CN103372379B - Preparation method of molecular sieve composite membrane by taking metallic oxide as carrier - Google Patents
Preparation method of molecular sieve composite membrane by taking metallic oxide as carrier Download PDFInfo
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Abstract
The invention discloses a preparation method of a molecular sieve composite membrane by taking a metallic oxide as a carrier. The preparation method comprises the following steps: firstly, diluting aluminum sol or silicon sol into a dilute solution by utilizing ethanol or water, dispersing molecular sieve granules in the dilute solution of the aluminum sol or the silicon sol, thereby obtaining a suspending liquid formed by the molecular sieve granules and the aluminum sol or the silicon sol, and carrying out ultrasonic treatment; and coating the suspending liquid on the surface of a metallic oxide granule by adopting a repeated spraying mode, drying and roasting to form a layer of composite membrane containing the molecular sieve granules and aluminum oxide or silicon oxide. The aluminum oxide layer or the silicon oxide layer is of a multihole structure, the molecular sieve granules are uniformly dispersed in the aluminum oxide or the silicon oxide, the molecular sieve composite membrane core-shell structure catalyst can be combined with a core metallic oxide catalyst and a shell molecular sieve catalyst to form a membrane reactor, so that two reactions or a plurality of reactions are coupled in one membrane reactor, the traditional contact mode of physically mixing the metallic oxide and the molecular sieve is improved, and the utilization efficiencies of two catalysts are improved.
Description
Technical field
The invention provides a kind of take metal oxide as the Zeolite composite film preparation method of carrier, belongs to inorganic material film preparation field.
Technical background
Metal oxide is comparatively common excellent catalyst, and as copper and zinc oxide are used for methanol-fueled CLC, manganese and ferriferous oxide are used for catalytic denitration process etc.Molecular sieve Heat stability is good, has good pore passage structure and high-specific surface area, is all used widely in catalysis and separation field.CHA, MFI, FAU, MOR molecular sieve analog has good acid active sites, and more is applied to the catalytic reaction process such as catalytic pyrolysis and dehydration.Molecular sieve is coated on metal oxide particle surface to be formed and there is nucleocapsid structure catalytic film reactor be used for catalytic process, can realizes two steps or multistep reaction being coupling in a reactor, improve the reaction efficiency of successive reaction.
Compare traditional by metal oxide and molecular sieve physical mixed catalyst, nucleocapsid structure considerably increases the contact area between nucleocapsid bi-material, and active sites is more evenly distributed, and can provide more reaction active site in unit volume.
The superior function of molecular screen membrane catalyst with core-casing structure set forth by a lot of document, but molecular screen membrane catalyst with core-casing structure preparation condition is harsh, acid or alkaline Zeolite synthesis liquid and high temperature crystallization process all can affect the catalytic performance of core catalyst, especially all there is dissolving or melting phenomenon in metal oxide catalyst in acidity or alkaline water thermal environment, or react with the template in synthesis liquid or reactive component the inert substance generating non-activity.(the J.Am.Chem.Soc. such as Yang, 2010,132, p8129) with cupric oxide zinc oxide aluminium for core and with HZSM-5 molecular sieve for shell obtains catalyst with core-casing structure and for being reacted by direct preparation of dimethyl ether by using synthesis gas, preparation condition is very harsh, and NaOH and halid existence all can reduce the activity of core metal oxide catalyst greatly, and synthesis liquid will be strict controlled in neutrality, crystallization temperature can not be too high, and these harsh conditions are all unfavorable for the growth of molecular screen membrane.
Chinese patent application CN103086395(take metal oxide as the SAPO Series Molecules sieve membrane preparation method of carrier) be namely directly prepare molecular screen membrane on metal oxide carrier, although preparation process is weak acid environment between 6-7 at pH value, still can have an impact to the catalytic activity of metal oxide carrier in high temperature crystallization process.Therefore, the extensive use of catalyst with core-casing structure preparation method to nucleocapsid result catalyst finding preparation condition gentleness has profound significance.
Summary of the invention
Instant invention overcomes metal oxide and molecular sieve physical mixed disperses uneven shortcoming for two kinds of catalyst during successive reaction, it also avoid the shortcoming that metal oxide active in molecular screen membrane preparation process reduces, providing a kind of take metal oxide as the Zeolite composite film preparation method of carrier simultaneously.
Take metal oxide as a Zeolite composite film preparation method for carrier, comprise the steps:
(1) spray coating liquor preparation: taking that 2 ~ 10g colloidal sol, 20 ~ 100g ethanol or water dilutes is weak solution, and add 1 ~ 5g molecular sieve powder again in described weak solution, ultrasonic vibration 2h, obtains spray coating liquor;
(2) composite membrane preparation: be that 1:30 ~ 60 take metal oxide and spray coating liquor according to metal oxide and described spray coating liquor mass ratio; Described spray coating liquor is sprayed on scattered metal oxide, is then placed in drying box dry, then sprays, drier, so repeat, until used up by spray coating liquor, by dry for the metal oxide sprayed, then namely roasting obtains Zeolite composite film.
In the preparation of step (1) spray coating liquor, described colloidal sol is Ludox or Alumina gel.
In the preparation of step (1) spray coating liquor, described molecular sieve is one or more in CHA, MFI, FAU, MOR molecular sieve.
Described molecular sieve, through pretreatment, changes its pore passage structure by acid or alkali treatment, or interpolation metal ion changes the distribution of its active sites.
In the preparation of step (2) composite membrane, metal oxide is one or more in cupric oxide, zinc oxide, zirconia, nickel oxide, cobalt oxide, cerium oxide, iron oxide, manganese oxide, aluminium oxide.
Metal oxide prepared by described method is a Zeolite composite film catalyst with core-casing structure for carrier, and core catalyst is metal oxide, and shell is Zeolite composite film.
Beneficial effect of the present invention: catalyst with core-casing structure obtains extensive concern because it successive reaction can be coupling in a reactor, time prepared by common molecular screen membrane catalyst with core-casing structure, the Acidity of Aikalinity of high temperature crystallization and synthesis liquid all can destroy the activity of core catalyst.And Zeolite composite film catalyst with core-casing structure preparation condition is gentleer than molecular screen membrane catalyst with core-casing structure, the molecular sieve prepared and Alumina gel or Ludox are sprayed on core catalyst surface, whole preparation process is on the catalyst performance of core catalyst without impact, and Zeolite composite film catalyst with core-casing structure has good catalytic efficiency to successive reaction coupling process.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of Zeolite composite film catalyst with core-casing structure and physical mixed catalyst.
Fig. 2 is Zeolite composite film catalyst with core-casing structure structural representation.
Fig. 3 is the SEM figure of embodiment 1 metal oxide carrier.
Fig. 4 is the SEM figure of embodiment 1 metal oxide particle Surface coating Zeolite composite film.
Fig. 5 is the SEM figure on the Zeolite composite film surface that embodiment 1 is synthesized.
Fig. 6 is the SEM figure in the cross section of embodiment 1 metal oxide particle Surface coating Zeolite composite film.
In Fig. 2,1. sieve particle, 2. Woelm Alumina or silicon oxide layer, 3. shell is the composite membrane be made up of molecular sieve and pellumina or silicon oxide film.
Detailed description of the invention
With accompanying drawing, the present invention is further elaborated in conjunction with the embodiments.
As shown in Figure 1, left side is traditional physical mixed catalyst, by two kinds of catalyst physical mixing; Right side is Zeolite composite film catalyst with core-casing structure, improve the way of contact of two kinds of catalyst, can effectively successive reaction be coupling in same reactor, can by being separated of the catalytic action of catalyst nucleus and molecular screen membrane, overall performance that catalytic process combines to improve catalyst.
The preparation process of Zeolite composite film is relatively gentle, that the weak solution of the molecular sieve prepared and Alumina gel or Ludox is sprayed on metal oxide surface, there is not acidity or alkaline water thermal environment and high temperature crystallization process, the activity of core metal oxide catalyst is unaffected in preparation process, more can give play to the advantage of catalyst with core-casing structure.As shown in Figure 2, wherein 1 is sieve particle, 2 is Woelm Alumina or silicon oxide layer, 3 for shell be the composite membrane be made up of molecular sieve and pellumina or silicon oxide film, after coated Zeolite composite film, single catalyst granules is a mini-size membrane reactor, " fence " effect of Zeolite composite film can stop or delay the inactivation of catalyst and the loss of active constituent to a great extent, also immediately removes core catalyst reaction heat to prevent catalyst overheating by the composite membrane of shell simultaneously.
embodiment 1
(1) spray coating liquor preparation: taking the dilution of 2g Alumina gel 20g ethanol is weak solution, or takes 2g Ludox, be weak solution with the dilution of 20g water, then add 1g molecular sieve powder, ultrasonic vibration 2h, obtains spray coating liquor.
(2) composite membrane preparation: be that 1:30 takes core catalyst and spray coating liquor according to metal oxide (Fig. 3) and spray coating liquor mass ratio.The spray coating liquor of preparation is sprayed on scattered metal oxide, sprays 2 times, be placed in 60 DEG C of dry 30min of drying box, spray 2 times again, drier, so repeat, until used up by spray coating liquor, by gained particle at 120 DEG C of dry 12h, namely 550 DEG C of roasting 5h obtain Zeolite composite film.Fig. 4 is the SEM figure of metal oxide particle Surface coating Zeolite composite film, Fig. 5 is that the SEM on Zeolite composite film surface schemes, and Fig. 6 is the section S EM figure of metal oxide particle Surface coating Zeolite composite film.
embodiment 2
(1) spray coating liquor preparation: taking the dilution of 5g Alumina gel 50g ethanol is weak solution, or takes 2 ~ 10g Ludox, be weak solution with the dilution of 50g water, then add 3g molecular sieve powder, ultrasonic vibration 2h, obtains spray coating liquor.
(2) composite membrane preparation: be that 1:50 takes core catalyst and spray coating liquor according to metal oxide and spray coating liquor mass ratio.The spray coating liquor of preparation is sprayed on scattered metal oxide, sprays 2 times, be placed in 60 DEG C of dry 30min of drying box, spray 2 times again, drier, so repeat, until used up by spray coating liquor, by gained particle at 120 DEG C of dry 12h, namely 550 DEG C of roasting 5h obtain Zeolite composite film.
embodiment 3
(1) spray coating liquor preparation: taking the dilution of 10g Alumina gel 100g ethanol is weak solution, or takes 10g Ludox, be weak solution with the dilution of 100g water, then add 5g molecular sieve powder, ultrasonic vibration 2h, obtains spray coating liquor.
(2) composite membrane preparation: be that 1:60 takes core catalyst and spray coating liquor according to metal oxide and spray coating liquor mass ratio.The spray coating liquor of preparation is sprayed on scattered metal oxide, sprays 3 times, be placed in 60 DEG C of dry 30min of drying box, spray 3 times again, drier, so repeat, until used up by spray coating liquor, by gained particle at 120 DEG C of dry 12h, namely 550 DEG C of roasting 5h obtain Zeolite composite film.
embodiment 4
(1) spray coating liquor preparation: taking the dilution of 6g Alumina gel 60g ethanol is weak solution, or takes 6g Ludox, be weak solution with the dilution of 60g water, then add 2g molecular sieve powder, ultrasonic vibration 2h, obtains spray coating liquor.
(2) composite membrane preparation: be that 1:40 takes core catalyst and spray coating liquor according to metal oxide and spray coating liquor mass ratio.The spray coating liquor of preparation is sprayed on scattered metal oxide, sprays 2 times, be placed in 60 DEG C of dry 30min of drying box, spray 2 times again, drier, so repeat, until used up by spray coating liquor, by gained particle at 120 DEG C of dry 12h, namely 550 DEG C of roasting 5h obtain Zeolite composite film.
embodiment 5
(1) spray coating liquor preparation: taking the dilution of 8g Alumina gel 70g ethanol is weak solution, or takes 8g Ludox, be weak solution with the dilution of 70g water, then add 3g molecular sieve powder, ultrasonic vibration 2h, obtains spray coating liquor.
(2) composite membrane preparation: be that 1:40 takes core catalyst and spray coating liquor according to metal oxide and spray coating liquor mass ratio.The spray coating liquor of preparation is sprayed on scattered metal oxide, sprays 3 times, be placed in 60 DEG C of dry 30min of drying box, spray 3 times again, drier, so repeat, until used up by spray coating liquor, by gained particle at 120 DEG C of dry 12h, namely 550 DEG C of roasting 5h obtain Zeolite composite film.
embodiment 6
(1) spray coating liquor preparation: taking the dilution of 3g Alumina gel 50g ethanol is weak solution, or takes 3g Ludox, be weak solution with the dilution of 50g water, then add 4g molecular sieve powder, ultrasonic vibration 2h, obtains spray coating liquor.
(2) composite membrane preparation: be that 1:60 takes core catalyst and spray coating liquor according to metal oxide and spray coating liquor mass ratio.The spray coating liquor of preparation is sprayed on scattered metal oxide, sprays 3 times, be placed in 60 DEG C of dry 30min of drying box, spray 3 times again, drier, so repeat, until used up by spray coating liquor, by gained particle at 120 DEG C of dry 12h, namely 550 DEG C of roasting 5h obtain Zeolite composite film.
embodiment 7
(1) spray coating liquor preparation: taking the dilution of 7g Alumina gel 90g ethanol is weak solution, or takes 7g Ludox, be weak solution with the dilution of 90g water, then add 4g molecular sieve powder, ultrasonic vibration 2h, obtains spray coating liquor.
(2) composite membrane preparation: be that 1:60 takes core catalyst and spray coating liquor according to metal oxide and spray coating liquor mass ratio.The spray coating liquor of preparation is sprayed on scattered metal oxide, sprays 2 times, be placed in 60 DEG C of dry 30min of drying box, spray 2 times again, drier, so repeat, until used up by spray coating liquor, by gained particle at 120 DEG C of dry 12h, namely 550 DEG C of roasting 5h obtain Zeolite composite film.
embodiment 8
(1) spray coating liquor preparation: taking the dilution of 4g Alumina gel 60g ethanol is weak solution, or takes 4g Ludox, be weak solution with the dilution of 60g water, then add 2g molecular sieve powder, ultrasonic vibration 2h, obtains spray coating liquor.
(2) composite membrane preparation: be that 1:60 takes core catalyst and spray coating liquor according to metal oxide and spray coating liquor mass ratio.The spray coating liquor of preparation is sprayed on scattered metal oxide, sprays 2 times, be placed in 60 DEG C of dry 30min of drying box, spray 2 times again, drier, so repeat, until used up by spray coating liquor, by gained particle at 120 DEG C of dry 12h, namely 550 DEG C of roasting 5h obtain Zeolite composite film.
Claims (6)
1. be a Zeolite composite film preparation method for carrier with metal oxide, it is characterized in that comprising the steps:
(1) spray coating liquor preparation: taking that 2 ~ 10g colloidal sol, 20 ~ 100g ethanol or water dilutes is weak solution, and add 1 ~ 5g molecular sieve powder again in described weak solution, ultrasonic vibration 2h, obtains spray coating liquor;
(2) composite membrane preparation: be that 1:30 ~ 60 take metal oxide and spray coating liquor according to metal oxide and described spray coating liquor mass ratio; Described spray coating liquor is sprayed on scattered metal oxide, is then placed in drying box dry, then sprays, drier, so repeat, until used up by spray coating liquor, by dry for the metal oxide sprayed, then namely roasting obtains Zeolite composite film; Described take metal oxide as the Zeolite composite film of carrier is catalyst with core-casing structure, and metal oxide is core catalyst, and Zeolite composite film is shell.
2. method according to claim 1, is characterized in that in the preparation of step (1) spray coating liquor, described colloidal sol is Ludox or Alumina gel.
3. method according to claim 1, is characterized in that in the preparation of step (1) spray coating liquor, described molecular sieve is one or more in CHA, MFI, FAU, MOR molecular sieve.
4. method according to claim 3, is characterized in that described molecular sieve is through pretreatment, changes its pore passage structure by acid or alkali treatment, or interpolation metal ion changes the distribution of its active sites.
5. method according to claim 1, is characterized in that in the preparation of step (2) composite membrane, metal oxide is one or more in cupric oxide, zinc oxide, zirconia, nickel oxide, cobalt oxide, cerium oxide, iron oxide, manganese oxide, aluminium oxide.
6. a Zeolite composite film catalyst with core-casing structure for what prepared by method according to claim 1 with metal oxide is carrier, it is characterized in that described metal oxide is core catalyst, described Zeolite composite film is shell.
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| CN104014253B (en) * | 2014-05-26 | 2016-03-09 | 浙江理工大学 | The Preparation method and use of NaA-NaY Zeolite composite film |
| CN107686378A (en) * | 2016-08-05 | 2018-02-13 | 湖南银和瓷业有限公司 | Micro- mesoporous composite molecular sieve film and preparation method thereof |
| KR20190132914A (en) * | 2018-05-21 | 2019-11-29 | 희성촉매 주식회사 | Modified zeolites with thermal stability and a catalyst composite using thereof |
| CN110054499A (en) * | 2019-05-29 | 2019-07-26 | 扬州市飞鹰电子科技有限公司 | A kind of silicon nitride microballoon of area load molecular sieve, preparation method and applications |
| CN113134344B (en) * | 2021-04-21 | 2023-08-11 | 浙江卫星能源有限公司 | Dechlorination agent and preparation method thereof |
| CN114459943A (en) * | 2021-12-31 | 2022-05-10 | 杭州诺蒙微晶生物科技有限公司 | Quartz crystal microbalance sensor and preparation method thereof |
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Effective date of registration: 20161228 Address after: Yaohuamen Yao Qixia District of Nanjing City, Jiangsu province 210046 New Village Patentee after: China Construction Industrial Equipment Installation Co., Ltd. Patentee after: Zhejiang Univ. Address before: 310027 Hangzhou, Zhejiang Province, Xihu District, Zhejiang Road, No. 38, No. Patentee before: Zhejiang Univ. Patentee before: China Construction Industrial Equipment Installation Co., Ltd. |
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Address after: 210046 Yaohua Menyao'an New Village, Qixia District, Nanjing City, Jiangsu Province Co-patentee after: Zhejiang University Patentee after: China Construction Installation Group Co., Ltd. Address before: 210046 Yaohua Menyao'an New Village, Qixia District, Nanjing City, Jiangsu Province Co-patentee before: Zhejiang University Patentee before: China Construction Industrial Equipment Installation Co., Ltd. |