CN103708488B - Method for preparing multilevel porous zeolite through microwave assisted decomposition of hydrogen peroxide - Google Patents
Method for preparing multilevel porous zeolite through microwave assisted decomposition of hydrogen peroxide Download PDFInfo
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- CN103708488B CN103708488B CN201310735144.7A CN201310735144A CN103708488B CN 103708488 B CN103708488 B CN 103708488B CN 201310735144 A CN201310735144 A CN 201310735144A CN 103708488 B CN103708488 B CN 103708488B
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Abstract
The invention belongs to the technical field of material chemistry and particularly relates to a method for preparing multilevel porous zeolite through microwave assisted decomposition of hydrogen peroxide. The method comprises the following steps: quickly decomposing hydrogen peroxide with certain concentration under the action of microwave radiation to generate a gas so as to produce instantaneous violent impact on zeolite to introduce secondary pores into beta zeolite. The method provided by the invention is simple in equipment, simple and convenient to operate and quick to react. The introduction of the secondary pores increases the specific surface area and the pore volume of the beta zeolite and reduces the crystal defects of the beta zeolite to ensure a more beautiful skeleton. The micro blasting pore-forming zeolite material has a huge application value in some macromolecular limited zeolite catalysis fields, for example, petroleum reforming, catalytic cracking and the like.
Description
Technical field
The invention belongs to material chemistry technical field, be specifically related to a kind of method that microwave-assisted decomposing hydrogen dioxide solution prepares porous zeotile.
Background technology
According to the international pure chemistry of IUPAC(and applied chemistry federation) classification to inorganic porous material, the size range in duct is called containing Microporous Compounds or molecular sieve at the material of 2 below nm, the material of pore size scope between 2 ~ 50 nm claims mesoporous material, and the material that pore size scope is greater than 50 nm is called large pore material.Zeolite molecular sieve is as important a member of inorganic microporous material, and because it has unique physicochemical property, as larger specific surface area, regular pore passage structure, controlled sour position and sour density etc., play an important role in catalysis, absorption and the field such as to be separated.
Traditional zeolitic material is generally less than 1nm due to its aperture, helpless for a lot of macromolecular reaction.Compared with traditional poromerics, mesoporous material has broader duct, but usually the hole wall of mesoporous material is unbodied, therefore its thermostability and hydrothermal stability poor, therefore also limit their widespread use.
In sum, micropore, mesoporous material cut both ways.How to learn from other's strong points to offset one's weaknesses, more reasonably the advantages of this bi-material got up, playing its respective advantage becomes the problem that people are concerned about, having micropore and mesoporous multilevel hole material becomes the focus that people pay close attention to day by day.There is high hydrothermal stability and cause the concern of people compared with the zeolite multilevel Porous materials that high acid strength includes again larger aperture.The method preparing multi-orifice zeolite material mainly contains four large classes: 1) remove skeleton building block atom (as dealuminzation desiliconization method) and formed in zeolite crystal mesoporous; 2) the induction assembling introducing intergranular of nano zeolite is mesoporous; 3) nano-sized carbon be hard template controlling crystallizing activated carbon is embedded in crystals formed intracrystalline mesoporous; 4) soft template synthesis method.These methods operation more complicated, template can not be eliminated completely, affects the performance and application of porous zeotile.
The method that the present invention proposes, use equipment simple, easy to operate, and use reagent to be hydrogen peroxide, degradation production is water and oxygen, clean and effective.H-type zeolite can directly use after treatment, in succession processes without the need to exchanging roasting etc., therefore has excellent and application prospect widely.
Summary of the invention
The object of the invention is to propose a kind of can clear up zeolite template completely method preparing porous zeotile with in short-term, easily controlling, obtain that template is eliminated completely, inorganic skeleton structure and surface properties retain nano zeolite that is good, good dispersity.
The present invention proposes a kind of method preparing porous zeotile, and be decomposing hydrogen dioxide solution under microwave exposure, original position produces a large amount of gas fast, and moment impact causes zeolite framework to produce new secondary pore.Concrete steps are as follows:
(1) beta zeolite being joined appropriate mass concentration is 30-50%(wt%) hydrogen peroxide in, shake up;
(2) appropriate distilled water is added; Supersound process, makes zeolite be dispersed in hydrogen peroxide reaction system;
(3) this system airtight, puts into microwave reactor, carries out microwave exposure;
(4), after reaction terminates, product is disperseed in distilled water, ultrasonic, washing, dry.
In the present invention, the massfraction of described hydrogen peroxide reaction system can be 2-50%, and the usage quantity processing every gram of zeolite is 2-200 ml.
In the present invention, described in carry out microwave exposure condition can be: temperature 40-210
oc, microwave exposure 2-120 minute; Power controls at 200-1000W.Optimum condition is: temperature 80-150
oc, microwave exposure 30-100 minute; Power controls at 400-800W.
Can directly use after h-type zeolite washing drying after the inventive method process.
The inventive method utilizes hydrogen peroxide fast decoupled under microwave exposure, produce a large amount of gas impact zeolite cavity thus introduce secondary pore in zeolite inside, by controlling the condition of reaction, both ultramicropore can be introduced, also can introduce the mesoporous of large-size, and modulation can be carried out to hole dimension and relative quantity.Compared with traditional method, the inventive method is swift in response, simple, and Environmental Safety is workable, and use reagent cheap and easy to get, and whole process cleans is efficient, the secondary pore of introducing is conducive to improving diffusional limitation, improves the catalytic performance of zeolitic material.
Accompanying drawing explanation
The transmission electron microscope photo (TEM) of the initial BEA zeolite of Fig. 1.
The transmission electron microscope photo (TEM) of BEA zeolite after Fig. 2 process.
The N of BEA zeolite before and after Fig. 3 process
2isothermal adsorption desorption curve.
The NLDFT pore size distribution (PSD) of BEA zeolite before and after Fig. 4 process.
The N of BEA zeolite before and after Fig. 5 process
2isothermal adsorption desorption curve.
The BJH pore size distribution (PSD) of BEA zeolite before and after Fig. 6 process.
The X light powder diffraction collection of illustrative plates (XRD) of BEA zeolite before and after Fig. 7 process.
The infrared spectra (FTIR) of BEA zeolite before and after Fig. 8 process.
Embodiment
Example below prepares multi-stage porous BEA zeolite to microwave exposure decomposing hydrogen dioxide solution provided by the present invention, further illustrate.
50 mg BEA zeolites are joined 3ml 30%(wt% by embodiment 1) hydrogen peroxide in, shake up; Then 2ml distilled water is added, ultrasonic 5 minutes.This system airtight is also transferred in microwave reactor, according to irradiation process listed in subordinate list 1, reacts 1 time, namely 100 minutes.After reaction terminates, be cooled to room temperature, by centrifugal under the product 1000r/min condition that obtains, discard supernatant liquor, then use distilled water repetitive scrubbing 3 times.Product TEM schemes as shown in Figure 2, and the TEM figure of initial sample as shown in Figure 1, contrasts two figure and clearly can find that β zeolite creates secondary pore after treatment.
150 mg BEA zeolites are joined 9ml 30%(wt% by embodiment 2) hydrogen peroxide in, shake up; Then 1ml distilled water is added, ultrasonic 5 minutes.This system airtight is also transferred in microwave reactor, according to irradiation process listed in subordinate list 1, reacts 1 time 100 minutes.After reaction terminates, be cooled to room temperature, by centrifugal under the product 1000r/min condition that obtains, discard supernatant liquor, then use distilled water repetitive scrubbing 3 times.The N of BEA zeolite before and after reaction
2as shown in Figure 3, the graph of pore diameter distribution that NLDFT method obtains as shown in Figure 4 for isothermal adsorption desorption graphic representation.Having there is obvious delayed winding in the isothermal adsorption desorption graphic representation that clearly can be found to process rear β zeolite by Fig. 3, shows the feature of obvious mesopore and micropore composite material.As shown in Figure 4, after process, the major bore distribution of β zeolite there occurs red shift, and this is because a large amount of generations of secondary pore cause.
Product B EA zeolite in example 2 joins in the hydrogen peroxide of 4ml 50% (wt%) by embodiment 3, shakes up; Add 2ml distilled water, ultrasonic 5 minutes.This system airtight is also transferred in microwave reactor, according to irradiation process listed in subordinate list 2, reacts 1 time 60 minutes.After reaction terminates, be cooled to room temperature, by centrifugal under the product 1000r/min condition that obtains, discard supernatant liquor, then after using distilled water repetitive scrubbing 2 times, repeat operating process last time, reprocessing once, is finally cooled to room temperature, by centrifugal under the product 1000r/min condition that obtains, discard supernatant liquor, then with the BEA zeolite obtaining after distilled water repetitive scrubbing 3 times processing repeatedly, the N before and after its reaction
2as shown in Figure 5, BJH graph of pore diameter distribution as shown in Figure 6 for isothermal adsorption desorption graphic representation.Clearly can find that the isothermal adsorption desorption graphic representation processing rear β zeolite has occurred obvious delayed winding in elevated pressures district by Fig. 5, show to introduce a large amount of mesoporous.As shown in Figure 6, after repeatedly processing, β zeolite creates new distribution of peaks in the mesoporous district of 10nm, absolutely proves that this method is for introducing mesoporous validity.Fig. 8 is known, and repeatedly after process, the skeleton degree of order of BEA zeolite improves.
500mg BEA zeolite is joined 10ml 30%(wt% by embodiment 4) hydrogen peroxide in, shake up, ultrasonic 5 minutes.This system airtight is also transferred in microwave reactor, according to irradiation process listed in subordinate list 1, reacts 1 time 100 minutes.After reaction terminates, be cooled to room temperature, by centrifugal under the product 1000r/min condition that obtains, discard supernatant liquor, then obtain the BEA zeolite of introducing secondary pore with distilled water repetitive scrubbing for 3 times.
250 mg BEA zeolites are joined 5ml 50%(wt% by embodiment 5) hydrogen peroxide in, shake up; Then 3ml distilled water is added, ultrasonic 5 minutes.This system airtight is also transferred in microwave reactor, according to irradiation process listed in subordinate list 3, reacts 1 time 15 minutes.After reaction terminates, be cooled to room temperature, by centrifugal under the product 1000r/min condition that obtains, discard supernatant liquor, then obtain the BEA zeolite of introducing secondary pore with distilled water repetitive scrubbing for 3 times.
150 mg BEA zeolites are joined 5ml 30%(wt% by embodiment 6) hydrogen peroxide in, shake up; Then 3ml distilled water is added, ultrasonic 5 minutes.This system airtight is also transferred in microwave reactor, according to irradiation process listed in subordinate list 2, reacts 1 time 60 minutes.After reaction terminates, be cooled to room temperature, by centrifugal under the product 1000r/min condition that obtains, discard supernatant liquor, then obtain the BEA zeolite of introducing secondary pore with distilled water repetitive scrubbing for 3 times.
400 mg BEA zeolites are joined 2ml 30%(wt% by embodiment 7) hydrogen peroxide in, shake up; Then 8ml distilled water is added, ultrasonic 5 minutes.This system airtight is also transferred in microwave reactor, according to irradiation process listed in subordinate list 2, reacts 1 time 60 minutes.After reaction terminates, be cooled to room temperature, by centrifugal under the product 1000r/min condition that obtains, discard supernatant liquor, then obtain the BEA zeolite of introducing secondary pore with distilled water repetitive scrubbing for 3 times.
200 mg BEA zeolites are joined 2ml 50%(wt% by embodiment 8) hydrogen peroxide in, shake up, ultrasonic 5 minutes.This system airtight is also transferred in microwave reactor, according to irradiation process listed in subordinate list 2, reacts 1 time 60 minutes.After reaction terminates, be cooled to room temperature, by centrifugal under the product 1000r/min condition that obtains, discard supernatant liquor, then obtain the BEA zeolite of introducing secondary pore with distilled water repetitive scrubbing for 3 times.
250 mg ZSM-5 zeolites are joined 6ml 30%(wt% by embodiment 9) hydrogen peroxide in, shake up; Then 4ml distilled water is added, ultrasonic 5 minutes.This system airtight is also transferred in microwave reactor, according to irradiation process listed in subordinate list 1, reacts 1 time 100 minutes.After reaction terminates, be cooled to room temperature, by centrifugal under the product 1000r/min condition that obtains, discard supernatant liquor, then obtain the ZSM-5 zeolite of introducing secondary pore with distilled water repetitive scrubbing for 3 times.
150 mg MOR zeolites are joined 5ml 30%(wt% by embodiment 10) hydrogen peroxide in, shake up; Then 3ml distilled water is added, ultrasonic 5 minutes.This system airtight is also transferred in microwave reactor, according to irradiation process listed in subordinate list 3, reacts 1 time 15 minutes.After reaction terminates, be cooled to room temperature, by centrifugal under the product 1000r/min condition that obtains, discard supernatant liquor, then obtain the MOR zeolite of introducing secondary pore with distilled water repetitive scrubbing for 3 times.
The inventive method is simple, Environmental Safety, effectively introduces ultramicropore and mesoporous, can improve the skeleton degree of order simultaneously under the prerequisite that well can keep zeolite crystal skeleton structure topographic properties, therefore has superior and application prospect widely.
subordinate list explanation
Microwave exposure program under table 1 controlled temperature conditions: pattern one
Microwave exposure program under table 2 controlled temperature conditions: pattern two
Microwave exposure program under table 3 controlled temperature conditions: pattern three
The pore structure character of the BEA zeolite before and after the process of table 4 microwave exposure hydrogen peroxide
。
Claims (1)
1. microwave-assisted decomposing hydrogen dioxide solution prepares a method for porous zeotile, it is characterized in that decomposing hydrogen dioxide solution under microwave exposure, and original position produces a large amount of gas fast, and moment impact causes zeolite framework to produce new secondary pore, and concrete steps are as follows:
(1) beta zeolite being joined appropriate mass concentration is in the hydrogen peroxide of 30-50%, shakes up;
(2) appropriate distilled water is added; Supersound process; Zeolite is made to be dispersed in hydrogen peroxide reaction system;
(3) this system airtight, puts into microwave reactor, carries out microwave exposure;
(4), after reaction terminates, product is disperseed in distilled water, ultrasonic, washing, dry;
The massfraction of described hydrogen peroxide reaction system is 2-50%, and the usage quantity processing every gram of zeolite is 2-200 ml;
Described condition of carrying out microwave exposure is: temperature 40-210 DEG C, microwave exposure 2-120 minute; Power controls at 200-1000W.
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| CN107032369B (en) * | 2017-05-10 | 2019-07-02 | 武汉凯迪工程技术研究总院有限公司 | Mesoporous Beta zeolite and preparation method thereof |
| CN113402012B (en) * | 2021-06-02 | 2023-12-12 | 浙江工业大学 | Aerobic composting reinforced horizontal subsurface flow constructed wetland denitrification device and application |
| CN114477207B (en) * | 2022-02-17 | 2023-04-11 | 复旦大学 | Thin-layer two-dimensional discrete layered zeolite material with vertical penetrating type mesopores in lamellar layer and preparation method and application thereof |
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