CN1108988C - Microwave synthesis of macroporous molecular sieve - Google Patents
Microwave synthesis of macroporous molecular sieve Download PDFInfo
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- CN1108988C CN1108988C CN99112754A CN99112754A CN1108988C CN 1108988 C CN1108988 C CN 1108988C CN 99112754 A CN99112754 A CN 99112754A CN 99112754 A CN99112754 A CN 99112754A CN 1108988 C CN1108988 C CN 1108988C
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- molecular sieve
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- large pore
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Abstract
The present invention relates to a microwave synthesizing method of a macroporous molecular sieve. Silicon source substances and aluminum source substances are used as raw materials, and the raw materials are mixed with additional reagents by inorganic acid or alkali to form an initial gel mixture. The present invention is characterized in that the initial gel mixture is heated under the condition of microwave radiation to back flow, the time is from 2 minutes to 10 hours, the microwave frequency is from 2.0 to 20.0GHz, and the power is from 50 to 2000W; the obtained solid powder is baked for 3 to 10 hours in air at the temperature of 500 to 600 DEG C, and then, an MCM-41 macroporous molecular sieve is formed. The present invention has the advantages of high crystallization speed, pure crystal forms and strong heat resistance, hydrothermal stability, acid resistance and alkali resistance, and has uniform and fine crystal particles and small specific surfaces.
Description
The present invention relates to the field of chemical synthesis, the microwave synthesis method of a kind of large pore molecular sieve MCM-41 is provided especially.
MCM-41 is the nineties initial stage, and (USP 5 by a kind of novel big-hole zeolite molecular sieve that U.S. Mobil company succeeds in developing, 057,296 and USP 5,108,725), it has hexagonal prism shape one-dimensional linear pore passage structure, and its aperture can be adjusted between 1.6～20nm by the additive reagent that adds different sizes.Because it has bigger aperture and stronger heat-resisting and hydrothermal stability, thereby in the fractionation by adsorption of macromole mixture and refining of petroleum, be with a wide range of applications in the processes such as catalytic cracking of heavy oil.But in the synthetic method of above-mentioned large pore molecular sieve, used two kinds of additive reagents as structure directing agent, its building-up process complexity.
The object of the present invention is to provide the microwave synthesis method of a kind of large pore molecular sieve MCM-41, compare with common hydrothermal synthesis method, its crystallization rate is fast and crystal formation is pure, uniform crystal particles is tiny, and has less specific surface, stronger heat-resisting and hydrothermal stability and antiacid alkali ability.
The invention provides the microwave synthesis method of a kind of large pore molecular sieve MCM-41, is raw material with silicon source material, aluminium source material, adds additive reagent, is mixed into initial gel mixture with mineral acid or alkali, it is characterized in that:
Proportioning between each raw material (by the oxide molecule ratio) is:
SiO
2/Al
2O
3＝5～50，
Na
2O/Al
2O
3＝2～15，
H
2O/Al
2O
3＝500～1500，
R/Al
2O
3=0.1～10, R is an additive reagent, and additive reagent adopts structure to be
Quaternary ammonium salt, R wherein
1, R
2, R
3Be C
1～C
5Alkyl, R ' is C
5～C
24Alkyl;
The initial gel mixture material is reflux under the microwave radiation condition, and 2 minutes～10 hours time, microwave frequency is at 2.0～20.0GHz, and power is 50～2000 watts; The roasting 3～10 hours in 500～600 ℃ of following air of gained solid powder promptly gets the MCM-41 large pore molecular sieve.
The pH value of initial gel described in the present invention is between 8～14, and used silicon source material is one or more the mixture in silicon sol, water glass or the amorphous silica; Aluminium source material is one or more the mixture in sodium metaaluminate or potassium metaaluminate, Tai-Ace S 150, aluminum nitrate, aluminum chloride or the aluminum oxide; Acid is one or more the mixture in sulfuric acid, nitric acid or the hydrochloric acid; Alkali is one or more the mixture in sodium hydroxide, potassium hydroxide or the ammonium hydroxide.
Silicon source material is selected inorganic silicon dioxide for use, and additive reagent only selects for use a kind of structure to be
Quaternary ammonium salt, R wherein
1, R
2, R
3Be C
1～C
5Alkyl, R ' is C
5～C
24Alkyl.
The present invention uses the microwave-excitation reflux, technology is simple, avoided simultaneously since microwave heating cumulative bad caused is difficult to the shortcomings such as microwave irradiation effect keeping constant temp and continue, can carry out the zeolite molecular sieve study on the synthesis under the microwave radiation condition more conveniently.In addition, the present invention does not use expensive silicon source or aluminium source material and other additive reagent, only use inorganic silicon dioxide, aluminium colloidal sol (or aluminate, aluminium salt) as raw material and a kind of quaternary ammonium salt as additive reagent.Synthetic method is simple, be easy to realize, and institute's synthetic molecular sieve crystal formation is pure, and uniform crystal particles is tiny, has less specific surface, stronger heat-resisting and hydrothermal stability and antiacid alkali ability.
By embodiment in detail the present invention is described in detail below in conjunction with accompanying drawing.
The microwave synthesizer of accompanying drawing 1 for having backflow functionality.
Accompanying drawing 2 is embodiment 1 a products therefrom XRD analysis spectrogram.
Accompanying drawing 3 is embodiment 1 a products therefrom stereoscan photograph.
Accompanying drawing 4 is comparative example 1 a products therefrom XRD analysis spectrogram.
Accompanying drawing 5 is comparative example 1 a products therefrom stereoscan photograph.
Accompanying drawing 6 is embodiment 1 and comparative example 1 products therefrom N2 adsorption isothermal line analysis of spectra.
With 10g C
16H
33(CH
3)
3NBr is dissolved in the 50ml deionized water, adds 6ml sodium metaaluminate colloidal sol and (contains Al
2O
31.0mol/l, Na
2O 2.0mol/1), in the 250ml beaker, mixes, slowly add 50ml water glass liquid again and (contain SiO
23.15mol/l, Na
2O 0.99mol/l), continue stirring and be no less than 30 minutes until mixing.The said mixture material is moved in the 1000ml flask, place the microwave oven (2450MHz that has reflux then, 80 watts) in, reflux is 2.0 hours under microwave irradiation effect, take out flask, product is extremely neutral with the deionized water washing, behind 120 ℃ of air dryings (being designated as MCM-41/M), obtain the former powder of MCM-41 large pore molecular sieve, roasting obtained the MCM-41 large pore molecular sieve in 5 hours in 550 ℃ of air.Its XRD spectrum as shown in Figure 2; Stereoscan photograph as shown in Figure 3, grain-size is about 0.15 μ m; N
2Adsorption isothermal line as shown in Figure 6, the BET specific surface area is 924sqm
2/ g.
Comparative Examples 1
In embodiment 1, only crystallization condition is changed into, the said mixture material moves in the synthesis reactor and seals, it is complete that crystallization made its crystallization in 144 hours in 120 ℃ of baking ovens, be cooled to room temperature then, solid product, (is designated as MCM-41/W) and gets the former powder of MCM-41 large pore molecular sieve to neutral with the deionized water washing behind 120 ℃ of air dryings, roasting obtained the MCM-41 large pore molecular sieve in 5 hours in 550 ℃ of air.Its XRD spectrum as shown in Figure 4, stereoscan photograph as shown in Figure 5, grain-size is about 5.6 μ m; N
2Adsorption isothermal line as shown in Figure 6, the BET specific surface area is 1025sqm
2/ g.
Add the 10ml sulphuric acid soln in the mixture in embodiment 1 and (contain H
2SO
42.0mol/ml), all the other components are constant, and product is the MCM-41 large pore molecular sieve, and its XRD spectra and stereoscan photograph are with embodiment 1.
Embodiment 3
Only changing 50ml water glass liquid into the 22g silicon sol (contains SiO in embodiment 1
240%), all the other components are constant, and product is the MCM-41 large pore molecular sieve, and its XRD spectra and stereoscan photograph are with embodiment 1.
Embodiment 4
Add 5ml sodium hydroxide solution (containing NaOH 4.0mol/l) in the mixture in embodiment 3, all the other components are constant, and product is the MCM-41 large pore molecular sieve, and its XRD spectra and stereoscan photograph are with embodiment 1.
Embodiment 5
Only change 6ml sodium metaaluminate colloidal sol into 1.2g sodium metaaluminate solid in embodiment 1, all the other components are constant, and product is the MCM-41 large pore molecular sieve, and its XRD spectra and stereoscan photograph are with embodiment 1.
In embodiment 1 only with 10g C
16H
33(CH
3)
3NBr changes 20ml octadecyl trimethyl ammonium chloride solution into and (contains C
18H
37(CH
3)
3NCl 30wt%, Industrial products), all the other components are constant, and product is the MCM-41 large pore molecular sieve, and its XRD spectra and stereoscan photograph are with embodiment 1.
Embodiment 7
Only changing the 22g silicon sol into the 9g amorphous silica (contains SiO in embodiment 3
295wt%), all the other components are constant, and product is the MCM-41 large pore molecular sieve, and its XRD spectra and stereoscan photograph are with embodiment 1.
In embodiment 1, only change 6ml sodium metaaluminate colloidal sol into 0.9g Al
2O
3Solid (contains Al
2O
372.2wt%), all the other components are constant, and product is the MCM-41 large pore molecular sieve, and its XRD spectra and stereoscan photograph are with embodiment 1.
Embodiment 9
Carried out heat-resisting with Comparative Examples 1 gained sample embodiment 1 and hydro-thermal and the experiment of antiacid alkali ability, its result is as shown in table 1.
The stability of table 1 MCM-41/W and MCM-41/M and absorption property
| Sample | Treatment condition | Relative crystallinity (%) | Water adsorption amount (%) | Benzene adsorptive capacity (%) |
| MCM-41/W | 10 ℃/min roasting to 1000 | 100 74 50 100 is unformed | 59 49 41 57 18 | 63 51 44 65 11 |
| MCM-41/M | 10 ℃/min roasting to 1000 | 100 81 72 100 71 | 55 50 48 54 45 | 68 56 51 69 48 |
Claims (3)
1. the microwave synthesis method of a large pore molecular sieve MCM-41 is a raw material with silicon source material, aluminium source material, adds additive reagent, is mixed into initial gel mixture with mineral acid or alkali, it is characterized in that:
Proportioning between each raw material (by the oxide molecule ratio) is:
SiO
2/Al
2O
3＝5～50，
Na
2O/Al
2O
3＝2～15，
H
2O/Al
2O
3＝500～1500，
R/Al
2O
3=0.1～10, R is an additive reagent, and additive reagent adopts structure to be
Quaternary ammonium salt, R wherein
1, R
2, R
3Be C
1～C
5Alkyl, R ' is C
5～C
24Alkyl;
The initial gel mixture material is reflux under the microwave radiation condition, and 2 minutes～10 hours time, microwave frequency is at 2.0～20.0GHz, and power is 50～2000 watts; The roasting 3～10 hours in 500～600 ℃ of following air of gained solid powder promptly gets the MCM-41 large pore molecular sieve.
2. according to the microwave synthesis method of the described large pore molecular sieve MCM-41 of claim 1, it is characterized in that: the pH value of described initial gel is between 8～14, and used silicon source material is one or more the mixture in silicon sol, water glass or the amorphous silica; Aluminium source material is one or more the mixture in sodium metaaluminate or potassium metaaluminate, Tai-Ace S 150, aluminum nitrate, aluminum chloride or the aluminum oxide; Acid is one or more the mixture in sulfuric acid, nitric acid or the hydrochloric acid; Alkali is one or more the mixture in sodium hydroxide, potassium hydroxide or the ammonium hydroxide.
3. according to the microwave synthesis method of the described large pore molecular sieve MCM-41 of claim 1, it is characterized in that: silicon source material is selected inorganic silicon dioxide for use, and additive reagent only selects for use a kind of structure to be
Quaternary ammonium salt, R wherein
1, R
2, R
3Be C
1～C
5Alkyl, R ' is C
5～C
24Alkyl.
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|---|---|---|---|
| CN99112754A CN1108988C (en) | 1999-03-17 | 1999-03-17 | Microwave synthesis of macroporous molecular sieve |
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|---|---|---|---|
| CN99112754A CN1108988C (en) | 1999-03-17 | 1999-03-17 | Microwave synthesis of macroporous molecular sieve |
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| CN1108988C true CN1108988C (en) | 2003-05-21 |
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| CN100410172C (en) * | 2006-05-25 | 2008-08-13 | 中国科学院大连化学物理研究所 | Method for synthesizing P-Al molecular sieve by microwave heating |
| CN112960679A (en) * | 2021-04-29 | 2021-06-15 | 钛纶新材料(昆山)有限公司 | Preparation method of modified MCM-41 molecular sieve |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5057296A (en) * | 1990-12-10 | 1991-10-15 | Mobil Oil Corp. | Method for synthesizing mesoporous crystalline material |
| US5108725A (en) * | 1990-01-25 | 1992-04-28 | Mobil Oil Corp. | Synthesis of mesoporous crystalline material |
| CN1110252A (en) * | 1994-04-11 | 1995-10-18 | 中国科学院大连化学物理研究所 | Method for synthetizing ultramacropore molecular sieve |
-
1999
- 1999-03-17 CN CN99112754A patent/CN1108988C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5108725A (en) * | 1990-01-25 | 1992-04-28 | Mobil Oil Corp. | Synthesis of mesoporous crystalline material |
| US5057296A (en) * | 1990-12-10 | 1991-10-15 | Mobil Oil Corp. | Method for synthesizing mesoporous crystalline material |
| CN1110252A (en) * | 1994-04-11 | 1995-10-18 | 中国科学院大连化学物理研究所 | Method for synthetizing ultramacropore molecular sieve |
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