CN117019154B - Photocatalyst based on microcrystalline graphite and preparation method and application thereof - Google Patents
Photocatalyst based on microcrystalline graphite and preparation method and application thereof Download PDFInfo
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- CN117019154B CN117019154B CN202311160540.1A CN202311160540A CN117019154B CN 117019154 B CN117019154 B CN 117019154B CN 202311160540 A CN202311160540 A CN 202311160540A CN 117019154 B CN117019154 B CN 117019154B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 176
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 174
- 239000010439 graphite Substances 0.000 title claims abstract description 174
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 80
- 238000005188 flotation Methods 0.000 claims abstract description 75
- 238000009830 intercalation Methods 0.000 claims abstract description 48
- 230000002687 intercalation Effects 0.000 claims abstract description 48
- 239000013049 sediment Substances 0.000 claims abstract description 38
- 239000012535 impurity Substances 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 33
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 19
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 15
- 239000000138 intercalating agent Substances 0.000 claims abstract description 11
- 239000003513 alkali Substances 0.000 claims abstract description 10
- 230000008569 process Effects 0.000 claims abstract description 8
- 230000001007 puffing effect Effects 0.000 claims abstract description 8
- 230000007797 corrosion Effects 0.000 claims abstract description 6
- 238000005260 corrosion Methods 0.000 claims abstract description 6
- 229910052755 nonmetal Inorganic materials 0.000 claims abstract description 5
- 238000004065 wastewater treatment Methods 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims description 32
- 239000002245 particle Substances 0.000 claims description 30
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 18
- 239000001257 hydrogen Substances 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 18
- 239000002994 raw material Substances 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 13
- 239000003245 coal Substances 0.000 claims description 12
- 229910052723 transition metal Inorganic materials 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 230000009467 reduction Effects 0.000 claims description 8
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000002351 wastewater Substances 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- 150000001805 chlorine compounds Chemical class 0.000 claims description 2
- 230000001678 irradiating effect Effects 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims description 2
- 235000012437 puffed product Nutrition 0.000 claims description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000004064 recycling Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 description 37
- 239000002002 slurry Substances 0.000 description 36
- 238000001035 drying Methods 0.000 description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 27
- 238000004140 cleaning Methods 0.000 description 24
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- 230000003197 catalytic effect Effects 0.000 description 14
- 239000000203 mixture Substances 0.000 description 13
- 239000004088 foaming agent Substances 0.000 description 12
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 229910052786 argon Inorganic materials 0.000 description 10
- 239000012141 concentrate Substances 0.000 description 10
- 239000003995 emulsifying agent Substances 0.000 description 10
- 238000007790 scraping Methods 0.000 description 10
- 239000004115 Sodium Silicate Substances 0.000 description 9
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 9
- 239000001768 carboxy methyl cellulose Substances 0.000 description 9
- 239000003350 kerosene Substances 0.000 description 9
- 230000007935 neutral effect Effects 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 9
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 9
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 9
- 229910052911 sodium silicate Inorganic materials 0.000 description 9
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 6
- 229960000907 methylthioninium chloride Drugs 0.000 description 6
- 239000003112 inhibitor Substances 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000007770 graphite material Substances 0.000 description 2
- 238000009775 high-speed stirring Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 2
- 229940012189 methyl orange Drugs 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000003403 water pollutant Substances 0.000 description 1
Classifications
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a photocatalyst based on microcrystalline graphite and a preparation method and application thereof. The preparation method of the photocatalyst based on microcrystalline graphite comprises the following steps: subjecting a microcrystalline graphite feedstock to a flotation process and collecting a sediment, the sediment comprising microcrystalline graphite containing impurities, wherein at least a portion of the impurities are intercalated with graphite, the impurities comprising metal oxides and non-metal oxides; intercalation treatment is carried out on the sediment by using an intercalating agent, and then puffing treatment is carried out, so that impurities are exposed out of graphite, and microcrystalline graphite puffing substances are obtained; corroding the microcrystalline graphite puffed material by using alkali solution to remove impurities partially and enable the impurities to have a three-dimensional interconnected porous structure; and (3) sequentially roasting and reducing the microcrystalline graphite puffed material subjected to the corrosion treatment to obtain the photocatalyst. The invention prepares the photocatalyst applicable to organic wastewater treatment by utilizing the microcrystalline graphite with high impurity content obtained by flotation treatment, thereby realizing the recycling utilization of the microcrystalline graphite with high impurity content and low grade.
Description
Technical Field
The invention particularly relates to a photocatalyst based on microcrystalline graphite, and a preparation method and application thereof, and belongs to the technical field of graphite materials.
Background
Microcrystalline graphite, also known as aphanitic graphite and earthy graphite, generally has a carbon content in the range of 60wt% to 80wt%, and has a relatively limited range of applications due to its low carbon content, high volatile matter and ash content, small crystal grains, and poor high-temperature oxidation resistance, as compared with crystalline flake graphite. In order to realize the high added value application of the microcrystalline graphite, the microcrystalline graphite is purified by a floatation method, and then the purified microcrystalline graphite is applied to electrode materials, fillers and the like of a secondary battery, but a considerable amount of low-grade tailings with high impurity content are separated in the process, and the tailings have low utilization value, but if stacked and stored, the cost of enterprises is increased, and the pollution to the land resource environment is caused. Therefore, how to realize the resource utilization of low-grade microcrystalline graphite with high impurity content has become a difficult problem to be solved in the field.
Disclosure of Invention
The invention mainly aims to provide a photocatalyst based on microcrystalline graphite, and a preparation method and application thereof, so as to overcome the defects in the prior art.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention comprises the following steps:
in one aspect, the invention provides a method for preparing a photocatalyst based on microcrystalline graphite, comprising the following steps:
subjecting a microcrystalline graphite feedstock to a flotation process and collecting a sediment, the sediment comprising microcrystalline graphite containing impurities, wherein at least a portion of the impurities are intercalated with graphite, the impurities comprising metal oxides and non-metal oxides;
performing intercalation treatment on the sediment by using an intercalating agent, and then performing puffing treatment to expose the impurities from graphite to obtain microcrystalline graphite puffed materials, wherein the intercalating agent comprises a compound containing transition metal elements;
corroding the microcrystalline graphite puffed material by using alkali solution to remove the impurity part and enable the impurity to have a three-dimensional interconnected porous structure;
and (3) sequentially roasting and reducing the microcrystalline graphite puffed material subjected to the corrosion treatment to obtain the photocatalyst.
Further, the microcrystalline graphite raw material comprises natural smokeless coal-based microcrystalline graphite.
Further, the particle size of the microcrystalline graphite material is smaller than 10. Mu.m, for example, 9.5. Mu.m, 9. Mu.m, 8.5. Mu.m, 7.2. Mu.m, 6. Mu.m, 5.5. Mu.m, 2.3. Mu.m, 1.1. Mu.m, 0.6. Mu.m, etc.
Further, the metal oxide includes at least one of aluminum oxide, iron oxide, and titanium oxide.
Further, the non-metal oxide includes silicon oxide.
Further, the intercalation process includes: mixing the sediment with an intercalation agent, and reacting at 350-500 ℃ to obtain the microcrystalline graphite intercalation.
Further, the mass ratio of the sediment to the intercalating agent is (1:1) to (1:5), for example, the mass ratio of the sediment to the intercalating agent may be 1:1, 1:1.5, 1:2, 1:2.1, 1:2.7, 1:3, 1:4, 1:5, or the like.
Further, the transition metal element includes at least one or a combination of two or more of iron, cobalt, nickel, copper, titanium, chromium, manganese, and molybdenum.
Further, the intercalating agent comprises at least one of or a combination of two or more of chlorides, nitrates, sulfates, permanganates, dichromates containing the transition metal element.
In one embodiment, the preparation method of the microcrystalline graphite-based photocatalyst comprises the following steps: and (3) performing the puffing treatment on the microcrystalline graphite intercalation material subjected to intercalation treatment in a microwave expansion mode, wherein the treatment power of the microwave expansion is 2500-4500W, and the treatment time is 5-10 min.
Further, the alkali solution comprises a strong alkali solution with a concentration of 15-20 wt%, and the strong alkali solution can be sodium hydroxide solution, potassium hydroxide solution, lithium hydroxide solution and the like.
In a specific embodiment, the preparation method of the microcrystalline graphite-based photocatalyst further comprises: and (3) carrying out the roasting treatment on the microcrystalline graphite puffed material subjected to the corrosion treatment in an air atmosphere, wherein the temperature of the roasting treatment is 300-350 ℃ and the time is more than 2 hours.
In a specific embodiment, the preparation method of the microcrystalline graphite-based photocatalyst further comprises: and (3) carrying out the reduction treatment on the baked microcrystalline graphite puffed product under the conditions of a reducing atmosphere and the temperature of 600-1000 ℃, wherein the reducing atmosphere contains hydrogen.
In one embodiment, the preparation method of the microcrystalline graphite-based photocatalyst specifically comprises the following steps: crushing the microcrystalline graphite puffed material subjected to the roasting treatment to a particle size of less than 1mm, and then carrying out the reduction treatment.
Further, the reducing atmosphere is formed of hydrogen and inert gas in a volume ratio of 1:1 to 3, for example, the volume ratio of hydrogen and inert gas in the reducing atmosphere may be 1:1, 1:1.2, 1:1.8, 1:2, 1:2.5, 1:3, or the like.
The invention also provides a photocatalyst based on microcrystalline graphite, which is obtained by the preparation method of the photocatalyst based on microcrystalline graphite.
The invention also provides the application of the photocatalyst based on microcrystalline graphite in organic sewage treatment.
The invention also provides an organic sewage treatment method, which comprises the steps of mixing the photocatalyst based on microcrystalline graphite with weak acid organic sewage to form a mixed system, and irradiating the mixed system at least with visible light.
Compared with the prior art, the invention has the advantages that:
(1) According to the preparation method of the photocatalyst based on the microcrystalline graphite, the photocatalyst applicable to organic wastewater treatment is prepared by utilizing the microcrystalline graphite with high impurity content obtained through flotation treatment, and the resource utilization of the microcrystalline graphite with high impurity content and low grade is realized.
(2) The photocatalyst based on microcrystalline graphite has the advantages of wide raw material sources, low cost, good adsorptivity, high catalytic activity, long service life, easy regeneration and good recycling performance, is particularly suitable for purifying acidic organic wastewater, has high purification efficiency, achieves the effect of treating waste by waste, and is beneficial to environmental protection.
Drawings
FIG. 1 is an electron microscopic view of the photocatalyst obtained in example 1 of the present invention.
Detailed Description
In view of the shortcomings in the prior art, the inventor of the present invention has long studied and practiced in a large number of ways to propose the technical scheme of the present invention. The technical scheme, the implementation process, the principle and the like are further explained as follows.
In a more specific embodiment, a method for preparing a microcrystalline graphite-based photocatalyst comprises the steps of:
s1, crushing and screening natural smokeless coal-based microcrystalline graphite to obtain a microcrystalline graphite flotation raw material with the particle size smaller than 10 mu m.
The step S1 may specifically include: crushing natural smokeless coal-based microcrystalline graphite by a jaw crusher and a ball mill in sequence, and separating particles with the particle size smaller than 10 mu m at least by a screen sieving or cyclone classification mode to obtain the flotation raw material.
S2, carrying out flotation treatment on the microcrystalline graphite flotation raw material, and collecting sediment.
The step S2 may specifically include:
s21, selecting a flotation tank with a waste residue outlet at the bottom, and uniformly mixing the flotation raw material and water in the flotation tank to form flotation slurry with the concentration of 15-25 wt%;
s22, sequentially adding an inhibitor, a collector and a foaming agent into the flotation slurry under the condition of continuous high-speed stirring, sequentially carrying out aeration and foam scraping treatment to collect concentrate, and rapidly separating sediment in the mixed feed liquid remained in the flotation tank.
The method comprises the steps of adding the inhibitor into the flotation slurry, stirring at a high speed for 5-10 min, adding the collector, stirring at a high speed for 3-10 min, adding the foaming agent, stirring at a high speed for 3-10 min, aerating at an air flow speed of 200-300L/h, scraping for 5-10 min, collecting concentrate, rapidly discharging sediment in the mixed feed liquid in the flotation tank from a waste residue outlet, and fully washing and drying to obtain sediment.
Specifically, the inhibitor comprises sodium silicate and sodium carboxymethyl cellulose with the mass ratio of 1:1-6:1, the collector comprises an emulsifier and kerosene with the mass ratio of 1:8-1:5, the emulsifier comprises MOA-3B, the foaming agent comprises No. 2 oil, the mass ratio of the inhibitor, the collector, the foaming agent and the flotation slurry is 6-8:2-3:2-4:1000, and the high-speed stirring speed is above 1000 r/min.
The sediment is microcrystalline graphite with high impurity content, and the impurities at least include metal oxides such as aluminum oxide, iron oxide, titanium oxide, and nonmetal oxides such as silicon oxide.
The sediment after flotation treatment is microcrystalline graphite with higher impurity content, so that on one hand, the microcrystalline graphite has lower utilization value, and on the other hand, the microcrystalline graphite has higher content of metal elements and the like.
S3, uniformly mixing the sediment and an intercalation agent according to the mass ratio of 1:1-1:5, then placing the mixture into a reactor such as a high-pressure reaction kettle, adding a solvent to form a liquid mixed system, and reacting for 8-24 hours at the temperature of 350-500 ℃ to obtain the microcrystalline graphite intercalation compound, wherein the intercalation agent comprises a compound containing transition metal elements, the transition metal elements comprise more than two of iron, cobalt, nickel, copper, titanium, chromium, manganese and molybdenum, and the intercalation agent comprises at least one of chloride, nitrate or sulfate or permanganate and dichromate containing the transition metal elements.
The sediment is mixed with the intercalation agent, so that the intercalation agent can be fully impregnated into the graphite, the longer the impregnation time of the intercalation treatment is, the more the intercalation agent enters the graphite layers, and the greater the subsequent expansion degree is, therefore, the subsequent expansion degree of the graphite can be controlled by controlling the impregnation time, the temperature and the like of the intercalation treatment.
Specifically, a compound containing a transition metal element is used as an intercalation agent, so that intercalation can be realized, subsequent expansion treatment is facilitated, impurities such as aluminum oxide and silicon oxide in the compound are fully exposed, and more catalytic active substances can be introduced into microcrystalline graphite to endow the microcrystalline graphite with stronger catalytic activity.
S4, carrying out microwave expansion treatment on the microcrystalline graphite intercalation, wherein the power of the microwave expansion treatment is 2500-4500W, the treatment time is 5-10 min, so as to obtain a microcrystalline graphite puffed material, and then cleaning and drying the obtained microcrystalline graphite puffed material.
Specifically, by adopting microwave expansion treatment, graphite can be heated uniformly, and an intercalation agent in the graphite can be decomposed more rapidly, so that the graphite can expand more uniformly and rapidly, impurities in the graphite can be fully exposed, and abundant and uniform gaps are formed between graphite layers, so that the graphite has a larger specific surface area.
S5, uniformly mixing the microcrystalline graphite puffed material with a strong alkali solution with the concentration of 15-20wt% and then naturally drying, roasting for 2-8 hours at 300-350 ℃ under the air condition, and then sequentially carrying out smashing, cleaning, drying and calcination on the obtained sintered material to obtain the photocatalyst. By roasting in the air atmosphere, the non-decomposed intercalation agent and the like can be thoroughly converted into metal oxide, so that the method is favorable for more sufficient reduction in the subsequent reduction process, and the catalytic activity of the photocatalyst is improved.
Specifically, step S5 specifically includes: the sinter is crushed to a particle size smaller than 1mm, then the sinter is fully washed by water until an eluate is neutral, then the mixture is dried and calcined for 1 to 3 hours under the conditions of a reducing atmosphere and 450 to 600 ℃ to obtain the photocatalyst, wherein the reducing atmosphere comprises hydrogen and inert gas with a volume ratio of 1:1 to 1:3, and the inert gas can be argon, helium and the like.
Specifically, the reduction treatment is preferably performed under a hydrogen/argon mixed atmosphere, and the volume ratio of the hydrogen is controlled so as to keep the reduction atmosphere stable and avoid the problem of explosion safety of high-concentration hydrogen at high temperature.
Specifically, the strong alkali solution can remove the impurities such as the exposed part of alumina, silica and the like, so that the content of other metal impurities is improved, the remained alumina and silica exist in microcrystalline graphite in a sol form, and a three-dimensional interconnection porous structure is formed between the graphite layers, thereby helping to fix the metal oxide (such as titanium oxide and the like) with catalytic activity, avoiding the metal oxide from falling off from the graphite, ensuring and improving the catalytic activity of the photocatalyst, and prolonging the service life of the photocatalyst.
Specifically, the sintered product is calcined in a reducing atmosphere, on one hand, the metal oxide between graphite layers reacts with hydrogen to be reduced, and on the other hand, the metal oxide between graphite layers can also react with graphite to form metal particles with high catalytic activity, and the porosity of the graphite is further improved.
In the preparation method of the photocatalyst, the microcrystalline graphite with high impurity content obtained by floatation treatment is selected as a raw material, partial catalytic active component precursors can be provided for the photocatalyst by utilizing the characteristic of higher impurity content of metal oxides such as ferric oxide, titanium oxide and the like, then the microcrystalline graphite with high impurity content is subjected to intercalation treatment and microwave puffing treatment by using an intercalation agent containing transition metal elements, the microcrystalline graphite is rapidly puffed to form a loose and porous structure, the photocatalyst is endowed with the advantages of large specific surface area and the like, the adsorption capacity for organic pollutants is enhanced, impurities mixed/embedded in the microcrystalline graphite are fully exposed, the intercalation agent also provides more catalytic active component precursors for the photocatalyst, and then the components such as silicon oxide, aluminum oxide and the like are partially removed by alkaline corrosion treatment, the other metal oxides, the intercalating agent and the like are reserved in the non-graphite, the residual silicon oxide, aluminum oxide and the like are in a three-dimensional network form formed by accumulating colloid particles and continuously exist on the surface and inside of the microcrystalline graphite, so that the catalytic active substances formed by the conversion of the other metal oxides and the intercalating agent can be protected to a certain extent, the risk of falling off the microcrystalline graphite is reduced, the catalytic activity of the photocatalyst is kept, the service life of the photocatalyst is prolonged, the contact of external water and organic pollutants with the catalytic active substances is not hindered, the specific surface area of the photocatalyst is further improved, the intercalating agent and the like can be more fully converted into the form of the metal oxide by roasting in the air atmosphere, the metal oxide can be more efficiently and thoroughly converted into metal simple substances with high catalytic activity in the subsequent thermal reduction treatment process, improving the catalytic capability of the photocatalyst.
The photocatalyst provided by the invention has excellent photocatalytic activity under solar spectrum, is suitable for carrying out photocatalytic purification treatment on acidic, alkaline and neutral organic wastewater with pH value within the range of 5-10, and has the advantages of difficult deactivation, long service life and the like in weak acidic organic wastewater.
The technical scheme, implementation process and principle and the like will be further explained in the following with reference to specific embodiments.
Example 1
1) Crushing natural smokeless coal-based microcrystalline graphite serving as a raw material sequentially by a jaw crusher with the diameter of 50mm and a jaw crusher with the diameter of 10mm, hammering and crushing by an impact hammer crusher with the diameter of 1mm, crushing microcrystalline graphite smaller than 1mm by a dry method by using an aluminum oxide ball of a horizontal stirring mill, performing cyclone classification on materials with the particle diameter of more than 10 mu m, and finally obtaining materials with the particle diameter of less than 10 mu m as flotation feeding materials;
2) Adding flotation feed into a flotation tank, adding a proper amount of water, controlling the concentration of the formed flotation slurry to be 30%, firstly adding 300g/t of sodium silicate and 250g/t of sodium carboxymethylcellulose into the flotation slurry, stirring for 5min, mixing an emulsifying agent MOA-3B and kerosene in a mass ratio of 1:5 in a high-speed stirrer at a high speed of 1000r/min for 5min to serve as a collector, adding the collector into the flotation slurry according to an addition amount of 2500g/t, and stirring for 2min; adding 300g/t of foaming agent No. 2 oil into the flotation slurry, stirring for 1min, aerating, controlling the air flow speed to be 250L/h, scraping bubbles for 5min, collecting concentrate for other purposes, collecting sediments, fully cleaning with clear water, and drying for later use;
3) Uniformly mixing the sediment and ferric nitrate according to the mass ratio of 1:1, then placing the mixture into a reactor such as a high-pressure reaction kettle and reacting for 10 hours at 400 ℃ to obtain the microcrystalline graphite intercalation compound.
4) And carrying out microwave expansion treatment on the microcrystalline graphite intercalation, wherein the power of the microwave expansion treatment is 3200W, the treatment time is 6min, so as to obtain a microcrystalline graphite puffed material, and then cleaning and drying the obtained microcrystalline graphite puffed material.
5) Uniformly mixing the microcrystalline graphite puffed material with a sodium hydroxide solution with the concentration of 15wt%, naturally drying, roasting at 300 ℃ for 8 hours under the air condition to obtain a sintered material, crushing the sintered material to a particle size of less than 1mm, fully cleaning with water until an eluate is neutral, drying, and roasting at 450 ℃ for 3 hours under the mixed atmosphere of hydrogen and argon with the volume ratio of 1:1 to obtain the photocatalyst, wherein the morphology of the photocatalyst is shown in figure 1.
Example 2
1) Crushing natural smokeless coal-based microcrystalline graphite serving as a raw material sequentially by a jaw crusher with the diameter of 50mm and a jaw crusher with the diameter of 10mm, hammering by an impact hammer crusher with the diameter of 1mm, and preparing a flotation feed with the granularity of less than 10 mu m by a horizontal stirring mill-dry method;
2) Adding flotation feed into a flotation tank, adding a proper amount of water, controlling the concentration of the formed flotation slurry to be 20%, firstly adding 500g/t sodium silicate and 300g/t sodium carboxymethylcellulose into the flotation slurry, and stirring for 5min; mixing an emulsifying agent MOA-3B and kerosene in a mass ratio of 1:5 in a high-speed stirrer at a high speed of 1000r/min for 5min and taking the mixture as a collector, adding the collector into flotation slurry according to an adding amount of 3000g/t, and stirring the mixture for 1min; adding 200g/t of foaming agent No. 2 oil into the flotation slurry, stirring for 1min, aerating, controlling the air flow speed to be 250L/h, scraping bubbles for 5min, collecting concentrate for other purposes, collecting sediments, fully cleaning with clear water, and drying for later use;
3) Uniformly mixing the sediment and ferric nitrate according to the mass ratio of 1:3, then placing the mixture into a reactor such as a high-pressure reaction kettle and reacting for 24 hours at the temperature of 350 ℃ to obtain the microcrystalline graphite intercalation material.
4) And performing microwave expansion treatment on the microcrystalline graphite intercalation, wherein the power of the microwave expansion treatment is 2500W, and the treatment time is 10min, so as to obtain a microcrystalline graphite puffed material, and then cleaning and drying the obtained microcrystalline graphite puffed material.
5) Uniformly mixing the microcrystalline graphite puffed material with a potassium hydroxide solution with the concentration of 20wt%, naturally drying, roasting at 320 ℃ for 4 hours under the air condition to obtain a sintered material, crushing the sintered material to a particle size of less than 1mm, fully cleaning with water until an eluate is neutral, drying, and roasting at 500 ℃ for 1.5 hours under the mixed atmosphere of hydrogen and argon with the volume ratio of 1:2 to obtain the photocatalyst.
Example 3
1) Crushing natural smokeless coal-based microcrystalline graphite serving as a raw material sequentially by a jaw crusher with the diameter of 50mm and a jaw crusher with the diameter of 10mm, hammering and crushing by an impact hammer crusher with the diameter of 1mm, crushing microcrystalline graphite smaller than 1mm by a dry method by using an aluminum oxide ball of a horizontal stirring mill, performing cyclone classification on materials with the particle diameter of more than 10 mu m, and finally obtaining materials with the particle diameter of less than 10 mu m as flotation feeding materials;
2) Adding flotation feed into a flotation tank, adding a proper amount of water, controlling the concentration of the formed flotation slurry to be 30%, firstly adding 300g/t of sodium silicate and 250g/t of sodium carboxymethylcellulose into the flotation slurry, stirring for 5min, mixing an emulsifying agent MOA-3B and kerosene in a mass ratio of 1:5 in a high-speed stirrer at a high speed of 1000r/min for 5min to serve as a collector, adding the collector into the flotation slurry according to an addition amount of 2500g/t, and stirring for 2min; adding 300g/t of foaming agent No. 2 oil into the flotation slurry, stirring for 1min, aerating, controlling the air flow speed to be 250L/h, scraping bubbles for 5min, collecting concentrate for other purposes, collecting sediments, fully cleaning with clear water, and drying for later use;
3) Uniformly mixing the sediment and ferric nitrate according to the mass ratio of 1:4, then placing the mixture into a reactor such as a high-pressure reaction kettle and reacting for 8 hours at 500 ℃ to obtain the microcrystalline graphite intercalation compound.
4) And carrying out microwave expansion treatment on the microcrystalline graphite intercalation, wherein the power of the microwave expansion treatment is 4000W, and the treatment time is 5min, so as to obtain a microcrystalline graphite puffed material, and then washing and drying the obtained microcrystalline graphite puffed material.
5) Uniformly mixing the microcrystalline graphite puffed material with a sodium hydroxide solution with the concentration of 18wt%, naturally drying, roasting at 300 ℃ for 5 hours under the air condition to obtain a sintered material, crushing the sintered material to a particle size of less than 1mm, fully cleaning with water until an eluate is neutral, drying, and roasting at 450 ℃ for 3 hours under the mixed atmosphere of hydrogen and argon with the volume ratio of 1:3 to obtain the photocatalyst.
Example 4
1) Crushing natural smokeless coal-based microcrystalline graphite serving as a raw material sequentially by a jaw crusher with the diameter of 50mm and a jaw crusher with the diameter of 10mm, hammering and crushing by an impact hammer crusher with the diameter of 1mm, crushing microcrystalline graphite smaller than 1mm by a dry method by using an aluminum oxide ball of a horizontal stirring mill, performing cyclone classification on materials with the particle diameter of more than 10 mu m, and finally obtaining materials with the particle diameter of less than 10 mu m as flotation feeding materials;
2) Adding flotation feed into a flotation tank, adding a proper amount of water, controlling the concentration of the formed flotation slurry to be 30%, firstly adding 300g/t of sodium silicate and 250g/t of sodium carboxymethylcellulose into the flotation slurry, stirring for 5min, mixing an emulsifying agent MOA-3B and kerosene in a mass ratio of 1:5 in a high-speed stirrer at a high speed of 1000r/min for 5min to serve as a collector, adding the collector into the flotation slurry according to an addition amount of 2500g/t, and stirring for 2min; adding 300g/t of foaming agent No. 2 oil into the flotation slurry, stirring for 1min, aerating, controlling the air flow speed to be 250L/h, scraping bubbles for 5min, collecting concentrate for other purposes, collecting sediments, fully cleaning with clear water, and drying for later use;
3) Uniformly mixing the sediment and ferric nitrate according to the mass ratio of 1:1, then placing the mixture into a reactor such as a high-pressure reaction kettle and reacting for 10 hours at 400 ℃ to obtain the microcrystalline graphite intercalation compound.
4) And carrying out microwave expansion treatment on the microcrystalline graphite intercalation, wherein the power of the microwave expansion treatment is 3200W, the treatment time is 6min, so as to obtain a microcrystalline graphite puffed material, and then cleaning and drying the obtained microcrystalline graphite puffed material.
5) Uniformly mixing the microcrystalline graphite puffed material with a sodium hydroxide solution with the concentration of 15wt%, naturally drying, roasting at the temperature of 350 ℃ for 2 hours under the air condition to obtain a sintered material, crushing the sintered material to the particle size of less than 1mm, fully cleaning with water until the eluate is neutral, drying, and roasting at the temperature of 600 ℃ for 1 hour under the mixed atmosphere of hydrogen and argon with the volume ratio of 1:2 to obtain the photocatalyst.
Comparative example 1
1) Crushing natural smokeless coal-based microcrystalline graphite serving as a raw material sequentially by a jaw crusher with the diameter of 50mm and a jaw crusher with the diameter of 10mm, hammering and crushing by an impact hammer crusher with the diameter of 1mm, crushing microcrystalline graphite smaller than 1mm by a dry method by using an aluminum oxide ball of a horizontal stirring mill, performing cyclone classification on materials with the particle diameter of more than 10 mu m, and finally obtaining materials with the particle diameter of less than 10 mu m as flotation feeding materials;
2) Adding flotation feed into a flotation tank, adding a proper amount of water, controlling the concentration of the formed flotation slurry to be 30%, firstly adding 300g/t of sodium silicate and 250g/t of sodium carboxymethylcellulose into the flotation slurry, stirring for 5min, and mixing an emulsifier MOA-3B and kerosene according to the mass ratio of 1:5, mixing for 5min at a high speed of 1000r/min in a high-speed stirrer and taking the mixture as a collector, adding the collector into the flotation slurry according to the addition amount of 2500g/t, and stirring for 2min; adding 300g/t of foaming agent No. 2 oil into the flotation slurry, stirring for 1min, aerating, controlling the air flow speed to be 250L/h, scraping bubbles for 5min, collecting concentrate for other purposes, collecting sediments, fully cleaning with clear water, and drying for later use;
3) Uniformly mixing the sediment and ferric nitrate according to the mass ratio of 1:1, then placing the mixture into a reactor such as a high-pressure reaction kettle and reacting for 10 hours at 400 ℃ to obtain the microcrystalline graphite intercalation compound.
4) Transferring the microcrystalline graphite intercalation material into a muffle furnace, carrying out expansion treatment for 1h at 900 ℃ to obtain a microcrystalline graphite expansion material, and then cleaning and drying the obtained microcrystalline graphite expansion material.
5) Uniformly mixing the microcrystalline graphite puffed material with a sodium hydroxide solution with the concentration of 15wt%, naturally drying, roasting at 300 ℃ for 8 hours under the air condition to obtain a sintered material, crushing the sintered material to a particle size of less than 1mm, fully cleaning with water until an eluate is neutral, drying, and roasting at 450 ℃ for 3 hours under the mixed atmosphere of hydrogen and argon with the volume ratio of 1:1 to obtain the photocatalyst.
Comparative example 2
1) Crushing natural smokeless coal-based microcrystalline graphite serving as a raw material sequentially by a jaw crusher with the diameter of 50mm and a jaw crusher with the diameter of 10mm, hammering and crushing by an impact hammer crusher with the diameter of 1mm, crushing microcrystalline graphite smaller than 1mm by a dry method by using an aluminum oxide ball of a horizontal stirring mill, performing cyclone classification on materials with the particle diameter of more than 10 mu m, and finally obtaining materials with the particle diameter of less than 10 mu m as flotation feeding materials;
2) Adding flotation feed into a flotation tank, adding a proper amount of water, controlling the concentration of the formed flotation slurry to be 30%, firstly adding 300g/t of sodium silicate and 250g/t of sodium carboxymethylcellulose into the flotation slurry, stirring for 5min, mixing an emulsifying agent MOA-3B and kerosene in a mass ratio of 1:5 in a high-speed stirrer at a high speed of 1000r/min for 5min to serve as a collector, adding the collector into the flotation slurry according to an addition amount of 2500g/t, and stirring for 2min; adding 300g/t of foaming agent No. 2 oil into the flotation slurry, stirring for 1min, aerating, controlling the air flow speed to be 250L/h, scraping bubbles for 5min, collecting concentrate for other purposes, collecting sediments, fully cleaning with clear water, and drying for later use;
3) Uniformly mixing the sediment and ferric nitrate according to the mass ratio of 1:1, then placing the mixture into a reactor such as a high-pressure reaction kettle and reacting for 10 hours at 400 ℃ to obtain the microcrystalline graphite intercalation compound.
4) And carrying out microwave expansion treatment on the microcrystalline graphite intercalation, wherein the power of the microwave expansion treatment is 3200W, the treatment time is 6min, so as to obtain a microcrystalline graphite puffed material, and then cleaning and drying the obtained microcrystalline graphite puffed material.
5) Roasting the microcrystalline graphite puffed material for 8 hours at 300 ℃ under the air condition to obtain a sintered material, crushing the sintered material to a particle size smaller than 1mm, and roasting for 3 hours under the condition of 450 ℃ under the mixed atmosphere of hydrogen and argon with the volume ratio of 1:1 to obtain the photocatalyst.
Comparative example 3
1) Crushing natural smokeless coal-based microcrystalline graphite serving as a raw material sequentially by a jaw crusher with the diameter of 50mm and a jaw crusher with the diameter of 10mm, hammering and crushing by an impact hammer crusher with the diameter of 1mm, crushing microcrystalline graphite smaller than 1mm by a dry method by using an aluminum oxide ball of a horizontal stirring mill, performing cyclone classification on materials with the particle diameter of more than 10 mu m, and finally obtaining materials with the particle diameter of less than 10 mu m as flotation feeding materials;
2) Adding flotation feed into a flotation tank, adding a proper amount of water, controlling the concentration of the formed flotation slurry to be 30%, firstly adding 300g/t of sodium silicate and 250g/t of sodium carboxymethylcellulose into the flotation slurry, stirring for 5min, mixing an emulsifying agent MOA-3B and kerosene in a mass ratio of 1:5 in a high-speed stirrer at a high speed of 1000r/min for 5min to serve as a collector, adding the collector into the flotation slurry according to an addition amount of 2500g/t, and stirring for 2min; adding 300g/t of foaming agent No. 2 oil into the flotation slurry, stirring for 1min, aerating, controlling the air flow speed to be 250L/h, scraping bubbles for 5min, collecting concentrate for other purposes, collecting sediments, fully cleaning with clear water, and drying for later use;
3) Uniformly mixing the sediment and ferric nitrate according to the mass ratio of 1:1, then placing the mixture into a reactor such as a high-pressure reaction kettle and reacting for 10 hours at 400 ℃ to obtain the microcrystalline graphite intercalation compound.
4) And carrying out microwave expansion treatment on the microcrystalline graphite intercalation, wherein the power of the microwave expansion treatment is 3200W, the treatment time is 6min, so as to obtain a microcrystalline graphite puffed material, and then cleaning and drying the obtained microcrystalline graphite puffed material.
5) Uniformly mixing the microcrystalline graphite puffed material with 15wt% hydrofluoric acid solution, naturally drying, roasting at 300 ℃ for 8 hours under air condition to obtain a sintered material, crushing the sintered material to a particle size smaller than 1mm, fully cleaning with water until the eluate is neutral, drying, and roasting at 450 ℃ for 3 hours under a mixed atmosphere of hydrogen and argon with a volume ratio of 1:1 to obtain the photocatalyst.
Comparative example 4
1) Crushing natural smokeless coal-based microcrystalline graphite serving as a raw material sequentially by a jaw crusher with the diameter of 50mm and a jaw crusher with the diameter of 10mm, hammering and crushing by an impact hammer crusher with the diameter of 1mm, crushing microcrystalline graphite smaller than 1mm by a dry method by using an aluminum oxide ball of a horizontal stirring mill, performing cyclone classification on materials with the particle diameter of more than 10 mu m, and finally obtaining materials with the particle diameter of less than 10 mu m as flotation feeding materials;
2) Adding flotation feed into a flotation tank, adding a proper amount of water, controlling the concentration of the formed flotation slurry to be 30%, firstly adding 300g/t of sodium silicate and 250g/t of sodium carboxymethylcellulose into the flotation slurry, stirring for 5min, mixing an emulsifying agent MOA-3B and kerosene in a mass ratio of 1:5 in a high-speed stirrer at a high speed of 1000r/min for 5min to serve as a collector, adding the collector into the flotation slurry according to an addition amount of 2500g/t, and stirring for 2min; adding 300g/t of foaming agent No. 2 oil into the flotation slurry, stirring for 1min, aerating, controlling the air flow speed to be 250L/h, scraping bubbles for 5min, collecting concentrate for other purposes, collecting sediments, fully cleaning with clear water, and drying for later use;
3) Uniformly mixing the sediment and ferric nitrate according to the mass ratio of 1:1, then placing the mixture into a reactor such as a high-pressure reaction kettle and reacting for 10 hours at 400 ℃ to obtain the microcrystalline graphite intercalation compound.
4) And carrying out microwave expansion treatment on the microcrystalline graphite intercalation, wherein the power of the microwave expansion treatment is 3200W, the treatment time is 6min, so as to obtain a microcrystalline graphite puffed material, and then cleaning and drying the obtained microcrystalline graphite puffed material.
5) Uniformly mixing the microcrystalline graphite puffed material with a sodium hydroxide solution with the concentration of 15wt%, naturally drying, crushing the microcrystalline graphite puffed material to a particle size of less than 1mm, fully cleaning with water until an eluate is neutral, drying, and calcining for 3 hours under the condition of 450 ℃ in a mixed atmosphere of hydrogen and argon with the volume ratio of 1:1 to obtain the photocatalyst.
The organic wastewater was also simulated with an aqueous methylene blue solution in the present invention, and the photocatalytic activity of the photocatalysts prepared in examples 1 to 4 and comparative examples 1 to 4 was tested under simulated sunlight and room temperature conditions. Before illumination, a reaction system formed by mixing the photocatalysts with the same mass and the methylene blue water solution with the same mass and the saturated concentration is continuously stirred for 30 minutes in the dark, so that adsorption-desorption equilibrium is established. After stirring, it was observed that the color of the reaction system to which the photocatalysts of examples 1 to 4 were added was significantly lighter than that of the methylene blue aqueous solution of saturated concentration as a blank group, and the color of the reaction system to which the photocatalysts of comparative example 1 were added was slightly lighter, and the color of the reaction system to which the photocatalysts of comparative examples 2, 3, and 4 were added was substantially unchanged.
After continuous stirring and continuous illumination for 60min, the photocatalysts in each reaction system are centrifugally separated, the content of methylene in each remained liquid phase system is tested, and infrared tests are carried out after each photocatalyst is dried at 40 ℃, so that the results show that: in the reaction systems to which the photocatalysts of examples 1 to 4 were added, the decrease in methylene blue content was about 88.5%, 85.3%, 86.7%, and 85.8%, respectively; in the reaction systems to which the photocatalysts of comparative examples 1 to 4 were added, the decrease in methylene content was 70.9%, 62.4%, 56.3%, 58.5%, respectively. No methylene blue related peak appeared in the infrared spectrograms of the photocatalysts of examples 1-4, and methylene blue related peaks appeared in the infrared spectrograms of the photocatalysts of comparative examples 1-4.
The photocatalytic activity of the photocatalysts prepared in examples 1 to 4 and comparative examples 1 to 4 was also tested in the present invention using a saturated aqueous solution of methyl orange (pH of about 3) to which hydrochloric acid was added to simulate organic wastewater under conditions of simulated sunlight and room temperature. The results showed that the decrease in methyl orange content was about 92.4%, 88.6%, 90.1% and 89.6% in the reaction system to which the photocatalyst of examples 1 to 4 was added, respectively, when examples 1 to 4 were repeatedly used up to 10 th time (after each use, washing with deionized water only, drying at 40 ℃ C., and no regeneration treatment was performed); in the reaction systems to which the photocatalysts of comparative examples 1 to 4 were added, the decrease in methylene content was 50.3%, 33.2%, 36.1% and 34.1%, respectively.
It should be understood that the above embodiments are merely for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the present invention and implement the same according to the present invention without limiting the scope of the present invention. All equivalent changes or modifications made in accordance with the spirit of the present invention should be construed to be included in the scope of the present invention.
Claims (13)
1. A method for preparing a photocatalyst based on microcrystalline graphite, comprising the steps of:
subjecting a microcrystalline graphite feedstock to a flotation process and collecting a sediment, the sediment comprising microcrystalline graphite containing impurities, wherein at least a portion of the impurities are intercalated with graphite, the impurities comprising metal oxides including at least one of alumina, iron oxide, titanium oxide, and non-metal oxides including silicon oxide;
the sediment is subjected to intercalation treatment by an intercalation agent, and then is subjected to puffing treatment so as to expose the impurities from graphite, thus obtaining the microcrystalline graphite puffed material, wherein the intercalation agent comprises a compound containing transition metal elements, and the transition metal elements comprise at least one or more than two of iron, cobalt, nickel, copper, titanium, chromium, manganese and molybdenum, and the intercalation treatment comprises: mixing the sediment with an intercalation agent, and reacting at the temperature of 350-500 ℃ to obtain a microcrystalline graphite intercalation, wherein the puffing treatment comprises the following steps: performing the puffing treatment on the microcrystalline graphite intercalation material subjected to intercalation treatment in a microwave expansion mode, wherein the treatment power of the microwave expansion is 2500-4500W, and the treatment time is 5-10 min;
corroding the microcrystalline graphite puffed material by using alkali solution to remove the impurity part and enable the impurity to have a three-dimensional interconnected porous structure;
and (3) sequentially roasting and reducing the microcrystalline graphite puffed material subjected to the corrosion treatment to obtain the photocatalyst.
2. The method for preparing the microcrystalline graphite-based photocatalyst according to claim 1, wherein: the microcrystalline graphite raw material comprises natural smokeless coal-based microcrystalline graphite.
3. The method for preparing the microcrystalline graphite-based photocatalyst according to claim 1, wherein: the grain size of the microcrystalline graphite raw material is smaller than 10 mu m.
4. The method for preparing the microcrystalline graphite-based photocatalyst according to claim 1, wherein: the mass ratio of the sediment to the intercalating agent is (1:1) - (1:5).
5. The method for preparing a microcrystalline graphite-based photocatalyst according to any one of claims 1 to 4, wherein: the intercalating agent comprises at least one or a combination of two or more of chlorides, nitrates, sulfates, permanganates, dichromates of the transition metal elements.
6. The method for preparing the microcrystalline graphite-based photocatalyst according to claim 1, wherein: the alkali solution comprises a strong alkali solution with the concentration of 15-20wt%.
7. The method for preparing a microcrystalline graphite-based photocatalyst according to claim 1, further comprising: and (3) carrying out the roasting treatment on the microcrystalline graphite puffed material subjected to the corrosion treatment in an air atmosphere, wherein the temperature of the roasting treatment is 300-350 ℃ and the time is more than 2 hours.
8. The method for preparing a microcrystalline graphite-based photocatalyst according to claim 1, further comprising: and carrying out reduction treatment on the baked microcrystalline graphite puffed product under the conditions of a reducing atmosphere and a temperature of 600-1000 ℃, wherein the reducing atmosphere contains hydrogen.
9. The method for preparing the microcrystalline graphite-based photocatalyst according to claim 8, comprising the following steps: crushing the microcrystalline graphite puffed material subjected to the roasting treatment to a particle size of less than 1mm, and then carrying out the reduction treatment.
10. The method for preparing the microcrystalline graphite-based photocatalyst according to claim 9, wherein: the reducing atmosphere is formed by hydrogen and inert gas in a volume ratio of 1:1-3.
11. A photocatalyst based on microcrystalline graphite, characterized in that: the photocatalyst is obtained by the method for producing a microcrystalline graphite-based photocatalyst according to any one of claims 1 to 10.
12. Use of a microcrystalline graphite based photocatalyst according to claim 11 in organic wastewater treatment.
13. A method for treating organic wastewater, comprising: mixing the microcrystalline graphite-based photocatalyst of claim 11 with weakly acidic organic wastewater to form a mixed system, and irradiating the mixed system with at least visible light.
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