Titanium-doped ZEO-1 molecular sieve and synthesis method thereof, molecular sieve composition and use thereof

Abstract

The present invention relates to a titanium-doped ZEO-1 molecular sieve, a synthesis method thereof and a use thereof. The molecular sieve has the formula (TiO2) x (HAO2) y · SiO2 shows the schematic chemical composition, where A = Al or B, 0 ≤ x < 0.2, 0 ≤ y < 0.2. It is characterized in that the molecular sieve is synthesized by hydrothermal method under alkaline conditions (with OH ‑ as a mineralizer) or neutral conditions (with F ‑ Titanium atoms were successfully incorporated into the ZEO-1 molecular sieve framework, which has good thermal stability and can be used as an adsorbent or catalyst.

Description

Technical Field

[0001] The invention relates to a titanium-doped ZEO-1 molecular sieve, and also relates to a synthesis method thereof, a molecular sieve composition comprising the molecular sieve, and uses thereof. Background Art

[0002] Molecular sieve materials are inorganic microporous solid materials composed of TO4 (T represents an atom with a +4 or +3 valence oxidation state, such as Si, P, Al, B, Ge, Ga, etc.) tetrahedrons sharing vertices. The composition of molecular sieves can usually be expressed by the following empirical chemical formula: x(M 1 / n XO2):yYO2:zR:qH2O, where M represents one or more +n-valent organic or inorganic cations; X represents one or more trivalent elements; Y represents one or more tetravalent elements, usually Si; and R represents one or more organic molecules. For a molecular sieve of a certain structure obtained by a specific synthesis method, whether it is a freshly synthesized product or a sample after calcination, its chemical composition usually has a specific range of variation. In addition, a molecular sieve of a specific structure needs to be further distinguished by X-ray powder diffraction, because the difference in crystal structure makes different molecular sieves have different pore structures, and completely different diffraction patterns will be obtained in the X-ray powder diffraction test. The most important characteristics of molecular sieves are that they have variable pore chemical composition, adjustable pore diameter and pore shape. These excellent characteristics give molecular sieve materials a wide range of applications in adsorption, separation, catalysis, microelectronics and medical diagnosis.

[0003] The specific structure of the molecular sieve is determined by the X-ray diffraction spectrum (XRD). Zeolite molecular sieves with different structures have different XRD spectrum characteristics. Common known molecular sieves such as A-type zeolite (see US2882243), Y-type zeolite (see US3130007), ZSM-11 molecular sieve (see US3709979), ZSM-12 molecular sieve (see US3832449), etc. all have their own characteristic XRD spectra.

[0004] At the same time, zeolite molecular sieves with the same structure generally have the same XRD spectra characteristics, but different framework elements, which are also different molecular sieves. A typical example is the zeolite molecular sieve TS-1 (see US4410501) and ZSM-5 (see US3702886) which also have the MFI topological structure. The two have the same XRD spectroscopic characteristics, but different framework elements. They are two different molecular sieve materials. Specifically, the framework elements of ZSM-5 molecular sieve are Si and Al, which are mainly used in the field of acid catalysis, while the framework of TS-1 molecular sieve contains Si and Ti, which is mainly used in catalytic oxidation processes.

[0005] In addition, materials with the same topological structure, i.e., the same XRD spectroscopic characteristics, the same types of framework elements, but different relative contents of framework elements also belong to different molecular sieves. For example, X zeolite (see US2882244) and Y zeolite (US3130007) both have the same FAU topological structure, have the same XRD spectroscopic characteristics, and the framework elements are both Si and Al, but the relative contents of Si and Al are different, and they are also different molecular sieve materials.

[0006] Titanium silicate molecular sieve is a new type of heteroatom molecular sieve developed in the early 1980s. The main ones synthesized so far include TS-1 with MFI structure, TS-2 with MEL structure, Beta zeolite Ti-beta, and Ti-MCM-41 and Ti-MCM-48 with mesoporous channel structure. This type of molecular sieve has excellent catalytic activity and directional oxidation performance for many organic oxidation reactions, such as epoxidation of olefins, hydroxylation of aromatics, oximation of cyclohexanone, oxidation of alcohols, etc. They have important application value in industry as redox molecular sieve catalysts. Take TS-1 for example. Marco Taramasso et al. of Italy first disclosed its preparation method in 1981 (see GB2071071A, USP4410501). It not only has good catalytic oxidation of titanium to organic compounds, but also has the shape selectivity and excellent stability of ZSM-5 molecular sieve. In the organic oxidation reaction in which TS-1 participates, low-concentration hydrogen peroxide can be used as an oxidant, and has good reaction selectivity, avoiding the problems of industrial complexity and environmental pollution in conventional oxidation processes, and has the advantages of energy saving and environmental protection that are unmatched by traditional oxidation systems. According to the research results of Li Can et al. of Dalian Institute of Chemical Physics, a direct criterion for judging that Ti atoms enter the molecular sieve framework is that the absorption peak at about 220nm in the UV-visible absorption spectrum belongs to the Ti atoms in the tetracoordinate state in the molecular sieve framework (see Angew. Chem. Int. Ed., 1999, 38, 2220-2222), which also has catalytic active centers.

[0007] The pore diameter of TS-1 and TS-2 is about 5.5 angstroms, and that of Ti-beta is only 6.5 angstroms. The size of the reaction substrate molecule must be smaller than the pore diameter of the molecular sieve to achieve a good shape-selective catalytic effect, which seriously limits their further application. At the same time, Ti-MCM-41 and Ti-MCM-48 generally only have adjustable mesopore diameters of 15-100 angstroms. It can be seen that titanium silicon molecular sieve materials with pore diameters between 7-15 angstroms are vacant, which is in the molecular size range of a large number of high-value chemicals.

[0008] The ZEO-1 molecular sieve is an ultra-large pore silicate molecular sieve developed by the applicant (see CN202011346698.4), which is characterized in that the crystal structure of the molecular sieve has a three-dimensional cross-pore system of (16+12)×(16+12)×(16+12) membered rings, and the pore diameter is between 7-15 angstroms.

[0009] The ultra-large pore ZEO-1 molecular sieve has the powder X-ray diffraction characteristics shown in Table 1:

[0010] Table 1

[0011]

[0012]

[0013] In the above data, w, mw, m, s, vs represent the diffraction peak intensity, w is weak, mw is medium to weak, m is medium, s is strong, vs is very strong, which is known to those skilled in the art. Generally speaking, w is less than 10, mw is 10-20, m is 20-40, s is 4-70, and vs is greater than 70.

[0014] After structural analysis and topological analysis, the framework structure of ZEO-1 molecular sieve has 21 topologically independent T atoms, 43 topologically different edges (lines composed of adjacent T atoms and T atoms), 41 topologically different faces (planes composed of T atoms), and 19 topologically different structural units composed of T atoms. Among them, the framework structure of ZEO-1 molecular sieve has the topological properties of 21 topologically independent T atoms (including coordination sequence and vertex symbols), and its topological characteristics are shown in Table 2:

[0015] Table 2

[0016]

[0017]

[0018] From T1 to T21, they represent 21 topologically different T atoms in the framework structure of the ultra-large pore ZEO-1 molecular sieve of the present invention; from N1 to N12, they represent the coordination sequences of these T atoms from the first layer to the twelfth layer. Due to the different naming order of T atoms, the 21 topologically independent T atoms named in different orders may not correspond one-to-one with the coordination sequences and vertex symbols of the T atom sequence in this table, but the structures belonging to the ZEO-1 topology all contain and only contain the coordination sequences and vertex symbols of the 21 topologically independent T atoms in this table, and the coordination sequences and vertex symbols correspond one-to-one.

[0019] The successful development of the titanium-doped ultra-large pore ZEO-1 molecular sieve fills the gap in the field of ultra-large pore titanium silicate molecular sieves and has very important potential industrial application value. Summary of the invention

[0020] In the first aspect, the present invention provides a titanium-doped ultra-large pore ZEO-1 molecular sieve. It is the first ultra-large pore titanium-silicon molecular sieve, and titanium atoms are successfully doped into the framework of the ZEO-1 molecular sieve, which has important practical application value.

[0021] In a second aspect, the present invention further provides a method for preparing the titanium-doped ultra-large pore ZEO-1 molecular sieve, the method comprising:

[0022] (1) mixing a silicon source, a boron group element compound, an organic template, a titanium source, water and a mineralizer to obtain a mixture;

[0023] (2) crystallizing the mixture;

[0024] (3) calcining the crystallized product to remove the template, and then washing and drying the target molecular sieve.

[0025] The organic template has a tetrahedral spatial configuration represented by the following general formula:

[0026]

[0027] Wherein, R1 is cyclohexyl; R2 and R3 are phenyl or cyclohexyl; R4 is C 1-8 Alkyl, preferably C 1-4 Alkyl, more preferably C 1-2 Alkyl; X is phosphorus or nitrogen, preferably phosphorus.

[0028] The titanium-doped ZEO-1 molecular sieve of the present invention is the first ultra-large pore titanium silicon molecular sieve, which fills the blank in this field and provides a new choice for the application of molecular sieve materials in industrial catalysis.

[0029] In a third aspect, the present invention further provides a molecular sieve composition, which comprises the titanium-doped ZEO-1 molecular sieve of the present invention and a binder.

[0030] In a fourth aspect, the molecular sieve composition of the present invention can be used as an adsorbent or a catalyst.

[0031] In the above method, before preparing the reaction gel, all organic cationic templates can be exchanged into hydroxide form by ion exchange resin, and the concentration thereof can be calibrated by 0.1M hydrochloric acid solution before use. Alternatively, they can be directly introduced in the form of chloride, bromide or iodide salts.

[0032] Generally, trivalent elements and tetravalent elements other than the silicon source are first added to the alkaline template solution, stirred to dissolve, and then a suitable silicon source is added. If necessary, hydrofluoric acid is added after stirring evenly, and the system is heated under an infrared lamp or in an oven to remove excess water and ethanol to obtain the target gel. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 These are the powder X-ray diffraction patterns of ZEO-1 molecular sieve before and after high-temperature calcination at 600°C and 1000°C to remove the template (the light source is Cu target Kα rays).

[0034] Figure 2 This is an X-ray diffraction pattern (the light source is Cu target Kα rays) of the titanium-doped ZEO-1 molecular sieve (in-situ synthesized sample and after calcination) of the present invention.

[0035] Figure 3 This is a scanning electron microscope (SEM) image of titanium-doped ZEO-1 molecular sieve.

[0036] Figure 4 This is the UV spectrum of titanium-doped ZEO-1 molecular sieve (in-situ synthesized sample and after calcination). DETAILED DESCRIPTION

[0037] The titanium-doped ZEO-1 molecular sieve of the present invention has the formula (TiO2) x (HAO2) y · Schematic chemical composition shown as SiO2, wherein A = Al or B, 0≤x<0.2, 0≤y<0.2, preferably 0.01≤x≤0.1, 0.01≤y≤0.1.

[0038] In the synthesis method of the ultra-large pore molecular sieve of the present invention, specific examples of the organic template include but are not limited to any one or more of the ones shown in Table 3:

[0039] Table 3

[0040]

[0041] The organic template is preferably selected from any one or more of Template 1, Template 6, Template 7 and Template 8, and more preferably selected from any one or more of Template 6 and Template 8.

[0042] The method for synthesizing the ultra-large pore molecular sieve of the present invention more specifically comprises:

[0043] (1) Under static or dynamic stirring, a silicon source, a boron group element compound, an organic template, a titanium source, water and a mineralizer are mixed uniformly in proportion to form a reaction gel having a chemical composition of rROH:aHF:xTiO2:yAO1.5 :SiO2:wH2O, wherein R represents the positively charged group of the organic template; A represents the boron group element; the corresponding value ranges of r, x, y and w are: r = 0.1-5.0, a = 0-5.0, x = 0-0.2, y = 0-0.2, w = 1-100;

[0044] (2) placing the reaction gel under an infrared lamp or in an oven, removing excess solvent, and then transferring the reaction gel to a stainless steel reaction kettle, and reacting at a temperature of 80-240° C., preferably 120-220° C., for 1-60 days, preferably 2-45 days, under sealed conditions to perform crystallization;

[0045] (3) The crystallized product is washed, centrifuged, and dried, and then calcined in an air atmosphere at 400-650° C. for 2-5 hours to remove the template, and then washed with water and dried to obtain the target product.

[0046] In step (1), the chemical composition of the reaction gel is rROH:aHF:xTiO2:yAO 1.5 In :SiO2:wH2O, A is preferably Al or B, and the corresponding preferred value ranges of r, a, x, y and w are: r=0.1-2.0, a=0-2.0, x=0.01-0.1, y=0.01-0.1, w=5-30.

[0047] The silicon source can be selected from at least one of silicic acid, silica gel, silica sol, tetraalkyl silicate and water glass, preferably water glass, silica sol or tetraethyl orthosilicate. The boron compound can be selected from at least one of sodium aluminate, aluminum isopropoxide, aluminum sulfate hexahydrate, aluminum hydroxide or boric acid, preferably sodium aluminate, aluminum isopropoxide, aluminum sulfate hexahydrate or boric acid. The titanium source can be one or a mixture of two or more of tetrabutyl orthotitanate, titanium tetrachloride, titanium trichloride and titanium sulfate. The mineralizer can be OH derived from an alkaline organic template solution. - , or F from additionally added HF or NH4F - The addition of a mineralizer can accelerate the crystallization of the molecular sieve and may be beneficial to the structural orientation. - as mineralizer) and alkaline conditions (no HF, with OH - as a mineralizer) can obtain the titanium-doped ZEO-1 molecular sieve of the present invention.

[0048] In the preparation method of the present invention, no germanium or germanium-containing compound is used.

[0049] The materials can be added and mixed in any order. For example, the boron group element (Al or B) can be first added to the alkaline template solution, stirred to dissolve, and then a suitable silicon source and titanium source can be added. If necessary, a mineralizer is added after stirring evenly, and the excess solvent in the system is removed by heating under an infrared lamp or in an oven to obtain the target gel.

[0050] Before preparing the reaction gel, all organic cationic templates can be exchanged into hydroxide form by ion exchange resin, and the concentration thereof can be calibrated by 0.1M hydrochloric acid solution before use. Alternatively, they can be directly introduced in the form of chloride, bromide or iodide salts.

[0051] In step (2), the temperature of the oven may be, for example, 80°C.

[0052] The crystallization conditions may include, for example: a crystallization temperature of 80 to 240° C., preferably 120 to 220° C., more preferably 140 to 210° C.; a crystallization time of 1 to 60 days, preferably 2 to 45 days, more preferably 3 to 30 days.

[0053] The mixture of the preparation method of the present invention may further contain seed crystals. The content of the seed crystals may be 0.01 ppm by weight to 10000 ppm by weight. The ultra-large pore molecular sieve of the present invention may be used as the seed crystal. The presence of the seed crystal may accelerate the reaction process and reduce the reaction cost.

[0054] In step (3), washing, centrifugation and drying can be performed in any manner conventionally known in the art. For example, washing can be performed multiple times with water or ethanol; and drying can be performed by drying.

[0055] The X-ray diffraction pattern of the titanium-doped ZEO-1 molecular sieve of the present invention is as follows: Figure 2 As shown. Figure 1 By comparing the X-ray diffraction pattern of the ZEO-1 molecular sieve, it can be judged that it has a ZEO-1 framework structure from the position and intensity of the diffraction peak.

[0056] The SEM results of the titanium-doped ZEO-1 molecular sieve of the present invention are as follows: Figure 3 , indicating that the experimentally synthesized titanium-doped ZEO-1 molecular sieve has uniform particle size, good crystallization, and no impurities such as amorphous compounds or anatase; its UV spectrum is shown in Figure 4 As shown, the titanium-doped ZEO-1 molecular sieve before and after calcination has a strong absorption peak at about 220 nm. This peak is attributed to the Ti atoms in the tetracoordinated state in the molecular sieve framework, proving that the Ti atoms are successfully incorporated into the ZEO-1 molecular sieve framework.

[0057] Example

[0058] In order to more clearly illustrate the present invention, the following examples are listed, but they do not limit the present invention in any way.

[0059] Embodiment 1:

[0060] The gel for molecular sieve synthesis is prepared according to the molar ratio of SiO2: 0.02Al2O3: 0.04TiO2: 0.5ROH: 20H2O. The steps are as follows: weigh an appropriate amount of the exchanged template 6 basic solution, add 0.08mmol (0.016g) of aluminum isopropoxide powder to it, stir for about half an hour, add 2mmol (0.417g) of tetraethyl orthosilicate, stir for about two hours at room temperature to completely dissolve the tetraethyl orthosilicate, finally add 0.08mmol (0.027g) of tetrabutyl orthotitanate and stir overnight, place the mixed gel under an infrared lamp or in an 80℃ oven, remove excess solvent to theoretical weight. The resulting reaction gel is transferred to a 15ml stainless steel reactor with a polytetrafluoroethylene liner, reacted at 190℃ for 30 days under sealed conditions, and the product is washed twice with water and twice with ethanol, and dried for use. The product is directly used for X-ray powder diffraction phase identification to show that it has a ZEO-1 skeleton structure. Take an appropriate amount of sample and calcine it in a muffle furnace at 600℃ in air atmosphere for 2 hours to remove the template. After washing and drying, the sample is analyzed by elemental analysis and its molecular formula is H 0.04 Al 0.04 Ti 0.04 Si 0.92 O2.

[0061] Embodiment 2:

[0062] Prepare the molecular sieve synthesis gel according to the molar ratio of SiO2: 0.01Al2O3: 0.02TiO2: 0.5ROH: 15H2O, the steps are as follows: weigh an appropriate amount of the exchanged template 6 basic solution, add 0.04mmol (0.008g) of aluminum isopropoxide powder to it, stir for about half an hour, add 2mmol (0.417g) of tetraethyl orthosilicate, stir for about two hours at room temperature to completely dissolve the tetraethyl orthosilicate, finally add 0.04mmol (0.014g) of tetrabutyl orthotitanate and stir overnight, place the mixed gel under an infrared lamp or in an 80℃ oven, remove excess solvent to theoretical weight. Transfer the resulting reaction gel to a 15ml stainless steel reactor with a polytetrafluoroethylene liner, react at 175℃ for 30 days under sealed conditions, wash the product twice with water, wash it twice with ethanol, and dry it for use. The product is directly used for X-ray powder diffraction phase identification to show that it has a ZEO-1 skeleton structure. Take an appropriate amount of sample and calcine it in a muffle furnace at 600℃ in air atmosphere for 2 hours to remove the template. After washing and drying, the sample is analyzed by elemental analysis and its molecular formula is H 0.02 Al 0.02 Ti 0.02 Si0.96 O2.

[0063] Embodiment 3:

[0064] The gel for molecular sieve synthesis is prepared according to the molar ratio of SiO2: 0.02Al2O3: 0.02TiO2: 0.5ROH: 0.5HF: 7H2O, and the steps are as follows: weigh an appropriate amount of the exchanged template 6 basic solution, add 0.08mmol (0.016g) of aluminum isopropoxide powder thereto, stir for about half an hour, add 2mmol (0.417g) of tetraethyl orthosilicate, stir for about two hours at room temperature to completely dissolve the tetraethyl orthosilicate, then add 0.04mmol (0.014g) of tetrabutyl orthotitanate and stir overnight, finally add the corresponding amount of hydrofluoric acid solution according to the above ratio, stir evenly, place the mixed gel under an infrared lamp or in an 80°C oven, and remove excess solvent to the theoretical weight. The resulting reaction gel is transferred to a 15ml stainless steel reactor with a polytetrafluoroethylene liner, react at 175°C for 30 days under sealed conditions, and the product is washed twice with water and twice with ethanol, and dried for use. The product was directly used for X-ray powder diffraction phase identification to show that it had a ZEO-1 skeleton structure. An appropriate amount of sample was calcined in a muffle furnace at 600°C in air atmosphere for 2 hours to remove the template agent. After the sample was washed and dried, elemental analysis showed that its molecular formula was H 0.04 Al 0.04 Ti 0.02 Si 0.94 O2.

[0065] Embodiment 4:

[0066] The gel for molecular sieve synthesis is prepared according to the molar ratio of SiO2: 0.02B2O3: 0.04TiO2: 0.5ROH: 10H2O. The steps are as follows: weigh an appropriate amount of the exchanged template 6 alkaline solution, add 0.08mmol (0.005g) of boric acid, stir for about half an hour, add 2mmol (0.417g) of tetraethyl orthosilicate, stir for about two hours at room temperature to completely dissolve the tetraethyl orthosilicate, finally add 0.08mmol (0.027g) of tetrabutyl orthotitanate and stir overnight, place the mixed gel under an infrared lamp or in an 80℃ oven, remove excess solvent to theoretical weight. The resulting reaction gel is transferred to a 15ml stainless steel reactor with a polytetrafluoroethylene liner, reacted at 190℃ for 30 days under sealed conditions, and the product is washed twice with water and twice with ethanol, and dried for use. The product is directly used for X-ray powder diffraction phase identification to show that it has a ZEO-1 skeleton structure. Take an appropriate amount of sample and calcine it in a muffle furnace at 600℃ in air atmosphere for 2 hours to remove the template. After washing and drying, the sample is analyzed by elemental analysis and its molecular formula is H 0.04 B 0.04 Ti 0.04 Si0.92 O2.

[0067] Embodiment 5:

[0068] The gel for molecular sieve synthesis is prepared according to the molar ratio of SiO2: 0.02B2O3: 0.02TiO2: 0.5ROH: 15H2O. The steps are as follows: weigh an appropriate amount of the exchanged template 6 alkaline solution, add 0.08mmol (0.005g) of boric acid, stir for about half an hour, add 2mmol (0.417g) of tetraethyl orthosilicate, stir for about two hours at room temperature to completely dissolve the tetraethyl orthosilicate, finally add 0.04mmol (0.014g) of tetrabutyl orthotitanate and stir overnight, place the mixed gel under an infrared lamp or in an 80℃ oven, remove excess solvent to theoretical weight. The resulting reaction gel is transferred to a 15ml stainless steel reactor with a polytetrafluoroethylene liner, reacted at 175℃ for 30 days under sealed conditions, the product is washed twice with water, washed twice with ethanol, and dried for use. The product is directly used for X-ray powder diffraction phase identification to show that it has a ZEO-1 skeleton structure. Take an appropriate amount of sample and calcine it in a muffle furnace at 600℃ in air atmosphere for 2 hours to remove the template. After washing and drying, the sample is analyzed by elemental analysis and its molecular formula is H 0.04 B 0.04 Ti 0.02 Si 0.94 O2.

Claims

1. Titanium-doped ZEO-1 molecular sieve, said molecular sieve having a schematic chemical composition of (TiO2) x ·(HAO2) y ·SiO2, where A = Al or B, 0 < x < 0.2, 0 < y < 0.2, and said molecular sieve having the powder X-ray diffraction characteristics shown in the following table The molecular sieve has a three-dimensional cross-channel system of (16+12)×(16+12)×(16+12) rings in its crystal structure.

2. The titanium-doped ZEO-1 molecular sieve according to claim 1, wherein in the formula (TiO2) x (HAO2) y ·In SiO2, 0.01≤x≤0.1, 0.01≤y≤0.

1.

3. The method for synthesizing the titanium-doped ZEO-1 molecular sieve according to claim 1, the method comprising the following steps in sequence: (1) Mix the organic template agent solution, boron group element compound, silicon source, titanium source, water and mineralizing agent evenly in proportion. The resulting mixture forms a reaction gel, and the chemical composition of the reaction gel is rROH: aHF: xTiO2: yAO 1.5 :SiO2: wH2O, where R represents the positively charged group of the organic template agent; A represents the boron group element; the value ranges of the corresponding r, a, x, y, and w are respectively: r = 0.1 - 5.0, a = 0 - 5.0, 0 < x < 0.2, 0 < y < 0.2, w = 1 - 100, and the organic template agent is selected from any one or more of the following: (2) placing the reaction gel under an infrared lamp or in an oven to remove excess solvent, and then transferring the reaction gel to a stainless steel reaction kettle, and reacting at a temperature of 80-240° C. for 1-60 days under sealed conditions to perform crystallization; (3) After washing and drying the crystallized product, calcining it in an air atmosphere at 400-650° C. for 2-5 hours to remove the template.

4. The method according to claim 3, characterized in that In step (2), the reaction is carried out at a temperature of 120-220°C.

5. The method according to claim 3, characterized in that In step (2), the reaction is carried out for 2-45 days.

6. The method according to claim 3, characterized in that The chemical composition of the reaction gel is rROH:aHF:xTiO2:yAO 1.5 In :SiO2:wH2O, A is Al or B, and the corresponding value ranges of r, a, x, y and w are: r=0.1-2.0, a=0-2.0, x=0.01-0.1, y=0.01-0.1, w=5-30.

7. The method according to any one of claims 3 to 6, characterized in that The organic template is selected from any one or more of the following:

8. The method according to any one of claims 3 to 6, characterized in that The organic template is selected from any one or more of the following:

9. The method according to any one of claims 3 to 6, characterized in that The silicon source is selected from at least one of silicic acid, silica gel, silica sol, tetraalkyl silicate and water glass.

10. The method according to any one of claims 3 to 6, characterized in that The boron group element compound is selected from at least one of sodium aluminate, aluminum isopropoxide, aluminum sulfate hexahydrate, aluminum hydroxide or boric acid.

11. The method according to any one of claims 3 to 6, characterized in that: The titanium source is one of tetrabutyl orthotitanate, titanium tetrachloride, titanium trichloride and titanium sulfate, or a mixture of two or more thereof.

12. The method according to any one of claims 3 to 6, characterized in that The mineralizer is OH from an alkaline organic template aqueous solution. - .

13. The method according to any one of claims 3 to 6, characterized in that The mineralizer is F derived from additionally added HF or NH4F - .

14. A molecular sieve composition comprising the titanium-doped ZEO-1 molecular sieve according to claim 1 or 2 or the titanium-doped ZEO-1 molecular sieve synthesized according to the method of any one of claims 3 to 13, and a binder.

15. Use of the molecular sieve composition according to claim 14 as an adsorbent or catalyst.

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