CN112537782A - Method for preparing molecular sieve with TON structure - Google Patents
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Abstract
The invention relates to a method for preparing a molecular sieve with a TON structure, which comprises the step of carrying out crystallization treatment on a mixture formed by a silicon source, an aluminum source, an alkali source, a template agent, fluoride and water to obtain the molecular sieve with the TON structure. In the mixture, SiO is used2Calculated silicon source, calculated as Al2O3Calculated as Al source and OH‑Alkali source in F‑The molar composition of fluoride, templating agent and water is calculated as follows: SiO 22/Al2O315 to 500; templating agent/SiO20.01 to 0.5; OH group‑/SiO20.01 to 0.50; h2O/SiO29 to 30; f‑/SiO20.005 to 0.50. The molecular sieve crystal prepared by the method has the advantages of sheet shape, small thickness and low silica-alumina ratio, and meets different requirements for catalysts in chemical production.
Description
Technical Field
The invention belongs to the field of catalysts, and particularly relates to a method for preparing a molecular sieve with a TON structure and the molecular sieve prepared by the method.
Background
The molecular sieve with TON structure is a molecular sieve defined by International molecular Sieve Association, belonging to orthorhombic system, space group is Cmc21The structural units of the molecular sieve comprise five-membered rings, six-membered rings and ten-membered rings, and the ZSM-22 molecular sieve is representative of the molecular sieve.
The ZSM-22 molecular sieve is firstly synthesized by Dwyer et al of Mobil company in the 20 th century in 80 years, the main channel of the ZSM-22 molecular sieve is a one-dimensional elliptic straight channel, the opening of the channel is a 10-membered ring, the aperture is 0.46nm multiplied by 0.57nm, and the parameters of unit cells are
Due to the mild acid property and the space shape-selective effect, the ZSM-22 molecular sieve is applied to the fields of isomerization reaction of straight-chain paraffin, olefin preparation from methanol, alkylation of aromatic hydrocarbon, hydrocracking, catalytic dewaxing, aromatization of paraffin and the like.
Both theoretical and experimental studies show that most of the reactions catalyzed by the ZSM-22 molecular sieve occur in the pore opening, so that the crystal morphology is an important factor influencing the catalytic performance of the molecular sieve.
The ZSM-22 molecular sieve is usually synthesized by a hydrothermal crystallization method, generally using an organic template agent, such as 1,6 hexanediamine (US 4902406, US 5707600), ethylenediamine (US 4556477) and the like, uniformly mixing a silicon source, an aluminum source, an alkali source, the organic template agent and water, crystallizing and roasting to obtain the ZSM-22 molecular sieve. CN 105565339A (Shanxi institute of coal chemistry, China academy of sciences, USA, 2016.03.02) discloses a preparation method of a small-grain ZSM-22 molecular sieve, which comprises the steps of uniformly mixing one or more of 1-ethyl pyridine bromide, 1, 6-hexamethylene diamine, N-methyl imidazole biquaternary ammonium salt, diethylamine, N-butylamine and 1, 8-diaminooctane by using one or more of 1-ethyl pyridine bromide, 1, 6-hexamethylene diamine, N-methyl imidazole biquaternary ammonium salt, diethylamine, N-butylamine and 1, 8-diaminooctane as a template agent to form an initial gel mixture, adding one or more of active carbon, graphite, graphene, carbon black, starch microspheres, chitosan and polylactic acid microspheres, uniformly stirring, crystallizing, filtering and separating a solid product, washing the solid product to be neutral by using deionized water, drying and roasting to obtain the small-grain ZSM-22 molecular sieve. CN 107814392A (university of Henan university, 2017.10.12) discloses a preparation method of a ZSM-22 molecular sieve, which takes imidazole ionic liquid 1-ethyl-3 methyl-imidazole chloride ([ EMIm ] Cl) and 1-butyl-3 methyl-imidazole chloride ([ BMIm ] Cl) as structure directing agents and prepares the ZSM-22 molecular sieve by crystallization at 180 ℃. CN 109502607A (Shanxi institute of coal chemistry, China academy of sciences, USA, 2018.11.30) discloses a method for synthesizing a nano ZSM-22 molecular sieve, which comprises the steps of uniformly mixing a silicon source, an aluminum source, an alkali source, a template agent and deionized water to form an initial gel mixture, carrying out hydrothermal crystallization at 140-180 ℃ autogenous pressure to obtain a pre-crystallized solid, uniformly mixing the pre-crystallized solid, the alkali source, the template agent and the deionized water to form a mixture, carrying out hydrothermal crystallization at 140-180 ℃ autogenous pressure, washing, drying and roasting to obtain the nano ZSM-22 molecular sieve. The template agent is one or a mixture of more of 1-ethyl pyridine bromide, 1, 6-hexamethylene diamine, N-methyl imidazole biquaternary ammonium salt, diethylamine and 1, 8-diaminooctane. The ZSM-22 molecular sieve synthesized in the way is a rod-shaped or needle-shaped crystal, has small external specific surface area and large organic molecule diffusion resistance, cannot be used in chemical reaction with macromolecules, is easy to activate, and greatly limits the application of the ZSM-22 molecular sieve.
Chinese patent 201310047018.2 Zhejiang university 2013.02.01 discloses a method for synthesizing ZSM-22 molecular sieve by using a seed crystal method, wherein aluminum sulfate is used as an aluminum source, and tetraethoxysilane is used as a silicon source. Chinese patent CN201310353621.3 (institute of chemical and physical sciences, university of Chinese academy of sciences, 2013.08.14) discloses a method for synthesizing a ZSM-22 molecular sieve, wherein the ZSM-22 molecular sieve is used as a seed crystal, and an organic template is not used, and the ZSM-22 molecular sieve and the Me-ZSM-22 molecular sieve are synthesized by hydrothermal reaction under alkaline conditions. Chinese patent 201510072221.4 Zhejiang university 2015.02.11 discloses a method for synthesizing ZSM-22 molecular sieve without organic template and seed crystal, which adopts aluminum sulfate as aluminum source, alkali source as potassium hydroxide or sodium hydroxide, and silicon source as tetraethyl orthosilicate or white carbon black. Chinese patent 201510708781.4 (Beijing chemical university, 2015.10.27) discloses a method for rapidly preparing a ZSM-22 molecular sieve by using seed crystals. However, the ZSM-22 molecular sieves synthesized by the method are all rod-shaped crystals.
Chinese patent 201510084713.5[ Heilongjiang university, 2015.02.16] discloses a preparation method of a ZSM-22 molecular sieve nanosheet: 1) preparing a prefabricated seed crystal by using aluminum sulfate octadecahydrate, ethyl orthosilicate, 1, 6-hexanediamine, potassium hydroxide and deionized water; 2) preparing gel by using aluminum sulfate octadecahydrate, silica sol, potassium hydroxide and deionized water; 3) crystallizing and roasting. The alkaline source used in the method is KOH, the prepared ZSM-22 molecular sieve nanosheets are stacked together, the first nanosheet is covered by the second nanosheet, the area of the first nanosheet is large, the exposed area of the first nanosheet is small, and the thickness of the first nanosheet reaches 20 nanometers. No diffusion advantage is exhibited compared to conventional ZSM-22 molecular sieves in rod or needle form.
CN 107285332A (Shanghai Petroleum chemical research institute, 2016.04.12, China petrochemical Co., Ltd.) discloses a synthesis method of a ZSM-22 molecular sieve and the ZSM-22 molecular sieve synthesized by the same, but a ZSM-22 molecular sieve nanosheet (Cryst Eng Comm,2016,18,5611) can be obtained only when the feeding silica-alumina ratio is high (about 200).
As can be seen from the above review, although the method for synthesizing the ZSM-22 molecular sieve is mature, it is difficult to synthesize ZSM-22 molecular sieve nanosheets, and the synthesis phase region is narrow, thereby resulting in that the application of the ZSM-22 molecular sieve is greatly limited.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for preparing a molecular sieve with a TON structure aiming at the defects of the prior art, and the molecular sieve crystal prepared by the method has a flaky shape, is smaller in thickness and adjustable in silicon-aluminum ratio, and meets different requirements for catalysts in chemical production.
According to one aspect of the present invention, a method for preparing a molecular sieve having a TON structure is provided, which includes crystallizing a mixture of a silicon source, an aluminum source, an alkali source, a template, a fluoride and water to obtain the molecular sieve having a TON structure.
In some embodiments, the mixture is in SiO2Calculated silicon source, calculated as Al2O3Calculated as Al source and OH-Alkali source in F-The molar composition of fluoride, templating agent and water is calculated as follows: SiO 22/Al2O315 to 500; templating agent/SiO20.01 to 0.5; OH group-/SiO20.01 to 0.50; h2O/SiO29 to 30; f-/SiO20.005 to 0.50.
In some embodiments, the mixture is in SiO2Calculated silicon source, calculated as Al2O3Calculated as Al source and OH-Alkali source in F-The molar composition of fluoride, templating agent and water is calculated as follows: SiO 22/Al2O320 to 400; templating agent/SiO20.05 to 0.5; OH group-/SiO20.05 to 0.40; h2O/SiO210 to 26; f-/SiO20.01 to 0.40.
In some embodiments, the silicon source comprises at least one of silica gel, silica sol, and tetraalkyl silicate, preferably silica sol.
In some embodiments, the aluminum source comprises at least one of sodium aluminate, aluminum nitrate, aluminum sulfate, aluminum oxide, aluminum hydroxide, and aluminum isopropoxide, preferably sodium aluminate.
In some embodiments, the templating agent is 1-ethylpyridinium bromide.
In some embodiments, the fluoride is an alkali metal fluoride, preferably sodium fluoride.
In some embodiments, the crystallization conditions comprise: the crystallization temperature is 80-180 ℃, and preferably 100-180 ℃; the crystallization time is 10 hours to 10 days, preferably 1 to 5 days.
According to another aspect of the present invention, there is provided a molecular sieve having a TON structure prepared according to the above method, wherein the molecular sieve crystals have a plate-like morphology and a crystal thickness of 5 to 20nm, preferably 8 to 20 nm.
In some embodiments, the molecular sieve has a silica to alumina ratio of 15 to 300 and contains the element F.
Compared with the prior art, the method enlarges the synthetic phase area for preparing the molecular sieve with the TON structure in the sheet shape, and the SiO is fed2/Al2O3The molecular sieve with the TON structure and the flaky morphology can be synthesized under the condition of 15-500, the silicon-aluminum ratio of the product is adjustable, and different requirements for catalysts in chemical production are met. The thickness of the crystal of the obtained TON structure molecular sieve with the sheet shape is 5-20nm, which is beneficial to the diffusion of molecules and is not easy to accumulate carbon when used as a catalyst; meanwhile, the silicon-aluminum ratio of the TON structure molecular sieve with the sheet shape is more than 15 and less than 60, so that the limitation that only the sheet TON structure molecular sieve with high silicon-aluminum ratio can be synthesized in the prior art is broken through, the acid density of the molecular sieve is improved, and the application range of the molecular sieve is favorably expanded; the TON structure molecular sieve with the sheet shape contains F element, which is beneficial to improving the acid strength after the conversion of the F element into hydrogen type molecular sieve.
Drawings
FIG. 1 is an SEM photograph of the molecular sieve prepared in example 1;
FIG. 2 is an SEM photograph of the molecular sieve prepared in example 2;
fig. 3 is an SEM photograph of the molecular sieve prepared in comparative example 1.
Detailed Description
In order that the present invention may be more readily understood, the following detailed description of the invention is given by way of example only, and is not intended to limit the scope of the invention.
The operations and treatments involved in the present invention are conventional in the art unless otherwise specified.
The apparatus used in the present invention is an apparatus conventional in the art unless otherwise specified.
The raw materials involved in the specific embodiment of the invention are as follows:
(A) silica sol: containing SiO240 wt%, industrial product;
(B) sodium aluminate: containing Al2O3Amount 41 wt%, commercial product;
(C) 1-ethyl pyridine bromide: a commercially available product;
(D) sodium fluoride, content 98% by weight, commercially available;
(E) sodium hydroxide: content 96 wt%, commercial product.
The detection method related in the specific embodiment of the invention is as follows:
(1) determination of the thickness of the molecular sieve:
and (3) importing the SEM picture of the prepared molecular sieve into Nano Measurer software, calibrating a ruler, and then carrying out software measurement on the thickness of the molecular sieve sheet, so as to obtain the thickness distribution of the sheet-shaped molecular sieve after ensuring that the statistics of the molecular sieve samples is more than or equal to 100, and measuring the average thickness of the molecular sieve.
(2) And (3) determining the silicon-aluminum ratio of the molecular sieve:
the composition of the molecular sieve is measured by adopting an ICP-AES internal standard method (analytical test technology and instrument, 2004,10(1), 30-33), and the silicon-aluminum ratio of the molecular sieve is obtained by calculating according to the measurement result of the content of Si and Al elements.
Example 1
Dissolving 19 g of 1-ethyl pyridine bromide, 0.5 g of sodium aluminate, 1.25 g of sodium hydroxide and 1.7 g of sodium fluoride in 94 g of deionized water, slowly adding 60 g of silica sol under the condition of stirring, then adding 1.2 g of ZSM-22 molecular sieve seed crystal, continuously stirring for one hour, then placing into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and crystallizing for 3 days at 150 ℃. And after crystallization, filtering, washing and drying to obtain 27.8 g of the molecular sieve nanosheet with the TON structure.
The material ratio (mol ratio) of the reactants is as follows: SiO 22/Al2O3200 parts of a total weight; 1-Ethyl pyridine bromide/SiO2＝0.25；OH-/SiO2＝0.075；H2O/SiO2＝18；F-/SiO2＝0.1。
The XRD diffraction results of the molecular sieve having TON structure prepared in example 1 are shown in table 1.
TABLE 1
SEM photograph of the molecular sieve having TON structure prepared in example 1 is shown in fig. 1, and it was measured that the molecular sieve had an average thickness of 15 nm and the plate-shaped crystals were randomly staggered rather than regularly stacked. The silica to alumina ratio of the molecular sieve was 54.6.
Example 2
Dissolving 19 g of 1-ethyl pyridine bromide, 2 g of sodium aluminate, 1.25 g of sodium hydroxide and 1.7 g of sodium fluoride in 94 g of deionized water, slowly adding 60 g of silica sol under the condition of stirring, then adding 1.2 g of ZSM-22 molecular sieve seed crystal, continuously stirring for one hour, then placing into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and crystallizing for 3 days at 150 ℃. And after crystallization, filtering, washing and drying to obtain 27.8 g of the molecular sieve nanosheet with the TON structure.
The material ratio (mol ratio) of the reactants is as follows: SiO 22/Al2O350; 1-Ethyl pyridine bromide/SiO2＝0.25；OH-/SiO2＝0.075；H2O/SiO2＝18；F-/SiO2＝0.1。
The SEM photograph of the molecular sieve having the TON structure obtained in example 2 is shown in fig. 2, and it was found that the average thickness was 10 nm, and the plate-shaped crystals were randomly staggered rather than regularly stacked. The silica to alumina ratio of the molecular sieve was 21.4.
Example 3
Except that the material ratio (mol ratio) of the reactants is as follows: SiO 22/Al2O320; 1-Ethyl pyridine bromide/SiO2＝0.25；OH-/SiO2＝0.075；H2O/SiO2＝18；F-/SiO2The procedure of example 1 was repeated except that 0.1 was used.
The average thickness of the prepared molecular sieve with the TON structure is 18 nanometers, and the silicon-aluminum ratio is 15.8.
Example 4
Except that the material ratio (mol ratio) of the reactants is as follows: SiO 22/Al2O3100; 1-Ethyl pyridine bromide/SiO2＝0.25；OH-/SiO2＝0.075；H2O/SiO2＝18；F-/SiO2The procedure of example 1 was repeated except that 0.1 was used.
The average thickness of the prepared molecular sieve with the TON structure is 8 nanometers, and flaky crystals are randomly staggered and are not regularly stacked together. The silica to alumina ratio of the molecular sieve was 49.2.
Example 5
Except that the material ratio (mol ratio) of the reactants is as follows: SiO 22/Al2O3150; 1-Ethyl pyridine bromide/SiO2＝0.25；OH-/SiO2＝0.075；H2O/SiO2＝18；F-/SiO2The procedure of example 1 was repeated except that 0.1 was used.
The average thickness of the prepared molecular sieve with the TON structure is 9 nanometers, and flaky crystals are randomly staggered and are not regularly stacked together. The silica-alumina ratio of the molecular sieve nano-sheet is 49.9.
Example 6
Except that the material ratio (mol ratio) of the reactants is as follows: SiO 22/Al2O350; 1-Ethyl pyridine bromide/SiO2＝0.05；OH-/SiO2＝0.075；H2O/SiO2＝18；F-/SiO2The procedure of example 1 was repeated except that 0.1 was used.
The average thickness of the prepared molecular sieve with the TON structure is 12 nanometers, and flaky crystals are randomly staggered and are not regularly stacked together. The silica-alumina ratio of the molecular sieve nano-sheet is 22.6.
Example 7
Except that the material ratio (mol ratio) of the reactants is as follows: SiO 22/Al2O350; 1-Ethyl pyridine bromide/SiO2＝0.1；OH-/SiO2＝0.075；H2O/SiO2＝18；F-/SiO2The procedure of example 1 was repeated except that 0.1 was used.
The average thickness of the prepared molecular sieve with the TON structure is 12 nanometers, and flaky crystals are randomly staggered and are not regularly stacked together. The silica-alumina ratio of the molecular sieve nano-sheet is 22.9.
Example 8
Except that the material ratio (mol ratio) of the reactants is as follows: SiO 22/Al2O350; 1-Ethyl pyridine bromide/SiO2＝0.5；OH-/SiO2＝0.075；H2O/SiO2＝18；F-/SiO2The procedure of example 1 was repeated except that 0.1 was used.
The average thickness of the prepared molecular sieve with the TON structure is 7 nanometers, and flaky crystals are randomly staggered and are not regularly stacked together. The silica-alumina ratio of the molecular sieve nano-sheet is 23.7.
Example 9
Except that the material ratio (mol ratio) of the reactants is as follows: SiO 22/Al2O350; 1-Ethyl pyridine bromide/SiO2＝0.25；OH-/SiO2＝0.05；H2O/SiO2＝18；F-/SiO2The procedure of example 1 was repeated except that 0.1 was used.
The average thickness of the prepared molecular sieve with the TON structure is 8 nanometers, and flaky crystals are randomly staggered and are not regularly stacked together. The silica-alumina ratio of the molecular sieve nano-sheet is 23.2.
Example 10
Except that the material ratio (mol ratio) of the reactants is as follows: SiO 22/Al2O350; 1-Ethyl pyridine bromide/SiO2＝0.25；OH-/SiO2＝0.20；H2O/SiO2＝18；F-/SiO2The procedure of example 1 was repeated except that 0.1 was used.
The average thickness of the prepared molecular sieve with the TON structure is 6 nanometers, and flaky crystals are randomly staggered and are not regularly stacked together. The silica-alumina ratio of the molecular sieve nano-sheet is 24.3.
Example 11
Except that the material ratio (mol ratio) of the reactants is as follows: SiO 22/Al2O350; 1-Ethyl pyridine bromide/SiO2＝0.25；OH-/SiO2＝0.40；H2O/SiO2＝18；F-/SiO2The procedure of example 1 was repeated except that 0.1 was used.
The average thickness of the prepared molecular sieve with the TON structure is 6 nanometers, and flaky crystals are randomly staggered and are not regularly stacked together. The silica-alumina ratio of the molecular sieve nano-sheet is 24.8.
Example 12
Except that the material ratio (mol ratio) of the reactants is as follows: SiO 22/Al2O350; 1-Ethyl pyridine bromide/SiO2＝0.25；OH-/SiO2＝0.075；H2O/SiO2＝18；F-/SiO2The procedure of example 1 was repeated except that the amount of the compound was changed to 0.01.
The average thickness of the prepared molecular sieve with the TON structure is 11 nanometers, and flaky crystals are randomly staggered and are not regularly stacked together. The silica-alumina ratio of the molecular sieve nano-sheet is 21.2.
Example 13
Except that the material ratio (mol ratio) of the reactants is as follows: SiO 22/Al2O350; 1-Ethyl pyridine bromide/SiO2＝0.25；OH-/SiO2＝0.075；H2O/SiO2＝18；F-/SiO2The procedure of example 1 was repeated except that the amount of the compound was changed to 0.20.
The average thickness of the prepared molecular sieve with the TON structure is 12 nanometers, and flaky crystals are randomly staggered and are not regularly stacked together. The silica-alumina ratio of the molecular sieve nano-sheet is 22.5.
Example 14
Except that the material ratio (mol ratio) of the reactants is as follows: SiO 22/Al2O350; 1-Ethyl pyridine bromide/SiO2＝0.25；OH-/SiO2＝0.075；H2O/SiO2＝18；F-/SiO2The procedure of example 1 was repeated except that 0.40 was used.
The average thickness of the prepared molecular sieve with the TON structure is 10 nanometers, and flaky crystals are randomly staggered and are not regularly stacked together. The silica-alumina ratio of the molecular sieve nano-sheet is 21.3.
Example 15
The same procedure as in example 1 was repeated, except that the crystallization temperature was 100 ℃.
The average thickness of the prepared molecular sieve with the TON structure is 6 nanometers, and flaky crystals are randomly staggered and are not regularly stacked together. The silica-alumina ratio of the molecular sieve nano-sheet is 54.0.
Example 16
The same procedure as in example 1 was repeated, except that the crystallization temperature was 120 ℃.
The average thickness of the prepared molecular sieve with the TON structure is 7 nanometers, and flaky crystals are randomly staggered and are not regularly stacked together. The silica-alumina ratio of the molecular sieve nano-sheet is 54.0.
Example 17
The same procedure as in example 1 was repeated, except that the crystallization temperature was 180 ℃.
The average thickness of the prepared molecular sieve with the TON structure is 15 nanometers, and flaky crystals are randomly staggered and are not regularly stacked together. The silicon-aluminum ratio of the molecular sieve nanosheet is 55.0.
Example 18
The same procedure as in example 1 was repeated, except that the crystallization time was 1 day.
The average thickness of the prepared molecular sieve with the TON structure is 8 nanometers, and flaky crystals are randomly staggered and are not regularly stacked together. The silicon-aluminum ratio of the molecular sieve nanosheet is 50.4.
Example 19
The same procedure as in example 1 was repeated, except that the crystallization time was 5 days.
The average thickness of the prepared molecular sieve with the TON structure is 12 nanometers, and flaky crystals are randomly staggered and are not regularly stacked together. The silica-alumina ratio of the molecular sieve nano-sheet is 52.4.
Example 20
The same procedure as in example 1 was repeated, except that the crystallization time was 10 days.
The average thickness of the prepared molecular sieve with the TON structure is 12 nanometers, and flaky crystals are randomly staggered and are not regularly stacked together. The silica-alumina ratio of the molecular sieve nano-sheet is 52.6.
Example 21
Except that the material ratio (mol ratio) of the reactants is as follows: SiO 22/Al2O3400; 1-Ethyl pyridine bromide/SiO2＝0.25；OH-/SiO2＝0.075；H2O/SiO2＝18；F-/SiO2The procedure of example 1 was repeated except that 0.1 was used.
The average thickness of the prepared molecular sieve with the TON structure is 10 nanometers, and flaky crystals are randomly staggered and are not regularly stacked together. The silicon-aluminum ratio of the molecular sieve nanosheet is 99.2.
Comparative example 1
Dissolving 19 g of 1-ethyl pyridine bromide, 2 g of sodium aluminate and 1.25 g of sodium hydroxide in 94 g of deionized water, slowly adding 60 g of silica sol under the condition of stirring, then adding 1.2 g of ZSM-22 molecular sieve seed crystal, continuously stirring for one hour, then placing into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and dynamically crystallizing for 3 days at 150 ℃. And after crystallization, filtering, washing and drying to obtain 28.2 g of a solid product, wherein XRD detection results show that the solid product is a mixture of a low-crystallinity ZSM-22 molecular sieve and amorphous silicon-aluminum.
The material ratio (mol ratio) of the reactants is as follows: SiO 22/Al2O350; 1-Ethyl pyridine bromide/SiO2＝0.25；OH-/SiO2＝0.075；H2O/SiO2＝18。
The SEM photograph of the solid product obtained in comparative example 1 is shown in fig. 3, in which a large amount of amorphous silica-alumina is present and the molecular sieve is a plate-like laminate having a thickness of more than 50 nm. The silica to alumina ratio of the product was 69.6.
Comparative example 2
Except that the material ratio (mol ratio) of the reactants is as follows: SiO 22/Al2O320; 1-Ethyl pyridine bromide/SiO2＝0.25；OH-/SiO2＝0.075；H2O/SiO2The comparative example 1 was repeated except for 18.
The prepared solid product is amorphous silicon-aluminum, and the silicon-aluminum ratio of the product is 18.6 according to the calculation of the element content measurement result.
Comparative example 3
The procedure of example 1 was followed, except that the templating agent was hexamethylenediamine.
The prepared solid product is rod-shaped ZSM-22, and the silica-alumina ratio of the molecular sieve is 186 according to the calculation of the element content measurement result.
Comparative example 4
Except that the material ratio (mol ratio) of the reactants is as follows: SiO 22/Al2O3600; 1-Ethyl pyridine bromide/SiO2＝0.25；OH-/SiO2＝0.075；H2O/SiO2＝18；F-/SiO2The procedure of example 1 was repeated except that 0.1 was used.
The prepared solid product is flaky ZSM-22 with a silicon-aluminum ratio of 364.
Comparative example 5
Except that the material ratio (mol ratio) of the reactants is as follows: SiO 22/Al2O350; 1-Ethyl pyridine bromide/SiO2＝0.65；OH-/SiO2＝0.075；H2O/SiO2＝18；F-/SiO2The procedure of example 1 was repeated except that 0.1 was used.
The prepared solid product is a sheet-shaped molecular sieve with a TON structure, partial stacks exist among the sheet-shaped crystals, the average thickness of the sheet-shaped crystals is 35 nanometers, and the silica-alumina ratio of the molecular sieve nanosheet is 22.5.
Comparative example 6
Except that the material ratio (mol ratio) of the reactants is as follows: SiO 22/Al2O350; 1-Ethyl pyridine bromide/SiO2＝0.25；OH-/SiO2＝0.75；H2O/SiO2＝18；F-/SiO2The procedure of example 1 was repeated except that 0.1 was used.
The solid product obtained was a needle-shaped ZSM-22 molecular sieve with an average particle size of 10 x 100 nm and a silica/alumina ratio of 19.6.
Comparative example 7
Except that the material ratio (mol ratio) of the reactants is as follows: SiO 22/Al2O350; 1-Ethyl pyridine bromide/SiO2＝0.25；OH-/SiO2＝0.075；H2O/SiO2＝18；F-/SiO2The procedure of example 1 was repeated except that 0.70 was used.
The obtained solid product is a sheet-shaped molecular sieve with TON structure, partial stacks exist among the sheet-shaped crystals, and the average thickness of the product is 55 nanometers. According to the calculation of the element content measurement result, the silicon-aluminum ratio of the molecular sieve is 24.8.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (10)
1. A method for preparing a molecular sieve with a TON structure comprises the step of carrying out crystallization treatment on a mixture formed by a silicon source, an aluminum source, an alkali source, a template agent, fluoride and water to obtain the molecular sieve with the TON structure.
2. The method of claim 1, wherein the mixture is SiO2Calculated silicon source, calculated as Al2O3Calculated as Al source and OH-Alkali source in F-The molar composition of fluoride, templating agent and water is calculated as follows: SiO 22/Al2O315 to 500; templating agent/SiO20.01 to 0.5; OH group-/SiO20.01 to 0.50; h2O/SiO29 to 30; f-/SiO20.005 to 0.50.
3. Method according to claim 1 or 2, characterized in that in the mixture, SiO is used2Calculated silicon source, calculated as Al2O3Calculated as Al source and OH-Alkali source in F-The molar composition of fluoride, templating agent and water is calculated as follows: SiO 22/Al2O320 to 400; templating agent/SiO20.05 to 0.5; OH group-/SiO20.05 to 0.40; h2O/SiO210 to 26; f-/SiO20.01 to 0.40.
4. The method of any one of claims 1-3, wherein the silicon source comprises at least one of silica gel, silica sol, and tetraalkyl silicate.
5. The method of any one of claims 1-4, wherein the aluminum source comprises at least one of sodium aluminate, aluminum nitrate, aluminum sulfate, aluminum oxide, aluminum hydroxide, and aluminum isopropoxide.
6. The method of any one of claims 1-5, wherein the templating agent is 1-ethylpyridinium bromide.
7. The method according to any one of claims 1 to 6, wherein the crystallization conditions comprise: the crystallization temperature is 80-180 ℃, and preferably 100-180 ℃; the crystallization time is 10 hours to 10 days, preferably 1 to 5 days.
8. The molecular sieve having the TON structure prepared by the method of any one of claims 1-7, wherein the molecular sieve crystals have a plate-like morphology and a crystal thickness of 5-20 nm.
9. The molecular sieve of claim 8, wherein the molecular sieve has a silica to alumina ratio of 15 to 300.
10. The molecular sieve of claim 8 or 9, wherein the molecular sieve contains elemental F.
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