CN115722259A - Synthetic method of space-adjacent bimetallic heteroatom molecular sieve - Google Patents

Synthetic method of space-adjacent bimetallic heteroatom molecular sieve Download PDF

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CN115722259A
CN115722259A CN202110990405.4A CN202110990405A CN115722259A CN 115722259 A CN115722259 A CN 115722259A CN 202110990405 A CN202110990405 A CN 202110990405A CN 115722259 A CN115722259 A CN 115722259A
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molecular sieve
beta molecular
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CN115722259B (en
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王晨光
孙朋垚
文承彦
廖玉河
徐祥龙
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Guangzhou Institute of Energy Conversion of CAS
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Abstract

The invention discloses a synthesis method of a space-adjacent bimetallic heteroatom molecular sieve, which comprises the steps of preparing amorphous gel of Sn-Al hydroxide, synthesizing the amorphous gel serving as a heteroatom precursor into the molecular sieve by a thick gel method, constructing a silicon hydroxyl nest adjacent to Sn in the molecular sieve by dealuminization on the basis of Sn-Al-beta, and realizing the change of a metal atom adjacent to the Sn atom by ion exchange, thereby realizing the accurate control of the adjacent atom of the Sn atom, obtaining the space-adjacent bimetallic heteroatom molecular sieve with a BEA single crystal structure, having high activity and stable performance, greatly improving the conversion efficiency from glucose to methyl lactate by serving as a catalyst in the reaction of catalyzing the conversion of glucose into the methyl lactate, and solving the problems that the prior art cannot accurately control the adjacent atom of the Sn atom and the catalytic activity of a single Sn site in the conventional Sn-beta molecular sieve is low.

Description

Synthetic method of space-adjacent bimetallic heteroatom molecular sieve
The technical field is as follows:
the invention relates to the field of catalysis, in particular to a synthesis method of a space proximity bimetallic heteroatom molecular sieve.
Background art:
the molecular sieve mainly comprises a silicate molecular sieve (zeolite) and a phosphate molecular sieve. Different chemical reactions have different requirements on the pore structure and the catalytic performance of the porous catalytic material. Therefore, the definition and the category of the molecular sieve are expanded by the functional design, the synthesis and the modification of the molecular sieve material. Particularly, the introduction of transition metal heteroatoms in the framework enables the molecular sieve to have multiple functions, further expands the application range of the molecular sieve, and is a catalytic material which is commonly concerned by academia and industry. The molecular sieve skeleton introduces hetero atoms, especially hetero atom molecular sieve with isomorphous transition metal ion substitution of specific catalytic performance, and the metal ions are separated in the molecular sieve skeleton and have high dispersivity and interaction with the molecular sieve skeleton, so that they have special catalytic function different from that of conventional transition metal oxide, and the performance of the molecular sieve is obviously different from that of the parent molecular sieve.
Exploring paths from biomass resources to high value chemicals and fuels has attracted industrial and academic interest. Among these, carbohydrates extracted from biomass are used to produce lactic acid and alkyl lactate, which can be used to produce many chemical intermediates. From the viewpoint of green chemistry and sustainable production, heterogeneous catalysts are worth popularizing in the conversion of carbohydrates to alkyl lactate. This process involves isomerization and retro-aldol condensation of sugars. Transition metal-containing heterozeolites have been developed as general purpose solid lewis acid catalysts for these applications. In particular, the BEA-type tin silicate zeolite, sn-beta, is considered the most advanced catalyst for the conversion of mono-and disaccharides to lactic acid and alkyl lactate.
Representative synthesis strategies for Sn-beta include a bottom-up hydrothermal synthesis strategy and a top-down post-synthesis strategy, i.e., solid phase grafting. Among them, the amount of framework tin incorporation that can be achieved by hydrothermal synthesis is very limited due to the thermodynamic limitations of crystallization, and the framework tin is considered as a catalytic carbonyl reaction center. After-synthesis, more framework Sn atoms can be grafted by an organic tin source, but the Sn atom state of the finished catalyst is difficult to control, and tin oxide is easy to generate. In addition, excessive silanol defects caused by the dealumination step of the post-synthesis process may cause increased side reactions, competitive adsorption of solvents and substrates, and decreased catalyst stability, among others.
Therefore, in addition to increasing the number of active sites, many studies have been conducted to deeply understand the catalytic reaction mechanism of a single Sn atom, thereby improving the reactivity thereof. It has been found that the local environment of the lewis acid centers in the zeolite framework, such as hydrophilicity and hydrophobicity, coordination openness, and other adjacent metal sites, dominates the changes in catalytic activity and selectivity. In particular, the catalytic activity of Sn sites is affected not only by the acidity of Sn atoms but also by the basicity of oxygen atoms bonded to metal atoms. However, in the synthesis strategies that have been published so far, the close atoms of Sn atoms cannot be precisely controlled. This is due to the high mobility of the tetrahedral central atoms, such as Sn, si, al, etc., under conventional zeolite synthesis conditions, which tends to make them randomly distributed in the zeolite framework.
The invention content is as follows:
the invention aims to provide a synthesis method of a space proximity double-metal heteroatom molecular sieve, which comprises the steps of preparing amorphous gel of Sn-Al hydroxide, synthesizing the molecular sieve by using the amorphous gel as a heteroatom precursor through a thick gel method, constructing a silicon hydroxyl nest adjacent to Sn in the molecular sieve through dealumination on the basis of Sn-Al-beta, and realizing the change of Sn atom proximity metal atoms through ion exchange, thereby realizing the accurate control of the Sn atom proximity atoms, obtaining the space proximity double-metal heteroatom molecular sieve with a topological structure of BEA single crystal structure, having high activity and stable performance, greatly improving the conversion efficiency from glucose to methyl lactate by using the molecular sieve as a catalyst in the reaction of catalyzing the conversion of the glucose to the methyl lactate, and solving the problems that the prior art cannot accurately control the Sn atom proximity atoms and the catalytic activity of a single Sn site in the existing Sn-beta molecular sieve is low.
The invention is realized by the following technical scheme:
a method for synthesizing a spatially-adjacent bimetallic heteroatom molecular sieve, the method comprising the steps of:
(1) Mixing and dissolving sodium hydroxide and an aluminum source in water until the mixture is clear, then adding a tin source to obtain hydroxide gel, fully mixing the hydroxide gel with a template agent and water, and aging the mixture for 48 hours at 90 ℃ in a sealed container; the aluminum source is selected from one or a combination of more of sodium metaaluminate, aluminum isopropoxide and aluminum hydroxide; the template agent is at least one of tetraethyl ammonium fluoride, tetraethyl ammonium chloride and tetraethyl ammonium bromide; the molar ratio of the sodium hydroxide, the aluminum source, the tin source, the template agent and the water is (0.1-1): (0.1-1) 1.0, (5-100) and (1-50);
(2) Then, adding a mixed solution of water and a silicon source, and stirring and hydrolyzing at room temperature; the silicon source is at least one of tetraethoxysilane, gas-phase white carbon black or silica sol; the molar ratio of the water, the silicon source and the tin source in the step (1) is (1-50): (100-200): 1.0;
(3) Then adding beta molecular sieve as seed crystal, and evaporating out all ethanol and partial water at 70-80 ℃; the beta molecular sieve is one or a combination of more of a silicon-aluminum beta molecular sieve, a boron-silicon beta molecular sieve or a pure silicon beta molecular sieve after dealumination;
(4) Then transferring the mixture into a closed container, and crystallizing the mixture for 2 to 40 days at a temperature of between 130 and 200 ℃; centrifugally washing the crystallized solid, drying at 60-150 ℃ for 6-72 hours, and calcining at 400-650 ℃ for 3-24 hours to obtain the Sn-Al-beta molecular sieve;
(5) Then, using acid solution to carry out reflux dealuminization treatment on the Sn-Al-beta molecular sieve for 2-10 times at the temperature of 30-100 ℃, then washing, drying for 6-72 hours at the temperature of 60-150 ℃, and calcining for 3-24 hours at the temperature of 400-650 ℃ to obtain the Sn-OH-beta molecular sieve; the acid is at least one selected from hydrochloric acid, nitric acid, sulfuric acid, acetic acid, oxalic acid and citric acid; the concentration of the acid solution is 0.05-5 mol/L;
(6) Then, carrying out ion exchange on the Sn-OH-beta molecular sieve by using a metal M nitrate aqueous solution to obtain the Sn-M-beta molecular sieve, namely the beta molecular sieve containing adjacent bimetallic heteroatoms; the metal M is selected from one of nickel, cobalt, iron, manganese, chromium, copper, zinc, yttrium and magnesium.
In the step (1), the tin source may be one or a mixture of inorganic tin sources such as tin tetrachloride and stannous chloride, or one or a mixture of organic tin sources such as tin oxalate, alkyl tin and organic tin acid ester.
In the step (6), the concentration of the metal M nitrate aqueous solution is 0.05-2 mol/L; the treatment temperature is 25-100 ℃; the treatment time is 3 to 48 hours; the treatment times are 2-10 times.
The beta molecular sieve containing bimetallic heteroatoms obtained by the invention can be directly used as a catalyst.
The beta functional molecular sieve catalyst containing the bimetallic heteroatom has good catalytic performance in a plurality of fine chemical reaction processes such as catalytic conversion of biomass, for example, catalytic conversion of glucose into methyl lactate and the like.
The invention has the following beneficial effects: the method comprises the steps of preparing amorphous gel of Sn-Al hydroxide, synthesizing a molecular sieve by using the amorphous gel as a heteroatom precursor through a thick gel method, constructing a silicon hydroxyl nest adjacent to Sn in the molecular sieve through dealuminization on the basis of Sn-Al-beta, and changing a metal atom adjacent to the Sn atom through ion exchange, so that the adjacent atom of the Sn atom is accurately controlled, and the spatially adjacent bimetallic heteroatom molecular sieve with a BEA single crystal structure is obtained.
Description of the drawings:
FIG. 1 is an XRD spectrum of the Sn-Co-beta molecular sieve prepared in example 1.
FIG. 2 is an XPS spectrum of Co element of Sn-Co-beta molecular sieve prepared in example 1
FIG. 3 is an XRD spectrum of Sn-Ni-beta molecular sieve prepared in example 2.
FIG. 4 is an XRD spectrum of the Sn-Ni-beta molecular sieve prepared in example 3.
FIG. 5 is an XPS spectrum of the Ni element of the Sn-Ni-beta molecular sieve prepared in example 2.
FIG. 6 is an XPS spectrum of the Ni element of the Sn-Ni-beta molecular sieve prepared in example 3.
FIG. 7 is an XPS spectrum of Ni element of Sn-Ni-beta molecular sieve prepared in comparative example 1.
The specific implementation mode is as follows:
the following is a further description of the invention and is not intended to be limiting.
Example 1:
calcining 3g of a beta molecular sieve (silicon-aluminum ratio = 21) at 550 ℃ for 4 hours, adding concentrated nitric acid according to the weight ratio of liquid to solid of 30, and performing reflux treatment at 120 ℃ for 24 hours to obtain the beta molecular sieve seed crystal.
0.04g of sodium hydroxide and 0.09g of sodium metaaluminate are mixed and dissolved in 6g of water until clear. 0.366g of hydrated tin tetrachloride solution was dissolved in 10g of water until it was clear, and it was slowly added dropwise to the above reaction system under vigorous stirring. The hydroxide gel was obtained by centrifugation, mixed well with 9.5g tetraethylammonium fluoride (TEAF) dissolved in an ultrasonic water bath, and aged in a sealed container at 90 ℃ for 48 hours. Subsequently, 12 grams of water was added and mixed with 20.94 grams of TEOS while stirring vigorously at room temperature until complete hydrolysis. Dispersing 0.25g of beta molecular sieve seed crystal in gel, and then evaporating all ethanol and partial water at 70 ℃ under infrared light to obtain a uniformly mixed crystallization mixture, namely SiO 2 :SnO 2 :Al 2 O 3 :TEAF:H 2 The molar ratio of O is 1:0.008:0.004:0.54:11. then transferred to a stainless steel vessel with a teflon liner and crystallized at 140 c for 15 days. The solid obtained after crystallization was centrifuged and washed five times with deionized water. Dried at 100 ℃ and calcined in flowing air at 550 ℃ for 6 hours.
The obtained solid was refluxed twice for 24 hours at 100 ℃ using a 5mol/L aqueous oxalic acid solution. The resulting solid was centrifuged again and washed five times with deionized water. Dried at 100 ℃ and calcined in flowing air at 550 ℃ for 6 hours.
The obtained solid was put into a 1.5mol/L aqueous solution of cobalt nitrate, charged in a ratio of 20 by weight of the liquid to the solid, and subjected to reflux treatment at 40 ℃ for 24 hours. The resulting solid was centrifuged again and washed five times with deionized water. Drying at 100 ℃ to obtain the beta molecular sieve containing bimetallic heteroatoms Sn and Co. The XRD spectrogram of the prepared Sn-Co-beta molecular sieve is shown in figure 1, and shows a remarkable diffraction peak corresponding to BEA topological structure, and other miscellaneous peaks are not found. Therefore, the molecular sieve obtained can be judged to be BEA single-component structure.
Example 2:
3g of borosilicate beta molecular sieve (silicon-boron ratio = 21) is firstly calcined for 4 hours at the temperature of 550 ℃, concentrated nitric acid is added according to the weight ratio of liquid to solid of 30, and reflux treatment is carried out for 24 hours at the temperature of 120 ℃, so as to obtain beta molecular sieve seed crystal.
0.04g of sodium hydroxide and 0.09g of sodium metaaluminate are mixed and dissolved in 6g of water until clear. 0.366g of hydrated tin tetrachloride solution was dissolved in 10g of water until it was clear, and it was slowly added dropwise to the above reaction system under vigorous stirring. The hydroxide gel was obtained by centrifugation, mixed well with 9.5g tetraethylammonium fluoride (TEAF) dissolved in an ultrasonic water bath, and aged in a sealed container at 90 ℃ for 48 hours. Subsequently, 12 grams of water was added and mixed with 20.94 grams of TEOS while stirring vigorously at room temperature until complete hydrolysis. Dispersing 0.25g of beta molecular sieve seed crystal in gel, and evaporating all ethanol and part of water under 70 ℃ infrared light to obtain uniformly mixed crystallization mixture, namely SiO 2 :SnO 2 :Al 2 O 3 :TEAF:H 2 Molar ratio of OExamples are 1:0.008:0.004:0.54:11, transferred to a stainless steel vessel with a teflon liner and crystallized at 140 ℃ for 25 days. The solid obtained after crystallization was centrifuged and washed five times with deionized water. Dried at 100 ℃ and calcined in flowing air at 550 ℃ for 6 hours.
The obtained solid was refluxed twice for 24 hours at 100 ℃ using a 5mol/L aqueous oxalic acid solution. The resulting solid was centrifuged again and washed five times with deionized water. Dried at 100 ℃ and calcined in flowing air at 550 ℃ for 6 hours.
The obtained solid was put into a 1.5mol/L aqueous solution of nickel nitrate, charged in a ratio of 20 by weight of the liquid to the solid, and subjected to reflux treatment at 40 ℃ for 24 hours. The resulting solid was centrifuged again and washed five times with deionized water. Drying at 100 ℃ to obtain the beta molecular sieve containing the bimetallic heteroatoms Sn and Ni. An XRD spectrogram of the prepared Sn-Ni-beta molecular sieve is shown in figure 3, and shows a remarkable diffraction peak corresponding to a BEA topological structure, and other miscellaneous peaks are not found. The molecular sieve thus obtained can be judged to be a BEA monocomponent structure. The XPS spectrogram of the Ni element of the prepared Sn-Ni-beta molecular sieve is shown in FIG. 5, and is obviously different from the XPS spectrogram of the Ni element in the bimetallic heteroatom molecular sieve obtained in comparative example 1, and the fact that the bimetallic heteroatom in the embodiment has the spatial proximity characteristic can be proved.
Example 3:
calcining the pure silicon beta molecular sieve at 550 ℃ for 4 hours to obtain the beta molecular sieve seed crystal.
0.02g of sodium hydroxide and 0.045g of sodium metaaluminate are mixed and dissolved in 6g of water until clear. Then, 0.183g of a hydrated tin tetrachloride solution was dissolved in 10g of water until it was clear, and this was slowly added dropwise to the above reaction system under vigorous stirring. The hydroxide gel was obtained by centrifugation, mixed well with 9.5g tetraethylammonium fluoride (TEAF) dissolved in an ultrasonic water bath, and aged in a sealed container at 90 ℃ for 48 hours. Subsequently, 12 grams of water was added and mixed with 20.94 grams of TEOS while stirring vigorously at room temperature until complete hydrolysis. 0.25g of beta molecular sieve seed crystal is dispersed in the gel, and then all ethanol and part of water are evaporated under infrared light at 70 ℃ to obtain a uniformly mixed crystallization mixture. Then transferred to a stainless steel vessel with a teflon liner and crystallized at 140 c for 25 days. The solid obtained after crystallization was centrifuged and washed five times with deionized water. Dried at 100 ℃ and calcined in flowing air at 550 ℃ for 6 hours.
The obtained solid was refluxed twice for 24 hours at 100 ℃ using a 5mol/L aqueous solution of oxalic acid. The resulting solid was centrifuged again and washed five times with deionized water. Dried at 100 ℃ and calcined in flowing air at 550 ℃ for 6 hours.
The obtained solid was put into a 1.5mol/L aqueous solution of nickel nitrate, charged in a ratio of 20 by weight of the liquid to the solid, and subjected to reflux treatment at 40 ℃ for 24 hours. The resulting solid was centrifuged again and washed five times with deionized water. Drying at 100 ℃ to obtain the beta molecular sieve containing the bimetallic heteroatoms Sn and Ni. The XRD spectrogram of the prepared Sn-Ni-beta molecular sieve is shown in figure 4, and shows a remarkable diffraction peak corresponding to BEA topological structure, and other miscellaneous peaks are not found. Therefore, the obtained molecular sieve can be judged as a BEA single-component structure. The XPS spectrogram of the Ni element of the prepared Sn-Ni-beta molecular sieve is shown as figure 6, and is obviously different from the XPS spectrogram of the Ni element in the bimetallic heteroatom molecular sieve obtained in the comparative example 1, so that the bimetallic heteroatom in the embodiment has a spatial proximity characteristic.
Comparative example 1:
the reference "the Tolborg" reference,
Figure BDA0003232249100000081
s, daba, irantzu; osmundsen, christian m.; fristrup, peter; holm, martin s.; taarning, esben (2015) Tin-relating Silicates: alkali Salts Improve Methyl Lactate from Sugars. In ChemSus chem 8 (4), pp.613-617.DOI: the proportion (weight ratio) of the solid of 20 was refluxed at 40 ℃ for 24 hours. The resulting solid was centrifuged again and washed five times with deionized water. Drying at 100 deg.CAnd drying to obtain the beta molecular sieve containing the bimetallic heteroatoms Sn and Ni. The XPS pattern of the Ni element is shown in FIG. 7, which is clearly different from that of example 3, and shows that the hetero atom in example 3 has a close-space property.
The application example is as follows:
reaction tests were carried out in the reaction of converting glucose into methyl lactate using the molecular sieves obtained in example 1, example 2, example 3 and comparative example 1 as catalysts. The reaction conditions are as follows: 200mg of catalyst and 500mg of glucose were added to 30ml of an aqueous methanol solution with a concentration of 90% by weight. The reaction was carried out in a stainless steel batch reactor at 443K. A gas chromatograph GC-2014C (Shimadzu, japan) equipped with an HP-5 (30 m.times.250 mm.times.0.25 μm) column and a FID detector was used for product analysis. The catalytic effect of several catalysts is shown in table 1.
TABLE 1
Figure BDA0003232249100000091

Claims (7)

1. A method for synthesizing a spatially-adjacent bimetallic heteroatom molecular sieve, the method comprising the steps of:
(1) Mixing and dissolving sodium hydroxide and an aluminum source in water until the mixture is clear, then adding a tin source to obtain hydroxide gel, fully mixing the hydroxide gel with a template agent and water, and aging the mixture for 48 hours at 90 ℃ in a sealed container; the aluminum source is selected from one or a combination of more of sodium metaaluminate, aluminum isopropoxide and aluminum hydroxide; the template agent is at least one of tetraethyl ammonium fluoride, tetraethyl ammonium chloride and tetraethyl ammonium bromide; the molar ratio of the sodium hydroxide, the aluminum source, the tin source, the template agent and the water is (0.1-1): 1.0, (5-100): 1-50);
(2) Then, adding a mixed solution of water and a silicon source, and stirring at room temperature for hydrolysis; the molar ratio of the water, the silicon source and the tin source in the step (1) is (1-50): (100-200): 1.0; the silicon source is at least one of tetraethoxysilane, gas-phase white carbon black or silica sol;
(3) Then adding beta molecular sieve as seed crystal, and evaporating out all ethanol and partial water at 70-80 ℃; the beta molecular sieve is one or a combination of more of a silicon-aluminum beta molecular sieve, a boron-silicon beta molecular sieve or a pure silicon beta molecular sieve after dealumination;
(4) Then transferring the mixture into a closed container, and crystallizing the mixture for 2 to 40 days at a temperature of between 130 and 200 ℃; centrifugally washing the crystallized solid, drying at 60-150 ℃ for 6-72 hours, and calcining at 400-650 ℃ for 3-24 hours to obtain the Sn-Al-beta molecular sieve;
(5) Then, using acid solution to carry out reflux dealuminization treatment on the Sn-Al-beta molecular sieve for 2-10 times at the temperature of 30-100 ℃, then washing, drying for 6-72 hours at the temperature of 60-150 ℃, and calcining for 3-24 hours at the temperature of 400-650 ℃ to obtain the Sn-OH-beta molecular sieve; the acid is at least one selected from hydrochloric acid, nitric acid, sulfuric acid, acetic acid, oxalic acid and citric acid; the concentration of the acid solution is 0.05-5 mol/L;
(6) Then, carrying out ion exchange on the Sn-OH-beta molecular sieve by using a metal M nitrate aqueous solution to obtain the Sn-M-beta molecular sieve, namely the beta molecular sieve containing adjacent bimetallic heteroatoms; the metal M is one of nickel, cobalt, iron, manganese, chromium, copper, zinc, yttrium and magnesium.
2. The method for synthesizing a sterically close bimetallic heteroatom molecular sieve as claimed in claim 1, wherein in step (1), the tin source is an inorganic tin source or an organic tin source.
3. The method of claim 2, wherein the inorganic tin source comprises tin tetrachloride or stannous chloride.
4. The method of claim 2, wherein the organotin source comprises tin oxalate, alkyltin, organotin acid ester.
5. The method for synthesizing a spatially-adjacent bimetallic heteroatom molecular sieve as claimed in claim 1, wherein in the step (6), the concentration of the metal M nitrate aqueous solution is 0.05-2 mol/L; the treatment temperature is 25-100 ℃; the treatment time is 3 to 48 hours; the treatment times are 2-10 times.
6. Use of a sterically close bimetallic heteroatom molecular sieve as claimed in any one of claims 1 to 5, as a catalyst in the synthesis of said sterically close bimetallic heteroatom molecular sieve.
7. The use of a sterically close bimetallic heteroatom molecular sieve as in claim 6, characterized in that it catalyzes the conversion of glucose to methyl lactate.
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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1149000A (en) * 1995-10-06 1997-05-07 中国石油化工总公司 Polymetal carrying alkyl aromatic hydrocarbon isomerization catalyst
CN102249258A (en) * 2011-05-06 2011-11-23 大连理工大学 Method for synthesizing heteroatom Sn-beta zeolite
CN103920527A (en) * 2014-04-24 2014-07-16 南开大学 Catalyst for preparing 1,2-glycol by epoxy compound through hydration as well as preparation method and application thereof
CN104707649A (en) * 2013-12-16 2015-06-17 中国科学院大连化学物理研究所 Tin-containing molecular sieve with BEA topological structure and preparation and application thereof
CN105879902A (en) * 2016-05-19 2016-08-24 郑州大学 Preparation method for molecular sieve catalyst of sugar conversion preparation of lactic acid and lactate
CN107311201A (en) * 2017-07-04 2017-11-03 江西师范大学 The method that nanometer Sn beta-molecular sieves and preparation method thereof and phenol hydroxylation react
US20180057364A1 (en) * 2016-08-29 2018-03-01 Purdue Research Foundation Processes for producing materials having a zeolite-type framework with heteroatoms incorporated therein
CN107899607A (en) * 2017-11-17 2018-04-13 中国石油大学(北京) A kind of modified beta molecular sieve and its preparation method and application
CN108212207A (en) * 2018-03-23 2018-06-29 陕西师范大学 A kind of catalyzed conversion glucose prepares solid acid catalyst of methyl lactate and preparation method thereof

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1149000A (en) * 1995-10-06 1997-05-07 中国石油化工总公司 Polymetal carrying alkyl aromatic hydrocarbon isomerization catalyst
CN102249258A (en) * 2011-05-06 2011-11-23 大连理工大学 Method for synthesizing heteroatom Sn-beta zeolite
CN104707649A (en) * 2013-12-16 2015-06-17 中国科学院大连化学物理研究所 Tin-containing molecular sieve with BEA topological structure and preparation and application thereof
CN103920527A (en) * 2014-04-24 2014-07-16 南开大学 Catalyst for preparing 1,2-glycol by epoxy compound through hydration as well as preparation method and application thereof
CN105879902A (en) * 2016-05-19 2016-08-24 郑州大学 Preparation method for molecular sieve catalyst of sugar conversion preparation of lactic acid and lactate
US20180057364A1 (en) * 2016-08-29 2018-03-01 Purdue Research Foundation Processes for producing materials having a zeolite-type framework with heteroatoms incorporated therein
CN107311201A (en) * 2017-07-04 2017-11-03 江西师范大学 The method that nanometer Sn beta-molecular sieves and preparation method thereof and phenol hydroxylation react
CN107899607A (en) * 2017-11-17 2018-04-13 中国石油大学(北京) A kind of modified beta molecular sieve and its preparation method and application
CN108212207A (en) * 2018-03-23 2018-06-29 陕西师范大学 A kind of catalyzed conversion glucose prepares solid acid catalyst of methyl lactate and preparation method thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
PENGYAO SUN ET AL.: "Rational Positioning of Metal Ions to Stabilize Open Tin Sites in Beta Zeolite for Catalytic Conversion of Sugars", 《ANGEW. CHEM. INT. ED.。, vol. 62, pages 202215737 *
QIANG CAI ET AL.: "Hierarchical Fe–Sn/Beta catalyzes the conversion of glucose to methyl lactate", 《JOURNAL OF POROUS MATERIALS》, vol. 28, pages 1315 - 1324, XP037552804, DOI: 10.1007/s10934-021-01082-4 *
康自华等: "杂原子 Sn-β 分子筛的脱铝补位两步法制备、表征及其催化 环己酮 Baeyer-Villiger 氧化性能", 《催化学报》, vol. 33, no. 5, pages 898 - 904 *

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