CN108928829B - SBA-15 mesoporous molecular sieve, preparation method and application thereof - Google Patents
SBA-15 mesoporous molecular sieve, preparation method and application thereof Download PDFInfo
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- CN108928829B CN108928829B CN201710373896.1A CN201710373896A CN108928829B CN 108928829 B CN108928829 B CN 108928829B CN 201710373896 A CN201710373896 A CN 201710373896A CN 108928829 B CN108928829 B CN 108928829B
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 141
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 138
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000010881 fly ash Substances 0.000 claims abstract description 54
- 238000006243 chemical reaction Methods 0.000 claims abstract description 52
- 239000000706 filtrate Substances 0.000 claims abstract description 50
- 239000011148 porous material Substances 0.000 claims abstract description 41
- 239000003513 alkali Substances 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 31
- 238000005216 hydrothermal crystallization Methods 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000004090 dissolution Methods 0.000 claims abstract description 21
- 239000012452 mother liquor Substances 0.000 claims abstract description 20
- 238000001914 filtration Methods 0.000 claims abstract description 17
- 239000000047 product Substances 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 16
- -1 polyethylene Polymers 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims abstract description 8
- 239000004698 Polyethylene Substances 0.000 claims abstract description 8
- 239000004743 Polypropylene Substances 0.000 claims abstract description 8
- 229920000573 polyethylene Polymers 0.000 claims abstract description 8
- 229920001155 polypropylene Polymers 0.000 claims abstract description 8
- 229920000428 triblock copolymer Polymers 0.000 claims abstract description 8
- 230000002378 acidificating effect Effects 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 24
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 15
- 229910052681 coesite Inorganic materials 0.000 claims description 15
- 229910052906 cristobalite Inorganic materials 0.000 claims description 15
- 239000000377 silicon dioxide Substances 0.000 claims description 15
- 229910052682 stishovite Inorganic materials 0.000 claims description 15
- 229910052905 tridymite Inorganic materials 0.000 claims description 15
- 229910052593 corundum Inorganic materials 0.000 claims description 10
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- 238000001179 sorption measurement Methods 0.000 claims description 7
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- 239000002585 base Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000000203 mixture Substances 0.000 abstract description 23
- 239000000463 material Substances 0.000 abstract description 11
- 239000000843 powder Substances 0.000 description 17
- 239000000084 colloidal system Substances 0.000 description 15
- 238000001354 calcination Methods 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- 238000001988 small-angle X-ray diffraction Methods 0.000 description 6
- 238000002336 sorption--desorption measurement Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000003245 coal Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000010979 pH adjustment Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 230000004927 fusion Effects 0.000 description 3
- 239000013335 mesoporous material Substances 0.000 description 3
- 238000000547 structure data Methods 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000007500 overflow downdraw method Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 238000004876 x-ray fluorescence Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229920000463 Poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) Polymers 0.000 description 1
- 229910002796 Si–Al Inorganic materials 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 239000010883 coal ash Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- 230000035772 mutation Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010117 shenhua Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000002383 small-angle X-ray diffraction data Methods 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/035—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites
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- B01J35/617—
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- B01J35/647—
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- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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Abstract
The invention relates to the field of utilization of fly ash, and discloses a method for preparing SBA-15 mesoporous molecular sieve from fly ash, the SBA-15 mesoporous molecular sieve and application. The method for preparing the SBA-15 mesoporous molecular sieve by using the fly ash comprises the following steps: (1) mixing fly ash, alkali and water to perform an alkali dissolution reaction, and filtering the obtained product to obtain a filtrate; (2) adjusting the pH value of the filtrate to be acidic, and mixing the filtrate with a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer to prepare a synthetic mother liquor; (3) and (3) putting the synthetic mother liquor into a high-pressure kettle, and carrying out hydrothermal crystallization reaction under the conditions of heating and pressurizing to obtain the SBA-15 mesoporous molecular sieve. The preparation of the fly ash can be realized to obtain the SBA-15 mesoporous molecular sieve, and the fly ash is utilized to obtain a high value-added material. The obtained SBA-15 mesoporous molecular sieve also contains Al in composition and has a mesoporous and microporous dual-pore structure.
Description
Technical Field
The invention relates to the field of utilization of fly ash, in particular to a method for preparing SBA-15 mesoporous molecular sieve from fly ash, the SBA-15 mesoporous molecular sieve and application.
Background
Coal plays a very important role in national economic development as fossil fuel. However, a large amount of fly ash waste discharged by coal combustion is increased year by year and is randomly stacked, so that a large amount of land resources are occupied, heavy metal pollution of underground water is caused, ecological balance is seriously damaged, and the environment is polluted. At present, the main method for treating the fly ash is brick making, and the fly ash is used as industrial fillers for bridge construction, paving, wall materials and the like, has the advantages of simple operation process, low technical requirement level, easy in-situ digestion and the like, but has lower added value.
The mesoporous molecular sieve is a new molecular sieve material, but the conventional mesoporous molecular sieve preparation uses sodium silicate or tetraethoxysilane as a silicon source, is expensive and toxic, and is not suitable for large-scale industrial production.
CN103818920A discloses a method for preparing Si-Al ordered mesoporous molecular sieve, which comprises the following steps: extracting waste fly ash of a thermal power plant as a raw material to obtain a solution containing silicon and aluminum, adding ethanol and water into CTAB (cetyl trimethyl ammonium bromide) serving as a template agent, quickly synthesizing a pre-product at room temperature, placing the pre-product in a muffle furnace, calcining to remove the template agent, and cooling to obtain a product; wherein the mole ratio of CTAB, water, ethanol and the total amount of silicon and aluminum in the solution is (0.4-0.6): (300-500): (50-60): 1. further disclosed is: the silicon-aluminum source extraction is to mix the fly ash and NaOH, calcine the mixture for 1 to 2 hours at the temperature of 550 ℃ and 600 ℃, grind the mixture after cooling, mix the ground mixture with water, and separate out supernate as a silicon-aluminum source solution; and adding CTAB, water and ethanol into the silica-alumina source solution to obtain a mixed solution, adjusting the pH of the mixed solution to 9-10 by adopting acid, and stirring to obtain a white solid. The method for treating the fly ash by the method is an alkali fusion method, high-temperature calcination is needed, the energy consumption is large, and the process is not green; and the mesoporous molecular sieve is obtained by an acid regulation method, but not by a hydrothermal crystallization method.
CN103861556A discloses a preparation method of fly ash-based SBA-15, which comprises the following steps: (1) mixing the fly ash and alkali, melting and cooling to obtain a mixture; (2) adding water to the mixture for dissolving and filtering to obtain a supernatant; (3) dissolving a surfactant P123 in water, adjusting the pH value to be acidic, then aging, filtering, washing and drying; (4) and (4) roasting the material dried in the step (3) to obtain a powdery material fly ash-based SBA-15. Discloses that the pore volume of the obtained mesoporous material is 0.6-0.9cm3Specific surface area of 370-3Per g, the aperture is 5-8 nm; it is not disclosed whether the composition of the mesoporous material contains aluminum or not, and whether the material has a microporous structure or not. The fly ash is treated by an alkali fusion method, high-temperature calcination is needed, energy consumption is large, and harsh conditions such as hydrothermal and the like are not used for synthesizing the mesoporous molecular sieve.
In the prior art, the energy consumption is high by adopting an alkali fusion reaction, the alkali fusion reaction is combined with acid regulation synthesis, and the coal ash is prepared into a mesoporous material without adopting a hydrothermal crystallization reaction. But in the fields of adsorption and catalysis, the material can have a microporous and mesoporous composite pore structure and can have better application prospect.
Disclosure of Invention
The invention aims to solve the problem of how to prepare an aluminum-containing mesoporous molecular sieve with a double-pore structure from fly ash, and provides a method for preparing an SBA-15 mesoporous molecular sieve from fly ash, the SBA-15 mesoporous molecular sieve and application. The SBA-15 mesoporous molecular sieve contains alumina in the composition and has a micropore and mesopore double-pore structure in the structure. The mesoporous molecular sieve can utilize the fly ash to produce the mesoporous molecular sieve with better composition and structure and high added value, and improves the utilization value of the fly ash.
In order to achieve the above object, in a first aspect of the present invention, there is provided a method for preparing SBA-15 mesoporous molecular sieve from fly ash, the method comprising: (1) mixing fly ash, alkali and water to perform an alkali dissolution reaction, and filtering the obtained product to obtain a filtrate; (2) adjusting the pH value of the filtrate to be acidic, and mixing the filtrate with a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer to prepare a synthetic mother liquor; (3) and (3) putting the synthetic mother liquor into a high-pressure kettle, and carrying out hydrothermal crystallization reaction under the conditions of heating and pressurizing to obtain the SBA-15 mesoporous molecular sieve.
Preferably, the mass ratio of the fly ash to the alkali to the water is 100: (64-90): (100-200).
Preferably, the alkali dissolution reaction temperature is 80-100 ℃, and the alkali dissolution reaction time is 4-6 h.
Preferably, the filtrate contains 45-55 g/L of SiO26 to 10g/L of Al2O3。
Preferably, the pH adjustment is carried out so that the pH of the filtrate is 3-5.
Preferably, the temperature of the hydrothermal crystallization reaction is 100-120 ℃, the pressure of the hydrothermal crystallization reaction is 2-6 MPa, and the time of the hydrothermal crystallization is 48-72 h.
In a second aspect of the present invention, there is provided a SBA-15 mesoporous molecular sieve prepared by the method of the present invention, wherein the mesoporous molecular sieve contains 10 to 20 wt% of Al based on the total weight of the mesoporous molecular sieve2O380 to 90% by weight of SiO2。
Preferably, the mesoporous molecular sieve contains micropores, and the volume of the micropores accounts for 10-20 vol% of the total pore volume of the mesoporous molecular sieve.
Preferably, the mesoporous molecular sieve has a mesoporous volume of 0.7-0.9 cm3The micropore volume of the mesoporous molecular sieve is 0.2-0.4 cm3/g。
Preferably, the specific surface area of the mesoporous molecular sieve is 740-900 m2(ii)/g; the pore diameter of the mesoporous molecular sieve is 6-10 nm, and the average particle size of the mesoporous molecular sieve is 12-21 nm.
In a third aspect of the invention, the invention provides the use of the SBA-15 mesoporous molecular sieve of the invention in catalytic reactions and adsorption.
According to the technical scheme, the fly ash is used as a raw material, and the alkali dissolution reaction and the hydrothermal crystallization reaction are combined, so that the SBA-15 mesoporous molecular sieve can be prepared from the fly ash, and a high value-added material can be obtained from the fly ash. Meanwhile, compared with the conventional SBA-15 mesoporous molecular sieve which is composed of all-silicon, the SBA-15 mesoporous molecular sieve obtained by the invention also contains Al in composition, has a micropore and mesopore double-pore structure and has a good application prospect.
Drawings
FIG. 1 is a schematic flow chart of the process for preparing SBA-15 mesoporous molecular sieve by using fly ash according to the present invention;
FIG. 2 is a small angle XRD spectrum of the SBA-15 mesoporous molecular sieve provided by the present invention;
FIG. 3 is a diagram of the nitrogen adsorption-desorption isotherm of the SBA-15 mesoporous molecular sieve provided by the present invention;
FIG. 4 is a graph showing the pore size distribution of the SBA-15 mesoporous molecular sieve provided by the present invention;
FIG. 5 is a TEM image of the SBA-15 mesoporous molecular sieve provided by the present invention.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In a first aspect of the present invention, a method for preparing SBA-15 mesoporous molecular sieve from fly ash is provided, as shown in fig. 1, the method comprises:
(1) mixing fly ash, alkali and water to perform an alkali dissolution reaction, and filtering the obtained product to obtain a filtrate;
(2) adjusting the pH value of the filtrate to be acidic, and preparing the filtrate with a triblock copolymer of polyethylene oxide-polypropylene oxide-polyethylene oxide to obtain a synthetic mother liquor;
(3) and (3) putting the synthetic mother liquor into a high-pressure kettle, and carrying out hydrothermal crystallization reaction under the conditions of heating and pressurizing to obtain the SBA-15 mesoporous molecular sieve.
In the invention, fly ash is used as a raw material. The fly ash may be coal residue from a coal fired power plant and may generally comprise: 35 to 55% by weight of Al2O330 to 50% by weight of SiO 20 to 0.5% by weight of SO3、0～0.3% by weight of K2O, 0 to 0.5 wt% CaO, 0 to 6 wt% TiO 20 to 1% by weight of Fe2O30 to 1 wt% of MgO and 0 to 5 wt% of other substances.
According to the invention, the silicon and aluminum elements in the fly ash can be activated through alkali dissolution reaction by adding alkali in the step (1), and the fly ash is treated to obtain a filtrate suitable for synthesizing the SBA-15 mesoporous molecular sieve. The respective amounts of the fly ash, the alkali and the water are only required to meet the requirement of the alkali dissolution reaction, and preferably, in the step (1), the mass ratio of the fly ash, the alkali and the water is 100: (64-90): (100-200); preferably, the mass ratio of the fly ash to the alkali to the water is 100: (64-90): 200.
according to the present invention, in step (1), preferably, the base is a strong base, preferably sodium hydroxide and/or potassium hydroxide;
according to the invention, the conditions of the alkali-soluble reaction in the step (1) are satisfied to obtain the filtrate suitable for synthesizing the SBA-15 mesoporous molecular sieve. Preferably, the alkali dissolution reaction temperature is 80-100 ℃, and the alkali dissolution reaction time is 4-6 h.
According to the invention, in the step (1), preferably, the filtrate contains 45-55 g/L of SiO26 to 10g/L of Al2O3。
According to the invention, the step (2) is used for further preparing the synthesis mother liquor required by the hydrothermal crystallization reaction of the step (3). Preferably, in step (2), the pH adjustment is such that the pH of the filtrate is no greater than 5; preferably, the pH is 3 to 5. Preferably, the pH adjustment can be performed by adding hydrochloric acid, sulfuric acid or nitric acid to the filtrate.
In the present invention, the polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123, PEO-PPO-PEO) in step (2) is used as a template for synthesizing the SBA-15 mesoporous molecular sieve, and is commercially available, such as P123 produced by BASF corporation, Germany. Preferably, the SiO is added to 100 parts by weight of the filtrate2The addition amount of the polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer is 95-120 parts by weight.
According to the invention, the mixing and preparing process in the step (2) can be adding the triblock copolymer of polyethylene oxide-polypropylene oxide-polyethylene oxide into the filtrate after pH adjustment, and stirring at 35-40 ℃ for at least 10h, such as 10-20 h; obtaining the prepared synthetic mother liquor.
According to the invention, the step (3) is carried out hydrothermal crystallization reaction, and the SBA-15 molecular sieve is prepared from the synthetic mother liquor obtained in the step (2). The hydrothermal crystallization reaction may be carried out by placing the synthesis mother liquor in a closed autoclave, for example, pouring into a stainless steel reaction kettle lined with polytetrafluoroethylene. Preferably, the temperature of the hydrothermal crystallization reaction is 100-120 ℃, the pressure of the hydrothermal crystallization reaction is 2-6 MPa, and the time of the hydrothermal crystallization is 48-72 h.
In the invention, after the hydrothermal crystallization reaction is finished, the obtained product can be sequentially filtered, washed, dried and calcined to obtain SBA-15 mesoporous molecular sieve powder. Wherein the washing step can be carried out by washing the colloid obtained by filtration with deionized water until the colloid is neutral. The drying can be carried out in an oven at 90-100 ℃ for 2-4 h. The calcination can be carried out at 500-600 ℃ for 4-8 h, wherein the heating rate can be 3-6 ℃/min.
In a second aspect of the present invention, there is provided a SBA-15 mesoporous molecular sieve prepared by the method of the present invention, wherein the mesoporous molecular sieve contains 10 to 20 wt% of Al based on the total weight of the mesoporous molecular sieve2O380 to 90% by weight of SiO2。
The conventional SBA-15 mesoporous molecular sieve is synthesized by taking tetraethoxysilane as a raw material and has the composition of SiO2. The SBA-15 mesoporous molecular sieve of the invention also contains Al with the content2O3. The composition of the SBA-15 mesoporous molecular sieve of the present invention can be determined by elemental analysis. Preferably, in the SBA-15 mesoporous molecular sieve of the invention, Al is contained2O3：SiO2The weight ratio of (A) may be 1: (5-7). The SBA-15 mesoporous molecular sieve with the characteristics can provide better application prospect. In addition, the SBA-15 mesoporous molecular sieve of the invention also contains a small amount of other substances which come from fly ash and can be TiO2、CaO、Fe2O3、K2O、MgO or SO3But does not affect the performance of the SBA-15 mesoporous molecular sieve.
The SBA-15 mesoporous molecular sieve of the invention can analyze the crystal structure thereof by small-angle XRD. As shown in the small-angle XRD spectrogram of fig. 2, a strong characteristic diffraction peak appears near 0.8 ° 2 θ, corresponding to the (100) crystal plane of molecular sieve SBA-15, and two weaker characteristic diffraction peaks appear between 1.2 ° and 2 °, corresponding to the (110) and (200) crystal planes of molecular sieve SBA-15, respectively, and are characteristic diffraction peaks of a typical two-dimensional hexagonal channel structure, thereby proving that the molecular sieve of the present invention is a mesoporous molecular sieve having the typical framework characteristics of the SBA-15 molecular sieve, and the SBA-15 mesoporous molecular sieve has good crystallinity and order degree.
Furthermore, the SBA-15 mesoporous molecular sieve has a micropore and mesopore double-pore structure. The SBA-15 mesoporous molecular sieve warp N of the invention2Adsorption/desorption test, resulting in N2The adsorption/desorption isotherm curve is shown in fig. 3, and the calculated pore size distribution of BJH is shown in fig. 4. From fig. 3, it is shown that this molecular sieve has a typical isothermal curve of type IV in IUPAC classification, which is a typical feature of mesoporous structure. The curve is at a relative pressure p/p0The obvious mutation is 0.4-0.8, and the phenomenon is caused by capillary condensation, and the hysteresis loop is H1 type. As can be seen from the pore size distribution diagram of FIG. 4, the SBA-15 mesoporous molecular sieve of the present invention has a highly ordered mesoporous structure, uniform pore size distribution and regular channels. Preferably, the mesoporous molecular sieve contains micropores, and the volume of the micropores accounts for 10-20 vol% of the total pore volume of the mesoporous molecular sieve. More preferably, the mesoporous molecular sieve has a mesoporous volume of 0.7-0.9 cm3The micropore volume of the mesoporous molecular sieve is 0.2-0.4 cm3(ii) in terms of/g. More preferably, the specific surface area of the mesoporous molecular sieve is 740-900 m2(ii) in terms of/g. According to the classification by IUPAC, pores with a pore size of less than 2nm are microporous and pores with a pore size between 2nm and 50nm are mesoporous.
The SBA-15 mesoporous molecular sieve can be further used for TEM observation. As shown in fig. 5a, 5b, a channel array structure of SBA-15 mesoporous molecular sieve was observed. Fig. 5c and 5d show hexagonal images and striped images of the SBA-15 mesoporous molecular sieve of the present invention in the (100) direction, which shows that the SBA-15 mesoporous molecular sieve of the present invention has a typical highly ordered two-dimensional hexagonal phase structure, and the mesoporous pore size and average particle size of the SBA-15 mesoporous molecular sieve of the present invention can be obtained from TEM images. Preferably, the pore diameter of the mesoporous molecular sieve is 6-10 nm, and the average particle size of the mesoporous molecular sieve is 12-21 nm.
In the invention, the combination of alkali dissolution reaction and hydrothermal crystallization reaction is adopted to realize the preparation of the SBA-15 mesoporous molecular sieve with the composition and the structural characteristics from the fly ash.
In a third aspect, the invention provides the use of the SBA-15 mesoporous molecular sieve of the invention in catalytic reactions and adsorption. Can have wide application prospect in the fields of catalysis, separation, biology, nano materials and the like.
The present invention will be described in detail below by way of examples.
In the following examples, the crystal structure of the molecular sieve produced was determined by small angle XRD analysis using D8ADVANCE from Bruker, Germany, with a test scan rate of 0.5 deg./min to 5 deg./min;
the pore structure of the prepared molecular sieve is determined by N2The adsorption method comprises using ASAP 2020 physical adsorption apparatus of Micromeritics, USA, and the adsorption medium is N2；
The mesoporous aperture and the average particle size of the prepared molecular sieve are measured by TEM, a JEMARM200F spherical aberration correction transmission electron microscope of JEOL company is used, and a sample is placed on a copper net to be observed after being subjected to ultrasonic dispersion in ethanol;
the composition of the molecular sieve obtained was measured by X-ray fluorescence elemental analysis using a ZSXPrimus X-ray fluorescence spectrometer from Rigaku corporation, Japan.
The fly ash used in the above examples was from Shenhua quasi-Geer energy Limited company and had a chemical composition as shown in Table 1:
TABLE 1
Example 1
(1) Mixing fly ash, NaOH and water according to a mass ratio of 100: 64: 200, then carrying out alkali dissolution reaction at 95 ℃ for 30min, then filtering the obtained product to obtain filtrate, and analyzing and determining that the filtrate contains 45g/L of SiO26g/L of Al2O3；
(2) Adding 2mol/L HCl into the filtrate, and adjusting the pH value of the filtrate to 3; then adding 43g of P123 into 1L of filtrate, and continuously stirring for 10h at 35 ℃ to prepare synthetic mother liquor;
(3) placing the synthetic mother liquor into a stainless steel reaction kettle (KH-100 ml autoclave of Nicotitaceae chemical equipment Co., Ltd.) with polytetrafluoroethylene lining, and performing hydrothermal crystallization reaction at 110 deg.C under 4MPa for 48 h; then filtering the product to obtain colloid, washing the colloid to be neutral by using deionized water, and drying the colloid for 3 hours at the temperature of 95 ℃; and then putting the mixture into a calcining furnace, heating to 550 ℃ at the speed of 5 ℃/min, and calcining for 6h to obtain the molecular sieve powder.
The obtained molecular sieve powder is subjected to a small-angle XRD test, and the obtained spectrogram is shown in figure 2, wherein a strong characteristic diffraction peak appears near 0.8 degrees of 2 theta, corresponds to a (100) crystal face of the molecular sieve SBA-15, two weaker characteristic diffraction peaks appear between 1.2 degrees and 2 degrees, respectively correspond to a (110) crystal face and a (200) crystal face of the molecular sieve SBA-15, are characteristic diffraction peaks of a typical two-dimensional hexagonal pore channel structure, and indicate that the molecular sieve has the material framework characteristics of the SBA-15 molecular sieve.
Subjecting the obtained molecular sieve powder to N2Adsorption/desorption test, resulting in N2The adsorption/desorption isotherm curve is shown in fig. 3, and the calculated pore size distribution of BJH is shown in fig. 4. The resulting pore structure data are shown in table 2.
The obtained molecular sieve powder was subjected to TEM observation as shown in fig. 5. As shown in fig. 5a, 5b, a channel array structure of SBA-15 mesoporous molecular sieve was observed. Fig. 5c and 5d show hexagonal images and striped images of the SBA-15 mesoporous molecular sieve of the present invention in the (100) direction, which shows that the SBA-15 mesoporous molecular sieve of the present invention has a typical highly ordered two-dimensional hexagonal phase structure, and the mesoporous pore size and average particle size of the SBA-15 mesoporous molecular sieve can be obtained from the TEM image, and the results are shown in table 2.
Example 2
(1) Mixing fly ash, KOH and water according to a mass ratio of 100: 90: 200, then carrying out alkali dissolution reaction at 100 ℃ for 40min, then filtering the obtained product to obtain filtrate, and analyzing and determining that the filtrate contains 55g/L of SiO210g/L of Al2O3；
(2) Adding 2mol/L HNO into the filtrate3Adjusting the pH value of the filtrate to 5; then adding 53g of P123 into 1L of filtrate, and continuously stirring for 10 hours at 35 ℃ to prepare synthetic mother liquor;
(3) putting the synthetic mother liquor into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and carrying out hydrothermal crystallization reaction for 48 hours at 110 ℃ and 6 MPa; then filtering the product to obtain colloid, washing the colloid to be neutral by using deionized water, and drying the colloid for 3 hours at the temperature of 95 ℃; and then putting the mixture into a calcining furnace, heating to 550 ℃ at the speed of 5 ℃/min, and calcining for 6h to obtain the molecular sieve powder.
And carrying out small-angle XRD (X-ray diffraction) test on the obtained molecular sieve powder, and indicating that the molecular sieve has the material framework characteristics of the SBA-15 molecular sieve.
Subjecting the obtained molecular sieve powder to N2The pore structure data obtained from the adsorption/desorption tests are shown in table 2.
The molecular sieve powder obtained was subjected to TEM observation, and the results of the mesoporous pore diameter and the average particle size of the SBA-15 mesoporous molecular sieve are shown in table 2.
Example 3
(1) Mixing fly ash, NaOH and water according to a mass ratio of 100: 64: 200, then carrying out alkali dissolution reaction at 95 ℃ for 30min, then filtering the obtained product to obtain filtrate, and analyzing and determining that the filtrate contains 51.5g/L of SiO27.9g/L of Al2O3；
(2) 2mol/L of H is added to the filtrate2SO4Adjusting the pH value of the filtrate to 3.5; then adding 49g of P123 into 1L of filtrate, and continuously stirring for 10 hours at 35 ℃ to prepare synthetic mother liquor;
(3) putting the synthetic mother liquor into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and carrying out hydrothermal crystallization reaction for 48 hours at 110 ℃ and 2 MPa; then filtering the product to obtain colloid, washing the colloid to be neutral by using deionized water, and drying the colloid for 3 hours at the temperature of 95 ℃; and then putting the mixture into a calcining furnace, heating to 550 ℃ at the speed of 5 ℃/min, and calcining for 6h to obtain the molecular sieve powder.
And carrying out small-angle XRD (X-ray diffraction) test on the obtained molecular sieve powder, and indicating that the molecular sieve has the material framework characteristics of the SBA-15 molecular sieve.
Subjecting the obtained molecular sieve powder to N2The pore structure data obtained from the adsorption/desorption tests are shown in table 2.
The molecular sieve powder obtained was subjected to TEM observation, and the results of the mesoporous pore diameter and the average particle size of the SBA-15 mesoporous molecular sieve are shown in table 2.
Comparative example 1
(1) Mixing fly ash, NaOH and water according to a mass ratio of 100: 64: 200, then carrying out alkali dissolution reaction at 95 ℃ for 30min, then filtering the obtained product to obtain filtrate, and analyzing and determining that the filtrate contains 45g/L of SiO26g/L of Al2O3；
(2) Adding 43g of P123 into 1L of filtrate to obtain a mixed solution; adding 2mol/L HCl into the mixed solution to adjust the pH value to 10, synthetic colloid cannot be obtained, and the molecular sieve cannot be produced.
Comparative example 2
(1) Mixing fly ash, NaOH and water according to a mass ratio of 100: 64: 200, then carrying out alkali dissolution reaction at 95 ℃ for 30min, then filtering the obtained product to obtain filtrate, and analyzing and determining that the filtrate contains 45g/L of SiO26g/L of Al2O3；
(2) Adding 43g of P123 into 1L of filtrate to obtain a mixed solution; adding 2mol/L HCl into the mixed solution to adjust the pH value to 3, fully stirring at 35-40 ℃, standing and aging in a 95 ℃ oven for 24 hours, filtering, washing to be neutral, and drying at 95 ℃ for 3 hours; and then putting the mixture into a calcining furnace, heating to 550 ℃ at the speed of 5 ℃/min, and calcining for 6h to obtain the molecular sieve powder.
The molecular sieve powder obtained was analyzed and the results are shown in table 2.
Comparative example 3
(1) Mixing fly ash and NaOH according to a mass ratio of 100: 64, then calcined at 550 ℃ for 2h, ground after cooling and mixed with water (fly ash: water mass ratio 100: 200). Because a large amount of hydrated SiO is formed in the water leaching process of adding the alkali sintering slag into the aluminum extraction residue by the acid method2Gel precipitation, no supernatant can be formed, and only suspension can be obtained;
(2) adding 2mol/L HCl into the suspension, and adjusting the pH value to 3; then adding 43g of P123 into 1L of filtrate, and continuously stirring for 10h at 35 ℃ to prepare synthetic mother liquor;
(3) putting the synthetic mother liquor into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and carrying out hydrothermal crystallization reaction for 48 hours at 110 ℃ and 4 MPa; then filtering the product to obtain colloid, washing the colloid to be neutral by using deionized water, and drying the colloid for 3 hours at the temperature of 95 ℃; and then putting the mixture into a calcining furnace, heating to 550 ℃ at the speed of 5 ℃/min, and calcining for 6h to obtain the molecular sieve powder.
The molecular sieve powder obtained was analyzed and the results are shown in table 2.
TABLE 2
| Numbering | Example 1 | Example 2 | Example 3 | Comparative example 2 | Comparative example 3 |
| Al2O3To weight percent | 12.4 | 13.6 | 15.5 | 11.2 | 0 |
| SiO2To weight percent | 83.4 | 82.1 | 80.2 | 80.5 | 90.5 |
| Specific surface area, m2/g | 749 | 894 | 796 | 694 | 632 |
| Total pore volume, cm3/g | 0.84 | 0.94 | 0.86 | 0.79 | 0.78 |
| Pore volume of micropores, cm3/g | 0.32 | 0.29 | 0.25 | 0 | 0.21 |
| Pore volume of mesoporous, cm3/g | 0.75 | 0.85 | 0.80 | 0.86 | 0.71 |
| The volume of the micropores accounts for the ratio, v% | 12 | 15 | 18 | 0 | 10 |
| Pore size, nm | 6.9 | 7.1 | 8.4 | 7.3 | 8.0 |
| Particle size, nm | 12 | 21 | 17.9 | 22.5 | 23 |
As can be seen from the examples and the data in Table 2, the present invention can realize the synthesis of SBA-15 mesoporous molecular sieve by using fly ash, wherein the SBA-15 mesoporous molecular sieve contains alumina and has a mesoporous and microporous dual-pore structure in the pore structure.
As can be seen from the preparation processes shown in the examples, the method for preparing the SBA-15 mesoporous molecular sieve from the fly ash provided by the invention comprises the steps of firstly treating the fly ash by an alkali dissolution reaction to obtain a filtrate suitable for synthesis of the mesoporous molecular sieve, then adjusting and preparing the filtrate into a synthesis mother solution, finally obtaining the SBA-15 mesoporous molecular sieve by a hydrothermal crystallization method, and combining the alkali dissolution reaction and the hydrothermal crystallization reaction to obtain the SBA-15 mesoporous molecular sieve with the composition characteristics and the double-pore structure.
In comparative example 1, the mesoporous molecular sieve could not be synthesized by using an alkali-soluble reaction in combination with the prior art to adjust the filtrate to be alkaline, rather than by hydrothermal crystallization.
In comparative example 2, the filtrate was adjusted to be acidic using an alkali-soluble reaction in combination with the prior art, but was aged by standing at 95 ℃ and the synthesized mesoporous molecular sieve had no micropores and did not have the double-pore structure of the SBA-15 mesoporous molecular sieve of the present invention.
In comparative example 3, the composition of the mesoporous molecular sieve obtained by using the alkali fusion reaction in combination with the hydrothermal crystallization reaction did not contain alumina, and the SBA-15 mesoporous molecular sieve having a composite pore structure and containing alumina could not be obtained.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (9)
1. A method for preparing SBA-15 mesoporous molecular sieve by fly ash comprises the following steps:
(1) mixing fly ash, alkali and water to perform an alkali dissolution reaction, and filtering the obtained product to obtain a filtrate;
(2) adjusting the pH value of the filtrate to be acidic, and mixing the filtrate with a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer to prepare a synthetic mother liquor;
(3) putting the synthetic mother liquor into a high-pressure kettle, and carrying out hydrothermal crystallization reaction under the conditions of heating and pressurizing to obtain an SBA-15 mesoporous molecular sieve;
in the step (1), the mass ratio of the fly ash to the alkali to the water is 100: (64-90): (100-200); the alkali is strong alkali; the alkali dissolution reaction temperature is 80-100 ℃, and the alkali dissolution reaction time is 4-6 h;
in the step (3), the temperature of the hydrothermal crystallization reaction is 100-120 ℃, the pressure of the hydrothermal crystallization reaction is 2-6 MPa, and the time of the hydrothermal crystallization is 48-72 h;
the filtrate contains 45-55 g/L of SiO26 to 10g/L of Al2O3。
2. The process of claim 1, wherein the base is sodium hydroxide and/or potassium hydroxide.
3. The method according to claim 1, wherein in the step (2), the pH is adjusted so that the pH of the filtrate is 3-5.
4. The method according to any one of claims 1 to 3, wherein the SiO is present in the filtrate in an amount of 100 parts by weight2The addition amount of the polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer is 95-120 parts by weight.
5. The method according to any one of claims 1 to 3, wherein in the step (2), the mixing and formulating process is carried out at 35-40 ℃ for at least 10h under stirring.
6. The SBA-15 mesoporous molecular sieve prepared by the method of any one of claims 1-5, wherein the mesoporous molecular sieve contains 10-20 wt% of Al based on the total weight of the mesoporous molecular sieve2O380 to 90% by weight of SiO2；
The mesoporous molecular sieve contains micropores, and the volume of the micropores accounts for 10-20% of the total pore volume of the mesoporous molecular sieve.
7. The SBA-15 mesoporous molecular sieve of claim 6, wherein the mesoporous molecular sieve has a mesoporous pore volume of 0.7-0.9 cm3The micropore volume of the mesoporous molecular sieve is 0.2-0.4 cm3/g。
8. The SBA-15 mesoporous molecular sieve of claim 6 or 7, wherein the specific surface area of the mesoporous molecular sieve is 740 to 900m2(ii)/g; the pore diameter of the mesoporous molecular sieve is 6-10 nm, and the average particle size of the mesoporous molecular sieve is 12-21 nm.
9. Use of the SBA-15 mesoporous molecular sieve of any of claims 6-8 in catalytic reactions and adsorption.
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