CN102942193B - 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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- CN102942193B CN102942193B CN201210485341.3A CN201210485341A CN102942193B CN 102942193 B CN102942193 B CN 102942193B CN 201210485341 A CN201210485341 A CN 201210485341A CN 102942193 B CN102942193 B CN 102942193B
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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 synthese chemistry and chemical catalyst crossing domain, relate to a kind of skeleton boracic Novel thin layer ZSM-5 zeolite and synthetic method thereof.
Background technology
ZSM-5 zeolite molecular sieve, by the exploitation [USP3702886] in 1972 of Mobil company, has two-dimentional ten-ring duct.Due to the pore passage structure of its uniqueness, good thermostability and hydrothermal stability, be widely used in the industry such as petrochemical complex, meticulous product synthesis, but its too small micropore size (<1nm) hinders macromolecular reaction substrate enters zeolite cavity, there is diffusional limitation in reaction, thus has influence on bulky molecular catalysis reactive behavior.
Reduce the diffusion that zeolite crystal thickness obviously can improve ZSM-5 zeolite, as synthesis of nano zeolite, layered zeolite are peeled off, made mesoporous and acid treatment dealuminzation etc., except layered zeolite is peeled off, other method is difficult to zeolite thickness to be down to below 5nm.Ryong professor Ryoo adopts organic macromolecule bi-quaternary ammonium salt template, first the stratiform ZSM-5 zeolite [M.Choi that b axial thickness only has 2nm has been synthesized, 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 in the thin layer zeolite of the method synthesis, have very high specific surface area, significantly improve the problem that macromole limits in zeolite surface adsorption and diffusion simultaneously.
For modulation ZSM-5 zeolite surface acidity bit density and strength of acid, the ZSM-5 zeolite Zeolite synthesis that heteroatoms replaces as B, Fe, Ti etc. causes extensive concern and research.Wherein the ZSM-5 molecular sieve (B-ZSM-5) of skeleton boracic shows outstanding advantage than conventional sial ZSM-5 zeolite in aldehyde-ketone rearrangement and dehydration reaction, but 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, having can the acid site density of modulation and intensity, have the advantage of thin layer sial ZSM-5 zeolite and conventional B-ZSM-5 zeolite concurrently, have a good application prospect in high polymer (as LDPE, HDPE and HDPP etc.) scission reaction and polysaccharide hydrolysis reaction.
The building-up process step that the present invention relates to is simply controlled, has a extensive future.
Summary of the invention
The skeleton boracic Novel thin layer ZSM-5 zeolite synthetic method that the object of the present invention is to provide a kind of building-up process step simply controlled.
Skeleton boracic thin layer ZSM-5 zeolite synthetic method provided by the invention, concrete steps are as follows:
1. synthesize C
22h
45-N (CH
3)
2-C
6h
12-N (CH
3)
2-C
6h
13br
2the difunctional structure directing agent of long-chain bi-quaternary ammonium salt, step is as follows:
A. by long-chain brominated alkanes (1-C
22h
45br) and diamines mixing, 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 in oil bath stirring and refluxing, controls reflux temperature 80 to 100 DEG C, return time 12 to 24 hours;
C. reflux complete products therefrom cold ether 3 times, vacuum-drying, controls drying temperature 50 to 60 DEG C, 12 to 24 hours time of drying;
D. by vacuum-drying after product and the mixing of 1-bromo normal hexane, toluene/acetonitrile mixing solutions is added.Molar ratio is vacuum-drying product: bromo normal hexane=1:(2 ~ 10), toluene/acetonitrile volume ratio is 1:(10 ~ 50);
E. by above-mentioned mixing solutions stirring and refluxing, backflow, washing, drying program is the same, finally obtains bi-quaternary ammonium salt template C
22h
45-N (CH
3)
2-C
6h
12-N (CH
3)
2-C
6h
13br
2.
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;
C. solution a is slowly added dropwise to solution b; By gained mixing solutions ageing 1 to 3 hour, control Aging Temperature and be 50 to 80 DEG C;
D. under stirring at room temperature, in mixing solutions, add silicon source fast, by gained mixing solutions ageing 1 to 3 hour, control Aging Temperature and be 50 to 80 DEG C; Controlling total molar ratio is: the SiO in silicon source
2: the Al in aluminium source
2o
3: the B in boron source
2o
3: C
22h
45-N (CH
3)
2-C
6h
12-N (CH
3)
2-C
6h
13br
2bi-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);
E. reactant is moved into crystallizing kettle Hydrothermal Synthesis under agitation;
F. controlling stirring velocity is 30 to 90rpm, and temperature of reaction is 120 to 180 DEG C, crystallization 5 to 14 days, the thin layer ZSM-5 zeolite of synthesis boracic;
G. in air atmosphere, 520 ~ 580 DEG C keep 5 ~ 8 hours, roasting removing template;
H. ion-exchange ammonification type ZSM-5 zeolite;
I. the zeolite after ion-exchange is placed in muffle furnace, in air atmosphere, 520 ~ 580 DEG C keep 5 ~ 8 hours, and roasting becomes Hydrogen boracic thin layer ZSM-5 zeolite.
In the present invention, described long-chain brominated alkanes is 1-bromo carbon docosane.
In the present invention, described diamines is N, N, N ', N '-tetramethyl--1,6-hexanediamine.
In the present invention, described silicon source is any one or several in silicon sol, tetraethoxy, water glass, water glass, is wherein preferably silicon sol.
In the present invention, described aluminium source is any one or several in Tai-Ace S 150, aluminum nitrate, sodium aluminate, aluminum isopropylate, is wherein preferably Tai-Ace S 150.
In the present invention, described boron source is any one or several in boric acid, boron trichloride, borophosphoric acid, Sodium Tetraborate, is wherein preferably boric acid.
In the present invention, described mineral acid is any one or several in sulfuric acid, hydrochloric acid and nitric acid, and mineral alkali is sodium hydroxide or ammoniacal liquor, regulator solution pH to 8 ~ 10.
In the present invention, in the synthesis of thin layer ZSM-5 zeolite, step f is further comprising the steps: after crystallization terminates, cold filtration reaction product, with deionized water wash, and dries at 80 ~ 120 DEG C, obtains crystallization product.
In the present invention, in the synthesis of thin layer ZSM-5 zeolite, the flow process of step h is: be that in the ammonium chloride of 0.1 ~ 1.0mol/L, ammonium nitrate solution, any one or two kinds of carry out continuous three secondary ions exchanges to roasting after product, each 1 ~ 4 hour by concentration; Wherein liquor capacity/product quality=6 ~ 10ml/g, ion-exchange temperature is 80 ~ 100 DEG C.
The Hydrogen boracic thin layer ZSM-5 zeolite of the present invention's synthesis, have unique laminated structure, its degree of crystallinity is high, and Extra specific surface area is large, and surface acid property is adjustable, and solid yields is high, has a extensive future.
Accompanying drawing explanation
Fig. 1 is 5000x scanning electronic microscope (SEM) photo of boracic thin layer ZSM-5 zeolite, shows that synthetic zeolite has uniform laminar surface pattern.
Fig. 2 is 20000x scanning electronic microscope (SEM) photo of boracic thin layer ZSM-5 zeolite, and enlarged photograph shows that zeolite has thin uniform layer pattern further, and monolithic zeolite thickness is about 20nm.
Fig. 3 is transmission electron microscope (TEM) photo under the 20nm yardstick of boracic thin layer ZSM-5 zeolite, shows to have obvious regular zeolite lattice on the boracic thin layer ZSM-5 zeolite monolithic of synthesis.
Fig. 4 is the XRD spectra 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 obtained after boron replaces has higher degree of crystallinity.
Fig. 5 be boracic thin layer ZSM-5 zeolite Magic angle spinning solid boron nuclear-magnetism (
11b MAS NMR) spectrogram, can find out that boron all enters 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 synthesis of bi-quaternary ammonium salt template
By 1-bromo carbon docosane and N, N, N ', N '-tetramethyl--1,6-hexanediamine adds round-bottomed flask, adds the mixing solutions of 100ml toluene and acetonitrile wherein, wherein the mol ratio of brominated alkanes and diamines is 1:10, toluene/acetonitrile (v/v)=1:1.Flask is placed in oil bath 100 DEG C backflow 12 hours.Products therefrom cold ether 3 times, 50 DEG C 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.
By gained C
22-6-0br, 1-bromo normal hexane and 100ml acetonitrile add in round-bottomed flask, wherein C
22-6-0the mol ratio of Br and bromo normal hexane is 1:3.Flask is placed in oil bath 100 DEG C backflow 24 hours.Products therefrom cold ether 3 times, 50 DEG C of vacuum-drying 18 hours, obtains White waxy 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 material: silicon source is silicon sol, aluminium source is Tai-Ace S 150, boron source is boric acid, template is C
22-6-6br
2, mineral acid is sulfuric acid, mineral alkali is sodium hydroxide and deionized water; Take each material in molar ratio, 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) first aluminium source, boron source, sulfuric acid are dissolved in 1/2 part of deionized water and form acid solution, template, sodium hydroxide are dissolved in 1/2 part of deionized water for stirring to transparent formation alkaline solution, ii) under whipped state, acid solution is slowly instilled in alkaline solution, iii) the 60 DEG C of water-baths of gained mixing solutions are refluxed 1 hour, iv) under vigorous stirring, silicon source is added fast in mixing solutions, v) by mixing solutions 60 DEG C of water-bath backflow ageings 2 hours, final formation zeolite synthesis reaction mixture.
C. hydrothermal crystallizing
Above-mentioned obtained reaction mixture is transferred in crystallizing kettle, in 150 DEG C of hydrothermal crystallizings 7 days under agitation condition, stirring velocity 60rpm; After crystallization, cold filtration product, with deionized water wash, and dries, obtains crystallization product at 80 ~ 120 DEG C.Use retort furnace roasting crystallization product, roasting process: room temperature program rises to 350 DEG C, temperature rise rate 5 DEG C/min, 350 DEG C stop 2 hours, continue to be warming up to 550 DEG C, temperature rise rate 2 DEG C/min, and 550 DEG C keep 6 hours, obtain the former powder of boracic thin layer ZSM-5 zeolite.
D. ion-exchange
By concentration be 1.0mol/L ammonium nitrate solution to the former powder of boracic thin layer ZSM-5 zeolite carry out continuous three secondary ions exchange, each 2 hours.Wherein liquor capacity/product quality=8ml/g, ion-exchange temperature is 90 DEG C.Exchange after product after washing, drying, be placed in retort furnace roasting, roasting process: from room temperature temperature programming to 550 DEG C, temperature rise rate 2 DEG C/min, keep 6 hours at 550 DEG C, obtain final skeleton boracic thin layer ZSM-5 zeolite, be labeled as L-BZSM5-1.
Embodiment 2
In the present embodiment catalyzer preparation process in, silicon source have employed water glass, and aluminium source have employed Tai-Ace S 150, boron source adopt boric acid.Template and synthesis step identical with embodiment 1, gained catalyzer is labeled as L-BZSM5-2.
Embodiment 3
In the present embodiment catalyzer preparation process in, silicon source have employed silicon sol, and aluminium source have employed aluminum nitrate, and boron source have employed Sodium Tetraborate.Template and synthesis step identical with embodiment 1, gained catalyzer is labeled as L-BZSM5-3.
Embodiment 4
Step in the present embodiment is identical with above-described embodiment 1.Unlike: in reaction mixture preparation process, each material mol ratio 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; Hydrothermal crystallizing 7 days at have employed 150 DEG C in hydrothermal crystallization process; Have employed in ion exchange process concentration be 0.1mol/L ammonium chloride solution to the former powder of boracic thin layer ZSM-5 zeolite carry out continuous three secondary ions exchange, each 2 hours.Wherein liquor capacity/product quality=10ml/g, ion-exchange temperature is 90 DEG C.Gained catalyzer is labeled as L-BZSM5-4.
Embodiment 5
Step in the present embodiment is identical with above-described embodiment 4.Unlike: in reaction mixture preparation process, silicon source have employed water glass, and aluminium source have employed aluminum nitrate, and boron source have employed boron trichloride.Gained catalyzer is labeled as L-BZSM5-5.
Embodiment 6
Step in the present embodiment is identical with above-described embodiment 1.Unlike: in reaction mixture preparation process, silicon source have employed water glass, and aluminium source have employed sodium aluminate, and boron source have employed Sodium Tetraborate; And each material mol ratio 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; Have employed 160 DEG C of hydrothermal crystallizings 7 days in water-heat process; The ammonium chloride solution that have employed in ion exchange process with concentration is 0.1mol/L carries out continuous three secondary ions exchanges to the former powder of boracic thin layer ZSM-5 zeolite, each 3 hours.Wherein liquor capacity/product quality=8ml/g, ion-exchange temperature is 100 DEG C.Gained catalyzer is labeled as L-BZSM5-6.
Claims (8)
1. a thin layer ZSM-5 zeolite synthetic method for skeleton boracic, is characterized in that concrete steps are 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;
C. acid solution is slowly added dropwise to alkaline solution; By gained mixing solutions ageing 1 to 3 hour, control Aging Temperature 50 to 80 DEG C;
D., under stirring at room temperature, in mixing solutions, silicon source is added fast; By gained mixing solutions ageing 1 to 3 hour, control Aging Temperature and be 50 to 80 DEG C; Controlling total molar ratio is: the SiO in silicon source
2: the Al in aluminium source
2o
3: the B in boron source
2o
3: C
22h
45-N (CH
3)
2-C
6h
12-N (CH
3)
2-C
6h
13br
2bi-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);
E. reactant is moved into crystallizing kettle Hydrothermal Synthesis under agitation;
F. controlling stirring velocity is 30 to 90 rpm, and temperature of reaction is 120 to 180 DEG C, crystallization 5 to 14 days, the thin layer ZSM-5 zeolite of synthesis boracic;
G. in air atmosphere, 520 ~ 580 DEG C keep 5 ~ 8 hours, roasting removing template;
H. ion-exchange ammonification type ZSM-5 zeolite;
I. the zeolite after ion-exchange is placed in muffle furnace, in air atmosphere, 520 ~ 580 DEG C keep 5 ~ 8 hours, and roasting becomes Hydrogen boracic thin layer ZSM-5 zeolite.
2. synthetic method according to claim 1, it is characterized in that, described silicon source is any one or several in silicon sol, tetraethoxy, water glass, water glass.
3. synthetic method according to claim 1, it is characterized in that, described aluminium source is any one or several in Tai-Ace S 150, aluminum nitrate, sodium aluminate, aluminum isopropylate.
4. synthetic method according to claim 1, it is characterized in that, described boron source is any one or several in boric acid, boron trichloride, borophosphoric acid, Sodium Tetraborate.
5. synthetic method according to claim 1, it is characterized in that, described mineral acid is any one or several in sulfuric acid, hydrochloric acid and nitric acid, and mineral alkali is sodium hydroxide or ammoniacal liquor, regulator solution pH to 8 ~ 10.
6. synthetic method according to claim 1, it is characterized in that, step f is further comprising the steps: after crystallization terminates, cold filtration reaction product, with deionized water wash, and dries at 80 ~ 120 DEG C, obtains crystallization product.
7. synthetic method according to claim 1, it is characterized in that, the flow process of described step h is: with concentration be the ammonium chloride of 0.1 ~ 1.0 mol/L, any one or two kinds of carry out continuous three secondary ions to roasting after product and exchange in ammonium nitrate solution, each 1 ~ 4 hour; Wherein liquor capacity/product quality=6 ~ 10 ml/g, ion-exchange temperature is 80 ~ 100 DEG C.
8. the boracic thin layer ZSM-5 zeolite prepared by the described method of one of claim 1-7.
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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 |
| CN106904634B (en) * | 2015-12-22 | 2019-05-07 | 中国石油天然气股份有限公司 | A kind of ZSM-5 molecular sieve and its synthetic method |
| 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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| CN101468805A (en) * | 2007-12-25 | 2009-07-01 | 中国石油化工股份有限公司 | Method for synthesizing ZSM-5 molecular sieve |
| CN102259013A (en) * | 2011-05-16 | 2011-11-30 | 复旦大学 | Boron-containing ZSM-5 zeolite catalyst for MTO (Methanol To Olefins) and preparation method thereof |
| CN102351718A (en) * | 2011-08-09 | 2012-02-15 | 太原理工大学 | Gemini cationic surfactant and preparation method thereof |
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| CN101468805A (en) * | 2007-12-25 | 2009-07-01 | 中国石油化工股份有限公司 | Method for synthesizing ZSM-5 molecular sieve |
| CN102259013A (en) * | 2011-05-16 | 2011-11-30 | 复旦大学 | Boron-containing ZSM-5 zeolite catalyst for MTO (Methanol To Olefins) and preparation method thereof |
| CN102351718A (en) * | 2011-08-09 | 2012-02-15 | 太原理工大学 | Gemini cationic surfactant and preparation method thereof |
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| 使用双子表面活性剂合成纳米层MFI分子筛;李振等;《无机化学学报》;20120531;第28卷(第5期);1009-1013 * |
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