CN108946755B - Synthesis method of germanium-free IWR zeolite molecular sieve - Google Patents

Synthesis method of germanium-free IWR zeolite molecular sieve Download PDF

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CN108946755B
CN108946755B CN201710361935.6A CN201710361935A CN108946755B CN 108946755 B CN108946755 B CN 108946755B CN 201710361935 A CN201710361935 A CN 201710361935A CN 108946755 B CN108946755 B CN 108946755B
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付文华
杨为民
袁志庆
滕加伟
乔健
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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    • 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
    • C01B39/04—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 using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
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Abstract

The invention relates to a method for synthesizing a germanium-free IWR zeolite molecular sieve, which aims to solve the problems of high cost of a template agent and Ge in the prior art for synthesizing the IWR zeolite molecular sieveLarge using amount, poor stability of the molecular sieve of the obtained IWR zeolite and the like. The invention is based on diethyldimethylammonium hydroxide/SiO by using, as organic template, a relatively less expensive, commercially available diethyldimethylammonium hydroxide2＝0.1～1.5，SiO2/B2O30.5 to 100 of oxide/SiO of hetero atom element W2＝0～0.2，F‑/SiO2＝0.1～1.5，H2O/SiO2And (2) carrying out hydrothermal crystallization on the mixture to obtain the porous crystalline IWR zeolite molecular sieve with the composition of 1-50. The IWR zeolite molecular sieve synthesized by the method has a stable structure; wide synthesis range, simple and easy operation and convenient popularization.

Description

Synthesis method of germanium-free IWR zeolite molecular sieve
Technical Field
The invention relates to a method for synthesizing a zeolite molecular sieve, in particular to a method for synthesizing a germanium-free IWR 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 231.
The IWR molecular sieve is ITQ-24, which is synthesized by a Corma project group by using a hexamethylene bis (trimethylammonium) dicationic template (US 7344696B), and Ge is introduced in the synthesis process to stabilize a double-four-membered ring (D4R) structural unit existing in an IWR structure.
The above method of synthesizing the IWR zeolite molecular sieve uses a commercially unavailable, expensive templating agent; a large amount of Ge is introduced as a framework element, so that the synthesis cost is increased; the existence of Ge greatly reduces the structural stability, especially the hydrothermal stability, of the zeolite molecular sieve, and is not beneficial to industrial popularization.
Disclosure of Invention
The invention aims to solve the problems of high cost of a template agent used for synthesizing an IWR zeolite molecular sieve, large usage amount of Ge, poor structural stability of the obtained IWR zeolite molecular sieve and the like in the prior art, and provides a method for synthesizing the IWR zeolite molecular sieve.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a method for synthesizing a germanium-free IWR zeolite molecular sieve comprises the following steps: mixing SiO2、B2O3Diethyl dimethyl ammonium hydroxide, an oxide of a hetero-atomic metal element W, a fluoride and water according to diethyl dimethyl ammonium hydroxide/SiO2＝0.1～1.5，SiO2/B2O30.5 to 100 of oxide/SiO of heteroatom metal element W2＝0～0.2，F-/SiO2＝0.1～1.5，H2O/SiO2Uniformly mixing the components in a molar ratio of 1-50 to obtain a mixture; carrying out hydrothermal crystallization on the mixture to obtain a crystallized product; and washing, separating, drying and calcining the crystallized product.
In the technical scheme, the organic template agent diethyl dimethyl ammonium hydroxide and SiO2The molar ratio of diethyl dimethyl ammonium hydroxide to SiO20.2 to 1.0, preferably the ratioDiethyldimethylammonium hydroxide/SiO2＝0.3～0.8。
In the above technical scheme, SiO2The precursor is at least one of water glass, silica sol, solid silica gel, gas phase white carbon black, amorphous silica, zeolite molecular sieve or organic silicon ester.
In the above technical scheme, SiO2And B2O3Has a molar ratio of SiO2/B2O32-60, and the more preferable ratio is SiO2/B2O3＝10～50。
In the above technical scheme, B2O3The precursor of (a) is at least one selected from boric acid, sodium tetraborate, amorphous boron oxide, potassium borate, sodium metaborate, ammonium pentaborate and organoboron esters.
In the technical scheme, the oxide and SiO of the heteroatom metal element W2oxide/SiO with molar ratio W between20 to 0.1, preferably W, oxide/SiO2＝0～0.05。
In the above technical solution, the heteroatom metal element M includes at least one selected from Mg, Al, Ga, Fe, Zn, Sn, Ti, Zr, and V.
In the above technical solution, the source of the oxide of the heteroatom metal element Al includes at least one selected from sodium metaaluminate, aluminum sulfate, aluminum nitrate, aluminum chloride, aluminum isopropoxide, pseudo-boehmite, a molecular sieve or amorphous alumina, and in an embodiment of the present invention, the zeolite molecular sieve is a USY molecular sieve; the source of the oxide of the heteroatom metallic element Ti includes at least one selected from titanium sulfate, amorphous titanium dioxide, and tetrabutyl titanate.
In the technical scheme, fluoride and SiO2The molar ratio of F to-/SiO20.2 to 1.0, preferably F-/SiO2＝0.3～0.8。
In the above technical solution, the fluoride is at least one selected from hydrofluoric acid, ammonium fluoride, sodium fluoride, and potassium fluoride.
In the above technical scheme, H in the synthesis2O and SiO2Has a molar ratio of H2O/SiO22-20, and the more preferable ratio is H2O/SiO2＝3～15。
In the technical scheme, the crystallization temperature is 100-200 ℃, and more preferably the crystallization temperature is 135-180 ℃; the crystallization time is 24 to 350 hours, and more preferably 40 to 240 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 firstly proposes to use the diethyl dimethyl ammonium hydroxide template to synthesize the germanium-free IWR molecular sieve, has the advantages of simple structure of the organic template and easy obtainment of raw materials, and saves the synthesis cost compared with the prior art. The B element is used for replacing the Ge element to play a role in stabilizing a double-quaternary ring structure in the IWR molecular sieve, so that the introduction of expensive Ge element in the synthesis is avoided, and the IWR zeolite molecular sieve has good structural stability by adopting diethyl dimethyl ammonium hydroxide as a template agent. Various heteroatom elements can be introduced to meet 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;
FIG. 3 is an X-ray diffraction (XRD) pattern of a calcined sample obtained in comparative example 3;
FIG. 4 is an X-ray diffraction (XRD) pattern of a calcined sample obtained in comparative example 4;
FIG. 5 is an X-ray diffraction (XRD) pattern of the calcined sample obtained in comparative example 4 after immersion in water.
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 ]
0.25g of boric acidDissolving in 5.96g of 20 wt% aqueous solution of diethyldimethylammonium hydroxide, adding L udox (HS-40, 40%) and stirring, and adding 1g of 37% NH4F, water solution. The vessel was left to stir open overnight 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 in an oven at 170 ℃ for crystallization for 168 hours. And filtering the reacted solid, washing the solid with distilled water and drying the solid at 100 ℃ to obtain the original powder solid. And (3) placing the raw powder solid in a muffle furnace to be roasted for 5 hours at the temperature of 550 ℃ to obtain a final product. The sample after calcination showed a stable IWR structure with an XRD pattern as shown in FIG. 1 and an SEM photograph as shown in FIG. 2.
The stability of the IWR zeolite molecular sieve was analyzed as follows: 1g of calcined IWR molecular sieve with the template agent removed is soaked in 30g of water at normal temperature for 24h, and the solid is obtained after filtration and drying at 100 ℃. The crystal retention of the water soaked solid was 98% compared to that before soaking.
[ example 2 ]
0.6g of boric acid was dissolved in 5.96g of 20 wt% aqueous diethyldimethylammonium hydroxide, 3g of L udox (HS-40, 40%) was added thereto, the mixture was stirred well, and finally 1g of 37% NH was added4F, water solution. The vessel was left to stir open overnight 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 in an oven at 170 ℃ for crystallization for 120 hours. And after the reaction, filtering, washing, drying and calcining the solid, wherein the obtained solid is the IWR molecular sieve.
[ example 3 ]
0.9g of boric acid was dissolved in 5.96g of 20 wt% aqueous diethyldimethylammonium hydroxide solution, 4.16g of Tetraethylorthosilicate (TEOS) was added, and 1.2g of 37% NH was added after hydrolysis was completed4F, water solution. The vessel was left to stir open overnight 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 160 ℃ oven for crystallization for 192 hours. And after the reaction, filtering, washing, drying and calcining the solid, wherein the obtained solid is the IWR molecular sieve.
[ example 4 ]
0.05g of boric acid is dissolved in 5.96g of 20 wt% aqueous solution of diethyldimethylammonium hydroxide, 1.2g of white carbon black is added and stirred uniformly, and finally 0.65g of 37% NH is added4F, water solution. The vessel was left to stir open overnight 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 in a drying oven at 150 ℃ for crystallization for 120 hours. After the reaction, the solid is filtered, washed, dried and calcined to obtain the solid which is the IWR molecular sieve containing about 5 percent of CDO molecular sieve impurities.
[ example 5 ]
0.25g of boric acid was dissolved in 9.536g of 20 wt% aqueous diethyldimethylammonium hydroxide, 3g of L udox (HS-40, 40%) was added and stirred well, the vessel was left open to stir overnight to volatilize part of the water, 0.8g of 40% HF solution was added and the amount of water was adjusted 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 120 hours. And after the reaction, filtering, washing, drying and calcining the solid, wherein the obtained solid is the IWR molecular sieve.
[ example 6 ]
0.124g of boric acid was dissolved in 1.788g of 20% by weight aqueous diethyldimethylammonium hydroxide, 3g of L udox (HS-40, 40%) was added and stirred well, the vessel was left open to stir overnight to volatilize part of the water, 0.3g of 40% HF solution was added and the amount of water was adjusted 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 192 hours. And after the reaction, filtering, washing, drying and calcining the solid, wherein the obtained solid is the IWR molecular sieve.
[ example 7 ]
0.25g of boric acid was dissolved in 5.96g of a 20 wt% aqueous solution of diethyldimethylammonium hydroxide, and 3g of L udox (HS-40, 40%) Stirring well, and finally adding 0.5g of 37% NH4Aqueous F and 0.25g of 40% HF solution. The vessel was left to stir open overnight 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 in an oven at 170 ℃ for crystallization for 72 hours. And filtering, washing, drying and calcining the reacted solid to obtain the solid IWR molecular sieve.
[ example 8 ]
0.381g of sodium tetraborate is dissolved in 5.96g of 20 wt% aqueous diethyldimethylammonium hydroxide, 3g of L udox (HS-40, 40%) is added and stirred uniformly, and finally 1g of 37% NH is added4F, water solution. The vessel was left to stir open overnight 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 put into an oven at 180 ℃ for crystallization for 192 hours. After the reaction, the solid is filtered, washed, dried and calcined to obtain the solid which is the IWR molecular sieve containing about 10 percent of AST molecular sieve impurities.
[ example 9 ]
0.25g of boric acid was dissolved in 5.96g of 20% by weight aqueous diethyldimethylammonium hydroxide solution, hydrolyzed completely by adding 4.16g of Tetraethylorthosilicate (TEOS) and 0.163g of aluminum isopropoxide, and finally 1g of 37% NH was added4F, water solution. The vessel was left to stir open 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 into an oven at 170 ℃ for crystallization for 196 hours. After the reaction, the solid is filtered, washed, dried and calcined to obtain the solid which is the aluminum-containing IWR molecular sieve, and the product SiO2/Al2O3＝52。
[ example 10 ]
Dissolving 0.25g boric acid in 5.96g 20 wt% diethyl dimethyl ammonium hydroxide aqueous solution, adding 1.2g white carbon black and 0.045g pseudo-boehmite, stirring well, finally adding 1g 37% NH4F, water solution. The vessel was left open to stir overnight to volatilize some of the waterUntil the reaction mixture reaches the final molar composition.
The mixture is put into a crystallization kettle with a polytetrafluoroethylene lining and is placed in a 185 ℃ oven for crystallization for 240 hours. After the reaction, the solid is filtered, washed, dried and calcined to obtain the solid which is the aluminum-containing IWR molecular sieve, and the product SiO2/Al2O3＝66。
[ example 11 ]
0.25g of boric acid was dissolved in 5.96g of 20 wt% aqueous diethyldimethylammonium hydroxide solution, and 1.6g of L udox (HS-40, 40%) and 1.4g of USY molecular Sieve (SiO)2/Al2O323) was stirred well and finally 1g of 37% NH was added4F, water solution. The vessel was left to stir open overnight 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 in an oven at 170 ℃ for crystallization for 240 hours. After the reaction, the solid is filtered, washed, dried and calcined to obtain the solid which is the aluminum-containing IWR molecular sieve, and the product SiO2/Al2O3＝31。
[ example 12 ]
0.05g of boric acid was dissolved in 5.96g of 20 wt% aqueous diethyldimethylammonium hydroxide solution, and 1.2g of white carbon black and 0.06g of the calcined IWR molecular sieve prepared in example 1 were added. After stirring well, 1g of 37% NH was added4F, water solution. The vessel was left to stir open overnight 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 in an oven at 170 ℃ for crystallization for 168 hours. And after the reaction, filtering, washing, drying and calcining the solid, wherein the solid obtained is the IWR molecular sieve without CDO molecular sieve impurities.
[ example 13 ]
0.25g of boric acid was dissolved in 5.96g of 20 wt% aqueous diethyldimethylammonium hydroxide, 3g of L udox (HS-40, 40%) and 0.034g of tetrabutyl titanate (TBOT) were added for hydrolysis and stirring to homogeneity, and finally 1g of 37% NH was added4F, water solution. The vessel was left open to stir overnight toThe butanol and some of the water were evaporated 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. After reaction, the solid is filtered, washed, dried and calcined to obtain the solid which is the titanium-containing IWR molecular sieve, and Si/Ti in the product is 220.
[ example 14 ]
0.25g of boric acid was dissolved in 7.152g of 20 wt% aqueous diethyldimethylammonium hydroxide solution, 4.16g of Tetraethylorthosilicate (TEOS) and 0.085g of tetrabutyltitanate were added and hydrolyzed and stirred well, and finally 0.6g of 37% NH was added4Aqueous F and 0.3g of 40% HF solution. 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 titanium-containing IWR molecular sieve, wherein Si/Ti in the product is 85.
Comparative example 1
0.25g of boric acid was dissolved in 5.89g of 25 wt% aqueous tetraethylammonium hydroxide, 3g of L udox (HS-40, 40%) was added and stirred well, and finally 1g of 37% NH was added4F, water solution. The vessel was left to stir open overnight 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 in an oven at 170 ℃ for crystallization for 168 hours. And filtering, washing, drying and calcining the reacted solid to obtain the solid BEC molecular sieve.
Comparative example 2
0.25g of boric acid was dissolved in 3.65g of 25 wt% aqueous tetramethylammonium hydroxide solution, 3g of L udox (HS-40, 40%) was added and stirred well, and finally 1g of 37% NH was added4F, water solution. The vessel was left to stir open overnight 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 in an oven at 170 ℃ for crystallization for 168 hours. And filtering, washing, drying and calcining the reacted solid to obtain the AST molecular sieve.
Comparative example 3
Dissolving 0.1g boric acid in 10ml 0.5M ammonium hexamethoxide solution, adding 4.16g tetraethyl orthosilicate (TEOS), stirring well, and finally adding 1g 37% NH4F, water solution. The vessel was left to stir open overnight 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 175 ℃ for crystallization for 336 hours. And after the reaction, filtering, washing, drying and calcining the solid to obtain the solid EUO molecular sieve, wherein an XRD (X-ray diffraction) spectrum is shown in figure 3.
Comparative example 4
1.046g of germanium oxide was dissolved in 30ml of 0.5M hexamethonium hydroxide solution, 4.16g of Tetraethylorthosilicate (TEOS) was 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 336 hours. After the reaction, the solid is filtered, washed, dried and calcined to obtain the solid of the IWR molecular sieve, and an XRD (X-ray diffraction) spectrum is shown in figure 4; after soaking in water for 24h, the molecular sieve framework collapses, the crystal retention is less than 1%, and the XRD pattern is shown in figure 5.

Claims (11)

1. A method for synthesizing a germanium-free IWR zeolite molecular sieve comprises the following steps:
a) mixing SiO2、B2O3Diethyl dimethyl ammonium hydroxide, oxide of hetero-atom metal element, fluoride and water according to diethyl dimethyl ammonium hydroxide/SiO2＝0.1～1.5，SiO2/B2O30.5 to 100 of oxide of heteroatom metal element/SiO2＝0～0.2，F-/SiO2＝0.1～1.5，H2O/SiO21 to 50 mol ratioMixing uniformly to obtain a mixture;
b) performing hydrothermal crystallization on the mixture to obtain a crystallized product;
c) and washing, separating, drying and calcining the crystallized product.
2. The method of synthesizing a germanium-free IWR zeolite molecular sieve of claim 1, wherein the organic templating agent is diethyldimethylammonium hydroxide and SiO2The molar ratio of diethyl dimethyl ammonium hydroxide to SiO2＝0.2～1.0。
3. The method of synthesizing a germanium-free IWR zeolite molecular sieve of claim 1, wherein SiO is2The precursor is selected from at least one of water glass, silica sol, solid silica gel, amorphous silica, zeolite molecular sieve or organic silicon ester; b is2O3The precursor of (a) is at least one selected from boric acid, sodium tetraborate, amorphous boron oxide, potassium borate, sodium metaborate, ammonium pentaborate and organoboron esters.
4. The method of synthesizing a germanium-free IWR zeolite molecular sieve of claim 1, wherein SiO is2The precursor is selected from fumed silica.
5. The method of synthesizing a germanium-free IWR zeolite molecular sieve of claim 1, wherein SiO is2And B2O3Has a molar ratio of SiO2/B2O3＝2～60。
6. The method of synthesizing a germanium-free IWR zeolite molecular sieve of claim 1, wherein the heteroatom metal element is selected from at least one of Mg, Al, Ga, Fe, Zn, Sn, Ti, Zr, V.
7. The method of synthesizing a germanium-free IWR zeolite molecular sieve of claim 1, wherein fluoride and SiO are present2The molar ratio of F to-/SiO2＝0.2～1.0。
8. The method of synthesizing a germanium-free IWR zeolite molecular sieve of claim 1, wherein the fluoride is at least one selected from the group consisting of hydrofluoric acid, ammonium fluoride, sodium fluoride, and potassium fluoride.
9. The method of synthesizing a germanium-free IWR zeolite molecular sieve of claim 1, wherein H is synthesized2O and SiO2Has a molar ratio of H2O/SiO2＝2～20。
10. The method for synthesizing the germanium-free IWR zeolite molecular sieve according to claim 1, wherein the reaction mixture is hydrothermally crystallized at 100-200 ℃ for 20-350 hours.
11. The germanium-free IWR zeolite molecular sieve synthesized by the process of any one of claims 1-10 is useful as a catalyst in catalytic hydrocarbon cracking, hydrocracking, aromatic alkylation, alkane isomerization, toluene disproportionation, dewaxing, methanol to olefins, methanol to aromatics, esterification, acylation, olefin epoxidation, Baeyer-Villiger oxidation, Meerwein-Ponndorf-Verley reaction processes.
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