CN101664695B - Method for preparing microporous-mesoporous composite molecular sieve - Google Patents
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Abstract
The invention discloses a method for preparing a microporous-mesoporous composite molecular sieve. A microporous molecular sieve and a mesoporous molecular sieve have limitation respectively. The method for preparing the microporous-mesoporous composite molecular sieve comprises the following steps: preparing silicon-aluminum source slurry, dissolving 0.5 to 1.5 weight portions of organic ammonium salt surfactant into 5 to 20 weight portions of deionized water, heating the mixture for dissolving, cooling the solution, mixing the cooled solution and the silicon-aluminum source slurry, violently stirring the mixture for 1 hour to form mixed gel, sealing the mixed gel in a stainless steel reaction kettle with a polytetrafluoroethylene inner gasket, crystallizing the mixed gel for 24 to 48 hours at the temperature of between 100 and 120 DEG C, then taking the crystallized gel out and cooling the crystallized gel to room temperature, regulating a pH value of the crystallized gel to 8.0 to 12.5 by using 2.0 mol/L of acetic acid aqueous solution, crystallizing the solution for 24 to 72 hours at the temperature of between 100 and 120 DEG C, cooling the crystallized product to room temperature, and filtering, washing, drying and roasting a product. The method is used for preparing a catalyst.
Description
Technical field:
The present invention relates to a kind of preparation method of microporous-mesoporous composite molecular sieve, belong to the synthetic and application of porous catalyst material.
Background technology:
Micro porous molecular sieve since have the adjustable sex change of uniqueness, regular crystal structure and aperture uniformly, bigger specific area and stronger adsorption capacity, stronger acid site and structure, good heat endurance with hydrothermal stability, separate with product easily, can realize that advantage such as productions has continuously obtained application widely as eco-friendly catalyst in field of petrochemical industry.But micro porous molecular sieve is because the aperture is less, and the big reactant molecule of dynamics size is difficult to be diffused in the duct on the one hand; The big molecular product that forms in the duct on the other hand can not rapid diffusion go out the duct, causes side reaction to take place, and catalyst makes the duct stop up inactivation because of area carbon or coking, and shorten service life, and its range of application has been subjected to considerable restraint.Synthesize and have mesoporous yardstick the molecular sieve of (aperture 2-50nm) is the problem that many scholars pays close attention to and endeavours to study to improve reactant and the diffusion of product molecule in molecular sieve pore passage.
Up to 1992, it is the M41S series mesopore molecular sieve of representative that Mobil company successfully develops with MCM-41, this molecular sieve analog is to adopt long carbochain organic ammonium salt surfactant to do the template agent to synthesize, it has regular duct, narrow pore-size distribution and aperture can be regulated between 1.5-20nm, have high specific area.Yet, this class mesoporous material because the amorphism of its hole wall reaches the existence by its exhibiting high surface silicon hydroxyl that causes, is easy to and water and other medium effect it in the regular mesopore orbit that provides people to expect, cause skeleton to cave in, so heat endurance and hydrothermal stability are poor; On the other hand, the aluminium great majority in the mesoporous material of sial occur with the hexa-coordinate form, can not produce the required acidity of catalytic reaction, and catalytic activity is low, has seriously limited its application in industrial circle.
In order to overcome the limitation that micro porous molecular sieve and mesopore molecular sieve exist separately, make the two mutual supplement with each other's advantages, the researcher makes organic surface active agent and the inorganic charged ion wish according to people by intermolecular self-assembling reaction, forms the heterogeneous orderly composite with multilayered structure.By synthesizing the existing mesoporous composite molecular screen that micropore is arranged again with different synthetic methods and different template agent, this composite molecular screen has multiplet and a plurality of catalytic center, specific area is big, the heat endurance height has bigger application potential as well behaved catalysis material in fields such as petrochemical industry and environmental protection.
China's naphthalene and methyl naphthalene aboundresources, this part resource reasonable use not as yet at present.With naphthalene or methyl naphthalene (MN) is raw material, by methylating or shifting synthetic important polyester material PEN (PEN) raw material monomer 2 of the one-step method that methylates, 6-dimethylnaphthalene (2,6-DMN) not only can improve naphthalene and methyl naphthalene utilization ratio of raw materials, and can be lowered into 2, the production cost of 6-DMN is to substitute multistep processes Synthetic 2, the synthetic route that 6-DMN is more suitable.But the DMN that according to said method makes has ten kinds of isomers, and boiling point is very approaching, particularly 2,6-DMN and 2, therefore the boiling-point difference of 7-DMN has only 0.3 ℃, separates very difficultly, develops high activity, to target product 2, catalyst and corresponding Catalytic processes that 6-DMN has high selectivity are to realize one-step method Synthetic 2, the key of 6-DMN.It is twelve-ring straight hole road that the ZSM-12 zeolite molecular sieve has the one dimension hole, compare with mesopore molecular sieve with other mesopore, more help having 2 of linear structure in the catalytic alkylation reaction product of naphthalene, generation (the US6388158B1 of 6-DMN, 2002-05-14, Stud.Surf.Sci.Catal.1991,60:291～301).Therefore, with the ZSM-12 molecular sieve is that the synthetic ZSM-12/MCM-41 composite molecular screen material with regular meso-hole structure of silicon and aluminum source is expected when having good acidity of ZSM-12 molecular sieve and hydrothermal stability, further improve the diffusion of product in having the duct of mesoporous yardstick, thereby improve its catalytic performance.ZSM-12/MCM-41 composite molecular screen and synthetic and be used for catalysis naphthalene and methanol alkylation reaction Synthetic 2, the method for 6-DMN still is not reported.
Because ZSM-12 is the silica-rich zeolite molecular sieve, the very a spot of Na of a surface enrichment
+, after adding, also be to have only minor N a as the Surfactant CTAB of template agent
+By CTA
+Replace the CTA on molecular sieve surface
+Concentration is low, is difficult to along the CTA on ZSM-12 molecular sieve surface
+Carry out the meso-hole structure of supermolecule assembling formation MCM-41.
With the micro porous molecular sieve after the certain density NaOH solution-treated as silicon and aluminum source, in the suitable condition of mesopore molecular sieve crystallization down in the micro-pore zeolite silicon source method of preparation composite molecular screen, the composite molecular screen easy because of the preparation method advantages such as the ratio of micropore and meso-hole structure and acid site adjustable number joint have more researching value.
Summary of the invention:
The preparation method who the purpose of this invention is to provide a kind of microporous-mesoporous composite molecular sieve is assembled into the composite molecular screen that has micropore and meso-hole structure simultaneously by adding a spot of surfactant in the silicon and aluminum source slurries after the NaOH solution-treated.
Above-mentioned purpose realizes by following technical scheme:
The preparation method of microporous-mesoporous composite molecular sieve, its composition comprises: preparation silicon and aluminum source slurries, to parts by weight is the NaOH aqueous solution 0.15-0.6 weight portion that 1 ZSM-12 molecular screen primary powder adds 0.2～1.0mol/L, fully stir and obtain the silicon and aluminum source slurries, organic ammonium salt surfactant 0.5-1.5 weight portion is dissolved in heating for dissolving in the 5-20 parts by weight of deionized water, cooling, cooled solution is mixed with the silicon and aluminum source slurries, strong agitation formed mixed gel in 1 hour, described mixed gel is sealed in the stainless steel cauldron of polytetrafluoroethyllining lining pad, take out after 24～48 hours in crystallization under 100～120 ℃ the temperature conditions and to be cooled to room temperature, being adjusted to pH value with the aqueous acetic acid of 2.0mol/L is 8.0～12.5, crystallization 24～72 hours under 100～120 ℃ temperature conditions is cooled to room temperature product is filtered again, washing, dry, roasting.
The preparation method of described microporous-mesoporous composite molecular sieve, the silica alumina ratio of described ZSM-12 molecular screen primary powder is 100～260.
The preparation method of described microporous-mesoporous composite molecular sieve, described organic ammonium salt surfactant is softex kw CTAB.
The preparation method of described microporous-mesoporous composite molecular sieve, described roasting is under 500～550 ℃ temperature conditions, roasting 4～8 hours.
Beneficial effect of the present invention:
1. the present invention adopts the micro porous molecular sieve of the homemade ZSM-12 of having perfect crystal structure as silicon and aluminum source, with making up MCM-41 meso-hole structure part around the ZSM-12 micro-pore zeolite after the certain density NaOH solution-treated, in the presence of organic ammonium salt surfactant softex kw CTAB, by the synthetic ZSM-12/MCM-41 composite molecular screen of the factors such as ratio of control crystallization condition and Na/Si, have that synthetic method is simple, the adjustable ratio control of micropore and meso-hole structure, be suitable for characteristics such as suitability for industrialized production.Prepared ZSM-12/MCM-41 composite molecular screen is as naphthalene and methanol alkylation reaction Synthetic 2, and the catalyst of 6-DMN shows good reaction activity and to 2, the selectivity that 6-DMN is higher.
2. do not need to add silicon and aluminum source, only with certain density NaOH solution degradation ZSM-12 zeolite molecular sieve (SiO
2/ Al
2O
3=100～260), the elementary or secondary structure unit that utilizes the ZSM-12 molecular sieve after degrading is realized the supermolecule self assembly then as silicon and aluminum source under the Action of Surfactant that adds, synthesize the ZSM-12/MCM-41 microporous-mesoporous composite molecular sieve.
3. only need in the ZSM-12 zeolite molecular sieve slurries after the NaOH solution-treated, add a spot of surfactant and just can be assembled into the ZSM-12/MCM-41 composite molecular screen that has micropore and meso-hole structure simultaneously.
4. by changing the ZSM-12 molecular sieve concentration of NaOH solution, the consumption of organic ammonium salt surfactant templates agent, the conditions such as pH value of crystallization system handled, the content of micropore and mesoporous two kinds of constituent elements in can the modulation composite molecular screen, the distribution that simultaneously can also modulation acidity and the distribution in aperture.
Description of drawings:
Accompanying drawing 1 is the XRD spectra of sample ZSM-12 among the embodiment 3.
Accompanying drawing 2 is sample ZM among the embodiment 4
1XRD spectra.
Accompanying drawing 3 is sample ZM among the embodiment 4
1The TEM photo.
Accompanying drawing 4 is sample ZM among the embodiment 5
2XRD spectra.
Accompanying drawing 5 is sample ZM among the embodiment 6
3XRD spectra.
Accompanying drawing 6 is sample ZM among the embodiment 7
4XRD spectra.
The specific embodiment:
Embodiment 1:
The preparation method of microporous-mesoporous composite molecular sieve, its composition comprises: preparation silicon and aluminum source slurries, 0.6 kilogram of the NaOH aqueous solution that in 1 kilogram ZSM-12 molecular screen primary powder, adds 0.2mol/L, fully stir and obtain the silicon and aluminum source slurries, 1.5 kilograms in organic ammonium salt surfactant is dissolved in heating for dissolving in 20 kilograms of deionized waters, cooling, cooled solution is mixed with the silicon and aluminum source slurries, strong agitation formed mixed gel in 1 hour, described mixed gel is sealed in the stainless steel cauldron of polytetrafluoroethyllining lining pad, take out after 24～48 hours in crystallization under 100～120 ℃ the temperature conditions and to be cooled to room temperature, being adjusted to pH value with the aqueous acetic acid of 2.0mol/L is 8.0～12.5, crystallization 24～72 hours under 100～120 ℃ temperature conditions is cooled to room temperature product is filtered again, washing, dry, roasting.
Embodiment 2:
The preparation method of microporous-mesoporous composite molecular sieve, its composition comprises: preparation silicon and aluminum source slurries, 0.15 kilogram of the NaOH aqueous solution that in 1 kilogram ZSM-12 molecular screen primary powder, adds 1.0mol/L, fully stir and obtain the silicon and aluminum source slurries, 0.5 kilogram in organic ammonium salt surfactant is dissolved in heating for dissolving in 5 kilograms of deionized waters, cooling, cooled solution is mixed with the silicon and aluminum source slurries, strong agitation formed mixed gel in 1 hour, described mixed gel is sealed in the stainless steel cauldron of polytetrafluoroethyllining lining pad, take out after 24～48 hours in crystallization under 100～120 ℃ the temperature conditions and to be cooled to room temperature, being adjusted to pH value with the aqueous acetic acid of 2.0mol/L is 8.0～12.5, crystallization 24～72 hours under 100～120 ℃ temperature conditions is cooled to room temperature product is filtered again, washing, dry, roasting.
Embodiment 3:
The preparation method of microporous-mesoporous composite molecular sieve, its composition comprises: preparation silicon and aluminum source slurries, 0.4 kilogram of the NaOH aqueous solution that in 1 kilogram ZSM-12 molecular screen primary powder, adds 0.5mol/L, fully stir and obtain the silicon and aluminum source slurries, 1.0 kilograms in organic ammonium salt surfactant is dissolved in heating for dissolving in 12.5 kilograms of deionized waters, cooling, cooled solution is mixed with the silicon and aluminum source slurries, strong agitation formed mixed gel in 1 hour, described mixed gel is sealed in the stainless steel cauldron of polytetrafluoroethyllining lining pad, take out after 24～48 hours in crystallization under 100～120 ℃ the temperature conditions and to be cooled to room temperature, being adjusted to pH value with the aqueous acetic acid of 2.0mol/L is 8.0～12.5, crystallization 24～72 hours under 100～120 ℃ temperature conditions is cooled to room temperature product is filtered again, washing, dry, roasting.
Embodiment 4:
The preparation method of above-mentioned microporous-mesoporous composite molecular sieve, the silica alumina ratio of described ZSM-12 molecular screen primary powder is 100～260, described silica alumina ratio is a mol ratio, is designated as SiO
2/ Al
2O
3=100～260.
Embodiment 5:
The preparation method of above-mentioned microporous-mesoporous composite molecular sieve, described organic ammonium salt surfactant is softex kw CTAB.
Embodiment 6:
The preparation method of above-mentioned microporous-mesoporous composite molecular sieve, described roasting is under 500～550 ℃ temperature conditions, roasting 4～8h.
Embodiment 7:
The microporous-mesoporous composite molecular sieve ZSM-12/MCM-41 that makes is applied in the alkylated reaction of naphthalene and methyl alcohol, utilizes fixed-bed micro-reactor, reaction condition is: temperature is 300～400 ℃, and pressure is 2.0～4.0MPa, and air speed is 1～3h
-1(mass number of the material that flows through in the unit mass catalyst unit interval), N
2Flow is 10～30ml/min.
The present invention introduces orderly MCM-41 meso-hole structure in the ZSM-12 micro porous molecular sieve, can when keeping ZSM-12 molecular sieve appropriate acid and high stability, improve the diffusion of alkylate during as naphthalene and methyl alcohol catalyst for reaction, thereby it improves catalytic performance.Make composite molecular screen have good reaction activity simultaneously and in the alkylate of naphthalene 2, the high selectivity of 6-DMN, and the service life of prolongation catalyst, at the ZSM-12 molecular sieve is the characteristics of silica-rich zeolite, adopt micro-pore zeolite silicon source method, obtain to have micropore and mesoporous composite molecular screen simultaneously, the pH value of concentration, template agent consumption and crystallization system by control NaOH solution prepare have different mesopore molecular sieve distribution proportions and acid can the ZSM-12/MCM-41 composite molecular screen.
Embodiment 8:
With 12g four bromic ether TEABr, 0.75g NaAlO2, 1.25g NaOH is dissolved in the 37g deionized water in certain sequence, under agitation slowly adds 69g Ludox (SiO
2Content is 40%), be stirred to and form even gel.Place stainless steel cauldron, in 160 ℃ of following crystallization 5 days.Product after filtration, the washing, 120 ℃ of following dried overnight, remove the template agent in 550 ℃ of roastings again, promptly get silica alumina ratio (SiO
2/ Al
2O
3) be 134 ZSM-12 molecular sieve, its XRD spectra is seen accompanying drawing 1.
Embodiment 9:
With 5g ZSM-12 zeolite molecular sieve (SiO
2/ Al
2O
3=134) join in the NaOH solution that 76ml concentration is 1.0mol/L, adding 68g concentration behind the stirring 0.5h is the CTAB aqueous solution of 9.2wt%, after at room temperature continuing to stir 1h, place 100 ℃ of crystallization still crystallization 24h, reduce to room temperature then, regulating PH with 2mol/L acetic acid is 11.5, again behind 100 ℃ of continuation crystallization 24h, obtain the sample of composite molecular screen behind 550 ℃ of following roasting 6h, be designated as ZM
1, its XRD spectra (see figure 2) explanation ZM
1The crystal phase structure that has MCM-41 mesopore molecular sieve and ZSM-12 micro porous molecular sieve simultaneously, the TEM photo (see figure 3) of sample shows that also the composite molecular screen that is synthesized has micropore and mesopore molecular sieve structure simultaneously.
Embodiment 10:
With 5gZSM-12 zeolite molecular sieve (SiO
2/ Al
2O
3=134) join in the NaOH solution that 76ml concentration is 0.5mol/L, adding 68g concentration behind the stirring 0.5h is the CTAB aqueous solution of 9.2wt%, after at room temperature stirring 1h, place 100 ℃ of static crystallization reactor crystallization 24h, reduce to room temperature then, regulating PH with 2mol/L acetic acid is 11.5, be 100 ℃ continue crystallization 24h after, obtain the sample of composite molecular screen behind 550 ℃ of following roasting 6h, be designated as ZM2.Characterize the crystal phase structure that (see figure 4) proof sample has MCM-41 mesopore molecular sieve and ZSM-12 micro porous molecular sieve simultaneously through XRD.
Embodiment 11:
With 2g ZSM-12 zeolite molecular sieve (SiO
2/ Al
2O
3=134) join in the NaOH solution that 30ml concentration is 1.0mol/L, adding 28g concentration behind the stirring 0.5h is the CTAB aqueous solution of 5.73wt%, after at room temperature stirring 1h, place 100 ℃ of static crystallization reactor crystallization 24h, reduce to room temperature then, regulating PH with 2mol/L acetic acid is 11.5, be 100 ℃ continue crystallization 24h after, obtain the sample of composite molecular screen behind 550 ℃ of following roasting 6h, be designated as ZM3.Characterize (see figure 5) through XRD, sample has the crystal phase structure of MCM-41 mesopore molecular sieve and ZSM-12 micro porous molecular sieve simultaneously.
Embodiment 12:
With 2g ZSM-12 zeolite molecular sieve (SiO
2/ Al
2O
3=134) join in the NaOH solution that 30ml concentration is 1.0mol/L, adding 28g concentration behind the stirring 0.5h is the CTAB aqueous solution of 9.2wt%, after at room temperature stirring 1h, place the crystallization still in 100 ℃ of following crystallization 24h, reduce to room temperature then, regulating PH with 2mol/L acetic acid is 8.5, after continuing crystallization 24h under 100 ℃, obtain the sample of composite molecular screen behind 550 ℃ of following roasting 6h, be designated as ZM4.Identify (see figure 6) through XRD, sample has the crystal phase structure of MCM-41 mesopore molecular sieve and ZSM-12 micro porous molecular sieve simultaneously.
With the ZM that obtains
2Microporous-mesoporous composite molecular sieve is as the catalyst of the alkylated reaction of naphthalene and methyl alcohol.Get 2g20～40 purpose ZM
2Dividing pack into long 350mm, internal diameter of compound son sieve sample is the flat-temperature zone of stainless steel reaction pipe of the fixed-bed micro-reactor of 9mm, and inertia quartz sand is equipped with at two ends.Sample 500 ℃ of activation 1h under nitrogen protection reduce to 350 ℃ of reactions then before the reaction, are 3.5MPa by counterbalance valve control reaction system pressure.To press naphthalene in advance: methyl alcohol: 1,2, the material liquid that 4-trimethylbenzene=1:2:8 (mol ratio) ratio prepares is gone into reactor by NP-KX-105 type acrotism fluidization tower plug infusion, and the mass space velocity WHSV of material liquid is 3h
-1, the flow of nitrogen is 10ml/min.The time of first product being flowed out reaction system is counted t=0 constantly, and certain hour is gathered product at interval, forms with the gas chromatographic analysis product.Behind the reaction 5h, the conversion ratio of reactant naphthalene still can reach 45.3%, 2,6-/2, and 7-DMN can arrive 1.75.
Table 1 is the specific area and the pore volume data of synthetic ZSM-12/MCM-41 composite molecular screen.(N
2The physical absorption characterization result)
Table 2 distributes for the acidic site of synthetic ZSM-12/MCM-41 composite molecular screen.(NH
3-TPD characterization result)
Table one
Table 2
Claims (3)
1.
A kind of preparation method of microporous-mesoporous composite molecular sieve, its composition comprises: preparation silicon and aluminum source slurries, it is characterized in that: to parts by weight is the NaOH aqueous solution 0.15-0.6 weight portion that 1 ZSM-12 molecular screen primary powder adds 0.2 ~ 1.0 mol/L, fully stir and obtain the silicon and aluminum source slurries, organic ammonium salt surfactant 0.5-1.5 weight portion is dissolved in heating for dissolving in the 5-20 parts by weight of deionized water, cooling, cooled solution is mixed with the silicon and aluminum source slurries, strong agitation formed mixed gel in 1 hour, described mixed gel is sealed in the stainless steel cauldron of polytetrafluoroethyllining lining pad, take out after 24 ~ 48 hours in crystallization under 100 ~ 120 ℃ the temperature conditions and to be cooled to room temperature, being adjusted to the pH value with the aqueous acetic acid of 2.0 mol/L is 8.0 ~ 12.5, crystallization 24 ~ 72 hours under 100 ~ 120 ℃ temperature conditions again, being cooled to room temperature filters product, washing, dry, roasting, the silica alumina ratio of described ZSM-12 molecular screen primary powder are 100 ~ 260.
2.
The preparation method of microporous-mesoporous composite molecular sieve according to claim 1 is characterized in that: described organic ammonium salt surfactant is softex kw CTAB.
3.
The preparation method of microporous-mesoporous composite molecular sieve according to claim 1 and 2 is characterized in that: described roasting is under 500 ~ 550 ℃ temperature conditions, roasting 4 ~ 8 hours.
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| CN103769205B (en) * | 2013-12-12 | 2016-04-20 | 中国海洋大学 | A kind of preparation method of the composite catalyst for oil-containing micro-algae hydrothermal liquefaction |
| CN109746035B (en) * | 2017-11-01 | 2021-11-30 | 中国石油化工股份有限公司 | Method for preparing methyl ethyl benzene and methyl styrene by side chain alkylation of xylene and methanol |
| CN110743605B (en) | 2018-07-23 | 2021-07-27 | 中国科学院大连化学物理研究所 | Catalyst for preparing ethylbenzene from ethanol and benzene and preparation and application thereof |
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