Porous molecular sieve material, manufacturing process and application thereof

Abstract

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

Description

TECHNICAL AREA

[0001] The present invention relates to an inorganic material, a manufacturing process and its application, in particular a molecular sieve material, a manufacturing process and its application. BACKGROUND

[0002] Porous materials are highly conducive to the conversion, adsorption, and other processes of specific substrate molecules due to their rich pore channel structures and the advantages of adjustable pore channel size and the position / state of active sites. Inorganic porous materials, whose main structure is composed of inorganic elements, have been extensively studied due to their structural stability, resistance to aggressive acid and alkali conditions, and broad range of applications. Based on their structure, inorganic porous materials can be divided into amorphous and crystalline materials. Molecular sieve materials, which belong to the crystalline group, are frequently used in processes such as chemical catalysis and adsorption separation.

[0003] Molecular sieves are a class of inorganic materials formed by the bonding of TO4 tetrahedra, exhibiting unique pore channel structures and active sites. Here, T is a framework element in a trivalent, tetravalent, pentavalent, or other valence state and can be Si, B, Al, Ga, C, Ge, Sn, Pb, Ti, V, Zr, Hf, P, etc. When some of the T elements are replaced by elements other than Si, the material can be described as a heteroatom-substituted molecular sieve. The stabilization of heteroatoms within the molecular sieve framework can lead to excellent physical and chemical properties.

[0004] Molecular sieves can exhibit regular pore channel structures based on the compound shape of TO4 tetrahedra. Depending on the size of the pore channels, they can be classified as small pores (pore openings consisting of T atoms of an 8-membered ring), medium pores (pore openings consisting of T atoms of a 10-membered ring), large pores (pore openings consisting of T atoms of a 12-membered ring), and extra-large pores. According to the classification rules recommended by the IUPAC, pore structures can also be categorized by size into micropores (pore channel size less than 2 nm), mesopores (pore channel size not less than 2 nm but less than 50 nm), and macropores (pore channel size not less than 50 nm). Typically, the starting materials used in industry for molecular sieves have pore sizes that are primarily in the micropore range.To achieve larger openings and good diffusion performance, they can also be subjected to a pore enlargement treatment.

[0005] CN1301599A discloses a method for treating a TS-1 molecular sieve with a solution containing an organic base to produce a titanium-silicon molecular sieve with intracrystalline cavities. However, these cavities have a closed structure, which still imposes a significant diffusion resistance on the substrate molecules. Furthermore, the manufacturing process involves complex processing steps, has a lengthy workflow, and results in high production costs.

[0006] The use of an inorganic base solution, such as sodium hydroxide, for pore expansion is more difficult than treatment with an organic base, because inorganic bases have poor structuring ability and can easily lead to the breakdown of the molecular sieve structure during treatment.

[0007] Silylation pore enlargement is a method developed in recent years that uses silylation reagents as synthetic pore enlargement agents for efficient pore enlargement. CN108726528A, CN106145147A, CN106145148A, and CN106145149A all disclose the fabrication of hierarchical pore titanium-silicon molecular sieves with larger mesopore volumes using improved silylation techniques. However, the titanium-silicon molecular sieves produced by this method exhibit increased structural disorder and poor stability, and are more suitable for the activation of organic peroxides, while performing poorly in reactions with hydrogen peroxide as the oxidizing agent.

[0008] In summary, porous molecular sieve inorganic materials produced using existing state-of-the-art pore expansion methods have problems such as a monotonous pore structure, poor structural stability, complex manufacturing, high costs, and limited applicability. SUMMARY OF THE INVENTION

[0009] A first objective of the present invention is to provide a porous molecular sieve material that is structurally stable and has different pore distribution properties than those of the prior art.

[0010] A second objective of the present invention is to provide a simple, cost-effective manufacturing process for a structurally stable porous molecular sieve material that has different pore distribution properties than those of the prior art.

[0011] A third objective of the present invention is to provide an application of the porous molecular sieve material of the present invention, for example as a catalytic material that enables a better 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 curve has at least three concave arcs and at least two, preferably two, adsorption-desorption hysteresis loops.

[0013] To achieve the second objective of the present invention, the present invention provides a method for producing a porous molecular sieve material, characterized in that a molecular sieve containing silicon as the first framework element is mixed with a polymeric quaternary ammonium base, water and optionally a low molecular weight nitrogen-containing basic compound, the mixture is treated at a temperature of 100 to 200°C for 1 to 72 hours, at least a portion of a solid product is separated from the treated mixture, and the solid product is dried and calcined.

[0014] To achieve the third objective of the present invention, the present invention provides an application method for the aforementioned porous molecular sieve material, characterized in that the porous molecular sieve material or the porous molecular sieve material produced by the said method is used or employed as a support in adsorption processes, catalytic reactions or catalyst preparations.

[0015] The porous molecular sieve material provided by the present invention has physicochemical characteristic technical features that differ from those of the prior art, which is mainly manifested in the fact that its low-temperature nitrogen adsorption isotherm curve has at least three concave arcs and at least two, preferably two, adsorption-desorption hysteresis loops.

[0016] The manufacturing process for the porous molecular sieve material of the present invention is characterized by a simple process, ease of execution, and low cost. It enables the production of porous molecular sieve materials with physicochemical technical characteristics that differ from those of the prior art, thereby overcoming problems such as monotonous pore structure, poor structural stability, and limited applicability in existing processes for the production of porous molecular sieve materials.

[0017] Due to its physicochemical properties, which differ from those of the prior art, the porous molecular sieve material of the present invention exhibits good performance in processes such as catalytic reactions and adsorption-desorption separations. As a catalytic material, for example, it displays a better reaction conversion rate and product selectivity. BRIEF DESCRIPTION OF THE FIGURES Fig. Figure 1 is an SEM image of the HTS sample of the hollow titanium-silicon molecular sieve produced in comparison example 1. Fig. Figure 2 is a TEM image of the hollow titanium-silicon molecular sieve HTS sample produced in comparison example 1. Fig. Figure 3 is a low-temperature nitrogen adsorption / desorption curve of the hollow titanium-silicon molecular sieve HTS sample produced in comparative example 1. Fig. Figure 4 is a SEM image of the Ti-Si molecular sieve comparison sample STS-D produced in comparison example 2. Fig. Figure 5 is a TEM image of the Ti-Si molecular sieve comparison sample STS-D produced in comparison example 2. Fig. Figure 6 is a low-temperature nitrogen adsorption / desorption curve of the Ti-Si molecular sieve comparison sample STS-D produced in comparison example 2. Fig.Figure 7 is an XRD spectrum of the porous molecular sieve material TS-1-1 produced in Example 1. Fig. Figure 8 is a SEM image of the porous molecular sieve material TS-1-1 produced in Example 1. Fig. Figure 9 is a TEM image of the porous molecular sieve material TS-1-1 produced in Example 1. Fig. Figure 10 is a low-temperature nitrogen adsorption-desorption curve of the porous molecular sieve material TS-1-1 produced in Example 1. Fig. Figure 11 is a SEM image of the molecular sieve comparison sample S-1-D, which consists entirely of silicon and was produced in comparison example 3. Fig. Figure 12 is a TEM image of the molecular sieve reference sample S-1-D, which consists entirely of silicon and was produced in comparison example 3. Fig.Figure 13 is a low-temperature nitrogen adsorption / desorption curve of the silicon-based molecular sieve reference sample S-1-D produced in comparative example 3. Fig. Figure 14 is a SEM image of the porous molecular sieve material S-1-1, which consists entirely of silicon and was produced in Example 7. Fig. Figure 15 is a low-temperature nitrogen adsorption-desorption curve of the porous molecular sieve material S-1-1, which consists entirely of silicon and was prepared in Example 7. Fig. Figure 16 is a SEM image of the tin-silicon molecular sieve comparison sample Sn-MEL-D produced in comparison example 4. Fig. Figure 17 is a low-temperature nitrogen adsorption / desorption curve of the tin-silicon molecular sieve comparison sample Sn-MEL-D produced in comparative example 4. Fig. Figure 18 is a SEM image of the porous molecular sieve material Sn-MEL produced in Example 10. Fig. Figure 19 is a low-temperature nitrogen adsorption-desorption curve of the porous molecular sieve material Sn-MEL produced in Example 10. Fig. Figure 20 is an SEM image of the zirconium-silicon molecular sieve comparison sample Zr-MFI-D produced in comparison example 5. Fig. Figure 21 is a low-temperature nitrogen adsorption / desorption curve of the zirconium-silicon molecular sieve reference sample Zr-MFI-D produced in comparative example 5. Fig. Figure 22 is a SEM image of the porous molecular sieve material Zr-MFI produced in Example 11. Fig. Figure 23 is a low-temperature nitrogen adsorption-desorption curve of the porous molecular sieve material Zr-MFI produced in Example 11. DETAILED DESCRIPTION

[0018] The present invention relates to 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.

[0019] The low-temperature nitrogen adsorption-desorption isotherm is obtained by measuring the adsorption and desorption behavior of a material for nitrogen at a liquid nitrogen temperature (e.g., 77 K). The shape of the low-temperature nitrogen adsorption-desorption isotherm allows for the determination of the material's surface structure, pore properties, and other characteristics. The IUPAC (International Union of Pure and Applied Chemistry) classifies adsorption isotherms into six types based on their shape. Furthermore, adsorption-desorption isotherms in which the adsorption and desorption branches do not coincide and form hysteresis loops are also classified into six types, broadly distinguishing the surface and pore structure properties of different materials.

[0020] The porous molecular sieve material of the present invention has at least three concave arcs in its low-temperature nitrogen adsorption isotherm curve, wherein the concave arc is an arc formed by the curve concave to one side. Conventional porous materials typically have only two or only one concave arc in their nitrogen adsorption curves. According to the porous molecular sieve material of the present invention, at least two concave arcs are located at a relative pressure (i.e., the ratio of the nitrogen adsorption pressure p to the nitrogen saturation vapor pressure P0 at the same temperature, p / p0) of less than 0.3, and one concave arc is located at a relative pressure of more than 0.7. The presence of three or more concave arcs indicates the rich surface and pore structures of the porous molecular sieve material of the present invention.

[0021] The hysteresis loops present in the low-temperature nitrogen adsorption-desorption isotherm curve of a porous molecular sieve material are generally closely related to the presence of mesopores in the material. A hysteresis loop is defined as the loop feature formed by the mismatch between the adsorption and desorption branches. 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 properties, whereas conventional porous materials exhibit at most one hysteresis loop.

[0022] Furthermore, the porous molecular sieve material of the present invention exhibits at least two concave arcs in the low-temperature nitrogen adsorption-desorption isotherm curve, including a first hysteresis loop and a second hysteresis loop, wherein the first hysteresis loop is located in the region of a relative pressure p / p0 of less than 0.3 and the second hysteresis loop is located in the region of a relative pressure p / p0 of more than 0.45. Due to changes in the surface properties of the material, the porous molecular sieve material of the present invention exhibits a reduced ability to adsorb nitrogen gas in the low-pressure range, resulting in two adsorption platforms, including a first adsorption platform and a second adsorption platform.Typically, the hysteresis loop of mesoporous materials begins at a relative pressure of about 0.45 in the high-pressure range, whereas the porous molecular sieve material of the present invention also exhibits a hysteresis loop in the range of a relative pressure of less than 0.3.

[0023] The porous molecular sieve material of the present invention contains a silicon element as the first framework element of the molecular sieve. It can, for example, contain only silicon and oxygen elements and exist as a pure silicon molecular sieve (consisting entirely of silicon). Alternatively, in addition to silicon and oxygen, it can contain further framework elements, for example, one or more selected from C, Ge, Sn, Pb, Ti, Zr, Hf, B, Al, and Ga as a second framework element, which exists as a heteroatom molecular sieve (e.g., TS-1, TS-2, tin-titanium-silicon molecular sieve, etc.). The framework element means that the element exists within the topological structure of the molecular sieve framework, is bonded to four neighboring atoms, and exists together with other framework elements in a tetrahedral coordination structure.For example, the porous molecular sieve material can contain SiO2, or SiO2 and one or more of GeO2, SnO2, PbO2, TiO2, ZrO2, HfO2, C, B2O3, Al2O3, or GA2O3 in the framework structure. Preferably, the second framework element is one or more of Ti, Sn, and Zr. For example, the porous molecular sieve material can contain SiO2 and one or more of SnO2, TiO2, and ZrO2. The molar ratio of the first framework element to the second framework 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).

[0024] Another feature of the porous molecular sieve material of the present invention is that, when viewed under a scanning electron microscope (SEM), its surface exhibits at least one surface pore with a maximum dimension (i.e., the maximum linear distance between any two points at the edge of the surface pore opening in the SEM image, also referred to here as the "maximum radial dimension") of not less than 5 nm and not more than 200 nm. This surface pore extends into the interior of the porous molecular sieve material and forms an open pore chamber. Preferably, the maximum radial dimension is not less than 10 nm, more preferably not less than 20 nm. When viewed with a transmission electron microscope (TEM), an open pore chamber can be observed, formed by the surface pores extending into the interior of the particles of the porous molecular sieve material.The pore size of this open pore chamber is not less than 10 nm, preferably not less than 20 nm, more preferably not less than 40 nm, and not more than 200 nm. Since the porous molecular sieve material of the present invention has open surface pore chambers, it can effectively shorten the diffusion path of substrate molecules and thus facilitate the rapid diffusion of substrate molecules to active sites.

[0025] According to the present invention, the pore size of the open pore chamber initially increases considerably and then decreases as it extends inward from the opening of the surface pores. In the direction extending inward from the opening of the surface pore, among all cross-sections perpendicular to the direction of expansion, the equivalent diameter of the cross-section with the largest area 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 inscribed circle of that cross-section. The direction of expansion can be determined as follows: In the case of an open pore chamber with one axis, the direction of expansion is the direction of that axis; or the open pore chamber can be differentiated in any way such that each differentiated open pore chamber has an axis and all axes can be combined to form the direction of expansion.

[0026] The equivalent diameter (d) of a particle of the porous molecular sieve material is defined as the diameter of the smallest sphere that can contain the particle, and the center of this smallest sphere is designated as point (O). The open pore chamber of the particle of the porous molecular sieve material extends inward from the particle surface. Among the points reached by the extension, the point closest to point O is designated as the extension range point (A). The ratio of the length of the line segment OA to the equivalent diameter is defined as the degree of extension of the open pore chamber of the particle of the porous molecular sieve material.The porous molecular sieve material is observed using a transmission electron microscope (TEM). The degree of expansion of the open pore chamber for each particle of the porous molecular sieve material in the image is determined, and the average of the degrees of expansion of the open pore chambers of 100 particles is taken as the degree of expansion of the open pore chamber of the porous molecular sieve material. The degree of expansion of the open pore chamber of the porous molecular sieve material of the present invention can be 0–0.2, preferably 0–0.1.

[0027] Optionally, the porous molecular sieve material of the present invention can, in addition to the aforementioned open pore chamber, also have 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 linear distance between any two points on the boundary curve of the intracrystalline pore observed in the TEM image. The isolated intracrystalline hollow structure means that the TEM image shows that this hollow structure is not connected to other intracrystalline hollow structures via a channel with a size of at least 5 nm. The porous molecular sieve material of the present invention exhibits various forms of mesopores, macropores, and open pore structures that promote the diffusion of substrate molecules and improve its application performance.

[0028] The structure of the porous molecular sieve material of the present invention can be determined by X-ray diffraction (XRD). The structure can be an amorphous structure with disordered atomic arrangement, an amorphous structure with short-range order and long-range disorder, or a crystalline structure with regularly arranged atoms, which 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 order can adopt a crystal system selected from cubic, trigonal, tetragonal, hexagonal, orthorhombic, monoclinic, and triclinic crystal systems. Preferably, the porous molecular sieve structure can be one or more of the structure codes approved by the International Zeolite Association (IZA), for example, one or more of the following: 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, BEC, CSV, CFI, CDO, CGF, CGF, CGF CGS, CHA, -CHI, -CLO, CON, CSV, CZP, DAC, DDR, DFO, DFT, DOH, DON, EAB, EDI, EEI, EMT, EON, EPI, ERI, ESV, ETL, ETR, ETV, EUO, EWO, EWS, -EWT, EZT, FAR, FER, FRA, FRA, GME, GME 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, JNT, JR, JST, JSW, JSW, JSW, JSW KFI, LAU, LEV, LIO,-LIT, LOS, LOV, LTA, LTF, LTJ, LTL, LTN, MAR, MAZ, MAY, MEL, MEP, MER, MFI, MFS, MON, MOR, MOZ, MRT, MSE, MSO, MTF, MTF, MTT, MTT, MW, MW, MW, MW, MW, NWAT, NWAT 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, RHO,-RON, RRO, RSN, RTH, RUT, RUT, RUT, RW, SWY 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, SSYT, 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-type topologies. Preferably, the porous molecular sieve material of the present invention has a crystal structure selected from MFI, MEL, MWW, BEA, and SVR-type topologies; more preferably, it has a crystal structure of an MFI-type topology.

[0029] The porous molecular sieve material of the present invention exhibits distributions of micropores, mesopores, macropores, and open-surface pores. There are no particular limitations regarding the specific surface area and pore volume distribution of its various pore structures. Optionally, the porous molecular sieve material, characterized by low-temperature nitrogen adsorption and desorption, has a BET-specific surface area of ​​350 to 460 m². 2 / g, preferably 370 to 430 m 2 / g, preferably 380 to 420 m 2 / g, a micropore volume of 0.15 to 0.19 cm³ 3 / g, preferably 0.16 to 0.18 cm 3 / g, and a mesopore volume of 0.1 to 0.15 cm³ 3 / g or 0.12 to 0.15 cm 3 / g, preferably 0.11 to 0.14 cm 3 / g, preferably 0.12 to 0.13 cm 3 / g on.

[0030] The present invention also provides a method for producing a porous molecular sieve material, characterized in that a molecular sieve containing silicon as the first framework element is mixed with a polymeric quaternary ammonium base, water and optionally a low molecular weight nitrogen-containing basic compound, the mixture is treated at a temperature of 100 to 200 °C, preferably 130 to 180 °C, more preferably 150 to 170 °C, for 1 to 72 hours, preferably 6 to 48 hours, more preferably 12 to 24 hours, at least a portion of a solid product is separated from the treated mixture, and the solid product is dried and calcined to produce the porous molecular sieve material.

[0031] In the manufacturing process provided by the present invention, the polymeric quaternary ammonium base is preferably a quaternary ammonium base polymer with 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 polymeric macromolecule chain.

[0032] For example, the polymeric quaternary ammonium base of the present invention comprises a polymeric macromolecular chain unit and one or more quaternary ammonium base units, wherein the ratio of the sum of the molecular weights of one or more quaternary ammonium bases (the sum of the molecular weights of R1, R2, R3, the N atom(s) and the hydroxide radical(s) or the sum of the molecular weights of the cyclic structural unit and the hydroxide radical(s)) to the molecular weight of the polymeric quaternary ammonium base is (0.01-0.4):1, preferably (0.1-0.38):1, more preferably (0.2-0.35):1.

[0033] The quaternary ammonium base unit can exhibit the following branched structures: where, in each occurrence, R1, R2 and R3 are each independently composed of C1-C 12-Alkyl groups and unsaturated groups (such as aromatic groups and alkenyl groups) are selected; wherein the groups may optionally be substituted and the substituents may be selected from halogen, hydroxyl, nitro, cyano, alkyl, alkenyl, alkynyl and alkoxy; and wherein the groups may also optionally be oxidized; or it can have the following cyclic structure: wherein the cyclic part, in addition to the quaternary nitrogen atom shown, also comprises 2-13 ring atoms, the ring atoms being selected from C, O, S and N, wherein the cyclic unit can be monocyclic or polycyclic (spiro-ring, condensed ring, bridged ring), wherein the cyclic unit can be aromatic or unsaturated or saturated; wherein the cyclic unit can optionally be substituted and the substituents are 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 ) can be; where the cyclic unit can also optionally be oxidized; represents the connection point of each quaternary ammonium base unit with the polymeric macromolecular chain unit.

[0034] The polymeric quaternary ammonium base is preferably produced by treating at least one of the following polymeric quaternary ammonium salts by means of hydroxide radical exchange: Polyquaternium-2, CAS No.: 68555-36-2, Poly[bis(2-chloroethyl)ether-alt-1,3-bis[3-(dimethylamino)propyl]urea], quaternized, with the following structural formula: Polyquaternium-6, CAS No.: 26062-79-3, Poly(diallyldimethylammonium chloride), with the following structural formula: Polyquaternium-7, CAS No.: 26590-05-6, poly(acrylamide-co-diallyldimethylammonium chloride), with the following structural formula: Polyquaternium-10, CAS No.: 68610-92-4, Chloro-2-hydroxy-3-(trimethylamino)propylpoly(ethylene oxide)cellulose ether, with the following structural formula: Polyquaternium-22, CAS No.: 53694-17-0, acrylic acid-diallyldimethylammonium chloride copolymer, polymerized from the following structural units: Polyquaternium-32, CAS No.: 35429-19-7, Ethanaminium, N,N,N-Trimethyl-2-[(2-methyl-1-oxo-2-propenyl)oxy]-, Chloride, Copolymer with 2-Propenamide, with the following structural formula: Polyquaternium-37, CAS No.: 26161-33-1, N,N,N-Trimethyl-2-[(2-methyl-1-oxo-2-propenyl)oxy]ethanaminium chloride homopolymer with the following structural formula: Polyquaternium-39, CAS No.: 25136-75-8, diallyldimethylammonium chloride-acrylamide-acrylic acid copolymer, polymerized from the following structural units: Polyquaternium-44, CAS No.: 150599-70-5, Poly[(3-methyl-1-vinylimidazolium methylsulfate)-co-(1-vinylpyrrolidone)], with the following structural formula: Polyquaternium-47, CAS No.: 197969-51-0, N,N,N-Trimethyl-3-[(2-methyl-1-oxo-2-propenyl)amino]-1-propanaminium chloride polymer with methyl 2-propenoate and 2-propenoic acid, polymerized from the following structural units: Polyquaternium-51, CAS No.: 125275-25-4, Poly(2-methacryloyloxyethylphosphorylcholine-co-n-butylmethacrylate), polymerized from the following structural units:

[0035] In the present invention, the polymeric quaternary ammonium salts are commercially available, and the present invention does not subject them to any special restrictions as long as they meet the above-mentioned requirements for the degree of polymerization.

[0036] The inventors unexpectedly discovered that the porous molecular sieve material produced by treatment with the polymeric quaternary ammonium base exhibits a novel pore structure. Among the polymeric quaternary ammonium bases, those obtained by hydroxide radical exchange of polyquaternium-2, polyquaternium-6, polyquaternium-7, polyquaternium-22, polyquaternium-32, polyquaternium-37, polyquaternium-39, or polyquaternium-47 are preferred; those obtained by hydroxide radical exchange of polyquaternium-32, polyquaternium-37, or polyquaternium-47 are most preferred. The process of hydroxide radical exchange of polymeric quaternary ammonium salts can be carried out by pushing the polymeric 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 hydroxide radical-containing solution can have a hydroxide radical concentration of 0.001 to 5 mol OH⁻ / L, preferably 0.05 to 2 mol OH⁻ / L, and more preferably 0.1 to 1 mol OH⁻ / L. The exchange time should be sufficient to achieve a degree of exchange of > 30%, preferably > 50%, more preferably > 70%, even more preferably > 90%, and most preferably > 98%. The stated degree of exchange refers to the molar percentage of anions replaced by hydroxide radicals, based on the total anions in the polymeric quaternary ammonium salt.

[0037] According to the manufacturing process provided by the present invention, the small molecular weight nitrogen-containing basic compounds comprise one or more organic ammonium salts having a carbon atom number of not more than 15 and inorganic ammonium salts.

[0038] The organic ammonium salts comprise straight-chain carboxylic acid ammonium salts, cyclic carboxylic acid ammonium salts, and aromatic carboxylic acid ammonium salts with a carbon atom number of no more than 15, preferably no more than 12, more preferably no more than 6; for example, the organic ammonium salt may be one or more of the following: ammonium formate, ammonium acetate, ammonium propionate, ammonium butyrate, ammonium valerate, ammonium cyclopentanecarboxylate, ammonium hexanoate, and ammonium hexenoate.

[0039] The inorganic ammonium salt may be one or more of the following: ammonium nitrate, ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium sulfate, ammonium hydrogen sulfate, ammonium sulfide, ammonium hydrogen sulfide, ammonium chloride, ammonium bromide, ammonium fluoride, ammonium carbonate and ammonium bicarbonate, and the preferred inorganic ammonium salt is one or more of ammonium nitrate, ammonium bicarbonate, ammonium carbonate and ammonium chloride.

[0040] According to the manufacturing process provided by the present invention, the ratio of the molecular sieve containing silicon as the first framework element (as silica, in mol), the polymeric quaternary ammonium base (in weight), water (in mol) and optionally the small molecular weight nitrogen-containing basic compound (in mol) is 1: (0.001-0.5): (5-100): (0-0.3), preferably 1: (0.005-0.2): (10-50): (0-0.15), more preferably 1: (0.01-0.1): (15-30) : (0.02-0.08).

[0041] According to the manufacturing process provided by the present invention, the manufacturing process can be repeated once or several times, for example, it can be repeated 1-10 times, and the technical effects of the present invention can be achieved.

[0042] According to the manufacturing process provided by the present invention, the molecular sieve containing silicon as the first framework element contains no other tetracoordinate framework elements, wherein the molecular sieve containing silicon as the first framework element is prepared by the following process: mixing a silicon source, a quaternary ammonium base and water to prepare a first mixture; aging the mixture at a temperature of 5 to 120°C for 0.5 to 24 hours (preferably at 20 to 100°C for 2 to 18 hours, more preferably at 40 to 90°C for 4 to 12 hours, even more preferably at 60 to 80°C for 5 to 10 hours) to obtain a sol; Subsequent crystallization of this sol at a temperature of 100 to 200°C for 2 to 168 hours (preferably at 130 to 180°C for 12 to 96 hours, more preferably at 150 to 170°C for 24 to 72 hours); separation of at least a portion of the product thereof;and subsequent drying and calcining of the product to produce at least part of the molecular sieve.;

[0043] According to the manufacturing process provided by the present invention, the molecular sieve containing silicon as a first framework element can further include a second framework element, wherein the second framework element is selected from one or more of the elements C, Ge, Sn, Pb, Ti, Zr, Hf, B, Al and Ga, preferably from one or more of Sn, Ti and Zr, wherein the molar ratio of silicon to the second framework element is 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), most preferably 1: (0.02-0.04).The molecular sieve, which contains silicon as the first framework element, is prepared by the following process: mixing a silicon source, a source for the second framework element, a quaternary ammonium base, and water to prepare a first mixture; aging the mixture at a temperature of 5 to 120°C for 0.5 to 24 hours (preferably at 20 to 100°C for 2 to 18 hours, more preferably at 40 to 90°C for 4 to 12 hours, and even more preferably at 60 to 80°C for 5 to 10 hours) to obtain a sol; subsequent crystallization of this sol at a temperature of 100 to 200°C for 2 to 168 hours (preferably at 130 to 180°C for 12 to 96 hours, and more preferably at 150 to 170°C for 24 to 72 hours). Separating at least part of the product; and subsequently drying and calcining the product to produce at least part of the molecular sieve.

[0044] According to the manufacturing process provided by the present invention, there are no special requirements for the silicon source used in the production of the molecular sieve containing silicon as the first framework element. Conventional silicon sources known to those skilled in the art can be used as the silicon source for the present invention. The silicon sources are further subdivided into monodisperse silicon sources and aggregated silicon sources, based on the degree of mutual combination of the silicon atoms. Monodisperse silicon sources are those in which silicon atoms are not connected to other silicon atoms via Si-O-Si bonds, while aggregated silicon sources are those in which at least some of the silicon atoms in the silicon source are connected to other silicon atoms via Si-O-Si bonds.

[0045] The silicon source can be a monodisperse silicon source and / or an aggregate silicon source. It is preferable to use both monodisperse and aggregate silicon sources as silicon sources. The monodisperse silicon sources comprise tetraalkoxysilanes, in particular one or more of tetramethyl orthosilicate, tetraethyl orthosilicate, tetrapropyl orthosilicate, and tetrabutyl orthosilicate. The aggregate silicon sources comprise silica white, silica gel, and silica sol. The molar ratio of the monodisperse silicon source to the aggregate silicon source (as silica) is preferably 1:(0.1-10), more preferably 1:(0.5-7), more preferably 1:(1-5), and even more preferably 1:(2-4). A silicon source with a silicon content as silica (in weight percent) of more than 80%, 90%, 95%, or 99% on a dry basis can be used as the silicon source of the present invention.Preferably, the silica content (in wt%) on a dry basis is greater than 95% and more preferably greater than 99%. The silica content (or the silicon content as silica) on a dry basis refers to the content (in wt%) of silica in the chemical composition of the silicon source obtained after drying to remove water and calcining at 880°C for 3 hours, measured by XRF.

[0046] According to the method for producing the molecular sieve containing silicon as the first framework element, the source for the second framework element, in the case that the second framework element is C, has a structure of A1A2A3Si-A4-SiA5A6A7, wherein A1, A2, A3, A5, A6 and A7 are each independently optionally substituted C1-C 10A1, A2, A3, A5, A6, and A7 are each independently alkoxy or halogen, and A4 is a C1-C3 alkyl; preferably, A1, A2, A3, A5, A6, and A7 are each independently a C1-C8 alkoxy or halogen, and A4 is a C1-C2 alkyl; more preferably, A1, A2, A3, A5, A6, and A7 are each independently a C1-C3 alkoxy or halogen, and A4 is a C1 alkyl. For example, if the second framework element is C, the source for the second framework element can be one or more of bis(trimethoxysilyl)methane, bis(triethoxysilyl)methane, bis(tripropoxysilyl)methane, bis(trichloromethylsilyl)methane, and bis(diethoxychlorosilyl)methane.

[0047] According to the method for producing the molecular sieve containing silicon as the first framework element, the source for the second framework element, if the second framework element is Ge, can be a conventional germanium source known to those skilled in the art. For example, if the second framework element is Ge, the source for the second framework element can be selected from oxides, salts, and organic metal salts of germanium, in particular from one or more of the following: germanium monoxide, germanium dioxide, germanium tetrafluoride, germanium tetrachloride, germanium tetrabromide, germanium tetraiodide, germanium sulfide, tetramethylgerman, tetraethylgerman, tetrapropylgerman, tetrabutylgerman, methylgerman, ethylgerman, propylgerman, and butylgerman.

[0048] According to the method for producing the molecular sieve containing silicon as the first framework element, the source for the second framework element, if the second framework element is Sn, can be a conventional tin source known to those skilled in the art. For example, if the second framework element is Sn, the source for the second framework element can be selected from oxides, salts, and organic metal salts of tin, in particular from one or more of the following: tin dioxide, tin(II) oxide, tin(II) chloride, tin trichloride, tin tetrachloride, potassium stannate, sodium stannate, metastannic acid, stannic acid, tetramethyltin, tetraethyltin, tetrapropyltin, and tetrabutyltin.

[0049] According to the method for producing the molecular sieve containing silicon as the first framework element, the source for the second framework element, if the second framework element is lead (Pb), can be derived from conventional lead sources known to those skilled in the art. For example, if the second framework element is lead (Pb), the source for the second framework element can be selected from oxides, salts, and organic metal salts of lead, in particular from one or more of the following: lead oxide, lead chloride, lead nitrate, lead sulfate, and lead acetate.

[0050] According to the method for producing the molecular sieve containing silicon as the first framework element, the source for the second framework element, if the second framework element is Ti, can be derived from conventional titanium sources known to those skilled in the art, e.g., salts and organic metal salts of titanium; in particular, it can be at least one of tetraalkoxytitanium, titanium tetrachloride, titanium trichloride, titanium sulfate, hexafluorotinateic 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.

[0051] According to the method for producing the molecular sieve containing silicon as the first framework element, the source for the second framework element, if the second framework element is Zr, can be derived from a conventional zirconium source known to those skilled in the art, for example, salts and organic metal salts of zirconium, in particular one or more of zirconium tetrachloride, zirconium trichloride, zirconium oxychloride, zirconium oxysulfate, zirconium nitrate, zirconium acetate and tetraalkoxyzirconium.

[0052] According to the method for producing the molecular sieve containing silicon as the first framework element, the source for the second framework element, if the second framework element is Hf, can be a conventional hafnium source known to those skilled in the art, for example oxides, salts and organic metal salts of hafnium, in particular one or more of hafnium oxide, hafnium tetrachloride, hafnium hydroxide, hafnium carbide and hafnium boride.

[0053] According to the method for producing the molecular sieve containing silicon as the first framework element, the source for the second framework element, if the second framework element is V, can be a conventional vanadium source known to those skilled in the art, for example oxides, salts and organic metal salts of vanadium, in particular one or more of vanadium trioxide (V2O3), vanadium pentoxide (V2O5), vanadium trichloride (VCl3) and ammonium metavanadate (NH4VO3).

[0054] According to the method for producing the molecular sieve containing silicon as the first framework element, the source for the second framework element, if the second framework element is B, can be a conventional boron source known to those skilled in the art, for example oxides, salts and organic boron salts of boron, in particular one or more from boron oxide, boric acid, borax, alkyl boron compounds and alkoxy boron compounds.

[0055] According to the method for producing the molecular sieve containing silicon as the first framework element, the source for the second framework element, if the second framework element is Al, can be a conventional source of aluminum known to those skilled in the art, for example, oxides, salts and organoaluminium compounds of aluminum, in particular one or more of the following: aluminum oxide, aluminum trichloride, aluminum sulfate, aluminum nitrate, aluminum phosphate, sodium aluminate, aluminum acetate, alkylaluminium compounds and alkoxyaluminium compounds.

[0056] According to the method for producing the molecular sieve containing silicon as the first framework element, the source for the second framework element, if the second framework element is Ga, can consist of usual gallium sources known to those skilled in the art, for example oxides, salts and organogallium compounds of gallium, in particular one or more of the following: gallium oxide, gallium chloride, gallium sulfate, gallium nitrate, gallium phosphate, sodium gallate, gallium acetate, alkylgallium compounds and alkoxygallium compounds.

[0057] According to the method for producing the molecular sieve, which contains silicon as the first framework element, the quaternary ammonium base has a structure of R1R2R3R4N + OH -, wherein 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 halogen (fluorine, chlorine, bromine, iodine), nitro, amino, hydroxyl, carboxyl, carbonyl, an aldehyde group, a ketone group, an ether group, an ester group, a sulfonic acid group, cyano, amide or an acyl halide group, for example one of 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, 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, 1,2-Dimethyl-2-propenyl, 1,1-Dimethyl-1-propenyl, 1,1-Dimethyl-2-propenyl, Chloroethyl, Chloropropyl, 2,3-Dichloropropyl, Chlorobutyl, Chlorpentyl, 1-Hydroxyethyl, 1-Hydroxypropyl, 2-Hydroxypropyl, 3-Hydroxypropyl, 2-Chloro-3-hydroxypropyl, 2-Hydroxy-3-chloropropyl, 2-Aminopropyl and 3-Aminopropyl. Preferably, R1, R2, R3 and R4 are each independently a linear or branched alkyl or alkenyl group with 3 carbon atoms, or a linear or branched alkyl or alkenyl group with 3 carbon atoms substituted with halogen (fluorine, chlorine, bromine, iodine), nitro, amino, hydroxyl, carboxyl, carbonyl, an aldehyde group, a ketone group, an ether group, an ester group, a sulfonic acid group, cyano, amide or an acyl halide 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 and 3-Aminopropyl.

[0058] According to the process for producing the molecular sieve, which contains silicon as the first framework element, the quaternary ammonium base can be present in the form of a hydroxide radical or in a state in which the hydroxide radical coexists with other anions (e.g., fluoride, chloride, bromide, iodide, nitrate radical, sulfate radical, phosphate radical, etc.). The molar fraction of the quaternary ammonium base present in the form of a hydroxide radical, based on the total number of moles of quaternary ammonium base, can be > 5%, preferably > 20%, more preferably > 50%, even more preferably > 80%, more preferably > 90%, and most preferably > 99%.

[0059] According to the process for producing the molecular sieve containing silicon as the first framework element, the silicon source, the quaternary ammonium base and water preferably have a molar composition in the feed of 1: (0.05-0.3): (5-60), preferably 1: (0.08-0.25): (10-50), more preferably 1: (0.12-0.2): (15-30).

[0060] According to the process for producing the molecular sieve, which contains silicon as the first framework element, a material with a crystalline structure can optionally be added prior to the crystallization treatment. The weight ratio of the crystalline material to the silicon source (as 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. Preferably, the crystalline material has an MFI structure. The crystalline material contains Si and O, or contains Si, O, and one or more of the elements C, Ge, Sn, Pb, Ti, Zr, Hf, V, B, Al, and Ga.For example, it can be at least one of the following molecular sieves: a solid silicon molecular sieve (a molecular sieve consisting entirely of silicon), a silicon-aluminum molecular sieve, a silicon-boron molecular sieve, a titanium-silicon molecular sieve, a tin-silicon molecular sieve, a zirconium-silicon molecular sieve, a vanadium-silicon molecular sieve, a silicon-gallium molecular sieve, a silicon-lead molecular sieve, and a silicon-hafnium molecular sieve. Preferably, the crystalline material is at least one of a solid silicon molecular sieve, a titanium-silicon molecular sieve, a zirconium-silicon molecular sieve, a tin-silicon molecular sieve, and a boron-silicon molecular sieve.

[0061] According to the manufacturing process provided by the present invention, the process of separating at least a portion of a solid product from the treated mixture comprises any method by which solid-liquid separation can be achieved, such as filtration, sedimentation, evaporation, membrane separation, adsorption separation, etc., which are not specifically limited in the present invention. Drying can be carried out under conditions ranging from room temperature to 200°C, preferably 50 to 160°C, more preferably 80 to 140°C, in an inert gas atmosphere or an oxygen-containing gas atmosphere. The drying time should be sufficient to achieve a water content (by weight) of the solid product of less than 30%, preferably less than 10%, more preferably less than 5%. The drying time can be, for example, 0.5 to 24 hours.Calcination can be carried out under conditions of 300 to 800°C, preferably 400 to 700°C, more preferably 500 to 600°C, in an inert gas atmosphere or an oxygen-containing gas atmosphere. The calcination time should be sufficient to achieve an organic content (by weight) of less than 5%, preferably less than 1%, and more preferably less than 0.1% in the solid product. For example, the calcination time can be 0.5 to 24 hours.

[0062] The present invention also relates to the porous molecular sieve material obtained by the manufacturing process described above.

[0063] The present invention further provides the application method of the aforementioned porous molecular sieve material.

[0064] The aforementioned porous molecular sieve material of the present invention can be used for adsorption processes, the production of catalysts or catalytic reactions, or as a support.

[0065] The adsorption process can include the use of the porous molecular sieve material of the present invention as an adsorbent for adsorption separation processes of hydrocarbons, gases, inorganic substances, etc.

[0066] The catalyst production can include the use of the porous molecular sieve catalyst material of the present invention as a catalytically active component, utilizing its unique framework elements, or its use as a support for further loading with active centers, or its mixing with other catalysts, co-catalysts, structural promoters, electronic promoters, binders, inert supports, etc., wherein processes such as mechanical mixing, kneading and shaping, tablet pressing, extrusion molding, spray drying, ball rolling and molding, oil droplet granulation, etc., can be used to produce a catalyst.

[0067] The catalytic reaction can include the direct use of the porous molecular sieve catalyst material of the present invention as a catalyst or its further processing to form a catalyst and the use of the catalyst in catalytic reactions.The catalytic reactions include, but are not limited to, oxidation reactions (olefin oxidation / epoxidation for the production of aldehydes, ketones, acids, epoxides, vicinal diols; alkane oxidation for the production of alcohols, aldehydes, acids; alcohol oxidation for the production of ketones, acids; aldehyde oxidation for the production of acids; aromatic oxidation for the production of phenols; sulfide oxidation for the production of sulfoxides, sulfones), reduction reactions, oximation reactions (aldehyde / keton oximation for the production of amides, lactams), aldol condensation reactions, substitution / halogenation reactions, elimination reactions, transesterification reactions, dehydration reactions, etherification reactions, esterification reactions, addition reactions at double / triple bonds, Diels-Alder reactions, Beckmann rearrangement reactions (Gas-phase rearrangement of cyclohexanone oxime to caprolactam), hydrogen transfer reactions, etc.

[0068] The application as a support can include the use of the porous molecular sieve catalyst material of the present invention as a support for loading other active components.

[0069] According to the application method of the porous molecular sieve material of the present invention, the porous molecular sieve catalyst material can be used in powder form or in shaped forms such as spheres, strips, tablets, granules, etc., and can be used in a mixture with other catalysts; the application 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 the catalyst can be supplied all at once, intermittently, or continuously, which is not limited in the present invention.

[0070] Experts will understand that, in the application process of the porous molecular sieve material of the present invention, the separation of product and catalyst can be achieved in various ways. For example, if the molecular sieve is used in powder form as the catalyst, the separation of the product and the recovery and reuse of the catalyst can be achieved by sedimentation, filtration, centrifugation, evaporation, membrane separation, etc. Alternatively, the catalyst can be formed and loaded 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 many existing literature sources and will not be discussed further here.

[0071] The present invention is further illustrated by the following examples, but is not limited thereto. In the following examples and comparisons:

[0072] The phase structure and relative crystallinity of the molecular sieves were determined by X-ray diffraction (XRD) analysis. The instrument used for characterization was a Philips Panalytical Empyrean X-ray diffractometer. The test conditions were: Cu target, Kα radiation, Ni filter, tube voltage 40 kV, tube current 40 mA, scintillation counter, step size 0.0131°, scan range 5°–35°. The relative crystallinity of the molecular sieve was calculated from the peak area of ​​the "five-finger peak" in the range of 2θ = 22°–26°. The chemical composition of the molecular sieve and the elemental ratio of heteroatoms to silicon were determined by XRF analysis. The instrument used for characterization was a Rigaku Corporation 3013 X-ray fluorescence spectrometer (Japan). The test conditions were: tungsten target, excitation voltage 40 kV, excitation current 250 mA. After the sample was pressed into a pellet, it emitted fluorescence under X-ray irradiation.The relationship between the fluorescence wavelength (λ) and the atomic number (Z) of the element is given by: A = K(ZS) - 2, where K is a constant. The element type could be determined by measuring the fluorescence wavelength. The intensity of each element's characteristic spectral line was measured using a scintillation counter and a proportional counter for semi-quantitative analysis.

[0073] The specific surface area of ​​the micropores was measured using the low-temperature nitrogen adsorption / desorption method and calculated according to the BET method; the pore volume and pore distribution were determined according to the method described in RIPP 151-90 in “Analytical Methods in Petrochemical Industry”, edited by Yang Cuiding et al. (Science Press, September 1990, first edition).

[0074] The morphology of the molecular sieve was determined using SEM. The instrument used for the analysis was a high-resolution cold-field emission scanning electron microscope, type Hitachi S4800, with an accelerating voltage of 20 kV.

[0075] The internal hollow morphology of the molecular sieve was determined using TEM. The instrument used for the analysis was a Tecnai G2F20S-TWIN transmission electron microscope from FEI Company. The analytical procedure involved dispersing the sample in an ethanol solution, applying it to a sample grid, drying it, and then measuring it. The accelerating voltage was 200 kV.

[0076] Unless otherwise stated, the raw materials used in the examples and comparative examples were reagents of analytical grade.

[0077] The catalytic reaction products were analyzed for their composition by gas chromatography, and the results were quantified using an external standard method. Chromatographic conditions included an Agilent 6890 chromatograph, an HP-5 capillary column, an injection volume of 0.5 µl, an inlet temperature of 280°C; the column temperature was held at 100°C for 2 minutes, then increased to 250°C at a rate of 15°C / min and held for 10 minutes; and an FID detector was used with a detector temperature of 300°C. In the examples and comparative examples:

[0078] Ti-Si molecular sieves were evaluated under the following reaction conditions using the cyclohexanone ammoximation reaction: Cyclohexanone, hydrogen peroxide, and ammonia water were subjected to an ammoximation reaction under the influence of a catalyst to produce cyclohexanone oxime. Cyclohexanone, hydrogen peroxide (30 wt%), ammonia water, and tert-butanol were placed in a three-necked flask in a molar ratio of 1:1, 1:2:10, and then the catalyst was added in an amount of 5 wt% of the cyclohexanone. The reaction was carried out under reflux at 80°C with a stirring speed of 400 rpm for 1 hour, after which the product was cooled and the liquid separated for chromatographic analysis.

[0079] Evaluation indicators: Cyclohexanone conversion (%) = (moles of cyclohexanone in the input - moles of cyclohexanone in the product) / moles of cyclohexanone in the input × 100% Cyclohexanone oxime selectivity (%) = Moles of cyclohexanone oxime in the product / (Moles of cyclohexanone in the input - Moles of cyclohexanone in the product) × 100%

[0080] All-silicon molecular sieves were evaluated using the gas-phase rearrangement of cyclohexanone oxime to produce caprolactam under the following reaction conditions: Cyclohexanone oxime underwent a gas-phase Beckmann rearrangement under the catalytic action of the all-silicon molecular sieve to produce caprolactam. 5 g of the molecular sieve, pressed and sieved to a particle size of 40–60 mesh, were loaded into a fixed-bed reactor. Cyclohexanone oxime was mixed with methanol as a solvent in a molar ratio of 1:20. The cyclohexanone oxime solution was pumped into the fixed-bed reactor at a space velocity of 10 h⁻¹, and the reaction was carried out at 380°C. The product was condensed and subsequently subjected to chromatographic analysis.

[0081] Evaluation indicators: Cyclohexanone oxime conversion (%) = (Amount of cyclohexanone oximine in the supply per unit time - Amount of cyclohexanone oxime in the product per unit time) / Amount of cyclohexanone oxime in the supply per unit time × 100% Caprolactam selectivity (%) = Moles of caprolactam produced in the product / Moles of cyclohexanone oxime consumed by all products × 100%

[0082] Tin-silicon molecular sieves were evaluated under the following reaction conditions using the cyclohexanone Baeyer-Villiger oxidation reaction (BV): 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, with a catalyst addition of 5 wt% of the cyclohexanone, using 1,4-dioxane as the solvent in a molar solvent-to-cyclohexanone ratio of 20:1. The mixture was reacted under reflux at 80°C with a stirring speed of 400 rpm for 8 hours. The product was cooled and separated, and the resulting liquid product was subjected to gas chromatographic analysis.

[0083] Evaluation indicators: Cyclohexanone conversion (%) = (moles of cyclohexanone in the input - moles of cyclohexanone in the product) / moles of cyclohexanone in the input × 100% ε−caprolactone−selectivity(%)=mole ε−caprolactone in product / (mole cyclohaxanone in feed−mole cyclohexanone in product)×100%

[0084] Zirconium-silicon molecular sieves were evaluated based on the reduction of levulinic acid with isopropanol via the Meerwein-Ponndorf-Verley reaction (MPV reaction) and subsequent esterification to produce γ-valerolactone. The reaction process proceeded schematically as follows:

[0085] Step (1) involved catalysis under the zirconium-silicon molecular sieve, while step (2) could be carried out under non-catalytic conditions (e.g., heating). The weight ratio of zirconium-silicon molecular sieve to levulinic acid was 0.05:1, the molar ratio of levulinic acid to isopropanol was 1:20, the reaction temperature was 80°C, and the reaction time was 8 hours. After the reaction, the product was separated in the liquid phase for chromatographic analysis.

[0086] Evaluation indicators: Levulinic acid conversion (%) = (moles of levulinic acid in the intake - moles of levulinic acid in the product) / (moles of levulinic acid in the intake × 100%) γ−Valerolactone yield (%) = Moles of γ−valerolactone in product / Moles of levulinic acid in input × 100% Production example 1

[0087] This manufacturing example illustrates the production of polymeric quaternary ammonium base compounds.

[0088] Ten grams of commercially available polyquaternium-2 with a degree of polymerization of 4500 were placed in a semipermeable membrane and immersed in a sodium hydroxide solution with a concentration of 0.5 mol / L. Hydroxide radical exchange was carried out with stirring, with each exchange lasting 24 hours. After completion of an exchange, the sodium hydroxide solution was replaced, and then another exchange was performed. A total of four exchanges were carried out. According to ion concentration measurements and calculations, the degree of exchange reached 99%. The resulting product was dehydrated and designated polymeric quaternary ammonium-2, ready for use. Its pKa value was measured to be approximately 12.8.

[0089] Polyquaternium-6, polyquaternium-7, polyquaternium-22, polyquaternium-32, polyquaternium-37 and polyquaternium-47 were treated in the same way to produce polymeric quaternary ammonium base-6, polymeric quaternary ammonium base-7, polymeric quaternary ammonium base-22, polymeric quaternary ammonium base-32, polymeric quaternary ammonium base-37 and polymeric quaternary ammonium base-47, each ready for use. Production example 2

[0090] This manufacturing example illustrates the production of a TS-1-A titanium-silicon molecular sieve of the MFI type.

[0091] Silicon source (tetraethyl orthosilicate and silica white, as SiO2), tetrabutyl titanate, tetrapropylammonium hydroxide (25 wt%, hydroxide purity greater than 99.5%) solution and water were mixed in a molar ratio of 1 (tetraethyl orthosilicate:silica white = 1:2):0.04:0.15:25 and aged for 6 hours at 80°C to obtain a sol; this sol was then crystallized for 48 hours at 170°C; finally, a solid product was obtained by filtering the resulting slurry, drying for a further 6 hours at 120°C and calcining for 6 hours at 550°C to obtain the molecular sieve TS-1-A. Production example 3

[0092] This manufacturing example illustrates the fabrication of an MFI-type S-1 molecular sieve made entirely of silicon.

[0093] Silicon source (tetraethyl orthosilicate and silica white, as SiO2), tetrapropylammonium hydroxide (25 wt%, hydroxide purity greater than 99.5%) solution and water were mixed in a molar ratio of 1 (tetraethyl orthosilicate:silica white = 1:4):0.2:30 and aged for 10 hours at 60°C to obtain a sol; this sol was then crystallized for 72 hours at 170°C; finally, a solid product was obtained by filtering the resulting slurry, drying for a further 6 hours at 120°C and calcining for 6 hours at 550°C to obtain the molecular sieve S-1. Production example 4

[0094] This manufacturing example illustrates the production of a tin-silicon molecular sieve Sn-MEL of the MEL type.

[0095] Silicon source (tetraethyl orthosilicate and silica white, as SiO2), tin chloride, tetrabutylammonium hydroxide (25 wt%, hydroxide purity greater than 99.5%) solution and water were mixed in a molar ratio of 1 (tetraethyl orthosilicate:silica white = 1:2):0.02:0.2:30 and aged for 5 hours at 70°C to obtain a sol; this sol was then crystallized for 24 hours at 170°C; finally, a solid product was obtained by filtering the resulting slurry, drying for a further 6 hours at 120°C and calcining for 6 hours at 550°C to obtain the Sn-MEL molecular sieve. Production example 5

[0096] This manufacturing example illustrates the production of a zirconium-silicon molecular sieve Zr-MFI of the MFI type.

[0097] Silicon source (tetraethyl orthosilicate and silica white, as SiO2), zirconium propoxide, tetrapropylammonium hydroxide (25 wt%, hydroxide purity greater than 99.5%) solution and water were mixed in a molar ratio of 1 (tetraethyl orthosilicate:silica white = 1:2):0.02:0.2:30 and aged for 5 hours at 80°C to obtain a sol; this sol was then crystallized for 72 hours at 170°C; finally, a solid product was obtained by filtering the resulting slurry, drying for a further 6 hours at 120°C and calcining for 6 hours at 550°C to obtain the Zr-MFI molecular sieve. Production example 6

[0098] This manufacturing example illustrates the production of a TS-1-B titanium-silicon molecular sieve of the MFI type.

[0099] Silicon source (tetraethyl orthosilicate, as SiO2), tetrabutyl titanate, tetrapropylammonium hydroxide (25 wt%, hydroxide purity greater than 99.5%) solution and water were mixed in a molar ratio of 1:0.04:0.15:25 and aged for 6 hours at 80°C to obtain a sol; this sol was then crystallized for 48 hours at 170°C; finally, a solid product was obtained by filtering the resulting slurry, drying for a further 6 hours at 120°C and calcining for 6 hours at 550°C to obtain the molecular sieve TS-1-B. Comparative example 1

[0100] This comparative example illustrates the fabrication, characterization, and evaluation of a hollow Ti-Si molecular sieve HTS.

[0101] The molecular sieve TS-1-B obtained in production example 6, sulfuric acid and water were mixed according to the ratio molecular sieve (g):sulfuric acid (mol):water (mol) = 100:0.15:150, reacted for 5.0 hours at 90°C, then filtered, washed and dried by conventional methods to obtain an acid-treated TS-1-B molecular sieve.

[0102] The above-mentioned acid-treated TS-1-B molecular sieve, triethanolamine, tetrapropylammonium hydroxide, and water (mol) were mixed according to the ratio molecular sieve (g):triethanolamine (mol) : tetrapropylammonium hydroxide (mol) :water (mol) = 100:0.20:0.15:180, placed in a sealed stainless steel reactor, and held under autogenous pressure at 190°C for 0.5 days. After cooling and pressure release, the product was filtered, washed, dried using conventional methods, and calcined for 3 hours at 550°C in an air atmosphere to obtain the hollow Ti-Si molecular sieve HTS.

[0103] The hollow Ti-Si molecular sieve HTS was characterized.

[0104] XRD analysis showed that the HTS molecular sieve had an MFI structure.

[0105] The REM result ( Fig. 1) showed that the hollow Ti-Si molecular sieve HTS exhibited a morphology of aggregation and growth of small crystal grains and that the molecular sieve surface did not have open pore chambers.

[0106] The TEM result ( Fig. 2) showed that the hollow Ti-Si molecular sieve HTS had some intracrystalline hollow structures and no open mesopores.

[0107] The result of the nitrogen adsorption-desorption characterization ( Fig. 3) showed that the nitrogen adsorption curve of the hollow Ti-Si molecular sieve HTS had two concave arcs, one at p / p0<0.3 and one at p / p0>0.7; after p / p0>0.45 there was a hysteresis loop.

[0108] The results of the characterization regarding chemical composition, specific surface area and pore volume are listed in Table 1.

[0109] The hollow Ti-Si molecular sieve HTS was evaluated in the cyclohexanone ammoximation reaction, and the result is shown in Table 1. Comparative example 2

[0110] This comparative example illustrates the fabrication, characterization and evaluation of a Ti-Si molecular sieve STS-D produced by the silylation process.

[0111] 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 then treated at 90°C for 12 hours. Subsequently, the treated product (SiO₂) and a 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, washed, dried at 120°C for 6 hours, and calcined at 550°C for 6 hours to prepare the STS-D expanded Ti-Si molecular sieve reference sample.

[0112] The Ti-Si molecular sieve comparison sample STS-D was expanded with the silylation reagent.

[0113] XRD analysis showed that the molecular sieve STS-D had an MFI structure.

[0114] The REM result ( Fig. 4) showed that the molecular sieve STS-D exhibited a morphology of small crystal grain accumulation and growth and that the surface of the molecular sieve did not have open pore chambers.

[0115] The TEM result ( Fig. 5) showed that STS-D had a “sponge-like” morphology with a loose accumulation of small particles, without open mesopores or hollow structures.

[0116] The result of the nitrogen adsorption-desorption characterization ( Fig. 6) showed that the nitrogen adsorption curve of STS-D had two concave arcs, one at p / p0<0.3 and one at p / p0>0.7; after p / p0>0.45 there was a hysteresis loop.

[0117] The characterization results for the chemical composition, specific surface area and pore volume are listed in Table 1.

[0118] The Ti-Si molecular sieve reference sample STS-D expanded with the silylation reagent was evaluated in the cyclohexanone ammoximation reaction, and the result is shown in Table 1. Example 1

[0119] This example illustrates the fabrication, characterization and evaluation of a porous molecular sieve material TS-1-1 of the present invention.

[0120] The Ti-Si molecular sieve obtained in Production Example 2 was mixed with polymeric quaternary ammonium base-47, water, and ammonium bicarbonate in a ratio of molecular sieve (mol):polymeric quaternary ammonium base (wt):water (mol):nitrogen-containing basic compound (mol) = 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, then a solid product was obtained by filtering the treated mixture. This solid product was then dried at 120°C for a further 6 hours and calcined at 550°C for 6 hours to obtain the porous molecular sieve material TS-1-1.

[0121] The porous molecular sieve material TS-1-1 was characterized.

[0122] XRD analysis showed that the molecular sieve TS-1-1 had an MFI structure ( Fig. 7).

[0123] The REM result ( Fig.8) showed that the molecular sieve TS-1-1 had an open pore chamber with a pore size of not less than 20 nm on its surface.

[0124] The TEM result ( Fig. 9) showed that the molecular sieve TS-1-1 had an open pore chamber with a pore size of not less than 20 nm; at the same time, it was observed that about 50% of the molecular sieve crystal grains had an isolated hollow structure.

[0125] The result of the nitrogen adsorption-desorption characterization ( Fig. 10) showed that the nitrogen adsorption curve of the molecular sieve TS-1-1 had four concave arcs (three at p / p0<0.3 and one at p / p0>0.7) and two hysteresis loops (the first hysteresis loop was in the range of relative pressure p / p0 of less than 0.3, and the second hysteresis loop was in the range of relative pressure p / p0 of greater than 0.45).

[0126] The results of the characterization for chemical composition, specific surface area and pore volume are listed in Table 1.

[0127] The porous molecular sieve material TS-1-1 was evaluated in the cyclohexanone ammoximation reaction, and the result is shown in Table 1.

[0128] The open pore chamber of the molecular sieve had a degree of expansion in the range of 0 to 0.1. Example 2

[0129] This example illustrates the fabrication, characterization and evaluation of a porous molecular sieve material TS-1-2 of the present invention.

[0130] The Ti-Si molecular sieve obtained in Production Example 2 was mixed with polymeric quaternary ammonium base-32, water, and ammonium nitrate in a ratio of molecular sieve (mol):polymeric quaternary ammonium base (wt):water (mol):nitrogen-containing basic compound (mol) = 1:0.05:15:0.02. The resulting mixture was treated at 160°C for 24 hours, then a solid product was obtained by filtering the treated mixture. This solid product was then dried at 120°C for a further 6 hours and calcined at 550°C for 6 hours to obtain the porous molecular sieve material TS-1-2.

[0131] The porous molecular sieve material TS-1-2 was characterized.

[0132] XRD analysis showed that the molecular sieve TS-1-2 had an MFI structure.

[0133] The SEM result showed that the molecular sieve TS-1-2 had an open pore chamber with a pore size of no less than 30 nm on its surface.

[0134] The TEM result showed that the molecular sieve TS-1-2 had an open pore chamber with a pore size of no less than 40 nm; at the same time, it was observed that about 40% of the molecular sieve crystal grains had an isolated hollow structure.

[0135] The result of the nitrogen adsorption-desorption characterization showed that the nitrogen adsorption curve of the molecular sieve TS-1-2 had three concave arcs (two at p / p0<0.3 and one at p / p0>0.7) and two hysteresis loops (the first hysteresis loop was in the range of relative pressure p / p0 of less than 0.3 and the second hysteresis loop was in the range of relative pressure p / p0 of greater than 0.45).

[0136] The results of the characterization for chemical composition, specific surface area and pore volume are listed in Table 1.

[0137] The porous molecular sieve material TS-1-2 was evaluated in the cyclohexanone ammoximation reaction, and the result is shown in Table 1.

[0138] The open pore chamber of the molecular sieve had a degree of expansion in the range of 0 to 0.1. Example 3

[0139] This example illustrates the fabrication, characterization and evaluation of a porous molecular sieve material TS-1-3 of the present invention.

[0140] The Ti-Si molecular sieve obtained in Production Example 2 was mixed with polymeric quaternary ammonium base-37, water, and ammonium carbonate in a ratio of molecular sieve (mol):polymeric quaternary ammonium base (wt):water (mol):nitrogen-containing basic compound (mol) = 1:0.01:30:0.08. The resulting mixture was treated at 170°C for 12 hours, then a solid product was obtained by filtering the treated mixture. This product was then dried at 120°C for a further 6 hours and calcined at 550°C for 6 hours. The above production process was repeated twice more to obtain the porous molecular sieve material TS-1-3.

[0141] The porous molecular sieve material TS-1-3 was characterized.

[0142] XRD analysis showed that the molecular sieve TS-1-3 had an MFI structure.

[0143] The SEM result showed that the molecular sieve TS-1-3 had an open pore chamber with a pore size of no less than 40 nm on its surface.

[0144] The TEM result showed that the molecular sieve TS-1-3 had an open pore chamber with a pore size of no less than 40 nm; at the same time, it was observed that about 60% of the molecular sieve crystal grains had an isolated hollow structure.

[0145] The result of the nitrogen adsorption-desorption characterization showed that the nitrogen adsorption curve of the molecular sieve TS-1-3 had three concave arcs (two at p / p0<0.3 and one at p / p0>0.7) and two hysteresis loops (the first hysteresis loop was in the range of relative pressure p / p0 of less than 0.3 and the second hysteresis loop was in the range of relative pressure p / p0 of greater than 0.45).

[0146] The results of the characterization for chemical composition, specific surface area and pore volume are listed in Table 1.

[0147] The porous molecular sieve material TS-1-3 was evaluated in the cyclohexanone ammoximation reaction, and the result is shown in Table 1.

[0148] The open pore chamber of the molecular sieve had a degree of expansion in the range of 0 to 0.1. Example 4

[0149] This example illustrates the fabrication, characterization and evaluation of a porous molecular sieve material TS-1-4 of the present invention.

[0150] The Ti-Si molecular sieve obtained in Production Example 2 was mixed with polymeric quaternary ammonium base-6 and water in a ratio of molecular sieve (mol):polymeric quaternary ammonium base (wt):water (mol) = 1:0.008:20. The resulting mixture was treated at 170°C for 6 hours, then a solid product was obtained by filtering the treated mixture. This solid product was dried at 120°C for a further 6 hours and calcined at 550°C for 6 hours to obtain the porous molecular sieve material TS-1-4.

[0151] The porous molecular sieve material TS-1-4 was characterized.

[0152] XRD analysis showed that the molecular sieve TS-1-4 had an MFI structure.

[0153] The SEM result showed that the molecular sieve TS-1-4 had an open pore chamber with a pore size of no less than 15 nm on its surface.

[0154] The TEM result showed that the molecular sieve TS-1-4 had an open pore chamber with a pore size of no less than 20 nm; no isolated hollow structures were observed in the molecular sieve crystal grains.

[0155] The result of the nitrogen adsorption-desorption characterization showed that the nitrogen adsorption curve of the molecular sieve TS-1-4 had three concave arcs (two at p / p0<0.3 and one at p / p0>0.7) and two hysteresis loops (the first hysteresis loop was in the range of relative pressure p / p0 of less than 0.3 and the second hysteresis loop was in the range of relative pressure p / p0 of greater than 0.45).

[0156] The results of the characterization for chemical composition, specific surface area and pore volume are listed in Table 1.

[0157] The porous molecular sieve material TS-1-4 was evaluated in the cyclohexanone ammoximation reaction, and the result is shown in Table 1.

[0158] The open pore chamber of the molecular sieve had a degree of expansion in the range of 0 to 0.1. Example 5

[0159] This example illustrates the fabrication, characterization and evaluation of a porous molecular sieve material TS-1-5 of the present invention.

[0160] The Ti-Si molecular sieve obtained in Production Example 2 was mixed with polymeric quaternary ammonium base-22 and water in a ratio of molecular sieve (mol):polymeric quaternary ammonium base (wt):water (mol) = 1:0.12:30. The resulting mixture was treated at 150°C for 36 hours, then a solid product was obtained by filtering the treated mixture. This solid product was then dried at 120°C for a further 6 hours and calcined at 550°C for 6 hours to obtain the porous molecular sieve material TS-1-5.

[0161] The porous molecular sieve material TS-1-5 was characterized.

[0162] XRD analysis showed that the molecular sieve TS-1-5 had an MFI structure.

[0163] The SEM result showed that the molecular sieve TS-1-5 had an open pore chamber with a pore size of no less than 15 nm on its surface.

[0164] The TEM result showed that the molecular sieve TS-1-5 had an open pore chamber with a pore size of no less than 30 nm; no isolated hollow structures were observed in the molecular sieve crystal grains.

[0165] The result of the nitrogen adsorption-desorption characterization showed that the nitrogen adsorption curve of the molecular sieve TS-1-5 had three concave arcs (two at p / p0<0.3 and one at p / p0>0.7) and two hysteresis loops (the first hysteresis loop was in the range of relative pressure p / p0 of less than 0.3 and the second hysteresis loop was in the range of relative pressure p / p0 of greater than 0.45).

[0166] The results of the characterization for chemical composition, specific surface area and pore volume are listed in Table 1.

[0167] The porous molecular sieve material TS-1-5 was evaluated in the cyclohexanone ammoximation reaction, and the result is shown in Table 1.

[0168] The open pore chamber of the molecular sieve had a degree of expansion in the range of 0 to 0.1. Example 6

[0169] This example illustrates the fabrication, characterization and evaluation of a porous molecular sieve material TS-1-6 of the present invention.

[0170] The Ti-Si molecular sieve obtained in Production Example 2 was mixed with polymeric quaternary ammonium base-37 and water in a ratio of molecular sieve (mol):polymeric quaternary ammonium base (wt):water (mol) = 1:0.2:50. The resulting mixture was treated at 145°C for 24 hours, then a solid product was obtained by filtering the treated mixture. This solid product was then dried at 120°C for a further 6 hours and calcined at 550°C for 6 hours to obtain the porous molecular sieve material TS-1-6.

[0171] The porous molecular sieve material TS-1-6 was characterized.

[0172] XRD analysis showed that the molecular sieve TS-1-6 had an MFI structure.

[0173] The SEM result showed that the molecular sieve TS-1-6 had an open pore chamber with a pore size of no less than 18 nm on its surface.

[0174] The TEM result showed that the molecular sieve TS-1-6 had an open pore chamber with a pore size of no less than 35 nm; no isolated hollow structures were observed in the molecular sieve crystal grains.

[0175] The result of the nitrogen adsorption-desorption characterization showed that the nitrogen adsorption curve of the molecular sieve TS-1-6 had three concave arcs (two at p / p0<0.3 and one at p / p0>0.7) and two hysteresis loops (the first hysteresis loop was in the range of relative pressure p / p0 of less than 0.3 and the second hysteresis loop was in the range of relative pressure p / p0 of greater than 0.45).

[0176] The results of the characterization for chemical composition, specific surface area and pore volume are listed in Table 1.

[0177] The porous molecular sieve material TS-1-6 was evaluated in the cyclohexanone ammoximation reaction, and the result is shown in Table 1.

[0178] The open pore chamber of the molecular sieve had a degree of expansion in the range of 0 to 0.1. Comparative example 3

[0179] This comparative example illustrates the characterization and evaluation of an all-silicon molecular sieve S-1-D, which was produced using a conventional method.

[0180] Tetraethyl orthosilicate, tetrapropylammonium hydroxide, and water were mixed to obtain a silica gel with a molar composition of SiO₂:tetrapropylammonium hydroxide:water = 1:0.2:30. This silica gel was aged for 10 hours at 60°C and then crystallized for 72 hours at 170°C. The crystallized product was filtered, washed, dried for 6 hours at 120°C, and calcined for 6 hours at 550°C to prepare the reference sample S-1-D of the all-silicon molecular sieve.

[0181] The reference sample S-1-D made of pure silicon molecular sieve was characterized.

[0182] XRD analysis showed that the molecular sieve S-1-D had an MFI structure.

[0183] The SEM result showed that S-1-D had no open pore chambers on its surface ( Fig. 11).

[0184] The TEM result showed that S-1-D had a dense structure without open mesopores or hollow structures ( Fig. 12).

[0185] The results of the nitrogen adsorption-desorption characterization showed that the nitrogen adsorption curve of the molecular sieve S-1-D exhibited two concave arcs (one at p / p0<0.3 and one at p / p0>0.7) and a hysteresis loop at p / p0>0.8 ( Fig. 13).

[0186] The results of the characterization regarding chemical composition, specific surface area and pore volume are listed in Table 1.

[0187] The comparison sample S-1-D made of pure silicon molecular sieve was evaluated in the gas phase of the Beckmann rearrangement reaction of cyclohexanone oxime, and the result is shown in Table 1. Example 7

[0188] This example illustrates the fabrication, characterization and evaluation of a porous molecular sieve material S-1-1 of the present invention.

[0189] The molecular sieve obtained in Production Example 3, consisting entirely of silicon, was mixed with polymeric quaternary ammonium base-7 and water in a ratio of molecular sieve (mol):polymeric quaternary ammonium base (wt):water (mol) = 1:0.005:10. The resulting mixture was treated at 180°C for 24 hours, then a solid product was obtained by filtering the treated mixture. This solid product was then dried at 120°C for a further 6 hours and calcined at 550°C for 6 hours to obtain the porous molecular sieve material S-1-1.

[0190] The porous molecular sieve material S-1-1 was characterized.

[0191] XRD analysis showed that the molecular sieve S-1-1 had an MFI structure.

[0192] The SEM result showed that the molecular sieve S-1-1 had an open pore chamber with a pore size of no less than 20 nm on its surface ( Fig. 14).

[0193] The TEM result showed that the molecular sieve S-1-1 had an open pore chamber with a pore size of no less than 35 nm; no isolated hollow structures were observed in the molecular sieve crystal grains.

[0194] The result of the nitrogen adsorption-desorption characterization ( Fig. 15) showed that the nitrogen adsorption curve of the molecular sieve S-1-1 had three concave arcs (two at p / p0<0.3 and one at p / p0>0.7) and two hysteresis loops (the first hysteresis loop was in the range of relative pressure p / p0 of less than 0.3 and the second hysteresis loop was in the range of relative pressure p / p0 of greater than 0.45).

[0195] The results of the characterization for chemical composition, specific surface area and pore volume are listed in Table 1.

[0196] The porous molecular sieve material S-1-1 was evaluated in the gas-phase Beckmann rearrangement reaction of cyclohexanone oxime, and the result is shown in Table 1.

[0197] The open pore chamber of the molecular sieve had a degree of expansion in the range of 0-0.1. Example 8

[0198] This example illustrates the fabrication, characterization and evaluation of a porous molecular sieve material S-1-2 of the present invention.

[0199] The solid silicon molecular sieve obtained in Production Example 3 was mixed with polymeric quaternary ammonium base-2 and water in a ratio of molecular sieve (mol):polymeric quaternary ammonium base (wt):water (mol) = 1:0.2:50. The resulting mixture was treated at 170°C for 48 hours, then a solid product was obtained by filtering the treated mixture. This solid product was then dried at 120°C for a further 6 hours and calcined at 550°C for 6 hours to obtain the porous molecular sieve material S-1-2.

[0200] The porous molecular sieve material S-1-2 was characterized.

[0201] XRD analysis showed that the molecular sieve S-1-2 had an MFI structure.

[0202] The SEM result showed that the molecular sieve S-1-2 had an open pore chamber with a pore size of no less than 15 nm on its surface.

[0203] The TEM result showed that the molecular sieve S-1-2 had an open pore chamber with a pore size of no less than 30 nm and that no isolated hollow structures were observed in the molecular sieve crystal grains.

[0204] The result of the nitrogen adsorption-desorption characterization showed that the nitrogen adsorption curve of the molecular sieve S-1-2 had three concave arcs (two at p / p0<0.3 and one at p / p0>0.7) and two hysteresis loops (the first hysteresis loop was in the range of relative pressure p / p0 of less than 0.3 and the second hysteresis loop was in the range of relative pressure p / p0 of greater than 0.45).

[0205] The results of the characterization for chemical composition, specific surface area and pore volume are listed in Table 1.

[0206] The porous molecular sieve material S-1-2 was evaluated in the gas-phase Beckmann rearrangement reaction of cyclohexanone oxime, and the result is shown in Table 1.

[0207] The open pore chamber of the molecular sieve had a degree of expansion in the range of 0-0.1. Example 9

[0208] This example illustrates the fabrication, characterization and evaluation of a porous molecular sieve material S-1-3 of the present invention.

[0209] The solid silicon molecular sieve obtained in Production Example 3 was mixed with polymeric quaternary ammonium base-32, water, and ammonium carbonate in a ratio of molecular sieve (mol):polymeric quaternary ammonium base (wt):water (mol):ammonium carbonate (mol) = 1:0.05:15:0.03. The resulting mixture was treated at 170°C for 12 hours, then a solid product was obtained by filtering the treated mixture. This solid product was then dried at 120°C for a further 6 hours and calcined at 550°C for 6 hours to obtain the porous molecular sieve material S-1-3.

[0210] The porous molecular sieve material S-1-3 was characterized.

[0211] XRD analysis showed that the molecular sieve S-1-3 had an MFI structure.

[0212] The SEM result showed that the molecular sieve S-1-3 had an open pore chamber with a pore size of at least 30 nm on its surface.

[0213] The TEM result showed that the molecular sieve S-1-3 had an open pore chamber with a pore size of no less than 40 nm; at the same time, it was observed that about 60% of the molecular sieve crystal grains had an isolated hollow structure.

[0214] The result of the nitrogen adsorption-desorption characterization showed that the nitrogen adsorption curve of the molecular sieve S-1-3 had three concave arcs (two at p / p0<0.3 and one at p / p0>0.7) and two hysteresis loops (the first hysteresis loop was in the range of relative pressure p / p0 of less than 0.3 and the second hysteresis loop was in the range of relative pressure p / p0 of greater than 0.45).

[0215] The results of the characterization for chemical composition, specific surface area and pore volume are listed in Table 1.

[0216] The porous molecular sieve material S-1-3 was evaluated in the gas-phase Beckmann rearrangement reaction of cyclohexanone oxime, and the result is shown in Table 1.

[0217] The open pore chamber of the molecular sieve had a degree of expansion in the range of 0-0.1. Comparative example 4

[0218] This comparative example illustrates the characterization and evaluation of a molecular sieve Sn-MEL-D produced using a conventional method.

[0219] Tetraethyl orthosilicate, tin 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 = 1:0.02:0.2:20. This sol was crystallized at 170°C for 72 hours. Finally, a solid product was obtained by filtering the resulting slurry, drying it at 120°C for a further 6 hours, and calcining it at 550°C for 6 hours to prepare the molecular sieve reference sample Sn-MEL-D.

[0220] The molecular sieve reference sample Sn-MEL-D was characterized.

[0221] XRD analysis showed that the molecular sieve Sn-MEL-D had a MEL structure.

[0222] The SEM result showed that the molecular sieve Sn-MEL-D had no open pore chambers on its surface ( Fig. 16).

[0223] The TEM result showed that the molecular sieve Sn-MEL-D had a dense structure without open mesopores or hollow structures.

[0224] The results of the nitrogen adsorption-desorption characterization showed that the nitrogen adsorption curve of the molecular sieve Sn-MEL-D exhibited two concave arcs (one at p / p0<0.3 and one at p / p0>0.7) and a hysteresis loop at p / p0>0.8 ( Fig. 17).

[0225] The results of the characterization regarding chemical composition, specific surface area and pore volume are listed in Table 1.

[0226] The molecular sieve reference sample Sn-MEL-D was evaluated in the cyclohexanone Baeyer-Villiger oxidation reaction (BV), and the result is shown in Table 1. Example 10

[0227] This example illustrates the fabrication, characterization and evaluation of a porous molecular sieve material Sn-MEL of the present invention.

[0228] The tin-silicon molecular sieve obtained in Production Example 4 was mixed with polymeric quaternary ammonium base-6 and water in a ratio of molecular sieve (mol):polymeric quaternary ammonium base (wt):water (mol) = 1:0.003:5. The resulting mixture was treated at 140°C for 6 hours, then a solid product was obtained by filtering the treated mixture. This solid product was dried at 120°C for a further 6 hours and calcined at 550°C for 6 hours to obtain the porous molecular sieve material Sn-MEL.

[0229] The porous molecular sieve material Sn-MEL was characterized.

[0230] XRD analysis showed that the molecular sieve Sn-MEL had a MEL structure.

[0231] The SEM result showed that the molecular sieve Sn-MEL had an open pore chamber with a pore size of no less than 10 nm on its surface ( Fig. 18).

[0232] The TEM result showed that the Sn-MEL molecular sieve had an open pore chamber with a pore size of no less than 20 nm; no hollow structures were observed in the molecular sieve crystal grains.

[0233] The result of the nitrogen adsorption-desorption characterization ( Fig. 19) showed that the nitrogen adsorption curve of the Sn-MEL molecular sieve had three concave arcs (two at p / p0<0.3 and one at p / p0>0.7) and two hysteresis loops (the first hysteresis loop was in the range of relative pressure p / p0 of less than 0.3 and the second hysteresis loop was in the range of relative pressure p / p0 of greater than 0.45).

[0234] The results of the characterization for chemical composition, specific surface area and pore volume are listed in Table 1.

[0235] The porous molecular sieve material Sn-MEL was evaluated in the cyclohexanone Baeyer-Villiger oxidation reaction (BV), and the result is shown in Table 1.

[0236] The open pore chamber of the molecular sieve had a degree of expansion in the range of 0-0.1. Comparative example 5

[0237] This comparative example illustrates the characterization and evaluation of a Zr-MFI-D molecular sieve produced using a conventional method.

[0238] 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, a solid product was obtained by filtering the resulting slurry, drying it at 120°C for a further 6 hours, and calcining it at 550°C for 6 hours to prepare the molecular sieve reference sample Zr-MFI-D.

[0239] The molecular sieve reference sample Zr-MFI-D was characterized.

[0240] XRD analysis showed that the molecular sieve Zr-MFI-D had an MFI structure.

[0241] The SEM result showed that the molecular sieve Zr-MFI-D had no open pore chambers on its surface ( Fig. 20).

[0242] The TEM result showed that the molecular sieve Zr-MFI-D had a dense structure without open mesopores or hollow structures.

[0243] The results of the nitrogen adsorption-desorption characterization showed that the nitrogen adsorption curve of the Zr-MFI-D molecular sieve exhibited two concave arcs (one at p / p0<0.3 and one at p / p0>0.7) and a hysteresis loop at p / p0>0.45 ( Fig. 21).

[0244] The results of the characterization regarding chemical composition, specific surface area and pore volume are listed in Table 1.

[0245] The molecular sieve comparison sample Zr-MFI-D was evaluated in the Meerwein-Ponndorf-Verley reaction (MPV) with levulinic acid, and the result is shown in Table 1. Example 11

[0246] This example illustrates the production, characterization and evaluation of the porous molecular sieve material Zr-MFI of the present invention.

[0247] The zirconium-silicon molecular sieve obtained in Production Example 5 was mixed with polymeric quaternary ammonium base-7 and water in a ratio of molecular sieve (mol):polymeric quaternary ammonium base (wt):water (mol) = 1:0.003:5. The resulting mixture was treated at 140°C for 6 hours, then a solid product was obtained by filtering the treated mixture. This solid product was then dried at 120°C for a further 6 hours and calcined at 550°C for 6 hours to obtain the porous molecular sieve material Zr-MFI.

[0248] The porous molecular sieve material Zr-MFI was characterized.

[0249] XRD analysis showed that the molecular sieve Zr-MFI had an MFI structure.

[0250] The SEM result showed that the Zr-MFI molecular sieve had an open pore chamber with a pore size of no less than 10 nm on its surface ( Fig. 22).

[0251] The TEM result showed that the Zr-MFI molecular sieve had an open pore chamber with a pore size of no less than 20 nm; and no hollow structures were observed in the molecular sieve crystal grains.

[0252] The result of the nitrogen adsorption-desorption characterization ( Fig. 23) showed that the nitrogen adsorption curve of the Zr-MFI molecular sieve had three concave arcs (two at p / p0<0.3 and one at p / p0>0.7) and two hysteresis loops (the first hysteresis loop was in the range of relative pressure p / p0 of less than 0.3 and the second hysteresis loop was in the range of relative pressure p / p0 of greater than 0.45).

[0253] The results of the characterization for the chemical composition, specific surface area and pore volume are shown in Table 1.

[0254] The porous molecular sieve material Zr-MFI was evaluated in the levulinic acid Meerwein-Ponndorf-Verley reaction (MPV), and the result is shown in Table 1.

[0255] The open pore chamber of the molecular sieve had a degree of expansion in the range of 0 to 0.1. Example 12

[0256] This example illustrates the fabrication, characterization and evaluation of a porous molecular sieve material TS-1-7 of the present invention.

[0257] The Ti-Si molecular sieve obtained in Production Example 6 was mixed with polymeric quaternary ammonium base-47, water, and ammonium bicarbonate in a ratio of molecular sieve (mol):polymeric quaternary ammonium base (wt):water (mol):nitrogen-containing basic compound (mol) = 1:0.1:20:0.05 to obtain a mixture. This mixture was treated at 150°C for 18 hours, then a solid product was obtained by filtering the treated mixture. This solid product was then dried at 120°C for a further 6 hours and calcined at 550°C for 6 hours to obtain the porous molecular sieve material TS-1-7.

[0258] The porous molecular sieve material TS-1-7 was characterized.

[0259] XRD analysis showed that the molecular sieve TS-1-7 had an MFI structure.

[0260] The SEM result showed that the molecular sieve TS-1-7 had an open pore chamber with a pore size of no less than 10 nm on its surface.

[0261] The TEM result showed that the molecular sieve TS-1-7 had an open pore chamber with a pore size of no less than 20 nm; at the same time, it was observed that about 40% of the molecular sieve crystal grains had an isolated hollow structure.

[0262] The result of the nitrogen adsorption-desorption characterization showed that the nitrogen adsorption curve of the molecular sieve TS-1-7 had three concave arcs (two at p / p0<0.3 and one at p / p0>0.7) and two hysteresis loops (the first hysteresis loop was in the range of relative pressure p / p0 of less than 0.3 and the second hysteresis loop was in the range of relative pressure p / p0 of greater than 0.45).

[0263] The results of the characterization for chemical composition, specific surface area and pore volume are listed in Table 1.

[0264] The porous molecular sieve material TS-1-7 was evaluated in the cyclohexanone ammoximation reaction, and the result is shown in Table 1.

[0265] The open pore chamber of the molecular sieve had a degree of expansion in the range of 0 to 0.1. Example 13

[0266] This example illustrates the fabrication, characterization and evaluation of a porous molecular sieve material S-1-4 of the present invention.

[0267] The solid silicon molecular sieve obtained in comparative example 3 was mixed with polymeric quaternary ammonium base-32, water, and ammonium carbonate in a ratio of molecular sieve (mol):polymeric quaternary ammonium base (wt):water (mol):ammonium carbonate (mol) = 1:0.05:15:0.03. The resulting mixture was treated at 170°C for 12 hours, then a solid product was obtained by filtering the treated mixture. This solid product was then dried at 120°C for a further 6 hours and calcined at 550°C for 6 hours to obtain the porous molecular sieve material S-1-4.

[0268] The porous molecular sieve material S-1-4 was characterized.

[0269] XRD analysis showed that the molecular sieve S-1-4 had an MFI structure.

[0270] The SEM result showed that the molecular sieve S-1-4 had an open pore chamber with a pore size of no less than 20 nm on its surface.

[0271] The TEM result showed that the molecular sieve S-1-4 had an open pore chamber with a pore size of no less than 20 nm; at the same time, it was observed that about 60% of the molecular sieve crystal grains had an isolated hollow structure.

[0272] The result of the nitrogen adsorption-desorption characterization showed that the nitrogen adsorption curve of the molecular sieve S-1-4 had three concave arcs (two at p / p0<0.3 and one at p / p0>0.7) and two hysteresis loops (the first hysteresis loop was in the range of relative pressure p / p0 of less than 0.3 and the second hysteresis loop was in the range of relative pressure p / p0 of greater than 0.45).

[0273] The results of the characterization for chemical composition, specific surface area and pore volume are listed in Table 1.

[0274] The porous molecular sieve material S-1-4 was evaluated in the gas-phase Beckmann rearrangement reaction of cyclohexanone oxime, and the result is shown in Table 1.

[0275] The open pore chamber of the molecular sieve had a degree of expansion in the range of 0 to 0.1. Example 14

[0276] This example illustrates the production, characterization and evaluation of the porous molecular sieve material Sn-MEL-2 of the present invention.

[0277] The molecular sieve Sn-MEL-D obtained in comparative example 4 was mixed with polymeric quaternary ammonium base-6 and water in a ratio of molecular sieve (mol):polymeric quaternary ammonium base (wt):water (mol) = 1:0.003:5. The resulting mixture was treated at 140°C for 6 hours, then a solid product was obtained by filtering the treated mixture. This solid product was dried at 120°C for a further 6 hours and calcined at 550°C for 6 hours to obtain the porous molecular sieve material Sn-MEL-2.

[0278] The porous molecular sieve material Sn-MEL-2 was characterized.

[0279] XRD analysis showed that the molecular sieve Sn-MEL-2 had a MEL structure.

[0280] The SEM result showed that the molecular sieve Sn-MEL-2 had an open pore chamber with a pore size of no less than 10 nm on its surface.

[0281] The TEM result showed that the molecular sieve Sn-MEL-2 had an open pore chamber with a pore size of no less than 20 nm and that no hollow structures were observed in the molecular sieve crystal grains.

[0282] The result of the nitrogen adsorption-desorption characterization showed that the nitrogen adsorption curve of the molecular sieve Sn-MEL-2 had three concave arcs (two at p / p0<0.3 and one at p / p0>0.7); and two hysteresis loops (the first hysteresis loop was in the range of relative pressure p / p0 of less than 0.3 and the second hysteresis loop was in the range of relative pressure p / p0 of greater than 0.45).

[0283] The results of the characterization for chemical composition, specific surface area and pore volume are listed in Table 1.

[0284] The porous molecular sieve material Sn-MEL-2 was evaluated in the cyclohexanone Baeyer-Villiger oxidation reaction (BV), and the result is shown in Table 1.

[0285] The open pore chamber of the molecular sieve had a degree of expansion in the range of 0-0.1. Example 15

[0286] This example illustrates the fabrication, characterization and evaluation of the porous molecular sieve material Zr-MFI-2 of the present invention.

[0287] The zirconium-silicon molecular sieve Zr-MFI-D obtained in comparative example 5 was mixed with polymeric quaternary ammonium base-7 and water in a ratio of molecular sieve (mol):polymeric quaternary ammonium base (wt):water (mol) = 1:0.003:5. The resulting mixture was treated at 140°C for 6 hours, then a solid product was obtained by filtering the treated mixture. This solid product was then dried at 120°C for a further 6 hours and calcined at 550°C for 6 hours to obtain the porous molecular sieve material Zr-MFI-2.

[0288] The porous molecular sieve material Zr-MFI-2 was characterized.

[0289] XRD analysis showed that the molecular sieve Zr-MFI-2 had an MFI structure.

[0290] The SEM result showed that the molecular sieve Zr-MFI-2 had an open pore chamber with a pore size of no less than 10 nm on its surface.

[0291] The TEM result showed that the Zr-MFI-2 molecular sieve had an open pore chamber with a pore size of no less than 20 nm; no hollow structures were observed in the molecular sieve crystal grains.

[0292] The result of the nitrogen adsorption-desorption characterization showed that the nitrogen adsorption curve of the molecular sieve Zr-MFI-2 had three concave arcs (two at p / p0<0.3 and one at p / p0>0.7) and two hysteresis loops (the first hysteresis loop was in the range of relative pressure p / p0 of less than 0.3 and the second hysteresis loop was in the range of relative pressure p / p0 of greater than 0.45).

[0293] The results of the characterization for chemical composition, specific surface area and pore volume are listed in Table 1.

[0294] The porous molecular sieve material Zr-MFI-2 was evaluated in the levulinic acid Meerwein-Ponndorf-Verley reaction (MPV), and the result is shown in Table 1.

[0295] The open pore chamber of the molecular sieve had a degree of expansion in the range of 0 to 0.1. Comparative example 6

[0296] This comparative example differs from Example 1 in that the polymeric quaternary ammonium base-47 was replaced by polyquaternium-47 to obtain TS-1-1-A.

[0297] The porous molecular sieve material TS-1-1-A was characterized.

[0298] XRD analysis revealed that the molecular sieve TS-1-1-A had an MFI structure.

[0299] The SEM result showed that the molecular sieve TS-1-1-A had no open pore chambers on its surface.

[0300] The TEM result showed that the molecular sieve TS-1-1-A had neither open pore chambers nor an intracrystalline hollow structure.

[0301] The result of the nitrogen adsorption-desorption characterization showed that the nitrogen adsorption curve of the molecular sieve TS-1-1-A did not differ from that of the conventional TS-1, with two concave arcs (one at p / p0<0.3 and one at p / p0>0.7) without significant hysteresis loop. Comparative example 7

[0302] This comparative example was carried out according to the procedure of Example 1, except that the polymeric quaternary ammonium base-47 was replaced by a mixture of polyquaternium-47 and sodium hydroxide. The amount of sodium hydroxide used was adjusted so that the pH of the system was the same as in Example 1 to obtain TS-1-1-B.

[0303] The porous molecular sieve material TS-1-1-B was characterized.

[0304] XRD analysis showed that the molecular sieve TS-1-1-B had an MFI structure.

[0305] The SEM result showed that the molecular sieve TS-1-1-B had an open pore chamber with a pore size of more than 10 nm on its surface.

[0306] The TEM result showed that the molecular sieve TS-1-1-B had an open pore chamber with a pore size of more than 10 nm and that about 30% of the molecular sieve crystal grains had intracrystalline hollow structures.

[0307] The open pore chamber of the molecular sieve TS-1-1-B had a degree of expansion that was not in the range of 0-0.2.

[0308] The result of the nitrogen adsorption-desorption characterization showed that the nitrogen adsorption curve of the molecular sieve TS-1-1-B exhibited three concave arcs (two at p / p0<0.3 and one at p / p0>0.7) and a hysteresis loop at a relative pressure p / p0>0.45.

[0309] The porous molecular sieve material TS-1-1-B had a sodium content (as Na2O) of more than 2%. Table 1 Example No. Sample No. Si:Ti / Sn / Zr (molar ratio) BET-specific surface (m²) 2 / G) Micropore volume (cm 3 / g) Mesoporenvolumen (cm 3 / g) conversion Selectivity / Yield Comparative example 1 HTS 1:0,043 447 0,18 0,17 82% 97% Comparative example 2 STS-D 1:0,048 700 0,29 0,13 35% 66% Example 1 TS-1-1 1:0,045 403 0,17 0,12 100% 99% Example 2 TS-1-2 1:0,043 418 0,18 0,12 100% 99% Example 3 TS-1-3 1:0,042 390 0,16 0,13 100% 99% Table 1 - continued Example No. Sample No. Si:Ti / Sn / Zr (molar ratio) BET-specific surface (m²) 2 / G) Micropore volume (cm 3 / g) Mesoporenvolumen (cm 3 / g) conversion Selectivity / Yield Example 4 TS-1-4 1:0,043 375 0,15 0,14 98% 99% Example 5 TS-1-5 1:0,041 377 0,15 0,14 98% 99% Example 6 TS-1-6 1:0,042 371 0,15 0,14 98% 99% Comparison example 3 S-1-D - 473 0,18 0,17 88% 96% Example 7 S-1-1 - 422 0,19 0,14 97% 97% Example 8 S-1-2 - 428 0,19 0,14 97% 97% Example 9 S-1-3 - 415 0,18 0,13 100% 98% Comparative example 4 Sn-MEL-D 1:0,023 503 0,18 0,21 43% 96% Example 10 Sn-MEL 1:0,025 365 0,15 0,15 82% 99% Comparative example 5 Zr-MFI-D 1:0,022 442 0,18 0,17 65% 63% Example 11 Zr-MFI 1:0,023 374 0,16 0,14 82% 81% Example 12 TS-1-7 1:0,046 385 0,17 0,13 96% 99% Example 13 S-1-4 - 410 0,18 0,14 97% 96% Example 14 Sn-MEL-2 1:0,024 356 0,15 0,15 78% 98% Example 15 Zr-MFI-2 1:0,023 352 0,16 0,15 77% 80%

[0310] As can be seen from the table above, the low-temperature nitrogen adsorption isotherm curve of the porous molecular sieve material of the present invention has at least three concave arcs and two hysteresis loops, and the molecular sieve has an open pore chamber extending from the surface into the interior, a BET-specific surface area of ​​350-460 m². 2 / g, a micropore volume of 0.15-0.19 cm³ 3 / g and a mesopore volume of 0.1-0.15 cm³ 3 / g or 0.12-0.15 cm 3The manufacturing process for the porous molecular sieve material of the present invention is easy to handle and simple to carry out. Due to the generation of novel pore structures, the reaction transformation and product selectivity (yield) are superior compared to molecular sieves with conventional pore structures.

[0311] The preferred embodiments of the present invention have been described in detail above in conjunction with the figures. However, the present invention is not limited to the specific details of the embodiments mentioned above. Within the technical concept of the present invention, various simple modifications to the technical solutions of the present invention can be made, and these simple modifications are all within the scope of protection of the present invention.

[0312] Furthermore, it should be noted that the various specific technical features described in the aforementioned specific embodiments can be combined in any suitable manner without contradiction. To avoid unnecessary repetition, the various possible combinations are not described further in the present invention.

[0313] Furthermore, the various embodiments of the present invention can also be combined arbitrarily, as long as they do not deviate from the idea of ​​the present invention, and they should also be considered as the content disclosed in the present invention. QUOTES INCLUDED IN THE DESCRIPTION

[0000] This list of documents cited by the applicant was automatically generated and is included solely for the reader's convenience. The list is not part of the German patent or utility model application. The DPMA accepts no liability for any errors or omissions. Cited patent literature

[0000] CN 1301599A

[0005] CN 108726528A

[0007] CN 106145147A

[0007] CN 106145148A

[0007] CN 106145149A

[0007]

Claims

[1] Porous molecular sieve material, characterized by that its low-temperature nitrogen adsorption isotherm curve has at least three concave arcs and at least two, preferably two, adsorption-desorption hysteresis loops. [2] Porous molecular sieve material according to claim 1, characterized by , that in the low-temperature nitrogen adsorption isotherm curve there are at least two concave arcs at a relative pressure p / p0 < 0.3 and at least one concave arc at a relative pressure p / p0 > 0.7; there are at least two hysteresis loops, including a first hysteresis loop and a second hysteresis loop, the first hysteresis loop being in the range of a relative pressure p / p0 of less than 0.3 and the second hysteresis loop being in the range of a relative pressure p / p0 of more than 0.

45. [3] Porous molecular sieve material according to at least one of the preceding claims, characterized by, that it contains silicon as a first framework element of the molecular sieve and furthermore contains one or more of the elements C, Ge, Sn, Pb, Ti, Zr, Hf, B, Al and Ga as a second framework element. [4] Porous molecular sieve material according to claim 3, characterized by that the second framework element is one or more of the elements Sn, Ti and Zr. [5] Porous molecular sieve material according to claim 3 or 4, characterized by , that the molar ratio of the first framework element to the second framework element is 1: (0.0001-1), preferably the molar ratio of the first framework element to the second framework element is 1: (0.001-0.4). [6] Porous molecular sieve material according to claim 1 or 2, characterized by, that it comprises a first framework element, optionally a second framework element and optionally a third framework element, wherein the first framework element is a silicon element, the second framework element is one or more of the elements Sn, Ti, Zr, the third framework element is aluminum, wherein the molar ratio of the first framework element, the second framework element and the third framework element is 100: (0 or 0.01-100): (0 or 0.01-5), preferably 100: (0 or 0.1-40): (0 or 0.1-2), more preferably 100: (0 or 1-10): (0 or 0.2-1). [7] Porous molecular sieve material according to at least one of the preceding claims, characterized by , that When characterized by SEM, its surface has at least one surface pore with a maximum radial dimension of not less than 5 nm, preferably not less than 10 nm, more preferably not less than 20 nm, wherein the surface pore extends into the interior of the porous molecular sieve material and thus forms an open pore chamber; preferably the maximum radial dimension is not greater than 200 nm; and / or When characterized by TEM, the open pore chamber has a pore size of not less than 10 nm, preferably not less than 20 nm, more preferably not less than 40 nm; preferably the open pore chamber has a pore size of not more than 200 nm. [8] Porous molecular sieve material according to at least one of the preceding claims, characterized by , that its crystal structure is selected from one or more of the following: BEA, MFI, MEL, MWW and SVR, preferably MFI or MEL. [9] Porous molecular sieve material according to at least one of the preceding claims, characterized by , that its BET-specific surface area, measured by low-temperature nitrogen adsorption / desorption, is 350 to 460 m² 2 / g, its micropore volume is 0.15 to 0.19 cm³ 3 / g and its mesopore volume is 0.1 to 0.15 cm³ 3 / g, preferably 0.12 to 0.15 cm 3 / g, is the amount. [10] Porous molecular sieve material according to at least one of the preceding claims, characterized by that the open pore chamber of the porous molecular sieve material has a degree of expansion 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 wt.%, e.g. less than 1 wt.%, less than 0.5 wt.%, less than 0.2 wt.% or less than 0.1 wt.%, but preferably more than 1 ppm. [11] Method for producing a porous molecular sieve material, characterized byMixing a molecular sieve containing silicon as a first framework 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 a 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; the polymeric quaternary ammonium base is obtained by hydroxide radical exchange of a polymeric quaternary ammonium salt; The polymeric quaternary ammonium base is more preferably obtained by hydroxide radical exchange of polyquaternium-2, polyquaternium-6, polyquaternium-7, polyquaternium-22, polyquaternium-32, polyquaternium-37, polyquaternium-39, polyquaternium-47. [12] The method of claim 11, wherein the porous molecular sieve material is obtained by post-modification of a molecular sieve containing silicon as a first framework element, the post-modification comprising: mixing the molecular sieve containing silicon as the first framework 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 a solid product from the treated mixture, and drying and calcining the solid product; wherein the polymeric quaternary ammonium base has an average degree of polymerization of 10 to 100,000, preferably 100 to 50,000, more preferably 500 to 100,000.000, most preferably 1000-5000, wherein the average degree of polymerization refers to the average number of repeating units contained in the polymeric macromolecular chain, wherein the polymeric quaternary ammonium base is obtained by hydroxide radical exchange of a polymeric quaternary ammonium salt, wherein the exchange has a degree of exchange of > 30%, e.g. > 50%, preferably > 70%, more preferably > 90%, most preferably > 98%; wherein the degree of exchange refers to the molar percentage of the anions that are replaced by hydroxide radicals, based on the total anions in the polymeric quaternary ammonium salt; The polymeric quaternary ammonium base is more preferably obtained by hydroxide radical exchange of polyquaternium-2, polyquaternium-6, polyquaternium-7, polyquaternium-22, polyquaternium-32, polyquaternium-37, polyquaternium-39, polyquaternium-47. [13] Method according to at least one of claims 11-12, wherein the polymeric quaternary ammonium base has a pKa value of 11 to 13.5, e.g., approximately 12.8; and / or the polymeric quaternary ammonium base comprises a polymeric macromolecular chain unit and one or more quaternary ammonium base units, wherein the ratio of the sum of the molecular weights of one or more quaternary ammonium bases (the sum of the molecular weights of R1, R2, R3, the N atom(s) and the hydroxide radical(s) or the sum of the molecular weights of the cyclic structural unit and the hydroxide radical(s)) to the molecular weight of the polymeric quaternary ammonium base is (0.01-0.4):1, preferably (0.1-0.38):1, more preferably (0.2-0.35):1; The quaternary ammonium base unit can exhibit the following branched structures: where, at each occurrence, R1, R2 and R3 are each independently derived from C1-C 12-Alkyl groups and unsaturated groups (such as aromatic groups and alkenyl groups) are selected; wherein the groups may optionally be substituted and the substituents may be selected from halogen, hydroxyl, nitro, cyano, alkyl, alkenyl, alkynyl and alkoxy; and wherein the groups may also optionally be oxidized; or may have the following cyclic structure: wherein the cyclic unit comprises, in addition to the quaternary nitrogen atom shown, 2-13 ring atoms, wherein the ring atoms are selected from C, O, S and N, wherein the cyclic unit can be monocyclic or polycyclic (spiro-ring, condensed ring, bridged ring), wherein the cyclic unit can be aromatic or unsaturated or saturated; wherein the cyclic unit can optionally be substituted and the substituents are 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 ) can be; where the cyclic unit can also optionally be oxidized; represents the connection point of each quaternary ammonium base unit with the polymeric macromolecular chain unit. [14] A method according to at least one of claims 11 to 13, wherein the small-molecule nitrogen-containing basic compound is selected from one or more organic ammonium salts having a carbon number of not more than 15 and inorganic ammonium salts; preferably the organic ammonium salts are straight-chain carboxylic acid ammonium salts, cyclic carboxylic acid ammonium salts and aromatic carboxylic acid ammonium salts having a carbon number of not more than 15, preferably not more than 12, more preferably not more than 6; even 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;The inorganic ammonium salt is one or more of the following: ammonium nitrate, ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium sulfate, ammonium hydrogen sulfate, ammonium sulfide, ammonium hydrogen sulfide, ammonium chloride, ammonium bromide, ammonium fluoride, ammonium carbonate and ammonium bicarbonate. [15] A process according to at least one of claims 11 to 14, wherein in the mixture of the molecular sieve containing silicon as the first framework element, the polymeric quaternary ammonium base, water and the optionally added low molecular weight nitrogen-containing basic compound, the ratio of the molecular sieve containing silicon as the first framework element, the polymeric quaternary ammonium base, the water and the optionally added low molecular weight nitrogen-containing basic compound is 1: (0.001-0.5): (5-100): (0-0.3), wherein the molecular sieve containing silicon as the first framework element is calculated in moles of silica, the polymeric quaternary ammonium base is calculated in grams, water is calculated in grams and the low molecular weight nitrogen-containing basic compound is calculated in moles; preferably the above manufacturing process is repeated 1-10 times. [16] Method according to at least one of claims 11-15, wherein The molecular sieve, which contains silicon as a first framework element, contains no other tetracoordinate framework elements, wherein the molecular sieve containing silicon as a first framework element is prepared by the following process: mixing a silicon source, a quaternary ammonium base, and water to prepare a first mixture, wherein the feed molar ratio of the silicon source, the quaternary ammonium base, and the water is preferably 1: (0.05-0.3): (5-60); aging the mixture at a temperature of 5 to 120°C for 0.5 to 24 hours to obtain a sol; subsequent crystallization of this sol at a temperature of 100 to 200°C for 2 to 168 hours; separating at least a portion of the product therefrom; and subsequent drying and calcining of the product to produce at least a portion of the molecular sieve;Optionally, prior to crystallization, a material with a crystalline structure is added, wherein the weight ratio of the material with a crystalline structure to the silicon source as SiO2 is (0.001-2):1; preferably the material with a crystalline structure has an MFI structure, the material with a crystalline structure contains Si and O and is free of one or more elements from C, Ge, Sn, Pb, Ti, Zr, Hf, B, Al and Ga; or; The molecular sieve, which contains silicon as a first framework element, further comprises a second framework element, wherein the second framework element is selected from one or more of the elements C, Ge, Sn, Pb, Ti, Zr, Hf, B, Al and Ga, wherein the molar ratio of silicon to the second framework element is 1:(0.001-1), preferably 1:(0.0001-1), wherein the molecular sieve containing silicon as a first framework element is prepared by the following process: mixing a silicon source, a source for the second framework element, a quaternary ammonium base and water to prepare a first mixture, wherein the molar ratio of the silicon source, the quaternary ammonium base and the water is preferably 1:(0.05-0.3):(5-60); aging the mixture at a temperature of 5 to 120°C for 0.5 to 24 hours to obtain a sol; subsequent crystallization of this sol at a temperature of 100 to 200°C for 2 to 168 hours;Separating at least a portion of the product; and subsequently drying and calcining the product to produce at least a portion of the molecular sieve; optionally, prior to crystallization, adding a material with a crystalline structure, wherein the weight ratio of the material with a crystalline structure to the silicon source as SiO2 is (0.001-2):1; preferably the material with a crystalline structure has an MFI structure, the material with a crystalline structure contains Si and O and one or more elements from C, Ge, Sn, Pb, Ti, Zr, Hf, B, Al and Ga; or; The molecular sieve, which contains silicon as a first framework element, further comprises a second framework element and optionally a third framework element, wherein the second framework element is one or more of Sn, Ti and Zr, and the third framework element is aluminum, wherein the molar ratio of the first framework element : of the second framework element : of the third framework element is 100:(0 or 0.01-100): (0 or 0.01-5), preferably 100: (0 or 0.1-40): (0 or 0.1-2), more preferably 100: (0 or 1-10): (0 or 0.2-1); The molecular sieve, which contains silicon as a first framework element, is prepared by the following process: mixing a silicon source, a source for a second framework element, an optional source for a third framework element, a quaternary ammonium base, and water to prepare a first mixture, preferably having a molar ratio of the silicon source, the quaternary ammonium base, and the water of 1: (0.05-0.3): (5-60); aging the mixture at a temperature of 5 to 120°C for 0.5 to 24 hours to obtain a sol; subsequent crystallization of this sol at a temperature of 100 to 200°C for 2 to 168 hours; separating at least a portion of the product therefrom; and subsequent drying and calcining of the product to produce at least a portion of the molecular sieve.Optionally, prior to crystallization, a material with a crystalline structure is added, wherein the weight ratio of the material with a crystalline structure to the silicon source as SiO2 is (0.001-2):1; preferably the material with a crystalline structure has an MFI structure, the material with a crystalline structure contains Si and O and one or more elements from Sn, Ti and Zr and optionally Al; preferably: The silicon source is a monodisperse silicon source and / or an aggregate silicon source; the monodisperse silicon source is tetraalkoxysilane; the aggregate 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 aggregate silicon source; the molar ratio of the monodisperse silicon source to the aggregate silicon source is 1:(0.1-10), preferably 1:(0.5-7), more preferably 1:(1-5), and even more preferably 1:(2-4); the aggregate silicon source is calculated as silica; and / or preferably: If the second scaffold element is C, the source for the second scaffold element has the structure A1A2A3Si-A4-SiA5A6A7, wherein A1, A2, A3, A5, A6 and A7 are each independently optionally substituted C1-C 10A1, A2, A3, A5, A6 and A7 are each independently alkoxy or halogen, A4 is C1-C3 alkyl; preferably, A1, A2, A3, A5, A6 and A7 are each independently alkoxy or halogen, A4 is C1-C2 alkyl; more preferably, A1, A2, A3, A5, A6 and A7 are each independently alkoxy or halogen, A4 is C1 alkyl; in particular, if the second framework element is C, the source for the second framework 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 framework element is Ge, the source for the second framework element is selected from oxides, salts and organic metal salts of germanium, in particular from one or more of the following: germanium monoxide, germanium dioxide, germanium tetrafluoride, germanium tetrachloride, germanium tetrabromide, germanium tetraiodide, germanium sulfide, tetramethylgerman, tetraethylgerman, tetrapropylgerman, tetrabutylgerman, methylgerman, ethylgerman, propylgerman and butylgerman; and / or If the second framework element is Sn, the source for the second framework element is selected from oxides, salts and organic metal salts of tin, in particular one or more of the following: tin dioxide, tin oxide, tin chloride, tin trichloride, tin tetrachloride, potassium stannate, sodium stannate, metastanic acid, stannic acid, tetramethyltin, tetraethyltin, tetrapropyltin and tetrabutyltin; and / or If the second framework element is Pb, the source for the second framework element is selected from oxides, salts and organic metal salts of lead, in particular from one or more of the following: lead oxide, lead chloride, lead nitrate, lead sulfate and lead acetate; and / or If the second framework element is Ti, the source for the second framework element is selected from salts and organic metal salts of titanium, in particular at least one from tetraalkoxytitanium, titanium tetrachloride, titanium trichloride, titanium sulfate, hexafluorotinateic acid, bis(cyclopentadienyl)titanium(IV) dichloride and titanium nitrate, preferably at least one from tetraalkoxytitanium and titanium tetrachloride, more preferably at least one from tetraethyl titanate, tetrapropyl titanate and tetrabutyl titanate; and / or If the second framework element is Zr, the source for the second framework element is selected from salts and organic metal salts of zirconium, in particular from one or more of zirconium tetrachloride, zirconium trichloride, zirconium oxychloride, zirconium oxysulfate, zirconium nitrate, zirconium acetate and tetraalkoxyzirconium; and / or If the second framework element is Hf, the source for the second framework element is selected from oxides, salts and organic metal salts of hafnium, in particular from one or more of hafnium oxide, hafnium tetrachloride, hafnium hydroxide, hafnium carbide and hafnium boride; and / or If the second framework element is B, the source for the second framework element is selected from oxides, salts and organic boron salts of boron, in particular one or more from boron oxide, boric acid, borax, alkyl boron compounds and alkoxybore compounds; and / or If the second / third framework element is Al, the source for the second framework element is selected from oxides, salts and organoaluminium compounds of aluminum, in particular from one or more of the following: aluminum oxide, aluminum trichloride, aluminum sulfate, aluminum nitrate, aluminum phosphate, sodium aluminate, aluminum acetate, alkylaluminium compounds and alkoxyaluminium compounds; and / or If the second framework element is Ga, the source for the second framework element is selected from oxides, salts and organogallium compounds of gallium, in particular from one or more of the following: gallium oxide, gallium chloride, gallium sulfate, gallium nitrate, gallium phosphate, sodium gallate, gallium acetate, alkylgallium compound and alkoxygallium compound; and / or preferably: the quaternary ammonium base has a structure of R1R2R3R4N + OH -wherein R1, R2, R3 and R4 are each independently C2-5 alkyl or C2-5 alkenyl, preferably R1, R2, R3 and R4 are each independently C3 alkyl or C3 alkenyl.

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