CN1257839C - Process of preparing mesoporous molecular sieve with ionic liquid as template agent - Google Patents
Process of preparing mesoporous molecular sieve with ionic liquid as template agent Download PDFInfo
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- CN1257839C CN1257839C CN 200410066435 CN200410066435A CN1257839C CN 1257839 C CN1257839 C CN 1257839C CN 200410066435 CN200410066435 CN 200410066435 CN 200410066435 A CN200410066435 A CN 200410066435A CN 1257839 C CN1257839 C CN 1257839C
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Abstract
The present invention relates to a method for preparing an Al-MCM-41 mesoporous molecular sieve with ionic liquid as a template agent. Ionic liquid adopts 1-palmityl-3-methylimidazole bromide, namely [C16 mim] Br. Sodium silicate; aluminum sulfate, sulphuric acid and water are used as raw materials. Through a preparation step of a template agent, a preparation step of a reaction mixture and a hydrothermal crystallizing step, an Al-MCM-41 mesoporous molecular sieve is prepared by filtering operation, water washing operation, drying operation and roasting operation. The method has the advantages of simple preparation process and low crystallizing temperature.
Description
Technical field
The present invention relates to a kind of is the method that template prepares mesopore molecular sieve with the ionic liquid, definitely says, relating to a kind of is the method that template prepares the Al-MCM-41 mesopore molecular sieve with the ionic liquid, belongs to inorganic chemical synthesis technical field.
Background technology
1992, the people such as Kresege of Mobil research and development company are at Nature, 1992, the last reported first of 359:710 with tensio-active agent---the chain alkyl trimethyl quaternary ammonium salt is a template, synthetic mesoporous silicate and silico-aluminate under alkaline condition with single aperture, its structure is a long-range order, and specific surface is at 700m
2More than/the g (J.Am.Chem.Soc., 1992,114:10834).This material family is called as M41S, and it comprises hexagonal system (Hexagonal) MCM-41, isometric system (Cubic) MCM-48 and laminate structure (Lamellar) MCM-50.Mesopore molecular sieve MCM-41 has the one-dimensional tunnel structure of hexagonal array, and its aperture can be by the length of the chain alkyl of chain alkyl trimethyl quaternary ammonium salt or by add-on modulation between 1.8～10nm of auxiliary agent such as 1.Have the specific surface height, the big mesopore molecular sieve MCM-41 in aperture can be used as catalyzer, sorbent material or support of the catalyst etc., in the chemical reaction that heavy oil upgrading and macromole are participated in, have broad application prospects especially.But the MCM-41 of pure silicon does not have tart, lacks active ingredient in the lattice, and ion-exchange capacity is little, possesses the ability of catalyzed reaction hardly.Therefore, be necessary it is carried out study on the modification.Directly introducing other heteroatomss in synthetic MCM-41 process is one of directions of study on the modification.When the doped with Al atomic time, the Si in the MCM-41 skeleton is just replaced by Al, generates Al-MCM-41.Tervalent Al four-coordination in skeleton produces Al-O (H)-Si bridge, form easily the Lewis acid sites (Appl.Catal.A-Gen., 1999,184:49).Al-MCM-41 has ion-exchange capacity, and protonated back produces Bronsted acid acid sites.Therefore, Al-MCM-41 can replace the disadvantageous traditional F riedel-Craft catalyst A of environment lCl
3, HF, H
2SO
4, etc. as catalyst for reaction such as alkylation, acylations (J.Mol.Catal.A-Chem., 2003,197:255).
In recent years, people utilize different tensio-active agents to synthesize many different mesopore molecular sieves, as being template synthetic M41S series with long chain alkyl ammonium salt/base cations, bromo chain alkyl pyridine tensio-active agent, with the long-chain primary amine is template synthetic HMS series, with polyoxyethylene groups ethers nonionogenic tenside is template synthetic MSU-x series, and is polytype mesopore molecular sieves such as template synthetic MSU-V, MSU-G with diamines type nonionogenic tenside.
Synthesizing of Al-MCM-41 mesopore molecular sieve, be most commonly in the S under chain alkyl QAE (CTMA) cation sites
+I
-The supramolecule assembling process (US 6,117, and 411; US 6,712, and 972; Chem.Mater., 1999,11:11342), can obtain the higher molecular sieve of degree of crystallinity, but building-up process requires higher 135～170 ℃ of crystallization temperature.
Summary of the invention
The purpose of this invention is to provide a kind of is the method that template prepares the Al-MCM-41 mesopore molecular sieve with the ionic liquid, and this method has following advantage: preparation process is simple, and crystallization temperature is low.
The technical solution used in the present invention is characterised in that ionic liquid is bromination 1-hexadecyl-3-Methylimidazole, i.e. [C
16Mim] Br, be the silicon source with the water glass, with Tai-Ace S 150 the aluminium source, through the preparation and three steps of hydrothermal crystallizing of the preparation of template, reaction mixture, more after filtration, washing, drying and roasting, make the Al-MCM-41 mesopore molecular sieve.Method preparation process of the present invention is simple, in lower temperature, carries out hydrothermal crystallizing under 80～100 ℃, can obtain the higher Al-MCM-41 mesopore molecular sieve of degree of crystallinity.The present invention not only provides a kind of new synthetic method for the preparation heteroatom mesopore molecular sieve, has also opened up a new way for ion liquid application.
Technical scheme of the present invention now is described in detail in detail.A kind of is the method that template prepares the Al-MCM-41 mesopore molecular sieve with the ionic liquid, it is characterized in that operation steps:
The preparation of the first step template
N-Methylimidazole and bromohexadecane are to mix at 1: 1 in molar ratio, at nitrogen protection and 110 ℃ reaction 48h down, are cooled to normal temperature; make light yellow waxy solid, use the chloroform recrystallization, make white powder; ionic liquid bromination 1-hexadecyl-3-Methylimidazole, i.e. [C
16Mim] Br;
The preparation of the second step reaction mixture
Under the normal temperature, earlier with Na
2SiO
39H
2O is dissolved in the deionized water, splashes into Al in succession
2(SO
4)
3And ionic liquid [C
16Mim] aqueous solution of Br, use H
2SO
4The pH value to 9.5 of regulator solution makes reaction mixture, and the proportioning raw materials for preparing described reaction mixture is Na
2SiO
39H
2Si among the O: [C
16Mim] Br: Al
2(SO
4)
3In Al: H
2SO
4: H
2The mol ratio of O=1: 0.5: (0.01～0.066): 0.8: (93～140);
The 3rd step hydrothermal crystallizing
Second reaction mixture that make of step is placed autoclave, 80～100 ℃ of following hydrothermal crystallizings 0.5～10 day, the good reactant of crystallization after filtration, washing, drying and roasting obtain the Al-MCM-41 mesopore molecular sieve.
The technical solution used in the present invention is further characterized in that, in the 3rd step, the good reactant of crystallization after filtration, washing, drying obtains former powder, goes into retort furnace, 500～600 ℃ of following roasting 5h obtain the Al-MCM-41 mesopore molecular sieve.
Compare with background technology, advantage of the present invention: preparation process is simple, and crystallization temperature is low.
Description of drawings
Fig. 1 is the XRD spectra of the molecular sieve of embodiment 1 preparation.
Fig. 2 is the IR spectrogram of the molecular sieve of embodiment 1,2 preparations.
Embodiment
Embodiment 1
The preparation of the first step template
N-Methylimidazole and bromohexadecane are to mix at 1: 1 in molar ratio, at nitrogen protection and 110 ℃ reaction 48h down, are cooled to normal temperature; make light yellow waxy solid, use the chloroform recrystallization, make white powder; ionic liquid bromination 1-hexadecyl-3-Methylimidazole, i.e. [C
16Mim] Br;
The preparation of the second step reaction mixture
Press Na
2SiO
39H
2Si among the O: [C
16Mim] Br: Al
2(SO
4) Al in 3: H
2SO
4: H
2The mol ratio of O=1: 0.5: 0.02: 0.8: 124 configuration raw material, preparation feedback mixture (Si/Al=50) is under the normal temperature, with 7.1gNa
2SiO
39H
2O is dissolved in the 12.5g deionized water, drips the Al of 2.67g 3.27%wt earlier to this solution
2(SO
4)
3The aqueous solution contains 4.8g[C to this solution dropping again
16Mim] aqueous solution of Br, use H
2SO
4The pH value to 9.5 of regulator solution makes reaction mixture;
The 3rd step hydrothermal crystallizing
Reaction mixture is placed two stainless steel cauldrons in two batches, respectively at 80 ℃, 100 ℃ following one weeks of crystallization, the good reactant of crystallization after filtration, washing, drying obtains former powder, goes into retort furnace, 550 ℃ of following roasting 5h obtain the Al-MCM-41 mesopore molecular sieve.The Al-MCM-41 mesopore molecular sieve that obtains under two kinds of situations XRD spectra, IR spectrogram similar with Fig. 1 and Fig. 2 respectively.
The XRD of Al-MCM-41 mesopore molecular sieve, IR spectrogram are seen Fig. 1 and Fig. 2.XRD determining is to carry out on German Bruker axs type X-ray diffractometer, adopts CuK α.From XRD spectra as can be known, about 2 θ=2 °, very strong (a 100) crystal face diffraction peak is arranged, between 3～6 °, also can be observed 3 weak peaks.This has just confirmed that the synthetic sample is the Al-MCM-41 mesopore molecular sieve of hexagonal system under this suitable condition, and more complete hexagonal system structure and long-range order are well arranged.The IR spectrum analysis is to carry out the KBr compressing tablet at the U.S. NEXUS670 of Nicolet company type FT-IR spectrograph.From the IR spectrogram as can be known, at 1250～1000cm
-1Stronger absorption peak occurred, it is the tetrahedral nonsymmetrical vibration of skeleton.The tetrahedral stretching vibration band of skeleton that contains the Al sample slightly moves to lower wave number relative to the MCM-41 of pure silicon (Si-MCM-41) mesopore molecular sieve, and this shows that the Al atom has entered framework of molecular sieve.At 960cm
-1The vibrations at place cause owing to containing Al in the skeleton.But sample Na
+Existence, make the mesopore molecular sieve of pure silicon more weak peak relatively also occur.
Operating process except for the following differences, all the other are with embodiment 1:
The preparation of the second step reaction mixture
Press Na
2SiO
39H
2Si among the O: [C
16Mim] Br: Al
2(SO
4)
3In Al: H
2SO
4: H
2The mol ratio of O=1: 0.5: 0.01: 0.8: 93 configuration raw material, preparation feedback mixture (Si/Al=100).
The 3rd step hydrothermal crystallizing
Former powder is gone into retort furnace, and 520 ℃ of following roasting 5h obtain the Al-MCM-41 mesopore molecular sieve.
The XRD spectra of the Al-MCM-41 mesopore molecular sieve that obtains and IR spectrogram are similar with Fig. 1 and Fig. 2 respectively.
Embodiment 3
Operating process except for the following differences, all the other are with embodiment 1:
The preparation of the second step reaction mixture
Press Na
2SiO
39H
2Si among the O: [C
16Mim] Br: Al
2(SO
4)
3In Al: H
2SO
4: H
2The mol ratio of O=1: 0.5: 0.05: 0.8: 106 configuration raw material, preparation feedback mixture (Si/Al=20).
The 3rd step hydrothermal crystallizing
Former powder is gone into retort furnace, and 580 ℃ of following roasting 5h obtain the Al-MCM-41 mesopore molecular sieve.
The XRD spectra of the Al-MCM-41 mesopore molecular sieve that obtains and IR spectrogram are similar with Fig. 1 and Fig. 2 respectively.
Embodiment 4
Operating process except for the following differences, all the other are with embodiment 1:
The preparation of the second step reaction mixture
Press Na
2SiO
39H
2Si among the O: [C
16Mim] Br: Al
2(SO
4)
3In Al: H
2SO
4: H
2The mol ratio of O=1: 0.5: 0.066: 0.8: 140 configuration raw material, preparation feedback mixture (Si/Al=15).
The 3rd step hydrothermal crystallizing
In two batches respectively 90 ℃ of following crystallization 4 days, 7 days.
The Al-MCM-41 mesopore molecular sieve that obtains XRD spectra and Fig. 1 is similar, IR spectrogram and Fig. 2 are similar.
Claims (2)
1. one kind is the method that template prepares the Al-MCM-41 mesopore molecular sieve with the ionic liquid, it is characterized in that, ionic liquid is bromination 1-hexadecyl-3-Methylimidazole, with the water glass is the silicon source, with Tai-Ace S 150 is the aluminium source, through the preparation and three steps of hydrothermal crystallizing of the preparation of template, reaction mixture, more after filtration, washing, drying and roasting, make the Al-MCM-41 mesopore molecular sieve, operation steps:
The preparation of the first step template
N-Methylimidazole and bromohexadecane are to mix at 1: 1 in molar ratio, at nitrogen protection and 110 ℃ reaction 48h down, are cooled to normal temperature, make light yellow waxy solid, use the chloroform recrystallization, make white powder, ionic liquid bromination 1-hexadecyl-3-Methylimidazole;
The preparation of the second step reaction mixture
Under the normal temperature, earlier with Na
2SiO
39H
2O is dissolved in the deionized water, splashes into Al in succession
2(SO
4)
3With the aqueous solution of ionic liquid bromination 1-hexadecyl-3-Methylimidazole, use H
2SO
4The pH value to 9.5 of regulator solution makes reaction mixture, and the proportioning raw materials for preparing described reaction mixture is Na
2SiO
39H
2Si among the O: bromination 1-hexadecyl-3-Methylimidazole: Al
2(SO
4)
3In Al: H
2SO
4: H
2The mol ratio of O=1: 0.5: 0.01～0.066: 0.8: 93～140;
The 3rd step hydrothermal crystallizing
Second reaction mixture that make of step is placed autoclave, 80～100 ℃ of following hydrothermal crystallizings 0.5～10 day.
2. the synthetic method of Al-MCM-41 mesopore molecular sieve according to claim 1 is characterized in that, the good reactant of crystallization after filtration, washing, drying obtains former powder, goes into retort furnace, 500～600 ℃ of following roasting 5h.
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| CN100391842C (en) * | 2006-06-20 | 2008-06-04 | 浙江大学 | Method for synthesizing ultra-stable ordered mesoporous Si-Al molecular sieve |
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