CN101024499A - Method for synthesizing MWW mole cular sieve - Google Patents
Method for synthesizing MWW mole cular sieve Download PDFInfo
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Abstract
The invention supplies a method to compound MWW molecular sieve. It adopts two-stage hydrothermal crystallization method that the room temperature at -119.9 degree centigrade is the first stage and 120-180 degree centigrade is the second stage. The alkali resource is one or two or three of hydroxide of Na, K and Ba. The silicon resource could be solid silica gel or liquid silica gel. And template agent could be HMI or the mixture of HMI and organic amine, quaternary ammonium salt, alcohols, and polyether. The invention has the advantages of compound method and condition is easy to control and low cost. The acid of the product could be altered by changing alkali resources.
Description
Technical field
The present invention relates to a kind of synthetic method of molecular sieve, particularly a kind of synthetic method with MWW structure molecular screen.
Background technology
Zeolite molecular sieve be a kind of be the inorganic poromerics that basic structural unit constitutes with silicon-oxy tetrahedron and aluminum-oxygen tetrahedron, be widely used in fields such as catalysis, absorption and ion-exchange; As good solid acid catalyst, successfully be applied to the acid catalyzed organic chemical industry's process of kind more than 70.Because the aperture size of molecular sieve catalyst is suitable with the size of the organic molecule that participates in reaction, generally has higher selectivity, people are called the shape selective of molecular sieve.When the kinetics radius of reactant or resultant during greater than the aperture of molecular sieve, just can not be by the aperture of molecular sieve.Therefore, along with the development of petrochemical complex and fine chemistry industry, urgent wish exploitation not only had the acidity of molecular sieve and stability, but also the novel molecular sieve that is suitable for big organic molecule reaction as catalyzer.
The molecular sieve of synthetic larger aperture is chemical research persons' pursuit.In the micropore Si-Al molecular sieve, UTD-1 have maximum aperture (1.0 * 0.75nm), contain 14 yuan of rings of one dimension (1D) (MR) structure.Recently, synthesized another kind of CIT-5 molecular sieve again with 1D14MR structure.Yet concerning many important chemical reactions, the aperture of these molecular sieves is still too little.The mesoporous silicate material of Chu Xianing in recent years, as M41S family material, although have the aperture of 2.5-10nm and the pore passage structure of homogeneous, the pure silica mesopore molecular sieve is unformed because of hole wall, thereby hydrothermal stability is relatively poor; Because silicon-oxy tetrahedron is a charge balance system, make that lattice imperfection is few in the skeleton, surface acid center concentration is low and acid very weak.Therefore, though a large amount of research reports is arranged, do not enter industrial applications so far yet.It is generally acknowledged, although the silanol base is more than acidic site on the molecular sieve crystal outside surface, but certain topological framework still can expose the B acid position of larger proportion, if the acidic site of these molecular sieve crystal outsides of reinforcement in molecular sieve synthetic, make it be used as catalytic active center, also can be used for more macromolecular conversion.Molecular sieve with this topological framework is at first to be succeeded in developing by the U.S. Mobil company nineties in 20th century, the molecular sieve that is called as the MWW structure, its main member has MCM-22[USP4954325], SSZ-25 [USP 4826667], ERB-1[EP 293032], PSH-3[USP4439409]), MCM-49 [USP 5236575], MCM-36[USP 5229341], MCM-56[USP 5362697], ITQ-1[23] and ITQ-2[USP 6231751] etc.
Nineteen ninety Mobil company discloses the synthetic method of the MCM-22 molecular sieve with MWW structure first, and uses it for very soon in the catalyzer of industrial synthesizing ethyl benzene and isopropyl benzene.The MCM-22 molecular sieve is with { 4
35
66
3[4
3] cage is the crystal that basic structural unit constitutes, spacer is P6/mmm, with not being both it and having mutually Uncrossed independent channel system of two covers of other molecular sieve maximum, wherein a cover is that (size is that (size is 0.71 * 0.71 * 1.82nm) to 0.4 * 0.54nm) the cylindrical supercage of 12MR that is communicated with, and each supercage has 6 holes (0.40 * 0.55nm) by the 10MR window; Another set of is that (size is 0.4 * 0.59nm) the sinusoidal duct of cross one another two dimension that constitutes, and also has a little cage (0.64 * 0.69nm) along each sinusoidal duct by 10MR.
The synthetic method of the MCM-22 that USP 4954325 describes is with after each mixing of materials, under agitation condition in 145 ℃-150 ℃ constant temperature 6-8 days, can obtain target product; Isao Mochida etc. has reported at 170 ℃ and has synthesized MCM-22 molecular sieve (Zeolites 18:142-151,1997); CN1594089A discloses a kind of high silica alumina ratio MWW synthesis method of zeolite molecular sieve; CN1616350A has announced a kind of method of aluminium refilling synthesizing high-silicon MWW molecular sieve; CN 1361060A then discloses a kind of synthetic method of MCM-49 zeolite.These documents all adopt one section hydrothermal crystallization method to synthesize the MWW molecular sieve.The present invention finds through a large amount of experiments, when adopting one section hydrothermal method to synthesize the MWW molecular sieve, reaction mixture is crystallization at high temperature directly, and very easily association or to change crystalline substance be that ZSM-5, ZSM-35, ZSM-12 equimolecular sieve is difficult to obtain having the molecular sieve of pure phase MWW structure.
CN 99123719.6 discloses a kind of synthetic method of MCM-22 molecular sieve, taked first high temperature after cryogenic two sections constant temperature methods synthesize the MCM-22 molecular sieve.Earlier 160 ℃～200 ℃ constant temperature 1～20 hour, the back was 130 ℃～155 ℃ constant temperature 8～100 hours.But cryogenic method is prone to stray crystal MCM-35 after adopting first high temperature, makes the synthetic wayward of product.
The inventor is on the basis of the synthetic MWW molecular sieve of three sections hydrothermal crystallization methods (ZL 03142805.3), find through experiment, by two sections hydrothermal crystallizing methods of pyritous behind the first low temperature, the pure phase MWW structure molecular screen that also can synthesize high-crystallinity, thereby simplified synthesis technique, save generated time, reduced synthetic cost.
At present, sodium aluminate is all adopted in the synthetic used aluminium source of MWW molecular sieve, easily the impurity in the sodium aluminate is introduced in the synthetic molecular sieve, and the sodium aluminate of different manufacturers or different batches differs bigger on forming simultaneously, the composition of wayward raw material when synthetic; Synthetic system basicity is regulated and is all adopted sodium hydroxide, and institute's synthetic molecular sieve all is a sodium type molecular sieve, if obtain containing other ionic molecular sieves, must improve the synthetic cost of molecular sieve greatly by the way of exchange; In addition MWW molecular sieve synthetic all to adopt hexamethylene imine (HMI) or add the diamantane quaternary ammonium hydroxide therein be template, these template cost an arm and a leg, and cause the production cost of MWW molecular sieve higher.
Summary of the invention
The object of the present invention is to provide a kind of synthetic method of MWW molecular sieve, with the scope of expansion aluminium source, alkali source and template, and make synthesis condition more easy to control, thereby improve the quality of sintetics, avoid the appearance of stray crystal, reduce synthetic cost.
Molecular sieve water heat synthetic method provided by the invention, comprise various raw materials and water are mixed with colloid according to ordinary method, then this colloid is carried out hydrothermal crystallizing synthetic after, obtain the purpose product, wherein said hydrothermal crystallizing is the two-stage method hydrothermal crystallizing, be that room temperature-129.9 ℃ is first section, 120 ℃-180 ℃ is second section.To be 60-119.9 ℃ be first section to temperature range preferably, and 120-165 ℃ is second section.But the time of two sections Temperature Treatment is not limit.General first period is 8 hours-10 days, and optimum is 8 hours-2 days; Second period treatment time is 1-15 days, and optimum is 1 day-10 days.
Wherein said raw material comprises silicon source (Y), aluminium source or boron source (X), organic formwork agent (R).The molar ratio range of each component is in the above-mentioned raw materials:
YO
2/ X
2O
3=5-150 is preferably 20-150;
H
2O/YO
2=10-110 is preferably 10-110, is preferably 10-100;
R/YO
2=0.05-4 is preferably 0.05-1.
Here R is one or more the mixture in hexamethylene imine (hereinafter to be referred as HMI) or HMI and organic amine (being preferably hydramine), quaternary ammonium salt, alcohols or the polyethers.Wherein said alcohols is preferably glycerol; Said organic amine is preferably hexahydroaniline, quadrol, hexanediamine or aniline; Polyethers is a water soluble polyether.
The Si oxide weight content is not less than 20% in the described silicon source.
Colloidal pH value is not less than 7.
Synthetic MWW molecular sieve has following composition YO according to the method described above
2/ X
2O
3=n, n 〉=5 here, n can be 5-150, X is 3 valency elements, and Y is 4 valency elements, and X is preferably Al, B or Fe element, and Y is preferably the Si element, and its X-ray diffracting spectrum is as shown in Figure 1.
Its molecular sieve precursor is formed, with the YO of n mole
2Be standard, then in its precursor other material by oxide compound and YO
2Mol ratio be:
(0.002-0.1) M
2O or MO: (1-4) R: X
2O
3: (n) YO
2
Here n 〉=5 are preferably 5-150; X is 3 valency elements, is preferably Al, B or Fe element, and Y is 4 valency elements, preferably Si element; R is a template.Original cationic wherein is that the hybrid ionic of sodium ion or potassium ion or barium ion or they any two or three can be by all or part of replacement of other positively charged ion, and these ions comprise the metal ion among IIA, IIIA, IVA, IB, IIB, IIIB, IVB and the VIIIB in the hydrogen ion and the periodic table of elements.The raw material ratio of indication of the present invention all is a mol ratio.
Has the characteristic that after concentration is the following strong acid treatment of 10M, does not change structure according to the synthetic MWW of the inventive method institute molecular sieve.
Description of drawings
Fig. 1 is for pressing the XRD spectra of sample after the precursor of embodiment 1 method synthetic molecular sieve and the roasting;
Fig. 2 is for regulating the XRD spectra of the molecular sieve that obtains after the pH value of synthetic liquid with hydrated barta by the method for embodiment 2;
Fig. 3 has different SiO for the method synthetic by embodiment 3
2/ Al
2O
3The XRD spectra of the molecular sieve of ratio;
Fig. 4 is for regulating the XRD spectra of the molecular sieve that obtains after the pH value of synthetic liquid with potassium hydroxide by the method for embodiment 4;
Fig. 5 is the XRD spectra of pressing the method synthetic molecular sieve of embodiment 5;
The method of Fig. 6 for pressing embodiment 6, the XRD spectra of the molecular sieve that obtains after the pH value with sodium hydroxide and the synthetic liquid of potassium hydroxide adjusting;
The method of Fig. 7 for pressing embodiment 7, the XRD spectra of the molecular sieve that obtains after the pH value with hydrated barta and the synthetic liquid of potassium hydroxide adjusting;
Fig. 8 replaces the XRD spectra of the sample of aluminium with boron for the method synthetic of pressing embodiment 8;
The method of Fig. 9 for pressing embodiment 9 is the XRD spectra of template synthetic sample with HMI and glycerol;
The method of Figure 10 for pressing embodiment 10 is the XRD spectra of template synthetic sample with HMI and polyethers;
The method of Figure 11 for pressing embodiment 11 is the XRD spectra of template synthetic sample with HMI and quaternary ammonium salt;
Figure 12 is for pressing the XRD spectra of the inventive method synthetic sample after strong acid treatment.
Figure 13 (a) is the XRD spectra by enforcement Comparative Examples 13 synthetic ZSM-35 molecular sieves.
Figure 13 (b) is the XRD spectra by enforcement Comparative Examples 13 synthetic MCM-22 molecular sieves.
Embodiment
After under agitation joining the 0.435g aluminum oxide in the 72.7g water, add 3.1g HMI again, regulate about pH value to 12, add silica gel (99%) with NaOH, the formation reaction mixture, each component composed as follows:
SiO
2/ Al
2O
3=20, H
2O/SiO
2=45, R/SiO
2=0.35, reaction mixture pH=12
Here R represents HMI.Reaction mixture is placed reactor, after 8 hours, be warming up to 150 ℃ of following constant temperature 10 days at 110 ℃ of following constant temperature; Reactant after filtration, the washing after, 120 ℃ of oven dry, the gained sample is designated as MCM-22 (P); MCM-22 (P) is after 550 ℃ of following roastings, and the gained sample is designated as MCM-22 (C).The x-ray diffraction collection of illustrative plates (XRD) of MCM-22 (P) and MCM-22 (C) as shown in Figure 1.
According to the step of embodiment 1, with the pH value of hydrated barta regulation system, the mixture that preparation table 1 is formed, 119 ℃ of following constant temperature 5 days, 155 ℃ of constant temperature 8 days, reactant after filtration, after the washing, 120 ℃ of oven dry, 550 ℃ of following roastings, the XRD figure of each sample spectrum is seen Fig. 2.
The mixture of table 1 embodiment 2 is formed
| No. | SiO 2/Al 2O 3 | H 2O/SiO 2 | HMI/SiO 2 | Ba/SiO 2 | The |
| 1 2 3 4 5 6 | 60 60 60 60 60 60 | 22.5 22.5 22.5 22.5 22.5 22.5 | 0.18 0.18 0.18 0.18 0.18 0.18 | 0.0015 0.0061 0.0122 0.0244 0.0488 0.0610 | MCM-22 MCM-22 MCM-22 MCM-22 MCM-22 MCM-22 |
According to the method for embodiment 1, prepared SiO
2/ Al
2O
3=25,30,35,40,45,50,85,100,150 MCM-22 molecular sieve, the XRD figure spectrum of products therefrom is as shown in Figure 3.The result shows that the synthetic sample is the MCM-22 molecular sieve.
According to the step of embodiment 1, the mixture that preparation table 2 is formed, 90 ℃ of following constant temperature 8 days, 150 ℃ of constant temperature 10 days, reactant after filtration, after the washing, 120 ℃ of oven dry, 550 ℃ of following roastings, the XRD figure of each sample spectrum is seen Fig. 4.
The mixture of table 2 embodiment 4 is formed
| No. | SiO 2/Al 2O 3 | H 2O/SiO 2 | HMI/SiO 2 | K/SiO 2 | The |
| 1 2 3 4 5 | 60 60 60 60 30 | 22.5 22.5 22.5 22.5 45 | 0.112 0.112 0.112 0.112 0.313 | 0.0040 0.0173 0.0243 0.0427 0.0972 | MCM-22 MCM-22 MCM-22 MCM-22 MCM-22 |
With the 27.1g sodium aluminate solution in 3490g water, add 151g HMI, stir, with about potassium hydroxide solution adjust pH to 10, add 258g silica gel, form reaction mixture, this mixture is placed stainless steel cauldron, 125 ℃ of following constant temperature 10 days, 160 ℃ of following constant temperature 2 days, reactant after filtration, the washing after, 120 ℃ of oven dry.The consisting of of each component in this embodiment reaction mixture:
SiO
2/ Al
2O
3=30, H
2O/SiO
2=45, R/SiO
2=0.82, reaction mixture pH=10
The XRD spectra of this oven dry sample is seen Fig. 5.The result shows that sample is the MCM-22 molecular sieve.
According to the step of embodiment 1, the resulting solution that preparation table 3 is formed, 90 ℃ of following constant temperature 8 days, 150 ℃ of constant temperature 10 days, reactant after filtration, after the washing, 120 ℃ of oven dry, each XRD figure spectrum of drying sample is seen Fig. 6.
The composition of the resulting solution of table 3 embodiment 6
| No. | SiO 2/Al 2O 3 | H 2O/SiO 2 | HMI/SiO 2 | KOH/SiO 2 | NaOH/SiO 2 | The |
| 1 2 3 | 60 60 60 | 22.5 22.5 22.5 | 0.112 0.112 0.112 | 0.0486 0.0365 0.0243 | 0.0185 0.0185 0.0185 | MCM-22 MCM-22 MCM-22 |
Embodiment 7
According to the step of embodiment 1, the resulting solution of forming shown in the preparation table 4,120 ℃ of following constant temperature 10 days, 155 ℃ of constant temperature 10 days, reactant after filtration, after the washing, 120 ℃ of oven dry, 550 ℃ of following roastings, the XRD figure of sample spectrum is as shown in Figure 7 after each roasting.The result shows that sample is the MCM-22 molecular sieve.
The composition of the resulting solution of table 4 embodiment 7
| No. | SiO 2/Al 2O 3 | H 2O/SiO 2 | HMI/SiO 2 | K/SiO 2 | Ba/SiO 2 | The |
| 1 2 3 4 | 60 60 60 60 | 22.5 22.5 22.5 22.5 | 0.18 0.18 0.18 0.18 | 0.0243 0.0243 0.0243 0.0243 | 0.0031 0.0061 0.0122 0.0244 | MCM-22 MCM-22 MCM-22 MCM-22 |
According to embodiment 1 described method, 55.6g silica gel, 35.4g sodium hydroxide, 31g HMI, 8.1g boric acid is soluble in water, after stirring, 100 ℃ of following constant temperature 5 days, 150 ℃ were reacted 15 days down, reaction mixture after filtration, washing is back dries down at 120 ℃, and the XRD spectra of gained sample as shown in Figure 8.
According to the step of embodiment 1, be the mixed templates component with the glycerol, prepare consisting of of resulting solution: SiO
2/ Al
2O
3=60, H
2O/SiO
2=22.5, HMI/SiO
2=0.112, Na/SiO
2=0.056, K/SiO
2=0.0486, glycerol/SiO
2Than seeing Table 5.129 ℃ of following constant temperature 8 days, 155 ℃ of constant temperature 9 days, reactant after filtration, after the washing, 120 ℃ of oven dry, 550 ℃ of following roastings, the XRD figure of each sample spectrum is seen Fig. 9.
The composition of table 5 embodiment 9 resulting solutions
| No. | GL/SiO 2 | The |
| 1 2 3 | 0.121 0.242 0.363 | MCM-22 MCM-22 MCM-22 |
According to the step of embodiment 1, be the mixed templates component with the polyethers, prepare consisting of of resulting solution: SiO
2/ Al
2O
3=60, H
2O/SiO
2=22.5, HMI/SiO
2=0.112, Na/SiO
2=0.038, K/SiO
2=0.0486, the mass concentration of polyethers in water is as shown in table 6.120 ℃ of following constant temperature 8 days, 150 ℃ of constant temperature 9 days.Reactant after filtration, after the washing, 120 ℃ of oven dry, the XRD figure of each sample spectrum is seen Figure 10.
The composition of table 6 embodiment 10 resulting solutions
| No. | Polyethers/W% | The |
| 1 2 3 4 5 | 4.13 6.88 9.63 12.38 15.13 | MCM-22 MCM-22 MCM-22 MCM-22 MCM-22 |
Embodiment 11
According to the step of embodiment 1, be the mixed templates component with cetyl trimethylammonium bromide (CTAB), prepare consisting of of resulting solution: SiO
2/ Al
2O
3=30, H
2O/SiO
2=45, Na/SiO
2=0.18, (HMI+CTBA)=3.2g, CTAB/SiO
2Than as shown in table 7.Crystallization condition is 120 ℃ and 150 ℃ each 5 days.Reactant after filtration, after the washing, 120 ℃ of oven dry, the XRD figure of each sample spectrum is seen Figure 11
The composition of the resulting solution of table 7 embodiment 11
| No. | CTAB/SiO 2 | The |
| 1 2 3 4 | 0.0159 0.0319 0.0476 0.0635 | MCM-22 MCM-22 MCM-22 MCM-22 |
With the sample of 120 ℃ of oven dry of embodiment 1 gained, use the HNO of 0.01M, 0.1M, 1M and 10M respectively
3Solution was handled 6 hours under the boiling condition, and then after filtration, washing back is 120 ℃ of oven dry, 550 ℃ of roastings, the XRD spectra of sample as shown in figure 12 after the roasting.Still keep skeleton structure constant through the MCM-22 of excessive concentrations strong acid treatment molecular sieve.
Implement Comparative Examples 13
We are according to document US P4, and prescription and the method for 954,325 embodiment 1 are synthesized at 150 ℃ of following direct crystallizations, and the product that obtains is not a purpose product MCM-22 molecular sieve, but the ZSM-35 molecular sieve shown in Figure 13 (a); With same prescription and resulting solution, adopt two sections crystallization methods of this patent, then obtain the MCM-22 molecular sieve, shown in Figure 13 (b).
Claims (10)
1. a molecular sieve water heat synthetic method comprises raw material and water are mixed with colloid, then this colloid is carried out obtaining product behind the hydrothermal crystallizing, it is characterized in that, said hydrothermal crystallizing is the two-stage method hydrothermal crystallizing, and promptly room temperature-129.9 ℃ is first section, and 130 ℃-180 is second section.
2. according to the described synthetic method of claim 1, it is characterized in that said hydrothermal crystallizing is the two-stage method hydrothermal crystallizing, promptly 60-119.9 ℃ is first section, and 140-165 ℃ is second section.
3. according to claim 1 or 2 described synthetic methods, it is characterized in that it is 8 hours-10 days that the time of two sections processing is respectively first period, second period treatment time is 1 day-15 days.
4. according to the described synthetic method of claim 3, it is characterized in that it is 8 hours-2 days that the time of two sections processing is respectively first period; Second period treatment time is 1 day-10 days.
5. according to the described synthetic method of claim 1, it is characterized in that said raw material comprises silicon source (Y), aluminium source or boron source (X), template (R) and alkali source (M), the molar ratio range of each component is:
YO
2/X
2O
3＝5-150；
H
2O/YO
2＝10-110；
R/YO
2＝0.05-4。
6. according to the described synthetic method of claim 5, it is characterized in that wherein R is one or more the mixture in HMI or HMI and quaternary ammonium salt, alcohols or the polyethers.
7. according to the described synthetic method of claim 6, it is characterized in that wherein said organic amine is a quadrol; Quaternary ammonium salt is the cetyl trimethyl ammonium halide, the alcohols glycerol, and polyethers is the polymkeric substance of different molecular weight.
8. according to the described synthetic method of claim 5, it is characterized in that a kind of in the oxyhydroxide that wherein said alkali source is sodium, potassium or barium or any two or three mixture.
9. according to the described synthetic method of claim 5, it is characterized in that wherein said aluminium source is a sodium aluminate, a kind of in the aluminum oxide or both mixtures.
10. one kind according to the described method synthetic of claim 1 molecular sieve, it is characterized in that the composition of molecular sieve has following relationship: YO
2/ X
2O
3〉=5.
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| US11091372B2 (en) | 2016-04-27 | 2021-08-17 | China Petroleum & Chemical Corporation | Molecular sieve, its preparation and application thereof |
| JP7051709B2 (en) | 2016-04-27 | 2022-04-11 | 中国石油化工股▲ふん▼有限公司 | Molecular sieves, their manufacturing methods and applications |
| CN106517234A (en) * | 2016-11-07 | 2017-03-22 | 西北大学 | Dynamic hydrothermal synthesis method of exfoliated type MWW lamellar molecular sieve |
| CN107199048A (en) * | 2017-04-14 | 2017-09-26 | 钦州学院 | A kind of preparation method for being used to prepare the catalyst of isooctane |
| CN109665543A (en) * | 2017-10-17 | 2019-04-23 | 中国石油化工股份有限公司 | Lamellar zeolite and preparation method |
| CN109665543B (en) * | 2017-10-17 | 2022-04-05 | 中国石油化工股份有限公司 | Layered molecular sieve and preparation method thereof |
| CN108439425A (en) * | 2018-04-27 | 2018-08-24 | 南开大学 | A kind of ETL types molecular sieve and its manufacturing method |
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