CN109694091B - Preparation method of IWR/CDO cocrystallized zeolite molecular sieve - Google Patents
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- CN109694091B CN109694091B CN201710982592.5A CN201710982592A CN109694091B CN 109694091 B CN109694091 B CN 109694091B CN 201710982592 A CN201710982592 A CN 201710982592A CN 109694091 B CN109694091 B CN 109694091B
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- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
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Abstract
The invention relates to a synthesis method of an IWR/CDO cocrystallization zeolite molecular sieve. The invention adopts an organic template agent Choline hydroxide Choline YO2:X2O3:H2And (3) carrying out hydrothermal crystallization on the mixture at the temperature of 100-200 ℃ for 30-300 hours to obtain the porous IWR/CDO cocrystallized zeolite molecular sieve material, wherein Y is at least one tetravalent element and X is at least one trivalent framework element. The IWR/CDO co-crystallization molecular sieve is synthesized by using a cheap organic template, and the relative proportion of the two molecular sieves is adjusted within the range of 1-99%; the synthesis method is simple and easy to implement and convenient to popularize.
Description
Technical Field
The invention relates to a method for synthesizing a zeolite molecular sieve, in particular to a method for synthesizing an IWR/CDO cocrystallized zeolite molecular sieve.
Technical Field
Zeolitic molecular sieves are crystalline porous silicate materials that are widely used as adsorbents, ion exchangers, and industrial catalysts. At present, the molecular sieve topology approved by the international molecular sieve association has reached 235 species.
The IWR molecular sieve has a 12 x 10-membered ring channel structure, 12-membered ring straight channels along the c-axis direction, 12-membered ring zigzag channels along the a-axis direction, and 10-membered ring straight channels along the b-axis direction. The organic templating agent for preparing IWR molecular sieves is typically hexamethylene bis (trimethylammonium) hydroxide dication (US 7344696B).
The CDO molecular sieve has a pore channel structure with 8 multiplied by 8 membered rings, and the pore channel trends are in the directions of [010] and [001 ]. The CDO molecular sieve is a molecular sieve with a layered structure, can be converted from a plurality of silicate precursors, and comprises PLS-1(Angew. chem. int. Ed.,2004,43, 4892-containing 4896), UZM-17(US 7867474), RUB-48(Dalton trans.,2014,43, 10396-containing 10416), MCM-65(US 6869587) and the like, and organic templates adopted in the preparation process are tetramethylammonium, ethyltrimethylammonium, trimethylisopropylammonium, quinuclidine and the like.
Co-crystalline molecular sieves refer to co-crystals formed from two or more molecular sieves, or composite crystals having structural characteristics of two or more molecular sieves, such molecular sieves often having different properties than a single molecular sieve. Common cocrystallized molecular sieves such as ZSM-5/ZSM-11(CN 1137022A), MCM-22/ZSM-35(CN 1689972A), etc.
Disclosure of Invention
The invention aims to solve the problem that an IWR/CDO cocrystallization zeolite molecular sieve is not used in the prior art, and provides a synthetic method of the IWR/CDO cocrystallization zeolite molecular sieve. The method adopts a cheap organic template agent to synthesize the IWR/CDO cocrystallization zeolite molecular sieve, and particularly uses choline hydroxide as the template agent to synthesize the IWR/CDO cocrystallization zeolite molecular sieve.
The technical scheme adopted by the invention is as follows:
a synthetic method of IWR/CDO cocrystallization zeolite molecular sieve comprises the following steps: oxide YO of skeleton tetravalent element Y2Oxide X of skeleton trivalent element X2O3The organic template agent Choline hydroxide Choline and water are according to Choline: YO2:X2O3:H2Uniformly mixing O0.15-0.95: 1: 0-0.08: 2-28 in a molar ratio to obtain a mixture; performing hydrothermal crystallization on the mixture to obtain a crystallized product; and washing, separating, drying and calcining the crystallized product.
In the above technical scheme, the preferred molar ratio of each component of the reactant is Choline YO2:X2O3:H2O＝0.35～0.75:1:0～0.05:2.5～14。
In the technical scheme, the framework tetravalent element Y is one or a mixture of Si, Ge, Ti, Sn and Zr; the silicon source is at least one of water glass, silica sol, solid silica gel, gas-phase white carbon black, amorphous silica, diatomite, zeolite molecular sieve and tetraethyl orthosilicate; the germanium source is at least one of amorphous germanium dioxide or organic germanium ester; the titanium source is at least one selected from titanium sulfate, amorphous titanium dioxide and tetrabutyl titanate. The molar ratio of Si to Ge is preferably 0.05 to 100, and more preferably 0.2 to 20.
In the technical scheme, the framework trivalent element comprises one or more of Al, B, Ga, Fe, Cr and In; wherein the aluminum source comprises at least one of sodium metaaluminate, aluminum sulfate, aluminum nitrate, aluminum chloride, aluminum isopropoxide, pseudo-boehmite, zeolite molecular sieve or amorphous alumina; the boron source comprises at least one of boric acid, sodium tetraborate, amorphous boron oxide, potassium borate, sodium metaborate, ammonium tetraborate, and organoboron esters.
In the technical scheme, the crystallization temperature is 100-200 ℃, and more preferably 120-180 ℃. The crystallization time is 30 to 300 hours, preferably 45 to 195 hours.
In the above technical scheme, the washing, separation, drying and calcination of the crystallized product are carried out by the conventional washing, separation, drying and calcination means in the art.
The invention provides a synthesis method of the IWR/CDO cocrystallization molecular sieve for the first time, and simultaneously has the advantages of low price of the organic template agent and low synthesis cost; the weight percentage of the IWR molecular sieve in the co-crystallization molecular sieve is adjustable within the range of 1-99%; a plurality of elements such as Al, Ti, Zr, Fe and the like can be introduced into the framework to generate different catalytic active centers, thereby meeting the requirements of different catalytic reactions. The method has the advantages of simple synthesis steps, strong operability, wide synthesis range and convenience in popularization.
Drawings
FIG. 1 is an X-ray diffraction (XRD) pattern of a calcined sample obtained in example 1
FIG. 2 is a Scanning Electron Microscope (SEM) photograph of a calcined sample obtained in example 1
Detailed Description
The present invention will be described in further detail with reference to the following specific examples, but the present invention is not limited to the following examples.
[ example 1]
2.1g of germanium oxide was dissolved in 10.8g of 45 wt% aqueous choline hydroxide solution, 18.7g of tetraethyl orthosilicate (TEOS) and 0.41g of aluminum isopropoxide were added, and after hydrolysis was complete the vessel was left open to stir overnight to volatilize ethanol, propanol and some of the water until the reaction mixture reached the final molar composition.
The mixture is put into a crystallization kettle with a polytetrafluoroethylene lining and is placed in an oven at 150 ℃ for crystallization for 168 hours. And filtering, washing, drying and calcining the reacted solid to obtain the solid which is the IWR/CDO cocrystallized molecular sieve, wherein the proportion of the IWR molecular sieve is 65 percent. The XRD pattern of the sample is shown in FIG. 1, and the scanning electron micrograph is shown in FIG. 2.
[ example 2 ]
5.2g of germanium oxide were dissolved in 13.5g of 45 wt% aqueous choline hydroxide solution, 20.8g of tetraethyl orthosilicate (TEOS) were added and after hydrolysis was complete the vessel was left open to stir overnight to volatilize ethanol and some of the water until the reaction mixture reached the final molar composition.
The mixture is put into a crystallization kettle with a polytetrafluoroethylene lining and is placed in an oven at 170 ℃ for crystallization for 72 hours. And filtering, washing, drying and calcining the reacted solid to obtain the solid which is the IWR/CDO cocrystallized molecular sieve, wherein the proportion of the IWR molecular sieve is 5%.
[ example 3 ]
5.2g of germanium oxide was dissolved in 13.5g of 45 wt% aqueous choline hydroxide solution, and 20.8g of Tetraethylorthosilicate (TEOS) and 0.6g of HBeta molecular Sieve (SiO)2/Al2O325) the vessel was left to stir open overnight after hydrolysis was complete to volatilize ethanol and some water until the reaction mixture reached the final molar composition.
The mixture is put into a crystallization kettle with a polytetrafluoroethylene lining and is placed in a 160 ℃ oven for crystallization for 120 hours. And filtering the reacted solid, washing with distilled water, drying and calcining to obtain the solid of the IWR/CDO cocrystallized molecular sieve, wherein the IWR molecular sieve accounts for 77 percent.
[ example 4 ]
5.2g of germanium oxide was dissolved in 13.5g of 45% by weight aqueous choline hydroxide solution, and 11.44g of Tetraethylorthosilicate (TEOS) and 3.3g of HBeta molecular Sieve (SiO)2/Al2O325) the vessel was left to stir open overnight after hydrolysis was complete to volatilize ethanol and some water until the reaction mixture reached the final molar composition.
The mixture is put into a crystallization kettle with a polytetrafluoroethylene lining and is placed into an oven at 170 ℃ for crystallization for 144 hours. And filtering, washing, drying and calcining the reacted solid to obtain the solid which is the IWR/CDO cocrystallized molecular sieve, wherein the proportion of the IWR molecular sieve is 95%.
[ example 5 ]
5.2g of germanium oxide was dissolved in 13.5g of 45% by weight aqueous choline hydroxide solution, and 11.44g of Tetraethylorthosilicate (TEOS) and 3.3g of HBeta molecular Sieve (SiO)2/Al2O325) the vessel was left to stir open overnight after hydrolysis was complete to volatilize ethanol and some water until the reaction mixture reached the final molar composition.
The mixture is put into a crystallization kettle with a polytetrafluoroethylene lining and is put into an oven at 170 ℃ for crystallization for 48 hours. And filtering, washing, drying and calcining the reacted solid to obtain the solid which is the IWR/CDO cocrystallized molecular sieve, wherein the content of the IWR molecular sieve is 15%.
[ example 6 ]
5.2g of germanium oxide was dissolved in 13.5g of 45% by weight aqueous choline hydroxide solution, and 11.44g of Tetraethylorthosilicate (TEOS) and 3.3g of HBeta molecular Sieve (SiO)2/Al2O325) the vessel was left to stir open overnight after hydrolysis was complete to volatilize ethanol and some water until the reaction mixture reached the final molar composition.
The mixture is put into a crystallization kettle with a polytetrafluoroethylene lining and is placed in a 160 ℃ oven for crystallization for 72 hours. And filtering, washing, drying and calcining the reacted solid to obtain the solid which is the IWR/CDO cocrystallized molecular sieve, wherein the content of the IWR molecular sieve is 36%.
[ example 7 ]
5.2g of germanium oxide was dissolved in 13.5g of 45% by weight aqueous choline hydroxide solution, and 11.44g of Tetraethylorthosilicate (TEOS) and 3.3g of HBeta molecular Sieve (SiO)2/Al2O325) the vessel was left to stir open overnight after hydrolysis was complete to volatilize ethanol and some water until the reaction mixture reached the final molar composition.
The mixture is put into a crystallization kettle with a polytetrafluoroethylene lining and is put into a drying oven at 150 ℃ for crystallization for 96 hours. And filtering, washing, drying and calcining the reacted solid to obtain the solid which is the IWR/CDO cocrystallized molecular sieve, wherein the content of the IWR molecular sieve is 54 percent.
[ example 8 ]
5.2g of germanium oxide was dissolved in 13.5g of 45% by weight aqueous choline hydroxide solution, and 11.44g of Tetraethylorthosilicate (TEOS) and 3.3g of HBeta molecular Sieve (SiO)2/Al2O325) the vessel was left to stir open overnight after hydrolysis was complete to volatilize ethanol and some water until the reaction mixture reached the final molar composition.
The mixture is put into a crystallization kettle with a polytetrafluoroethylene lining and is placed in an oven at 140 ℃ for crystallization for 120 hours. And filtering, washing, drying and calcining the reacted solid to obtain the solid which is the IWR/CDO cocrystallized molecular sieve, wherein the content of the IWR molecular sieve is 80%.
[ example 9 ]
2.08g of germanium oxide was dissolved in 16g of 45 wt% aqueous choline hydroxide solution, and 8g of Ludox-AS-40 silica sol and 2.5g of USY molecular Sieve (SiO)2/Al2O337) the vessel was left to stir open overnight after hydrolysis was complete to volatilize some of the water until the reaction mixture reached the final molar composition.
The mixture is put into a crystallization kettle with a polytetrafluoroethylene lining and is placed into a 160 ℃ oven for crystallization for 144 hours. And filtering, washing, drying and calcining the reacted solid to obtain the solid which is the IWR/CDO cocrystallized molecular sieve, wherein the content of the IWR molecular sieve is 20%.
[ example 10]
1.05g of germanium oxide was dissolved in 18g of 45 wt% aqueous choline hydroxide solution, 4.8g of silica and 0.12g of amorphous alumina were added, and after stirring well, the vessel was left open to stir overnight to volatilize part of the water until the reaction mixture reached the final molar composition.
The mixture is put into a crystallization kettle with a polytetrafluoroethylene lining and is put into an oven at 180 ℃ for crystallization for 96 hours. And filtering, washing, drying and calcining the reacted solid to obtain the solid which is the IWR/CDO cocrystallized molecular sieve, wherein the content of the IWR molecular sieve is 25%.
[ example 11 ]
4.2g of germanium oxide was dissolved in 20.2g of 45 wt% aqueous choline hydroxide solution, 20.8g of tetraethyl orthosilicate, 0.245g of boric acid and 0.34g of tetrabutyl titanate were added, and after hydrolysis was complete the vessel was left open to stir overnight to volatilize ethanol, butanol and some of the water until the reaction mixture reached the final molar composition.
The mixture is put into a crystallization kettle with a polytetrafluoroethylene lining and is placed in an oven at 150 ℃ for crystallization for 168 hours. And filtering, washing, drying and calcining the reacted solid to obtain the solid which is the IWR/CDO cocrystallized molecular sieve, wherein the content of the IWR molecular sieve is 85 percent.
Comparative example 1
2.1g of germanium oxide was dissolved in 29.5g of 25 wt% aqueous tetraethylammonium hydroxide, 18.7g of Tetraethylorthosilicate (TEOS) and 0.41g of aluminum isopropoxide were added, and after hydrolysis was complete the vessel was left open to stir overnight to volatilize ethanol, propanol and some of the water until the mixture reached the final molar composition.
The mixture is put into a crystallization kettle with a polytetrafluoroethylene lining and is placed in an oven at 150 ℃ for crystallization for 168 hours. And filtering, washing, drying and calcining the reacted solid to obtain the solid which is the BEA molecular sieve.
Comparative example 2
2.1g of germanium oxide was dissolved in 18.25g of 25 wt% aqueous tetramethylammonium hydroxide, 18.7g of Tetraethylorthosilicate (TEOS) and 0.41g of aluminum isopropoxide were added, and after hydrolysis was complete the vessel was left open to stir overnight to volatilize ethanol, propanol and some of the water until the reaction mixture reached the final molar composition.
The mixture is put into a crystallization kettle with a polytetrafluoroethylene lining and is placed in an oven at 150 ℃ for crystallization for 168 hours. And filtering, washing, drying and calcining the reacted solid to obtain the solid which is the RUT molecular sieve.
Claims (9)
1. A synthetic method of IWR/CDO cocrystallization zeolite molecular sieve comprises the following synthetic steps:
a) oxide YO of skeleton tetravalent element Y2Oxide X of skeleton trivalent element X2O3The organic template agent Choline hydroxide Choline and water are according to Choline: YO2:X2O3:H2Uniformly mixing O0.15-0.95: 1: 0-0.08: 2-28 in a molar ratio to obtain a mixture;
b) performing hydrothermal crystallization on the mixture to obtain a crystallized product, wherein the crystallization temperature of the reaction mixture is 100-200 ℃, and the crystallization time of the reaction mixture is 30-300 hours;
c) and washing, separating, drying and calcining the crystallized product.
2. The method for synthesizing IWR/CDO co-crystallized zeolite molecular sieve of claim 1, wherein in step (1), the molar ratio of each reactant is Choline YO2:X2O3:H2O＝0.35～0.75:1:0～0.05:2.5～14。
3. The method of synthesizing an IWR/CDO co-crystalline zeolite molecular sieve of claim 1, wherein in step (1) the framework tetravalent element Y is selected from at least one of Si, Ge, Ti, Sn, Zr.
4. The method of synthesizing an IWR/CDO co-crystalline zeolite molecular sieve of claim 1, wherein the framework trivalent element In step (1) is selected from at least one of Al, B, Ga, Fe, Cr, In.
5. The method for synthesizing the IWR/CDO co-crystallized zeolite molecular sieve of claim 1, wherein in the step (2), the crystallization temperature of the reaction mixture is 120-180 ℃ and the crystallization time of the reaction mixture is 45-195 hours.
6. The method of synthesizing an IWR/CDO co-crystalline zeolitic molecular sieve of claim 3, characterized in that the oxide SiO of tetravalent framework element Si2The precursor is selected from one or more of water glass, silica sol, solid silica gel, fumed silica, amorphous silica, diatomite, zeolite molecular sieve and tetraethyl orthosilicate; GeO oxide of tetravalent framework element Ge2The precursor is selected from one or more of amorphous germanium dioxide or organic germanium ester; TiO oxide of tetravalent skeleton element Ti2The precursor is selected from one or more of titanium sulfate, amorphous titanium dioxide and tetrabutyl titanate.
7. The method of synthesizing an IWR/CDO co-crystalline zeolitic molecular sieve of claim 1, characterized in that the oxide of trivalent framework element Al, is Al2O3The precursor is selected from one or more of sodium metaaluminate, aluminum sulfate, aluminum nitrate, aluminum chloride, aluminum isopropoxide, pseudo-boehmite, zeolite molecular sieve or amorphous alumina; oxide B of trivalent framework element B2O3The precursor of (a) is selected from one or more of boric acid, sodium tetraborate, amorphous boron oxide, potassium borate, sodium metaborate, ammonium tetraborate and organoboron esters.
8. The method for synthesizing the IWR/CDO co-crystalline zeolite molecular sieve of any one of claims 1-7, wherein the IWR molecular sieve accounts for 1-99% by weight of the co-crystalline molecular sieve.
9. An IWR/CDO co-crystalline zeolite molecular sieve synthesized by the process of any one of claims 1 to 7 for use as a gas adsorbent and as a catalyst in catalytic cracking or hydrocracking of hydrocarbons or in alkylation of aromatic hydrocarbons or isomerization of alkanes or disproportionation or dewaxing of toluene or in the production of olefins or aromatics from methanol or esterification or acylation or epoxidation of olefins or Baeyer-Villiger oxidation or Meerwein-Ponndorf-Verley reaction processes.
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