with polymer-based quaternary ammonium base-37 and water in a ratio of molecular sieve (moles): polymer-based quaternary ammonium base (weight): water (moles) = 1:0.2:50. The resulting mixture was treated at 145°C for 24 hours, then filtered to recover the solid product, which was further dried at 120°C for 6 hours and calcined at 550°C for 6 hours to obtain porous molecular sieve material TS-1-6.

[0169] We evaluated the properties of the porous molecular sieve material TS-1-6.

[0170] XRD analysis revealed that TS-1-6 molecular sieves possess an MFI structure.

[0171] SEM results showed that the surface of the TS-1-6 molecular sieve contains open pore chambers with a pore size of 18 nm or larger.

[0172] TEM results showed that TS-1-6 molecular sieves have open pore chambers of 35 nm or larger, while no isolated hollow structures were observed within the molecular sieve grains.

[0173] The results of the nitrogen adsorption-desorption characteristic evaluation showed that the nitrogen adsorption curve of the TS-1-6 molecular sieve had three concave arcs (two with p / p0 < 0.3 and one with p / p0 > 0.7) and two hysteresis loops (the first hysteresis loop was located in the range where the relative pressure p / p0 was less than 0.3, and the second hysteresis loop was located in the range where the relative pressure p / p0 was greater than 0.45).

[0174] Table 1 shows the results of the characterization evaluation regarding chemical composition, specific surface area, and pore volume.

[0175] Table 1 shows the results of evaluating the porous molecular sieve material TS-1-6 using the cyclohexanone amoximation reaction.

[0176] The open pore chambers of the molecular sieves had an elongation degree in the range of 0 to 0.1.

[0177] Comparative Example 3 This comparative example shows the characterization of S-1-D, a total silicon molecular sieve prepared by a conventional method.

[0178] Tetraethyl orthosilicate, tetrapropylammonium hydroxide, and water were mixed to obtain silica gel with a molar composition of SiO2:tetrapropylammonium hydroxide:water = 1:0.2:30. This silica gel was aged at 60°C for 10 hours, and then crystallized at 170°C for 72 hours. The crystallized product was filtered and washed, dried at 120°C for 6 hours, and then calcined at 550°C for 6 hours to obtain a total silicon molecular sieve comparative sample S-1-D.

[0179] The characteristics of the total silicon molecular sieve comparative sample S-1-D were evaluated.

[0180] XRD analysis revealed that the S-1-D molecular sieve possesses an MFI structure.

[0181] SEM results showed that there are no open pore chambers on the surface of S-1-D (Figure 11).

[0182] TEM results showed that S-1-D has a dense structure and does not contain open mesopores or hollow structures (Figure 12).

[0183] The results of the nitrogen adsorption-desorption characteristic evaluation showed that the nitrogen adsorption curve of the S-1-D molecular sieve has two concave arcs (one located at p / p0 < 0.3 and the other at p / p0 > 0.7) and one hysteresis loop located at p / p0 > 0.8 (Figure 13).

[0184] Table 1 shows the results of the characterization of chemical composition, specific surface area, and pore volume.

[0185] Table 1 shows the results of evaluating the total silicon molecular sieve comparative sample S-1-D using the gas-phase Beckmann rearrangement reaction of cyclohexanone oxime.

[0186] Example 7 This example demonstrates the preparation, characterization, and evaluation of the porous molecular sieve material S-1-1 of the present invention.

[0187] The total silicon molecular sieve obtained in Preparation Example 3 was mixed with polymer-based quaternary ammonium base-7 and water in a ratio of molecular sieve (moles): polymer-based quaternary ammonium base (weight): water (moles) = 1:0.005:10. The resulting mixture was treated at 180°C for 24 hours, then filtered to recover the solid product, which was further dried at 120°C for 6 hours and calcined at 550°C for 6 hours to obtain porous molecular sieve material S-1-1.

[0188] The porous molecular sieve material S-1-1 was characterized.

[0189] XRD analysis revealed that the S-1-1 molecular sieve possesses an MFI structure.

[0190] SEM results showed that the surface of the S-1-1 molecular sieve contains open pore chambers with a pore diameter of 20 nm or more (Figure 14).

[0191] TEM results showed that the S-1-1 molecular sieves have open pore chambers of 35 nm or larger, and no isolated hollow structures were observed within the molecular sieve grains.

[0192] The nitrogen adsorption-desorption characteristics evaluation results (Figure 15) showed that the nitrogen adsorption curve of the S-1-1 molecular sieve had three concave arcs (two with p / p0 < 0.3 and one with p / p0 > 0.7) and two hysteresis loops (the first hysteresis loop was located in the range where the relative pressure p / p0 was less than 0.3, and the second hysteresis loop was located in the range where the relative pressure p / p0 was greater than 0.45).

[0193] Table 1 shows the results of the characterization evaluation regarding chemical composition, specific surface area, and pore volume.

[0194] Table 1 shows the results of evaluating the porous molecular sieve material S-1-1 using the gas-phase Beckmann rearrangement reaction of cyclohexanone oxime.

[0195] The open pore chambers of the molecular sieves had an elongation degree in the range of 0 to 0.1.

[0196] Example 8 This example demonstrates the preparation, characterization, and evaluation of the porous molecular sieve material S-1-2 of the present invention.

[0197] The total silicon molecular sieve obtained in Preparation Example 3 was mixed with polymer-based quaternary ammonium base-2 and water in a ratio of molecular sieve (moles): polymer-based quaternary ammonium base (weight): water (moles) = 1:0.2:50. The resulting mixture was treated at 170°C for 48 hours, then filtered to recover the solid product, which was further dried at 120°C for 6 hours and calcined at 550°C for 6 hours to obtain porous molecular sieve material S-1-2.

[0198] The porous molecular sieve material S-1-2 was characterized.

[0199] XRD analysis revealed that the S-1-2 molecular sieve possesses an MFI structure.

[0200] SEM results showed that the surface of the S-1-2 molecular sieve contains open pore chambers with a pore size of 15 nm or larger.

[0201] TEM results showed that the S-1-2 molecular sieves have open pore chambers of 30 nm or more on their surface, and no isolated hollow structures were observed within the molecular sieve grains.

[0202] The nitrogen adsorption-desorption characteristics were evaluated, and it was found that the nitrogen adsorption curve of the S-1-2 molecular sieve had three concave arcs (two located at p / p0 < 0.3 and one at p / p0 > 0.7) and two hysteresis loops (the first hysteresis loop was located in the range where the relative pressure p / p0 was less than 0.3, and the second hysteresis loop was located in the range where the relative pressure p / p0 was greater than 0.45).

[0203] Table 1 shows the results of the characterization evaluation regarding chemical composition, specific surface area, and pore volume.

[0204] Table 1 shows the results of evaluating the porous molecular sieve material S-1-2 using the gas-phase Beckmann rearrangement reaction of cyclohexanone oxime.

[0205] The open pore chambers of the molecular sieves had an elongation degree in the range of 0 to 0.1.

[0206] Example 9 This example demonstrates the preparation, characterization, and evaluation of the porous molecular sieve material S-1-3 of the present invention.

[0207] The total silicon molecular sieve obtained in Preparation Example 3 was mixed with polymer-based quaternary ammonium base-32, water, and ammonium carbonate in a ratio of molecular sieve (moles): polymer-based quaternary ammonium base (weight): water (moles): ammonium carbonate (moles) = 1:0.05:15:0.03. The resulting mixture was treated at 170°C for 12 hours, then filtered to recover the solid product, which was then dried at 120°C for 6 hours and calcined at 550°C for 6 hours to obtain porous molecular sieve material S-1-3.

[0208] The porous molecular sieve material S-1-3 was characterized.

[0209] XRD analysis revealed that the S-1-3 molecular sieve possesses an MFI structure.

[0210] SEM results showed that the surface of the S-1-3 molecular sieve contains open pore chambers with a pore diameter of 30 nm or more.

[0211] TEM results showed that the S-1-3 molecular sieves have open pore chambers of 40 nm or more, and it was observed that approximately 60% of the molecular sieve grains have an isolated hollow structure.

[0212] The nitrogen adsorption-desorption characteristics were evaluated, and the nitrogen adsorption curve of the S-1-3 molecular sieve was shown to have three concave arcs (two with p / p0 < 0.3 and one with p / p0 > 0.7) and two hysteresis loops (the first hysteresis loop was located in the range where the relative pressure p / p0 was less than 0.3, and the second hysteresis loop was located in the range where the relative pressure p / p0 was greater than 0.45).

[0213] Table 1 shows the results of the characterization evaluation regarding chemical composition, specific surface area, and pore volume.

[0214] Table 1 shows the results of evaluating the porous molecular sieve material S-1-3 using the gas-phase Beckmann rearrangement reaction of cyclohexanone oxime.

[0215] The open pore chambers of the molecular sieves had an elongation degree in the range of 0 to 0.1.

[0216] Comparative Example 4 This comparative example shows the characterization of molecular sieve Sn-MEL-D prepared by a conventional method.

[0217] Tetraethyl orthosilicate, stannous chloride, tetrapropylammonium hydroxide, and water were mixed and treated at 60°C for 12 hours to obtain a sol with a molar composition of SiO2:SnO2:tetrapropylammonium hydroxide:water of 1:0.02:0.2:20. This sol was crystallized at 170°C for 72 hours. Finally, the resulting slurry was filtered, dried at 120°C for 6 hours, and calcined at 550°C for 6 hours to obtain a solid product, producing molecular sieve comparison sample Sn-MEL-D.

[0218] We evaluated the characteristics of the molecular sieve comparison sample Sn-MEL-D.

[0219] XRD analysis revealed that the Sn-MEL-D molecular sieve possesses a MEL structure.

[0220] SEM results showed that there are no open pore chambers on the surface of the Sn-MEL-D molecular sieve (Figure 16).

[0221] TEM results showed that the Sn-MEL-D molecular sieve had a dense structure, and neither open mesopores nor hollow structures were observed.

[0222] The nitrogen adsorption-desorption characteristics were evaluated, and the nitrogen adsorption curve of the Sn-MEL-D molecular sieve was shown to have two concave arcs (one located at p / p0 < 0.3 and the other at p / p0 > 0.7) and one hysteresis loop located at p / p0 > 0.8 (Figure 17). The characterization results for chemical composition, specific surface area, and pore volume are shown in Table 1.

[0223] Table 1 shows the results of evaluating the molecular sieve comparison sample Sn-MEL-D using the cyclohexanone Bayer-Villiger (BV) oxidation reaction.

[0224] Example 10 This example demonstrates the preparation, characterization, and evaluation of the porous molecular sieve material Sn-MEL according to the present invention.

[0225] The tin-silicon molecular sieve obtained in Preparation Example 4 was mixed with polymer-based quaternary ammonium base-6 and water in a ratio of molecular sieve (moles): polymer-based quaternary ammonium base (weight): water (moles) = 1:0.003:5. The resulting mixture was treated at 140°C for 6 hours, then filtered to recover the solid product, which was further dried at 120°C for 6 hours and calcined at 550°C for 6 hours to obtain the porous molecular sieve material Sn-MEL.

[0226] We evaluated the properties of the porous molecular sieve material Sn-MEL.

[0227] XRD analysis revealed that the Sn-MEL molecular sieve possesses a MEL structure.

[0228] The SEM results showed that there were open pore chambers of 10 nm or more on the surface of the Sn-MEL molecular sieve (Figure 18).

[0229] The TEM results showed that the Sn-MEL molecular sieve had open pore chambers of 20 nm or more, and no void structure was observed within the molecular sieve crystallites.

[0230] From the nitrogen adsorption-desorption characteristic evaluation results (Figure 19), it was shown that the nitrogen adsorption curve of the Sn-MEL molecular sieve had three concave arcs (two with p / p0 < 0.3 and one with p / p0 > 0.7), and two hysteresis loops (the first hysteresis loop was located in the range where the relative pressure p / p0 was less than 0.3, and the second hysteresis loop was located in the range where the relative pressure p / p0 exceeded 0.45).

[0231] The characteristic evaluation results regarding the chemical composition, specific surface area, and pore volume are shown in Table 1.

[0232] Table 1 shows the results of evaluating the porous molecular sieve material Sn-MEL in the cyclohexanone Baeyer-Villiger (BV) oxidation reaction.

[0233] The open pore chambers of the molecular sieve had an elongation in the range of 0 to 0.1.

[0234] Comparative Example 5 This comparative example shows the characteristic evaluation of the molecular sieve Zr-MFI-D prepared by the conventional method.

[0235] Tetraethyl orthosilicate, zirconium propoxide, tetrapropylammonium hydroxide, and water were mixed and treated at 60°C for 12 hours to obtain a sol with a molar composition of SiO2:ZrO2:tetrapropylammonium hydroxide:water = 1:0.02:0.2:20. This sol was crystallized at 170°C for 72 hours. Finally, the resulting slurry was filtered, dried at 120°C for 6 hours, and calcined at 550°C for 6 hours to obtain a solid product, producing molecular sieve comparison sample Zr-MFI-D.

[0236] The molecular sieve comparison sample Zr-MFI-D was characterized.

[0237] XRD analysis revealed that the Zr-MFI-D molecular sieve possesses an MFI structure.

[0238] SEM results showed that there are no open pore chambers on the surface of the Zr-MFI-D molecular sieve (Figure 20).

[0239] TEM results showed that the Zr-MFI-D molecular sieve had a dense structure, and neither open mesopores nor hollow structures were observed.

[0240] The nitrogen adsorption-desorption characteristics were evaluated, and the nitrogen adsorption curve of the Zr-MFI-D molecular sieve was shown to have two concave arcs (one at p / p0 < 0.3 and the other at p / p0 > 0.7) and one hysteresis loop at p / p0 > 0.45 (Figure 21). The characterization results for chemical composition, specific surface area, and pore volume are shown in Table 1.

[0241] Table 1 shows the results of evaluating the molecular sieve comparison sample Zr-MFI-D using the Meerwein-Ponndorf-Verley (MPV) reaction with levulinic acid.

[0242] Example 11 This example demonstrates the preparation, characterization, and evaluation of the porous molecular sieve material Zr-MFI of the present invention.

[0243] The zirconium-silicon molecular sieve obtained in Preparation Example 5 was mixed with polymer-based quaternary ammonium base-7 and water in a ratio of molecular sieve (moles): polymer-based quaternary ammonium base (weight): water (moles) = 1:0.003:5. The resulting mixture was treated at 140°C for 6 hours, then filtered to recover the solid product, which was further dried at 120°C for 6 hours and calcined at 550°C for 6 hours to obtain the porous molecular sieve material Zr-MFI.

[0244] We evaluated the properties of the porous molecular sieve material Zr-MFI.

[0245] XRD analysis revealed that the Zr-MFI molecular sieve possesses an MFI structure.

[0246] SEM results showed that open pore chambers of 10 nm or more exist on the surface of the Zr-MFI molecular sieve (Figure 22).

[0247] TEM results showed that the Zr-MFI molecular sieves had open pore chambers of 20 nm or more, and no cavity structures were observed within the molecular sieve grains.

[0248] The nitrogen adsorption-desorption characteristics evaluation results (Figure 23) showed that the nitrogen adsorption curve of the Zr-MFI molecular sieve had three concave arcs (two with p / p0 < 0.3 and one with p / p0 > 0.7) and two hysteresis loops (the first hysteresis loop was located in the range where the relative pressure p / p0 was less than 0.3, and the second hysteresis loop was located in the range where the relative pressure p / p0 was greater than 0.45).

[0249] Table 1 shows the results of the characterization evaluation regarding chemical composition, specific surface area, and pore volume.

[0250] Table 1 shows the results of evaluating the porous molecular sieve material Zr-MFI using the Meerwein-Ponndorf-Verley (MPV) reaction with levulinic acid.

[0251] The open pore chamber of the molecular sieve had an elongation in the range of 0 to 0.1.

[0252] Example 12 This example shows the preparation, property evaluation, and assessment of the porous molecular sieve material TS-1-7 of the present invention.

[0253] The Ti-Si molecular sieve obtained in Preparation Example 6 was mixed with a polymer quaternary ammonium base - 47, water, and ammonium bicarbonate at a ratio of molecular sieve (mol): polymer quaternary ammonium base (weight): water (mol): nitrogen-containing basic compound (mol) = 1:0.1:20:0.05 to obtain a mixture. After treating this mixture at 150 °C for 18 hours, the treated mixture was filtered to obtain a solid product, which was further dried at 120 °C for 6 hours and calcined at 550 °C for 6 hours to obtain the porous molecular sieve material TS-1-7.

[0254] The porous molecular sieve material TS-1-7 was subjected to property evaluation.

[0255] XRD analysis showed that the TS-1-7 molecular sieve has an MFI structure.

[0256] The SEM results showed that there are open pore chambers with pore diameters of 10 nm or more on the surface of the TS-1-7 molecular sieve.

[0257] The TEM results showed that the TS-1-7 molecular sieve has open pore chambers of 20 nm or more, and on the other hand, it was observed that about 40% of the molecular sieve crystallites have an isolated hollow structure.

[0258] The results of the nitrogen adsorption-desorption characteristic evaluation showed that the nitrogen adsorption curve of the TS-1-7 molecular sieve had three concave arcs (two with p / p0 < 0.3 and one with p / p0 > 0.7) and two hysteresis loops (the first hysteresis loop was located in the range where the relative pressure p / p0 was less than 0.3, and the second hysteresis loop was located in the range where the relative pressure p / p0 was greater than 0.45).

[0259] Table 1 shows the results of the characterization evaluation regarding chemical composition, specific surface area, and pore volume.

[0260] Table 1 shows the results of evaluating the porous molecular sieve material TS-1-7 using the cyclohexanone amoximation reaction.

[0261] The open pore chambers of the molecular sieves had an elongation degree in the range of 0 to 0.1.

[0262] Example 13 This example demonstrates the preparation, characterization, and evaluation of the porous molecular sieve material S-1-4 of the present invention.

[0263] The total silicon molecular sieve obtained in Comparative Example 3 was mixed with polymer-based quaternary ammonium base-32, water, and ammonium carbonate in a ratio of molecular sieve (moles): polymer-based quaternary ammonium base (weight): water (moles): ammonium carbonate (moles) = 1:0.05:15:0.03. The resulting mixture was treated at 170°C for 12 hours, then filtered to recover the solid product, which was further dried at 120°C for 6 hours and calcined at 550°C for 6 hours to obtain porous molecular sieve material S-1-4.

[0264] The porous molecular sieve material S-1-4 was characterized.

[0265] XRD analysis revealed that the S-1-4 molecular sieve possesses an MFI structure.

[0266] SEM results showed that the surface of the S-1-4 molecular sieve contains open pore chambers with a pore diameter of 20 nm or more.

[0267] TEM results showed that S-1-4 molecular sieves have open pore chambers of 20 nm or more, while approximately 60% of the molecular sieve grains were observed to have isolated hollow structures.

[0268] The results of the nitrogen adsorption-desorption characteristic evaluation showed that the nitrogen adsorption curve of the S-1-4 molecular sieve had three concave arcs (two with p / p0 < 0.3 and one with p / p0 > 0.7) and two hysteresis loops (the first hysteresis loop was located in the range where the relative pressure p / p0 was less than 0.3, and the second hysteresis loop was located in the range where the relative pressure p / p0 was greater than 0.45).

[0269] Table 1 shows the results of the characterization evaluation regarding chemical composition, specific surface area, and pore volume.

[0270] Table 1 shows the results of evaluating the porous molecular sieve material S-1-4 using the gas-phase Beckmann rearrangement reaction of cyclohexanone oxime.

[0271] The open pore chambers of the molecular sieves had an elongation degree in the range of 0 to 0.1.

[0272] Example 14 This example demonstrates the preparation, characterization, and evaluation of the porous molecular sieve material Sn-MEL-2 of the present invention.

[0273] The Sn-MEL-D molecular sieve obtained in Comparative Example 4 was mixed with polymer-based quaternary ammonium base-6 and water in a ratio of molecular sieve (moles): polymer-based quaternary ammonium base (weight): water (moles) = 1:0.003:5. The resulting mixture was treated at 140°C for 6 hours, then filtered to recover the solid product, which was further dried at 120°C for 6 hours and calcined at 550°C for 6 hours to obtain the porous molecular sieve material Sn-MEL-2.

[0274] The porous molecular sieve material Sn-MEL-2 was characterized.

[0275] XRD analysis revealed that the Sn-MEL-2 molecular sieve possesses a MEL structure.

[0276] SEM results showed that the surface of the Sn-MEL-2 molecular sieve contains open pore chambers larger than 10 nm.

[0277] TEM results showed that the Sn-MEL-2 molecular sieves have open pore chambers of 20 nm or more, and no cavity structure was observed within the molecular sieve grains.

[0278] The results of the nitrogen adsorption-desorption characteristic evaluation showed that the nitrogen adsorption curve of the Sn-MEL-2 molecular sieve had three concave arcs (two located at p / p0 < 0.3 and one at p / p0 > 0.7) and two hysteresis loops (the first hysteresis loop was located in the range where the relative pressure p / p0 was less than 0.3, and the second hysteresis loop was located in the range where the relative pressure p / p0 was greater than 0.45).

[0279] Table 1 shows the results of the characterization evaluation regarding chemical composition, specific surface area, and pore volume.

[0280] Table 1 shows the results of evaluating the porous molecular sieve material Sn-MEL-2 using the cyclohexanone Baeyer-Villiger (BV) oxidation reaction.

[0281] The open pore chambers of the molecular sieves had an elongation degree in the range of 0 to 0.1.

[0282] Example 15 This example demonstrates the preparation, characterization, and evaluation of the porous molecular sieve material Zr-MFI-2 of the present invention.

[0283] The zirconium-silicon molecular sieve Zr-MFI-D obtained in Comparative Example 5 was mixed with polymer-based quaternary ammonium base-7 and water in a ratio of molecular sieve (moles): polymer-based quaternary ammonium base (weight): water (moles) = 1:0.003:5. The resulting mixture was treated at 140°C for 6 hours, then filtered to recover the solid product, which was further dried at 120°C for 6 hours and calcined at 550°C for 6 hours to obtain porous molecular sieve material Zr-MFI-2.

[0284] We evaluated the properties of the porous molecular sieve material Zr-MFI-2.

[0285] XRD analysis revealed that the Zr-MFI-2 molecular sieve possesses an MFI structure.

[0286] SEM results showed that open pore chambers of 10 nm or larger exist on the surface of the Zr-MFI-2 molecular sieve.

[0287] TEM results showed that the Zr-MFI-2 molecular sieves have open pore chambers of 20 nm or more, and no cavity structures were observed within the molecular sieve grains.

[0288] The results of the nitrogen adsorption-desorption characteristic evaluation showed that the nitrogen adsorption curve of the Zr-MFI-2 molecular sieve had three concave arcs (two located at p / p0 < 0.3 and one at p / p0 > 0.7) and two hysteresis loops (the first hysteresis loop was located in the range where the relative pressure p / p0 was less than 0.3, and the second hysteresis loop was located in the range where the relative pressure p / p0 was greater than 0.45).

[0289] Table 1 shows the results of the characterization evaluation regarding chemical composition, specific surface area, and pore volume.

[0290] Table 1 shows the results of evaluating the porous molecular sieve material Zr-MFI-2 using the Meerwein-Ponndorf-Verley (MPV) reaction with levulinic acid.

[0291] The open pore chambers of the molecular sieves had an elongation degree in the range of 0 to 0.1.

[0292] Comparative Example 6 This comparative example differs from Example 1 in that it obtains TS-1-1-A by replacing the polymer-based quaternary ammonium base-47 with polyquaternium-47.

[0293] We evaluated the properties of the porous molecular sieve material TS-1-1-A.

[0294] XRD analysis revealed that the TS-1-1-A molecular sieve possesses an MFI structure.

[0295] SEM results showed that there are no open pore chambers on the surface of the TS-1-1-A molecular sieve.

[0296] TEM results showed no open mesopores or hollow structures in the TS-1-1-A molecular sieve.

[0297] The results of the nitrogen adsorption-desorption characteristic evaluation showed that the nitrogen adsorption curve of the TS-1-1-A molecular sieve was no different from that of the conventional TS-1, and had two concave arcs (one located at p / p0 < 0.3 and the other at p / p0 > 0.7) without a prominent hysteresis loop.

[0298] Comparative Example 7 This comparative example was carried out according to the method of Example 1, but differed in that the polymer-based quaternary ammonium salt base-47 was replaced with a mixture of polyquaternium-47 and sodium hydroxide. The amount of sodium hydroxide used was adjusted so that the overall pH of the system was the same as in Example 1, and TS-1-1-B was obtained.

[0299] The properties of the porous molecular sieve material TS-1-1-B were evaluated.

[0300] XRD analysis revealed that the TS-1-1-B molecular sieve possesses an MFI structure.

[0301] SEM results showed that the surface of the TS-1-1-B molecular sieve contains open pore chambers with pore diameters exceeding 10 nm.

[0302] TEM results showed that TS-1-1-B molecular sieves have open pore chambers exceeding 10 nm, and that approximately 30% of the molecular sieve grains have an intracrystalline cavity structure.

[0303] The open pore chambers of the TS-1-1-B molecular sieve did not have an elongation degree in the range of 0 to 0.2.

[0304] The results of the nitrogen adsorption-desorption characteristic evaluation showed that the nitrogen adsorption curve of the TS-1-1-B molecular sieve has three concave arcs (two located at p / p0 < 0.3 and one at p / p0 > 0.7) and one hysteresis loop located at a relative pressure of p / p0 > 0.45.

[0305] The porous molecular sieve material TS-1-1-B had a sodium content exceeding 2% (in terms of Na2O).

[0306] [Table 1]

[0307] As can be seen from the table above, the low-temperature nitrogen adsorption isotherm of the porous molecular sieve material of the present invention has at least three concave arcs and two hysteresis loops, the molecular sieve has open pore chambers extending from the surface to the interior, and the BET specific surface area is 350-460 m². 2 / g, micropore volume 0.15~0.19 cm³ 3 / g, mesopore volume 0.1~0.15cm³ 3 / g or 0.12-0.15cm 3It has a concentration of / g. The method for preparing porous molecular sieve material according to the present invention is simple and easy to perform. Due to the creation of a new pore structure, the reaction conversion rate and product selectivity (yield) are superior compared to conventional molecular sieves with a pore structure.

[0308] Preferred embodiments of the present invention have been described in detail with reference to the drawings. However, the present invention is not limited to the specific details of the above embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention, and all such simple modifications fall within the scope of protection of the present invention.

[0309] Furthermore, it should be noted that the various specific technical features described in the above-described embodiments can be combined in any suitable manner without contradiction. To avoid unnecessary repetition, the present invention will not further describe the various possible combination modes.

[0310] Furthermore, various different embodiments of the present invention can be arbitrarily combined without departing from the spirit of the invention and should likewise be considered to be within the scope of the disclosures herein.

Claims

1. A porous molecular sieve material characterized in that its low-temperature nitrogen adsorption isotherm has at least three concave arcs and at least two, preferably two, adsorption-desorption hysteresis loops.

2. The porous molecular sieve material according to claim 1, characterized in that, in the low-temperature nitrogen adsorption isotherm, at least two concave arcs are located in the range of relative pressure p / p0 < 0.3 and at least one concave arc is located in the range of relative pressure p / p0 > 0.7; and at least two hysteresis loops are present, comprising a first hysteresis loop and a second hysteresis loop, wherein the first hysteresis loop is located in the range of relative pressure p / p0 less than 0.3 and the second hysteresis loop is located in the range of relative pressure p / p0 greater than 0.

45.

3. A porous molecular sieve material according to claim 1 or 2, characterized in that it contains silicon as the first structural element of the molecular sieve, and further contains one or more of C, Ge, Sn, Pb, Ti, Zr, Hf, B, Al, and Ga as the second structural element.

4. The porous molecular sieve material according to claim 3, characterized in that the second skeletal element is one or more of Sn, Ti, and Zr.

5. The porous molecular sieve material according to claim 3 or 4, characterized in that the molar ratio of the first skeletal element to the second skeletal element is 1:(0.0001 to 1), preferably the molar ratio of the first skeletal element to the second skeletal element is 1:(0.001 to 0.4).

6. A porous molecular sieve material according to claim 1 or 2, characterized by comprising a first skeletal element, optionally comprising a second skeletal element, and optionally comprising a third skeletal element, wherein the first skeletal element is silicon, the second skeletal element is one or more of Sn, Ti, and Zr, and the third skeletal element is aluminum, and the molar ratio of the first skeletal element, the second skeletal element, and the third skeletal element is 100:(0 or 0.01 to 100):(0 or 0.01 to 5), preferably 100:(0 or 0.1 to 40):(0 or 0.1 to 2), more preferably 100:(0 or 1 to 10):(0 or 0.2 to 1).

7. When characterized by SEM, the surface has at least one surface pore with a maximum radius dimension of 5 nm or more, preferably 10 nm or more, more preferably 20 nm or more, the surface pore extends into the interior of the porous molecular sieve material to form an open pore chamber, preferably with a maximum radius dimension of 200 nm or less, and / or The porous molecular sieve material according to any one of claims 1 to 6, characterized by TEM, wherein the open pore chamber has a pore size of 10 nm or more, preferably 20 nm or more, more preferably 40 nm or more, and preferably the pore size of the open pore chamber is 200 nm or less.

8. A porous molecular sieve material according to any one of claims 1 to 7, characterized in that the crystal structure is selected from one or more of BEA, MFI, MEL, MWW, and SVR, preferably MFI or MEL.

9. When measured by the low-temperature nitrogen adsorption-desorption method, the BET specific surface area is 350-460 m². ２ / g, micropore volume of 0.15–0.19 cm³ ３ / g, mesopore volume of 0.1–0.15 cm³ ３ / g, preferably 0.12 to 0.15 cm ３ A porous molecular sieve material according to any one of claims 1 to 8, characterized in that it is / g.

10. The porous molecular sieve material according to any one of claims 1 to 9, wherein the open pore chambers of the porous molecular sieve material have an elongation of 0 to 0.2, preferably 0 to 0.1, and / or the porous molecular sieve material has a total content of alkali metals and alkaline earth metals (as oxides) of less than 2% by weight, for example less than 1% by weight, less than 0.5% by weight, less than 0.2% by weight, or less than 0.1% by weight, but preferably more than 1 ppm.

11. A method for preparing a porous molecular sieve material, characterized by mixing a molecular sieve containing silicon as the primary skeletal element with a polymeric quaternary ammonium base, water, and optionally a low molecular weight nitrogen-containing basic compound; treating the mixture at a temperature of 100 to 200°C for 1 to 72 hours; separating at least a portion of the solid product from the treated mixture; and drying and calcining the solid product; preferably, the polymeric quaternary ammonium base has an average degree of polymerization of 10 to 100,000, and the polymeric quaternary ammonium base is obtained by hydroxide radical exchange of a polymeric quaternary ammonium salt; more preferably, the polymeric quaternary ammonium base is obtained by hydroxide radical exchange of polyquaternium-2, polyquaternium-6, polyquaternium-7, polyquaternium-22, polyquaternium-32, polyquaternium-37, polyquaternium-39, and polyquaternium-47.

12. Porous molecular sieve materials are obtained by post-modification of molecular sieves containing silicon as the first skeletal element, the post-modification comprising: mixing the molecular sieve containing silicon as the first skeletal element with a polymeric quaternary ammonium base, water, and optionally a low molecular weight nitrogen-containing basic compound; treating the mixture at a temperature of 100 to 200°C for 1 to 72 hours; separating at least a portion of the solid product from the treated mixture; and drying and calcining the solid product; The polymer-based quaternary ammonium base has an average degree of polymerization of 10 to 100,000, preferably 100 to 50,000, more preferably 500 to 10,000, and most preferably 1,000 to 5,000, where the average degree of polymerization refers to the average number of repeating units contained in the polymer chain, and the polymer-based quaternary ammonium base is obtained by hydroxide radical exchange of a polymer-based quaternary ammonium salt, wherein the exchange is >30%, for example >50%, preferably >70%, more preferably >90%, and most preferably >98%. The method according to claim 11, wherein the exchange rate is expressed as the ratio of the molar percentage of anions substituted by hydroxide radicals to the total number of anions in the polymeric quaternary ammonium salt; more preferably, the polymeric quaternary ammonium base is obtained by hydroxide radical substitution of polyquaternium-2, polyquaternium-6, polyquaternium-7, polyquaternium-22, polyquaternium-32, polyquaternium-37, polyquaternium-39, and polyquaternium-47.

13. The polymeric quaternary ammonium base has a pKa of 11 to 13.5, for example, about 12.8, and / or The polymer-based quaternary ammonium base comprises a polymer polymer chain portion and one or more quaternary ammonium base portions, and the sum of the molecular weights of the one or more quaternary ammonium bases (R １ , R ２ , R ３ The ratio of the molecular weight of the N atom and the sum of the molecular weights of the hydroxide radical (or the sum of the molecular weights of the cyclic structure portion and the hydroxide radical) to the molecular weight of the polymeric quaternary ammonium base is (0.01 to 0.4):1, preferably (0.1 to 0.38):1, and more preferably (0.2 to 0.35):1; The aforementioned quaternary ammonium base substructure may have the following branched structure: 【Chemistry 1】 Here, at each occurrence, R １ , R ２ and R ３ are each independently selected from C １ -C １２ alkyl groups and unsaturated groups (such as aromatic groups and alkenyl groups); these groups may be optionally substituted, and the substituents may be halogen, hydroxyl, nitro, cyano, alkyl, alkenyl, alkynyl, alkoxy; also, these groups may be optionally oxidized; Alternatively, it could be the following ring structure: 【Chemistry 2】 Here, the cyclic portion comprises 2 to 13 ring atoms in addition to the indicated quaternary nitrogen atom, the ring atoms being selected from C, O, S, and N, the cyclic portion may be monocyclic or polycyclic (spiro ring, fused ring, bridging ring), and the cyclic portion may be aromatic, unsaturated, or saturated; the cyclic portion may optionally be substituted, the substituents being halogen, hydroxyl, nitro, cyano, alkyl (e.g., C １ -C １２ ), alkenyl (for example, C ２ -C １２ ), alkynyl (for example, C ２ -C １２ ), alkoxy (e.g., C １ -C １２ ) may be; the cyclic portion may be optionally oxidized; 【Transformation 3】 The method according to claim 11 or 12, wherein is the bonding point between each quaternary ammonium base portion and the polymer chain portion.

14. The method according to any one of claims 11 to 13, wherein the low molecular weight nitrogen-containing basic compound is selected from one or more organic ammonium salts having 15 or fewer carbon atoms and inorganic ammonium salts; preferably, the organic ammonium salt is a linear ammonium carboxylate salt, a cyclic ammonium carboxylate salt, and an aromatic ammonium carboxylate salt having 15 or fewer carbon atoms, preferably 12 or fewer, more preferably 6 or fewer carbon atoms; more preferably, the organic ammonium salt is one or more of ammonium formate, ammonium acetate, ammonium propionate, ammonium butyrate, ammonium valerate, ammonium cyclopentanecarboxylate, ammonium hexanoate, and ammonium hexenoate; and the inorganic ammonium salt is one or more of ammonium nitrate, ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium sulfate, ammonium bisulfite, ammonium sulfite, ammonium bisulfite, ammonium chloride, ammonium bromide, ammonium fluoride, ammonium carbonate, and ammonium bicarbonate.

15. A mixture of molecular sieves containing silicon as a first skeletal element, a polymer-based quaternary ammonium base, water, and optionally added low molecular weight nitrogen-containing basic compounds, wherein the ratio of the molecular sieves (containing silicon as a first skeletal element), polymer-based quaternary ammonium base, water, and optionally added low molecular weight nitrogen-containing basic compounds is 1:(0.001 to 0.5):(5 to 100):(0 to 0.3), where the molecular sieves containing silicon as a first skeletal element are calculated in moles as silica, the polymer-based quaternary ammonium base is calculated in grams, the water is calculated in grams, and the low molecular weight nitrogen-containing basic compound is calculated in moles; preferably, the above preparation step is repeated 1 to 10 times, according to any one of claims 11 to 14.

16. The molecular sieve containing silicon as the first framework element does not contain any other four-coordinate framework elements, and the molecular sieve containing silicon as the first framework element is prepared in the following steps: Mix a silicon source, a quaternary ammonium base, and water to produce a first mixture, preferably with a molar ratio of silicon source, quaternary ammonium base, and water of 1:(0.05-0.3):(5-60); age the mixture at a temperature of 5-120°C for 0.5-24 hours to obtain a sol; then crystallize this sol at a temperature of 100-200°C for 2-168 hours; separate at least a portion of the product therefrom; then dry and calcine the product to produce at least a portion of the molecular sieve; optionally, add a material having a crystalline structure before crystallization, and mix the material having a crystalline structure with the silicon source (SiO ２ The weight ratio of (as) is (0.001 to 2):1; preferably, the material having the crystalline structure has an MFI structure, and the material having the crystalline structure contains Si and O, but does not contain C, Ge, Sn, Pb, Ti, Zr, Hf, B, Al and Ga; or The molecular sieve containing silicon as the first skeleton element further contains a second skeleton element, the second skeleton element being selected from one or more of C, Ge, Sn, Pb, Ti, Zr, Hf, B, Al, and Ga, the molar ratio of silicon to the second skeleton element being 1:(0.001 to 1), preferably 1:(0.0001 to 1), and the molecular sieve containing silicon as the first skeleton element is prepared by the following steps: mixing a silicon source, a second skeleton element source, a quaternary ammonium base, and water to make a first mixture A material is produced, preferably with a supply molar ratio of silicon source, quaternary ammonium base, and water of 1:(0.05-0.3):(5-60); the mixture is aged at 5-120°C for 0.5-24 hours to obtain a sol; this sol is then crystallized at 100-200°C for 2-168 hours; at least a portion is separated from the product; the product is then dried and calcined to produce at least a portion of the molecular sieve; optionally, a material having a crystalline structure is added before crystallization, and the material having a crystalline structure and the silicon source (SiO ２ The weight ratio of (as) is (0.001 to 2):1; preferably, the material having the crystalline structure has an MFI structure, and the material having the crystalline structure contains Si and O, and further contains one or more of C, Ge, Sn, Pb, Ti, Zr, Hf, B, Al and Ga; or The molecular sieve containing silicon as the first skeleton element further comprises a second skeleton element and optionally a third skeleton element, where the second skeleton element is one or more of Sn, Ti, and Zr, and the third skeleton element is aluminum, where the molar ratio of the first skeleton element:second skeleton element:third skeleton element is 100:(0 or 0.01 to 100):(0 or 0.01 to 5), preferably 100:(0 or 0.1 to 40):(0 or 0.1 to 2), more preferably 100:(0 or 1 to 10):(0 or 0.2 to 1); The molecular sieve containing silicon as the first skeleton element is prepared by the following steps: mixing a silicon source, a second skeleton element source, an optional third skeleton element source, a quaternary ammonium base, and water to produce a first mixture, preferably with a molar ratio of silicon source, quaternary ammonium base, and water of 1:(0.05-0.3):(5-60); aging the mixture at 5-120°C for 0.5-24 hours to obtain a sol; then crystallizing this sol at 100-200°C for 2-168 hours; separating at least a portion of the product therefrom; then drying and calcining the product to produce at least a portion of the molecular sieve; optionally, adding a material having a crystalline structure before crystallization, and mixing the material having a crystalline structure with the silicon source (SiO ２ The weight ratio of (as) is (0.001 to 2):1; preferably, the material having the crystalline structure has an MFI structure, and the material having the crystalline structure contains Si and O, one or more elements from Sn, Ti and Zr, and optionally contains Al; Preferably: The silicon source is a monodisperse silicon source and / or an agglomerated silicon source, the monodisperse silicon source is a tetraalkoxysilane, and the agglomerated silicon source is selected from silica gel, silica sol, and silica white; preferably, the silicon source is a mixture of the monodisperse silicon source and the agglomerated silicon source, the molar ratio of the monodisperse silicon source to the agglomerated silicon source is 1:(0.1 to 10), preferably 1:(0.5 to 7), more preferably 1:(1 to 5), more preferably 1:(2 to 4), and the agglomerated silicon source is calculated as silica; and / or Preferably: If the second skeletal element is C, then the source of the second skeletal element is A １ A ２ A ３ Si-A ４ Si-A ５ A ６ A ７ It has the structure, and here A １ A ２ A ３ A ５ A ６ , and A ７ Each of these is independently and arbitrarily substituted C １ -C １０ It is an alkoxy group or a halogen group, A ４ is C １ -C ３ It is alkyl; preferably A １ A ２ A ３ A ５ A ６ , and A ７ Each is independently C １ -C ８ It is an alkoxy group or halogen, A ４ is C １ -C ２ It is an alkyl group; more preferably, A １ A ２ A ３ A ５ A ６ , and A ７ Each is independently C １ -C ３ It is an alkoxy group or halogen, A ４ is C １ It is an alkyl group; specifically, if the second skeletal element is C, the source of the second skeletal element is one or more of bis(trimethoxysilyl)methane, bis(triethoxysilyl)methane, bis(tripropoxysilyl)methane, bis(trichloromethylsilyl)methane, and bis(diethoxychlorosilyl)methane; and / or If the second skeletal element is Ge, the source of the second skeletal element is selected from one or more of germanium oxides, salts, and organometallic salts, specifically germanium monoxide, germanium dioxide, germanium tetrafluoride, germanium tetrachloride, germanium tetrabromide, germanium tetraiodide, germanium sulfide, tetramethylgermane, tetraethylgermane, tetrapropylgermane, tetrabutylgermane, methylgermane, ethylgermane, propylgermane, and butylgermane; and / or If the second skeletal element is Sn, the source of the second skeletal element is selected from one or more of tin oxides, salts, and organometallic salts, specifically tin dioxide, stannous oxide, stannous chloride, stannous trichloride, stannous tetrachloride, potassium stannate, sodium stannate, metastannic acid, stannic acid, tetramethyltin, tetraethyltin, tetrapropyltin, and tetrabutyltin; and / or If the second skeletal element is Pb, the source of the second skeletal element is selected from one or more of lead oxides, salts, and organometallic salts, specifically lead oxide, lead chloride, lead nitrate, lead sulfate, and lead acetate; and / or When the second skeletal element is Ti, the source of the second skeletal element is titanium salts and organometallic salts; specifically, at least one of tetraalkoxytitanium, titanium tetrachloride, titanium trichloride, titanium sulfate, hexafluorotitanium acid, bis(cyclopentadienyl)titanium(IV) dichloride, and titanium nitrate, preferably at least one of tetraalkoxytitanium and titanium tetrachloride, more preferably at least one of tetraethyl titanate, tetrapropyl titanate, and tetrabutyl titanate; and / or If the second skeletal element is Zr, the source of the second skeletal element is selected from one or more of zirconium salts and organometallic salts, specifically zirconium tetrachloride, zirconium trichloride, zirconium oxychloride, zirconium oxysulfate, zirconium nitrate, zirconium acetate, and tetraalkoxyzirconium; and / or If the second skeletal element is Hf, the source of the second skeletal element is selected from one or more of the oxides, salts, and organometallic salts of hafnium, specifically hafnium oxide, hafnium tetrachloride, hafnium hydroxide, hafnium carbide, and hafnium boride; and / or If the second skeletal element is B, the source of the second skeletal element is selected from one or more of boron oxides, salts and organoboro salts, specifically boron oxide, boric acid, borax, alkylboron compounds and alkoxyboron compounds; and / or If the second / third skeletal element is Al, the source of the second skeletal element is selected from one or more of the following: aluminum oxides, salts, and organoaluminum compounds, specifically aluminum oxide, aluminum chloride, aluminum sulfate, aluminum nitrate, aluminum phosphate, sodium aluminate, aluminum acetate, alkylaluminum compounds, and alkoxyaluminum compounds; and / or If the second skeletal element is Ga, the source of the second skeletal element is selected from one or more of gallium oxides, salts, and organogallium compounds, specifically gallium oxide, gallium chloride, gallium sulfate, gallium nitrate, gallium phosphate, sodium gallate, gallium acetate, alkylgallium compounds, and alkoxygallium compounds; and / or Preferably: The quaternary ammonium base is R １ R ２ R ３ R ４ N ＋ OH － It has a structure, R １ , R ２ , R ３ and R ４ Each is independently C ２－５ Alkyl or C ２－５ It is an alkenyl, preferably R １ , R ２ , R ３ and R ４ Each is independently C ３ Alkyl or C ３ The method according to any one of claims 11 to 15, wherein the alkenyl is used.

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