CN103193247A - Method for directly preparing composite porous zeolite molecular sieve ball - Google Patents
Method for directly preparing composite porous zeolite molecular sieve ball Download PDFInfo
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- CN103193247A CN103193247A CN2013100956491A CN201310095649A CN103193247A CN 103193247 A CN103193247 A CN 103193247A CN 2013100956491 A CN2013100956491 A CN 2013100956491A CN 201310095649 A CN201310095649 A CN 201310095649A CN 103193247 A CN103193247 A CN 103193247A
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Abstract
The invention belongs to the fields of inorganic chemistry and physical chemistry, and in particular discloses a method for directly preparing a composite porous zeolite molecular sieve ball. According to the preparation method disclosed by the invention, a high-molecular polymer participates in a synthesis system to directly synthesize a high-catalytic-activity zeolite molecular sieve ball which is comparatively large in specific surface area and easy to separate and use with a composite pore structure. The preparation method disclosed by the invention is simple and easy to implement, a mesoporous template is low in cost, and the prepared composite porous zeolite molecular sieve ball material has a comparatively strong acidity and good catalytic performance. The material provided by the invention has a wide application range in petrochemical industry and industrial catalysis fields.
Description
Technical field
The invention belongs to inorganic chemistry, physical chemistry, materials chemistry and field of chemical engineering, specially refer to direct synthesis zeolite ball and technology of preparing thereof.
Background technology
Zeolite molecular sieve crystal makes it in absorption and catalytic field a lot of application be arranged with its special pore passage structure.Zeolite molecular sieve crystal has very strong hydrothermal stability and acidity, and these advantages make it be widely used in the Industrial Catalysis field, use many as ZSM-5, Beta, Y, LTA and heteroatoms zeolite molecular sieve thereof.But because zeolite molecular sieve has less specific surface, the velocity of diffusion of catalyzed reaction has been limited and greatly to the catalytic applications of organic macromolecule in narrower duct.For this reason, MCM-41 series ordered mesoporous molecular sieve has been invented by Mobil company, the mesopore molecular sieve specific surface area is big, the aperture is big, overcome the shortcoming of zeolite molecular sieve to a certain extent, but because the unformed hole wall of mesopore molecular sieve has caused its hydrothermal stability low, acid low, and its preparation cost is higher, has limited the further application of mesopore molecular sieve.Molecular sieve of Nano zeolite has bigger outer surface area, and more active sites is arranged accordingly, but separate difficultly will to carry out high speed centrifugation usually with control, and is higher to equipment requirements.And nano zeolite is very easily reunited in these processes, is agglomerated into the block that does not have rule, makes outer surface area reduce greatly, has reduced activity.Therefore, synthetic zeolite molecular sieve with high catalytic activity of the composite pore structural that stability is high, strength of acid is high has important practical significance and industrial value.
Summary of the invention
The technical problem to be solved in the present invention is to utilize high molecular polymer to participate in and have than bigger serface compound pore passage structure, the easy zeolite molecular sieve ball that separates the high catalytic activity that uses, suitable industrial production and application direct synthesizing of synthetic system.
The zeolite of indication of the present invention mainly is zeolite for example some atoms metals for example Cu, Ni, Mo, Zn, the Ti etc. of structural zeolite such as MFI, FAU, BEA, LTA and doping skeleton thereof that are applied in the various structures of petrochemical industry.
High molecular polymer used in the present invention is industrial macromolecule products such as polyquaternium or polyvinyl alcohol.
The synthetic method that the present invention is used: under the participation of high molecular polymers such as polyquaternium or polyvinyl alcohol, be the silicon source with the tetraethoxy, various metal-salts are as heteroatomic source, and through hydrothermal treatment consists and roasting, ion-exchange obtains having the zeolite molecular sieve ball of certain composite pore structural.The temperature of hydrothermal treatment consists is 100～180 ℃, and the time of placement is 2-8 days.At last, this sample was calcined 4-6 hour at 500～600 ℃.
Method of the present invention is compared with background technology, introduce high molecular polymer, make its effect of in the synthetic process of nano zeolite, playing connection, make nano zeolite directly the self-service hundreds of nanometer of dressing up to the zeolite molecular sieve ball of the adjustable high catalytic activity with certain composite pore structural of several micron diameters.Above method all can be introduced multiple atoms metal, can be widely used at chemical field as sorbent material, catalyzer and support of the catalyst.Because the geometrical dimension of the nano zeolite of composition zeolite molecular sieve ball is very little, about tens nanometers, so it has the advantage of nano zeolite.These nano zeolites directly are assembled into the zeolite molecular sieve ball that is evenly distributed and can separate by simple filtering easily and reclaim.The zeolite molecular sieve ball that the present invention obtains will be widely used in petrochemical complex and Industrial Catalysis field.
Embodiment
The preparation of embodiment 1:MFI type zeolite molecular sieve ball
With an amount of TPAOH (20%) solution and 20ml H
2O mixes, and adds NaAlO in above-mentioned solution
2, work as NaAlO
2Slowly add TEOS (20%) again after the dissolving fully, vigorous stirring is homogeneous phase to solution, adds the 1-2g polyvinyl alcohol to above-mentioned solution, continue to stir 3-6h, the reactor of packing into then places 150-180 ℃ of baking oven to place 36-72h, takes out reactor, be cooled to room temperature, by filtration, drying, roasting 4-6h in 500-600 ℃ of air atmosphere, namely obtain having the spherical zeolite molecular sieve of MFI type that composite holes distributes, the diameter of molecular sieve spheres can be controlled at 300-3000nm.
The preparation of embodiment 2:BEA type zeolite molecular sieve ball
With an amount of TEAOH (20%) solution and 20ml H
2O mixes, and under agitation adds an amount of NaAlO
2And NaOH, treat to dissolve fully the back and add white carbon black, continue vigorous stirring after the solution clarification, continue to stir 3-6h, add the 1-2g polyvinyl alcohol to above-mentioned solution, continue to stir fast 4-8h, then the above-mentioned solution reactor of packing into, place 130-160 ℃ of baking oven to place 36-96h, take out reactor, be cooled to room temperature, by filtration, drying, roasting 4-6h in 500-600 ℃ of air atmosphere namely obtains having the spherical zeolite molecular sieve of BEA type that composite holes distributes.
The preparation of embodiment 3:FAU zeolite molecular sieve ball
With a certain proportion of NaAlO
2, NaOH and H
2O mixes stirring and dissolving, treats that adding water glass after the solution clarification continues to be stirred to the solution clarification, with above-mentioned solution ageing 8-12h at ambient temperature, adds water glass solution, H according to proportioning
2O, Al
2(SO4)
3Solution and NaAlO
2Solution mixes, stir 1-2h, add the 1-2g polyquaternium to above-mentioned solution, continue to stir 4-8h, the above-mentioned solution reactor of packing into, place 100-120 ℃ of baking oven to place 15-30h, take out reactor, be cooled to room temperature, by filtration, drying, roasting 4-6h in 500-600 ℃ of air atmosphere namely obtains having the spherical zeolite molecular sieve of FAU type that composite holes distributes.
The preparation of embodiment 4:LTA zeolite molecular sieve ball
0.1-0.3gNaOH is dissolved in the deionized water, stirs until molten entirely, add the 2-4g sodium aluminate, add the 3-6g water glass again, stir about 1-2h adds the 1-2g polyquaternium to above-mentioned solution, continue to stir 4-8h, the above-mentioned solution reactor of packing into, place 100-120 ℃ of baking oven to place 12-36h, take out reactor, be cooled to room temperature, by filtration, drying, roasting 4-6h in 500-600 ℃ of air atmosphere namely obtains having the spherical zeolite molecular sieve of LTA type that composite holes distributes.
Claims (6)
1. composite hole zeolite molecular sieve ball, it is characterized in that utilizing high molecular polymer to participate in has than bigger serface direct synthesizing of synthetic system, compound pore passage structure, the zeolite molecular sieve ball of the high catalytic activity of separation use is fit to industrial production and application easily.
2. composite hole zeolite ball according to claim 1 mainly is zeolite for example some atoms metals for example Cu, Ni, Mo, Zn, the Ti etc. of structural zeolite such as MFI, FAU, BEA, LTA and doping skeleton thereof that are applied in the various structures of petrochemical industry.
3. according to the preparation method of the described composite hole zeolite molecular sieve ball of claim 1 to 2, it is characterized in that the synthesis temperature of these zeolite molecular sieve balls about 100～180 ℃, generated time was at 2-8 days.
4. according to the described preparation method of claim 1 to 3, it is characterized in that the former powder of composite hole zeolite molecular sieve ball was further come template agent removing at 500-600 ℃ of roasting 4-6 hour.
5. according to the described composite hole zeolite molecular sieve ball of claim 1 to 4, it is characterized in that having micropore and meso-hole structure simultaneously, mesoporous aperture be distributed in 10-50nm.
6. according to the described composite hole zeolite molecular sieve ball of claim 1 to 5, it is characterized in that to form diameter in the molecular sieve spheres of 0.3-3 micron.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105148980A (en) * | 2013-12-04 | 2015-12-16 | 淮南师范学院 | Hydrodesulfurization catalyst with composite hole zeolite molecular sieve loading precious metal |
| CN106745036A (en) * | 2017-03-17 | 2017-05-31 | 中触媒新材料股份有限公司 | With the microporous mesoporous molecular sieves of multi-stage porous SSZ 13 and its synthetic method and application |
| CN110655090A (en) * | 2019-11-07 | 2020-01-07 | 中国石油化工股份有限公司 | Millimeter-scale microspherical molecular sieve and preparation method thereof |
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| CN110655090A (en) * | 2019-11-07 | 2020-01-07 | 中国石油化工股份有限公司 | Millimeter-scale microspherical molecular sieve and preparation method thereof |
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Application publication date: 20130710 |