CN111847460A - Method for synthesizing mesoporous silica MCM-41 by using organic silicon waste residues - Google Patents
Method for synthesizing mesoporous silica MCM-41 by using organic silicon waste residues Download PDFInfo
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 166
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 70
- 239000010703 silicon Substances 0.000 title claims abstract description 70
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 64
- 239000002699 waste material Substances 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 37
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 87
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 51
- 238000003756 stirring Methods 0.000 claims abstract description 37
- 239000006228 supernatant Substances 0.000 claims abstract description 29
- 239000003093 cationic surfactant Substances 0.000 claims abstract description 20
- 229910001868 water Inorganic materials 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 4
- 230000015572 biosynthetic process Effects 0.000 claims abstract 3
- 238000003786 synthesis reaction Methods 0.000 claims abstract 3
- 239000000428 dust Substances 0.000 claims description 37
- 239000000779 smoke Substances 0.000 claims description 37
- 238000006243 chemical reaction Methods 0.000 claims description 35
- 239000002893 slag Substances 0.000 claims description 35
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 33
- 238000001354 calcination Methods 0.000 claims description 33
- 239000008367 deionised water Substances 0.000 claims description 26
- 229910021641 deionized water Inorganic materials 0.000 claims description 26
- 238000002156 mixing Methods 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 22
- 239000000047 product Substances 0.000 claims description 22
- 230000032683 aging Effects 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 13
- 229910020489 SiO3 Inorganic materials 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- -1 polytetrafluoroethylene Polymers 0.000 claims description 11
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 11
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims 2
- 229910021486 amorphous silicon dioxide Inorganic materials 0.000 claims 1
- 238000003760 magnetic stirring Methods 0.000 claims 1
- 238000010979 pH adjustment Methods 0.000 claims 1
- 238000001308 synthesis method Methods 0.000 claims 1
- 239000000284 extract Substances 0.000 abstract description 11
- 239000002440 industrial waste Substances 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000003513 alkali Substances 0.000 abstract 1
- 238000004090 dissolution Methods 0.000 abstract 1
- 230000004927 fusion Effects 0.000 abstract 1
- 239000012265 solid product Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 12
- 239000011734 sodium Substances 0.000 description 11
- 239000012153 distilled water Substances 0.000 description 10
- 238000000605 extraction Methods 0.000 description 10
- 239000004570 mortar (masonry) Substances 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 239000004094 surface-active agent Substances 0.000 description 10
- 238000005216 hydrothermal crystallization Methods 0.000 description 9
- 239000011148 porous material Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000004071 soot Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 238000009826 distribution Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 238000001988 small-angle X-ray diffraction Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000011464 hollow brick Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/124—Preparation of adsorbing porous silica not in gel form and not finely divided, i.e. silicon skeletons, by acidic treatment of siliceous materials
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
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Abstract
The invention discloses a method for synthesizing mesoporous silica MCM-41 by using organic silicon waste residue, which uses organic silicon waste residue containing silicon simple substance and amorphous silica as a synthetic raw material, alkali fusion calcinates the waste residue and NaOH, extracts silicon supernatant after water dissolution, uses a cationic surfactant as a template agent, uniformly mixes and stirs the waste residue and the silicon supernatant, ages and cools after hydrothermal reaction, centrifugally washes a solid product, and then calcinates to remove the template agent, thereby finally obtaining the mesoporous silica MCM-41. The raw materials of the mesoporous silica prepared by the invention are waste residues generated in the production of organic silicon enterprises, so that the industrial wastes are recycled, and a cheap silicon source is found for the synthesis of the mesoporous silica. The invention has short synthesis process flow, simple operation and better application prospect.
Description
Technical Field
The invention belongs to the technical field of resource utilization of industrial wastes and preparation of porous materials, and particularly relates to a method for synthesizing mesoporous silica MCM-41 by using organic silicon waste residues.
Background
The M41 series mesoporous silica material is first successfully developed by Mobil corporation in 1992, and MCM-41 is the most widely used mesoporous silica, and has high application potential as a catalyst carrier, an adsorbent and other materials due to the excellent characteristics of uniform pore distribution (2-50nm), high specific surface area (1000M 2/g), good hydrothermal stability, thermal stability, hydrolytic stability and the like. The main raw material for synthesizing MCM-41 type mesoporous silica is silicon, the main sources are inorganic silicate (water glass) and organic silicate (ethyl orthosilicate), the price of the silicon is expensive, and the silicon brings many limitations for the production of the mesoporous silica, so that the search of cheap alternative silicon sources is one of the key points of the current research.
A large amount of waste residues can be generated in the production process of an organic silicon enterprise, the waste residues can be mainly divided into smoke dust collected in the incineration process of an incinerator and furnace end residues settled at the bottom, the generated waste residues need to be processed in time, and the environment can be greatly influenced by random stacking. The waste residue treatment mode usually adopted by organic silicon enterprises is mainly the treatment of cement factories or the manufacture of hollow bricks paid by enterprises, and not only has small treatment amount, but also has high treatment cost. The organic silicon waste residue contains a large amount of silicon simple substances and amorphous mesoporous silica, the silicon content is 97 percent, the reaction activity is high, and the silicon-containing organic silicon waste residue is an ideal silicon source for preparing the mesoporous silica. The waste residue generated in the production process of an organic silicon enterprise is recycled to prepare the multifunctional MCM-41 type mesoporous silica material, so that an ideal way is found for the treatment of the waste residue, the waste can be changed into valuable, and the material can be industrially applied as a new adsorption or catalysis material.
Disclosure of Invention
Aiming at the defects and problems in the prior art, the invention aims to provide a method for synthesizing mesoporous silica MCM-41 by using organic silicon waste residues. The invention relates to a method for preparing mesoporous silica MCM-41 by carrying out hydrothermal reaction on industrial waste and a cationic surfactant, wherein organic silicon enterprise waste residues containing a large amount of silicon simple substances and amorphous silica are used as a silicon source, and the industrial waste is recycled, so that the environmental problem caused by the massive stacking of the enterprise waste residues can be solved, and the cost problem of synthesizing the mesoporous silica can be greatly reduced.
The invention is realized by the following technical scheme:
a method for synthesizing mesoporous silica MCM-41 by using organic silicon waste residues comprises the following steps:
(1) extracting silicon from waste residues: grinding and crushing waste residue materials (furnace head residue and smoke dust), drying until no moisture exists, and mixing the waste residue: uniformly mixing NaOH in a mass ratio of 1: 0.5-1: 3, calcining at 350-650 ℃ for 0.5-4 h, dissolving calcined product and water in a solid-liquid ratio of 1: 20-1: 100 at a magnetic stirrer rotating speed of 600rpm, stirring for 2-24 h, extracting supernatant, and measuring the silicon content in the waste residue supernatant by using ICP (inductively coupled plasma atomic emission spectrometry);
(2) Preparation of mesoporous silica MCM-41: taking a cationic surfactant as a template agent, and taking Na in the waste residue supernatant prepared in the step (1)2SiO3: cationic surfactant: mixing deionized water at a molar ratio of 1:0.05: 100-1: 0.3:100 to prepare a mixed solution A, and adding H to the mixed solution A2SO4And NaOH is used for adjusting the pH value of the mixed solution A to 6.0-12.0, a magnetic stirrer is used for stirring for 1-4 hours at the rotating speed of 1000rpm, the mixed solution A is placed into a reaction kettle with a polytetrafluoroethylene lining, the reaction is carried out for 6-24 hours at the reaction temperature of 80-160 ℃, after the reaction is finished, the mixed solution A is aged and cooled, the aging time is 24-72 hours, reactants are subjected to centrifugal solid-liquid separation, deionized water is used for washing 3 times of reaction products, the reaction products are dried, and then a muffle furnace is used for calcining for 4-7 hours at the temperature of 500-700 ℃ to remove the MCM agent, so that the mesoporous silica-.
Further, the mass ratio of the furnace head slag to NaOH in the step (1) is preferably 1: 1.2; the mass ratio of the smoke dust to the NaOH is preferably 1: 2; the calcination temperature in the step (1) is preferably 550 ℃; the calcination time in the step (1) is preferably 2 h; the ratio of the waste residue calcined product to the water-solid-liquid ratio in the step (1) is preferably 1: 50; the stirring time of the water-soluble waste residue calcined product in the step (1) is preferably 6 hours.
Further, the cationic surfactant used in step (2) is preferably cetyltrimethylammonium bromide (CTAB); the preferable molar ratio of the waste residue extracting solution prepared in the step (2) to the cationic surfactant and the deionized water is 1:0.1: 100; the pH value of the mixed solution A in the step (2) is preferably adjusted to be 7; the stirring time in the step (2) is preferably 2 hours; the hydrothermal reaction temperature in the reaction kettle in the step (2) is preferably 120 ℃; the hydrothermal reaction time in the reaction kettle in the step (2) is preferably 12 h; the aging, cooling and aging time after the reaction in the step (2) is preferably 48 h; the calcination temperature for removing the template by calcination in the step (2) is preferably 600 ℃; the calcination time for removing the template by calcination in the step (2) is preferably 5 h.
Compared with the prior art, the invention has the beneficial effects that:
(1) the mesoporous silica MCM-41 synthesized by the method has the advantages of uniform and controllable pores, large specific surface area, good hydrothermal stability, thermal stability and hydrolytic stability, and is a good adsorption and catalysis material.
(2) The invention synthesizes the mesoporous silicon dioxide material by taking waste residues (smoke dust and furnace head residues) as silicon sources, thereby not only leading the industrial wastes to be recycled and solving the environmental problem caused by random accumulation of industrial wastes of enterprises, but also finding cheap alternative silicon sources for synthesizing the mesoporous silicon dioxide and solving the problem of expensive silicon sources of the synthesized mesoporous silicon dioxide.
(3) The method for synthesizing mesoporous silica MCM-41 by utilizing waste residues of organic silicon enterprises in a resource manner is simple in preparation process, low in energy consumption, free of secondary pollution in the production process and capable of well realizing industrial production.
Drawings
FIG. 1 is SEM image (A) and small-angle XRD image (B) and wide-angle XRD image (inset) of synthesized example 1 in the present invention.
FIG. 2 is a graph showing the nitrogen physisorption-desorption isotherms and pore distribution of example 1 synthesized in accordance with the present invention (inset).
FIG. 3 is a SEM image (A) and a small-angle XRD image (B) of a wide-angle XRD image (inset) of example 2 synthesized by the present invention.
FIG. 4 is a graph showing the nitrogen physisorption-desorption isotherms and pore distribution of example 2 synthesized in accordance with the present invention (inset).
Detailed Description
The invention will be further described with reference to the accompanying drawings.
Example 1
In this example, smoke dust is used to synthesize mesoporous silica MCM-41, and the method is as follows:
(1) grinding the smoke dust by using a mortar, drying, uniformly mixing the smoke dust and solid sodium hydroxide according to the mass ratio of 1:2, calcining for 2 hours in a muffle furnace at 550 ℃ until the smoke dust and NaOH completely react, taking out the crucible from the muffle furnace, and cooling to obtain a product after the smoke dust is calcined.
(2) Mixing the calcined smoke dust with deionized water at a solid-to-liquid ratio of 1:50, stirring for 6h at a rotating speed of 600rpm by using a magnetic stirrer, centrifugally extracting supernatant, measuring the silicon content by using ICP, and calculating the silicon extraction rate.
(3) According to n (Na)2SiO3):n(CTAB):n(H2O) molar ratio is 1:0.2:100, cationic surfactant Cetyl Trimethyl Ammonium Bromide (CTAB) is added into deionized water solution until the surfactant is completely dissolved, the solution is clarified, and then the solution is stirred and added with soot silicon extract and H2SO4Adjusting the pH value to 7, stirring for 2h at the rotating speed of 1000rpm of a magnetic stirrer, putting into a reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal crystallization for 12h at the reaction temperature of 120 ℃, aging for 48h, pouring out supernatant, carrying out centrifugal washing with distilled water and ethanol, drying at the temperature of 80 ℃, and calcining for 5h in air at the temperature of 600 ℃ to obtain the mesoporous silica sample.
Fig. 1(a) is an SEM image of mesoporous silica prepared in example 1, and the material shows a great monolithic aggregation property. Fig. 1(B) is an XRD pattern of the mesoporous silica prepared in example 1, and it can be seen from fig. 1(B) that the pores of the formed silica material correspond to a hexagonal mesoporous structure with good order. FIG. 2 is a nitrogen adsorption/desorption isotherm diagram of the mesoporous silica prepared in example 1, and it can be seen from FIG. 2 that the mesoporous silica synthesized under the conditions of example 1 has a pore diameter of 3.264nm and a specific surface area of 783.23m2Per gram of MCM-41 material.
Example 2
In the embodiment, the mesoporous silica MCM-41 is synthesized by using furnace end slag, and the method comprises the following steps:
(1) grinding the furnace head slag by using a mortar, drying, uniformly mixing the smoke dust and solid sodium hydroxide according to the mass ratio of 1:1.2, calcining for 2 hours in a muffle furnace at 550 ℃ until the furnace head slag and NaOH completely react, taking out the crucible from the muffle furnace, and cooling to obtain a product after the furnace head slag is calcined.
(2) Mixing the calcined product of the furnace end slag with deionized water at a solid-to-liquid ratio of 1:50, stirring for 6 hours at a rotating speed of 600rpm by using a magnetic stirrer, centrifugally extracting supernatant, measuring the silicon content by using ICP, and calculating the silicon extraction rate.
(3) According to n (Na) 2SiO3):n(CTAB):n(H2O) molar ratio is 1:0.3:100, cationic surfactant Cetyl Trimethyl Ammonium Bromide (CTAB) is added into deionized water solution until the surfactant is completely dissolved, the solution is clarified, then furnace head slag silicon extract is added by stirring, H is used2SO4Adjusting the pH value to 7, stirring for 2h at the rotating speed of 1000rpm of a magnetic stirrer, putting into a reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal crystallization for 12h at the reaction temperature of 120 ℃, aging for 48h, pouring out supernatant, carrying out centrifugal washing with distilled water and ethanol, drying at the temperature of 80 ℃, and calcining for 5h in air at the temperature of 600 ℃ to obtain the mesoporous silica sample.
Fig. 3(a) is an SEM image of the mesoporous silica prepared in example 2, and it can be seen from fig. 3(a) that the material shows a great monolithic aggregation property. Fig. 3(B) is an XRD pattern of the mesoporous silica prepared in example 2, and it can be seen from fig. 3(B) that the pores of the formed silica material correspond to a hexagonal mesoporous structure with good order. FIG. 4 is a nitrogen adsorption/desorption isotherm diagram of the mesoporous silica prepared in example 2, and it can be seen from FIG. 4 that the mesoporous silica synthesized under the conditions of example 2 has a pore diameter of 2.6761nm and a specific surface area of 826.27m2Per gram of MCM-41 material.
Example 3
In this example, smoke dust is used to synthesize mesoporous silica MCM-41, and the method is as follows:
(1) grinding the smoke dust by using a mortar, drying, then mixing the smoke dust and solid sodium hydroxide in a mass ratio of 1:0.5 uniformly, calcining for 0.5h in a muffle furnace at 350 ℃ until the smoke dust and NaOH completely react, taking out the crucible from the muffle furnace, and cooling to obtain a product after the smoke dust is calcined.
(2) Mixing the calcined smoke dust with deionized water at a solid-to-liquid ratio of 1:20, stirring for 2h at a rotation speed of 600rpm by using a magnetic stirrer, centrifugally extracting supernatant, measuring the silicon content by using ICP, and calculating the silicon extraction rate.
(3) According to n (Na)2SiO3):n(CTAB):n(H2O) molar ratio is 1:0.1:100, cationic surfactant Cetyl Trimethyl Ammonium Bromide (CTAB) is added into deionized water solution until the surfactant is completely dissolved, the solution is clarified, then the soot silicon extract is added by stirring, H is used2SO4Adjusting the pH value to 6, stirring for 1h at the rotating speed of 1000rpm of a magnetic stirrer, putting into a reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal crystallization for 6h at the reaction temperature of 160 ℃, aging for 36h, pouring out supernatant, carrying out centrifugal washing with distilled water and ethanol, drying at 80 ℃, and calcining for 4h in air at 500 ℃ to obtain the mesoporous silica sample.
Example 4
In the embodiment, the mesoporous silica MCM-41 is synthesized by using furnace end slag, and the method comprises the following steps:
(1) grinding the furnace head slag by using a mortar, drying, uniformly mixing the furnace head slag and solid sodium hydroxide according to the mass ratio of 1:3, calcining for 4 hours in a muffle furnace at 650 ℃ until the furnace head slag and NaOH completely react, taking out the crucible from the muffle furnace, and cooling to obtain a product after the furnace head slag is calcined.
(2) Mixing the calcined product of the furnace end slag with deionized water according to the solid-liquid ratio of 1:100, stirring for 24 hours at the rotating speed of 600rpm by using a magnetic stirrer, centrifugally extracting supernatant, measuring the silicon content by ICP, and calculating the silicon extraction rate.
(3) According to n (Na)2SiO3):n(CTAB):n(H2O) molar ratio is 1:0.4:100, cationic surfactant Cetyl Trimethyl Ammonium Bromide (CTAB) is added into deionized water solution until the surfactant is completely dissolved, the solution is clarified, then furnace head slag silicon extract is added by stirring, H is used2SO4Adjusting pH to 8, stirring at 1000rpm for 2 hr with a magnetic stirrer, and charging with polytetrafluoroethyleneHydrothermal crystallization is carried out for 10h at the reaction temperature of 140 ℃ in a reaction kettle with an olefin lining, the supernatant is poured out after aging for 50h, centrifugal washing is carried out by distilled water and ethanol, drying is carried out at the temperature of 80 ℃, and calcination is carried out for 7h in the air at the temperature of 700 ℃ to obtain a mesoporous silicon dioxide sample.
Example 5
In this example, smoke dust is used to synthesize mesoporous silica MCM-41, and the method is as follows:
(1) grinding the smoke dust by using a mortar, after drying, uniformly mixing the smoke dust and solid sodium hydroxide according to the mass ratio of 1:2.5, calcining for 1h in a muffle furnace at 450 ℃ until the smoke dust and NaOH completely react, taking out the crucible from the muffle furnace, and cooling to obtain a product after the smoke dust is calcined.
(2) Mixing the calcined smoke dust with deionized water at a solid-to-liquid ratio of 1:40, stirring for 8h at a rotation speed of 600rpm by using a magnetic stirrer, centrifugally extracting supernatant, measuring the silicon content by using ICP, and calculating the silicon extraction rate.
(3) According to n (Na)2SiO3):n(CTAB):n(H2O) molar ratio is 1:0.2:100, cationic surfactant Cetyl Trimethyl Ammonium Bromide (CTAB) is added into deionized water solution until the surfactant is completely dissolved, the solution is clarified, then the soot silicon extract is added by stirring, H is used2SO4Adjusting the pH value to 11, stirring for 4h at the rotating speed of 1000rpm of a magnetic stirrer, putting into a reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal crystallization for 15h at the reaction temperature of 130 ℃, aging for 65h, pouring out supernatant, carrying out centrifugal washing with distilled water and ethanol, drying at the temperature of 80 ℃, and calcining for 7h in air at the temperature of 600 ℃ to obtain a mesoporous silica sample.
Example 6
In the embodiment, the mesoporous silica MCM-41 is synthesized by using furnace end slag, and the method comprises the following steps:
(1) crushing the furnace head slag by using a mortar, drying, uniformly mixing the furnace head slag and solid sodium hydroxide according to the mass ratio of 1:1, calcining for 2.5 hours in a muffle furnace at 550 ℃ until the furnace head slag and NaOH completely react, taking out the crucible from the muffle furnace, and cooling to obtain a product of the calcined furnace head slag.
(2) Mixing the calcined product of the furnace end slag with deionized water according to the solid-liquid ratio of 1:80, stirring for 12 hours at the rotating speed of 600rpm by using a magnetic stirrer, centrifugally extracting supernatant, measuring the silicon content by ICP, and calculating the silicon extraction rate.
(3) According to n (Na)2SiO3):n(CTAB):n(H2O) molar ratio is 1:0.05:100, cationic surfactant Cetyl Trimethyl Ammonium Bromide (CTAB) is added into deionized water solution until the surfactant is completely dissolved, the solution is clarified, then furnace head slag silicon extract is added by stirring, H is used for reaction, and the mixture is stirred and stirred2SO4Adjusting the pH value to 12, stirring for 2h at the rotating speed of 1000rpm of a magnetic stirrer, putting into a reaction kettle with a polytetrafluoroethylene lining, performing hydrothermal crystallization for 20h at the reaction temperature of 120 ℃, aging for 60h, pouring out supernatant, centrifugally washing with distilled water and ethanol, drying at 80 ℃, and calcining for 6h in air at 500 ℃ to obtain a mesoporous silica sample.
Example 7
In this example, smoke dust is used to synthesize mesoporous silica MCM-41, and the method is as follows:
(1) grinding the smoke dust by using a mortar, drying, uniformly mixing the smoke dust and solid sodium hydroxide according to the mass ratio of 1:3, calcining for 3 hours in a muffle furnace at 550 ℃ until the smoke dust and NaOH completely react, taking out the crucible from the muffle furnace, and cooling to obtain a product after the smoke dust is calcined.
(2) Mixing the calcined smoke dust with deionized water at a solid-to-liquid ratio of 1:70, stirring for 10h at a rotation speed of 600rpm by using a magnetic stirrer, centrifugally extracting supernatant, measuring the silicon content by using ICP, and calculating the silicon extraction rate.
(3) According to n (Na)2SiO3):n(CTAB):n(H2O) molar ratio is 1:0.2:100, cationic surfactant Cetyl Trimethyl Ammonium Bromide (CTAB) is added into deionized water solution until the surfactant is completely dissolved, the solution is clarified, then the soot silicon extract is added by stirring, H is used2SO4Adjusting pH to 7, stirring at 1000rpm for 2h with magnetic stirrer, placing in a reaction kettle with polytetrafluoroethylene lining, performing hydrothermal crystallization at 80 deg.C for 22h, aging for 24h, pouring out supernatant, centrifuging with distilled water and ethanol, washing at 80 deg.C, oven drying at 650 deg.C in airAnd calcining for 4.5h to obtain a mesoporous silica sample.
Example 8
In the embodiment, the mesoporous silica MCM-41 is synthesized by using furnace end slag, and the method comprises the following steps:
(1) crushing the furnace head slag by using a mortar, drying, uniformly mixing the furnace head slag and solid sodium hydroxide according to the mass ratio of 1:1.5, calcining for 3.5 hours in a muffle furnace at 500 ℃ until the furnace head slag and NaOH completely react, taking out the crucible from the muffle furnace, and cooling to obtain a product after the furnace head slag is calcined.
(2) Mixing the calcined product of the furnace end slag with deionized water according to the solid-liquid ratio of 1:100, stirring for 12 hours at the rotating speed of 600rpm by using a magnetic stirrer, centrifugally extracting supernatant, measuring the silicon content by ICP, and calculating the silicon extraction rate.
(3) According to n (Na)2SiO3):n(CTAB):n(H2O) molar ratio is 1:0.2:100, cationic surfactant Cetyl Trimethyl Ammonium Bromide (CTAB) is added into deionized water solution until the surfactant is completely dissolved, the solution is clarified, then furnace head slag silicon extract is added by stirring, H is used2SO4Adjusting the pH value to 9, stirring for 3h at the rotating speed of 1000rpm of a magnetic stirrer, putting into a reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal crystallization for 20h at the reaction temperature of 90 ℃, aging for 70h, pouring out supernatant, carrying out centrifugal washing by using distilled water and ethanol, drying at 80 ℃, and calcining for 6h in air at 550 ℃ to obtain the mesoporous silica sample.
Example 9
In this example, smoke dust is used to synthesize mesoporous silica MCM-41, and the method is as follows:
(1) grinding the smoke dust by using a mortar, drying, uniformly mixing the smoke dust and solid sodium hydroxide according to the mass ratio of 1:2, calcining for 1.5h in a muffle furnace at 400 ℃ until the smoke dust and NaOH completely react, taking out the crucible from the muffle furnace, and cooling to obtain a product after the smoke dust is calcined.
(2) Mixing the calcined smoke dust with deionized water at a solid-to-liquid ratio of 1:90, stirring for 20h at a rotation speed of 600rpm by using a magnetic stirrer, centrifugally extracting supernatant, measuring the silicon content by using ICP, and calculating the silicon extraction rate.
(3) According to n (Na)2SiO3):n(CTAB):n(H2O) molar ratio is 1:0.1:100, cationic surfactant Cetyl Trimethyl Ammonium Bromide (CTAB) is added into deionized water solution until the surfactant is completely dissolved, the solution is clarified, then the soot silicon extract is added by stirring, H is used2SO4Adjusting the pH value to 10, stirring for 2h at the rotating speed of 1000rpm of a magnetic stirrer, putting into a reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal crystallization for 8h at the reaction temperature of 100 ℃, aging for 40h, pouring out supernatant, carrying out centrifugal washing with distilled water and ethanol, drying at 80 ℃, and calcining for 6.5h in air at 450 ℃ to obtain a mesoporous silica sample.
Example 10
In the embodiment, the mesoporous silica MCM-41 is synthesized by using furnace end slag, and the method comprises the following steps:
(1) grinding the furnace head slag by using a mortar, drying, uniformly mixing the furnace head slag and solid sodium hydroxide according to the mass ratio of 1:2, calcining for 2 hours in a muffle furnace at 600 ℃ until the furnace head slag and NaOH completely react, taking out the crucible from the muffle furnace, and cooling to obtain a product after the furnace head slag is calcined.
(2) Mixing the calcined product of the furnace end slag with deionized water at a solid-to-liquid ratio of 1:60, stirring for 16h at a rotating speed of 600rpm by using a magnetic stirrer, centrifugally extracting supernatant, measuring the silicon content by using ICP, and calculating the silicon extraction rate.
(3) According to n (Na)2SiO3):n(CTAB):n(H2O) molar ratio is 1:0.1:100, cationic surfactant Cetyl Trimethyl Ammonium Bromide (CTAB) is added into deionized water solution until the surfactant is completely dissolved, the solution is clarified, then the soot silicon extract is added by stirring, H is used2SO4Adjusting the pH value to 7, stirring for 1h at the rotating speed of 1000rpm of a magnetic stirrer, putting into a reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal crystallization for 24h at the reaction temperature of 80 ℃, aging for 72h, pouring out supernatant, carrying out centrifugal washing with distilled water and ethanol, drying at the temperature of 80 ℃, and calcining for 5h in air at the temperature of 600 ℃ to obtain the mesoporous silica sample.
The foregoing merely represents preferred embodiments of the invention, which are described in some detail and detail, and therefore should not be construed as limiting the scope of the invention. It should be noted that, for those skilled in the art, various changes, modifications and substitutions can be made without departing from the spirit of the present invention, and these are all within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (8)
1. A method for synthesizing mesoporous silica MCM-41 by using organic silicon waste residues is characterized by comprising the following steps: the method adopts organosilicon waste residues containing silicon simple substances and amorphous silicon dioxide as synthesis raw materials, wherein the organosilicon waste residues are furnace head residues or smoke dust, and the synthesis method comprises the following steps:
(1) extracting silicon from waste residues: grinding and crushing the organic silicon waste residue material, drying until no moisture exists, and preparing the organic silicon waste residue material according to the following steps: uniformly mixing NaOH in a mass ratio of 1: 0.5-1: 3, calcining at 350-650 ℃ for 0.5-4 h, uniformly mixing the calcined product with water in a solid-liquid mass ratio of 1: 20-1: 100, dissolving the calcined product in water by using a magnetic stirrer, stirring for 2-24 h, extracting supernatant, and measuring the silicon content in the extracted supernatant by using an ICP emission spectrometer;
(2) Preparation of mesoporous silica MCM-41: taking a cationic surfactant as a template agent, and adding Na in the supernatant prepared in the step (1)2SiO3: cationic surfactant: mixing deionized water according to the molar ratio of 1:0.05: 100-1: 0.3:100 to prepare a mixed solution A; sequentially carrying out pH adjustment, magnetic stirring for 1-4 h and heating reaction for 6-24 h on the mixed solution A, wherein the pH is adjusted to 6.0-12.0, the heating reaction vessel is a reaction kettle with a polytetrafluoroethylene lining, and the reaction temperature is 80-160 ℃; and after the reaction is finished, sequentially carrying out aging cooling for 24-72 hours, centrifugal solid-liquid separation, deionized water washing for a plurality of times, drying, and finally calcining in a muffle furnace at 500-700 ℃ for 4-7 hours to remove the template agent to obtain the mesoporous silica MCM-41.
2. The method for synthesizing mesoporous silica MCM-41 from waste organosilicon residues as claimed in claim 1, wherein the method comprises the following steps: in the step (1), the mass ratio of the furnace head slag to the NaOH is 1: 1.2; the mass ratio of the smoke dust to the NaOH is 1: 2.
3. the method for synthesizing mesoporous silica MCM-41 from waste organosilicon residues as claimed in claim 1, wherein the method comprises the following steps: and (2) calcining the waste residues and NaOH in the step (1) at 550 ℃ for 2 h.
4. The method for synthesizing mesoporous silica MCM-41 from waste organosilicon residues as claimed in claim 1, wherein the method comprises the following steps: the mass ratio of the calcined product in the step (1) to water is 1:50, and the stirring time of the calcined product of the water-soluble waste residue is 6 hours.
5. The method for synthesizing mesoporous silica MCM-41 from waste organosilicon residues as claimed in claim 1, wherein the method comprises the following steps: the cationic surfactant in the step (2) is preferably cetyl trimethyl ammonium bromide; the molar ratio of the prepared supernatant to the cationic surfactant and the molar ratio of the prepared deionized water are 1:0.1: 100.
6. The method for synthesizing mesoporous silica MCM-41 from waste organosilicon residues as claimed in claim 1, wherein the method comprises the following steps: and (3) adjusting the pH value of the mixed solution A in the step (2) to 7, and magnetically stirring for 2 hours.
7. The method for synthesizing mesoporous silica MCM-41 from waste organosilicon residues as claimed in claim 1, wherein the method comprises the following steps: the hydrothermal reaction temperature in the reaction kettle in the step (2) is 120 ℃, the hydrothermal reaction time is 12 hours, and the aging, cooling and aging time after the reaction is 48 hours.
8. The method for synthesizing mesoporous silica MCM-41 from waste organosilicon residues as claimed in claim 1, wherein the method comprises the following steps: the calcination temperature for removing the template agent in the step (2) is 600 ℃, and the calcination time is 5 h.
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| CN112675814A (en) * | 2020-12-10 | 2021-04-20 | 四川大学 | Silicon-rich biomass-based biochar/mesoporous silica composite material and preparation method and application thereof |
| CN113526511A (en) * | 2021-08-17 | 2021-10-22 | 日月光半导体制造股份有限公司 | Method for producing porous silica |
| CN115554976A (en) * | 2022-10-13 | 2023-01-03 | 合肥工业大学 | Preparation method of biomass ash-based mesoporous silicon adsorbent |
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