CN105439166A - A method of synthesizing a MWW-structure molecular sieve - Google Patents
A method of synthesizing a MWW-structure molecular sieve Download PDFInfo
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Abstract
The invention relates to a method of synthesizing a MWW-structure molecular sieve, and mainly overcomes a problem in the prior art, namely low synthesis speeds of MWW-structure molecular sieves. According to a technical scheme adopted by the method, the method includes a) a step of mixing a silicon source, an aluminum source, an alkali source containing OH<->, a template R and water to obtain a reaction mixture, b) a step of stirring the reaction mixture, drying and grinding to obtain dry gel powder, and c) a step of mixing the dry gel powder with water, crystallizing, washing the crystallization product with water, drying and calcining to obtain the MWW-structure molecular sieve. The problem is overcome by adoption of the technical scheme. The method can be used for industrial production of the MWW-structure molecular sieve.
Description
Technical field
The present invention relates to a kind of method of synthesizing MWW structure molecular screen.
Background technology
Say in the narrow sense, molecular sieve is silicate or the silico-aluminate of crystal form, be connected by oxo bridge key by silicon-oxy tetrahedron or aluminum-oxygen tetrahedron and formed duct and the cavity system of molecular dimension size, there is the crystalline structure of high-sequential, regular uniform Subnano-class duct.Divide by duct size, the molecular sieve that pore size is less than 2nm, 2 ~ 50nm and is greater than 50nm is called micropore, mesoporous and large pore molecular sieve.Molecular sieve has been widely used in the every field such as catalysis, absorption and ion-exchange as important material.
MWW structure molecular screen is a series of general designations with the molecular sieve of MWW topological framework, has the 10 membered ring channel systems that two covers are independently not connected: a set of two-dimentional sinusoidal pattern intersection duct, cross section, duct is oval, aperture
another set of duct has and is of a size of
cylindrical 12 ring supercages, supercage by 10 ring windows of distortion slightly (
) be in communication with the outside (Science, 1994,264:1910).In addition, MCM-22 molecular sieve also has 12 bowl-shape ring half supercages and is positioned at outside surface.
MCM-22 molecular sieve synthesizes (USP4 by Mobil company first in nineteen ninety, 954,325), Leonowicz in 1994 etc. determine the structure of MCM-22 by high-resolution electron microscopy and X-ray powder diffraction analysis, 1997 International Zeolite Association meeting (IZA) be MCM-22 (Micro.Meso.Mater.1998 by this molecular sieve definite designation, 22,551), be attributed to MWW structure, belong to P6/mmm point group (Zeolites1995,15,188).The molecular sieve belonging to MWW topological framework also has MCM-56 (US5,362,697), MCM-36 (US5,229,341), MCM-49 (US5,236,575), PSH-3 (US4,439,409), SSZ-25 (US4,826,667), EMM-10 (Micro.Meso.Mater.2011,142,168) etc.
In recent years, the domestic and international patent about MWW topological framework Zeolite synthesis and document constantly increase, and its synthetic method is also varied, but research focuses mostly in the MCM-22 molecular sieve that synthesis has MWW topological framework, and other molecular sieves relate to less.Chinese patent CN99123719.6 has reported a kind of synthetic method with the molecular sieve (MCM-22) of special crystal structure, by silicon source, aluminium source, alkali source, organic formwork agent and water first 160 ~ 200 DEG C of crystallization 1 ~ 20 hour, 130 ~ 150 DEG C of crystallization 8 ~ 100 hours after cooling, the MCM-22 molecular sieve with MWW topological framework can be synthesized in a static condition.Chinese patent CN00116529.1 is in order to reduce the time of MCM-22 Zeolite synthesis, adopt stirring and interpolation in MCM-22 sieve synthesis procedure to be selected from the technical scheme of alkali metal cation, alkaline earth metal cation, the IIIth subgroup positively charged ion and composition thereof, crystallization time is shortened to 10 ~ 100 hours.Chinese patent CN02145234.2 adopts and controls molecular sieve precursor mixture basicity and by mixture elder generation's ageing technical scheme of 0.5 ~ 720 hour at 0 ~ 100 DEG C before crystallization, control crystallization time at 5 ~ 100 hours.
The method for shortening the synthesis MWW topological framework molecular sieve time mentioned in above-mentioned patent, relate generally to the synthesis of MCM-22, the molecular sieve kind of other MWW topological framework relates to less, and its synthesis needed for crystallization time also relatively long, be unfavorable for molecular sieve industrial production and reduce costs.
Summary of the invention
Technical problem to be solved by this invention is that prior art exists the long problem of MWW topological framework Zeolite synthesis crystallization time, provides a kind of method of synthesis MWW structure molecular screen newly.The method can Fast back-projection algorithm MWW topological framework molecular sieve, and can synthesize multiple MWW topological framework molecular sieve.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method of synthesizing MWW structure molecular screen, comprises the following steps:
A) by silicon source, aluminium source, containing OH
-alkali source, template R and water mixing, obtain reaction mixture;
B) described reaction mixture is stirred, dry, grind to form dry glue powder end;
C) crystallization after described dry glue powder end being mixed with water; Crystallization product obtains described MWW structure molecular screen after washing, oven dry, roasting.
In technique scheme, preferably, described reaction mixture is with molar ratio computing Al
2o
3: SiO
2: OH
-: R:H
2o=(0.01 ~ 0.20): 1:(0.01 ~ 0.40): (0.01 ~ 0.50): (5 ~ 50).More preferably, Al
2o
3: SiO
2: OH
-: R:H
2o=(0.02 ~ 0.10): 1:(0.02 ~ 0.30): (0.05 ~ 0.40): (10 ~ 35).
In technique scheme, preferably, step b) whipping temp is room temperature, churning time is 1 ~ 10 hour, and bake out temperature is 40 ~ 90 DEG C.More preferably, churning time is 2 ~ 5 hours, and bake out temperature is 50 ~ 80 DEG C.
In technique scheme, preferably, step c) dry glue powder end is 1:(1 ~ 20 with the weight ratio of water), crystallization temperature is 120 ~ 180 DEG C, and crystallization time is 5 ~ 40 hours.More preferably, dry glue powder end is 1:(2 ~ 10 with the weight ratio of water), crystallization temperature is 140 ~ 160 DEG C, and crystallization time is 10 ~ 30 hours.
In technique scheme, preferably, described silicon source is selected from least one in White Carbon black, water glass, silicon sol or silicone grease.
In technique scheme, preferably, described aluminium source is selected from least one in Tai-Ace S 150, aluminum nitrate, sodium aluminate, sodium metaaluminate, aluminum chloride, aluminium hydroxide, aluminum oxide, polynite or kaolin.
In technique scheme, preferably, described containing OH
-alkali source be selected from least one in lithium hydroxide, sodium hydroxide, potassium hydroxide or rubidium hydroxide.
In technique scheme, preferably, described template R is selected from least one in hexahydroaniline, hexanediamine, hexamethylene imine, heptamethylene imines, pyridine, piperidines, quadrol, Isopropylamine, ethyl-trimethyl ammonium hydroxide, diethyl-dimethyl ammonium hydroxide or triethyl methyl ammonium hydroxide.
In the inventive method, the washing of crystallization product, oven dry, roasting process are for known in the art.Generally, bake out temperature is 100 ~ 150 DEG C, and maturing temperature is 500 ~ 600 DEG C, and roasting time is 1 ~ 10 hour.
The inventive method can be used for synthesizing multiple MWW topological framework molecular sieve, such as MCM-22, MCM-49, MCM-56.
Raw material first at room temperature stirs by the inventive method, introduce dry glue step, make collosol and gel bake the degree of supersaturation exacerbating sol-gel system in dry glue process, make to form a large amount of nucleus fast in system, thus make the crystallization process adopted afterwards significantly shorten.Synthesize the required crystallization time of MWW topological framework molecular sieve in this way, compared with the crystallization time needed for conventional hydrothermal crystallization method, crystallization time significantly can be reduced to 5 ~ 40 hours, achieve good technique effect.
Accompanying drawing explanation
The XRD spectra with the MCM-22 molecular sieve of MWW topological framework that Fig. 1 synthesizes for [embodiment 1].
The XRD spectra with the MCM-56 molecular sieve of MWW topological framework that Fig. 2 synthesizes for [embodiment 5].
The XRD spectra with the MCM-49 molecular sieve of MWW topological framework that Fig. 3 synthesizes for [embodiment 8].
XRD determining adopts CuK diffraction, sweep limit 2theta=2 ~ 40 °.
As can be seen from Figure 1, there is strong diffraction peak at 2theta=3.2 °, 6.4 °, 7.1 °, 7.7 °, 9.5 °, 19.7 °, 22.1 °, 25.2 °, 26.3 °, illustrate that it is the MCM-22 molecular sieve with typical MWW topological framework.
As can be seen from Figure 2, there is strong diffraction peak at 2theta=7.2 °, 8.1 ° ~ 9.7 °, 14.3 °, 22.4 °, 24.9 °, 25.9 °, 26.5 °, illustrate that it is the MCM-56 molecular sieve with typical MWW topological framework.
As can be seen from Figure 3, there is strong diffraction peak at 2theta=3.2 °, 7.1 °, 7.9 °, 9.8 °, 20.1 °, 22.3 °, 22.6 °, 26.0 °, illustrate that it is the MCM-49 molecular sieve with typical MWW topological framework.
Below by embodiment, the present invention is further elaborated, but application of the present invention is not by the restriction of these embodiments.
Embodiment
[embodiment 1]
By 3.3 grams of Al
2(SO
4)
318H
2o is dissolved in 49.9 grams of water, add 1.8 grams of sodium hydroxide to make it to dissolve, then under the condition stirred, add 3.8 grams of piperidines, then add the silicon sol of 22.5 gram 40%, dry under 75 DEG C of conditions after making above-mentioned reaction mixture stir 5 hours at ambient temperature, and grind to form dry glue powder end; Then crystallization still is loaded, crystallization 26 hours under 140 DEG C of conditions after being mixed according to the weight ratio of 1:5 with water at above-mentioned dry glue powder end; Finally, above-mentioned crystallization product taking-up after washing, oven dry, roasting are obtained the MCM-22 molecular sieve (see accompanying drawing 1) with MWW topological framework.
[embodiment 2]
By 2.0 grams of Al
2(SO
4)
318H
2o is dissolved in 36.5 grams of water, add 2.5 grams of sodium hydroxide to make it to dissolve, then under the condition stirred, add 5.1 grams of hexamethylene imines, then add the silicon sol of 22.5 gram 40%, dry under 55 DEG C of conditions after making above-mentioned reaction mixture stir 8 hours at ambient temperature, and grind to form dry glue powder end; Then crystallization still is loaded, crystallization 20 hours under 150 DEG C of conditions after being mixed according to the weight ratio of 1:3 with water at above-mentioned dry glue powder end; Finally, above-mentioned crystallization product taking-up after washing, oven dry, roasting are obtained the MCM-22 molecular sieve with MWW topological framework, and its XRD spectra is similar to the XRD spectra shown in accompanying drawing 1.
[embodiment 3]
3.9 grams of sodium metaaluminates are dissolved in 46.7 grams of water, add 2.4 grams of potassium hydroxide to make it to dissolve, then under the condition stirred, 6.5 grams of hexamethylene imines are added, add 44.8 grams of tetraethoxys again, dry under 55 DEG C of conditions after making above-mentioned reaction mixture stir 3 hours at ambient temperature, and grind to form dry glue powder end; Then crystallization still is loaded, crystallization 20 hours under 150 DEG C of conditions after being mixed according to the weight ratio of 1:3 with water at above-mentioned dry glue powder end; Finally, above-mentioned crystallization product taking-up after washing, oven dry, roasting are obtained the MCM-22 molecular sieve with MWW topological framework, and its XRD spectra is similar to the XRD spectra shown in accompanying drawing 1.
[embodiment 4]
With [embodiment 1], just reaction mixture is dried under 60 DEG C of conditions, and dry glue powder end is 1:8 with water ratio, and the molecular sieve obtained is the MCM-22 molecular sieve with MWW topological framework, and its XRD spectra is similar to the XRD spectra shown in accompanying drawing 1.
[embodiment 5]
2.3 grams of sodium metaaluminates are dissolved in 61.0 grams of water, add 1.3 grams of sodium hydroxide to make it to dissolve, then under the condition stirred, 2.0 grams of piperidines and 1.2 grams of quadrols are added, add 6.5 grams of white carbon blacks again, dry under 55 DEG C of conditions after making above-mentioned reaction mixture stir 6 hours at ambient temperature, and grind to form dry glue powder end; Then crystallization still is loaded, crystallization 15 hours under 150 DEG C of conditions after being mixed according to the weight ratio of 1:5 with water at above-mentioned dry glue powder end; Finally, above-mentioned crystallization product taking-up after washing, oven dry, roasting are obtained the MCM-56 molecular sieve (see accompanying drawing 2) with MWW topological framework.
[embodiment 6]
By 2.6 grams of Al (NO
3)
39H
2o is dissolved in 32.0 grams of water, add 0.2 gram of lithium hydroxide to make it to dissolve, then under the condition stirred, 0.6 gram of diethyl-dimethyl ammonium hydroxide is added, add 15.0 grams of water glass again, dry under 75 DEG C of conditions after making above-mentioned reaction mixture stir 5 hours at ambient temperature, and grind to form dry glue powder end; Then crystallization still is loaded, crystallization 12 hours under 160 DEG C of conditions after being mixed according to the weight ratio of 1:8 with water at above-mentioned dry glue powder end; Finally, above-mentioned crystallization product taking-up after washing, oven dry, roasting are obtained the MCM-56 molecular sieve with MWW topological framework, and its XRD spectra is similar to the XRD spectra shown in accompanying drawing 2.
[embodiment 7]
With [embodiment 6], just reaction mixture is dried under 60 DEG C of conditions, and dry glue powder end is 1:5 with water ratio, and the molecular sieve obtained is the MCM-56 molecular sieve with MWW topological framework, and its XRD spectra is similar to the XRD spectra shown in accompanying drawing 2.
[embodiment 8]
By 3.2 grams of Al
2(SO
4)
318H
2o is dissolved in 49.9 grams of water, add 2.9 grams of sodium hydroxide to make it to dissolve, then under the condition stirred, add 4.6 grams of hexamethylene imines, then add the silicon sol of 22.5 gram 40%, dry under 50 DEG C of conditions after making above-mentioned reaction mixture stir 5 hours at ambient temperature, and grind to form dry glue powder end; Then crystallization still is loaded, crystallization 28 hours under 140 DEG C of conditions after being mixed according to the weight ratio of 1:3 with water at above-mentioned dry glue powder end; Finally, above-mentioned crystallization product taking-up after washing, oven dry, roasting are obtained the MCM-49 molecular sieve (see accompanying drawing 3) with MWW topological framework.
[embodiment 9]
0.5 gram of sodium metaaluminate is dissolved in 35.9 grams of water, add 1.7 grams of potassium hydroxide to make it to dissolve, then under the condition stirred, 0.4 gram of hexamethylene imine and 1.1 grams of hexahydroaniline are added, add 23.0 grams of tetraethoxys again, dry under 75 DEG C of conditions after making above-mentioned reaction mixture stir 5 hours at ambient temperature, and grind to form dry glue powder end; Then crystallization still is loaded, crystallization 22 hours under 150 DEG C of conditions after being mixed according to the weight ratio of 1:10 with water at above-mentioned dry glue powder end; Finally, above-mentioned crystallization product taking-up after washing, oven dry, roasting are obtained the MCM-49 molecular sieve with MWW topological framework, and its XRD spectra is similar to the XRD spectra shown in accompanying drawing 3.
[embodiment 10]
With [embodiment 8], just reaction mixture is dried under 75 DEG C of conditions, and dry glue powder end is 1:8 with water ratio, and the molecular sieve obtained is the MCM-49 molecular sieve with MWW topological framework, and its XRD spectra is similar to the XRD spectra shown in accompanying drawing 3.
[comparative example]
By 3.3 grams of Al
2(SO
4)
318H
2o is dissolved in 49.9 grams of water, adds 2.5 grams of sodium hydroxide and makes it to dissolve, then under the condition stirred, add 3.8 grams of piperidines, then add the silicon sol of 22.5 gram 40%, makes above-mentioned reaction mixture crystallization 72 hours under 150 DEG C of conditions; Finally, above-mentioned crystallization product taking-up after washing, oven dry, roasting are obtained the MCM-22 molecular sieve with MWW topological framework, and its XRD spectra is similar to accompanying drawing 1.
Claims (10)
1. synthesize a method for MWW structure molecular screen, comprise the following steps:
A) by silicon source, aluminium source, containing OH
-alkali source, template R and water mixing, obtain reaction mixture;
B) described reaction mixture is stirred, dry, grind to form dry glue powder end;
C) crystallization after described dry glue powder end being mixed with water; Crystallization product obtains described MWW structure molecular screen after washing, oven dry, roasting.
2. synthesize the method for MWW structure molecular screen according to claim 1, it is characterized in that described reaction mixture is with molar ratio computing Al
2o
3: SiO
2: OH
-: R:H
2o=(0.01 ~ 0.20): 1:(0.01 ~ 0.40): (0.01 ~ 0.50): (5 ~ 50).
3. synthesize the method for MWW structure molecular screen according to claim 2, it is characterized in that reaction mixture is with molar ratio computing Al
2o
3: SiO
2: OH
-: R:H
2o=(0.02 ~ 0.10): 1:(0.02 ~ 0.30): (0.05 ~ 0.40): (10 ~ 35).
4. synthesizing the method for MWW structure molecular screen according to claim 1, it is characterized in that step b) whipping temp is room temperature, churning time is 1 ~ 10 hour, and bake out temperature is 40 ~ 90 DEG C.
5. synthesize the method for MWW structure molecular screen according to claim 4, it is characterized in that step b) churning time is 2 ~ 5 hours, bake out temperature is 50 ~ 80 DEG C.
6. synthesize the method for MWW structure molecular screen according to claim 1, it is characterized in that step c) dry glue powder end is 1:(1 ~ 20 with the weight ratio of water), crystallization temperature is 120 ~ 180 DEG C, and crystallization time is 5 ~ 40 hours.
7. synthesize the method for MWW structure molecular screen according to claim 6, it is characterized in that step c) dry glue powder end is 1:(2 ~ 10 with the weight ratio of water), crystallization temperature is 140 ~ 160 DEG C, and crystallization time is 10 ~ 30 hours.
8. synthesize the method for MWW structure molecular screen according to claim 1, it is characterized in that described silicon source is selected from least one in White Carbon black, water glass, silicon sol or silicone grease; Described aluminium source is selected from least one in Tai-Ace S 150, aluminum nitrate, sodium aluminate, sodium metaaluminate, aluminum chloride, aluminium hydroxide, aluminum oxide, polynite or kaolin.
9. synthesize the method for MWW structure molecular screen according to claim 1, it is characterized in that described containing OH
-alkali source be selected from least one in lithium hydroxide, sodium hydroxide, potassium hydroxide or rubidium hydroxide.
10. synthesize the method for MWW structure molecular screen according to claim 1, it is characterized in that described template R is selected from least one in hexahydroaniline, hexanediamine, hexamethylene imine, heptamethylene imines, pyridine, piperidines, quadrol, Isopropylamine, ethyl-trimethyl ammonium hydroxide, diethyl-dimethyl ammonium hydroxide or triethyl methyl ammonium hydroxide.
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| ES2739646A1 (en) * | 2018-08-01 | 2020-02-03 | Univ Valencia Politecnica | SYNTHESIS PROCEDURE OF THE MWW MATERIAL IN ITS FORM NANOCRISTALINE AND ITS USE IN CATALYTIC APPLICATIONS (Machine-translation by Google Translate, not legally binding) |
| CN112551539A (en) * | 2019-09-26 | 2021-03-26 | 中国石油大学(北京) | Single-layer MWW molecular sieve and preparation method and application thereof |
| WO2024098502A1 (en) * | 2022-11-08 | 2024-05-16 | 中国石油天然气股份有限公司 | Solid acid alkylation catalyst, and preparation method therefor and use thereof |
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