CN1328164C - Molecular screen ECNU-3 and synthesizing method thereof - Google Patents

Abstract

A molecular sieve ECNU-3 and its synthesis method belong to the technical field of inorganic chemicals and its synthesis. The molecular sieve uses at least one element among germanium, boron, oxygen and silicon, titanium, aluminum, iron, and gallium as its skeleton element, and its molar composition is expressed as GeO ₂ :xB ₂ O ₃ in anhydrous form of oxide: ySiO ₂ :zTiO ₂ :φM ₂ O ₃ , where M represents aluminum, iron, gallium, x=0-0.5, y=0-10, z=0-0.5, φ=0-2. The synthesis method of the molecular sieve comprises the following operation steps: preparation of reaction mixture, crystallization and roasting. The novel structure of the molecular sieve exhibits characteristic peaks at 2θ=7.86°, 10.93°, 20.49°, 21.44°, 22.77°, and 26.87°. The molecular sieve, when its main skeleton composition is expressed as GeO ₂ -B ₂ O ₃ -SiO ₂ -TiO ₂ in the anhydrous form of the oxide, is an active component of a catalytic oxidation catalyst for the preparation of hydrocarbon oxygenates; when When its main skeleton composition is expressed as GeO ₂ -B ₂ O ₃ -SiO ₂ -Al ₂ O ₃ in anhydrous form of oxide, it is an active component of solid acid catalyst.

Description

A kind of molecular sieve ECNU-3 and its synthetic method

technical field

The invention relates to a molecular sieve ECNU-3 and a synthesis method thereof. The molecular sieve is a molecular sieve with a novel structure marked as ECNU-3, and belongs to the technical field of inorganic chemicals and its synthesis.

Background technique

In general, "zeolite" is a general term designating a crystalline porous silica-alumina molecular sieve. The basic units of the zeolite structure are SiO ₄ and AlO ₄ tetrahedra. However, since the 1980s, it has been confirmed that the above-mentioned zeolite structure-specific or similar structures also exist in other oxides, such as aluminophosphate (US 4,310,440), such as germanium silicon oxide (US 6,077,498).

In addition, the International Zeolite Association ("IZA") further defined zeolite at the 13th International Molecular Sieve Conference (http:∥www.iza-online.org/) in 2001. According to the association's definition, zeolites include natural and synthetic zeolites, molecular sieves, and microporous, mesoporous materials with zeolite-related structures and/or properties. . Therefore, the term "zeolite molecular sieve" may include not only silica-alumina molecular sieves, but also materials similar in structure to silica-alumina molecular sieves, such as silicon-germanium molecular sieves. At the same time, zeolite molecular sieve means that the pores of the substance are filled with water molecules, and the water molecules may be removed without its skeleton collapsing (US 4,439,409).

Usually, the specific structure of zeolite molecular sieve is determined by X-ray diffraction spectrum (XRD). Different zeolite molecular sieves have different XRD spectrum characteristics. Existing synthetic zeolite molecular sieves, such as A-type molecular sieve (US 2,882,243), X-type molecular sieve (US 2,882,244), Y-type molecular sieve (US 3,130,007), PHS molecular sieve (US 4,439,409), MCM-22 molecular sieve (US 4,954,325), all XRD spectrum features with their own characteristics. At the same time, it has the same XRD spectrum characteristics, but different skeleton elements and different properties, and it is also a different molecular sieve. For example, TS-1 molecular sieve (US 4,410,501) and ZSM-5 molecular sieve (US3,702,886), AlPO-n (n refers to the code of molecular sieves with different structures) molecular sieve (US4,310,440) and SAPO-n (n and AlPO-n The same n) molecular sieves (US4,440,871), both of them have the same XRD spectrum characteristics, but the skeleton elements are different and the properties are different. Specifically, TS-1 molecular sieve has catalytic oxidation function, while ZSM-5 molecular sieve has acid catalytic function; AlPO-n molecular sieve framework is electrically neutral, has no ion exchange performance and no catalytic performance, while SAPO-n molecular sieve framework is negatively charged It has ion exchange performance and acid catalytic performance.

Contents of the invention

One of the objects of the present invention is to provide a molecular sieve ECNU-3, characterized in that the molecular sieve is made of germanium, silicon, oxygen or at least one of germanium, silicon, oxygen and boron, titanium, aluminum, iron, gallium This element is its skeleton element, and its molar composition is expressed as GeO ₂ :xB ₂ O ₃ :ySiO ₂ :zTiO ₂ :_M ₂ O ₃ in the anhydrous form of the oxide, where M represents aluminum, iron, gallium, and x=0 ～0.28, y=1.7～8.7, z=0～0.27, _=0～0.8, its XRD spectrogram contains the XRD spectral line shown in Table 1,

Table 1

2θ/° d/A° I/I0×100 7.06±0.327.86±0.2410.52±0.1310.93±0.0816.36±0.2519.49±0.4120.49±0.3321.44±0.2321.93±0.0622.77±0.4226.87±0.3228.46+0.28 12.51±0.0611.24±0.068.40±0.088.09±0.055.41±0.064.55±0.084.33±0.054.14±0.054.05±0.043.90±0.023.31±0.023.13±0.04 wvsw-mmwwmw-mmmw-mw

29.02±0.2233.05±0.35 3.07±0.042.71±0.03 ww

^* w: <20; m: 20-70; s: 70-90; vs: 90-100.

A further feature of the described molecular sieve ECNU-3 is that the molecular sieve uses germanium, boron, silicon, titanium, and oxygen as its skeleton elements, and its molar composition is expressed as GeO ₂ :xB ₂ O ₃ in the anhydrous form of oxides: ySiO ₂ :zTiO ₂ , x=0.11~0.20, y=1.7~6.3, z=0.08~0.27, in its UV-VIS spectrum, the molecular sieve skeleton Ti(IV) characteristic absorption peak appears at the wavelength of 210~220nm, which is An active component of a catalytic oxidation catalyst for the preparation of hydrocarbon oxygen compounds.

The molecular sieve ECNU-3 is further characterized in that the molecular sieve uses germanium, boron, silicon, aluminum, and oxygen as its skeleton elements, and its molar composition is expressed as GeO ₂ :xB ₂ O ₃ in the anhydrous form of oxides :ySiO ₂ :_Al ₂ O ₃ , x＝0.11～0.18, y＝1.8～6.1, _＝0.07～0.8, the characteristic vibration peak of molecular sieve skeleton Al-OH appears at the wavenumber of 3618cm ^-1 in the FTIR spectrum, which is A solid acid catalytic catalyst active component.

The second object of the present invention is to provide a method for synthesizing the above-mentioned molecular sieve ECNU-3. The technical scheme for realizing the object comprises the following operation steps: preparation of reaction mixture, crystallization and roasting.

A kind of synthetic method of molecular sieve ECNU-3 is characterized in that, operating steps:

Preparation of the first step reaction mixture

GeO ₂ in germanium source : B ₂ O ₃ in boron source : SiO ₂ in silicon source : TiO ₂ in titanium source : M ₂ O ₃ in M : organic template agent : F in fluorine source -:H ₂ O is 1:(0~6):(2~9):(0~0.3 5):(0~1.2):(2.66~13):(0~5):(21~100) Prepare the reaction mixture, the germanium source is germanium dioxide, the boron source is boric acid or borate, the silicon source is silicic acid, silica gel, silica sol or tetraalkyl silicate, the Titanium source is tetraalkyl titanate, titanium halide, titanium oxide, described aluminum source is sodium metaaluminate, aluminum isopropoxide, aluminum hydroxide, activated alumina or aluminum salt, and described iron source is ferric nitrate, ferric sulfate, ferric chloride, the gallium source is gallium nitrate, the fluorine source is sodium fluoride, ammonium fluoride, hydrofluoric acid, fluorosilicate and fluorosilicate, and the Organic templates are TMBA (Benzyltrimethylammonium, phenyltrimethylammonium hydroxide), DMHMI (dimethylhexamethyleneimine, dimethylhexamethyleneamine), DABCO (1,4-diazabicyclo[2.2.2]octane, 1,4- At least one of two azocyclooctane) and TMAD N, N (N, N, N', N'-tetramethylazodicarboxamide, N, N-tetramethylazodicarboxamide), the germanium source and the boron source are dissolved in the In the organic template solution, stir evenly, add silicon source, titanium source, aluminum source, iron source, gallium source, fluorine source, continue stirring evenly to obtain a reaction mixture;

The second step of crystallization

The reaction mixture prepared in the first step is hydrothermally crystallized at 130-200°C for 5 hours-20 days, filtered, washed and dried to obtain a crystallized product;

The third step roasting

Calcining the crystallized product obtained in the second step at 400-700° C. for 3-40 hours to obtain the product molecular sieve ECNU-3.

The further feature of the technical solution of the present invention is that in the first step, GeO ₂ in the germanium source: B ₂ O ₃ in the boron source: SiO ₂ in the silicon source: TiO ₂ in the titanium source: M M ₂ O ₃ in: organic template agent: F- in fluorine source: H ₂ O is 1: (0.66~6): (2~7): (0.1~0.35): 0: (2.66~13): (0～5):(21～100) Prepare reaction mixture; In the second step, the reaction mixture prepared in the first step is hydrothermally crystallized at 150～180° C. for 3 hours～15 days; In the third step , calcining the crystallized product obtained in the second step at 500-650° C. for 5-20 hours.

The advantages that the present invention has:

1. The molecular sieve ECNU-3 of the present invention has a complete and novel crystalline structure, and the structure is stable;

2. The molecular sieve ECNU-3 that the present invention obtains, when its main skeleton composition is expressed as GeO ₂ -B ₂ O ₃ -SiO ₂ -TiO ₂ with the anhydrous form of oxide, its UV-VIS spectrogram in the wavelength is The characteristic absorption peak of molecular sieve skeleton Ti(IV) appears at 210-220nm, and it is an active component of catalytic oxidation catalyst for preparing hydrocarbon oxygen-containing compounds.

3. The molecular sieve ECNU-3 that the present invention obtains, when its main framework composition is expressed as GeO ₂ -B ₂ O ₃ -SiO ₂ -Al ₂ O ₃ with the anhydrous form of oxide, its FTIR spectrogram has a wavenumber of The characteristic vibration peak of molecular sieve skeleton Al-OH appears near 3618cm ^-1 , which is an active component of solid acid catalyst.

Description of drawings

Fig. 1 is the XRD spectrogram of the product of the present invention that embodiment 1 obtains. The XRD measurement was carried out on a German Bruker axs X-ray diffractometer, using CuKα. It can be seen from the XRD spectrum that compared with the XRD spectrum of the existing molecular sieve, the new structure of the molecular sieve has characteristic peaks at 2θ=7.86°, 10.93°, 20.49°, 21.44°, 22.77°, and 26.87.

Detailed ways

All embodiments are operated according to the operation steps of the above-mentioned technical solutions.

Example 1

The germanium source is germanium dioxide, the silicon source is silica gel, the boron source is boric acid, and the organic template agent is TMBA (Benzyltrimethylammonium).

Preparation of the first step reaction mixture

GeO ₂ in the germanium source: B ₂ O ₃ in the boron source: SiO ₂ in the silicon source: organic template: H ₂ O is 1: 0.66: 2: 2.66: 21 to prepare the reaction mixture. Dissolve the boron source and the boron source in the organic template solution, stir evenly, add the silicon source, and continue to stir evenly to obtain a reaction mixture.

The second step of crystallization

The reaction mixture prepared in the first step was hydrothermally crystallized at 170° C. for 14 days, filtered, washed, and dried to obtain a crystallized product.

The third step roasting

The crystallized product obtained in the second step was calcined at 550° C. for 5 hours to obtain the product molecular sieve ECNU-3.

The molar composition of the product molecular sieve ECNU-3 is represented by the anhydrous form of the oxide as GeO ₂ : 0.12B ₂ O ₃ : 1.8SiO ₂ , x=0.12, y=1.8.

The XRD spectrum data of the product molecular sieve ECNU-3 is shown in Table 2, which conforms to the data shown in Table 1, and the XRD spectrum is shown in Figure 1.

Table 2

2θ/° d/A° I/I0×100 7.067.86 12.5111.24 10.6100.0

10.5210.9316.3619.4920.4921.4421.9322.7726.8728.4629.0233.05 8.408.095.414.554.334.144.053.903.313.133.072.71 15.940.25.79.630.711.828.028.713.07.28.76.2

^* w: <20; m: 20-70; s: 70-90; vs: 90-100.

Example 2

Implementation process is except following difference, and all the other are the same as embodiment 1.

Preparation of the first step reaction mixture

The reaction mixture was prepared at a molar ratio of GeO ₂ in the germanium source: B ₂ O ₃ in the boron source: SiO ₂ in the silicon source: organic template agent: H ₂ O was 1:6:9:13:100.

The second step of crystallization

Hydrothermal crystallization at 180°C for 5 days.

The molar composition of the product molecular sieve ECNU-3 is represented by the anhydrous form of the oxide as GeO ₂ :0.28B ₂ O ₃ :8.4SiO ₂ , x=0.28, y=8.4.

The XRD pattern of the product molecular sieve ECNU-3 is similar to that shown in Figure 1.

Embodiment 3～6

Implementation process is except following difference, and all the other are the same as embodiment 1.

Example 3

The organic template is a mixture of TMBA (Benzyltrimethylammonium) and DMHMI (dimethylhexamethyleneimine), and the molar ratio of the two is 1:1.

Example 4

The boron source is sodium borate, the silicon source is silica sol, and the organic template is DMHMI (dimethylhexamethyleneimine).

Example 5

The organic template is DABCO (1,4-diazabieyelo[2.2.2]octane).

Example 6

The organic template is TMAD (N, N, N', N'-tetramethylazodicarboxamide).

The molar composition of the product molecular sieve ECNU-3 is expressed as:

Example 3 GeO ₂ : 0.11B ₂ O ₃ : 1.9SiO ₂ , x=0.11, y=1.9.

The XRD pattern of the product molecular sieve ECNU-3 is similar to that shown in Figure 1.

Example 4 GeO ₂ : 0.12B ₂ O ₃ : 1.8SiO ₂ , x=0.12, y=1.8.

The XRD pattern of the product molecular sieve ECNU-3 is similar to that shown in Figure 1.

Example 5 GeO ₂ : 0.12B ₂ O ₃ : 1.7SiO ₂ , x=0.12, y=1.7.

The XRD pattern of the product molecular sieve ECNU-3 is similar to that shown in Figure 1.

Example 6 GeO ₂ : 0.10B ₂ O ₃ : 1.9SiO ₂ , x=0.10, y=1.9.

The XRD pattern of the product molecular sieve ECNU-3 is similar to that shown in Figure 1.

Example 7

Implementation process is except following difference, and all the other are the same as embodiment 1.

Fluorine source is hydrofluoric acid

Preparation of the first step reaction mixture

GeO ₂ in germanium source: B ₂ O ₃ in boron source: SiO ₂ in silicon source: F- in fluorine source: organic template agent: H ₂ O in molar ratio: 1:6:9:5:13 : 100 to prepare the reaction mixture, first dissolve the germanium source and the boron source in the organic template solution, stir evenly, add the silicon source, continue to stir evenly, add the fluorine source, continue to stir evenly, and obtain the reaction mixture.

The molar composition of the product molecular sieve ECNU-3 is represented by the anhydrous form of the oxide as GeO ₂ :0.25B ₂ O ₃ :8.2SiO ₂ , x=0.25, y=8.2.

The XRD pattern of the product molecular sieve ECNU-3 is similar to that shown in Figure 1.

Example 8

The implementation process is the same as in Example 7 except the following differences.

The fluorine source is sodium fluoride, the organic template is a mixture of TMBA (Benzyltrimethylammonium) and DABCO (1,4-diazabicyclo[2.2.2]octane), and the molar ratio of the two is 1:1.

The molar composition of the product molecular sieve ECNU-3 is represented by the anhydrous form of the oxide as GeO ₂ :0.24B ₂ O ₃ :8.5SiO ₂ , x=0.27, y=8.5.

The XRD pattern of the product molecular sieve ECNU-3 is similar to that shown in Figure 1.

Example 9

Implementation process is except following difference, and all the other are the same as embodiment 1.

The titanium source is tetrabutyl titanate.

Preparation of the first step reaction mixture

GeO ₂ in germanium source: B ₂ O ₃ in boron source: SiO ₂ in silicon source: TiO ₂ in titanium source: organic template agent: H ₂ O in molar ratio: 1:0.66:2:0.1:2.66 : 21 to prepare the reaction mixture, first dissolve the titanium source, the germanium source and the boron source in the organic template solution, stir evenly, add the silicon source, and continue to stir evenly to obtain the reaction mixture.

The molar composition of the product molecular sieve ECNU-3 is represented by the anhydrous form of the oxide as GeO ₂ :0.11B ₂ O ₃ :1.7SiO ₂ :0.08TiO ₂ , x=0.11, y=1.7, Z=0.08.

The XRD pattern of the product molecular sieve ECNU-3 is similar to that shown in Figure 1.

Example 10

Implementation process is except following difference, all the other are with embodiment 7,

The source of titanium is titanium tetrachloride.

Preparation of the first step reaction mixture

GeO ₂ in germanium source: B ₂ O ₃ in boron source: SiO ₂ in silicon source: TiO ₂ in titanium source: F- in fluorine source: organic template agent: H ₂ O is 1: 6:7:0.35:5:13:100 Prepare the reaction mixture: first dissolve the titanium source, germanium source, and boron source in the organic template solution, stir evenly, add the silicon source, continue to stir evenly, add the fluorine source, and continue to stir uniform to obtain a reaction mixture.

The molar composition of the product molecular sieve ECNU-3 is represented by the anhydrous form of the oxide as GeO ₂ :0.20B ₂ O ₃ :6.3SiO ₂ :0.27TiO ₂ , x=0.20, y=6.3, z=0.27.

The XRD pattern of the product molecular sieve ECNU-3 is similar to that shown in Figure 1.

Example 11

Implementation process is except following difference, and all the other are the same as embodiment 1.

The aluminum source is sodium metaaluminate.

Preparation of the first step reaction mixture

_GeO2 in germanium source: _B2O3 in _boron source _: SiO2 in silicon source: _Al2O3 in _aluminum source: organic template agent: _H2O in molar ratio: 1:0.66:2:0.2 : 2.66: 21 To prepare the reaction mixture, first dissolve the aluminum source, the germanium source and the boron source in the organic template solution, stir evenly, add the silicon source, and continue to stir evenly to obtain the reaction mixture.

The molar composition of the product molecular sieve ECNU-3 is represented by the anhydrous form of the oxide as GeO ₂ :0.11B ₂ O ₃ :1.8SiO ₂ :0.15Al ₂ O ₃ , x=0.11, y=1.8, _=0.15.

The XRD pattern of the product molecular sieve ECNU-3 is similar to that shown in Figure 1.

Example 12

The implementation process is the same as in Example 7 except the following differences.

The aluminum source is activated alumina.

Preparation of the first step reaction mixture

GeO ₂ in germanium source: B ₂ O ₃ in boron source: SiO ₂ in silicon source: Al ₂ O ₃ in aluminum source: F- in fluorine source: organic template agent: H ₂ O in molar ratio 1: 6: 7: 1.2: 5: 13: 100 Prepare the reaction mixture: first dissolve the aluminum source, germanium source, and boron source in the organic template solution, stir evenly, add the silicon source, continue to stir evenly, add the fluorine source, Continue stirring evenly to obtain a reaction mixture.

The molar composition of the product molecular sieve ECNU-3 is represented by the anhydrous form of the oxide as GeO ₂ :0.18B ₂ O ₃ :6.1SiO ₂ :0.8Al ₂ O ₃ , x=0.18, y=6.1, _=0.8.

The XRD pattern of the product molecular sieve ECNU-3 is similar to that shown in Figure 1.

Example 13

The implementation process is the same as in Example 11 except for the following differences.

The iron source was ferric chloride.

Preparation of the first step reaction mixture

GeO ₂ in germanium source: B ₂ O ₃ in boron source: SiO ₂ in silicon source: Fe ₂ O ₃ in iron source: organic template agent: H ₂ O in molar ratio: 1:0.66:2:0.1 : 2.66: 21 To prepare the reaction mixture, first dissolve the germanium source, the iron source and the boron source in the organic template solution, stir evenly, add the silicon source, and continue to stir evenly to obtain the reaction mixture.

The molar composition of the product molecular sieve ECNU-3 is represented by the anhydrous form of the oxide as GeO ₂ :0.11B ₂ O ₃ :1.9SiO ₂ :0.07Fe ₂ O ₃ , x=0.11, y=1.9, _=0.07.

The XRD spectrum of the product molecular sieve Al-ECNU-3 is similar to that shown in Figure 1.

Example 14

The implementation process is the same as in Example 7 except the following differences.

The gallium source was gallium nitrate.

Preparation of the first step reaction mixture

GeO ₂ in the germanium source: B ₂ O ₃ in the boron source: SiO ₂ in the silicon source: Ga ₂ O ₃ in the gallium source: F- in the fluorine source: organic template agent: H ₂ O is 1: 6: 7: 0.8: 5: 13: 100 Prepare the reaction mixture: first dissolve the gallium source, germanium source, and boron source in the organic template solution, stir evenly, add the silicon source, continue to stir evenly, add the fluorine source, Continue stirring evenly to obtain a reaction mixture.

The molar composition of the product molecular sieve ECNU-3 is represented by the anhydrous form of the oxide as GeO ₂ :0.18B ₂ O ₃ :6.1SiO ₂ :0.52Ga ₂ O ₃ , x=0.18, y=6.1, _=5.2.

The XRD pattern of the product molecular sieve ECNU-3 is similar to that shown in Figure 1.

Example 15

Implementation process is except following difference, and all the other are all the same with embodiment 1:

Preparation of the first step reaction mixture

A reaction mixture was prepared at a molar ratio of GeO ₂ in the germanium source: B ₂ O ₃ in the boron source: SiO ₂ in the silicon source: organic template: H ₂ O was 1:0:9:13:100.

The molar composition of the product molecular sieve ECNU-3 is represented by the anhydrous form of the oxide as GeO ₂ :8.7SiO ₂ , y=8.7.

The XRD pattern of the product molecular sieve ECNU-3 is similar to that shown in Figure 1.

Claims (6)

1. A molecular sieve ECNU-3, characterized in that the molecular sieve uses germanium, silicon, oxygen element or at least one element in germanium, silicon, oxygen element and boron, titanium, aluminum, iron, gallium element as its skeleton element , its molar composition is represented by the anhydrous form of the oxide as GeO ₂ :xB ₂ O ₃ :ySiO ₂ :zTiO ₂ :_M ₂ O ₃ , where M represents aluminum, iron, gallium, x=0～0.28, y=1.7 ～8.7, z=0～0.27, _=0～0.8, its XRD spectrogram contains the XRD spectral line shown in Table 1, Table 1 2θ/° d/A° I/I _o ×100 7.06±0.327.86±0.2410.52±0.1310.93±0.0816.36±0.2519.49±0.4120.49±0.3321.44±0.2321.93±0.0622.77±0.4226.87±0.3228.46±0.2829.02± 0.2233.05±0.35 12.51±0.0611.24±0.068.40±0.088.09±0.055.41±0.064.55±0.084.33±0.054.14±0.054.05±0.043.90±0.023.31±0.023.13±0.043.07± 0.042.71±0.03 wvsw-mmwwmw-mmmw-mwww ^* w: <20; m: 20-70; s: 70-90; vs: 90-100. 2. according to the described molecular sieve ECNU-3 of claim 1, it is characterized in that, this molecular sieve uses germanium, silicon, oxygen element as its skeleton element, and its molar composition is expressed as GeO ₂ :ySiO ₂ with the anhydrous form of oxide, y =1.7～8.7. 3. according to the described molecular sieve ECNU-3 of claim 1, it is characterized in that, this molecular sieve is its skeleton element with germanium, boron, silicon, titanium, oxygen element, and its molar composition is represented as GeO with the anhydrous form of oxide ₂ : xB ₂ O ₃ :ySiO ₂ :zTiO ₂ , x=0.11~0.20, y=1.7~6.3, z=0.08~0.27, molecular sieve skeleton Ti(IV) appears at the wavelength of 210~220nm in the UV-VIS spectrum The characteristic absorption peak is an active component of a catalytic oxidation catalyst for the preparation of hydrocarbon oxygenates. 4. according to the described molecular sieve ECNU-3 of claim 1, it is characterized in that, this molecular sieve is its skeleton element with germanium, boron, silicon, aluminum, oxygen element, and its molar composition is expressed as GeO with the anhydrous form of oxide ₂ : xB ₂ O ₃ :ySiO ₂ :_Al ₂ O ₃ , x＝0.11～0.18, y＝1.8～6.1, _＝0.07～0.8, the characteristic of molecular sieve skeleton Al-OH appears at the wavenumber of 3618cm ^-1 in the FTIR spectrum The vibration peak is an active component of a solid acid catalytic catalyst. 5. the synthetic method of the molecular sieve ECNU-3 described in claim 1,2,3 or 4, is characterized in that, operating steps: Preparation of the first step reaction mixture GeO ₂ in germanium source : B ₂ O ₃ in boron source : SiO ₂ in silicon source : TiO ₂ in titanium source : M ₂ O ₃ in M : organic template agent : F in fluorine source ^{- :} H ₂ O is prepared as 1:(0~6):(2~9):(0~0.35):(0~1.2):(2.66~13):(0~5):(21~100) The reaction mixture, the germanium source is germanium dioxide, the boron source is boric acid or borate, the silicon source is silicic acid, silica gel, silica sol or tetraalkyl silicate, and the titanium The source is tetraalkyl titanate, titanium halide, titanium oxide, the aluminum source is sodium metaaluminate, aluminum isopropoxide, aluminum hydroxide, activated alumina or aluminum salt, and the iron source is Ferric nitrate, ferric sulfate, ferric chloride, the gallium source is gallium nitrate, the fluorine source is sodium fluoride, ammonium fluoride, hydrofluoric acid, fluorosilicic acid and fluorosilicate, the organic The templating agent is at least one of phenyltrimethylammonium hydroxide, dimethylhexamethyleneamine, 1,4-diazocyclooctane and N,N-tetramethylazoamide. Dissolve the germanium source and the boron source in the organic template solution, stir evenly, add silicon source, titanium source, aluminum source, iron source, gallium source, fluorine source, and continue to stir evenly to obtain a reaction mixture; The second step of crystallization The reaction mixture prepared in the first step is hydrothermally crystallized at 130-200°C for 5 hours-20 days, filtered, washed and dried to obtain a crystallized product; The third step roasting Calcining the crystallized product obtained in the second step at 400-700° C. for 3-40 hours to obtain the product molecular sieve ECNU-3. 6. the synthetic method of molecular sieve ECNU-3 described in claim 4 is characterized in that, in the first step, GeO in molar ratio germanium source : B ₂ O ₃ in boron source: SiO in silicon _{source 2} : TiO ₂ in titanium source: M ₂ O ₃ in M: organic template: F ⁻ in fluorine source: H ₂ O is 1: (0.66～6): (2～7): (0.1～0.35 ): 0: (2.66～13): (0～5): (21～100) to prepare the reaction mixture; in the second step, the reaction mixture prepared in the first step is hydrothermally crystallized at 150～180 ℃ for 3 hours to 15 days; in the third step, calcining the crystallized product obtained in the second step at 500-650° C. for 5-20 hours.