CN105253898A - Preparation method for nanometer ZSM-5 molecular sieve aggregation - Google Patents
Preparation method for nanometer ZSM-5 molecular sieve aggregation Download PDFInfo
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- CN105253898A CN105253898A CN201510824529.XA CN201510824529A CN105253898A CN 105253898 A CN105253898 A CN 105253898A CN 201510824529 A CN201510824529 A CN 201510824529A CN 105253898 A CN105253898 A CN 105253898A
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Abstract
The invention discloses a preparation method for nanometer ZSM-5 molecular sieve aggregation. The preparation method comprises the following steps: (1) dissolving sodium metaaluminate into water and successively adding a NaOH aqueous solution, seed crystal, an alkyl trimethyl amine saline solution and ludox under a stirring condition; crystallizing for 1-144h at 120-190 DEG C; (2) cooling to room temperature, performing solid-liquid separation, washing the solid with deionized water, drying, and then roasting, thereby acquiring the nanometer ZSM-5 molecular sieve aggregation. The primary particle of the molecular sieve aggregation according to the invention is less than 20nm. The molecular sieve aggregation can be served as a high-activity and carbon deposit-preventing catalyst applied to various petrochemical engineering processes, such as, catalytic cracking, toluene disproportionation, xylene isomerization, methanol conversion gasoline preparation, methanol conversion propylene preparation, methanol conversion aromatic hydrocarbon preparation, alkylation and methylbenzene alkylation. The molecular sieve aggregation is generated in the form of aggregation, so that the solid-liquid separation is easily performed, the industrial production is benefited and the production cost is low.
Description
Technical field
The present invention relates to a kind of preparation method of ZSM-5 molecular sieve aggregate.
Background technology
ZSM-5 molecular sieve is the molecular sieve of the Mobil company exploitation seventies in last century.ZSM-5 system three-dimensional straight channels intersect structure, channel type has two kinds: be parallel to the sinusoidal channels in (100) face and be parallel to the straight channel in (010) face.Channel size is respectively 0.54nmx0.56nm and 0.51nmx0.55nm.Crystalline structure has monocline and oblique side's symmetry, and belong to pnma spacer, unit cell parameters a=2.01nm, b=1.92nm, c=1.34nm. unit cell atomicity is 96.ZSM-5, because having good hydrothermal stability, skeleton thermostability and stronger acidity, is the ideal material of catalysis.According to investigations, ZSM-5 can be used for more than 20 kind of petrochemical process as catalyzer, as catalytic cracking, toluene disproportionation, xylene isomerization, methanol conversion gasoline, preparing propylene by methanol transformation, methanol conversion for preparing arene, benzene alkylation, alkylation of toluene etc.In addition, ZSM-5 can also be used for lubricating oil distillate dewaxing etc. as sorbent material.The industrialization of above-mentioned multiple use.
Since ZSM-5 occurs, investigators all the time optimum synthesis condition obtain the catalyzer with corresponding catalytic perfomance.Nanocrystal ZSM-5 mono-aspect has the external surface area active sites that larger external surface area can provide more, on the other hand there is shorter intracrystalline duct, thus there is higher micropore diffusion speed, reactant molecule can be made to be easy to arrive catalyst activity position, and the product generated can spread out very soon from duct.Therefore, nanocrystal ZSM-5 improving the utilization ratio of catalyzer, strengthen macromolecular conversion capability, reduce the deep reaction of product and reduce in catalyzer coking and deactivation speed etc. all there is superior performance.
CN101643219 discloses a kind of synthetic method of nano-ZSM-5 molecular sieve, the method joins in the gelling system of Template-free method synthesis of nano ZSM-5 molecular sieve by pre-crystallization crystal seed, crystallization 24 hours at 160 ~ 180 DEG C again, is cooled to the ZSM-5 molecular sieve that product centrifuging, washing, drying, roasting are obtained the nanoscale of high aggregation by room temperature.
CN102671693A discloses a kind of synthetic method of high silica alumina ratio nano-ZSM-5 molecular sieve, the method adopts organic formwork agent method, organosilane is directly added in molecular sieve original solution, and under cooling for reflux condition silane graft on ZSM-5 molecular sieve crystal seed, roasting removing organic formwork agent and organosilane.This method synthesis nano-ZSM-5 molecular sieve particle diameter between 0.1 ~ 500nm, silica alumina ratio SiO
2/ Al
2o
3be not less than 30, molecular sieve have 0.5 ~ 2nm micropore.
CN1715186A discloses a kind of preparation method of small crystal grain ZSM-5 zeolite, that the aqueous mixture of alumino silica gel particle and organic formwork agent is carried out hydrothermal crystallizing, the method is avoided using the raw material containing sodium ion in synthetic system, thus decrease ammonium exchange, filtration, a series of process of roasting, improve the yield of zeolite product, simplify Production Flow Chart.
CN201410645467 discloses a kind of synthetic method of super low-Na and high-Si nano-ZSM-5 molecular sieve, and NaOH is dissolved in the water by the method, slowly adds silicon source, template and aluminium source, ageing 8 hours under room temperature.First control temperature pre-crystallization 110 ~ 130 DEG C time after 3 hours, is warming up to crystallization temperature 180 DEG C, crystallization time 40 ~ 80 hours.Namely product is obtained through the filtration of routine, washing, drying, roasting.
In sum, by using template can synthesize the less ZSM-5 molecular sieve of particle diameter, but template costly, is unfavorable for industrial application, and template enters in molecular sieve, produces a large amount of oxynitride, polluted air at firing stage.In addition, directly synthesis nano-ZSM-5 particle due to particle diameter very little, from mother liquor, bad separation, is unfavorable for suitability for industrialized production.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of preparation method of nano-ZSM-5 molecular sieve aggregate of low cost is provided.
Technical scheme of the present invention is summarized as follows:
A preparation method for nano-ZSM-5 molecular sieve aggregate, is made up of following steps:
(1) sodium metaaluminate is dissolved in the water, under stirring, adds the NaOH aqueous solution, crystal seed, the alkyl trimethyl amine salt aqueous solution, SiO that mass content is 0.001% ~ 50% successively
2mass content is the silicon sol of 15 ~ 40%; At 120 ~ 190 DEG C of crystallization 1 ~ 144h; Al in described sodium metaaluminate
2o
3, NaOH, crystal seed, alkyl trimethyl amine salt, SiO
2with the ratio of the total amount of water be: 0.0001 ~ 0.1mol:0.001 ~ 0.4mol:0.05 ~ 6g:0.001 ~ 0.1mol:1mol:15 ~ 100mol;
(2) be cooled to room temperature, carry out solid-liquid separation, solid deionized water is washed till pH lower than 9, and after drying, at 450 ~ 750 DEG C, roasting 2 ~ 48h in atmosphere, obtains nano-ZSM-5 molecular sieve aggregate.
Described alkyl trimethyl amine salt is preferably trimethyl ammonia chloride, trimethyl amine bromide, trimethyl oxyammonia, tetradecyltrimethylammonium ammonia chloride, tetradecyltrimethylammonium amine bromide, tetradecyltrimethylammonium oxyammonia, cetyl trimethyl ammonia chloride, hexadecyl trimethyl ammonium bromide, cetyl trimethyl oxyammonia, octadecyl trimethyl ammonia chloride, octadecyl trimethyl amine bromide or octadecyl trimethyl oxyammonia.
The preferred si molecular sieves of described crystal seed or ZSM-5.
Advantage of the present invention:
The present invention adopts crystal seed method, adds a small amount of alkyl trimethyl amine salt simultaneously, synthesis of nano ZSM-5 molecular sieve aggregate, and the primary particle in its nano-ZSM-5 molecular sieve aggregate can be less than 20nm.On the one hand, because the ultimate particle of ZSM-5 molecular sieve is little, be expected to for multiple petrochemical process such as catalytic cracking, toluene disproportionation, xylene isomerization, methanol conversion gasoline, preparing propylene by methanol transformation, methanol conversion for preparing arene, benzene alkylation, alkylation of toluene as high reactivity, the catalyzer of anti-carbon deposit simultaneously.On the other hand, because nano-ZSM-5 molecular sieve generates with aggregate form, the median size of aggregate, between 400nm-570nm, is easily carried out solid-liquid separation, is conducive to suitability for industrialized production.And production cost is low.
Accompanying drawing explanation
Fig. 1 is the XRD figure of the si molecular sieves that embodiment 1 is synthesized.
Fig. 2 is the stereoscan photograph of the si molecular sieves that embodiment 1 is synthesized.
Fig. 3 is the XRD figure of the ZSM-5 molecular sieve of the 2-in-1 one-tenth of embodiment.
Fig. 4 is the ZSM-5 molecular sieve stereoscan photograph of the 2-in-1 one-tenth of embodiment.
Fig. 5 is the XRD figure of the nano-ZSM-5 molecular sieve aggregate that embodiment 3 is synthesized.
Fig. 6 is the stereoscan photograph of the nano-ZSM-5 molecular sieve aggregate that embodiment 3 is synthesized.
Fig. 7 is the XRD figure of the nano-ZSM-5 molecular sieve aggregate that embodiment 4 is synthesized.
Fig. 8 is the stereoscan photograph of the nano-ZSM-5 molecular sieve aggregate that embodiment 4 is synthesized.
Fig. 9 is the XRD figure of the nano-ZSM-5 molecular sieve aggregate that embodiment 5 is synthesized.
Figure 10 is the stereoscan photograph of the nano-ZSM-5 molecular sieve aggregate that embodiment 5 is synthesized.
Figure 11 is the XRD figure of the nano-ZSM-5 molecular sieve aggregate that embodiment 6 is synthesized.
Figure 12 is the stereoscan photograph of the nano-ZSM-5 molecular sieve aggregate that embodiment 6 is synthesized.
Embodiment
Below in conjunction with specific embodiment, the present invention is further illustrated.
Embodiment 1
The preparation method of si molecular sieves, is made up of following steps:
(1) in four n-propyl oxyammonia solution, under stirring, tetraethoxy is added, at 170 DEG C of crystallization 72h; SiO in described tetraethoxy
2, four n-propyl oxyammonias and water the ratio of total amount be: 1mol:0.25mol:2500mol;
(2) be cooled to room temperature, carry out solid-liquid separation, solid deionized water is washed till pH lower than 9, and after drying, at 550 DEG C, roasting 6h in atmosphere, obtains nano-silicon molecular sieve.
XRD figure and the stereoscan photograph of si molecular sieves are shown in Fig. 1 and Fig. 2 respectively.
As can be seen from XRD spectra, the si molecular sieves of this comparative example synthesis, purity is higher, not containing stray crystal.Stereoscan photograph shows, and the si molecular sieves even particle size distribution of synthesis, median size is 150nm.This si molecular sieves is used as the crystal seed of nano-ZSM-5 molecular sieve aggregate of the present invention synthesis.
Embodiment 2
The preparation method of ZSM-5 molecular sieve, is made up of following steps:
(1) sodium metaaluminate is dissolved in the water, under stirring, adds the NaOH aqueous solution, the 4-propyl bromide aqueous solution, SiO that mass content is 30% successively
2mass content is the silicon sol of 30%; At 150 DEG C of crystallization 70h; Al in described sodium metaaluminate
2o
3, NaOH, tetrapropyl amine bromide, SiO
2with the ratio of the total amount of water (comprising the water in water that sodium metaaluminate dissolves, the NaOH aqueous solution, the water comprised in the water in tetrapropyl amine bromide salt brine solution and silicon sol) be: 0.01mol:0.12mol:0.08mol:1mol:25mol;
(2) be cooled to room temperature, carry out solid-liquid separation, solid deionized water is washed till pH lower than 9, and after drying, at 480 DEG C, roasting 4h, obtains ZSM-5 molecular sieve in atmosphere.
XRD spectra and the stereoscan photograph of ZSM-5 molecular sieve are shown in Fig. 3 and Fig. 4 respectively.
As can be seen from XRD spectra, the ZSM-5 molecular sieve of synthesis, purity is higher, not containing stray crystal.Stereoscan photograph shows, and the ZSM-5 molecular sieve even particle size distribution of synthesis, median size is 450nm.This ZSM-5 molecular sieve is used as the crystal seed of nano-ZSM-5 molecular sieve aggregate of the present invention synthesis.
Method disclosed in embodiment 1 and 2, understand the present invention better to enable those skilled in the art to, but be not limited to the present invention, that other method obtains, that character is similar to above-mentioned molecular sieve si molecular sieves or ZSM-5 crystal seed, also may be used for the present invention.
Embodiment 3
A preparation method for nano-ZSM-5 molecular sieve aggregate, is made up of following steps:
(1) sodium metaaluminate is dissolved in the water, under stirring, adds the NaOH aqueous solution, si molecular sieves crystal seed, trimethyl aqueous ammonium chloride solution, SiO that mass content is 30% successively
2mass content is the silicon sol of 30%; At 150 DEG C of crystallization 70h; Al in described sodium metaaluminate
2o
3, NaOH, si molecular sieves crystal seed, trimethyl ammonia chloride, SiO
2with the ratio of the total amount of water (comprising the water in water that sodium metaaluminate dissolves, the NaOH aqueous solution, the water comprised in the water in trimethyl aqueous ammonium chloride solution and silicon sol) be: 0.001mol:0.1mol:3g:0.05mol:1mol:55mol;
(2) be cooled to room temperature, carry out solid-liquid separation, solid deionized water is washed till pH lower than 9, and after drying, at 600 DEG C, roasting 24h in atmosphere, obtains nano-ZSM-5 molecular sieve aggregate.
XRD figure and the stereoscan photograph of nano-ZSM-5 molecular sieve aggregate are shown in Fig. 5 and Fig. 6 respectively.XRD figure shows, the nano-ZSM-5 molecular sieve aggregate of synthesis belongs to the MFI structure by the classification of International Molecular sieve association, does not have stray crystal.Stereoscan photograph shows, the median size 450nm of the nano-ZSM-5 molecular sieve aggregate of synthesis, its primary particle size is less than 20nm.Document (CN101643219 and CN201410645467) also has the report of ZSM-5 molecular sieve aggregate, but its ultimate particle is all much larger than 20nm.
Experiment proves, the trimethyl ammonia chloride of the present embodiment is substituted with trimethyl amine bromide or trimethyl oxyammonia, other same the present embodiment, the primary particle of the nano-ZSM-5 molecular sieve aggregate obtained and aggregate particle similar to the nano-ZSM-5 molecular sieve aggregate of the present embodiment.
Embodiment 4
A preparation method for nano-ZSM-5 molecular sieve aggregate, is made up of following steps:
(1) sodium metaaluminate is dissolved in the water, under stirring, adds the NaOH aqueous solution, ZSM-5 crystal seed, the tetradecyltrimethylammonium amine bromide aqueous solution, SiO that mass content is 0.001% successively
2mass content is the silicon sol of 15%; At 120 DEG C of crystallization 144h; Al in described sodium metaaluminate
2o
3, NaOH, ZSM-5 crystal seed, tetradecyltrimethylammonium amine bromide, SiO
2with the ratio of the total amount of water (comprising the water in water that sodium metaaluminate dissolves, the NaOH aqueous solution, the water comprised in the water in the tetradecyltrimethylammonium amine bromide aqueous solution and silicon sol) be: 0.0001mol:0.001mol:0.05g:0.001mol:1mol:15mol;
(2) be cooled to room temperature, carry out solid-liquid separation, solid deionized water is washed till pH lower than 9, and after drying, at 450 DEG C, roasting 48h in atmosphere, obtains nano-ZSM-5 molecular sieve aggregate.
XRD spectra and the stereoscan photograph of nano-ZSM-5 molecular sieve aggregate are shown in Fig. 7 and Fig. 8 respectively.XRD figure shows, the nano-ZSM-5 molecular sieve aggregate of synthesis belongs to the MFI structure by the classification of International Molecular sieve association, does not have stray crystal.Stereoscan photograph shows, the median size 480nm of the nano-ZSM-5 molecular sieve aggregate of synthesis, its primary particle size is less than 20nm.
Experiment proves, the tetradecyltrimethylammonium amine bromide of the present embodiment is substituted with tetradecyltrimethylammonium ammonia chloride or tetradecyltrimethylammonium oxyammonia, other same the present embodiment, the primary particle of the nano-ZSM-5 molecular sieve aggregate obtained and aggregate particle similar to the nano-ZSM-5 molecular sieve aggregate of the present embodiment.
Embodiment 5
A preparation method for nano-ZSM-5 molecular sieve aggregate, is made up of following steps:
(1) sodium metaaluminate is dissolved in the water, under stirring, adds the NaOH aqueous solution, si molecular sieves crystal seed, cetyl trimethyl aqueous ammonium hydroxide, SiO that mass content is 50% successively
2mass content is the silicon sol of 40%; At 190 DEG C of crystallization 1h; Al in described sodium metaaluminate
2o
3, NaOH, si molecular sieves crystal seed, cetyl trimethyl oxyammonia, SiO
2with the ratio of the total amount of water (comprising the water in water that sodium metaaluminate dissolves, the NaOH aqueous solution, the water comprised in the water in cetyl trimethyl aqueous ammonium hydroxide and silicon sol) be: 0.1mol:0.4mol:6g:0.1mol:1mol:100mol;
(2) be cooled to room temperature, carry out solid-liquid separation, solid deionized water is washed till pH lower than 9, and after drying, at 750 DEG C, roasting 2h in atmosphere, obtains nano-ZSM-5 molecular sieve aggregate.
XRD spectra and the stereoscan photograph of nano-ZSM-5 molecular sieve aggregate are shown in Fig. 9 and Figure 10 respectively.XRD figure shows, the nano-ZSM-5 molecular sieve aggregate of synthesis belongs to the MFI structure by the classification of International Molecular sieve association, does not have stray crystal.Stereoscan photograph shows, the median size 570nm of the nano-ZSM-5 molecular sieve aggregate of synthesis, its primary particle size is less than 20nm.
Experiment proves, the cetyl trimethyl oxyammonia of the present embodiment is substituted with cetyl trimethyl ammonia chloride or hexadecyl trimethyl ammonium bromide, other same the present embodiment, the primary particle of the nano-ZSM-5 molecular sieve aggregate obtained and aggregate particle similar to the nano-ZSM-5 molecular sieve aggregate of the present embodiment.
Embodiment 6
A preparation method for nano-ZSM-5 molecular sieve aggregate, is made up of following steps:
(1) sodium metaaluminate is dissolved in the water, under stirring, adds the NaOH aqueous solution, si molecular sieves crystal seed, octadecyl trimethyl aqueous ammonium chloride solution, SiO that mass content is 10% successively
2mass content is the silicon sol of 20%; At 140 DEG C of crystallization 50h; Al in described sodium metaaluminate
2o
3, NaOH, si molecular sieves crystal seed, octadecyl trimethyl ammonia chloride, SiO
2with the ratio of the total amount of water (comprising the water in water that sodium metaaluminate dissolves, the NaOH aqueous solution, the water comprised in the water in octadecyl trimethyl aqueous ammonium chloride solution and silicon sol) be: 0.01mol:0.1mol:1g:0.05mol:1mol:20mol;
(2) be cooled to room temperature, carry out solid-liquid separation, solid deionized water is washed till pH lower than 9, and after drying, at 550 DEG C, roasting 36h in atmosphere, obtains nano-ZSM-5 molecular sieve aggregate.
XRD spectra and the stereoscan photograph of nano-ZSM-5 molecular sieve aggregate are shown in Figure 11 and Figure 12 respectively.XRD figure shows, the nano-ZSM-5 molecular sieve aggregate of synthesis belongs to the MFI structure by the classification of International Molecular sieve association, does not have stray crystal.Stereoscan photograph shows, the median size 400nm of the nano-ZSM-5 molecular sieve aggregate of synthesis, its primary particle size is less than 20nm.
Experiment proves, the octadecyl trimethyl ammonia chloride of the present embodiment is substituted with octadecyl trimethyl amine bromide or octadecyl trimethyl oxyammonia, other same the present embodiment, the primary particle of the nano-ZSM-5 molecular sieve aggregate obtained and aggregate particle similar to the nano-ZSM-5 molecular sieve aggregate of the present embodiment.
Claims (3)
1. a preparation method for nano-ZSM-5 molecular sieve aggregate, is characterized in that being made up of following steps:
(1) sodium metaaluminate is dissolved in the water, under stirring, adds the NaOH aqueous solution, crystal seed, the alkyl trimethyl amine salt aqueous solution, SiO that mass content is 0.001% ~ 50% successively
2mass content is the silicon sol of 15 ~ 40%; At 120 ~ 190 DEG C of crystallization 1 ~ 144h; Al in described sodium metaaluminate
2o
3, NaOH, crystal seed, alkyl trimethyl amine salt, SiO
2with the ratio of the total amount of water be: 0.0001 ~ 0.1mol:0.001 ~ 0.4mol:0.05 ~ 6g:0.001 ~ 0.1mol:1mol:15 ~ 100mol;
(2) be cooled to room temperature, carry out solid-liquid separation, solid deionized water is washed till pH lower than 9, and after drying, at 450 ~ 750 DEG C, roasting 2 ~ 48h in atmosphere, obtains nano-ZSM-5 molecular sieve aggregate.
2. the preparation method of a kind of nano-ZSM-5 molecular sieve aggregate according to claim 1, it is characterized in that described alkyl trimethyl amine salt is trimethyl ammonia chloride, trimethyl amine bromide, trimethyl oxyammonia, tetradecyltrimethylammonium ammonia chloride, tetradecyltrimethylammonium amine bromide, tetradecyltrimethylammonium oxyammonia, cetyl trimethyl ammonia chloride, hexadecyl trimethyl ammonium bromide, cetyl trimethyl oxyammonia, octadecyl trimethyl ammonia chloride, octadecyl trimethyl amine bromide or octadecyl trimethyl oxyammonia.
3. the preparation method of a kind of nano-ZSM-5 molecular sieve aggregate according to claim 1, is characterized in that described crystal seed is si molecular sieves or ZSM-5.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107970989A (en) * | 2016-10-25 | 2018-05-01 | 中国石油化工股份有限公司 | A kind of preparation method of xylene isomerization catalyst |
| CN109694086A (en) * | 2017-10-20 | 2019-04-30 | 中国石油化工股份有限公司 | The preparation method of nano-sized ZSM-5 zeolite Molecular sieve aggregate |
| CN110467198A (en) * | 2019-08-08 | 2019-11-19 | 大连理工大学 | A kind of multi-stage porous ZSM-5 Micelle-like Nano-structure of Two microballoon and preparation method |
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| CN101643219A (en) * | 2009-08-27 | 2010-02-10 | 黑龙江大学 | Preparation method of nano-ZSM-5 molecular sieve |
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| CN101643219A (en) * | 2009-08-27 | 2010-02-10 | 黑龙江大学 | Preparation method of nano-ZSM-5 molecular sieve |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107970989A (en) * | 2016-10-25 | 2018-05-01 | 中国石油化工股份有限公司 | A kind of preparation method of xylene isomerization catalyst |
| CN107970989B (en) * | 2016-10-25 | 2021-02-09 | 中国石油化工股份有限公司 | Preparation method of xylene isomerization catalyst |
| CN109694086A (en) * | 2017-10-20 | 2019-04-30 | 中国石油化工股份有限公司 | The preparation method of nano-sized ZSM-5 zeolite Molecular sieve aggregate |
| CN109694086B (en) * | 2017-10-20 | 2020-12-29 | 中国石油化工股份有限公司 | Preparation method of nano ZSM-5 zeolite molecular sieve aggregate |
| CN110467198A (en) * | 2019-08-08 | 2019-11-19 | 大连理工大学 | A kind of multi-stage porous ZSM-5 Micelle-like Nano-structure of Two microballoon and preparation method |
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Application publication date: 20160120 |