CN105293521A - Method for preparing high-bulk-density spherical ZSM-5 zeolite - Google Patents
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Abstract
The invention relates to a preparation method of high-bulk-density spherical ZSM-5 zeolite, mainly solves the problems that in the prior art, the synthesized spherical ZSM-5 zeolite is low in bulk density or is small in specific surface area while high in bulk density, and provides the method for synthesizing spherical ZSM-5 zeolite with high specific surface area and bulk density. The method comprises the following steps: a) preparing a silicon source, an aluminum source, organic amine, an organic high polymer, MOH and deionized water into a raw material mixture; b) carrying out hydrothermal crystallization, wherein M is at least one element of the alkali elements; the organic high polymer is at least one selected from polyethylene glycol and starch. Through the adoption of the technical scheme, the problems are well solved, and the method is applicable to industrial preparation of ZSM-5 zeolite.
Description
Technical field
The present invention relates to a kind of method preparing the spherical ZSM-5 zeolite of high-bulk-density.
Background technology
ZSM-5 zeolite is the high silicon 3 D straight channel zeolite that Mobil company of the U.S. develops in 20 century 70s, belongs to micro-pore zeolite, not easily carbon distribution in catalytic process, and has fabulous thermostability, acid resistance, shape selectivity, hydrothermal stability.In ZSM-5 zeolite skeleton, silicon (aluminium) oxygen tetrahedron connects into more special basic structural unit, and this structural unit is made up of eight five-rings, and the limit by sharing between structural unit is connected to chain, and then is linked to be sheet again.The preferred material of catalysis is become due to the relative activity that there is unique three dimensional intersection pore canal system and require Hydrothermal Synthesis system.Simultaneously, because it belongs to high silica alumina ratio zeolite, thus have high hydrothermal stability and the ability of oleophilic drainage, be therefore widely used in catalytic pyrolysis, catalytic reforming in petroleum industry the earliest, Application Areas is again gradually to the future development of fine chemistry industry thereafter.
The technology of synthetic ZSM-5 zeolite is ripe, but the ZSM-5 zeolite study on the synthesis of different grain size is still carrying out.The ZSM-5 zeolite of water heat transfer, its grain-size from nano level to ultra-fine, micron order, to such an extent as to can synthesize the large grain size zeolite of more than 100 μm.[the IverSchmidt such as Iver, ClausMadsen, andClausJ.H.Jacobsen.ConfinedSpaceSynthesis.ANovelRoutet oNanosizedZeolites.Inorg.Chem., 2000,39 (11), PP2279-2283] confinement synthesizes the ZSM-5 zeolite of 20 ~ 75nm; [the WangXiqu such as Wang, AllanJJ.MaterialsResearchSociety, 2001, (658): 55 ~ 61] adopt high temperature (250 DEG C), high pressure (80MPa) synthesizes 200 μm × 700 μm large grain size ZSM-5 zeolites.For zeolite catalyst, zeolite grain size affects reactant molecule in zeolite micropore diffusion and reactive behavior, and little crystal grain zeolite has large outside surface and acidic site, high catalytic activity and longer catalyst life, but shape selective catalysis selectivity is inadequate; And large grain size zeolite shape selectivity is better, but there is silica alumina ratio skewness, the activity of catalyzer is relatively low.The zeolite that crystal grain is too little or too large is all inappropriate to Industrial Catalysis application, and the grain-size of general industry zeolite is between 1 ~ 10 μm, so the zeolite that modulation zeolite grain size obtains differential responses performance is very necessary.
Summary of the invention
The technical problem to be solved in the present invention is that to synthesize spherical ZSM-5 zeolite tap density low or have high-bulk-density but the little problem of specific surface area in the past, provides a kind of method of synthesizing high specific surface area, the spherical zeolite of high-bulk-density ZSM-5.The spherical ZSM-5 zeolite that the method obtains contains the features such as large specific surface area, high-bulk-density, even particle distribution.
Current ZSM-5 molecular sieve with small crystal grains is widely used, and it is suitable for the requirement of some catalyzed reaction, but when studying the such as diffusion physico-chemical property relevant with this molecular sieve feature structure with Studies On The Shape-selective Catalysis etc., ZSM-5 molecular sieve with small crystal grains can not meet the demands.At this moment, having high-bulk-density large grain size ZSM-5 molecular sieve will be desired by research work.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: the method preparing the spherical ZSM-5 zeolite of high-bulk-density, comprises the steps: a) raw silicon source, aluminium source, MOH, organic amine, organic polymer and water to be mixed to get raw mixture; B) hydrothermal crystallizing; Wherein M is at least one of alkali metal; Described organic polymer is selected from least one in polyoxyethylene glycol, starch.The preferred polyoxyethylene glycol of described organic polymer; More preferably the number-average molecular weight of polyoxyethylene glycol is more than or equal to 6000, and the tap density of the spherical ZSM-5 zeolite now synthesized compares when adopting the polyoxyethylene glycol of lower number-average molecular weight higher.The number-average molecular weight scope of such as polyoxyethylene glycol can be 6000 ~ 20000, also can also be 8000 ~ 20000 or 10000 ~ 20000.Wherein M is at least one of alkali metal, and M can be at least one in Li, Na, K, Rb and Cs, economically considers at least one in more conventional Na and K.
In technique scheme, at least one of described silicon source preferably in tetraethoxy, silicon sol, silica gel, water glass or White Carbon black.
In technique scheme, at least one of described aluminium source preferably in aluminum isopropylate, sodium metaaluminate, Tai-Ace S 150.
In technique scheme, at least one of described organic amine preferably in tetraethyl ammonium hydroxide, TPAOH, TBAH, Tetrabutyl amonium bromide, tetraethylammonium bromide, 4-propyl bromide, n-Butyl Amine 99, butanediamine, triethylamine, Monoethanolamine MEA BASF, diethanolamine, trolamine or hexanediamine.
In technique scheme, described organic amine with SiO
2the mol ratio in meter silicon source is preferably 0.01 ~ 0.3.Be more preferably 0.015 ~ 0.3.
In technique scheme, described with M
2o count MOH with SiO
2the mol ratio in meter silicon source is preferably 0.01 ~ 0.3; Be more preferably 0.01 ~ 0.25.
In technique scheme, the water in described raw mixture with SiO
2the mol ratio in meter silicon source is preferably 5 ~ 50; Be more preferably 6 ~ 40.
In technique scheme, organic polymer with SiO
2the mol ratio in meter silicon source is preferably 0.0001 ~ 0.01; Be more preferably 0.0001 ~ 0.001.
In technique scheme, with Al
2o
3meter aluminium source with SiO
2the mol ratio in meter silicon source is preferably 0.005 ~ 0.1; Be more preferably 0.02 ~ 0.06.
In technique scheme, step b) temperature of hydrothermal crystallizing is preferably 60 ~ 200 DEG C; More preferably 100 ~ 200 DEG C.
In technique scheme, step b) time of hydrothermal crystallizing is preferably 8 ~ 480 hours; More preferably 12 ~ 240 hours.
In technique scheme, as for step a) in be not key of the present invention by the order that raw silicon source, aluminium source, MOH, organic amine, organic polymer and water carry out mixing, adopt ordinary method can obtain described raw mixture when those skilled in the art see step described raw material composition a).Only as an example, the order mixed by raw material can be: first that MOH is soluble in water, stir to obtain material I, aluminium source is joined in material I, stirring obtains material II, in material II, add organic amine stirring obtain material III, in material III, add silicon source and organic polymer, stir to obtain described raw mixture.
Tap density is that dust or powder are freely filled in a certain container, mass per volume measured after just having filled.The present invention synthesizes spherical ZSM-5 zeolite and has high-crystallinity, even particle distribution, and tap density can reach 0.99 grams per milliliter, and specific surface area can reach 380 grams/m.Preparation method is simply controlled, and low raw-material cost is with short production cycle, can be applicable to suitability for industrialized production.
Below by embodiment, the present invention is further elaborated, but these embodiments are not limit scope of the present invention.
Accompanying drawing explanation
Fig. 1 is the XRD figure spectrum of embodiment 1 product.
Fig. 2 is the SEM figure of embodiment 1 product.
Embodiment
The molecular formula of the Tai-Ace S 150 adopted in embodiment is Al
2(SO
4)
3.18H
2o; Sodium metaaluminate adopts anhydrous sodium metaaluminate; The silicon sol of the silicon sol adopted to be concentration be 40w%.
[embodiment 1]
Prepare a method for the spherical ZSM-5 zeolite of high-bulk-density, comprise the steps:
A) first 3g sodium hydroxide is dissolved in 50g deionized water, vigorous stirring obtains material I, 5g Tai-Ace S 150 is joined in material I, vigorous stirring obtains material II, 4.5g hexanediamine, 10.3g 4-propyl bromide is added in material II, vigorous stirring obtains material III, in material III, add 42g silicon sol, 28g PEG20000, vigorous stirring obtains raw mixture.Wherein the mol ratio of hexanediamine and 4-propyl bromide is 1, Na
2siO in O and silicon sol
2mol ratio be 0.134, Al in Tai-Ace S 150
2o
3with SiO in silicon sol
2mol ratio be 0.027, SiO in PEG20000 and silicon sol
2mol ratio be 0.01, SiO in deionized water and silicon sol
2mol ratio be 10.
B) by raw mixture obtained for a) step under crystallization temperature is 180 DEG C of conditions, hydrothermal crystallizing 120 hours, then washs, filters, dries and to obtain the spherical ZSM-5 zeolite of pure phase.
Concrete preparation condition is in table 1, and Product bulk density and pore structure parameter are in table 2.
[embodiment 2]
Prepare a method for the spherical ZSM-5 zeolite of high-bulk-density, comprise the steps:
A) first 3g sodium hydroxide is dissolved in 50g deionized water, vigorous stirring obtains material I, 5g Tai-Ace S 150 is joined in material I, vigorous stirring obtains material II, 4.5g hexanediamine, 10.3g 4-propyl bromide is added in material II, vigorous stirring obtains material III, in material III, add 42g silicon sol, 5.6g PEG 20000, vigorous stirring obtains raw mixture.Wherein hexanediamine be 1, Na with the mol ratio of 4-propyl bromide
2siO in O and silicon sol
2mol ratio be 0.134, Al in Tai-Ace S 150
2o
3with SiO in silicon sol
2mol ratio be 0.027, SiO in PEG 20000 and silicon sol
2mol ratio be 0.001, SiO in deionized water and silicon sol
2mol ratio be 10.
B) by raw mixture obtained for a) step under crystallization temperature is 160 DEG C of conditions, hydrothermal crystallizing 120 hours, then washs, filters, dries and to obtain the spherical ZSM-5 zeolite of pure phase.
Concrete preparation condition is in table 1, and Product bulk density and pore structure parameter are in table 2.
[embodiment 3]
Prepare a method for the spherical ZSM-5 zeolite of high-bulk-density, comprise the steps:
A) first 1.5g sodium hydroxide is dissolved in 75.6g deionized water, vigorous stirring obtains material I, 22.848g aluminum isopropylate is joined in material I, vigorous stirring obtains material II, 14.896g 4-propyl bromide is added in material II, vigorous stirring obtains material III, in material III, add 42g silicon sol, 11.2g PEG20000, vigorous stirring obtains raw mixture.Wherein SiO in 4-propyl bromide and silicon sol
2mol ratio be 0.2, Na
2siO in O and silicon sol
2mol ratio be 0.067, Al in aluminum isopropylate
2o
3with SiO in silicon sol
2mol ratio be 0.05, SiO in PEG20000 and silicon sol
2mol ratio be 0.001, SiO in deionized water and silicon sol
2mol ratio be 15.
B) by raw mixture obtained for a) step 110 DEG C of ageings 48 hours, hydrothermal crystallizing 96 hours at 180 DEG C, then washs, filters, dries and to obtain the spherical ZSM-5 zeolite of pure phase.
Concrete preparation condition is in table 1, and Product bulk density and pore structure parameter are in table 2.
[embodiment 4]
Prepare a method for the spherical ZSM-5 zeolite of high-bulk-density, comprise the steps:
A) first 1.12g sodium hydroxide is dissolved in 126g deionized water, vigorous stirring obtains material I, 9.14g aluminum isopropylate is joined in material I, vigorous stirring obtains material II, 11.172g 4-propyl bromide, 9.74g hexanediamine is added in material II, vigorous stirring obtains material III, in material III, add 60g tetraethoxy, 2.24g PEG 8000, vigorous stirring obtains raw mixture.Wherein the mol ratio of 4-propyl bromide and hexanediamine is 0.5, Na
2siO in O and tetraethoxy
2mol ratio be 0.05, Al in aluminum isopropylate
2o
3with SiO in tetraethoxy
2mol ratio be 0.02, SiO in organic polymer and tetraethoxy
2mol ratio be 0.001, SiO in deionized water and tetraethoxy
2mol ratio be 25.
B) by raw mixture obtained for a) step 110 DEG C of ageings 48 hours, hydrothermal crystallizing 96 hours at 180 DEG C, then washs, filters, dries and to obtain the spherical ZSM-5 zeolite of pure phase.
Concrete preparation condition is in table 1, and Product bulk density and pore structure parameter are in table 2.
[embodiment 5]
Prepare a method for the spherical ZSM-5 zeolite of high-bulk-density, comprise the steps:
A) first 5.6g sodium hydroxide is dissolved in 200g deionized water, vigorous stirring obtains material I, 22.38g Tai-Ace S 150 is joined in material I, vigorous stirring obtains material II, 6.16g butanediamine, 8.12g hexanediamine is added in material II, vigorous stirring obtains material III, in material III, add silicon sol 42g, 0.84g polyoxyethylene glycol (6000), vigorous stirring obtains raw mixture.Wherein the mol ratio of butanediamine and hexanediamine is 1, Na
2siO in O and silicon sol
2mol ratio be 0.25, Al in Tai-Ace S 150
2o
3with SiO in silicon sol
2mol ratio be 0.06, SiO in organic polymer and silicon sol
2mol ratio be 0.0005, SiO in deionized water and silicon sol
2mol ratio be 40.
B) by raw mixture obtained for a) step under crystallization temperature is 190 DEG C of conditions, hydrothermal crystallizing 96 hours, then washs, filters, dries and to obtain the spherical ZSM-5 zeolite of pure phase.
Concrete preparation condition is in table 1, and Product bulk density and pore structure parameter are in table 2.
[embodiment 6]
Prepare a method for the spherical ZSM-5 zeolite of high-bulk-density, comprise the steps:
A) first 2.24g sodium hydroxide is dissolved in 40g deionized water, vigorous stirring obtains material I, 2.28g Tai-Ace S 150 is joined in material I, vigorous stirring obtains material II, 6.13g n-Butyl Amine 99,9.74g hexanediamine is added in material II, vigorous stirring obtains material III, in material III, add silicon sol 42g, 5.6g PEG 20000, vigorous stirring obtains raw mixture.Wherein the mol ratio of n-Butyl Amine 99 and hexanediamine is 1, Na
2siO in O and silicon sol
2mol ratio be 0.1, Al in Tai-Ace S 150
2o
3with SiO in silicon sol
2mol ratio be 0.02, SiO in PEG 20000 and silicon sol
2mol ratio be 0.001, SiO in deionized water and silicon sol
2mol ratio be 8.
B) by raw mixture obtained for a) step under crystallization temperature is 170 DEG C of conditions, hydrothermal crystallizing 96 hours, then washs, filters, dries and to obtain the spherical ZSM-5 zeolite of pure phase.
Concrete preparation condition is in table 1, and Product bulk density and pore structure parameter are in table 2.
[embodiment 7]
Prepare a method for the spherical ZSM-5 zeolite of high-bulk-density, comprise the steps:
A) first 3.36g sodium hydroxide is dissolved in 50g deionized water, vigorous stirring obtains material I, 2.28g Tai-Ace S 150 is joined in material I, vigorous stirring obtains material II, 7.35g triethylamine is added in material II, vigorous stirring obtains material III, in material III, add silicon sol 42g, 5.6g PEG 20000, vigorous stirring obtains raw mixture.Wherein SiO in triethylamine and silicon sol
2mol ratio be 0.26, Na
2siO in O and silicon sol
2mol ratio be 0.15, Al in Tai-Ace S 150
2o
3with SiO in silicon sol
2mol ratio be 0.02, SiO in organic polymer and tetraethoxy
2mol ratio be 0.001, SiO in deionized water and silicon sol
2mol ratio be 10.
B) by raw mixture obtained for a) step under crystallization temperature is 160 DEG C of conditions, hydrothermal crystallizing 108 hours, then washs, filters, dries and to obtain the spherical ZSM-5 zeolite of pure phase.
Concrete preparation condition is in table 1, and Product bulk density and pore structure parameter are in table 2.
[embodiment 8]
Prepare a method for the spherical ZSM-5 zeolite of high-bulk-density, comprise the steps:
A) first 4.48g sodium hydroxide is dissolved in 12g deionized water, vigorous stirring obtains material I, 3.43g Tai-Ace S 150 is joined in material I, vigorous stirring obtains material II, 91g TPAOH, 6.5g hexanediamine is added in material II, vigorous stirring obtains material III, in material III, add silicon sol 42g, 0.56g PEG 20000, vigorous stirring obtains raw mixture.Wherein TPAOH and hexanediamine mol ratio are 2, Na
2siO in O and silicon sol
2mol ratio be 0.2, Al in Tai-Ace S 150
2o
3with SiO in silicon sol
2mol ratio be 0.03, SiO in organic polymer and silicon sol
2mol ratio be 0.0001, SiO in deionized water and silicon sol
2mol ratio be 21.
B) by raw mixture obtained for a) step under crystallization temperature is 160 DEG C of conditions, hydrothermal crystallizing 84 hours, then washs, filters, dries and to obtain the spherical ZSM-5 zeolite of pure phase.
Concrete preparation condition is in table 1, and Product bulk density and pore structure parameter are in table 2.
[embodiment 9]
Prepare a method for the spherical ZSM-5 zeolite of high-bulk-density, comprise the steps:
A) first 6.9g potassium hydroxide is dissolved in 22.5g deionized water, vigorous stirring obtains material I, 4.57g Tai-Ace S 150 is joined in material I, vigorous stirring obtains material II, 91g TBAH, 6.5g hexanediamine is added in material II, vigorous stirring obtains material III, in material III, add silicon sol 42g, 1.68g PEG 20000, vigorous stirring obtains raw mixture.Wherein the mol ratio of TBAH and hexanediamine is 2, K
2siO in O and silicon sol
2mol ratio be 0.22, Al in Tai-Ace S 150
2o
3with SiO in silicon sol
2mol ratio be 0.04, SiO in organic polymer and silicon sol
2mol ratio be 0.0003, SiO in deionized water and silicon sol
2mol ratio be 18.
B) by raw mixture obtained for a) step under crystallization temperature is 120 DEG C of conditions, hydrothermal crystallizing 196 hours, then washs, filters, dries and to obtain the spherical ZSM-5 zeolite of pure phase.
Concrete preparation condition is in table 1, and Product bulk density and pore structure parameter are in table 2.
[embodiment 10]
Prepare a method for the spherical ZSM-5 zeolite of high-bulk-density, comprise the steps:
A) first 5.6g sodium hydroxide is dissolved in 100g deionized water, vigorous stirring obtains material I, 5.7g Tai-Ace S 150 is joined in material I, vigorous stirring obtains material II, 20.85g 4-propyl bromide, 45.5g hexanediamine is added in material II, vigorous stirring obtains material III, in material III, add silicon sol 42g, 3.36g PEG 20000, vigorous stirring obtains raw mixture.Wherein the mol ratio of 4-propyl bromide and hexanediamine is 0.2, Na
2siO in O and silicon sol
2mol ratio be 0.22, Al in Tai-Ace S 150
2o
3with SiO in silicon sol
2mol ratio be 0.05, SiO in organic polymer and silicon sol
2mol ratio be 0.0006, SiO in deionized water and silicon sol
2mol ratio be 20.
B) by raw mixture obtained for a) step under crystallization temperature is 150 DEG C of conditions, hydrothermal crystallizing 168 hours, then washs, filters, dries and to obtain the spherical ZSM-5 zeolite of pure phase.
Concrete preparation condition is in table 1, and Product bulk density and pore structure parameter are in table 2.
[embodiment 11]
Prepare a method for the spherical ZSM-5 zeolite of high-bulk-density, comprise the steps:
A) first 4.032g sodium hydroxide is dissolved in 75.6g deionized water, vigorous stirring obtains material I, 5.14g Tai-Ace S 150 is joined in material I, vigorous stirring obtains material II, 13.41g 4-propyl bromide, 11.7g hexanediamine is added in material II, vigorous stirring obtains material III, in material III, add silicon sol 42g, 2.8g PEG 20000, vigorous stirring obtains raw mixture.Wherein the mol ratio of 4-propyl bromide and hexanediamine is 0.5, Na
2siO in O and silicon sol
2mol ratio be 0.18, Al in Tai-Ace S 150
2o
3with SiO in silicon sol
2mol ratio be 0.045, SiO in organic polymer and silicon sol
2mol ratio be 0.0005, SiO in deionized water and silicon sol
2mol ratio be 15.
B) by raw mixture obtained for a) step under crystallization temperature is 100 DEG C of conditions, hydrothermal crystallizing 240 hours, then washs, filters, dries and to obtain the spherical ZSM-5 zeolite of pure phase.
Concrete preparation condition is in table 1, and Product bulk density and pore structure parameter are in table 2.
[embodiment 12]
Prepare a method for the spherical ZSM-5 zeolite of high-bulk-density, comprise the steps:
A) first 3.36g sodium hydroxide is dissolved in 50g deionized water, vigorous stirring obtains material I, 3.43g Tai-Ace S 150 is joined in material I, vigorous stirring obtains material II, 12.67g 4-propyl bromide, 55.3g hexanediamine is added in material II, vigorous stirring obtains material III, in material III, add silicon sol 42g, 1.12g PEG 20000, vigorous stirring obtains raw mixture.Wherein the mol ratio of 4-propyl bromide and hexanediamine is 0.1, Na
2siO in O and silicon sol
2mol ratio be 0.15, Al in Tai-Ace S 150
2o
3with SiO in silicon sol
2mol ratio be 0.03, SiO in organic polymer and silicon sol
2mol ratio be 0.0002, SiO in deionized water and silicon sol
2mol ratio be 16.
B) by raw mixture obtained for a) step under crystallization temperature is 130 DEG C of conditions, hydrothermal crystallizing 200 hours, then washs, filters, dries and to obtain the spherical ZSM-5 zeolite of pure phase.
Concrete preparation condition is in table 1, and Product bulk density and pore structure parameter are in table 2.
[comparative example 1]
A) first 0.23g sodium hydroxide is dissolved in 50g deionized water, vigorous stirring obtains material I, 2.4g sodium metaaluminate is joined in material I and fully stir to obtain material II, 42g silicon sol is joined in material II, then in material II, adds 7.39g directed agents 4-propyl bromide obtain raw mixture; Wherein 4-propyl bromide and SiO
2mol ratio be 0.1, Al
2o
3with SiO
2mol ratio be 0.02, Na
2o and SiO
2mol ratio be 0.01, deionized water and SiO
2mol ratio be 15.
B) by raw mixture obtained for a) step under crystallization temperature is 180 DEG C of conditions, hydrothermal crystallizing 72 hours, then washs, filters, dries and to obtain product.
[comparative example 2]
A) first 3g sodium hydroxide is dissolved in 50g deionized water, vigorous stirring obtains material I, 5g Tai-Ace S 150 is joined in material I, vigorous stirring obtains material II, 4.5g hexanediamine, 10.3g 4-propyl bromide is added in material II, vigorous stirring obtains material III, in material III, add 42g silicon sol, 5.6g Macrogol 2000, vigorous stirring obtains raw mixture.Wherein hexanediamine be 1, Na with the mol ratio of 4-propyl bromide
2siO in O and silicon sol
2mol ratio be 0.134, Al in Tai-Ace S 150
2o
3with SiO in silicon sol
2mol ratio be 0.027, SiO in Macrogol 2000 and silicon sol
2mol ratio be 0.01, SiO in deionized water and silicon sol
2mol ratio be 10.
B) by raw mixture obtained for a) step under crystallization temperature is 180 DEG C of conditions, hydrothermal crystallizing 120 hours, then washs, filters, dries and to obtain the spherical ZSM-5 zeolite of pure phase.
Concrete preparation condition is in table 1, and Product bulk density and pore structure parameter are in table 2.
Table 1 (continued)
A. raw mixture was 110 DEG C of ageings 48 hours, hydrothermal crystallizing 96 hours at 180 DEG C;
B. raw mixture was 110 DEG C of ageings 48 hours, hydrothermal crystallizing 96 hours at 180 DEG C.
Table 1 (Continued)
A. raw mixture was 110 DEG C of ageings 48 hours, hydrothermal crystallizing 96 hours at 180 DEG C;
B. raw mixture was 110 DEG C of ageings 48 hours, hydrothermal crystallizing 96 hours at 180 DEG C.
Table 2
Claims (10)
1. prepare the method for the spherical ZSM-5 zeolite of high-bulk-density, comprise the steps:
A) raw silicon source, aluminium source, MOH, organic amine, organic polymer and water are mixed to get raw mixture;
B) hydrothermal crystallizing;
Wherein M is at least one of alkali metal; Described organic polymer is selected from least one in polyoxyethylene glycol, starch.
2. method according to claim 1, is characterized in that described silicon source is selected from least one in tetraethoxy, silicon sol, silica gel, water glass or White Carbon black.
3. method according to claim 1, is characterized in that described aluminium source is selected from least one in aluminum isopropylate, sodium metaaluminate, Tai-Ace S 150.
4. method according to claim 1, is characterized in that described organic amine is selected from least one in tetraethyl ammonium hydroxide, TPAOH, TBAH, Tetrabutyl amonium bromide, tetraethylammonium bromide, 4-propyl bromide, n-Butyl Amine 99, butanediamine, triethylamine, Monoethanolamine MEA BASF, diethanolamine, trolamine or hexanediamine.
5. method according to claim 1, it is characterized in that described organic amine with SiO
2the mol ratio in meter silicon source is 0.01 ~ 0.3.
6. method according to claim 1, is characterized in that described with M
2o count MOH with SiO
2the mol ratio in meter silicon source is 0.01 ~ 0.3.
7. method according to claim 1, it is characterized in that water in described raw mixture with SiO
2the mol ratio in meter silicon source is 5 ~ 50.
8. method according to claim 1, it is characterized in that organic polymer with SiO
2the mol ratio in meter silicon source is 0.0001 ~ 0.01.
9. method according to claim 1, is characterized in that step b) temperature of hydrothermal crystallizing is 60 ~ 200 DEG C.
10. method according to claim 1, is characterized in that step b) time of hydrothermal crystallizing is 8 ~ 480 hours.
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| CN109265819A (en) * | 2018-08-09 | 2019-01-25 | 道晟拉链科技（太仓）有限公司 | A kind of slide fastener coupling element antibiotic plastic and preparation method thereof |
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