CN115722259B - Synthesis method of space adjacent bimetallic heteroatom molecular sieve - Google Patents

Synthesis method of space adjacent bimetallic heteroatom molecular sieve Download PDF

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CN115722259B
CN115722259B CN202110990405.4A CN202110990405A CN115722259B CN 115722259 B CN115722259 B CN 115722259B CN 202110990405 A CN202110990405 A CN 202110990405A CN 115722259 B CN115722259 B CN 115722259B
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CN115722259A (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 is characterized in that amorphous gel of Sn-Al hydroxide is prepared and is used as a heteroatom precursor to synthesize the molecular sieve by a thick gel method, on the basis of Sn-Al-beta, silicon hydroxyl nest adjacent to Sn in the molecular sieve is constructed by dealumination, and then the change of Sn atoms adjacent to metal atoms is realized by ion exchange, so that the accurate control of the Sn atoms adjacent to the metal atoms is realized, and the space adjacent bimetallic heteroatom molecular sieve with a BEA monocrystal structure is obtained.

Description

Synthesis method of space adjacent bimetallic heteroatom molecular sieve
Technical field:
the invention relates to the field of catalysis, in particular to a synthesis method of a space adjacent bimetallic heteroatom molecular sieve.
The background technology is as follows:
the molecular sieve mainly comprises silicate molecular sieve (zeolite) and phosphate molecular sieve. Different chemical reactions have different requirements on the pore channel structure and the catalytic performance of the porous catalytic material. Therefore, the definition and the category of the molecular sieve are enlarged by functional design, synthesis and modification of the molecular sieve material. In particular, the introduction of the transition metal hetero atoms in the framework enables the molecular sieve to have multifunction, further expands the application range of the molecular sieve, and is a catalytic material which is concerned by the academic world and the industry together. The molecular sieve skeleton introduces hetero atoms, especially hetero atom molecular sieve with specific catalytic performance and obtained through isomorphous substitution of transition metal ion, and has special catalytic function, different from that of the parent molecular sieve, owing to the interaction with the parent molecular sieve skeleton, the metal ion has excellent acidity and surface performance, and is favorable to multifunctional catalysis.
The exploration of paths from biomass resources to high value chemicals and fuels has attracted industry and academia. Among them, carbohydrates extracted from biomass are used to produce lactic acid and alkyl lactate, and can be used to produce many chemical intermediates. From the standpoint of green chemistry and sustainable production, heterogeneous catalysts are worth popularizing in terms of the conversion of carbohydrates to alkyl lactate. The process involves isomerization and reverse aldol condensation of sugars. Transition metal containing heterozeolites have been developed as versatile solid lewis acid catalysts for these applications. In particular, BEA-type tin silicate zeolites, sn-beta, are considered to be the most advanced catalysts for the conversion of mono-and disaccharides into lactic acid and alkyl lactate.
Representative synthetic 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 hydrothermal synthesis can achieve very limited incorporation of framework tin due to the limitation of crystallization thermodynamics, and framework tin is considered as a catalytic carbonyl reaction center. After synthesis, more skeleton Sn atoms can be grafted through an organotin source, but the Sn atom state of a 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 lead to increased side reactions, competitive adsorption of solvents and substrates, and reduced catalyst stability, etc.
Thus, in addition to increasing the number of active sites, much research has been devoted to understanding the catalytic reaction mechanism of a single Sn atom, thereby improving its reactivity. It has been found that the local environment of lewis acid centers in the zeolite framework, such as hydrophilicity and hydrophobicity, coordination openness, and other adjacent metal sites, dominate the variation in catalytic activity and selectivity. In particular, the catalytic activity of Sn sites is affected not only by the acidity of the Sn atoms but also by the basicity of oxygen atoms bound to the metal atoms. However, in the synthesis strategies already published at present, precise control of the adjacent atoms of Sn atoms is not possible. This is due to the high mobility of tetrahedral central atoms such as Sn, si, al, etc. under conventional zeolite synthesis conditions, which tend to randomly distribute them in the zeolite framework.
The invention comprises the following steps:
the invention aims to provide a synthesis method of a space adjacent bimetallic heteroatom molecular sieve, which is characterized in that amorphous gel of Sn-Al hydroxide is prepared and is used as a heteroatom precursor to synthesize the molecular sieve by a thick gel method, on the basis of Sn-Al-beta, a silicon hydroxyl nest adjacent to Sn in the molecular sieve is constructed by dealumination, and then the change of Sn atoms adjacent to metal atoms is realized by ion exchange, so that the accurate control of the Sn atoms adjacent to the metal atoms is realized, the space adjacent bimetallic heteroatom molecular sieve with a BEA monocrystal structure is obtained, the molecular sieve has high activity and stable performance, the conversion efficiency of glucose to methyl lactate is greatly improved as a catalyst in the reaction of catalyzing the conversion of glucose to methyl lactate, and the problems that the prior art cannot accurately control the Sn atoms adjacent to the metal atoms and the catalytic activity of a single Sn site in the prior Sn-beta molecular sieve is lower are solved.
The invention is realized by the following technical scheme:
a method for synthesizing a spatially adjacent bimetallic heteroatom molecular sieve, comprising the steps of:
(1) Mixing and dissolving sodium hydroxide and an aluminum source in water until the mixture is clear, adding a tin source to obtain hydroxide gel, fully mixing the hydroxide gel with a template agent and water, and aging the mixture in a sealed container at 90 ℃ for 48 hours; the aluminum source is selected from one or a combination of several of sodium metaaluminate, aluminum isopropoxide and aluminum hydroxide; the template agent is at least one of tetraethylammonium fluoride, tetraethylammonium chloride and tetraethylammonium bromide; the molar ratio of the sodium hydroxide to the aluminum source to the tin source to the template agent to the water is (0.1-1): (0.1-1) 1.0 (5-100) 1-50);
(2) Then adding the 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 mol 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, evaporating all ethanol and partial water at 70-80 deg.C; the beta molecular sieve is one or a combination of a plurality of dealuminated silicon-aluminum beta molecular sieves, boron-silicon beta molecular sieves or pure silicon beta molecular sieves;
(4) Then transferring the mixture into a closed container, and crystallizing the mixture for 2 to 40 days at the temperature of between 130 and 200 ℃; centrifugally washing the solid obtained by crystallization, 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, carrying out reflux dealumination treatment on the Sn-Al-beta molecular sieve for 2-10 times at 30-100 ℃ by using an acid solution, washing, drying at 60-150 ℃ for 6-72 hours, and calcining at 400-650 ℃ for 3-24 hours to obtain the Sn-OH-beta molecular sieve; the acid is at least one of 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 may be one or a mixture of several organic tin sources such as tin oxalate, alkyl tin, and organic stannate.
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 the bimetallic heteroatom can be directly used as a catalyst.
The beta functional molecular sieve catalyst containing the bimetallic heteroatom has good catalytic performance in the processes of biomass catalytic conversion, such as catalytic conversion of glucose into methyl lactate and other fine chemical reactions.
The beneficial effects of the invention are as follows: according to the invention, the amorphous gel of the Sn-Al hydroxide is prepared, and is used as a hetero atom precursor to synthesize the molecular sieve by a thick gel method, on the basis of Sn-Al-beta, the silicon hydroxyl nest adjacent to Sn in the molecular sieve is constructed by dealumination, and then the change of the adjacent metal atoms of Sn atoms is realized by ion exchange, so that the accurate control of the adjacent atoms of Sn atoms is realized, and the spatial adjacent bimetallic hetero atom molecular sieve with the topological structure of BEA single crystal structure is obtained.
Description of the drawings:
FIG. 1 is an XRD spectrum of a Sn-Co-beta molecular sieve prepared in example 1.
FIG. 2 is an XPS spectrum of the Co element of the Sn-Co-beta molecular sieve prepared in example 1
FIG. 3 is an XRD spectrum of the 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 Ni element of the Sn-Ni-beta molecular sieve prepared in example 2.
FIG. 6 is an XPS spectrum of Ni element of the Sn-Ni-beta molecular sieve prepared in example 3.
FIG. 7 is an XPS spectrum of Ni element of the Sn-Ni-beta molecular sieve prepared in comparative example 1.
The specific embodiment is as follows:
the following is a further illustration of the invention and is not a limitation of the invention.
Example 1:
3g of beta molecular sieve (silicon aluminum ratio=21) is calcined for 4 hours at 550 ℃, concentrated nitric acid is added according to the weight ratio of liquid to solid being 30, and reflux treatment is carried out for 24 hours at 120 ℃, thus obtaining the beta molecular sieve seed crystal.
0.04g of sodium hydroxide and 0.09g of sodium metaaluminate were dissolved in 6g of water in a mixture until clear. Then, 0.366g of a tin tetrachloride hydrate solution was dissolved in 10g of water until it became clear, and the solution was slowly added dropwise to the above reaction system with vigorous stirring. Hydroxide gel was obtained by centrifugation, thoroughly mixed with 9.5g tetraethylammonium fluoride (TEAF) dissolved in an ultrasonic water bath, and aged in a sealed vessel at 90℃for 48 hours. Subsequently, 12 g of water was added and mixed with 20.94 g of TEOS while vigorously stirring at room temperature until complete hydrolysis. Dispersing beta molecular sieve seed crystal 0.25g in gel, evaporating all ethanol and partial water at 70deg.C under infrared light to obtain crystallized mixture, 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 polytetrafluoroethylene lining and crystallized at 140 ℃ for 15 days. The solid obtained after crystallization was centrifuged and washed five times with deionized water. Drying at 100deg.C, and calcining in flowing air at 550deg.C for 6 hr.
The resulting solid was refluxed for 24 hours at 100℃twice using 5mol/L oxalic acid aqueous solution. The resulting solid was centrifuged and washed five times with deionized water. Drying at 100deg.C, and calcining in flowing air at 550deg.C for 6 hr.
The solid obtained was put into a 1.5mol/L aqueous cobalt nitrate solution, and the mixture was fed in a ratio of 20 by weight of liquid to solid, and was subjected to reflux treatment at 40℃for 24 hours. The resulting solid was centrifuged and washed five times with deionized water. Drying at 100 ℃ to obtain the beta molecular sieve containing bimetallic hetero atoms Sn and Co. The XRD spectrum of the prepared Sn-Co-beta molecular sieve is shown in figure 1, shows remarkable diffraction peaks corresponding to BEA topological structure, and does not find other miscellaneous peaks. It can thus be judged that the molecular sieve obtained is of BEA monocomponent structure.
Example 2:
3g of boron-silicon beta molecular sieve (silicon-boron ratio=21) is calcined for 4 hours at 550 ℃, concentrated nitric acid is added according to the weight ratio of liquid to solid being 30, and reflux treatment is carried out for 24 hours at 120 ℃, thus obtaining the beta molecular sieve seed crystal.
0.04g of sodium hydroxide and 0.09g of sodium metaaluminate were dissolved in 6g of water in a mixture until clear. Then, 0.366g of a tin tetrachloride hydrate solution was dissolved in 10g of water until it became clear, and the solution was slowly added dropwise to the above reaction system with vigorous stirring. Hydroxide gel was obtained by centrifugation, thoroughly mixed with 9.5g tetraethylammonium fluoride (TEAF) dissolved in an ultrasonic water bath, and aged in a sealed vessel at 90℃for 48 hours. Subsequently, 12 g of water was added and mixed with 20.94 g of TEOS while vigorously stirring at room temperature until complete hydrolysis. Dispersing beta molecular sieve seed crystal 0.25g in gel, evaporating all ethanol and part of water at 70deg.C under infrared light to obtain uniformly mixed crystallization mixture, 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 transferred to a stainless steel vessel with polytetrafluoroethylene liner and crystallized at 140 ℃ for 25 days. The solid obtained after crystallization was centrifuged and washed five times with deionized water. Drying at 100deg.C, and calcining in flowing air at 550deg.C for 6 hr.
The resulting solid was refluxed for 24 hours at 100℃twice using 5mol/L oxalic acid aqueous solution. The resulting solid was centrifuged and washed five times with deionized water. Drying at 100deg.C, and calcining in flowing air at 550deg.C for 6 hr.
The resulting solid was put into a 1.5mol/L nickel nitrate aqueous solution, and the mixture was fed in a ratio of 20 by weight of liquid to solid, and was subjected to reflux treatment at 40℃for 24 hours. The resulting solid was centrifuged and washed five times with deionized water. Drying at 100 ℃ to obtain the beta molecular sieve containing bimetallic hetero atoms Sn and Ni. The XRD spectrum of the prepared Sn-Ni-beta molecular sieve is shown in figure 3, shows remarkable diffraction peaks corresponding to BEA topological structure, and does not find other miscellaneous peaks. It can thus be judged that the molecular sieve obtained is of BEA monocomponent structure. The XPS spectrum of the Ni element of the prepared Sn-Ni-beta molecular sieve is shown in FIG. 5, which is obviously different from that of the Ni element in the bimetallic heteroatom molecular sieve obtained in comparative example 1, and the bimetallic heteroatom in the embodiment can be proved to have a space adjacent characteristic.
Example 3:
calcining the pure silicon beta molecular sieve for 4 hours at 550 ℃ to obtain beta molecular sieve seed crystal.
0.02g of sodium hydroxide and 0.045g of sodium metaaluminate were dissolved in 6g of water in a mixture until clear. Then, 0.183g of a hydrated tin tetrachloride solution was dissolved in 10g of water until clear, and slowly dropped into the above-mentioned reaction system with vigorous stirring. Hydroxide gel was obtained by centrifugation, thoroughly mixed with 9.5g tetraethylammonium fluoride (TEAF) dissolved in an ultrasonic water bath, and aged in a sealed vessel at 90℃for 48 hours. Subsequently, 12 g of water was added and mixed with 20.94 g of TEOS while vigorously stirring at room temperature until complete hydrolysis. Beta molecular sieve seed crystals 0.25g were dispersed in the gel, and then all ethanol and part of the water were evaporated under 70 ℃ infrared light to obtain a well-mixed crystallization mixture. Then transferred to a stainless steel vessel with polytetrafluoroethylene lining and crystallized at 140 ℃ for 25 days. The solid obtained after crystallization was centrifuged and washed five times with deionized water. Drying at 100deg.C, and calcining in flowing air at 550deg.C for 6 hr.
The resulting solid was refluxed for 24 hours at 100℃twice using 5mol/L oxalic acid aqueous solution. The resulting solid was centrifuged and washed five times with deionized water. Drying at 100deg.C, and calcining in flowing air at 550deg.C for 6 hr.
The resulting solid was put into a 1.5mol/L nickel nitrate aqueous solution, and the mixture was fed in a ratio of 20 by weight of liquid to solid, and was subjected to reflux treatment at 40℃for 24 hours. The resulting solid was centrifuged and washed five times with deionized water. Drying at 100 ℃ to obtain the beta molecular sieve containing bimetallic hetero atoms Sn and Ni. The XRD spectrum of the prepared Sn-Ni-beta molecular sieve is shown in figure 4, shows remarkable diffraction peaks corresponding to BEA topological structure, and does not find other miscellaneous peaks. It can thus be judged that the molecular sieve obtained is of BEA monocomponent structure. The XPS spectrum of the Ni element of the prepared Sn-Ni-beta molecular sieve is shown in figure 6, and is obviously different from that of the Ni element in the bimetallic heteroatom molecular sieve obtained in comparative example 1, so that the bimetallic heteroatom in the embodiment has the space adjacent characteristic.
Comparative example 1:
the reference "tolberg,s.a.daba., irantzu; osmundsen, christian m; fristrup, peter; holm, martin s.; taanning, esben (2015): tin-containing Silicates: alkali Salts Improve Methyl Lactate Yield from Sugars. In chemSuschem 8 (4), pp.613-617.DOI:10.1002/cssc.201403057, "the Sn-beta molecular sieve was synthesized by a one-step synthesis method given by" putting the obtained Sn-beta molecular sieve into 1.5mol/L nickel nitrate aqueous solution, and mixing the obtained Sn-beta molecular sieve with a liquid: the solids were in a ratio of 20 (weight ratio) and were refluxed at 40 ℃ for 24 hours. The resulting solid was centrifuged and washed five times with deionized water. Drying at 100 ℃ to obtain the beta molecular sieve containing bimetallic hetero atoms Sn and Ni. The XPS diagram of the Ni element is shown in FIG. 7, which shows that the hetero atoms in example 3 have spatially adjacent properties, which is clearly different from those in example 3.
Application examples:
reaction tests were performed in a reaction for 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 having 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 corporation, japan) equipped with an HP-5 (30 m. Times.250 mm. Times.0.25 μm) column and a FID detector was used for the product analysis. The catalytic effect of several catalysts is shown in table 1.
TABLE 1

Claims (7)

1. The synthesis method of the space adjacent bimetallic heteroatom molecular sieve is characterized by comprising the following steps of:
(1) Mixing and dissolving sodium hydroxide and an aluminum source in water until the mixture is clear, adding a tin source to obtain hydroxide gel, fully mixing the hydroxide gel with a template agent and water, and aging the mixture in a sealed container at 90 ℃ for 48 hours; the aluminum source is selected from one or a combination of several of sodium metaaluminate, aluminum isopropoxide and aluminum hydroxide; the template agent is at least one of tetraethylammonium fluoride, tetraethylammonium chloride and tetraethylammonium bromide; the mol ratio of the sodium hydroxide to the aluminum source to the tin source to the template agent to the water is (0.1-1): 1.0 (5-100): 1-50);
(2) Then adding the mixed solution of water and a silicon source, and stirring and hydrolyzing at room temperature; the mol 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, evaporating all ethanol and partial water at 70-80 deg.C; the beta molecular sieve is one or a combination of a plurality of dealuminated silicon-aluminum beta molecular sieves, boron-silicon beta molecular sieves or pure silicon beta molecular sieves;
(4) Then transferring the mixture into a closed container, and crystallizing the mixture for 2 to 40 days at the temperature of between 130 and 200 ℃; centrifugally washing the solid obtained by crystallization, 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, carrying out reflux dealumination treatment on the Sn-Al-beta molecular sieve for 2-10 times at 30-100 ℃ by using an acid solution, washing, drying at 60-150 ℃ for 6-72 hours, and calcining at 400-650 ℃ for 3-24 hours to obtain the Sn-OH-beta molecular sieve; the acid is at least one of 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.
2. The method of claim 1, wherein in step (1), the tin source is an inorganic tin source or an organic tin source.
3. The method for synthesizing a spatially adjacent bi-metallic heteroatom molecular sieve according to claim 2, wherein the inorganic tin source comprises tin tetrachloride, stannous chloride.
4. The method of synthesizing a spatially adjacent bi-metallic heteroatom molecular sieve according to claim 2, wherein the organotin source comprises tin oxalate, alkyl tin, or an organotin ester.
5. The method for synthesizing spatially adjacent bimetallic heteroatom molecular sieves according to claim 1, characterized in that in step (6), the concentration of the aqueous solution of metal M nitrate 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 spatially adjacent bi-metallic heteroatom molecular sieve obtained by the method of synthesis of spatially adjacent bi-metallic heteroatom molecular sieves according to any of claims 1 to 5, characterized in that it is used as a catalyst.
7. The use of a spatially adjacent bi-metallic heteroatom molecular sieve according to claim 6, in which the conversion of glucose to methyl lactate is catalysed.
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