CN117085669A - Method for preparing mesoporous silica/titanium dioxide composite photocatalytic material from coal gasification coarse slag and application of mesoporous silica/titanium dioxide composite photocatalytic material - Google Patents
Method for preparing mesoporous silica/titanium dioxide composite photocatalytic material from coal gasification coarse slag and application of mesoporous silica/titanium dioxide composite photocatalytic material Download PDFInfo
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- CN117085669A CN117085669A CN202311228601.3A CN202311228601A CN117085669A CN 117085669 A CN117085669 A CN 117085669A CN 202311228601 A CN202311228601 A CN 202311228601A CN 117085669 A CN117085669 A CN 117085669A
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- coal gasification
- mesoporous silica
- coarse slag
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- titanium dioxide
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 147
- 239000000463 material Substances 0.000 title claims abstract description 109
- 239000002893 slag Substances 0.000 title claims abstract description 108
- 239000003245 coal Substances 0.000 title claims abstract description 103
- 238000002309 gasification Methods 0.000 title claims abstract description 103
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 73
- 239000002131 composite material Substances 0.000 title claims abstract description 53
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 44
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 41
- 239000002253 acid Substances 0.000 claims abstract description 74
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 70
- 238000004090 dissolution Methods 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 238000011068 loading method Methods 0.000 claims abstract description 21
- 239000002994 raw material Substances 0.000 claims abstract description 19
- 239000000945 filler Substances 0.000 claims abstract description 4
- 230000001105 regulatory effect Effects 0.000 claims abstract description 3
- 239000002002 slurry Substances 0.000 claims description 87
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 56
- 238000003756 stirring Methods 0.000 claims description 48
- 238000000227 grinding Methods 0.000 claims description 43
- 229910052799 carbon Inorganic materials 0.000 claims description 41
- 238000000926 separation method Methods 0.000 claims description 37
- 238000005188 flotation Methods 0.000 claims description 35
- 238000005406 washing Methods 0.000 claims description 33
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 32
- 238000001035 drying Methods 0.000 claims description 31
- 239000007787 solid Substances 0.000 claims description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 20
- 239000004570 mortar (masonry) Substances 0.000 claims description 15
- 239000000047 product Substances 0.000 claims description 15
- 238000001354 calcination Methods 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 14
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 11
- 239000012629 purifying agent Substances 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 8
- 230000007062 hydrolysis Effects 0.000 claims description 8
- 238000006460 hydrolysis reaction Methods 0.000 claims description 8
- CYUOWZRAOZFACA-UHFFFAOYSA-N aluminum iron Chemical compound [Al].[Fe] CYUOWZRAOZFACA-UHFFFAOYSA-N 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 7
- 238000001556 precipitation Methods 0.000 claims description 7
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 6
- 150000003608 titanium Chemical class 0.000 claims description 6
- 229910021645 metal ion Inorganic materials 0.000 claims description 5
- 238000001179 sorption measurement Methods 0.000 claims description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 239000007791 liquid phase Substances 0.000 claims description 4
- 239000011343 solid material Substances 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000004566 building material Substances 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims 1
- 235000011941 Tilia x europaea Nutrition 0.000 claims 1
- 239000004571 lime Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 9
- 230000000593 degrading effect Effects 0.000 abstract description 6
- 239000002910 solid waste Substances 0.000 abstract description 6
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 5
- 150000004706 metal oxides Chemical class 0.000 abstract description 5
- 238000000746 purification Methods 0.000 abstract description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract 1
- 230000001276 controlling effect Effects 0.000 abstract 1
- 239000010936 titanium Substances 0.000 abstract 1
- 229910052719 titanium Inorganic materials 0.000 abstract 1
- 239000011148 porous material Substances 0.000 description 24
- 239000007789 gas Substances 0.000 description 11
- 239000002956 ash Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 239000000706 filtrate Substances 0.000 description 6
- 239000002699 waste material Substances 0.000 description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- 241000282414 Homo sapiens Species 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 230000006378 damage Effects 0.000 description 4
- 239000011941 photocatalyst Substances 0.000 description 4
- 239000012855 volatile organic compound Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 239000013335 mesoporous material Substances 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000003570 air Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000010883 coal ash Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000009423 ventilation Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-O hydridodioxygen(1+) Chemical compound [OH+]=O MYMOFIZGZYHOMD-UHFFFAOYSA-O 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000011325 microbead Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
Classifications
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/007—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by irradiation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2259/00—Type of treatment
- B01D2259/45—Gas separation or purification devices adapted for specific applications
- B01D2259/4508—Gas separation or purification devices adapted for specific applications for cleaning air in buildings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2259/00—Type of treatment
- B01D2259/80—Employing electric, magnetic, electromagnetic or wave energy, or particle radiation
Abstract
The invention relates to a method for preparing mesoporous silica/titanium dioxide composite photocatalytic material by coal gasification coarse slag and application thereof, wherein the raw material of the invention is coal gasification coarse slag, and the mesoporous silica material with adjustable aperture can be obtained by regulating and controlling dissolution under mild conditions by utilizing the characteristics of high activity of metal oxide in the coal gasification coarse slag and easy dissolution by reaction with acid; the mesoporous silica material prepared by acid dissolution has higher specific surface area, thus providing feasibility for loading titanium dioxide and loading the prepared mesoporous silica/titanium dioxideThe specific surface area of the composite photocatalytic material is more than 200m 2 The/g can be used as a wall material for adsorbing and photo-catalytically degrading formaldehyde gas, and is used as a product prepared from solid waste, and the formaldehyde purification rate is higher than that of other products sold in the market; the composite photocatalytic material can also be used as a filler to be mixed with other wall materials, so that the comprehensive performance is improved.
Description
Technical Field
The invention relates to a preparation method and application of a photocatalytic material, in particular to a method for preparing mesoporous silica/titanium dioxide composite photocatalytic material from coal gasification coarse slag and application thereof.
Background
Coal gasification technology is rapidly developed in China as a clean coal treatment technology. Coal gasification is a process of generating clean synthetic gas (such as hydrogen and carbon dioxide) by reacting gasifying agents (such as air, oxygen, water vapor and the like) with raw coal and water slurry in a high-temperature gasifier under certain temperature and pressure conditions. In the process, inorganic components in the coal and the carbon components which are not completely oxidized are converted into slag to be discharged out of the high-temperature furnace, and finally solid waste, namely gas slag, is formed. Wherein the slag with smaller granularity circulates in the furnace along with the airflow, is cooled, and is discharged from the evaporation hot water tower along with the coal ash water to become coal gasification fine slag; and slag with larger granularity and weight flows to the furnace bottom through the water cooling chamber and is discharged, namely coal gasification coarse slag. In the large-area stacking process of the coal gasification slag, the coal gasification slag occupies land, pollutes the environment and also endangers the health of human beings, and the sustainable development of the coal gasification industry is restrained, so the coal gasification slag is a new solid waste to be solved urgently. In recent years, around the beginning of the utilization of gas slag, attention has been paid to some scholars, the hazard of gas slag is recognized, the composition structure and characteristics of the gas slag are researched from different angles, and the disposal and utilization problems of the gas slag are emphasized.
Investigation shows that people learn work and life indoors for most of the time each day,various indoor decoration materials release various organic species, and indoor Volatile Organic Compounds (VOCs) are chemical substances with high vapor pressure and low boiling point, and are discharged into the air to generate pollutants through atmospheric photochemical reaction, so that the VOCs are one of important precursors for causing air pollution. In addition, VOCs easily enter the human body through the respiratory tract, the alimentary canal and the skin, and further have toxic effects on the human body, wherein formaldehyde (HCHO) has strong toxicity and poses a great threat to the health of the human body. There are many ways to reduce formaldehyde in the room, such as thermal catalysis, photocatalysis, phytoremediation, ventilation, plasma technology, biochemical technology, and physical or chemical adsorption. Wherein, the thermal catalysis needs very high temperature, the plasma technology is subject to strict experimental conditions, and a large amount of energy is consumed in the implementation process, so that the methods are difficult to apply in actual life; although methods of phytoremediation and ventilation are relatively simple, it takes a long time to observe a practical effect. The photocatalytic degradation technology is widely applied due to the advantages of low energy consumption, good effect, wide range, convenient operation and the like, and the key point of the photocatalytic degradation technology is the selection of the photocatalyst, and among a plurality of photocatalysts, tiO 2 The photocatalyst has the advantages of good resistance to photochemical corrosion, strong oxidizing property, no toxicity, low cost, easy photocatalytic reaction, low energy consumption and the like, and can play a role under the condition of low temperature, thereby becoming an ideal photocatalyst. In recent years, around TiO 2 The use of photocatalytic materials to degrade organic matter has attracted considerable attention.
Comprehensive research reports on the coal gasification slag show that the existing utilization of the coal gasification slag mainly aims at fine slag, but the research on the utilization of coarse slag is rare. Because the coal gasification coarse slag has the characteristics of large specific surface area and low carbon content, the coal gasification coarse slag can be used as a wall material for adsorbing and degrading harmful gases such as formaldehyde, and the research on preparing the photocatalytic composite material by taking the coal gasification coarse slag as a raw material and loading titanium dioxide is not yet seen at present, and the invention is researched in the field.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for preparing mesoporous silica/titanium dioxide composite photocatalytic material from coal gasification coarse slag, which comprises the following steps:
(1) Taking a proper amount of coal gasification coarse slag raw material, and adding water to prepare coal gasification coarse slag slurry with the solid content of 10-30wt%;
(2) Fully stirring the slurry prepared in the step (1), then removing carbon through flotation separation, collecting flotation tailing slurry, and grinding until the granularity of the flotation tailing is more than 10 meshes; drying the ground tailing pulp, and collecting low-carbon coal gasification coarse slag;
(3) Mixing a proper amount of acid solution with the low-carbon coal gasification coarse slag to obtain slurry, and stirring to perform acid dissolution reaction; the molar ratio of the acid ash ratio in the obtained slurry is 0.8-1.2; the acid concentration is 5-20wt%, the acid dissolution reaction temperature is 30-90 ℃, and the stirring time is 2-10h;
(4) Carrying out solid-liquid separation on the reacted materials, washing, drying and grinding the solid materials, wherein the granularity reaches more than 100 meshes, and obtaining the mesoporous silica material;
(5) Adding water into the mesoporous silica material obtained in the step (4) to prepare slurry with the solid content of 10-30wt%, stirring the prepared slurry, heating to 70-90 ℃, adding titanium salt solution for reaction, and carrying out hydrolysis precipitation to obtain TiO 2 Loading on mesoporous silica material to form composite material precursor;
(6) And (3) carrying out solid-liquid separation on the reacted materials, washing, drying, grinding and calcining the solid materials, wherein the calcining temperature is 500-800 ℃, and the mesoporous silica/titanium dioxide composite photocatalytic material is obtained.
The coal gasification coarse slag raw material in the step (1) refers to residues discharged through the bottom of the coal gasification furnace in the coal gasification process, and the coal gasification process is well known in the art and is not repeated herein. It is understood by those skilled in the art that the coal gasification raw slag feed consists essentially of inorganic mineral components that form coal ash and char that remains from incomplete gasification during gasification, with the highest silica ratio followed by alumina, calcium oxide, iron oxide, and the like. The carbon content of the coal gasification coarse slag raw material is lower than 10wt%.
Further, the solid content of the coal gasification raw slag slurry in the step (1) is preferably 15wt% to 25wt%, such as 20wt%; the prepared coal gasification coarse slag slurry is stirred for at least 1h and then is subjected to the next stirring treatment, such as 1.5h and 2h, so that the coal gasification coarse slag raw material is fully contacted and wetted with water, and the subsequent flotation separation is facilitated.
Further, in the step (2), fully stirring the slurry, then carrying out flotation separation, and collecting flotation tailings to obtain low-carbon coal gasification coarse slag; the flotation separation can be carried out by adopting a flotation machine, in the flotation separation, due to the action of gravity, the carbon components with smaller density and granularity in the coal gasification coarse slag raw material float on the water surface for preferential separation, and the coal gasification coarse slag with larger density and granularity is left to be tailings, so that the separation is realized. The tailings left from the flotation separation contain little carbon, with a carbon content of less than 1wt%. The flotation tailings contain materials with larger granularity, so that the overall granularity of the tailings is further required to be reduced, flotation tailing pulp is collected and subjected to wet grinding through a sand mill, and the granularity of the tailings after grinding is more than 10 meshes, so that the subsequent acid dissolution is facilitated; drying the ground tailing pulp at 100-120 ℃; the solid obtained after drying is the coal gasification coarse slag with low carbon content.
In the coal gasification process, slag adheres to the inner wall of the gasification furnace, flows into the furnace bottom to be chilled in a molten state to form coal gasification coarse slag, the time of the chilling process is short, crystalline phases cannot be formed, all components exist in a glassy state, the lower crystallinity indicates that the activity of metal oxides in the coarse slag is higher, the metal oxides are easy to react with acid to dissolve out, and the residual siliceous components form unordered porous microbead states with different pore diameters and porosities along with the different dissolving-out amounts of metal ions, so that the siliceous skeleton mesoporous material can be obtained. Further, in step (3), the acid concentration is 5 to 20wt%, for example 5wt%, 10wt%, 15wt% or 20wt%; the temperature is 30-90deg.C, such as 30deg.C, 50deg.C, 70deg.C or 90deg.C; stirring for 2-10h; the acid solution is an acid solution which is favorable for dissolving out metal elements such as aluminum, calcium, iron and the like in coal gasification coarse slag, and the acid solution is hydrochloric acid or nitric acid aqueous solution.
Further, in the step (4), the solid-liquid separation mode is filter pressing or suction filtration; the washing mode is that acid washing is carried out firstly and then water washing is carried out, so that impurities on the surface of the material are removed; the drying temperature is 100-120 ℃; the grinding mode is mortar grinding, and the granularity is further reduced by more than 100 meshes, so that the follow-up loading is facilitated; through the steps, the acid-soluble regulation type mesoporous silica material is obtained.
When the acid solution is hydrochloric acid, the liquid phase product obtained by the solid-liquid separation after the acid dissolution is mainly chloride containing metal ions such as aluminum, iron, calcium and the like, so that the water purifying agent can be further prepared, the comprehensive utilization is realized, and the economic benefit is further improved. When the concentration of hydrochloric acid is 10-20wt%, the concentration of aluminum chloride can reach 29wt% by simply adjusting the concentration of metal ions such as aluminum, iron, calcium and the like in the liquid phase product, so that the aluminum-iron water purifying agent is prepared.
Further, in the step (5), the mesoporous silica material is taken and added with water to prepare slurry with the solid content of 10wt%, 20wt% or 30wt%; stirring the prepared slurry for at least 0.5h, and then heating to 70-90 ℃; adding the prepared titanium salt solution at a constant rate of 1-2mL/min through a flowmeter in the process of continuous stirring; simultaneously, the pH value of the solution is regulated to be 1-4 by the prepared alkali solution; continuing stirring the slurry for 1-6h; the titanium salt solution is titanium sulfate or titanium chloride aqueous solution with the concentration of 0.1-0.5mol/L, and the alkali solution is sodium hydroxide or potassium hydroxide aqueous solution with the concentration of 1-3mol/L.
Further, in the step (6), the solid-liquid separation mode is suction filtration or centrifugation; the drying temperature is 70-90 ℃; the grinding mode is mortar grinding, and aims to reduce the granularity and keep the granularity above 100 meshes; thereby facilitating subsequent calcination; the calcination temperature is 500-800 ℃; the calcination time is 2-4h; the purpose of calcination is to cause the composite precursor to form anatase, brookite or rutile phases, thereby obtaining the property of photocatalytic degradation of formaldehyde.
Through the steps, the mesoporous silica/titanium dioxide composite photocatalytic material capable of degrading formaldehyde by photocatalysis is obtained.
The mesoporous silica/titanium dioxide composite photocatalytic material finally obtained by the invention can be used for degrading formaldehyde by photocatalysis.
The mesoporous silica/titanium dioxide composite photocatalytic material finally obtained by the invention can be used for preparing wall materials with formaldehyde adsorption and photocatalytic degradation functions or used as a filler with formaldehyde adsorption and photocatalytic degradation functions to be mixed with other building materials.
The working principle of the invention is as follows:
the raw material of the invention is coal gasification coarse slag, the carbon content is extremely low and less than 1%, and the lower carbon content ensures that the product obtained after the subsequent steps, such as acid dissolution and loading, of the invention is white. The product of the invention can be directly used as the wall material without the step of calcining to remove carbon because the application scene of the wall material mostly requires the product to be white in color; the pore structure of the product is not destroyed due to collapse caused by high temperature without the step of calcining and removing carbon, and the obtained product can be ensured to have larger specific surface area. According to the characteristics of large density and granularity of coal gasification coarse slag and easiness in separation from carbon components with small density and granularity, a flotation method is innovatively used for physical carbon removal, and the method has a good carbon removal effect and does not damage the pore structure of raw materials. The density and granularity of coal gasification fine slag are smaller, and the difference between the density and granularity and the carbon component is smaller, so that the condition of flotation and carbon removal is not provided.
In the invention, the granularity of the gasified coarse slag before acid dissolution is controlled to be more than 10 meshes, and if the granularity is too large, the acid and the coarse slag can not be completely contacted during acid dissolution, so that the dissolution rate is affected; if the granularity is too small, the acid and the coarse slag react too fast during acid dissolution because the activity of the metal oxide in the coarse slag is higher, which is unfavorable for the smooth progress of the reaction and the formation of a good pore structure.
The invention explores the influence of the acid ash ratio, the acid dissolution temperature, the acid dissolution time, the hydrochloric acid concentration and the like on the acid dissolution when the coal gasification coarse slag is acid-dissolved, and the exploration of the acid ash ratio saves the consumption of hydrochloric acid on the premise of good acid dissolution effect, avoids unnecessary waste of hydrochloric acid and saves energy sources; investigation of the acid dissolution temperature showed that: under the condition of longer acid dissolution time, better acid dissolution effect can be obtained at lower acid dissolution temperature, and energy sources are saved as well; the exploration of the concentration of the hydrochloric acid provides a theoretical basis for further comprehensive utilization of the filtrate obtained after acid dissolution as a water purifying agent.
The mesoporous silica material obtained after the acid dissolution of coal gasification coarse slag is used as a raw material, titanium dioxide is loaded in a hydrolysis precipitation mode, the granularity of the mesoporous material before loading is controlled to be more than 100 meshes, and the purpose of requiring smaller granularity is to facilitate the better dispersion of the mesoporous material in an aqueous solution and facilitate the next step of loading of titanium dioxide.
As the material is subjected to intense friction and impact during the grinding process, these forces may damage or alter the pore structure in the material, particularly smaller or shallower pores, and abrasive particles and grinding tools may also enter the pores during the grinding process, filling the pores or blocking the pore mouths, resulting in partial or complete destruction of the pores. In order to avoid the damage of the pore structure of the material due to the excessive force in the machine grinding process, the invention adopts a relatively mild mode of mortar grinding to the porous material obtained by acid dissolution, and the pore structure of the porous material is damaged as least as possible while the granularity of the material is reduced.
According to the invention, the mesoporous silica material is used as the material after acid dissolution pore-forming, and according to the prior experience, the difficulty of loading titanium dioxide by using the mesoporous silica material as the raw material is high.
The invention has the beneficial effects that:
the method for preparing the mesoporous silica/titanium dioxide composite photocatalytic material from the coal gasification coarse slag and the application thereof can realize the development of high added value products of the coal gasification coarse slag, and can regulate and control the dissolution under mild conditions to obtain the mesoporous silica material with adjustable aperture by utilizing the characteristics of higher activity of metal oxides in the coal gasification coarse slag and easy dissolution by reaction with acid; in addition, the metal ions dissolved by the acid can be used for further preparing the water purifying agent, thereby realizing the comprehensive total components of the gas slagThe utilization of the waste materials is changed into valuable. The mesoporous silica material prepared by acid dissolution has higher specific surface area, thus providing feasibility for loading titanium dioxide, and the specific surface area of the mesoporous silica/titanium dioxide composite photocatalytic material prepared by loading is more than 200m 2 The/g can be used as a wall material for adsorbing and photo-catalytically degrading formaldehyde gas, and is used as a product prepared from solid waste, and the formaldehyde purification rate is higher than that of other products sold in the market; meanwhile, the composite photocatalytic material can be used as a filler to be mixed with other wall materials, so that the comprehensive performance is improved. The composite photocatalytic material prepared by the invention saves the resource cost, realizes the development and application of the gas slag in the field of removing harmful gases, and realizes the treatment of waste by waste.
Detailed Description
The present invention will be described in detail with reference to examples, but the present invention is not limited thereto.
In the following examples, the characterization method of the relevant parameters is described as follows:
formaldehyde purification efficiency-measured according to JC/T1074-2008;
the other parameters are characterized by adopting national standard or a conventional characterization mode in the field.
In the following examples, the coal gasification coarse slag used was from the quaighl major industrial park of the law of the inner mongolia, the municipality, in combination as follows: the carbon content was 0.49wt%, the silica was 48.80wt%, the alumina was 23.14wt%, the calcium oxide was 12.72wt%, the iron oxide was 8.97wt%, and all components were amorphous.
In the examples below, the reagents used were all analytically pure unless otherwise specified.
Example 1:
the method for preparing the mesoporous silica/titanium dioxide composite photocatalytic material from the coal gasification coarse slag provided by the embodiment comprises the following steps:
(1) Taking a certain amount of coal gasification coarse slag raw material, and adding water to prepare coal gasification coarse slag slurry with the solid content of 20wt%; stirring the prepared coal gasification coarse slag slurry for at least 1 h;
(2) Fully stirring the slurry prepared in the step (1), then removing carbon through flotation separation, collecting flotation tailing slurry, and grinding until the granularity of the flotation tailing is more than 10 meshes; drying the ground tailing slurry at 110 ℃, and collecting low-carbon coal gasification coarse slag;
(3) 140mL of 37wt% concentrated hydrochloric acid is taken, water is added for dilution to 285mL, and the diluted concentrated hydrochloric acid is mixed with 100g of low-carbon coal gasification coarse slag to obtain slurry, and stirred for acid dissolution reaction; the molar ratio of the acid ash ratio in the obtained slurry is 0.8; the concentration of the acid in the slurry is about 20wt%, the temperature of the acid dissolution reaction water bath is 50 ℃, and the stirring time is 2 hours;
(4) Carrying out solid-liquid separation on the reacted material, wherein the filtrate can be used for preparing aluminum-iron water purifying agent; washing, drying and grinding the solid, wherein the washing mode is that acid washing is carried out firstly and then water washing is carried out, the drying temperature is 120 ℃, the grinding mode is that mortar grinding is carried out, the granularity reaches more than 100 meshes, and the mesoporous silica material is obtained;
(5) Adding water into 50g of mesoporous silica material obtained in the step (4) to prepare slurry with the solid content of 10wt%, stirring the prepared slurry for at least 0.5h, heating to 80 ℃, and taking 53g (TiO 2 The loading was 30%, water was added to dilute 625mL of a titanium sulfate solution formulated as 0.3mol/L, followed by adding to the above slurry at a rate of 1mL/min to perform a reaction, and ph=2 of the slurry was adjusted with a sodium hydroxide solution of 2mol/L, stirring was continued for 2 hours, and TiO was obtained by a hydrolysis precipitation method 2 Loading on mesoporous silica material to form composite material precursor;
(6) Solid-liquid separation is carried out on the reacted materials, the solid is washed, dried at 80 ℃, ground by a mortar, calcined at 500 ℃ for 2 hours, and the mesoporous silica/titanium dioxide composite photocatalytic material with the specific surface area of 196.38m is obtained 2 Per gram, pore volume of 0.19cm 3 The pore diameter is 3.83nm, and the formaldehyde removal rate is 48.69% after 24 hours.
Example 2:
the method for preparing the mesoporous silica/titanium dioxide composite photocatalytic material from the coal gasification coarse slag provided by the embodiment comprises the following steps:
(1) Taking a certain amount of coal gasification coarse slag raw material, and adding water to prepare coal gasification coarse slag slurry with the solid content of 20wt%; stirring the prepared coal gasification coarse slag slurry for at least 1 h;
(2) Fully stirring the slurry prepared in the step (1), then removing carbon through flotation separation, collecting flotation tailing slurry, and grinding until the granularity of the flotation tailing is more than 10 meshes; drying the ground tailing slurry at 110 ℃, and collecting low-carbon coal gasification coarse slag;
(3) 160mL of 37wt% concentrated hydrochloric acid is taken, water is added for dilution to 320mL, and the mixture is mixed with 100g of low-carbon coal gasification coarse slag to obtain slurry, and acid dissolution reaction is carried out by stirring; the molar ratio of the acid ash ratio in the obtained slurry is 0.9; the concentration of the acid in the slurry is about 20wt%, the temperature of the acid dissolution reaction water bath is 70 ℃, and the stirring time is 4 hours;
(4) Carrying out solid-liquid separation on the reacted material, wherein the filtrate can be used for preparing aluminum-iron water purifying agent; washing, drying and grinding the solid, wherein the washing mode is that acid washing is carried out firstly and then water washing is carried out, the drying temperature is 120 ℃, the grinding mode is that mortar grinding is carried out, the granularity reaches more than 100 meshes, and the mesoporous silica material is obtained;
(5) Adding water into 50g of mesoporous silica material obtained in the step (4) to prepare slurry with the solid content of 15wt%, stirring the prepared slurry for at least 0.5h, heating to 85 ℃, and taking 53g (TiO 2 The loading was 30%, water was added to dilute 625mL of a titanium sulfate solution formulated as 0.3mol/L, then added to the above slurry at a rate of 2mL/min to perform a reaction, and ph=2.5 of the slurry was adjusted with a sodium hydroxide solution of 2mol/L, stirring was continued for 2 hours, and TiO was obtained by a hydrolysis precipitation method 2 Loading on mesoporous silica material to form composite material precursor;
(6) Carrying out solid-liquid separation on the reacted materials, washing the solid, drying at 80 ℃, grinding in a mortar, calcining at 550 ℃ for 2 hours to obtain the mesoporous silica/titanium dioxide composite photocatalytic material, and measuring the specific surface area of the mesoporous silica/titanium dioxide composite photocatalytic material to be 307.43m 2 Per gram, pore volume of 0.21cm 3 The pore diameter is 3.75nm, and the formaldehyde removal rate is 53.04% after 24 hours.
Example 3:
the method for preparing the mesoporous silica/titanium dioxide composite photocatalytic material from the coal gasification coarse slag provided by the embodiment comprises the following steps:
(1) Taking a certain amount of coal gasification coarse slag raw material, and adding water to prepare coal gasification coarse slag slurry with the solid content of 20wt%; stirring the prepared coal gasification coarse slag slurry for at least 1 h;
(2) Fully stirring the slurry prepared in the step (1), then removing carbon through flotation separation, collecting flotation tailing slurry, and grinding until the granularity of the flotation tailing is more than 10 meshes; drying the ground tailing slurry at 110 ℃, and collecting low-carbon coal gasification coarse slag;
(3) Taking 175mL of 37wt% concentrated hydrochloric acid, adding water to dilute to 355mL, mixing with 100g of low-carbon coal gasification coarse slag to obtain slurry, and stirring to perform acid dissolution reaction; the molar ratio of the acid ash ratio in the obtained slurry is 1.0; the concentration of the acid in the slurry is about 20wt%, the temperature of the acid dissolution reaction water bath is 90 ℃, and the stirring time is 2 hours;
(4) Carrying out solid-liquid separation on the reacted material, wherein the filtrate can be used for preparing aluminum-iron water purifying agent; washing, drying and grinding the solid, wherein the washing mode is that acid washing is carried out firstly and then water washing is carried out, the drying temperature is 120 ℃, the grinding mode is that mortar grinding is carried out, the granularity reaches more than 100 meshes, and the mesoporous silica material is obtained;
(5) Adding water into 50g of mesoporous silica material obtained in the step (4) to prepare slurry with the solid content of 20wt%, stirring the prepared slurry for at least 0.5h, heating to 90 ℃, and taking 53g (TiO 2 The loading was 30%, water was added to dilute 625mL of a titanium sulfate solution formulated as 0.3mol/L, followed by adding to the above slurry at a rate of 1mL/min to perform a reaction, and pH=3 of the slurry was adjusted with a sodium hydroxide solution of 2mol/L, stirring was continued for 2 hours, and TiO was precipitated by hydrolysis 2 Loading on mesoporous silica material to form composite material precursor;
(6) Carrying out solid-liquid separation on the reacted materials, washing the solid, drying at 80 ℃, grinding in a mortar, and calcining at 550 ℃ for 3 hours to obtain the mesoporous materialSilicon dioxide/titanium dioxide composite photocatalytic material with specific surface area of 361.53m 2 Per gram, pore volume of 0.22cm 3 The pore diameter is 3.73nm, and the formaldehyde removal rate is 70.14% after 24 hours.
Example 4:
the method for preparing the mesoporous silica/titanium dioxide composite photocatalytic material from the coal gasification coarse slag provided by the embodiment comprises the following steps:
(1) Taking a certain amount of coal gasification coarse slag raw material, and adding water to prepare coal gasification coarse slag slurry with the solid content of 20wt%; stirring the prepared coal gasification coarse slag slurry for at least 1 h;
(2) Fully stirring the slurry prepared in the step (1), then removing carbon through flotation separation, collecting flotation tailing slurry, and grinding until the granularity of the flotation tailing is more than 10 meshes; drying the ground tailing slurry at 110 ℃, and collecting low-carbon coal gasification coarse slag;
(3) Taking 195mL of 37wt% concentrated hydrochloric acid, adding water to dilute to 390mL, mixing with 100g of low-carbon coal gasification coarse slag to obtain slurry, and stirring to perform acid dissolution reaction; the molar ratio of the acid ash ratio in the obtained slurry is 1.1; the concentration of the acid in the slurry is about 20wt%, the temperature of the acid dissolution reaction water bath is 70 ℃, and the stirring time is 6 hours;
(4) Carrying out solid-liquid separation on the reacted material, wherein the filtrate can be used for preparing aluminum-iron water purifying agent; washing, drying and grinding the solid, wherein the washing mode is that acid washing is carried out firstly and then water washing is carried out, the drying temperature is 120 ℃, the grinding mode is that mortar grinding is carried out, the granularity reaches more than 100 meshes, and the mesoporous silica material is obtained;
(5) Adding water into 50g of mesoporous silica material obtained in the step (4) to prepare slurry with the solid content of 10wt%, stirring the prepared slurry for at least 0.5h, heating to 80 ℃, and taking 53g (TiO 2 The loading was 30%, water was added to dilute 625mL of a titanium sulfate solution formulated as 0.3mol/L, followed by adding to the above slurry at a rate of 1.5mL/min to perform a reaction, and ph=2.5 of the slurry was adjusted with a sodium hydroxide solution of 2mol/L, stirring was continued for 2 hours, and TiO was obtained by a hydrolysis precipitation method 2 Mesoporous silica materialForming a composite material precursor on the material;
(6) Solid-liquid separation is carried out on the reacted materials, the solid is washed, dried at 80 ℃, ground by a mortar, calcined at 500 ℃ for 2 hours, and the mesoporous silica/titanium dioxide composite photocatalytic material with the specific surface area of 358.8m is obtained 2 Per gram, pore volume of 0.24cm 3 And/g, the pore diameter is 3.63nm, and the formaldehyde removal rate is 68.69% in 24 hours.
Example 5:
the method for preparing the mesoporous silica/titanium dioxide composite photocatalytic material from the coal gasification coarse slag provided by the embodiment comprises the following steps:
(1) Taking a certain amount of coal gasification coarse slag raw material, and adding water to prepare coal gasification coarse slag slurry with the solid content of 20wt%; stirring the prepared coal gasification coarse slag slurry for at least 1 h;
(2) Fully stirring the slurry prepared in the step (1), then removing carbon through flotation separation, collecting flotation tailing slurry, and grinding until the granularity of the flotation tailing is more than 10 meshes; drying the ground tailing slurry at 110 ℃, and collecting low-carbon coal gasification coarse slag;
(3) Taking 230mL of 37wt% concentrated hydrochloric acid, adding water to dilute to 470mL, mixing with 100g of low-carbon coal gasification coarse slag to obtain slurry, and stirring to perform acid dissolution reaction; the molar ratio of the acid ash ratio in the obtained slurry is 1.2; the concentration of the acid in the slurry is about 20wt%, the temperature of the acid dissolution reaction water bath is 70 ℃, and the stirring time is 10 hours;
(4) Carrying out solid-liquid separation on the reacted material, wherein the filtrate can be used for preparing aluminum-iron water purifying agent; washing, drying and grinding the solid, wherein the washing mode is that acid washing is carried out firstly and then water washing is carried out, the drying temperature is 120 ℃, the grinding mode is that mortar grinding is carried out, the granularity reaches more than 100 meshes, and the mesoporous silica material is obtained;
(5) Adding water into 50g of mesoporous silica material obtained in the step (4) to prepare slurry with the solid content of 15wt%, stirring the prepared slurry for at least 0.5h, heating to 90 ℃, and taking 53g (TiO 2 30% loading), diluted with water to 625mL of 0.3mol/L titanium sulfate solutionThen adding into the slurry at a rate of 1mL/min for reaction, adjusting the pH of the slurry to be 2 by using 2mol/L sodium hydroxide solution, continuously stirring for 2 hours, and adding TiO by a hydrolysis precipitation method 2 Loading on mesoporous silica material to form composite material precursor;
(6) Carrying out solid-liquid separation on the reacted materials, washing the solid, drying at 80 ℃, grinding in a mortar, calcining at 550 ℃ for 4 hours to obtain the mesoporous silica/titanium dioxide composite photocatalytic material, and measuring the specific surface area of the mesoporous silica/titanium dioxide composite photocatalytic material to be 396.28m 2 Per gram, pore volume of 0.31cm 3 The pore diameter is 3.65nm, and the formaldehyde removal rate is 77.39% after 24 hours.
As can be seen from the performance data of the above examples 1-5, the specific surface areas of the mesoporous silica/titania composite photocatalytic materials obtained by the present invention are all greater than 200m 2 The photocatalytic degradation rate of formaldehyde is more than 50%, and the highest photocatalytic degradation rate can reach nearly 80%. In order to better understand the formaldehyde removing performance of the product, five commercial products are taken, and the photocatalytic degradation rates of the product are 36.91%, 40.44%, 22.06%, 21.83% and 18.55% respectively measured under the same conditions, which are obviously lower than that of the product, therefore, the formaldehyde degrading performance of the mesoporous silica/titanium dioxide composite photocatalytic material is obviously better than that of the commercial product, and the invention fully utilizes the coal gasification coarse slag of the solid waste, thereby realizing the treatment of waste by waste and truly realizing the high added value utilization of the solid waste.
Claims (10)
1. A method for preparing mesoporous silica/titanium dioxide composite photocatalytic material from coal gasification coarse slag is characterized by comprising the following steps: the method comprises the following steps:
(1) Taking a proper amount of coal gasification coarse slag raw material, and adding water to prepare coal gasification coarse slag slurry with the solid content of 10-30wt%;
(2) Fully stirring the slurry prepared in the step (1), then removing carbon through flotation separation, collecting flotation tailing slurry, and grinding until the granularity of the flotation tailing is more than 10 meshes; drying the ground tailing pulp, and collecting low-carbon coal gasification coarse slag;
(3) Mixing a proper amount of acid solution with the low-carbon coal gasification coarse slag to obtain slurry, and stirring to perform acid dissolution reaction; the molar ratio of the acid ash ratio in the obtained slurry is 0.8-1.2; the acid concentration is 5-20wt%, the acid dissolution reaction temperature is 30-90 ℃, and the stirring time is 2-10h;
(4) Carrying out solid-liquid separation on the reacted materials, washing, drying and grinding the solid materials, wherein the granularity reaches more than 100 meshes, and obtaining the mesoporous silica material;
(5) Adding water into the mesoporous silica material obtained in the step (4) to prepare slurry with the solid content of 10-30wt%, stirring the prepared slurry, heating to 70-90 ℃, adding titanium salt solution for reaction, and carrying out hydrolysis precipitation to obtain TiO 2 Loading on mesoporous silica material to form composite material precursor;
(6) And (3) carrying out solid-liquid separation on the reacted materials, washing, drying, grinding and calcining the solid materials, wherein the calcining temperature is 500-800 ℃, and the calcining time is 2-4 hours, so as to obtain the mesoporous silica/titanium dioxide composite photocatalytic material.
2. The method for preparing mesoporous silica/titanium dioxide composite photocatalytic material from coal gasification coarse slag according to claim 1, which is characterized in that: the coal gasification coarse slag raw material in the step (1) refers to residues discharged through the bottom of a coal gasification furnace in the coal gasification process, and the carbon content in the coal gasification coarse slag raw material is lower than 10wt%; the solid content of the coal gasification coarse slag slurry is 15-25 wt%; and stirring the prepared coal gasification coarse slag slurry for at least 1 h.
3. The method for preparing mesoporous silica/titanium dioxide composite photocatalytic material from coal gasification coarse slag according to claim 1, which is characterized in that: in the step (2), the flotation separation is carried out by adopting a flotation machine, and the carbon content of tailings left by the flotation separation is less than 1wt%; and drying the ground tailing pulp at 100-120 ℃.
4. The method for preparing mesoporous silica/titanium dioxide composite photocatalytic material from coal gasification coarse slag according to claim 1, which is characterized in that: in the step (3), the molar ratio of the lime to the slurry obtained by mixing is 0.8, 0.9, 1.0, 1.1 or 1.2; the acid concentration is 5wt%, 10wt%, 15wt% or 20wt%; the reaction temperature is 30 ℃,50 ℃, 70 ℃ or 90 ℃; stirring time is 2h, 4h, 6h or 10h; the acid solution is hydrochloric acid or nitric acid aqueous solution.
5. The method for preparing mesoporous silica/titanium dioxide composite photocatalytic material from coal gasification coarse slag according to claim 1, which is characterized in that: in the step (4), the adopted solid-liquid separation mode is filter pressing or suction filtration; the washing mode is that acid washing is carried out firstly and then water washing is carried out, and impurities on the surface of the material are removed; the drying temperature is 100-120 ℃; the grinding mode is mortar grinding.
6. The method for preparing mesoporous silica/titanium dioxide composite photocatalytic material from coal gasification coarse slag according to claim 1, which is characterized in that: in the step (4), when the acid solution is hydrochloric acid, a liquid phase obtained by solid-liquid separation after acid dissolution is used for preparing the water purifying agent; when the concentration of hydrochloric acid is 10-20wt%, the concentration of aluminum chloride reaches 29wt% by adjusting the concentration of aluminum, iron and calcium metal ions in the liquid phase product, so that the aluminum-iron water purifying agent is prepared.
7. The method for preparing mesoporous silica/titanium dioxide composite photocatalytic material from coal gasification coarse slag according to claim 1, which is characterized in that: in the step (5), the solid content of slurry prepared by adding water into the mesoporous silica material is 10wt%, 20wt% and 30wt%; stirring the prepared slurry for at least 0.5h, and then heating to 70-90 ℃; adding the prepared titanium salt solution at a constant rate of 1-2mL/min through a flowmeter in the process of continuous stirring; simultaneously, the pH value of the solution is regulated to be 1-4 by the prepared alkali solution; continuing stirring the slurry for 1-6h; the titanium salt solution is titanium sulfate or titanium chloride aqueous solution with the concentration of 0.1-0.5mol/L, and the alkali solution is sodium hydroxide or potassium hydroxide aqueous solution with the concentration of 1-3mol/L.
8. The method for preparing mesoporous silica/titanium dioxide composite photocatalytic material from coal gasification coarse slag according to claim 1, which is characterized in that: in the step (6), the adopted solid-liquid separation mode is suction filtration or centrifugation; the drying temperature is 70-90 ℃; the grinding mode is mortar grinding, and the granularity is kept above 100 meshes.
9. The mesoporous silica/titania composite photocatalytic material obtained by the method for preparing mesoporous silica/titania composite photocatalytic material from coal gasification coarse slag according to any one of claims 1 to 8, which is used for photocatalytic degradation of formaldehyde.
10. The mesoporous silica/titania composite photocatalytic material obtained by the method for preparing mesoporous silica/titania composite photocatalytic material from coal gasification coarse slag according to any one of claims 1 to 8, which is used for preparing wall materials with formaldehyde adsorption and photocatalytic degradation functions or is used as a filler with formaldehyde adsorption and photocatalytic degradation functions to be mixed with other building materials.
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| CN117446814B (en) * | 2023-12-21 | 2024-03-26 | 内蒙古科技大学 | Method for preparing calcium silicate by using gas slag |
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