CN105523568A - One-dimensional rod-like ZSM-5 molecular sieve and synthesis method thereof - Google Patents
One-dimensional rod-like ZSM-5 molecular sieve and synthesis method thereof Download PDFInfo
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- CN105523568A CN105523568A CN201410573624.2A CN201410573624A CN105523568A CN 105523568 A CN105523568 A CN 105523568A CN 201410573624 A CN201410573624 A CN 201410573624A CN 105523568 A CN105523568 A CN 105523568A
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Abstract
The invention belongs to the technical field of zeolite molecular sieve synthesis and relates to a synthesis method of a one-dimensional rod-like ZSM-5 molecular sieve. Channel orientation and morphology control are important in the field of molecular sieve synthesis, in a catalytic reaction, product selectivity, reaction activity and stability of MFI zeolite molecular sieve catalysts with different crystal dimensions have difference. The synthesis method mainly utilizes a one-pot way to prepare ZSM-5 zeolite, has simple synthesis processes and can be industrialized easily. Through use of an effective template, product crystallinity and final morphology can be effectively controlled. A sample XRD shows that the product is the ZSM-5 molecular sieve and has good crystallinity. SEM shows that the zeolite has one-dimensional rod-like morphology and can be used for olefin cracking industrial application.
Description
Technical field
The invention belongs to zeolite molecular sieve synthetic technology field, be specially a kind of synthetic method of one-dimensional rod-like pattern ZSM-5 zeolite molecular sieve.
Background technology
ZSM-5 zeolite has MFI structure, has two-dimensional channel structure, and its main aperture road is that ten-ring duct is S-type, and aperture is 0.51nm × 0.55nm, and another ten-ring duct linearly type, aperture is 0.54nm × 0.56nm.Owing to having unique intersection pore passage structure, higher hydrothermal stability, shape selectivity and oleophilic drainage ability, MFI type zeolite progressively develops into the first-selected catalytic material of petrochemical industry, is widely used in the devices such as dimethyl ether propylene, alkylated reaction, methanol conversion gasoline, toluene disproportionation.
CN201210153420.4 describes a kind of hollow capsules shape nano-ZSM-5 molecular sieve and preparation method, SiO
2/ Al
2o
3mol ratio is 30 ~ 600, particle diameter 10 ~ 600nm, and thickness 50 ~ 200nm has 0.05 ~ 2nm micropore, wall thickness 1 ~ 10nm.Preparation method is the capsule shape ZSM-5 molecular sieve being formed hollow structure by alkaline purification desiliconization, obtains molecular sieve catalyst and has higher degree of crystallinity, the large cavity that branch is narrow, homogeneous, and cavity tuneable scope is large; Macropore and molecular sieve intracrystalline micropore in the middle of existing in molecular sieve catalyst, overcome the restriction of zeolite molecular sieve micropore to its catalytic performance simultaneously; Meanwhile, the specific surface area of catalyzer can also be increased, obtain catalyzed reaction high conversion.CN201110217559.6 the present invention discloses a kind of Gradient acid distribution ZSM-5 molecular sieve and preparation method thereof.ZSM-5 molecular sieve silica/alumina molar ratio prepared by the method is 25-200, possesses weak acid, strong acid and super acids simultaneously.Present method mainly by ZSM-5 molecular sieve is added aluminium source carry out secondary synthesis prepare have Gradient acid distribution ZSM-5 molecular sieve.The ZSM-5 molecular sieve product that the inventive method obtains has the Acidity of gradient, is with a wide range of applications in fields such as isomerization, alkylation and catalytic cracking.CN201410098297.X invention relates to a kind of method preparing hierarchical organization ZSM-5, is specially the method that grade hole ZSM-5 molecular sieve is prepared in soda acid coupling.Step forms suspension for proportionally being mixed to heat up to stir with alkali lye by business ZSM-5, is filtered by suspension, and filter cake water or acid solution washing, finally carry out ion-exchange with acid ammonium salt solution again, then roasting, obtain grade pore structure ZSM-5 molecular sieve.The method is intended to prepare rich secondary mesopore ZSM-5 molecular sieve, is first removed the part sial species in ZSM-5 by environmental friendliness choline processing mode, and preparation has the ZSM-5 molecular sieve of secondary pore structure; On the basis that secondary pore has been formed, and then by the mode of pickling or ion-exchange, allow ZSM-5 surface and the undefined structure stripping that is trapped in duct, improve pore volume and the specific surface area of rich secondary mesopore ZSM-5 simultaneously.By soda acid coupling processing, improve the distribution of the outer aluminium of ZSM-5 surface skeleton, therefore the rich secondary mesopore ZSM-5 for preparing of the method is in catalytic cracking, has very large application potential in hydrocracking.CN201210073742.8 provides a kind of preparation method of ZSM-5 zeolite molecular sieve microsphere, utilize methylic organo-siloxane and tetraethoxy to make silicon source single stage method and prepare ZSM-5 zeolite molecular sieve microsphere, microballoon is made up of tiny ZSM-5 zeolite crystal grain, change the addition containing methylsiloxane, the large I of microballoon is 3-8 μm of adjustment, and ZSM-5 zeolite molecular sieve microsphere size uniform, good dispersity, preparation process is simple, be easy to a large amount of preparation, can be applied in catalysis, absorption with in being separated etc.
In method described in above patent, seldom use the present invention template used dose of T2, and be static crystallization substantially, crystallization process, without stirring, can not get bar-shaped ZSM-5 zeolite.The present invention, by using template T1 and T2, controls its ratio, is stirred in crystallization process, obtain special one-dimensional rod-like pattern ZSM-5 zeolite.
Summary of the invention
Key technical problem to be solved by this invention is the problem that prior art is more difficult to get Rod-like shape ZSM-5 zeolite.The invention provides a kind of easy one-dimensional rod-like ZSM-5 molecular sieve preparation method, when the method is prepared for ZSM-5, there is synthesis step easy, be easy to industrialization, and the feature of special bar-shaped ZSM-5 can be obtained.
For solving the problems of the technologies described above, technical solution of the present invention is as follows:
A kind of Rod-like shape ZSM-5 zeolite molecular sieve, the wide X height of the long X of size is (1 ~ 50) μm X (0.02 ~ 3) μm X (0.02 ~ 1) μm, it is characterized in that long and high ratio is: 8 ~ 100, wide with high ratio is: 1 ~ 5.
In size, length is defined as crystal longest edge, and magnitude range is preferably 2 ~ 30 μm.
Widely in size be defined as crystal vice-minister limit, magnitude range is preferably 0.05 ~ 2 μm.
In size, height is defined as the most minor face of crystal, and magnitude range is preferably 0.04 ~ 1 μm.
Crystal length is preferably with high ratio: 10 ~ 50, and wide with high ratio is preferably: 2 ~ 5.
The crystal of above-mentioned size accounts for the weight ratio of gross product for being greater than 10%;
Preferably, the crystal of above-mentioned size accounts for the weight ratio of gross product for being greater than 30%;
More preferably, the crystal of above-mentioned size accounts for the weight ratio of gross product for being greater than 50%;
More preferably, the crystal of above-mentioned size accounts for the weight ratio of gross product for being greater than 70%;
More preferably, the crystal of above-mentioned size accounts for the weight ratio of gross product for being greater than 90%.
Concrete steps of the present invention are:
By material proportion be:
H
2o/SiO
2=5-500; T1/SiO
2=0.1-100; T2/SiO
2=0.1-100; Si/Al=50-∞; F
-/ SiO
2=0-100, takes template T1, T2, mineralizer, silicon source, aluminium source, adds in reactor, stir, under room temperature between gel aging 0-120 hour, 60-300 DEG C 50-1000rpm stir under crystallization 1-15 days; After being cooled to room temperature, product is washed centrifugal, after oven dry, obtain Rod-like shape ZSM-5 zeolite; Described template T1 is at least one in 4-propyl bromide, TPAOH, 4 bromide, tetraethylammonium bromide, Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, and template T2 is at least one in hexamethylene diisocyanate, hexamethylene-diamine, vulkacit H and derivative (urotropine and derivative thereof) thereof; Described mineralizer is fluorochemical.
In technique scheme,
Crystallization process medium speed is preferably 150-250rpm; Silicon source is preferably at least one in silicon sol, tetraethoxy or amorphous silicon oxide powder, silicate, and aluminium source is preferably at least one in Patent alum, aluminum isopropylate or meta-aluminate, aluminate; Crystallization time is preferably 2-5 days; Crystallization temperature is preferably 100-180 DEG C; Acid-base modifier is preferably oxyhydroxide, and the hierarchy of control is alkalescence; Mineralizer is preferably Sodium Fluoride; T2/T1 preferable range is 0.02-50, H
2o/SiO
2preferable range is 5-200, T1/SiO
2preferable range is 0.2-10, T2/SiO
2preferable range is 0.2-30.
The present invention mainly uses double template to control ZSM-5 zeolite pattern, obtains the sample with good crystallinity and unique one-dimensional rod-like pattern, and characterizes sample with XRD and SEM.
Product of the present invention is one-dimensional rod-like ZSM-5 molecular sieve, by regulating the ratio of preferred crystallization process rotating speed, template T1 and T2, can effective Quality control crystalline state, and regulate sample grain-size.Meanwhile, this synthetic method utilizes not only can improve combined coefficient, reduces synthesis cost, also has the features such as good collimation, repeatability, operability, have better practicality and validity.Present method synthesis of molecular sieve obtains unforeseeable technique effect, avoids the tedious steps of different solutions configuration and mixing in conventional precursors preparation method, is more suitable for industrialization, simple and feasible.Be applied to by the one-dimensional rod-like ZSM-5 zeolite prepared by the method in olefin cracking reaction, during temperature of reaction 550 DEG C, after 6 hours reaction times, ZSM-5 catalyzer has good catalytic effect, and butene conversion reaches 70%, and Propylene Selectivity reaches 26%.
Example below will be described further Rod-like shape ZSM-5 molecular sieve synthetic method provided by the invention.
Accompanying drawing explanation
Part picture in example is listed in Figure of description.
Fig. 1 is the XRD spectra of embodiment 1 product.
Fig. 2 is the SEM photo of embodiment 1 product.
Fig. 3 is the XRD spectra of comparative example 1 product.
Fig. 4 is the SEM photo of comparative example 3 product.
Embodiment
The invention is further illustrated by the following examples.
Embodiment 1
Synthetic method: the sodium hydroxide solution of 10g massfraction 40%, 1g Sodium Fluoride, 13g 4-propyl bromide, 16g vulkacit H, 0.21g Patent alum, 15g massfraction be 40% silicon sol add in 50g water, after stirring, under room temperature, gel is aging.Afterwards, 180 DEG C, 150rpm stirs lower crystallization 5 days, and after being cooled to room temperature, centrifugal 3 times of deionized water wash, dries 12h, obtain the finished product for 80 DEG C.
Fig. 1 is the XRD spectra of embodiment 1 products therefrom, can see that product has the characteristic diffraction peak of ZSM-5, and have higher degree of crystallinity.Fig. 2 is the SEM photo of embodiment 1 products obtained therefrom, can see that sample presents one-dimensional rod-like pattern, thickness about 200-400nm.
Embodiment 2
Adopt and the same terms in example 1, change 4-propyl bromide consumption is 24g, obtains the finished product.Sample XRD characterization result, can see that product has ZSM-5 characteristic diffraction peak, and SEM photo interpret sample presents Rod-like shape.
Embodiment 3
Adopt and example 1 in the same terms, change water consumption is 88g, and 4-propyl bromide consumption is 15g, obtains the finished product.Sample XRD characterization result, can see that product has ZSM-5 characteristic diffraction peak, and SEM photo interpret sample presents Rod-like shape.
Embodiment 4
Adopt and the same terms in example 1, change vulkacit H consumption is 28g, obtains the finished product.Sample XRD characterization result, can see that product has ZSM-5 characteristic diffraction peak, and SEM photo interpret sample presents Rod-like shape.
Embodiment 5
Synthetic method: the sodium hydroxide solution of 12g massfraction 40%, 0.6g Sodium Fluoride, 2g TPAOH, 10g vulkacit H, 0.1g Patent alum, 6.7g tetraethoxy are added in 50g water, after stirring, the aging 8h of gel under room temperature.Afterwards, 180 DEG C, 150rpm stirs lower crystallization 5 days, and after being cooled to room temperature, centrifugal 3 times of deionized water wash, dries 12h, obtain the finished product for 80 DEG C.Sample XRD characterization result, can see that product has ZSM-5 characteristic diffraction peak, and SEM photo interpret sample presents Rod-like shape.
Embodiment 6
Synthetic method: the sodium hydroxide solution of 10g massfraction 40%, 0.56g Sodium Fluoride, 32g TPAOH, 14g vulkacit H, 0.014g aluminum isopropylate, 6.7g tetraethoxy are added in 60g water, after stirring, the aging 24h of gel under room temperature.Afterwards, 180 DEG C, 150rpm stirs lower crystallization 5 days, and after being cooled to room temperature, centrifugal 3 times of deionized water wash, dries 12h, obtain the finished product for 80 DEG C.Sample XRD characterization result, can see that product has ZSM-5 characteristic diffraction peak, and SEM photo interpret sample presents Rod-like shape.
Embodiment 7
Synthetic method: the sodium hydroxide solution of 1.5g massfraction 40%, 1.088g Sodium Fluoride, 13.8g 4-propyl bromide, 24g vulkacit H, 0.014g aluminum isopropylate, 6.7g tetraethoxy are added in 35g water, after stirring, under room temperature, gel is aging.Afterwards, 180 DEG C, 150rpm stirs lower crystallization 5 days, and after being cooled to room temperature, centrifugal 3 times of deionized water wash, dries 12h, obtain the finished product for 80 DEG C.Sample XRD characterization result, can see that product has ZSM-5 characteristic diffraction peak, and SEM photo interpret sample presents Rod-like shape.
Comparative example 1
Adopt and the same terms in example 1, change 4-propyl bromide consumption is 0g, obtains the finished product.
Fig. 3 is sample XRD characterization result, can see that product is amorphous substance.
Comparative example 2
Adopt and the same terms in example 1, change 4-propyl bromide ratio, makes T2/T1=1000, obtains the finished product.XRD interpret sample is amorphous substance.
Comparative example 3
Adopt and the same terms in example 1, change vulkacit H consumption is 0g, obtains the finished product.XRD interpret sample has ZSM-5 characteristic diffraction peak, and Fig. 4 is sample SEM photo, interpret sample can present spherical morphology, and size is 2 microns, and has the bar-shaped small-particle of distributing inhomogeneity to exist around.
Comparative example 4
Adopt and example 1 in the same terms, change crystallization time is 12h, obtains the finished product.Sample XRD characterization result, can see that product degree of crystallinity declines, and sample SEM photo can see that sample presents spherical morphology and has amorphous spherical small-particle dispersion around.
Claims (10)
1. a Rod-like shape ZSM-5 zeolite molecular sieve, the wide X height of the long X of size is: (1 ~ 50) μm X (0.02 ~ 3) μm X (0.02 ~ 1) μm, it is characterized in that long and high ratio is: 8 ~ 100, wide with high ratio is: 1 ~ 5.
2. Rod-like shape ZSM-5 molecular sieve according to claim 1, it is characterized in that in size, length is defined as crystal longest edge, size is 2 ~ 20 μm.
3. Rod-like shape ZSM-5 molecular sieve according to claim 1, it is characterized in that widely in size being defined as crystal vice-minister limit, size is 0.05 ~ 2 μm.
4. Rod-like shape ZSM-5 molecular sieve according to claim 1, it is characterized in that in size, height is defined as the most minor face of crystal, size is 0.04 ~ 1 μm.
5. Rod-like shape ZSM-5 molecular sieve according to claim 1, it is characterized in that ZSM-5 zeolite molecular sieve length with high ratio is: 10 ~ 50, wide with high ratio is: 2 ~ 5.
6. the preparation method of Rod-like shape ZSM-5 molecular sieve described in any one of Claims 1 to 5, is characterized in that concrete steps are:
By material proportion be:
H
2o/SiO
2=5-500; T1/SiO
2=0.1-100; T2/SiO
2=0.1-100; Si/Al=50-∞; F
-/ SiO
2=0-100, takes template T1, T2, mineralizer, silicon source, aluminium source, adds in reactor, stir, under room temperature gel aging between 0-120 hour, 60-300oC 50-1000rpm stir under crystallization 1-15 days; After being cooled to room temperature, product is washed centrifugal, after oven dry, obtain Rod-like shape ZSM-5 zeolite; Described template T1 is at least one in 4-propyl bromide, TPAOH, 4 bromide, tetraethylammonium bromide, Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, and template T2 is at least one in hexamethylene diisocyanate, hexamethylene-diamine, vulkacit H and derivative (urotropine and derivative thereof) thereof; Described mineralizer is Sodium Fluoride or Potassium monofluoride.Use acid-base modifier is oxyhydroxide, and the hierarchy of control is alkalescence.
7. Rod-like shape ZSM-5 molecular sieve preparation method according to claim 6, is characterized in that stirring with 150-250rpm rotating speed in crystallization process.
8. Rod-like shape ZSM-5 molecular sieve preparation method according to claim 6, it is characterized in that, described silicon source is at least one in silicon sol, tetraethoxy or amorphous silicon oxide powder, silicate, and aluminium source is at least one in Patent alum, aluminum isopropylate or meta-aluminate, aluminate.
9. Rod-like shape ZSM-5 molecular sieve preparation method according to claim 6, is characterized in that crystallization temperature is 100-180 DEG C.
10. Rod-like shape ZSM-5 molecular sieve preparation method according to claim 6, is characterized in that crystallization time is 2-5 days.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107055563A (en) * | 2017-05-17 | 2017-08-18 | 汕头大学 | A kind of molecular sieves of nano whiskers SAPO 34 and its preparation and application |
| CN109678176A (en) * | 2017-10-19 | 2019-04-26 | 中国石油化工股份有限公司 | The synthetic method of the needle-shaped ZSM-5 molecular sieve of size tunable |
| CN110156040A (en) * | 2018-02-12 | 2019-08-23 | 中国石油天然气股份有限公司 | ZSM-5 molecular sieve and preparation method thereof |
| CN114572998A (en) * | 2020-11-18 | 2022-06-03 | 中国石油化工股份有限公司 | Strip aggregate molecular sieve and synthesis method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5064630A (en) * | 1988-01-04 | 1991-11-12 | Exxon Chemical Patents Inc. | Zeolite l preparation |
| CN1332114A (en) * | 2001-06-28 | 2002-01-23 | 复旦大学 | Optimized and oriented growth process of MFT-type zeolite crystal |
| JP2011153047A (en) * | 2010-01-28 | 2011-08-11 | Sumitomo Chemical Co Ltd | METHOD FOR PRODUCING ZEOLITE AND METHOD FOR PRODUCING epsi-CAPROLACTAM |
-
2014
- 2014-10-24 CN CN201410573624.2A patent/CN105523568B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5064630A (en) * | 1988-01-04 | 1991-11-12 | Exxon Chemical Patents Inc. | Zeolite l preparation |
| CN1332114A (en) * | 2001-06-28 | 2002-01-23 | 复旦大学 | Optimized and oriented growth process of MFT-type zeolite crystal |
| JP2011153047A (en) * | 2010-01-28 | 2011-08-11 | Sumitomo Chemical Co Ltd | METHOD FOR PRODUCING ZEOLITE AND METHOD FOR PRODUCING epsi-CAPROLACTAM |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107055563A (en) * | 2017-05-17 | 2017-08-18 | 汕头大学 | A kind of molecular sieves of nano whiskers SAPO 34 and its preparation and application |
| CN107055563B (en) * | 2017-05-17 | 2019-05-17 | 汕头大学 | A kind of nano whiskers SAPO-34 molecular sieve and its preparation and application |
| CN109678176A (en) * | 2017-10-19 | 2019-04-26 | 中国石油化工股份有限公司 | The synthetic method of the needle-shaped ZSM-5 molecular sieve of size tunable |
| CN109678176B (en) * | 2017-10-19 | 2021-05-11 | 中国石油化工股份有限公司 | Synthesis method of needle-shaped ZSM-5 molecular sieve with controllable particle size |
| CN110156040A (en) * | 2018-02-12 | 2019-08-23 | 中国石油天然气股份有限公司 | ZSM-5 molecular sieve and preparation method thereof |
| CN114572998A (en) * | 2020-11-18 | 2022-06-03 | 中国石油化工股份有限公司 | Strip aggregate molecular sieve and synthesis method and application thereof |
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