EXTRA-LARGE PORE MOLECULAR SIEVE ZEO-1, ITS SYNTHESIS AND USE

Abstract

Provided are a ZEO-1 silicate molecular sieve having a new structure, a synthesis method therefor and the use thereof. An X-ray powder diffraction feature, a pore channel system and a topology feature of the ZEO-1 molecular sieve are characterized. Further, titanium atoms are successfully introduced in the framework of the ZEO-1 molecular sieve. The ZEO-1 molecular sieve of the present invention has a good thermal stability and can be used as an adsorbent or a catalyst.

Claims

1. A silicate molecular sieve comprising a molecular sieve has a chemical composition of (TiO.sub.2).sub.y.Math.(HAO.sub.2).sub.x.Math.SiO.sub.2, wherein A is a boron group element; 0x1.0; 0y<0.2, and wherein the crystal structure of the molecular sieve has a three-dimensional intersecting channel system of (16+12)(16+12)(16+12)-membered rings.

2. The molecular sieve according to claim 1, wherein the framework of the molecular sieve has the topological characteristics shown in the table below. TABLE-US-00004 T atom Coordination sequences No. N1 N2 N3 N4 N5 N6 N7 N8 N9 N10 N11 N12 Vertex symbols T1 4 12 17 27 42 62 85 109 136 161 205 247 5.5.5.6.5(2).12(4) T2 4 11 18 28 40 62 80 101 131 166 206 258 4.5(2).5.5.5.6 T3 4 9 16 26 41 59 80 106 132 159 201 250 4.5.4.5.4.12(2) T4 4 10 20 29 40 60 88 109 128 166 214 256 4.6.4.12(5).5.6(2) T5 4 11 16 25 43 60 84 115 139 161 196 242 4.5.5.6.5.12(4) T6 4 11 18 26 40 63 87 105 128 164 204 250 4.5(2).5.6(2).6.6(2) T7 4 11 18 28 43 61 80 105 138 165 207 251 4.6(2).5.6.5.12(6) T8 4 10 20 29 41 59 85 111 136 170 202 243 4.6.4.12(5).5.5 T9 4 11 18 26 40 60 88 113 132 158 196 250 4.5(2).5.5.5.6 T10 4 10 20 30 45 56 79 100 134 174 213 259 4.6.4.12(6).5.5 T11 4 9 17 29 40 58 81 108 141 167 197 238 4.4.4.12(5).5.5 T12 4 9 16 25 39 59 84 116 139 156 194 237 4.5.4.5.4.16(7) T13 4 9 16 25 39 60 85 112 135 157 196 244 4.5.4.6(2).4.12(2) T14 4 9 16 25 39 61 88 113 140 168 191 231 4.4.4.6(2).5.16(5) T15 4 9 17 28 40 60 85 106 130 163 204 251 4.4.4.12(5).5.6(3) T16 4 9 17 30 43 58 73 102 135 167 205 258 4.4.4.12(6).5.5 T17 4 9 16 26 41 62 83 103 132 168 203 247 4.4.4.6(2).5.16(5) T18 4 9 16 25 39 63 90 110 132 165 200 240 4.4.4.6(2).6(3).16(4) T19 4 12 19 30 42 65 76 100 132 175 220 248 5.5.5(2).12(7).6.6 T20 4 12 15 24 42 60 92 120 133 155 188 250 5.5.5.5.5(2).16(8) T21 4 10 16 25 44 61 78 108 143 163 196 244 4.4.6.6.6(2).12(5)

3. (canceled)

4. The molecular sieve according to claim 1, wherein the molecular sieve has the X-ray powder diffraction characteristics shown in the table below. TABLE-US-00005 d-Spacing () Relative intensity 21.64 0.27 m 15.33 0.13 w 12.62 0.09 vs 10.87 0.07 w 8.25 0.04 m 7.95 0.04 w 7.23 0.03 mw 6.85 0.03 w 6.28 0.02 w 6.00 0.02 w 5.41 0.02 w 5.20 0.02 w 5.12 0.01 w 5.00 0.01 w 4.75 0.01 w 4.75 0.01 w 4.61 0.01 mw 4.35 0.01 mw 4.22 0.01 w 4.11 0.01 s 4.04 0.01 w 3.90 0.01 mw 3.74 0.01 w 3.57 0.01 w 3.53 0.01 w 3.48 0.01 w 3.47 0.01 w 3.42 0.01 w 3.36 0.01 w 3.32 0.01 mw 3.10 0.01 w 3.10 0.01 w 3.02 0.01 w 2.90 0.01 w 2.78 0.01 w 2.17 0.01 w

5. A method for the synthesis of the molecular sieve according to claim 1, the method comprising: (1) mixing a silicon source, a boron group element compound, an organic template, water, a mineralizer and optionally a titanium source to obtain a mixture; (2) crystallizing the mixture; (3) calcining the crystallized product to remove the template, wherein the organic template has a tetrahedral spatial configuration represented by the following general formula: ##STR00010## wherein, R.sub.1 is cyclohexyl; R.sub.2 and R.sub.3 are phenyl or cyclohexyl; R.sub.4 is C.sub.1-8 alkyl; X is phosphorus or nitrogen.

6. The method according to claim 5, wherein the organic template is any one or more selected from the following: ##STR00011##

7. The method according to claim 5, further comprising: (1) under stirring, mixing a silicon source, a boron group element compound, an organic template, water, a mineralizer and optionally a titanium source uniformly in proportions, and forming a reaction gel by the obtained mixture with a chemical composition of rROH:aHF:yTiO.sub.2:xA.sub.2O.sub.3:SiO.sub.2:wH.sub.2O, wherein R represents the positive charge group of the organic template; A is a boron group element; the corresponding value intervals of r, a, x and w are: r=0.1-5.0, a=0-5.0, x=0-1.0, y=0-0.2, w=1-100; (2) placing the reaction gel under an infrared lamp or in an oven, after the removal of excess solvent, transferring the reaction gel to a stainless steel autoclave to react for 1-60 days, under sealed condition and at a temperature of 80-240 C., for crystallization; (3) after washing and drying the crystallized product, calcining it for 2-5 hours in an air atmosphere at 400-650 C. to remove the template.

8. The method according to claim 5, wherein the silicon source is at least one selected from the group consisting of silicic acid, silica gel, silica sol, tetraalkyl orthosilicate and water glass.

9. The method according to claim 5, wherein the boron group element compound is at least one selected from the group consisting of sodium metaaluminate, aluminum isopropoxide, aluminum sulfate hexadecahydrate, aluminum hydroxide and boric acid.

10. The method according to claim 5, wherein the titanium source is one or a mixture of two or more of tetrabutyl orthotitanate, titanium tetrachloride, titanium trichloride, and titanium sulfate.

11. The method according to claim 5, wherein the mineralizer is OH.sup. from an alkaline aqueous solution of the organic template, or F.sup. from additionally added HF or NH.sub.4F.

12. The method according to claim 5, wherein crystallization conditions in step (2) include: crystallization temperature of 80 to 240 C.; and crystallization time of 1 to 60 days.

13. The method according to claim 5, wherein the mixture further comprises a seed crystal.

14. The method according to claim 13, wherein the seed crystal comprises the molecular sieve having the chemical composition of (TiO.sub.2).sub.y.Math.(HAO.sub.2).sub.x.Math.SiO.sub.2, wherein A is a boron group element; 0x1.0; 0y<0.2, and wherein the crystal structure of the molecular sieve has the three-dimensional intersecting channel system of (16+12)(16+12)(16+12)-membered rings.

15. A molecular sieve composition, comprising the molecular sieve according to claim 1, and a binder.

16. (canceled)

17. A molecular sieve composition, comprising the molecular sieve synthesized according to the method of claim 5, and a binder.

Description

DESCRIPTION OF DRAWINGS

[0030] FIG. 1 is an X-ray powder diffraction pattern of the ZEO-1 molecular sieve with no introduction of titanium in the present invention before and after calcination at temperatures of 600 C. and 1000 C. to remove the template (Wavelength: Cu K).

[0031] FIG. 2 is an X-ray diffraction pattern of the ZEO-1 molecular sieve as-synthesized with no introduction of titanium in the present invention (synchrotron radiation with wavelength 0.457926 angstroms).

[0032] FIG. 3 is a scanning electron micrograph (SEM) of the ZEO-1 molecular sieve with no introduction of titanium in the present invention.

[0033] FIG. 4 is a diagram of the channel structure of the ZEO-1 molecular sieve of the present invention.

[0034] FIG. 5 is an X-ray diffraction pattern of the titanosilicate ZEO-1 molecular sieve (in-situ synthesized sample and the calcined one) of the present invention (Wavelength: Cu K).

[0035] FIG. 6 is a scanning electron micrograph (SEM) of the titanosilicate ZEO-1 molecular sieve of the present invention.

[0036] FIG. 7 is the ultraviolet spectrogram of the titanosilicate ZEO-1 molecular sieve (in-situ synthesized sample and the calcined one) of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

[0037] The crystal structure of the ZEO-1 molecular sieve of the present invention is shown in FIG. 4. It can be seen from FIG. 4 that in both the a-axis direction and b-axis direction of the ZEO-1 crystal structure, there are penetrating 16- and 12-membered ring channels. In addition, there are 16- and 12-membered ring channels in the direction near the (a+b+c) axis of the ZEO-1 crystal structure. Therefore, the structure is described as a three-dimensional intersecting channel system of (16+12)(16+12)(16+12)-membered rings.

[0038] The ZEO-1 molecular sieve of the present invention is subjected to structural analysis and topology analysis. The molecular sieve framework structure has 21 topologically independent T atoms, 43 topologically different edges (lines constituted by adjacent T atom and T atom), 41 topologically different planes (planes constituted by T atoms), and 19 topologically different tiles constituted by T atoms. Among them, the topological properties (including coordination sequences and vertex symbols) of the 21 topologically independent T atoms of the framework structure of the ZEO-1 material are shown in Table 1.

[0039] Among the 19 different tiles in the framework structure of the ZEO-1 molecular sieve, there are three kinds of supercage structures, that is, the first supercage structure built by four 16-membered ring, the second supercage structure with two 16-membered ring and two 12-membered ring, and the third supercage structure containing four 12-membered ring. Compared with the supercage in Zeolite Y (structure code: FAU) which has four 12-membered ring (this supercage is also the important catalytic center of Zeolite Y), ZEO-1 has larger pore size, a larger available volume and a richer channel diversity.

[0040] The ZEO-1 molecular sieve of the present invention after calcining has a chemical composition of (TiO.sub.2).sub.y(HAO.sub.2).sub.x.Math.SiO.sub.2, wherein A is a boron group element, preferably Al or B, 0x1.0, preferably 0x0.5, more preferably 0x<0.2, most preferably 0.01x0.1, 0y<0.2, preferably 0.01y0.1.

[0041] After being calcined in air at 1000 C. for 3 hours to remove molecules of the template, the ZEO-1 molecular sieve of the present invention still maintains a stable framework (as shown in FIG. 2), which shows a better stability compared with the other reported extra-large pore molecular sieve materials. Meanwhile, heteroatoms such as aluminum, boron and the like can be directly introduced into the framework of the molecular sieve. These characteristics endow the molecular sieve material with potential application prospects in the fields of adsorption, separation, catalysis, etc.

[0042] The X-ray diffraction pattern of the titanium-containing ZEO-1 molecular sieve of the present invention is shown in FIG. 5. Comparing with the X-ray diffraction pattern of the ZEO-1 molecular sieve in FIG. 1, similar position and intensity of the diffraction peaks can be observed, indicating that the obtained titanosilicate material possesses the structure of ZEO-1 zeolite.

[0043] The SEM images of the titanium-containing ZEO-1 molecular sieve of the present invention are shown in FIG. 6, which indicates that the as-synthesized titanium-containing ZEO-1 molecular sieve has uniform particle size and good crystallinity without impurities such as amorphous compounds or anatase. Its ultraviolet-visible spectrum is shown in FIG. 7. The titanium-containing ZEO-1 molecular sieves before and after calcination both have a strong absorption peak at about 220 nm, corresponding to the Ti atom in tetra-coordinated state in the molecular sieve framework, proving that Ti atoms have been successfully introduced into the ZEO-1 molecular sieve framework.

[0044] In the method for the preparation of the ZEO-1 molecular sieve of the present invention, specific examples of the organic templates include but are not limited to any one or more shown in the following Table 3:

TABLE-US-00003 TABLE 3 Examples of organic templates No. Structural diagram 1 [00002] 2 [00003] 3 [00004] 4 [00005] 5 [00006] 6 [00007] 7 [00008] 8 [00009]

[0045] The organic template is preferably any one or more selected from the group consisting of template 1, template 6, template 7 and template 8, more preferably any one or more selected from the group consisting of template 6 and template 8.

[0046] The method for the synthesis of the ZEO-1 molecular sieve of the present invention more specifically comprises: [0047] (1) under static or dynamic stirring, a silicon source, a boron group element compound, an organic template, water, a mineralizer and optionally a titanium source were mixed uniformly in proportions and a reaction gel was formed with a chemical composition of rROH:aHF:yTiO.sub.2:xA.sub.2O.sub.3:SiO.sub.2:wH.sub.2O, wherein R represents the organic template cation; A is a boron group element, preferably Al or B; the corresponding value intervals of r, a, x and w are: r=0.1-5.0, a=0-5.0, x=0-1.0, y=0-0.2. w=1-100, preferably r=0.1-5.0, a=0-5.0, x=0-0.1, y=0-0.2, w=1-100, more preferably r=0.1-2.0, a=0-2.0, x=0.005-0.05, y=0.01-0.1, w=5-30; [0048] (2) the reaction gel was placed under an infrared lamp or in an oven in order to remove the excess solvent, then the gel was transferred into a stainless steel autoclave at a temperature of 80-240 C., preferably 120-220 C., for 1-60 days, preferably 2-45 days, under sealed condition for crystallization; [0049] (3) after crystallization, after washing, centrifuging, and drying to get the as-synthesized product. The as-synthesized sample was then calcined for 2-5 hours in air at 400-650 C. to remove the template.

[0050] The silicon source can be at least one selected from the group consisting of silicic acid, silica gel, silica sol, tetraalkyl orthosilicate and water glass, preferably water glass, silica sol or tetraethyl orthosilicate. The boron group element compound can be at least one selected from the group consisting of sodium metaaluminate, aluminum isopropoxide, aluminum sulfate hexadecahydrate, aluminum hydroxide and boric acid, preferably sodium metaaluminate, aluminum isopropoxide, aluminum sulfate hexadecahydrate 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.sup. from an alkaline solution of the organic template, or F.sup. from additionally added HF or NH.sub.4F. The addition of a mineralizer can speed up the crystallization of molecular sieve and may be beneficial for structure direction. The preparation method of the present invention can obtain the ZEO-1 molecular sieve of the present invention under both neutral condition (using F.sup. as the mineralizer) and alkaline condition (HF free, using OH.sup. as the mineralizer).

[0051] In the preparation method of the present invention, germanium or germanium-containing compounds are not used.

[0052] The various materials can be added and mixed in any order. For example, firstly a boron group element (such as Al or B) can be added to an obtained alkaline solution of template to be stirred and dissolved, and then a suitable silicon source and titanium source can be added. If necessary, a mineralizer is added after being stirred uniformly, and the materials are heated under an infrared lamp or in an oven to remove the excess solvent in the system to obtain a target gel.

[0053] Before the preparation of the reaction gel, all of the organic cationic templates can be exchanged into the hydroxide form via an ion exchange resin, and their concentration is calibrated by 0.1M hydrochloric acid solution for later use, or they may be introduced directly in the form of a chloride salt, a bromide salt or an iodide salt.

[0054] In step (2), the temperature of the oven may be, for example, 80 C.

[0055] Crystallization conditions may include, for example: crystallization temperature of 80 C. to 240 C., preferably 120 C. to 220 C., more preferably 140 C. to 210 C.; and crystallization time of 1 to 60 days, preferably 2 to 45 days, more preferably 3 to 30 days.

[0056] The mixture in the preparation method of the present invention may further comprise a seed crystal. The content of the seed crystal may be 0.01 ppm by weight to 10000 ppm by weight. The ZEO-1 molecular sieve of the present invention can be used as seed crystal. The presence of the seed crystal can speed up the reaction process and reduce the reaction cost.

[0057] In step (3), washing, centrifuging 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 done by oven drying.

EXAMPLES

[0058] In order to illustrate the present invention more clearly, the following examples are provided. These examples do not limit the protection scope of the present invention in any way.

Example 1: Synthesis of Template

[0059] Template 6 was taken as an example to illustrate the general process for the synthesis of a template. 28.04 g of tricyclohexylphosphine and 150 ml of acetonitrile were mixed in a 250 ml round bottom flask. At room temperature, 21.29 g of methyl iodide was added dropwise to the mixture. The system was kept for two days under stirring at room temperature, and the solvent was removed from the mixture by rotary evaporation to obtain a crude product, which was recrystallized with ethanol to obtain 40.55 g of product, with a yield of 96%.The product was characterized by liquid NMR (D20) and electrospray mass spectrometry, and confirmed to be the target compound.

[0060] The resulting product was dispersed in 400 mL of deionized water, and the pretreated 717 strong base-type anion exchange resin (manufacturer: Sinopharm Group, China) was used for anion exchange in a column in order to obtained aqueous solution of template agent 6. An appropriate amount of this solution was weighed, and titrated with a 0.1 mol/L solution of hydrochloric acid, using phenolphthalein as an indicator. The titrated structure confirmed an exchange ratio from iodide salt to hydroxide radical up to 97%.

Example 2: Preparation of ZEO-1 Molecular Sieve

Example 2-1

[0061] According to the molar ratio of 0.5 ROH:0.5 HF:0.01 Al.sub.2O.sub.3:SiO.sub.2:5 H.sub.2O, a gel for the synthesis of molecular sieve was prepared by the following steps: an appropriate amount of the solution of template in Example 1 after exchange was weighed, 0.04 mmol (0.008 g) of aluminum isopropoxide powder was add thereto, and stirred for about half an hour, and then 2 mmol (0.417 g) of tetraethyl orthosilicate was added, and stirred at room temperature for about two hours so that tetraethyl orthosilicate was completely dissolved, followed by adding a corresponding amount of a solution of hydrofluoric acid according to the above ratio and stirring uniformly, the mixed gel was placed under an infrared lamp or in an oven at 80 C., to remove the excess solvent to the theoretical weight. The finally obtained mixture gel was transferred to a 5 mL stainless steel autoclave with Teflon liner, and crystallized at 175 C. for 28 days under sealed condition, the product was washed twice with water and twice with ethanol, and oven dried for use. The product was directly subjected to phase identification by X-ray powder diffraction, and the pattern was confirmed as that of ZEO-1. An appropriate amount of the sample was calcined in a muffle furnace at 600 C. in air for 2 hours to remove the template, the product was washed with water, centrifuged, and dried. The elemental analysis showed that the Si/Al ratio was 20.5, and its molecular formula was (HAlO.sub.2).sub.0.047.Math.SiO.sub.2.

Example 2-2

[0062] According to the molar ratio of 0.5 ROH:0.5 HF:0.02 Al.sub.2O.sub.3:SiO.sub.2:7 H.sub.2O, a gel for the synthesis of molecular sieve was prepared by the following steps: an appropriate amount of the solution of template in Example 1 after exchange was weighed, 0.08 mmol (0.016 g) of aluminum isopropoxide powder was add thereto, and stirred for about half an hour, and then 2 mmol (0.417 g) of tetraethyl orthosilicate was added, and stirred at room temperature for about two hours so that tetraethyl orthosilicate was completely dissolved, followed by adding a corresponding amount of a solution of hydrofluoric acid according to the above ratio and stirring uniformly, the mixed gel was placed under an infrared lamp or in an oven at 80 C., to remove the excess solvent to the theoretical weight. The finally obtained mixture gel was transferred to a 5 mL stainless steel autoclave with Teflon liner, and crystallized at 190 C. for 7 days under sealed condition, the product was washed twice with water and twice with ethanol, and oven dried for use. The product was directly subjected to phase identification by X-ray powder diffraction, and the pattern was confirmed as that of ZEO-1. An appropriate amount of the sample was calcined in a muffle furnace at 600 C. in air for 2 hours to remove the template, the product was washed with water, centrifuged, and dried. The elemental analysis showed that the Si/Al ratio was 14.6, and its molecular formula was (HAlO.sub.2).sub.0.064.Math.SiO.sub.2.

Example 2-3

[0063] According to the molar ratio of 0.5 ROH:0.01 Al.sub.2O.sub.3:SiO.sub.2:10 H.sub.2O, a gel for the synthesis of molecular sieve was prepared by the following steps: an appropriate amount of the solution of template in Example 1 after exchange was weighed, 0.04 mmol (0.008 g) of aluminum isopropoxide powder was add thereto, and stirred for about half an hour, and then 2 mmol (0.417 g) of tetraethyl orthosilicate was added, and stirred at room temperature for about two hours so that tetraethyl orthosilicate was completely dissolved, the mixed gel was placed under an infrared lamp or in an oven at 80 C., to remove the excess solvent to the theoretical weight. The finally obtained mixture gel was transferred to a 15 mL stainless steel autoclave with Teflon liner, and crystallized at 175 C. for 30 days under sealed condition, the product was washed twice with water and twice with ethanol, and oven dried for use. The product was directly subjected to phase identification by X-ray powder diffraction, and the pattern was confirmed as that of ZEO-1. An appropriate amount of the sample was calcined in a muffle furnace at 600 C. in air for 2 hours to remove the template, the product was washed with water, centrifuged, and dried. The elemental analysis showed that the Si/Al ratio was 20.8, and its molecular formula was (HAlO.sub.2).sub.0.046.Math.SiO.sub.2.

Example 2-4

[0064] According to the molar ratio of 0.5 ROH:0.0167 Al.sub.2O.sub.3:SiO.sub.2:10 H.sub.2O, a gel for the synthesis of molecular sieve was prepared by the following steps: an appropriate amount of the solution of template in Example 1 after exchange was weighed, 0.067 mmol (0.013 g) of aluminum isopropoxide powder was add thereto, and stirred for about half an hour, and then 2 mmol (0.417 g) of tetraethyl orthosilicate was added, and stirred at room temperature for about two hours so that tetraethyl orthosilicate was completely dissolved, the mixed gel was placed under an infrared lamp or in an oven at 80 C., to remove the excess solvent to the theoretical weight. The finally obtained mixture gel was transferred to a 15 mL stainless steel autoclave with Teflon liner, and crystallized at 190 C. for 15 days under sealed condition, the product was washed twice with water and twice with ethanol, and oven dried for use. The product was directly subjected to phase identification by X-ray powder diffraction, and its pattern was confirmed as that of ZEO-1. An appropriate amount of the sample was calcined in a muffle furnace at 600 C. in air for 2 hours to remove the template, the product was washed with water, centrifuged, and dried The elemental analysis showed that the Si/Al ratio was 14.5, and its molecular formula was (HAlO.sub.2).sub.0.065.Math.SiO.sub.2.

[0065] Examples 2-1 to 2-4 all obtained a molecular sieve material with intact structure after calcination (600 C. or 1000 C.), indicating that its structure was stable. The X-ray powder diffraction patterns of the as-synthesized powder sample of the molecular sieve and that after high-temperature calcination were shown in FIG. 1 and FIG. 2. The crystals of ZEO-1 sample with appropriate size was selected, and the scanning electron microscope photograph was shown in FIG. 3.

Example 2-5

[0066] The molecular sieves of Examples 2-1 to 2-4 were subjected to continuous rotation electron diffraction (cRED) test, and the structural analysis results showed that the ZEO-1 molecular sieve structure had tetragonal symmetry with I4.sub.1/amd space group, the unit cell parameters obtained after refinement of the synchrotron radiation diffraction with a wavelength of 0.457926 angstroms (FIG. 2) were: a=b=43.50217(10) , c=24.94918(9) , V=47214.8(3) .sup.3.

[0067] Topological analysis was performed using the crystallographic information file (CIF file) obtained after the cRED test. The topological analysis software was based on ToposPro 5.3.0.2, and the analysis process and method were based on the operation manual given on the official website of the software (see ToposPro official website: https://topospro.com/software/).

[0068] The analysis results showed that the framework structure of the molecular sieve had 21 topologically independent T atoms, 43 topologically different edges, 41 topologically different planes, and 19 topologically different tiles constituted by T atoms. The more specific topological characteristics of the framework structure of ZEO-1 molecular sieve were shown in Table 2.

Example 3: Preparation of Titanium-Containing ZEO-1 Molecular Sieve

Example 3-1

[0069] According to the molar ratio of SiO.sub.2:0.02 Al.sub.2O.sub.3:0.04 TiO.sub.2:0.5 ROH:20 H.sub.2O, a gel for the synthesis of molecular sieve was prepared by the following steps: an appropriate amount of the basic solution of template 6 after exchange was weighed, 0.08 mmol (0.016 g) of aluminum isopropoxide powder was add thereto, and stirred for about half an hour, and then 2 mmol (0.417 g) of tetraethyl orthosilicate was added, and stirred at room temperature for about two hours so that tetraethyl orthosilicate was completely dissolved, finally 0.08 mmol (0.027 g) of tetrabutyl orthotitanate was added and stirred overnight, the mixed gel was placed under an infrared lamp or in an oven at 80 C., to remove the excess solvent to the theoretical weight. The finally obtained mixture gel was transferred to a 15 mL stainless steel autoclave with Teflon liner, and crystallized at 190 C. for 30 days under sealed condition, the product was washed twice with water and twice with ethanol, and oven dried for use. The product was directly subjected to phase identification by X-ray powder diffraction, and the pattern was confirmed as that of ZEO-1. An appropriate amount of the sample was calcined in a muffle furnace at 600 C. in air for 2 hours to remove the template, the sample was washed with water and dried. The elemental analysis showed that its molecular formula was H.sub.0.04Al.sub.0.04Ti.sub.0.04Si.sub.0.92O.sub.2.

Example 3-2

[0070] According to the molar ratio of SiO.sub.2:0.01 Al.sub.2O.sub.3:0.02 TiO.sub.2:0.5 ROH:15 H.sub.2O, a gel for the synthesis of molecular sieve was prepared by the following steps: an appropriate amount of the basic solution of template 6 after exchange was weighed, 0.04 mmol (0.008 g) of aluminum isopropoxide powder was add thereto, and stirred for about half an hour, and then 2 mmol (0.417 g) of tetraethyl orthosilicate was added, and stirred at normal temperature for about two hours so that tetraethyl orthosilicate was completely dissolved, finally 0.04 mmol (0.014 g) of tetrabutyl orthotitanate was added and stirred overnight, the mixed gel was placed under an infrared lamp or in an oven at 80 C., to remove the excess solvent to the theoretical weight. The finally obtained mixture gel was transferred to a 15 mL stainless steel autoclave with Teflon liner, and crystallized at 175 C. for 30 days under sealed condition, the product was washed twice with water and twice with ethanol, and oven dried for use. The product was directly subjected to phase identification by X-ray powder diffraction, and its pattern was confirmed as that of ZEO-1. An appropriate amount of the sample was calcined in a muffle furnace at 600 C. in air for 2 hours to remove the template, the sample was washed with water and dried. The elemental analysis showed that its molecular formula was H.sub.0.02Al.sub.0.02Ti.sub.0.02Si.sub.0.96O.sub.2.

Example 3-3

[0071] According to the molar ratio of SiO.sub.2:0.02 Al.sub.2O.sub.3:0.02 TiO.sub.2:0.5 ROH:0.5 HF:7 H.sub.2O, a gel for the synthesis of molecular sieve was prepared by the following step: an appropriate amount of the basic solution of template 6 after exchange was weighed, 0.08 mmol (0.016 g) of aluminum isopropoxide powder was add thereto, and stirred for about half an hour, and then 2 mmol (0.417 g) of tetraethyl orthosilicate was added, and stirred at room temperature for about two hours so that tetraethyl orthosilicate was completely dissolved, followed by adding 0.04 mmol (0.014 g) of tetrabutyl orthotitanate and stirring overnight, finally a corresponding amount of a hydrofluoric acid solution was added according to the above ratio and stirred uniformly, the mixed gel was placed under an infrared lamp or in an oven at 80 C., to remove the excess solvent to the theoretical weight. The finally obtained mixture gel was transferred to a 15 mL stainless steel autoclave with Teflon liner, and reacted at 175 C. for 30 days under sealed condition, the product was washed twice with water and twice with ethanol, and oven dried for use. The product was directly subjected to phase identification by X-ray powder diffraction, and the pattern was confirmed as which of ZEO-1. An appropriate amount of the sample was calcined in a muffle furnace at 600 C. in air for 2 hours to remove the template, the sample was washed with water and dried The elemental analysis showed that its molecular formula was H.sub.0.04Al.sub.0.04Ti.sub.0.02Si.sub.0.94O.sub.2.

Example 3-4

[0072] According to the molar ratio of SiO.sub.2:0.02 B.sub.2O.sub.3:0.04 TiO.sub.2:0.5 ROH:10 H.sub.2O, a gel for the synthesis of molecular sieve was prepared by the following steps: an appropriate amount of the basic solution of template 6 after exchange was weighed, 0.08 mmol (0.005 g) of boric acid was add thereto, and stirred for about half an hour, and then 2 mmol (0.417 g) of tetraethyl orthosilicate was added, and stirred at room temperature for about two hours so that tetraethyl orthosilicate was completely dissolved, finally 0.08 mmol (0.027 g) of tetrabutyl orthotitanate was added and stirred overnight, the mixed gel was placed under an infrared lamp or in an oven at 80 C., to remove the excess solvent to the theoretical weight. The finally obtained mixture gel was transferred to a 15 mL stainless steel autoclave with Teflon liner, and reacted at 190 C. for 30 days under sealed condition, the product was washed twice with water and twice with ethanol, and oven dried for use. The product was directly subjected to phase identification by X-ray powder diffraction, and its pattern was compared and confirmed as which of ZEO-1. An appropriate amount of the sample was calcined in a muffle furnace at 600 C. in air for 2 hours to remove the template, the sample was washed with water and dried. The elemental analysis showed that its molecular formula was H.sub.0.04B.sub.0.04Ti.sub.0.04Si.sub.0.92O.sub.2.

Example 3-5

[0073] According to the molar ratio of SiO.sub.2:0.02 B.sub.2O.sub.3:0.02 TiO.sub.2:0.5 ROH:15 H.sub.2O, a gel for the synthesis of molecular sieve was prepared by the following steps: an appropriate amount of the basic solution of template 6 after exchange was weighed, 0.08 mmol (0.005 g) of boric acid was add thereto, and stirred for about half an hour, and then 2 mmol (0.417 g) of tetraethyl orthosilicate was added, and stirred at room temperature for about two hours so that tetraethyl orthosilicate was completely dissolved, finally, 0.04 mmol (0.014 g) of tetrabutyl orthotitanate was added and stirred overnight, the mixed gel was placed under an infrared lamp or in an oven at 80 C., to remove the excess solvent to the theoretical weight. The finally obtained mixture gel was transferred to a 15 mL stainless steel autoclave with Teflon liner, and crystallized at 175 C. for 30 days under sealed condition, the product was washed twice with water and twice with ethanol, and oven dried for use. The product was directly subjected to phase identification by X-ray powder diffraction, and was compared and confirmed as which of ZEO-1. An appropriate amount of the sample was calcined in a muffle furnace at 600 C. in air for 2 hours to remove the template, the sample was washed with water and dried. The elemental analysis showed that its molecular formula was H.sub.0.04B.sub.0.04Ti.sub.0.02Si.sub.0.94O.sub.2.