CN110156038A - A kind of micropore-mesopore-macropore multi-stage porous SBA-15 molecular sieve and its preparation method and application - Google Patents
A kind of micropore-mesopore-macropore multi-stage porous SBA-15 molecular sieve and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of micropore-mesopore-macropore multi-stage porous SBA-15 molecular sieves and its preparation method and application.The total specific surface area of the micropore-mesopore-macropore multi-stage porous SBA-15 molecular sieve is 792.4~970.5m2/ g, micropore specific area are 92.8~203.6m2/ g, mesopore surface area are 472.8~571.3m2/ g, big pore specific surface area are 97.0~294.1m2/ g, average pore size are 6.5~14.7nm.The present invention realizes micropore, mesoporous and macropore constructing in SBA-15 molecular sieve, has been effectively retained the micro-porous adsorption site of molecular sieve, while improving molecular sieve to the circulation diffusion of large scale guest molecule；Gained molecular screen material is in biomass hydrolysate detoxification purification, CO2The absorption such as hydro-conversion or syngas catalytic conversion and catalytic field have preferable application potential.
Description
Technical field:
The present invention relates to Zeolite synthesis technical fields, and in particular to micropore-mesopore-macropore multi-stage porous SBA-15 points a kind of
Son sieve and its preparation method and application.
Background technique:
SBA-15 molecular sieve is a kind of with two-dimentional hexagonal hole road structure and the good mesoporous material of order, usually used
Nonionic triblock copolymer --- polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer P123
(EO20PO70EO20) it is that template is made through hydrothermal synthesis.By conditions such as change synthesis temperature, acid concentrations, or introduces other and change
Property agent or template may be implemented SBA-15 pattern and pore size controllable adjustment (Chemistry of Materials,
2000,12(2):275–279).SBA-15 molecular sieve has a mesopore orbit of high-sequential, biggish specific surface area and good
Hydrothermal stability, make its catalysis, absorption, measure with separate, drug conveying and nano-functional material field have it is extensive
Application prospect.
In the synthesis process of SBA-15 molecular sieve, due to the structure-directing effect of P123 template, hydrophily is stronger
EO chain can generate the micropore perpendicular to hexagonal hole road, penetrate silicon wall, leave micropore after calcining.Silicon source and P123 mould in starting material
The ratio of plate agent can have an impact network of the siloxanes in hole wall, so that micropore be made to change.This diplopore body
System makes SBA-15 material become the ideal chose adsorbed with catalytic applications.With the expansion of application field, in order to make bigger point
Son is able to enter duct, and the SBA-15 for possessing more large aperture has more advantage in the application.
Currently, the main path in the regulation aperture SBA-15 includes: chain length, the chemical structure that (1) changes copolymer；(2) change
Become starting material, such as the ratio of P123 and silicon source；(3) change reaction condition, such as reaction temperature, crystallization temperature；(4) cosolvent
Use, such as N-N- dimethylformamide (DMF)；(4) addition of expanding agent, such as alkane, mesitylene (TMB)；(5) it uses
Different synthetic methods.The TMB that Wang etc. is 1:1 by the addition in starting material and P123 mass ratio, and in crystallization
SBA-15 is carried out afterwards so that its average pore size is increased to 12nm by 3.6nm close to 200 DEG C of drying process, effectively improves metal
Load capacity (Catalysis Today, 2001,68 (1-3): 3-9s) of the Co in the duct SBA-15.However, the expansion of these methods
Hole effect is limited, and focuses primarily upon the research of mesoporous single-stage hole SBA-15 molecular sieve.In comparison, with hierarchical porous structure
SBA-15 molecular sieve has both the advantages that permeability is good, pore structure is flourishing, specific surface area and pore volume are big, is used as catalyst carrier
When diffuser efficiency of the reaction molecular in duct can be improved, to improve the transmission efficiency of substance in catalytic process.Pass through increasing
The molar ratio of TMB and P123 is 7.5 in big starting material, and the average pore size of SBA-15 molecular sieve can be made to be increased to by 12.5nm
22.7nm, at the same have small mesoporous-big mesopore-macropore this hierarchical porous structure (Langmuir, 2017,33:10632-
10644).But expanding agent TMB's is excessively added the loss that will lead to SBA-15 microporous molecular sieve, to make SBA-15 molecular sieve
Adsorption site greatly reduces.Currently, the controlledly synthesis of existing multi-stage porous SBA-15 molecular sieve is limited only to the shape of mesopore-macropore
At being provided simultaneously with micropore-mesopore-macropore hierarchical porous structure SBA-15 molecular sieve and not yet have been reported that.
Summary of the invention:
The object of the present invention is to provide a kind of micropore-mesopore-macropore hierarchical porous structure SBA-15 molecular sieve and its preparations
Methods and applications, the present invention realize micropore, mesoporous and macropore constructing in SBA-15 molecular sieve, have been effectively retained molecular sieve
Micro-porous adsorption site, while molecular sieve is improved to the circulation diffusion of large scale guest molecule.
The present invention is achieved by the following technical programs:
A kind of micropore-mesopore-macropore multi-stage porous SBA-15 molecular sieve, the micropore-mesopore-macropore multi-stage porous SBA-15
Total specific surface area of molecular sieve is 792.4~970.5m2/ g, micropore specific area are 92.8~203.6m2/ g, mesoporous specific surface
Product is 472.8~571.3m2/ g, big pore specific surface area are 97.0~294.1m2/ g, average pore size are 6.5~14.7nm.
Above-mentioned micropore-mesopore-macropore multi-stage porous SBA-15 molecular sieve preparation method, comprising the following steps:
(1) after mixing evenly by soft template P123, deionized water, mixed in hydrochloric acid, hard mould agent stirring is added, adds
Ethyl orthosilicate continues to stir, and obtains mixed solution；
(2) mixed solution that step (1) obtains is transferred to progress hydro-thermal reaction in reaction vessel and obtains molecular screen material,
The molecular screen material is through being filtered, washed to neutrality, and after drying, roasting, it is more to obtain the micropore-mesopore-macropore
Grade hole SBA-15 molecular sieve.
The present invention prepares micropore-mesopore-macropore multi-stage porous SBA-15 molecular sieve principle are as follows: contains hydrophilic and hydrophobic in both ends
The soft template P123 of group as meso-hole structure directed agents, 3DOM PMMA in dura mater plate agent as macroporous structure directed agents,
The neutral ethyl orthosilicate of addition and P123 are by hydrogen bond and electrostatic interaction, with the hydrolysis of silanol, condensation course,
Mesoporous framework structure is formed in the macropore of PMMA being mutually communicated.Polystyrene macroporous absorbent resin or acrylate modified benzene second
On the one hand alkene system macroporous absorbent resin is used as macroporous structure directed agents, further enhance the formation of mesopore-macropore skeleton structure, separately
On the one hand hydrophilic, the hydrophobic functional group for utilizing resin surface, play adjustment effect to the formation of micropore in mesopore-macropore hole wall.
Template agent removing is removed eventually by high-temperature roasting, micropore-mesopore-macropore multi-stage porous SBA-15 molecular sieve is prepared.
Above-mentioned micropore-mesopore-macropore multi-stage porous SBA-15 molecular sieve preparation method, specifically comprises the following steps:
(1) soft template P123, deionized water, hydrochloric acid are mixed according to the molar ratio of 1:9500~10000:350~1000
After conjunction, 3~6h is stirred at 35 DEG C~40 DEG C, hard mould agent is added and stirs 10~60min, is instilled ethyl orthosilicate dropwise and is continued
20~30h is stirred, obtains mixed solution, the molar ratio of the ethyl orthosilicate and soft template is 55~65:1；
(2) mixed solution that step (1) obtains is transferred in reaction vessel, the hydro-thermal reaction 24 at 100 DEG C~150 DEG C
~48h obtains molecular screen material, and the molecular screen material is washed through filtering, deionized water to neutrality, then through drying, roasting
Afterwards, the micropore-mesopore-macropore multi-stage porous SBA-15 molecular sieve is obtained.
Hydrochloric acid used in the present invention is the aqueous hydrochloric acid solution that mass fraction is 20%~60%.
Preferably, the mass ratio of the hard mould agent and soft template P123 are 1:1~5.
Preferably, the hard mould agent is by three-dimensional ordered macroporous polymethyl methacrylate (3DOM PMMA) and benzene
Ethylene system macroporous absorbent resin or the mixing of acrylate modified polystyrene macroporous absorbent resin are constituted, and the three-dimensional order is big
Hole polymethyl methacrylate and polystyrene macroporous absorbent resin or acrylate modified polystyrene macroporous absorbent resin
Mass ratio is 1:0.5~1.
Preferably, the three-dimensional ordered macroporous polymethyl methacrylate has by centrifugation self-assembly method preparation, three-dimensional
The partial size of sequence macropore polymethyl methacrylate is 200~800nm；The polystyrene macroporous absorbent resin is poly- by suspending
Legal preparation, polystyrene macroporous absorbent resin aperture are 50~200nm.
The three-dimensional ordered macroporous polymethyl methacrylate reference literature (Journal of Catalysis, 2013,
307:327-339) by centrifugation self-assembly method preparation, partial size is 200~800nm.The polystyrene macroporous absorbent resin
It is prepared referring to patent CN107417842A by suspension polymerization, the acrylate modified polystyrene macroporous absorbent resin ginseng
It is prepared according to patent CN108355626A by suspension polymerization, polystyrene macroporous absorption may be implemented by optimizing preparation parameter
The aperture of resin or acrylate modified polystyrene macroporous absorbent resin is adjusted within the scope of 50~200nm.
Preferably, the acrylate is selected from methyl methacrylate, methyl acrylate, ethyl acrylate, acrylic acid
One of butyl ester, hydroxy-ethyl acrylate and glycidyl acrylate.
The present invention also protect the micropore-mesopore-macropore multi-stage porous SBA-15 molecular sieve syngas catalytic conversion,
CO2The application of hydro-conversion or biomass hydrolysate detoxification purification.
Compared with prior art, the beneficial effects of the present invention are:
(1) present invention realizes micropore, mesoporous and macropore constructing in SBA-15 molecular sieve, has been effectively retained molecular sieve
Micro-porous adsorption site, while molecular sieve is improved to the circulation diffusion of large scale guest molecule.
(2) by changing the mass ratio of soft template and hard mould agent, it is multistage that micropore-mesopore-macropore can effectively be adjusted
The size and distribution in duct at different levels in the SBA-15 molecular sieve of hole realize it in different absorption and the application of catalytic field.
Detailed description of the invention:
Fig. 1 a is the scanning electron microscope (SEM) photograph for the SBA-15 molecular sieve being prepared in the embodiment of the present invention 1, wherein Fig. 1 a1It is
The SBA-15 molecular sieve being prepared in embodiment 1 amplifies 100,000 times of scanning electron microscope (SEM) photograph, Fig. 1 a2It is to be prepared into embodiment 1
To SBA-15 molecular sieve amplify 200,000 times of scanning electron microscope (SEM) photograph；
Fig. 1 b is the small angle X-ray diffraction figure for the SBA-15 molecular sieve being prepared in the embodiment of the present invention 1；
Fig. 1 c is the N for the SBA-15 molecular sieve being prepared in the embodiment of the present invention 12Adsorption-desorption isothermal；
Fig. 1 d is the micropore size distribution map for the SBA-15 molecular sieve being prepared in the embodiment of the present invention 1；
Fig. 1 e is the mesoporous pore size distribution map for the SBA-15 molecular sieve being prepared in the embodiment of the present invention 1；
Fig. 2 a is the scanning electron microscope (SEM) photograph for the SBA-15 molecular sieve being prepared in the embodiment of the present invention 2, wherein Fig. 2 a1It is
The SBA-15 molecular sieve being prepared in embodiment 2 amplifies 100,000 times of scanning electron microscope (SEM) photograph, Fig. 2 a2It is to be prepared into embodiment 2
To SBA-15 molecular sieve amplify 150,000 times of scanning electron microscope (SEM) photograph；
Fig. 2 b is the small angle X-ray diffraction figure for the SBA-15 molecular sieve being prepared in the embodiment of the present invention 2；
Fig. 2 c is the N for the SBA-15 molecular sieve being prepared in the embodiment of the present invention 22Adsorption-desorption isothermal；
Fig. 2 d is the mesoporous pore size distribution map for the SBA-15 molecular sieve being prepared in the embodiment of the present invention 2.
Specific embodiment:
It is to further explanation of the invention, rather than limiting the invention below.
Embodiment 1
According to P123: deionized water: the molar ratio of hydrochloric acid is that 1:9500:350 uniformly mixes P123, deionized water and hydrochloric acid
After conjunction, 3h is stirred at 40 DEG C, and the 3DOM PMMA and polystyrene-divinylbenzene that are 1:4 with P123 mass ratio is then added
The mixture of macroporous absorbent resin (mass ratio of 3DOM PMMA and polystyrene-divinylbenzene macroporous absorbent resin is 1:1)
10min is stirred, the ethyl orthosilicate for instilling 58.5 times of P123 molal quantitys dropwise continues stirring for 24 hours, obtains mixed solution；This is mixed
Close solution be transferred in high-pressure hydrothermal reaction kettle, at 100 DEG C hydro-thermal reaction for 24 hours, gained molecular screen material be filtered, washed to
After neutrality, in 100 DEG C of dry 12h, most afterwards after the rate of 2 DEG C/min is warming up to 500 DEG C of roasting 8h, it is big to obtain micropore-mesopore-
Hole multi-stage porous SBA-15 molecular sieve.
The micropore-mesopore-macropore multi-stage porous SBA-15 molecular sieve scanning electron microscope (SEM) photograph, small angle X-ray diffraction figure, N2It inhales
Attached-desorption isotherm, micropore size distribution map and mesoporous pore size distribution map are as shown in Figure 1.As can be seen that gained SBA-15 molecule
Sifter device has the Different Pore Structures such as micropore, mesoporous and macropore, and typical (100), (110) and (200) the crystal face peak SBA-15 is apparent.
The N of SBA-15 molecular sieve2Adsorption-desorption isothermal belongs to Section IV type adsorption isotherm, and thermoisopleth hysteresis loop belongs to H1 type.SBA-
The micropore size of 15 molecular sieves is concentrated mainly on 0.83nm or so, and mesoporous pore size is concentrated mainly on 6.6nm, and macropore diameter mainly collects
In in 159.6nm.
Application examples
Referring to the embodiment 4 of 102319575 B of patent CN, SBA-15 molecular sieve obtained by this implementation is carried as catalyst
Body load preparation has the Cu-Fe base catalyst of same composition, in pressure 5.5MPa, 320 DEG C of temperature, and air speed 6000h-1, H2/CO
When=2.0, the space-time yield of gained mixed alcohol is 316.0g (kgh)-1, C5+Alcohol content is 52.4wt%, respectively SiO2It is negative
Carry 1.84 times and 2.18 times of Cu-Fe base catalyst.
Embodiment 2
According to P123: deionized water: the molar ratio of hydrochloric acid is that 1:10000:650 is uniform by P123, deionized water and hydrochloric acid
After mixing, 5h is stirred at 38 DEG C, and the 3DOM PMMA and glycidyl acrylate that are 1:3 with P123 mass ratio is then added
(3DOM PMMA and glycidyl acrylate are modified poly- for modified polystyrene-divinylbenzene macroporous absorbent resin mixture
The mass ratio of styrene-divinylbenzene macroporous absorbent resin is 1:0.5) stirring 30min, 55 times of P123 molal quantitys are instilled dropwise
Ethyl orthosilicate continue stir 30h, obtain mixed solution；The mixed solution is transferred in high-pressure hydrothermal reaction kettle, 120
Hydro-thermal reaction 26h at DEG C, gained molecular screen material is through being filtered, washed to neutrality, in 80 DEG C of dry 10h, most afterwards through 1 DEG C/min
Rate be warming up to 550 DEG C of roasting 4h after, obtain micropore-mesopore-macropore multi-stage porous SBA-15 molecular sieve.
The micropore-mesopore-macropore multi-stage porous SBA-15 molecular sieve scanning electron microscope (SEM) photograph, small angle X-ray diffraction figure, N2It inhales
Attached-desorption isotherm, micropore size distribution map and mesoporous pore size distribution map are as shown in Figure 2.As can be seen that gained SBA-15 molecule
Sifter device has the Different Pore Structures such as significant micropore, mesoporous and macropore, and macropore duct is abundant.(100) of SBA-15 molecular sieve,
(110) and (200) crystal face peak is more apparent.The N of SBA-15 molecular sieve2Adsorption-desorption isothermal belongs to Section IV type adsorption isotherm,
Thermoisopleth hysteresis loop belongs to H1 type.The mesoporous pore size of SBA-15 molecular sieve is concentrated mainly on 6.6nm, and macropore diameter is concentrated mainly on
174nm。
Application examples
Referring to the embodiment 1 of 104815664 B of patent CN, SBA-15 molecular sieve obtained by this implementation is carried as catalyst
Body load preparation has the Cu-Zn-Fe base catalyst of same composition, in pressure 2.0MPa, 400 DEG C of temperature, and air speed 6000h-1,
H2/CO2When=2.0, CO2Conversion ratio is 42.7%, and low-carbon alcohols yield is 0.39g/mLcatH, respectively attapulgite/cerium zirconium
1.47 times and 1.56 times of solid solution composite material loaded Cu-Zn-Fe base catalyst.
Embodiment 3
According to P123: deionized water: the molar ratio of hydrochloric acid is that 1:9800:1000 is uniform by P123, deionized water and hydrochloric acid
After mixing, 6h is stirred at 35 DEG C, is then added modified poly- for the 3DOM PMMA and methyl acrylate of 1:1 with P123 mass ratio
Mixture (3DOM PMMA and the methyl acrylate modified polystyrene-diethyl of styrene-divinylbenzene macroporous absorbent resin
The mass ratio of alkenyl benzene macroporous absorbent resin is 1:0.8) stirring 60min, the positive silicic acid second of 65 times of P123 molal quantitys is instilled dropwise
Ester continues to stir 20h, obtains mixed solution；The mixed solution is transferred in high-pressure hydrothermal reaction kettle, hydro-thermal is anti-at 135 DEG C
48h is answered, gained molecular screen material is through being filtered, washed to neutrality, in 120 DEG C of dry 6h, most afterwards through the rate liter of 1.5 DEG C/min
After temperature to 600 DEG C of roasting 6h, micropore-mesopore-macropore multi-stage porous SBA-15 molecular sieve is obtained.
Application examples
Referring to the embodiment 1 of 102719490 B of patent CN, using cetyl trimethylammonium bromide (CTAB) to this reality
It is organically-modified to apply gained SBA-15 molecular sieve progress, prepares corn stover acid vapors explosion pre-hydrolyzed solution referring to embodiment 7, makes
Detoxification treatment carried out under the same conditions to the hydrolysis sugar liquid with modified SBA-15 molecular sieve, after adsorption treatment, in hydrolyzate
Hydroxymethylfurfural and total phenol removal rate are respectively 71.5% and 67.3%, respectively the 1.36 of CTAB modified alta-mud times and 1.18
Times.
Embodiment 4
According to P123: deionized water: the molar ratio of hydrochloric acid is that 1:9680:800 uniformly mixes P123, deionized water and hydrochloric acid
After conjunction, 4h is stirred at 40 DEG C, is then added modified poly- for the 3DOM PMMA and hydroxy-ethyl acrylate of 1:5 with P123 mass ratio
Mixture (3DOM PMMA and the hydroxy-ethyl acrylate modified polystyrene-two of styrene-divinylbenzene macroporous absorbent resin
The mass ratio of vinyl benzene macroporous absorbent resin is 1:0.6) stirring 40min, the positive silicic acid of 60 times of P123 molal quantitys is instilled dropwise
Ethyl ester continues to stir 26h, obtains mixed solution；The mixed solution is transferred in high-pressure hydrothermal reaction kettle, the hydro-thermal at 150 DEG C
36h is reacted, gained molecular screen material is through being filtered, washed to neutrality, in 105 DEG C of dry 8h, most afterwards through the rate liter of 1 DEG C/min
After temperature to 500 DEG C of roasting 8h, micropore-mesopore-macropore multi-stage porous SBA-15 molecular sieve is obtained.
Table 1 is each micropore-mesopore-macropore multi-stage porous SBA-15 molecular sieve texture prepared in above-described embodiment 1~4
Energy tables of data, in which: SBETIndicate total specific surface area, SMicroIndicate micropore specific area, SMesoIndicate mesopore surface area,
SMacroIndicate big pore specific surface area；VTotalIndicate total pore volume, VMicroIndicate Micropore volume, SMesoIndicate mesoporous Kong Rong, SMacroTable
Show that macropore hole holds.
Table 1
It is obtained by table 1, the SBA-15 molecular sieve that Examples 1 to 4 is prepared, micropore, mesoporous and macropore may be implemented
It constructs simultaneously.The total specific surface area of micropore-mesopore-macropore multi-stage porous SBA-15 molecular sieve is 792.4~970.5m2/ g, micropore
Specific surface area is 92.8~203.6m2/ g, mesopore surface area are 472.8~571.3m2/ g, big pore specific surface area be 97.0~
294.1m2/g；Total pore volume is 1.275~1.503cc/g, and Micropore volume is 0.054~0.271cc/g, mesoporous Kong Rongwei 0.845
~1.208m2/ g, it is 0.086~0.387cc/g that macropore hole, which holds,；Average pore size is 6.5~14.7nm.By changing soft template
With the mass ratio of hard mould agent, it can effectively adjust micropore in multi-stage porous SBA-15 molecular sieve, mesoporous and macropore size and divide
Cloth.
The above is only the preferred embodiment of the present invention, it is noted that above-mentioned preferred embodiment is not construed as pair
Limitation of the invention, protection scope of the present invention should be defined by the scope defined by the claims..For the art
For those of ordinary skill, without departing from the spirit and scope of the present invention, several improvements and modifications can also be made, these change
It also should be regarded as protection scope of the present invention into retouching.
Claims (9)
1. a kind of micropore-mesopore-macropore multi-stage porous SBA-15 molecular sieve, which is characterized in that the micropore-mesopore-macropore is more
Total specific surface area of grade hole SBA-15 molecular sieve is 792.4~970.5m2/ g, micropore specific area are 92.8~203.6m2/ g,
Mesopore surface area is 472.8~571.3m2/ g, big pore specific surface area are 97.0~294.1m2/ g, average pore size be 6.5~
14.7nm。
2. a kind of micropore-mesopore described in claim 1-macropore multi-stage porous SBA-15 molecular sieve preparation method, feature exist
In, comprising the following steps:
(1) after mixing evenly by soft template P123, deionized water, mixed in hydrochloric acid, hard mould agent stirring is added, adds positive silicon
Acetoacetic ester continues to stir, and obtains mixed solution；
(2) mixed solution that step (1) obtains is transferred to progress hydro-thermal reaction in reaction vessel and obtains molecular screen material, it is described
Molecular screen material be filtered, washed to neutrality, then after drying, roasting, obtain the micropore-mesopore-macropore multi-stage porous
SBA-15 molecular sieve.
3. micropore-mesopore according to claim 2-macropore multi-stage porous SBA-15 molecular sieve preparation method, feature exist
In specifically comprising the following steps:
(1) after soft template P123, deionized water, hydrochloric acid being mixed according to the molar ratio of 1:9500~10000:350~1000,
3~6h is stirred at 35 DEG C~40 DEG C, hard mould agent is added and stirs 10~60min, is instilled ethyl orthosilicate dropwise and is continued to stir
20~30h, obtains mixed solution, and the molar ratio of the ethyl orthosilicate and soft template is 55~65:1；
(2) mixed solution that step (1) obtains is transferred in reaction vessel, at 100 DEG C~150 DEG C hydro-thermal reaction 24~
48h obtains molecular screen material, and the molecular screen material is through being filtered, washed to neutrality, after drying, roasting, obtains described
Micropore-mesopore-macropore multi-stage porous SBA-15 molecular sieve.
4. micropore-mesopore according to claim 2 or 3-macropore multi-stage porous SBA-15 molecular sieve preparation method, feature
It is, the mass ratio of the hard mould agent and soft template P123 are 1:1~5.
5. micropore-mesopore according to claim 2 or 3-macropore multi-stage porous SBA-15 molecular sieve preparation method, feature
It is, the hard mould agent is by three-dimensional ordered macroporous polymethyl methacrylate and polystyrene macroporous absorbent resin or third
The ester modified polystyrene macroporous absorbent resin mixing of olefin(e) acid is constituted, the three-dimensional ordered macroporous polymethyl methacrylate and benzene
The mass ratio of ethylene system macroporous absorbent resin or acrylate modified polystyrene macroporous absorbent resin is 1:0.5~1.
6. micropore-mesopore according to claim 5-macropore multi-stage porous SBA-15 molecular sieve preparation method, feature exist
In the three-dimensional ordered macroporous polymethyl methacrylate passes through centrifugation self-assembly method preparation, three-dimensional ordered macroporous poly- methyl
The partial size of methyl acrylate is 200~800nm；The polystyrene macroporous absorbent resin is prepared by suspension polymerization, benzene
Ethylene system macroporous absorbent resin aperture is 50~200nm.
7. micropore-mesopore according to claim 5-macropore multi-stage porous SBA-15 molecular sieve preparation method, feature exist
In the acrylate is selected from methyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, acrylic acid hydroxyl
One of ethyl ester and glycidyl acrylate.
8. micropore-mesopore described in claim 1-macropore multi-stage porous SBA-15 molecular sieve is in syngas catalytic conversion, CO2Add hydrogen
The application of conversion or biomass hydrolysate detoxification purification.
9. micropore-mesopore-macropore multi-stage porous SBA-15 molecular sieve of the described in any item preparation method preparations of claim 2~7
In syngas catalytic conversion, CO2The application of hydro-conversion or biomass hydrolysate detoxification purification.
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