CN110156038B - Microporous-mesoporous-macroporous hierarchical pore SBA-15 molecular sieve and preparation method and application thereof - Google Patents
Microporous-mesoporous-macroporous hierarchical pore SBA-15 molecular sieve and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a microporous-mesoporous-macroporous hierarchical pore SBA-15 molecular sieve and a preparation method and application thereof. The total specific surface area of the microporous-mesoporous-macroporous hierarchical pore SBA-15 molecular sieve is 792.4-970.5 m2The specific surface area of the micropores is 92.8-203.6 m2The specific surface area of the mesoporous is 472.8-571.3 m2The specific surface area of the macropore is 97.0-294.1 m2(iv)/g, the average pore diameter is 6.5 to 14.7 nm. The invention realizes the construction of micropores, mesopores and macropores in the SBA-15 molecular sieve, effectively reserves the micropore adsorption sites of the molecular sieve and simultaneously improves the circulation diffusion performance of the molecular sieve to large-size object molecules; the obtained molecular sieve material is detoxified and refined in biomass hydrolysate, and CO is obtained2The catalyst has better application potential in the adsorption and catalysis fields of hydroconversion or catalytic conversion of synthesis gas and the like.
Description
The technical field is as follows:
the invention relates to the technical field of molecular sieve synthesis, in particular to a microporous-mesoporous-macroporous hierarchical pore SBA-15 molecular sieve and a preparation method and application thereof.
Background art:
the SBA-15 molecular sieve is a mesoporous material with a two-dimensional hexagonal pore structure and good orderliness, and a nonionic triblock copolymer, namely a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer P123 (EO) is generally used20PO70EO20) Is prepared by hydrothermal synthesis of a template agent. Controllable regulation of SBA-15 morphology and pore size can be achieved by changing conditions such as synthesis temperature, acid concentration, etc., or introducing other modifiers or templates (Chemistry of Materials,2000,12(2): 275-279). The SBA-15 molecular sieve has highly ordered mesoporous pore canals, larger specific surface area and good hydrothermal stability, so that the catalyst is catalyzedThe method has wide application prospect in the fields of chemical reaction, adsorption, determination and separation, drug delivery and nano functional materials.
In the synthesis process of the SBA-15 molecular sieve, because of the structure guiding effect of the P123 template, the EO chain with stronger hydrophilicity can generate micropores vertical to the hexagonal pore channels, penetrate through the silicon wall, and leave the micropores after calcination. The ratio of silicon source to P123 template in the starting material affects the network of siloxane in the pore walls, thereby changing the pore size of the micropores. This dual pore system makes SBA-15 materials an ideal choice for adsorption and catalytic applications. With the expansion of the application field, in order to enable larger molecules to enter the pore channels, the SBA-15 with larger pore diameters is more advantageous in application.
Currently, the major pathways for controlling SBA-15 pore size include: (1) changing the chain length and the chemical structure of the copolymer; (2) changing the ratio of starting materials, such as P123 to silicon source; (3) changing reaction conditions, such as reaction temperature, crystallization temperature and the like; (4) the use of co-solvents such as N-Dimethylformamide (DMF); (4) addition of pore-expanding agents, such as alkanes, mesitylene (TMB), etc.; (5) different synthetic methods were used. Wang et al prepared by adding to the starting material a mixture of P123: 1, and drying the SBA-15 at the temperature close to 200 ℃ after the crystallization reaction to increase the average pore diameter from 3.6nm to 12nm, thereby effectively improving the loading of metal Co in the pores of the SBA-15 (Catalysis Today,2001,68(1-3): 3-9). However, the pore-expanding effect of these methods is limited, and the research mainly focuses on mesoporous single-stage pore SBA-15 molecular sieves. In comparison, the SBA-15 molecular sieve with the hierarchical pore structure has the advantages of good permeability, developed pore structure, large specific surface area and pore volume and the like, and can improve the diffusion efficiency of reaction molecules in pores when used as a catalyst carrier, thereby improving the transfer efficiency of substances in the catalytic process. By increasing the molar ratio of TMB to P123 in the starting material to 7.5, the average pore diameter of the SBA-15 molecular sieve can be increased from 12.5nm to 22.7nm, and the molecular sieve has a hierarchical pore structure of small mesopores, large mesopores and large macropores (Langmuir,2017,33: 10632-10644). However, excessive addition of the pore-expanding agent TMB can cause loss of micropores of the SBA-15 molecular sieve, so that adsorption sites of the SBA-15 molecular sieve are greatly reduced. At present, the controllable synthesis of the existing hierarchical pore SBA-15 molecular sieve is only limited to the formation of mesopores and macropores, and the SBA-15 molecular sieve with a micropore-mesopore-macropore hierarchical pore structure is not reported.
The invention content is as follows:
the invention aims to provide an SBA-15 molecular sieve with a micropore-mesopore-macropore hierarchical pore structure, a preparation method and application thereof, and the invention realizes the construction of micropores, mesopores and macropores in the SBA-15 molecular sieve, effectively reserves micropore adsorption sites of the molecular sieve, and simultaneously improves the flow diffusion performance of the molecular sieve to large-size guest molecules.
The invention is realized by the following technical scheme:
the microporous-mesoporous-macroporous hierarchical pore SBA-15 molecular sieve is characterized in that the total specific surface area of the microporous-mesoporous-macroporous hierarchical pore SBA-15 molecular sieve is 792.4-970.5 m2The specific surface area of the micropores is 92.8-203.6 m2The specific surface area of the mesoporous is 472.8-571.3 m2The specific surface area of the macropore is 97.0-294.1 m2(iv)/g, the average pore diameter is 6.5 to 14.7 nm.
The preparation method of the microporous-mesoporous-macroporous hierarchical pore SBA-15 molecular sieve comprises the following steps:
(1) uniformly mixing and stirring the soft template agent P123, deionized water and hydrochloric acid, adding the hard template agent, stirring, adding tetraethoxysilane, and continuously stirring to obtain a mixed solution;
(2) and (2) transferring the mixed solution obtained in the step (1) to a reaction vessel for hydrothermal reaction to obtain a molecular sieve material, filtering and washing the molecular sieve material to be neutral, drying and roasting to obtain the microporous-mesoporous-macroporous hierarchical pore SBA-15 molecular sieve.
The principle of preparing the microporous-mesoporous-macroporous hierarchical pore SBA-15 molecular sieve comprises the following steps: the soft template agent P123 with hydrophilic and hydrophobic groups at two ends is used as a mesoporous structure guiding agent, 3DOM PMMA in the hard template agent is used as a macroporous structure guiding agent, the added neutral tetraethoxysilane and the P123 interact with each other through hydrogen bonds and static electricity, and a mesoporous framework structure is formed in mutually communicated macropores of the PMMA along with the hydrolysis and condensation processes of silanol. The styrene series macroporous adsorption resin or the acrylate modified styrene series macroporous adsorption resin is used as a macroporous structure directing agent to further enhance the formation of a mesoporous-macroporous skeleton structure, and is used for regulating the formation of micropores in the wall of the mesoporous-macroporous hole by utilizing hydrophilic and hydrophobic functional groups on the surface of the resin. And finally, removing the template agent through high-temperature roasting to prepare the microporous-mesoporous-macroporous hierarchical pore SBA-15 molecular sieve.
The preparation method of the microporous-mesoporous-macroporous hierarchical pore SBA-15 molecular sieve specifically comprises the following steps:
(1) mixing a soft template agent P123, deionized water and hydrochloric acid according to the weight ratio of 1: 9500-10000: mixing at a molar ratio of 350-1000, stirring for 3-6 h at 35-40 ℃, adding a hard template agent, stirring for 10-60 min, dropwise adding ethyl orthosilicate, and continuously stirring for 20-30 h to obtain a mixed solution, wherein the molar ratio of the ethyl orthosilicate to the soft template agent is 55-65: 1;
(2) and (2) transferring the mixed solution obtained in the step (1) into a reaction container, carrying out hydrothermal reaction for 24-48 h at 100-150 ℃ to obtain a molecular sieve material, filtering the molecular sieve material, washing the molecular sieve material with deionized water to be neutral, drying and roasting to obtain the microporous-mesoporous-macroporous hierarchical pore SBA-15 molecular sieve.
The hydrochloric acid used in the invention is a 20-60% hydrochloric acid aqueous solution by mass fraction.
Preferably, the mass ratio of the hard template agent to the soft template agent P123 is 1: 1 to 5.
Preferably, the hard template agent is formed by mixing three-dimensional ordered macroporous polymethyl methacrylate (3DOM PMMA) and styrene macroporous adsorption resin or acrylate modified styrene macroporous adsorption resin, wherein the mass ratio of the three-dimensional ordered macroporous polymethyl methacrylate to the styrene macroporous adsorption resin or acrylate modified styrene macroporous adsorption resin is 1: 0.5 to 1.
Preferably, the three-dimensional ordered macroporous polymethyl methacrylate is prepared by a centrifugal self-assembly method, and the particle size of the three-dimensional ordered macroporous polymethyl methacrylate is 200-800 nm; the styrene macroporous adsorption resin is prepared by a suspension polymerization method, and the pore diameter of the styrene macroporous adsorption resin is 50-200 nm.
The three-dimensional ordered macroporous polymethyl methacrylate reference literature (Journal of Catalysis,2013,307: 327-339) is prepared by a centrifugal self-assembly method, and the particle size is 200-800 nm. The styrene macroporous adsorption resin is prepared by a suspension polymerization method according to a patent CN107417842A, the acrylate modified styrene macroporous adsorption resin is prepared by a suspension polymerization method according to a patent CN108355626A, and the pore diameter of the styrene macroporous adsorption resin or the acrylate modified styrene macroporous adsorption resin can be adjusted within the range of 50-200 nm by optimizing preparation parameters.
Preferably, the acrylate is selected from one of methyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, hydroxyethyl acrylate and glycidyl acrylate.
The invention also protects the microporous-mesoporous-macroporous hierarchical pore SBA-15 molecular sieve from catalytic conversion of synthesis gas and CO2Hydrogenation conversion or biomass hydrolysate detoxification refining.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention realizes the construction of micropores, mesopores and macropores in the SBA-15 molecular sieve, effectively reserves micropore adsorption sites of the molecular sieve and simultaneously improves the circulation diffusion performance of the molecular sieve to large-size object molecules.
(2) By changing the mass ratio of the soft template agent to the hard template agent, the sizes and the distribution of all levels of pore channels in the microporous-mesoporous-macroporous SBA-15 molecular sieve can be effectively adjusted, and the application of the molecular sieve in different adsorption and catalysis fields is realized.
Description of the drawings:
FIG. 1a is a scanning electron micrograph of an SBA-15 molecular sieve prepared in example 1 of the present invention, wherein FIG. 1a1Is a scanning electron micrograph of the SBA-15 molecular sieve prepared in example 1 at 10 ten thousand times magnification, FIG. 1a2Is a scanning electron micrograph of the SBA-15 molecular sieve prepared in example 1, magnified 20 ten thousand times;
FIG. 1b is a small angle X-ray diffraction pattern of the SBA-15 molecular sieve prepared in example 1 of the present invention;
FIG. 1c is a diagram showing the N content of the SBA-15 molecular sieve prepared in example 1 of the present invention2Adsorption-desorption isotherms;
FIG. 1d is a pore size distribution diagram of the SBA-15 molecular sieve prepared in example 1 of the present invention;
FIG. 1e is a mesoporous distribution diagram of the SBA-15 molecular sieve prepared in example 1 of the present invention;
FIG. 2a is a scanning electron micrograph of an SBA-15 molecular sieve prepared in example 2 of the present invention, wherein FIG. 2a1Is a scanning electron micrograph of the SBA-15 molecular sieve prepared in example 2, magnified 10 ten thousand times, FIG. 2a2Is a scanning electron micrograph of the SBA-15 molecular sieve prepared in example 2, magnified 15 ten thousand times;
FIG. 2b is a small angle X-ray diffraction pattern of the SBA-15 molecular sieve prepared in example 2 of the present invention;
FIG. 2c shows N of SBA-15 molecular sieve prepared in example 2 of the present invention2Adsorption-desorption isotherms;
FIG. 2d is a mesoporous distribution diagram of the SBA-15 molecular sieve prepared in example 2 of the present invention.
The specific implementation mode is as follows:
the following is a further description of the invention and is not intended to be limiting.
Example 1
According to P123: deionized water: the molar ratio of the hydrochloric acid is 1: 9500: 350, uniformly mixing the P123, deionized water and hydrochloric acid, stirring for 3 hours at 40 ℃, and then adding a mixture of the P123 and the deionized water in a mass ratio of 1: 4 (the mass ratio of the 3DOM PMMA to the polystyrene-divinylbenzene macroporous adsorption resin is 1: 1), stirring for 10min, dropwise adding 58.5 times of ethyl orthosilicate with the mole number of P123, and continuously stirring for 24h to obtain a mixed solution; and transferring the mixed solution into a high-pressure hydrothermal reaction kettle, carrying out hydrothermal reaction for 24h at 100 ℃, filtering and washing the obtained molecular sieve material to be neutral, drying for 12h at 100 ℃, and finally heating to 500 ℃ at the speed of 2 ℃/min and roasting for 8h to obtain the microporous-mesoporous-macroporous hierarchical pore SBA-15 molecular sieve.
Scanning electron microscope picture, small-angle X-ray diffraction picture and N of microporous-mesoporous-macroporous hierarchical pore SBA-15 molecular sieve2The adsorption-desorption isotherms, the micropore distribution diagram and the mesopore distribution diagram are shown in FIG. 1. As can be seen, the obtained SBA-15 molecular sieve has different pore structures such as micropores, mesopores and macropores, and typical (100), (110) and (200) crystal face peaks of the SBA-15 are obvious. N of SBA-15 molecular sieve2The adsorption-desorption isotherm belongs to the type IV adsorption isotherm, and the isotherm hysteresis loop belongs to the type H1. The pore diameter of the micropores of the SBA-15 molecular sieve is mainly concentrated at about 0.83nm, the pore diameter of the mesopores is mainly concentrated at 6.6nm, and the pore diameter of the macropores is mainly concentrated at 159.6 nm.
Application example
Referring to example 4 of patent CN 102319575B, the SBA-15 molecular sieve obtained in the implementation is used as a catalyst carrier to load and prepare a Cu-Fe-based catalyst with the same composition, and the pressure is 5.5MPa, the temperature is 320 ℃, and the space velocity is 6000h-1，H2When CO is 2.0, the space-time yield of the resulting mixed alcohol is 316.0g (kg. h)-1，C5+The alcohol content was 52.4 wt%, each being SiO21.84 times and 2.18 times as much as the Cu — Fe based catalyst was supported.
Example 2
According to P123: deionized water: the molar ratio of the hydrochloric acid is 1: 10000: 650 uniformly mixing the P123, the deionized water and the hydrochloric acid, stirring for 5 hours at 38 ℃, and then adding a mixture of the P123 and the deionized water in a mass ratio of 1: stirring a mixture of 3DOM PMMA and glycidyl acrylate modified polystyrene-divinylbenzene macroporous adsorption resin (the mass ratio of the 3DOM PMMA to the glycidyl acrylate modified polystyrene-divinylbenzene macroporous adsorption resin is 1: 0.5) for 30min, dropwise adding ethyl orthosilicate with the mole number 55 times that of P123, and continuously stirring for 30h to obtain a mixed solution; and transferring the mixed solution into a high-pressure hydrothermal reaction kettle, carrying out hydrothermal reaction for 26h at 120 ℃, filtering and washing the obtained molecular sieve material to be neutral, drying the molecular sieve material for 10h at 80 ℃, and finally heating the molecular sieve material to 550 ℃ at the speed of 1 ℃/min and roasting the molecular sieve material for 4h to obtain the microporous-mesoporous-macroporous hierarchical pore SBA-15 molecular sieve.
The micro-pores and mediaScanning electron microscope picture, small-angle X-ray diffraction picture and N of pore-macropore hierarchical pore SBA-15 molecular sieve2The adsorption-desorption isotherms, the micropore distribution profile and the mesopore distribution profile are shown in fig. 2. It can be seen that the obtained SBA-15 molecular sieve has different pore structures such as obvious micropores, mesopores, macropores and the like, and the macropore pore channels are rich. The peaks of the (100), (110) and (200) crystal faces of the SBA-15 molecular sieve are obvious. N of SBA-15 molecular sieve2The adsorption-desorption isotherm belongs to the type IV adsorption isotherm, and the isotherm hysteresis loop belongs to the type H1. The mesoporous aperture of the SBA-15 molecular sieve is mainly concentrated at 6.6nm, and the macroporous aperture is mainly concentrated at 174 nm.
Application example
Referring to example 1 of patent CN 104815664B, the SBA-15 molecular sieve obtained in the implementation is used as a catalyst carrier to load and prepare a Cu-Zn-Fe-based catalyst with the same composition, and the pressure is 2.0MPa, the temperature is 400 ℃, and the space velocity is 6000h-1，H2/CO2When 2.0, CO2The conversion rate is 42.7 percent, and the yield of the low-carbon alcohol is 0.39g/mLcatH, which are respectively 1.47 times and 1.56 times of that of the Cu-Zn-Fe-based catalyst loaded on the attapulgite/cerium-zirconium solid solution composite material.
Example 3
According to P123: deionized water: the molar ratio of the hydrochloric acid is 1: 9800: 1000, uniformly mixing P123, deionized water and hydrochloric acid, stirring for 6 hours at 35 ℃, and then adding a mixture of the P123 and the deionized water in a mass ratio of 1: stirring a mixture of 1 DOM PMMA and methyl acrylate modified polystyrene-divinylbenzene macroporous adsorption resin (the mass ratio of the 3DOM PMMA to the methyl acrylate modified polystyrene-divinylbenzene macroporous adsorption resin is 1: 0.8) for 60min, dropwise adding 65 times of P123 mol number of tetraethoxysilane, and continuously stirring for 20h to obtain a mixed solution; and transferring the mixed solution into a high-pressure hydrothermal reaction kettle, carrying out hydrothermal reaction for 48h at 135 ℃, filtering and washing the obtained molecular sieve material to be neutral, drying the molecular sieve material for 6h at 120 ℃, and finally heating the molecular sieve material to 600 ℃ at the speed of 1.5 ℃/min and roasting the molecular sieve material for 6h to obtain the microporous-mesoporous-macroporous hierarchical pore SBA-15 molecular sieve.
Application example
Referring to example 1 of patent CN 102719490B, the SBA-15 molecular sieve obtained in this example was organically modified with cetyltrimethylammonium bromide (CTAB), the corn stalk acidic steam explosion prehydrolysis liquid was prepared according to example 7, the hydrolysis liquid was detoxified with the modified SBA-15 molecular sieve under the same conditions, and after adsorption treatment, the removal rates of hydroxymethylfurfural and total phenols in the hydrolysis liquid were 71.5% and 67.3%, respectively, which were 1.36 times and 1.18 times as high as those of CTAB modified bentonite, respectively.
Example 4
According to P123: deionized water: the molar ratio of the hydrochloric acid is 1: 9680: 800, uniformly mixing P123, deionized water and hydrochloric acid, stirring for 4 hours at 40 ℃, and then adding a mixture of the P123 and the deionized water in a mass ratio of 1: 5 (the mass ratio of the 3DOM PMMA to the hydroxyethyl acrylate modified polystyrene-divinylbenzene macroporous adsorption resin is 1: 0.6), stirring for 40min, dropwise adding 60 times of ethyl orthosilicate with the mole number of P123, and continuously stirring for 26h to obtain a mixed solution; and transferring the mixed solution into a high-pressure hydrothermal reaction kettle, carrying out hydrothermal reaction for 36h at 150 ℃, filtering and washing the obtained molecular sieve material to be neutral, drying for 8h at 105 ℃, and finally heating to 500 ℃ at the speed of 1 ℃/min and roasting for 8h to obtain the microporous-mesoporous-macroporous hierarchical pore SBA-15 molecular sieve.
Table 1 is a texture performance data table of each of the microporous-mesoporous-macroporous hierarchical pore SBA-15 molecular sieves prepared in examples 1 to 4, wherein: sBETDenotes the total specific surface area, SMicroDenotes the specific surface area of micropores, SMesoRepresents the mesoporous specific surface area, SMacroRepresents the specific surface area of macropores; vTotalDenotes the total pore volume, VMicroDenotes the pore volume of the micropores, SMesoRepresents the mesoporous volume, SMacroIndicating the pore volume of the macropores.
TABLE 1
As shown in table 1, the SBA-15 molecular sieves prepared in examples 1 to 4 can simultaneously construct micropores, mesopores, and macropores. Microporous-mesoporous-macroporous hierarchical poreThe total specific surface area of the SBA-15 molecular sieve is 792.4-970.5 m2The specific surface area of the micropores is 92.8-203.6 m2The specific surface area of the mesoporous is 472.8-571.3 m2The specific surface area of the macropore is 97.0-294.1 m2(ii)/g; the total pore volume is 1.275-1.503 cc/g, the micropore volume is 0.054-0.271 cc/g, and the mesopore volume is 0.845-1.208 m2The volume of the macropores is 0.086-0.387 cc/g; the average pore diameter is 6.5-14.7 nm. The sizes and the distribution of micropores, mesopores and macropores in the hierarchical pore SBA-15 molecular sieve can be effectively adjusted by changing the mass ratio of the soft template agent to the hard template agent.
The above is only a preferred embodiment of the present invention, and it should be noted that the above preferred embodiment should not be considered as limiting the present invention, and the protection scope of the present invention should be subject to the scope defined by the claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and these modifications and adaptations should be considered within the scope of the invention.
Claims (6)
1. The microporous-mesoporous-macroporous hierarchical pore SBA-15 molecular sieve is characterized in that the total specific surface area of the microporous-mesoporous-macroporous hierarchical pore SBA-15 molecular sieve is 792.4-970.5 m2The specific surface area of the micropores is 92.8-203.6 m2The specific surface area of the mesoporous is 472.8-571.3 m2The specific surface area of the macropore is 97.0-294.1 m2(iv)/g, the average pore diameter is 6.5 to 14.7 nm.
2. The preparation method of the microporous-mesoporous-macroporous hierarchical pore SBA-15 molecular sieve according to claim 1, which is characterized by comprising the following steps:
(1) mixing a soft template agent P123, deionized water and hydrochloric acid according to the weight ratio of 1: 9500-10000: mixing at a molar ratio of 350-1000, stirring for 3-6 h at 35-40 ℃, adding a hard template agent, stirring for 10-60 min, dropwise adding ethyl orthosilicate, and continuously stirring for 20-30 h to obtain a mixed solution, wherein the molar ratio of the ethyl orthosilicate to the soft template agent is 55-65: 1;
(2) transferring the mixed solution obtained in the step (1) into a reaction container, carrying out hydrothermal reaction for 24-48 h at 100-150 ℃ to obtain a molecular sieve material, filtering and washing the molecular sieve material to be neutral, drying and roasting to obtain the microporous-mesoporous-macroporous hierarchical pore SBA-15 molecular sieve;
the mass ratio of the hard template agent to the soft template agent P123 is 1: 1-5;
the hard template agent is formed by mixing three-dimensional ordered macroporous polymethyl methacrylate and styrene macroporous adsorption resin or acrylate modified styrene macroporous adsorption resin, wherein the mass ratio of the three-dimensional ordered macroporous polymethyl methacrylate to the styrene macroporous adsorption resin or acrylate modified styrene macroporous adsorption resin is 1: 0.5 to 1.
3. The preparation method of the microporous-mesoporous-macroporous hierarchical pore SBA-15 molecular sieve according to claim 2, wherein the three-dimensional ordered macroporous polymethyl methacrylate is prepared by a centrifugal self-assembly method, and the particle size of the three-dimensional ordered macroporous polymethyl methacrylate is 200-800 nm; the styrene macroporous adsorption resin is prepared by a suspension polymerization method, and the pore diameter of the styrene macroporous adsorption resin is 50-200 nm.
4. The method for preparing the microporous-mesoporous-macroporous hierarchical pore SBA-15 molecular sieve according to claim 2, wherein the acrylate is one selected from the group consisting of methyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, hydroxyethyl acrylate and glycidyl acrylate.
5. The microporous-mesoporous-macroporous hierarchical pore SBA-15 molecular sieve of claim 1 used for catalytic conversion of synthesis gas and CO conversion2Hydrogenation conversion or biomass hydrolysate detoxification refining.
6. The microporous-mesoporous-macroporous hierarchical pore SBA-15 molecular sieve prepared by the preparation method of any one of claims 2 to 4 is used for catalytic conversion of synthesis gas and CO2By hydroconversion orApplication of biomass hydrolysate in detoxification and refining.
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