CN102942193A - Method for synthesizing novel thin layer ZSM-5 zeolite with boron-containing framework - Google Patents
Method for synthesizing novel thin layer ZSM-5 zeolite with boron-containing framework Download PDFInfo
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Abstract
The invention belongs to the crossing field of inorganic synthesis chemistry and material chemistry and relates to a method for synthesizing a thin layer ZSM-5 zeolite with a boron-containing framework. The method includes that a silicon source, a boron source, an aluminum source and a biquaternary ammonium salt template agent are mixed with deionized water to synthesize the thin layer ZSM-5 zeolite with a framework simultaneously containing boron and aluminum in one step through a hydrothermal process. The synthesized zeolite has the advantages that the thin layer sheet shaped appearance is achieved, the degree of crystallinity is high, the synthesized zeolite is in a typical MFI structure, a large outer surface area is achieved, a surface acidity site is fully exposed, and acid strength and strong acid site proportion on the surface of the zeolite can be effectively controlled by adjusting a ratio of boron and aluminum in a fed material. The thin layer ZSM-5 zeolite with the boron-containing framework has an excellent application potential in an acid catalyzed reaction and particularly in a macromolecule splitting and polysaccharide hydrolysis reaction.
Description
Technical field
The invention belongs to materials chemistry, inorganic synthetic chemistry and chemical catalyst interleaving techniques field, relate to a kind of Novel thin layer ZSM-5 zeolite and synthetic method thereof of skeleton boracic.
Background technology
The ZSM-5 zeolite molecular sieve has two-dimentional ten-ring duct by the exploitation [USP 3702886] in 1972 of Mobil company.Because its unique pore passage structure, good thermostability and hydrothermal stability, the industries such as petrochemical complex, meticulous product be synthetic have been widely used in, yet its too small micropore size (＜1 nm) has hindered the macromolecular reaction substrate and has entered zeolite cavity, there is diffusional limitation in reaction, thereby has influence on the bulky molecular catalysis reactive behavior.
Reduce the diffusion that zeolite crystal thickness can obviously improve ZSM-5 zeolite, peel off, make mesoporous and acid treatment dealuminzation etc. such as synthesis of nano zeolite, layered zeolite, except layered zeolite was peeled off, other method was difficult to zeolite thickness is down to below 5 nm.Ryong professor Ryoo adopts organic macromolecule bi-quaternary ammonium salt template, at first synthesized stratiform ZSM-5 zeolite [the M. Choi that the b axial thickness only has 2 nm, K. Na, R. Ryoo et. al., Stable single-unit-cell nanosheets of zeolite MFI as active and long-lived catalysts, Nature, 2009,461,246-249], there is a large amount of micropore and mesoporous simultaneously in the synthetic thin layer zeolite of the method, has very high specific surface area, has obviously improved the problem of macromole in the restriction of zeolite surface adsorption and diffusion.
Be modulation ZSM-5 zeolite surface acidity bit density and strength of acid, the ZSM-5 zeolite Zeolite synthesis of the replacements such as heteroatoms such as B, Fe, Ti causes extensive concern and research.Wherein the ZSM-5 molecular sieve of skeleton boracic (B-ZSM-5) shows outstanding advantage than conventional sial ZSM-5 zeolite in aldehyde-ketone rearrangement and dehydration reaction, yet the diffusional limitation of conventional B-ZSM-5 zeolite has a strong impact on its application in macromolecular reaction.Different from traditional B-ZSM-5 zeolite, the skeleton boracic thin layer ZSM-5 zeolite that the present invention relates to has thin layer sheet structure and very high external surface area, but acidic site density and intensity with modulation, have the advantage of thin layer sial ZSM-5 zeolite and conventional B-ZSM-5 zeolite concurrently, in high polymer (such as LDPE, HDPE and HDPP etc.) scission reaction and polysaccharide hydrolysis reaction, have a good application prospect.
The building-up process step that the present invention relates to is simply controlled, has a extensive future.
Summary of the invention
The object of the present invention is to provide simple controlled skeleton boracic Novel thin layer ZSM-5 zeolite and the synthetic method thereof of a kind of building-up process step.
Skeleton boracic thin layer ZSM-5 zeolite synthetic method provided by the invention, concrete steps are as follows:
Is 1. (the bi-quaternary ammonium salt template same product to the synthetic difunctional structure directing agent of long-chain bi-quaternary ammonium salt? if use same title), step is as follows:
A. with long-chain brominated alkanes (1-C
nH
2n+1Br) and diamines mix, add toluene/acetonitrile mixing solutions.Molar ratio is long-chain brominated alkanes: diamines=1:(2 ~ 10), toluene/acetonitrile volume ratio is 1:(0.5 ~ 1.5);
B. above-mentioned mixing solutions is placed the oil bath stirring and refluxing, 80 to 100 ℃ of control reflux temperatures, return time 12 to 24 hours;
C. the complete products therefrom that refluxes washs 3 times with cold diethyl ether, vacuum-drying, 50 to 60 ℃ of control drying temperatures, 12 to 24 hours time of drying;
D. vacuum-drying after product and 1-bromo normal hexane are mixed, add toluene/acetonitrile mixing solutions.Molar ratio is the vacuum-drying product: bromo normal hexane=1:(2 ~ 10), toluene/acetonitrile volume ratio is 1:(10 ~ 50);
E. with above-mentioned mixing solutions stirring and refluxing, backflow, washing, drying program are the same, finally obtain the bi-quaternary ammonium salt template.
2. the Novel thin layer ZSM-5 zeolite synthetic method of skeleton boracic, step is as follows:
A. aluminium source, boron source, mineral acid are mixed with deionized water, be made into mixed acid solution;
B. bi-quaternary ammonium salt template, mineral alkali are mixed with deionized water, be made into mixed-alkali solution; Controlling total molar ratio is: the SiO in the silicon source
2: the Al in the aluminium source
2O
3: the B in the boron source
2O
3: bi-quaternary ammonium salt template: mineral acid: mineral alkali: H
2O=1:(0.0025 ~ 0.02): (0.0025 ~ 0.01): (0.08 ~ 0.12): (0.05 ~ 0.3): (0.1 ~ 0.3): (20 ~ 50);
C. solution a slowly is added dropwise to solution b; With gained mixing solutions ageing 1 to 3 hour, the control Aging Temperature was 50 to 80 ℃;
D. under the stirring at room, add fast the silicon source in mixing solutions, with gained mixing solutions ageing 1 to 3 hour, the control Aging Temperature was 50 to 80 ℃;
E. reactant is moved into crystallizing kettle Hydrothermal Synthesis under agitation condition;
F. controlling stirring velocity is 30 to 90 rpm, and temperature of reaction is 120 to 180 ℃, crystallization 5 to 14 days, the thin layer ZSM-5 zeolite of synthetic boracic;
G. under air atmosphere, 520 ~ 580 ℃ kept 5 ~ 8 hours, and template is removed in roasting;
H. ion-exchange ammonification type ZSM-5 zeolite;
I. the zeolite after the ion-exchange is placed muffle furnace, under air atmosphere, 520 ~ 580 ℃ kept 5 ~ 8 hours, and roasting becomes Hydrogen boracic thin layer ZSM-5 zeolite.
Among the present invention, described long-chain brominated alkanes carbon chain lengths be in 12 ~ 22 any, wherein be preferably 1-bromo carbon docosane.
Among the present invention, described diamines is N, N, N ', N '-tetramethyl-1,3-propane diamine, N, N, N ', N '-tetramethyl--Putriscine, N, N, N ', N '-tetramethyl--1, in the 6-hexanediamine any wherein is preferably N, N, N ', N '-tetramethyl--1,6-hexanediamine.
Among the present invention, described silicon source be in silicon sol, tetraethoxy, water glass, the water glass any or several, wherein be preferably silicon sol.
Among the present invention, described aluminium source be in Tai-Ace S 150, aluminum nitrate, sodium aluminate, the aluminum isopropylate any or several, wherein be preferably Tai-Ace S 150.
Among the present invention, described boron source be in boric acid, boron trichloride, borophosphoric acid, the Sodium Tetraborate any or several, wherein be preferably boric acid.
Among the present invention, described mineral acid be in sulfuric acid, hydrochloric acid and the nitric acid any or several, mineral alkali is sodium hydroxide or ammoniacal liquor, regulator solution pH to 8 ~ 10.
Among the present invention, step f was further comprising the steps during the thin layer ZSM-5 zeolite was synthetic: after crystallization finished, the cold filtration reaction product was used deionized water wash, and 80 ~ 120 ℃ of lower oven dry, obtained crystallization product.
Among the present invention, the flow process of step h was during the thin layer ZSM-5 zeolite was synthetic: be any one or two kinds ofly in the ammonium chloride, ammonium nitrate solution of 0.1 ~ 1.0 mol/L the roasting after product is carried out continuous three secondary ions to exchange each 1 ~ 4 hour with concentration; Liquor capacity/product quality=6 ~ 10 ml/g wherein, ion-exchange temperature is 80 ~ 100 ℃.
The Hydrogen boracic thin layer ZSM-5 zeolite that the present invention synthesizes has unique laminated structure, and its degree of crystallinity is high, and Extra specific surface area is large, and surface acid property is adjustable, and the solid yield is high, has a extensive future.
Description of drawings
Fig. 1 is 5000x scanning electronic microscope (SEM) photo of boracic thin layer ZSM-5 zeolite, shows that synthetic zeolite has uniform stratiform surface topography.
Fig. 2 is 20000x scanning electronic microscope (SEM) photo of boracic thin layer ZSM-5 zeolite, and enlarged photograph shows that further zeolite has even thin layer pattern, and monolithic zeolite thickness is 20nm approximately.
Fig. 3 is transmission electron microscope (TEM) photo under the 20 nm yardsticks of boracic thin layer ZSM-5 zeolite, shows at synthetic boracic thin layer ZSM-5 zeolite monolithic to have obvious regular zeolite lattice.
Fig. 4 is the XRD spectrogram of boracic thin layer ZSM-5 zeolite, can find out that this zeolite is typical MFI structure type zeolite.Illustrate that the boracic thin layer ZSM-5 zeolite that obtains after boron replaces has higher degree of crystallinity.
Fig. 5 be boracic thin layer ZSM-5 zeolite magic angle rotation solid boron nuclear-magnetism (
11B MAS NMR) spectrogram can find out that boron has all entered the skeleton structure of zeolite.
Embodiment
The present invention is further described for the following examples, but not thereby limiting the invention.
Embodiment 1
A. the bi-quaternary ammonium salt template is synthetic
With 1-bromo carbon docosane and N, N, N ', N '-tetramethyl--1, the 6-hexanediamine adds round-bottomed flask, and to the mixing solutions that wherein adds 100ml toluene and acetonitrile, wherein the mol ratio of brominated alkanes and diamines is 1:10, toluene/acetonitrile (v/v)=1:1.Place 100 ℃ of oil baths to reflux 12 hours in flask.Products therefrom is with cold diethyl ether washing 3 times, and 50 ℃ of vacuum-drying 18 hours obtains white waxy solid C
22H
45-N (CH
3)
2-C
6H
12-N (CH
3)
2Br is labeled as C
22-6-0Br.
With gained C
22-6-0Br, 1-bromo normal hexane and 100ml acetonitrile add in the round-bottomed flask, wherein C
22-6-0The mol ratio of Br and bromo normal hexane is 1:3.Flask places 100 ℃ of oil baths to reflux 24 hours.Products therefrom is with cold diethyl ether washing 3 times, and 50 ℃ of vacuum-drying 18 hours obtains white wax-like template C
22H
45-N (CH
3)
2-C
6H
12-N (CH
3)
2-C
6H
13Br
2, be labeled as C
22-6-6Br
2
B. the preparation of zeolite synthesis reaction mixture
Take following each material: the silicon source is that silicon sol, aluminium source are that Tai-Ace S 150, boron source are that boric acid, template are C
22-6-6Br
2, mineral acid is that sulfuric acid, mineral alkali are sodium hydroxide and deionized water; Take by weighing in molar ratio each material, i.e. SiO
2: Al
2O
3: B
2O
3: C
22-6-6Br
2: H
2SO
4: Na
2O:H
2O=1:0.008:0.002:0.085:0.174:0.3:40.
Preparation zeolite synthesis mixture program: i) aluminium source, boron source, sulfuric acid are dissolved in 1/2 part of deionized water form acid solution first, template, sodium hydroxide are dissolved in 1/2 part of deionized water for stirring to transparent formation alkaline solution, ii) under whipped state, slowly splash into acid solution in the alkaline solution, iii) 60 ℃ of water-baths of gained mixing solutions were refluxed 1 hour, iv) under the vigorous stirring, in mixing solutions, add fast the silicon source, v) with 60 ℃ of water-bath backflows of mixing solutions ageing 2 hours, finally form the zeolite synthesis reaction mixture.
C. hydrothermal crystallizing
The above-mentioned reaction mixture that makes is transferred in the crystallizing kettle, under the agitation condition in 150 ℃ of hydrothermal crystallizings 7 days, stirring velocity 60rpm; After the crystallization, the cold filtration product is used deionized water wash, and 80 ~ 120 ℃ of lower oven dry, obtains crystallization product.Use retort furnace roasting crystallization product, roasting process: the room temperature program rises to 350 ℃, 5 ℃/min of temperature rise rate, and 350 ℃ stopped 2 hours, continued to be warming up to 550 ℃, 2 ℃/min of temperature rise rate, 550 ℃ kept 6 hours, and obtained the former powder of boracic thin layer ZSM-5 zeolite.
D. ion-exchange
The ammonium nitrate solution that with concentration is 1.0mol/L carries out continuous three secondary ions exchange, each 2 hours to the former powder of boracic thin layer ZSM-5 zeolite.Liquor capacity/product quality=8ml/g wherein, ion-exchange temperature is 90 ℃.The exchange after product is through washing, after the drying, place the retort furnace roasting, roasting process: from room temperature temperature programming to 550 ℃, 2 ℃/min of temperature rise rate kept 6 hours at 550 ℃, obtained final skeleton boracic thin layer ZSM-5 zeolite, was labeled as L-BZSM5-1.
In the preparation process of catalyzer, water glass has been adopted in the silicon source in the present embodiment, and Tai-Ace S 150 has been adopted in the aluminium source, and boric acid is adopted in the boron source.Template and synthesis step and embodiment 1 are identical, and the gained catalyzer is labeled as L-BZSM5-2.
Embodiment 3
In the preparation process of catalyzer, silicon sol has been adopted in the silicon source in the present embodiment, and aluminum nitrate has been adopted in the aluminium source, and Sodium Tetraborate has been adopted in the boron source.Template and synthesis step and embodiment 1 are identical, and the gained catalyzer is labeled as L-BZSM5-3.
In the preparation process of catalyzer, the long-chain brominated alkanes had adopted 1-bromo carbon n-Hexadecane during template was synthetic in the present embodiment, and all the other synthesis steps and embodiment 1 are identical, and the gained catalyzer is labeled as L-BZSM5-4.
In the preparation process of catalyzer, the long-chain brominated alkanes had adopted 1-bromo carbon dodecane during template was synthetic in the present embodiment, and all the other synthesis steps and embodiment 1 are identical, and the gained catalyzer is labeled as L-BZSM5-5.
Embodiment 6
Step in the present embodiment and above-described embodiment 1 are identical.Different is: in the reaction mixture preparation process, each material mole proportioning is: SiO
2: Al
2O
3: B
2O
3: C
22-6-6Br
2: H
2SO
4: Na
2O:H
2O=1:0.005:0.005:0.085:0.18:0.3:40; Adopted 150 ℃ of lower hydrothermal crystallizings in the hydrothermal crystallization process 7 days; Having adopted concentration in the ion exchange process is that the ammonium chloride solution of 0.1mol/L carries out the exchange of continuous three secondary ions, each 2 hours to the former powder of boracic thin layer ZSM-5 zeolite.Liquor capacity/product quality=10ml/g wherein, ion-exchange temperature is 90 ℃.The gained catalyzer is labeled as L-BZSM5-6.
Embodiment 7
Step in the present embodiment and above-described embodiment 6 are identical.Different is: in the reaction mixture preparation process, water glass has been adopted in the silicon source, and aluminum nitrate has been adopted in the aluminium source, and boron trichloride has been adopted in the boron source.The gained catalyzer is labeled as L-BZSM5-7.
Embodiment 8
Step in the present embodiment and above-described embodiment 6 are identical.Different is: in the reaction mixture preparation process, water glass has been adopted in the silicon source, and sodium aluminate has been adopted in the aluminium source, and borophosphoric acid has been adopted in the boron source, and long chain alkane has adopted 1-bromo carbon n-Hexadecane in the template building-up process.The gained catalyzer is labeled as L-BZSM5-8.
Embodiment 9
Step in the present embodiment and above-described embodiment 6 are identical.Different is: in the reaction mixture preparation process, tetraethoxy has been adopted in the silicon source, and Tai-Ace S 150 has been adopted in the aluminium source, and boric acid has been adopted in the boron source, and long chain alkane has adopted 1-bromo carbon dodecane in the template building-up process.The gained catalyzer is labeled as L-BZSM5-9.
Step in the present embodiment and above-described embodiment 1 are identical.Different is: in the reaction mixture preparation process, water glass has been adopted in the silicon source, and sodium aluminate has been adopted in the aluminium source, and Sodium Tetraborate has been adopted in the boron source; And each material mole proportioning is: SiO
2: Al
2O
3: B
2O
3: C
22-6-6Br
2: H
2SO
4: Na
2O:H
2O=1:0.008:0.002:0.085:0.08:0.3:40; Adopted 160 ℃ of hydrothermal crystallizings in the water-heat process 7 days; Having adopted in the ion exchange process with concentration is that the ammonium chloride solution of 0.1mol/L carries out the exchange of continuous three secondary ions, each 3 hours to the former powder of boracic thin layer ZSM-5 zeolite.Liquor capacity/product quality=8 ml/g wherein, ion-exchange temperature is 100 ℃.The gained catalyzer is labeled as L-BZSM5-10.
Embodiment 11
Step in the present embodiment and above-described embodiment 10 are identical.Different is: in the reaction mixture preparation process, Tai-Ace S 150 has been adopted in the aluminium source, and boric acid has been adopted in the boron source; Long chain alkane had adopted 1-bromo carbon n-Hexadecane during template was synthetic, and the gained catalyzer is labeled as L-BZSM5-11.
Embodiment 12
Step in the present embodiment and above-described embodiment 10 are identical.Different is: in the reaction mixture preparation process, silicon sol has been adopted in the silicon source, and Tai-Ace S 150 has been adopted in the aluminium source, and boric acid has been adopted in the boron source; Long chain alkane had adopted 1-bromo carbon dodecane during template was synthetic, and the gained catalyzer is labeled as L-BZSM5-12.
Claims (8)
1. the Novel thin layer ZSM-5 zeolite synthetic method of a skeleton boracic, it is characterized in that: concrete steps are as follows:
A. silicon source, aluminium source, boron source, mineral acid are mixed with deionized water, be made into mixed acid solution;
B. bi-quaternary ammonium salt template, mineral alkali are mixed with deionized water, be made into mixed-alkali solution; Controlling total molar ratio is: the SiO in the silicon source
2: the Al in the aluminium source
2O
3: the B in the boron source
2O
3: bi-quaternary ammonium salt template: mineral acid: mineral alkali: H
2O=1:0.0025 ~ 0.02:0.0025 ~ 0.01:0.08 ~ 0.12:0.05 ~ 0.3:0.1 ~ 0.3:20 ~ 50;
C. acid solution slowly is added dropwise to alkaline solution; With gained mixing solutions ageing 1 to 3 hour, 50 to 80 ℃ of control Aging Temperatures;
D. under the stirring at room, add fast the silicon source in mixing solutions, with gained mixing solutions ageing 1 to 3 hour, the control Aging Temperature was 50 to 80 ℃;
E. reactant is moved into crystallizing kettle Hydrothermal Synthesis under agitation condition;
F. controlling stirring velocity is 30 to 90 rpm, and temperature of reaction is 120 to 180 ℃, crystallization 5 to 14 days, the thin layer ZSM-5 zeolite of synthetic boracic;
G. under air atmosphere, 520 ~ 580 ℃ kept 5 ~ 8 hours, and template is removed in roasting;
H. ion-exchange ammonification type ZSM-5 zeolite;
I. the zeolite after the ion-exchange is placed muffle furnace, under air atmosphere, 520 ~ 580 ℃ kept 5 ~ 8 hours, and roasting becomes Hydrogen boracic thin layer ZSM-5 zeolite.
2. the Novel thin layer ZSM-5 zeolite synthetic method of described skeleton boracic according to claim 1 is characterized in that: described silicon source be in silicon sol, tetraethoxy, water glass, the water glass any or several.
3. the Novel thin layer ZSM-5 zeolite synthetic method of described skeleton boracic according to claim 1 is characterized in that: described aluminium source be in Tai-Ace S 150, aluminum nitrate, sodium aluminate, the aluminum isopropylate any or several.
4. the Novel thin layer ZSM-5 zeolite synthetic method of described skeleton boracic according to claim 1 is characterized in that: described boron source be in boric acid, boron trichloride, borophosphoric acid, the Sodium Tetraborate any or several.
5. the Novel thin layer ZSM-5 zeolite synthetic method of described skeleton boracic according to claim 1 is characterized in that: described mineral acid be in sulfuric acid, hydrochloric acid and the nitric acid any or several, mineral alkali is sodium hydroxide or ammoniacal liquor, regulator solution pH to 8 ~ 10.
6. the Novel thin layer ZSM-5 zeolite synthetic method of described a kind of skeleton boracic according to claim 1, it is characterized in that: step f may further comprise the steps: after crystallization finished, the cold filtration reaction product was used deionized water wash, and 80 ~ 120 ℃ of lower oven dry, obtain crystallization product.
7. the Novel thin layer ZSM-5 zeolite synthetic method of described skeleton boracic according to claim 1, it is characterized in that: the flow process of described step h is: be any one or two kinds of in the ammonium chloride, ammonium nitrate solution of 0.1 ~ 1.0 mol/L the roasting after product to be carried out continuous three secondary ions exchange, each 1 ~ 4 hour with concentration; Liquor capacity/product quality=6 ~ 10 ml/g wherein, ion-exchange temperature is 80 ~ 100 ℃.
8. the boracic thin layer ZSM-5 zeolite that is prepared by the described method of one of claim 1-7.
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| CN104107709A (en) * | 2013-04-16 | 2014-10-22 | 中国石油化工股份有限公司 | Binder-free ZSM-5 molecular sieve catalyst, and preparation method and use thereof |
| CN106395853A (en) * | 2015-07-27 | 2017-02-15 | 中国石油化工股份有限公司 | Phosphorus-containing ZSM-5 molecular sieve, preparation method and applications thereof |
| CN106904634A (en) * | 2015-12-22 | 2017-06-30 | 中国石油天然气股份有限公司 | ZSM-5 molecular sieve and synthesis method thereof |
| CN112645350A (en) * | 2020-12-23 | 2021-04-13 | 中触媒新材料股份有限公司 | Synthesis method of nano ZSM-5 zeolite |
| CN116119681A (en) * | 2023-01-11 | 2023-05-16 | 中国石油大学(华东) | Preparation method for rapidly synthesizing ZSM-5 molecular sieve by inducer |
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| CN103191776A (en) * | 2013-03-22 | 2013-07-10 | 华东理工大学 | Preparation method of ZSM-5 molecular sieve catalyst |
| CN104107709A (en) * | 2013-04-16 | 2014-10-22 | 中国石油化工股份有限公司 | Binder-free ZSM-5 molecular sieve catalyst, and preparation method and use thereof |
| CN106395853A (en) * | 2015-07-27 | 2017-02-15 | 中国石油化工股份有限公司 | Phosphorus-containing ZSM-5 molecular sieve, preparation method and applications thereof |
| CN106904634A (en) * | 2015-12-22 | 2017-06-30 | 中国石油天然气股份有限公司 | ZSM-5 molecular sieve and synthesis method thereof |
| CN106904634B (en) * | 2015-12-22 | 2019-05-07 | 中国石油天然气股份有限公司 | ZSM-5 molecular sieve and synthesis method thereof |
| CN112645350A (en) * | 2020-12-23 | 2021-04-13 | 中触媒新材料股份有限公司 | Synthesis method of nano ZSM-5 zeolite |
| CN116119681A (en) * | 2023-01-11 | 2023-05-16 | 中国石油大学(华东) | Preparation method for rapidly synthesizing ZSM-5 molecular sieve by inducer |
| CN116119681B (en) * | 2023-01-11 | 2024-08-02 | 中国石油大学(华东) | Preparation method for rapidly synthesizing ZSM-5 molecular sieve by inducer |
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