CN105251441B - A kind of controllable adsorbent of molecular sieve of high-performance Jie micro-diplopore and its preparation and application - Google Patents
A kind of controllable adsorbent of molecular sieve of high-performance Jie micro-diplopore and its preparation and application Download PDFInfo
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Abstract
The invention belongs to technical field of air pollution control, and in particular to a kind of controllable adsorbent of molecular sieve of high-performance Jie micro-diplopore and its preparation and application.The preparation method comprises the following steps：It is Material synthesis mother liquor with silicon source, silicon source, microcellular structure directed agents, mesoporous template, organosilan and water, mother liquor utilizes microwave radiation technology hydro-thermal reaction, by the product centrifugation for reacting gained, dry, roasting, the controllable adsorbent of molecular sieve of high-performance Jie micro-diplopore is obtained.The present invention prepares the mesoporous type zeolite molecular sieve of high-ratio surface, high pore volume and high absorption property using a kind of efficient method, and generated time has been greatly shortened, and simplifies synthesis technology.The zeolite-type molecular sieve adsorbant that the present invention synthesizes is hierarchical porous structure, and aperture is adjustable, and resistance to mass tranfer is small, has high absorption property to VOCs, and with high hydrophobicity and hydrothermal stability, has higher application value in VOCs processing technology fields.
Description
Technical field
The invention belongs to technical field of air pollution control, and in particular to a kind of controllable molecular sieve of high-performance Jie micro-diplopore is inhaled
Attached dose and its prepare and application.
Background technology
Volatile organic matter (Volatile Organic Compounds, VOCs) refers to that saturated vapour pressure is big at normal temperatures
Organic compound of the boiling point within 260 DEG C under 70Pa, normal pressure.VOCs is a kind of common atmosphere pollution, main source
In industries such as printing, application, pharmacy, Furniture manufacture and petrochemical industries.These organic exhaust gas majorities are inflammable and explosive, and are often accompanied by different
Taste, stench distribute in air, can generate stimulation to the eye, nose, respiratory system of people under relatively low solubility, even
Human canceration, mutation can be induced.
With the enhancing of people's environmental protection consciousness, atmosphere pollutants emission standards are subject to various countries more and more to pay attention to,
China comes into effect on January 1st, 1997《Discharge standard of air pollutants》(GB16297-1996) toluene, two are defined
Industry VOCs discharge provincial standards have also been put into effect in the 14 class VOCs discharge standards such as toluene, vinyl chloride, various regions in succession.Common VOCs
Emission-reduction technology has adsorption condensing, direct oxidation, catalysis oxidation, photochemical catalytic oxidation and biological filter membrane etc..Wherein absorption method is that most have
One of method of effect, it is of low cost, easy to operate, has higher removal rate in low concentration.Activated carbon is that current use is most wide
General adsorbent, but inflammability limits the absorption property of activated carbon under the high temperature conditions；Silica gel is right in dry conditions
VOCs has higher adsorption capacity, but due to its hydrophilic property, under the conditions of complex industrial to VOCs large amount of adsorption
Width declines.Patent 201110006599.6 disclose it is a kind of to organic matter have superpower absorption property organic resin, but its
The limitation of matter property, this adsorbent can only use at a lower temperature；Patent 01126842.5 utilizes diatomite porous
Property high-ratio surface property synthesized a kind of fly ash-based adsorbent, although to VOCs have certain adsorption capacity, synthesis
Time is long, and energy consumption is high, is unfavorable for industrial applications.
The content of the invention
To solve the disadvantage that the prior art and shortcoming, primary and foremost purpose of the invention be to provide a kind of high-performance be situated between it is micro-
The preparation method of the controllable adsorbent of molecular sieve of diplopore.
Another object of the present invention is to provide the controllable molecular sieve of high-performance Jie micro-diplopore made from above-mentioned preparation method to inhale
Attached dose.
It is yet a further object of the present invention to provide the applications of the above-mentioned controllable adsorbent of molecular sieve of high-performance Jie micro-diplopore.
The object of the invention is achieved through the following technical solutions：
A kind of preparation method of the controllable adsorbent of molecular sieve of high-performance Jie micro-diplopore, comprises the following steps：With silicon source, aluminium
Source, microcellular structure directed agents, mesoporous template, organosilan and water are Material synthesis mother liquor, and mother liquor utilizes microwave radiation technology hydro-thermal
Reaction by the product centrifugation for reacting gained, dry, roasting, obtains the controllable adsorbent of molecular sieve of high-performance Jie micro-diplopore.
The silicon source is with SiO2Meter, silicon source is with Al2O3Meter, reaction raw materials mol ratio are SiO2:Water=0.025, SiO2:It is micro-
Pore structure directed agents=5, SiO2:Al2O3=50~400, SiO2:Organosilan=10~40, the addition of the mesoporous template
Amount may be selected in SiO2:Mesoporous template=5~20, product can be adjusted with dosage by being added by the species for changing mesoporous template
Pore-size distribution.
The mesoporous template is anion surfactant；The silicon source is ethyl orthosilicate；Source of aluminium is isopropyl
Aluminium alcoholates；The microcellular structure directed agents are tetrapropylammonium hydroxide (TPAOH), tetraethyl ammonium hydroxide (TEAOH) and ethylenediamine
At least one of.
The anion surfactant is preferably n-hexadecyl sodium sulfonate, myristyl sodium sulfonate, detergent alkylate
At least one of sodium sulfonate and sodium laurate.
The organosilan is preferably 3- aminopropyl triethoxysilanes, (3- mercaptopropyis) trimethoxy silane and chlorine third
At least one of ethyl triethoxy silicane alkane.
The preparation method is as follows：
(1) it is soluble in water that microcellular structure directed agents are weighed, add in silicon source, stirs to silicon source and hydrolyzes；Then in stirring condition
Lower addition silicon source, obtains A liquid；
(2) weigh mesoporous template to be added to the water, add in organosilan after stirring a period of time, obtain B liquid；
(3) B liquid made from step (2) is added in A liquid made from step (1), adjusts pH value, when continuing to stir one section
Between, obtain mother liquor；
(4) mother liquor made from step (3) is transferred to reaction kettle, microwave hydrothermal reaction；By the product centrifugation for reacting gained, do
Dry, roasting, obtains the controllable adsorbent of molecular sieve of high-performance Jie micro-diplopore.
The time stirred described in step (2) is 10~60 minutes；PH value described in step (3) for adjust to 8.8~
10.2；When the time of stirring described in step (3) is 1~2 small.
Microwave hydrothermal optimum condition described in step (4) is 80~170 DEG C of temperature setting, hydro-thermal reaction 0.5~4 is small
When.
Dry temperature described in step (4) is 80~110 DEG C, the dry time for 8~for 24 hours；The temperature of the roasting
Preferably 450~750 DEG C, when the time of roasting is preferably 4~12 small.Centrifugation described in step (4) refers to that repeatedly centrifugation is extremely
Supernatant is in neutrality.
The present invention also provides one kind controllable adsorbent of molecular sieve of high-performance Jie micro-diplopore as made from above-mentioned preparation method.
Mesoporous, the micropore ratio of the adsorbent can control, and adsorption capacity is strong and suitable for a variety of industrial conditions, and with high hydrophobicity and
Hydrothermal stability.
The above-mentioned controllable adsorbent of molecular sieve of high-performance Jie micro-diplopore can be applied to purifying organic, and particularly volatility is organic
Object (VOCs).Adsorption experiment has been carried out for simulation gas, adsorbance is up to 300~500mg/g in the present invention using toluene.
The present invention mechanism be：Mesoporous, raising molecule is constructed in traditional zeolite molecular sieve by adding mesoporous template
While sieve is to VOCs adsorption capacities, the original high hydrophobicity of zeolite molecular sieve, high thermal stability and high hydrothermally stable are maintained
Performance.This method utilizes microwave radiation technology hydro-thermal reaction, obtains mesoporous orderly, crystallinity height, the adjustable hydrophobic type zeolite in aperture point
Son sieve, and the adsorption experiment of low-concentration organic is carried out to the molecular sieve, the results show molecular sieve has VOCs high adsorb
Capacity.Present invention process is simple, and generated time is short, at low cost, and has good absorption property to volatile organic matter, is inhaling
Attached field has a good application prospect.
The prior art using synthesized by surfactant be pure mesoporous type molecular sieve, and hole wall be unformed shape
, this so that their thermal stability, hydrothermal stability and hydrophobicity are poor, limits the application in VOCs absorption.And this
The innovative point of invention is, mesoporous, synthesis Jie's micro-diplopore controllable zeolite type point is constructed in traditional zeolite type micro porous molecular sieve
Son sieve, this molecular sieve maintains the intrinsic thermal stability and hydrothermal stability of zeolite type micro porous molecular sieve, while expands aperture
Be conducive to the mass transfer of organic matter, the property of Jie's micropore is conducive to the VOCs gas absorptions of different molecular radius in addition.
Another of the invention innovative point be added in traditional zeolite type micro porous molecular sieve synthesis technology surfactant and
Organosilan constructs mesoporous (including medicament addition species, order), organosilan one by electrostatic assembly principle collective effect
End can be combined with silicon species, and the other end is combined with surfactant micellar, transgranular mesoporous so as to be formed in crystallization process.
Can generated time be improved with high degree using microwave radiation technology hydro-thermal, simplify synthesis technology, this technique is boiled in synthesis
Have in stone-type micro porous molecular sieve and used, but systematic research is yet there are no in Jie's micro porous molecular sieve technique is synthesized.The present invention
Generated time is shortened using microwave assisted aqueous extraction heat, while is also beneficial between silicon species and organosilan agent surfactant
With reference to promotion obtains the more preferable local specialties of crystallinity.
Compared with prior art, the present invention has the following advantages and beneficial effects：
(1) present invention prepares the mesoporous type boiling of high-ratio surface, high pore volume and high absorption property using a kind of efficient method
Generated time has been greatly shortened in stone molecular sieve, simplifies synthesis technology.
(2) the zeolite-type molecular sieve adsorbant that synthesizes of the present invention is hierarchical porous structure, mesoporous, micropore ratio is controllable, is passed
Matter resistance is small, is conducive to the adsorption desorption process of macromolecular VOCs.
(3) adsorbent of molecular sieve that the present invention synthesizes has high absorption property to VOCs, to toluene up to 300~500mg/
The adsorption capacity of g；And with high hydrophobicity and hydrothermal stability, the industrial condition that can be suitable for hot humid carries out VOCs
Adsorb emission reduction processing；There is higher application value in VOCs processing technology fields.
(4) technology of preparing of the present invention is flexible, can synthesize different types of zeolite molecular sieve according to structure directing agent is different,
Such as Y types, X, beta molecular sieve and ZSM-5 molecular sieve.
Description of the drawings
Fig. 1 is the N of the controllable adsorbent of molecular sieve of Jie's micro-diplopore of high absorption property synthesized by the embodiment of the present invention 32It inhales de-
Attached thermoisopleth.
Fig. 2 is the N of the controllable adsorbent of molecular sieve of Jie's micro-diplopore of high absorption property synthesized by the embodiment of the present invention 52It inhales de-
Attached thermoisopleth.
Fig. 3 is the controllable adsorbent of molecular sieve of Jie's micro-diplopore of high absorption property synthesized by the embodiment of the present invention 3 to toluene
Adsorption isotherm.
Fig. 4 is the controllable adsorbent of molecular sieve of Jie's micro-diplopore of high absorption property synthesized by the embodiment of the present invention 5 to toluene
Adsorption isotherm.
Specific embodiment
With reference to embodiment and attached drawing, the present invention is described in further detail, but embodiments of the present invention are unlimited
In this.
Microwave equipment used is preferably the MARS6 of U.S. CE M companies production high-throughput closed micro- in the embodiment of the present invention
Ripple digestion system.
Embodiment 1
The controllable adsorbent of molecular sieve of high-performance Jie's micro-diplopore is prepared according to following steps：
(1) 8.12g tetrapropylammonium hydroxide (TPAOH, 25% aqueous solution) is added in 20mL distilled water, stirred at room temperature
To aluminium isopropoxide 0.102g is added in after mixing, stir to aluminium isopropoxide complete hydrolysis；Ethyl orthosilicate 10.4g is weighed,
Above-mentioned solution is instilled dropwise under the stirring of 750r/min rotating speeds, obtains A liquid；
(2) 1.5g myristyl sodium sulfonates are dissolved in 16mL distilled water, 40 DEG C of stirring in water bath, 1 it is small when after, to solution
Middle addition 0.3g 3- chloropropyl triethoxysilanes, obtain B liquid；
(3) B liquid made from step (2) is added rapidly in A liquid made from step (1), adjusts pH=9.7, stirring 2 is small
When, obtain mother liquor；
(4) mother liquor made from step (3) is transferred in 100mL ptfe autoclaves, 80 DEG C of water under microwave radiation technology
When thermal response 4 is small；Centrifugation, drying when 450 DEG C of roastings 12 are small, remove template agent removing, obtain white powder samples, are the high property
The controllable adsorbent of molecular sieve of the micro-diplopore that can be situated between, labeled as A1.
Embodiment 2
The controllable adsorbent of molecular sieve of high-performance Jie's micro-diplopore is prepared according to following steps：
(1) 8.12g tetrapropylammonium hydroxide (TPAOH, 25% aqueous solution) is added in 20mL distilled water, stirred at room temperature
To aluminium isopropoxide 0.204g is added in after mixing, stir to aluminium isopropoxide complete hydrolysis.Ethyl orthosilicate 10.4g is weighed,
Above-mentioned solution is instilled dropwise under the stirring of 750r/min rotating speeds, obtains A liquid；
(2) 3.28g n-hexadecyl sodium sulfonates are dissolved in 16mL distilled water, 40 DEG C of stirring in water bath, 1 it is small when after, to
1.1g 3- aminopropyl triethoxysilanes are added in solution, obtain B liquid；
(3) B liquid made from step (2) is added rapidly in A liquid made from step (1), adjusts pH=8.8, stirring 2 is small
When,
(4) mixed liquor is transferred in 100mL ptfe autoclaves, 110 DEG C of hydro-thermal reactions 3 are small under microwave radiation technology
When；Centrifugation, drying when 550 DEG C of roastings 8 are small, remove template agent removing, obtain white powder samples, are high-performance Jie micro-diplopore
Controllable adsorbent of molecular sieve, labeled as A2.
Embodiment 3
The controllable adsorbent of molecular sieve of high-performance Jie's micro-diplopore is prepared according to following steps：
(1) 8.12g tetrapropylammonium hydroxide (TPAOH, 25% aqueous solution) is added in 20mL distilled water, stirred at room temperature
To aluminium isopropoxide 0.408g is added in after mixing, stir to aluminium isopropoxide complete hydrolysis；Ethyl orthosilicate 10.4g is weighed,
Above-mentioned solution is instilled dropwise under the stirring of 750r/min rotating speeds, obtains A liquid；
(2) 3.48g neopelexes are dissolved in 16mL distilled water, 40 DEG C of stirring in water bath, 1 it is small when after, to
0.55g 3- aminopropyl triethoxysilanes are added in solution, obtain B liquid；
(3) B liquid made from step (2) is added rapidly in A liquid made from step (1), adjusts pH=9.7, stirring 2 is small
When,
(4) mixed liquor is transferred in 100mL ptfe autoclaves, 140 DEG C of hydro-thermal reactions 2 are small under microwave radiation technology
When；Centrifugation, drying when 650 DEG C of roastings 6 are small, remove template agent removing, obtain white powder samples, are high-performance Jie micro-diplopore
Controllable adsorbent of molecular sieve, labeled as A3.
Embodiment 4
The controllable adsorbent of molecular sieve of high-performance Jie's micro-diplopore is prepared according to following steps：
(1) 8.12g tetrapropylammonium hydroxide (TPAOH, 25% aqueous solution) is added in 20mL distilled water, stirred at room temperature
To aluminium isopropoxide 0.051g is added in after mixing, stir to aluminium isopropoxide complete hydrolysis；Ethyl orthosilicate 10.4g is weighed,
Above-mentioned solution is instilled dropwise under the stirring of 750r/min rotating speeds, obtains A liquid；
(2) 0.56g lauric acid acid sodium is dissolved in 16mL distilled water, 40 DEG C of stirring in water bath, 1 it is small when after, into solution
0.49g (3- mercaptopropyis) trimethoxy silane is added in, obtains B liquid；
(3) B liquid made from step (2) is added rapidly in A liquid made from step (1), adjusts pH=10.2, stirring 2
Hour,
(4) mixed liquor is transferred in 100mL ptfe autoclaves, 170 DEG C of hydro-thermal reactions 0.5 are small under microwave radiation technology
When；Centrifugation, drying when 750 DEG C of roastings 4 are small, remove template agent removing, obtain white powder samples, are high-performance Jie micro-diplopore
Controllable adsorbent of molecular sieve, labeled as A4.
Embodiment 5
The controllable adsorbent of molecular sieve of high-performance Jie's micro-diplopore is prepared according to following steps：
(1) 7.35g tetraethyl ammonium hydroxides (TEAOH, 20% aqueous solution) are added in 20mL distilled water, stirred at room temperature
To aluminium isopropoxide 0.408g is added in after mixing, stir to aluminium isopropoxide complete hydrolysis；Ethyl orthosilicate 10.4g is weighed,
Above-mentioned solution is instilled dropwise under the stirring of 750r/min rotating speeds, obtains A liquid；
(2) 3.48g neopelexes are dissolved in 16mL distilled water, 40 DEG C of stirring in water bath, 1 it is small when after, to
0.55g 3- aminopropyl triethoxysilanes are added in solution, obtain B liquid；
(3) B liquid made from step (2) is added rapidly in A liquid made from step (1), adjusts pH=9.7, stirring 2 is small
When,
(4) mixed liquor is transferred in 100mL ptfe autoclaves, 140 DEG C of hydro-thermal reactions 2 are small under microwave radiation technology
When；Centrifugation, drying when 650 DEG C of roastings 6 are small, remove template agent removing, obtain white powder samples, are high-performance Jie micro-diplopore
Controllable adsorbent of molecular sieve, labeled as A5.
Embodiment 6：Pore passage structure analysis is carried out to the controllable adsorbent of molecular sieve of Jie's micro-diplopore of high absorption property；
Above-described embodiment 3 and the molecular sieve 0.1g prepared by embodiment 5 are taken, when 180 DEG C of degassings 8 are small；Use U.S. Mike
The ASAP2020 physical adsorption appearances of company's production are N to molecular sieve2Adsorption and desorption isotherms, as shown in Figure 1 and Figure 2；Using BET method,
T-plot methods and BJH equation calculations specific surface area, pore volume and pore-size distribution.Specific surface is respectively 478m2/ g and 444m2/ g, total hole
Hold for 0.43cm3/ g and 0.51cm3/g。
Embodiment 7：Adsorption of Toluene analysis is carried out to the controllable adsorbent of molecular sieve of Jie's micro-diplopore of high absorption property；
Above-described embodiment 3 and the molecular sieve 50mg prepared by embodiment 5 are taken, is surveyed using intelligent gravimetric method adsorption instrument IGA002
35 DEG C of Toluene adsorption isotherms are measured, as shown in Figure 3, Figure 4, the results showed that molecular sieve has high adsorption capacity to toluene, reaches
305mg/g and 502mg/g.
Embodiment 8：Hydrophobic performance analysis is carried out to the controllable adsorbent of molecular sieve of Jie's micro-diplopore of high absorption property；
Above-described embodiment 3 and the molecular sieve prepared by embodiment 5 are taken, using Dataphysics, 20 type contact angles of OCA are surveyed
It measures instrument and measures molecular sieve Static water contact angles, the results showed that contact angle is 129 ° and 106 ° during room temperature, illustrates that molecular sieve has height
Hydrophobicity, this is conducive to absorption of the molecular sieve to organic matter in wet environment.
Embodiment 9：Hydrothermally stable performance analysis is carried out to the controllable adsorbent of molecular sieve of Jie's micro-diplopore of high absorption property
Above-described embodiment 3 and the molecular sieve prepared by embodiment 5 are taken, it is dry after being put into when processing 100 is small in boiling water, do nitrogen
Aspiration desorption analysis, step are same as Example 6.It turns out that molecular sieve Adsorption and desorption isotherms almost phase after before and after boiling water treating
Together, specific surface drops to 422m respectively2/ g and 399m2/ g, total pore volume are reduced to 0.39cm3/ g and 0.47cm3/g, the range of decrease are smaller.Explanation
Molecular sieve has good hydrothermal stability.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention and from above-described embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (3)
1. a kind of preparation method of the controllable adsorbent of molecular sieve of high-performance Jie micro-diplopore, which is characterized in that comprise the following steps：With
Silicon source, silicon source, microcellular structure directed agents, mesoporous template, organosilan and water are Material synthesis mother liquor, and mother liquor is auxiliary using microwave
Hydro-thermal reaction is helped, by the product centrifugation for reacting gained, dry, roasting, the controllable molecular sieve of high-performance Jie micro-diplopore is obtained and inhales
Attached dose；
The silicon source is with SiO2Meter, silicon source is with Al2O3Meter, reaction raw materials mol ratio are SiO2:Water=0.025, SiO2:Micropore knot
Structure directed agents=5, SiO2:Al2O3=50~400, SiO2:Organosilan=10~40, SiO2:Mesoporous template=5~20；Institute
Hole template is given an account of as in n-hexadecyl sodium sulfonate, myristyl sodium sulfonate, neopelex and sodium laurate
It is at least one；
The preparation method is as follows：
(1) it is soluble in water that microcellular structure directed agents are weighed, add in silicon source, stirs to silicon source and hydrolyzes；Then add under agitation
Enter silicon source, obtain A liquid；The silicon source is ethyl orthosilicate；Source of aluminium is aluminium isopropoxide；The microcellular structure directed agents are four
At least one of propyl ammonium hydroxide, tetraethyl ammonium hydroxide and ethylenediamine；
(2) weigh mesoporous template to be added to the water, stirring 10~add in organosilan after sixty minutes obtains B liquid；The organosilicon
Alkane be 3- aminopropyl triethoxysilanes, (3- mercaptopropyis) trimethoxy silane and chloropropyl triethoxysilane at least
It is a kind of；
(3) B liquid made from step (2) is added in A liquid made from step (1), adjusts pH value to 8.8~10.2, continue to stir
Mix 1~2 it is small when, obtain mother liquor；
(4) mother liquor made from step (3) is transferred to reaction kettle, microwave hydrothermal reaction, the microwave hydrothermal reaction is 80~170 DEG C
When reaction 0.5~4 is small；By the product centrifugation for reacting gained, dry, roasting, the temperature of the roasting is 450~750 DEG C, roasting
Time for 4~12 it is small when, obtain the controllable adsorbent of molecular sieve of high-performance Jie micro-diplopore.
2. the preparation method of the controllable adsorbent of molecular sieve of high-performance Jie micro-diplopore according to claim 1, which is characterized in that
Dry temperature described in step (4) is 80~110 DEG C, the dry time for 8~for 24 hours.
3. a kind of preparation method system by any one of claim 1 to the 2 controllable adsorbent of molecular sieve of high-performance Jie micro-diplopore
The controllable adsorbent of molecular sieve of high-performance Jie's micro-diplopore obtained.
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| CN106629770B (en) * | 2016-12-25 | 2020-01-10 | 复旦大学 | Synthetic method of mesoporous and microporous zeolite molecular sieve based on dry glue preparation |
| CN106975444A (en) * | 2017-04-27 | 2017-07-25 | 东海岸环境科技无锡有限公司 | A kind of preparation method for the zeolite adsorbent for efficiently separating VOC |
| CN107308983B (en) * | 2017-06-30 | 2019-09-20 | 科比环保科技（天津自贸试验区）有限公司 | Room temperature removes the catalyst and preparation method thereof of interior VOC |
| CN108554388A (en) * | 2018-04-27 | 2018-09-21 | 南通大学 | Jie's micro porouse chitoglycan particle of the particle containing nano-catalytic and its application |
| CN109590010B (en) * | 2018-11-22 | 2021-06-18 | 东北石油大学 | Surface modification method for adjusting shell hydrophobicity of mesoporous core-shell catalyst |
| CN112076725A (en) * | 2019-06-12 | 2020-12-15 | 中国石油化工股份有限公司 | Modified mesoporous molecular sieve, and preparation method and application thereof |
| CN112076726A (en) * | 2019-06-12 | 2020-12-15 | 中国石油化工股份有限公司 | Mesoporous molecular sieve loaded with ionic liquid and preparation method and application thereof |
| CN112723375B (en) * | 2019-10-28 | 2023-02-03 | 中国石油化工股份有限公司 | Y-type molecular sieve and preparation method and application thereof |
| CN111229184B (en) * | 2020-01-19 | 2022-11-08 | 生态环境部华南环境科学研究所 | Silicon source-controllable modified mesoporous and microporous adsorbent and preparation method and application thereof |
| CN113198433B (en) * | 2021-03-30 | 2022-11-11 | 天津大学 | Molecular sieve and porous organic polymer core-shell structure composite adsorbent and preparation method thereof |
| CN114768748A (en) * | 2022-04-22 | 2022-07-22 | 山东亮剑环保新材料有限公司 | Preparation method of all-silicon micro-mesoporous composite molecular sieve VOCs adsorbent |
| CN116328739A (en) * | 2023-02-22 | 2023-06-27 | 东洋和光净化材料(江苏)有限公司 | Hydrophobic VOC adsorbent and production method thereof |
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| CN102530980A (en) * | 2012-01-13 | 2012-07-04 | 大连理工大学 | Hierarchical zeolite, preparation and application thereof |
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| C7碳氢化合物在纳米级介孔ZSM-5 沸石中的扩散性能;刘芝平等;《化工进展》;20141231;第33卷(第10期);第2711-2715、2721页 * |
| 多级孔道ZSM-5的合成及其催化应用;刘斯宝;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20121015(第10期);第B016-447页 * |
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