CN101574664A - Method for synthesizing zeolite on cordierite carrier - Google Patents
Method for synthesizing zeolite on cordierite carrier Download PDFInfo
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- CN101574664A CN101574664A CNA2008101061346A CN200810106134A CN101574664A CN 101574664 A CN101574664 A CN 101574664A CN A2008101061346 A CNA2008101061346 A CN A2008101061346A CN 200810106134 A CN200810106134 A CN 200810106134A CN 101574664 A CN101574664 A CN 101574664A
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- zeolite
- cordierite
- mcm
- acid
- synthetic
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Links
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 45
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000010457 zeolite Substances 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 34
- 229910052878 cordierite Inorganic materials 0.000 title claims abstract description 29
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 4
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 8
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- ZSIQJIWKELUFRJ-UHFFFAOYSA-N azepane Chemical compound C1CCCNCC1 ZSIQJIWKELUFRJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 5
- 230000008025 crystallization Effects 0.000 claims description 5
- 238000010306 acid treatment Methods 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 229910001868 water Inorganic materials 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 10
- 238000003786 synthesis reaction Methods 0.000 abstract description 9
- 239000003513 alkali Substances 0.000 abstract description 7
- 239000000919 ceramic Substances 0.000 abstract description 7
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 238000011065 in-situ storage Methods 0.000 abstract 1
- 238000003618 dip coating Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 1
- 241000264877 Hippospongia communis Species 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- -1 ZSM-11 Chemical compound 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910001657 ferrierite group Inorganic materials 0.000 description 1
- 230000009970 fire resistant effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
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- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
本发明提供一种在堇青石陶瓷载体上原位合成沸石的方法，包括先用酸对堇青石进行酸化处理，再用碱对其处理，然后将其置于MCM－22的合成液中在高温高压下进行合成，本发明的方法采用酸－碱联合处理堇青石，不仅可以增加堇青石的外表面积，而且溶出的氧化物可以在沸石合成液中形成大量的－OH，有利于MCM－22的负载合成，得到的负载沸石结合牢固，而且方法简单易掌握，合成条件易控制。The invention provides a method for synthesizing zeolite in situ on a cordierite ceramic carrier, which comprises first acidifying the cordierite with acid, then treating it with alkali, and then placing it in the synthesis liquid of MCM-22 at high temperature The synthesis is carried out under high pressure. The method of the present invention adopts acid-alkali joint treatment of cordierite, which not only can increase the outer surface area of cordierite, but also can form a large amount of -OH in the zeolite synthesis liquid from the dissolved oxides, which is beneficial to the formation of MCM-22. Loaded synthesis, the obtained loaded zeolite is firmly combined, and the method is simple and easy to master, and the synthesis conditions are easy to control.
Description
Technical field
The present invention relates to the method for load synthetic zeolite, be specifically related to the method for synthetic MCM-22 zeolite on the cordierite ceramic carrier.
Background technology
Support type zeolite (zeolite membrane on the carrier) has very on catalytic science and separation science, and important use is worth.As the membrane reactor that is used for the petrochemical industry separation process has all utilized the zeolite that loads on the different carriers with the monoblock type catalytic converter that is used for purifying automobile tail gas.General load zeolite has two kinds of methods: the one, and carrier immersed contain in the slurries of zeolite, make carrier surface load one deck zeolite, be called the load method, this method is simple to operate but can cause zeolite overlay and carrier surface in conjunction with not firm, and zeolite layer is peeled off easily.Another kind method is called original position load synthetic technology, is about to porous carrier and is immersed in the solution of synthetic zeolite, makes carrier surface one deck zeolite of firmly growing under the synthesis condition of zeolite.
Cordierite ceramic belongs to the category of high-performance ceramics, and its outstanding characteristics are that thermal coefficient of expansion is low, good adsorption performance, and specific area is big, fire-resistant degree height.Cordierite ceramic is widely used in vehicle exhaust to be handled, and ozone suppresses catalysis, and fields such as toxic gas purification are a kind of ecological environment material nds of function admirable.Patent US4800187 uses the original position synthetic technology to synthesize multiple zeolite on the ceramic honey comb surface, patent US4904518 has synthesized ZSM-5 in the silicon chip surface hydro-thermal, multiple zeolite such as ZSM-11, but what the shortcoming of above-mentioned patented technology was a zeolite in the carrier surface growth is very inhomogeneous, so patent CN99112822 has proposed elder generation's dip-coating one deck on cordierite ceramic and contains Al
2O
3, SiO
2And Na
2The coagulant liquid of O and then carrying out the synthetic method of load utilizes the series of chemical that takes place in the dip-coating process, can make very firm that carrier surface combines with zeolite layer.Its series of patents 99120818 adopts identical method to synthesize ferrierite on cordierite; The problem that the method is brought is that the dip-coating layer is introduced new material as the synthetic part material of zeolite, participates in building-up process, causes synthesis condition requirement harshness, is unfavorable for the synthetic of zeolite.
Summary of the invention
The invention provides the method for original position synthetic zeolite on a kind of cordierite carrier, by cordierite carrier is handled, effectively increase the outer specific surface that helps zeolite-loaded growth, and the original position that does not influence the MCM-22 zeolite is synthetic, make the load zeolite evenly firm, method is simple, and synthesis condition is easy to control.
Method provided by the invention is: cordierite is adopted the Combined Treatment of acid back alkali earlier, cordierite is immersed in the acid solution that mass concentration is 30-80%, handled 3-15 hour down at temperature 60-80 ℃, spend ion-cleaning after the taking-up, be in the sodium hydroxide solution of 4-20% in mass concentration again, handled 4-12 hour deionized water washing then, drying for temperature 60-80 ℃ down; With the cordierite carrier handled well in the synthetic liquid of 140-180 ℃ MCM-22 crystallization 3-10 days, make the load of MCM-22 zeolite original position grow in carrier surface.
In the method for the present invention, oxalic acid, citric acid, the more weak acid of acetic acid equal strength are preferably adopted in acid treatment.Processing procedure is gentle relatively, easily control.
In the method for the present invention, the synthetic liquid of described MCM-22 comprises common components such as silicon source, aluminium source, alkali, template agent and water, and wherein the silicon source is selected from silica gel, silicic acid or ethyl orthosilicate etc.; The aluminium source is selected from sodium metaaluminate or aluminum sulfate etc., and alkali is NaOH, and the template agent is hexamethylene imine (HMI), and the batching of the synthetic liquid of wherein said MCM-22 is calculated with oxide (mol ratio) and consisted of:
SiO
2∶Al
2O
3∶Na
2O∶HMI∶H
2O＝1∶(0.2-0.33)∶(0.1-0.3)∶(0.35-0.7)∶20。The collocation method of synthetic liquid and crystallization process are method commonly used.
Effect of the present invention: the present invention is directed to cordierite itself and consist of 2MgO2Al
2O
35SiO
2Component and crystal structure characteristics adopt the Combined Treatment of acid back alkali earlier to cordierite, utilize the crystal structure of acid treatment partial destruction cordierite earlier, make wherein part MgO and Al
2O
3Dissolving, and SiO
2Exist in the pottery in unformed mode, utilize aqueous slkali then SiO
2Stripping so not only can effectively increase the outer specific surface of cordierite and the part Si O of stripping
2And Al
2O
3In the synthetic liquid of MCM-22, form a large amount of-OH group, help the load growth of zeolite.Thus the cordierite carrier upper surface synthesize growth evenly, in conjunction with firm MCM-22 zeolite.The inventive method is simple, and synthesis condition is easy to control, and processing cost is low, is easy to industrialization, is applicable to various cordierite carriers.
Description of drawings
Fig. 1 is the typical XRD characterization result of load MCM-22 zeolite of the present invention.
Fig. 2 is cordierite area load MCM-22 zeolite Electronic Speculum result of the present invention.
The specific embodiment
Open in detail below in conjunction with embodiment to the present invention, but the invention is not restricted to following examples.
Embodiment 1
The cordierite that with volume is 5ml is in mass concentration is 50% oxalic acid solution, handled 6 hours down for 80 ℃, the deionized water washing is to neutral, put into mass concentration then and be 10% sodium hydroxide solution, handled 5 hours down for 80 ℃, the washing back puts it in the synthetic liquid of MCM-22 then 120 ℃ of dryings, and the mol ratio of each component is SiO in the synthetic liquid of MCM-22
2: Al
2O
3: Na
2O: HMI: H
2O=1: 0.33: 0.1: 0.35: 20, the silicon source of employing is a silica gel, the aluminium source is a sodium metaaluminate.Crystallization is 72 hours under 140 ℃ of degree.Take out the cordierite after handling, at 120 ℃ of dry 12h, 540 ℃ of roastings 10 hours, ultrasonic cleaning 20min, the XRD characterization result is seen Fig. 1, illustrates that the MCM-22 zeolite has been synthesized in load on carrier, Electronic Speculum as a result (see figure 2) show the cordierite surface firmly load one deck MCM-22 zeolite, ultrasonic processing can not make it peel off, and the computational load amount is 50%.
Vehicle treated process and load building-up process are with embodiment 1, and employing concentration is 60% citric acid, and treatment temperature is 70 ℃, and the time is 10 hours.Used silicon source is an ethyl orthosilicate, and XRD result shows that the load zeolite is the MCM-22 zeolite, and load capacity is 40%.
Embodiment 3
Vehicle treated process and load building-up process are with embodiment 1, and the mol ratio of synthetic each component of liquid of MCM-22 is SiO
2: Al
2O
3: Na
2O: HMI: H2O=1: 0.25: 0.12: 0.35: 20, XRD result shows that the load zeolite is MCM-22 and part modenite impurity.
Embodiment 4
Vehicle treated process and load building-up process are with embodiment 1, and 5% sodium hydroxide solution is adopted in the alkali treatment after the acid treatment, handle 8 hours down at 70 ℃, and the solution composition of the synthetic MCM-22 of load is SiO
2: Al
2O
3: Na
2O: HMI: H
2O=1: 0.33: 0.1: 0.4: crystallization is 72 hours under 20,150 ℃ of degree.Take out drying and roasting, XRD figure shows that the load zeolite is the MCM-22 zeolite, and the load capacity before and after the ultrasonic processing is respectively 55% and 50%, illustrates that zeolite and carrier are in conjunction with firm.
Claims (3)
1, a kind of method of synthesizing zeolite on cordierite carrier, it is characterized in that, earlier cordierite is immersed in the acid solution that mass concentration is 30-80%, handled 3-15 hour down at temperature 60-80 ℃, spending ion-cleaning after the taking-up, is in the sodium hydroxide solution of 4-20% in mass concentration then, handles 4-12 hour down for temperature 60-80 ℃, deionized water washing then, drying; With the cordierite carrier handled well in the synthetic liquid of 140-180 ℃ MCM-22 crystallization 3-10 days, make the load of MCM-22 zeolite original position grow in carrier surface.
According to the method for claim 1 synthetic zeolite, it is characterized in that 2, oxalic acid, citric acid or acetic acid are adopted in described acid treatment.
According to the method for claim 1 synthetic zeolite, it is characterized in that 3, the synthetic liquid of described MCM-22 is made up of silicon source, aluminium source, water and template agent hexamethylene imine, wherein the oxide mol ratio of each component is: SiO
2: Al
2O
3: Na
2O: HMI: H
2O=1: (0.2-0.33): (0.1-0.3): (0.35-0.7): 20.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101061346A CN101574664B (en) | 2008-05-09 | 2008-05-09 | Method for synthesizing zeolite on cordierite carrier |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101061346A CN101574664B (en) | 2008-05-09 | 2008-05-09 | Method for synthesizing zeolite on cordierite carrier |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101574664A true CN101574664A (en) | 2009-11-11 |
| CN101574664B CN101574664B (en) | 2011-11-09 |
Family
ID=41269814
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008101061346A Expired - Fee Related CN101574664B (en) | 2008-05-09 | 2008-05-09 | Method for synthesizing zeolite on cordierite carrier |
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|---|---|
| CN (1) | CN101574664B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102040231A (en) * | 2011-01-14 | 2011-05-04 | 山西大同大学 | Method for synthesizing zeolite ZSM-48 |
| CN107497479A (en) * | 2017-07-20 | 2017-12-22 | 沈阳化工大学 | A kind of cordierite is that carrier synthesis beta-molecular sieve prepares methoxy menthyl acetate method |
| CN107497473A (en) * | 2017-07-20 | 2017-12-22 | 沈阳化工大学 | A kind of Y molecular sieve method for preparing catalyst using cordierite as carrier |
| CN108854946A (en) * | 2018-06-07 | 2018-11-23 | 太原理工大学 | A kind of hierarchical porous structure zeolite absorption/catalyst and its construction method |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4904518A (en) * | 1988-06-29 | 1990-02-27 | Uop | Multiphase composite and processes for preparing same |
| CN1189245C (en) * | 2003-03-27 | 2005-02-16 | 南开大学 | Catalyst for car tail gas treatment and preparation thereof |
| CN100482341C (en) * | 2003-09-25 | 2009-04-29 | 昆明贵研催化剂有限责任公司 | Catalyst for decontaminating tail gas of motorcar and preparation method |
-
2008
- 2008-05-09 CN CN2008101061346A patent/CN101574664B/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102040231A (en) * | 2011-01-14 | 2011-05-04 | 山西大同大学 | Method for synthesizing zeolite ZSM-48 |
| CN102040231B (en) * | 2011-01-14 | 2012-05-23 | 山西大同大学 | Method for synthesizing zeolite ZSM-48 |
| CN107497479A (en) * | 2017-07-20 | 2017-12-22 | 沈阳化工大学 | A kind of cordierite is that carrier synthesis beta-molecular sieve prepares methoxy menthyl acetate method |
| CN107497473A (en) * | 2017-07-20 | 2017-12-22 | 沈阳化工大学 | A kind of Y molecular sieve method for preparing catalyst using cordierite as carrier |
| CN107497479B (en) * | 2017-07-20 | 2020-06-23 | 沈阳化工大学 | A method for preparing methyl methoxyacetate by synthesizing beta molecular sieve with cordierite as carrier |
| CN107497473B (en) * | 2017-07-20 | 2020-06-23 | 沈阳化工大学 | A kind of preparation method of Y molecular sieve catalyst with cordierite as carrier |
| CN108854946A (en) * | 2018-06-07 | 2018-11-23 | 太原理工大学 | A kind of hierarchical porous structure zeolite absorption/catalyst and its construction method |
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| Publication number | Publication date |
|---|---|
| CN101574664B (en) | 2011-11-09 |
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