CN112915990B - Coal gangue in-situ carbon activation material and preparation method and application thereof - Google Patents
Coal gangue in-situ carbon activation material and preparation method and application thereof Download PDFInfo
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- CN112915990B CN112915990B CN202110101600.7A CN202110101600A CN112915990B CN 112915990 B CN112915990 B CN 112915990B CN 202110101600 A CN202110101600 A CN 202110101600A CN 112915990 B CN112915990 B CN 112915990B
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- Prior art keywords
- coal gangue
- functional group
- acid
- treatment
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- 239000003245 coal Substances 0.000 title claims abstract description 138
- 230000004913 activation Effects 0.000 title claims abstract description 72
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 58
- 239000000463 material Substances 0.000 title claims abstract description 54
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 125000000524 functional group Chemical group 0.000 claims abstract description 64
- 238000001354 calcination Methods 0.000 claims abstract description 30
- 230000015556 catabolic process Effects 0.000 claims abstract description 27
- 238000006731 degradation reaction Methods 0.000 claims abstract description 27
- 239000012298 atmosphere Substances 0.000 claims abstract description 17
- 239000000126 substance Substances 0.000 claims abstract description 17
- 238000004137 mechanical activation Methods 0.000 claims abstract description 13
- -1 sulfydryl Chemical group 0.000 claims abstract description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 7
- 125000003368 amide group Chemical group 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims description 31
- 238000002386 leaching Methods 0.000 claims description 31
- 150000001875 compounds Chemical class 0.000 claims description 22
- 239000002957 persistent organic pollutant Substances 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 9
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052622 kaolinite Inorganic materials 0.000 claims description 7
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical group F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 5
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 4
- XTEGVFVZDVNBPF-UHFFFAOYSA-N naphthalene-1,5-disulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1S(O)(=O)=O XTEGVFVZDVNBPF-UHFFFAOYSA-N 0.000 claims description 4
- 235000011054 acetic acid Nutrition 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 3
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 2
- 239000005711 Benzoic acid Substances 0.000 claims description 2
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 2
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 claims description 2
- 150000001413 amino acids Chemical class 0.000 claims description 2
- 235000010233 benzoic acid Nutrition 0.000 claims description 2
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- 150000003573 thiols Chemical class 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- 238000005245 sintering Methods 0.000 claims 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 abstract description 26
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 16
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 13
- 238000000034 method Methods 0.000 description 12
- 238000010276 construction Methods 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 238000001914 filtration Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 230000001276 controlling effect Effects 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 230000003213 activating effect Effects 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 230000000593 degrading effect Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002910 solid waste Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 231100000049 endocrine disruptor Toxicity 0.000 description 2
- 239000000598 endocrine disruptor Substances 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 2
- 238000001727 in vivo Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- FMMWHPNWAFZXNH-UHFFFAOYSA-N Benz[a]pyrene Chemical compound C1=C2C3=CC=CC=C3C=C(C=C3)C2=C2C3=CC=CC2=C1 FMMWHPNWAFZXNH-UHFFFAOYSA-N 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- 102000005298 Iron-Sulfur Proteins Human genes 0.000 description 1
- 108010081409 Iron-Sulfur Proteins Proteins 0.000 description 1
- 239000012425 OXONE® Substances 0.000 description 1
- 229910001308 Zinc ferrite Inorganic materials 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002817 coal dust Substances 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000002048 multi walled nanotube Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- HJKYXKSLRZKNSI-UHFFFAOYSA-I pentapotassium;hydrogen sulfate;oxido sulfate;sulfuric acid Chemical compound [K+].[K+].[K+].[K+].[K+].OS([O-])(=O)=O.[O-]S([O-])(=O)=O.OS(=O)(=O)O[O-].OS(=O)(=O)O[O-] HJKYXKSLRZKNSI-UHFFFAOYSA-I 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 239000002351 wastewater 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0201—Oxygen-containing compounds
- B01J31/0202—Alcohols or phenols
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0215—Sulfur-containing compounds
- B01J31/0217—Mercaptans or thiols
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0215—Sulfur-containing compounds
- B01J31/0225—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0237—Amines
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0245—Nitrogen containing compounds being derivatives of carboxylic or carbonic acids
- B01J31/0247—Imides, amides or imidates (R-C=NR(OR))
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/06—Washing
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
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- 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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
-
- 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
- C02F2101/32—Hydrocarbons, e.g. oil
- C02F2101/327—Polyaromatic Hydrocarbons [PAH's]
-
- 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
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- 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
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Carbon And Carbon Compounds (AREA)
- Catalysts (AREA)
Abstract
The invention provides a coal gangue in-situ carbon activation material as well as a preparation method and application thereof, belonging to the technical field of catalytic materials. The invention provides a preparation method of a coal gangue in-situ carbon activation material, which comprises the following steps: sequentially carrying out mechanical activation, chemical activation, calcination and functional group grafting treatment on the coal gangue to obtain a coal gangue in-situ carbon activation material; the calcining atmosphere is inert atmosphere; the functional group in the functional group grafting treatment is at least one of hydroxyl, sulfydryl, amino, carboxyl, sulfonic group and amide group. The results of the examples show that when the addition amount of the coal gangue in-situ carbon activation material prepared by the preparation method provided by the invention is 0.5g/L, the degradation rate of phenol (25mg/L) for 10min exceeds 87%, and the degradation rate of naphthalene (10mg/L) for 10min exceeds 85%.
Description
Technical Field
The invention relates to the technical field of catalytic materials, in particular to a coal gangue in-situ carbon activation material and a preparation method and application thereof.
Background
In recent years, the pollution problem in the gathering area of the coal industry has received much attention. In the coal industry gathering area, coal mining, washing and dressing, power generation, coking, coal gasification, waste stacking and other processes can generate solid waste such as coal gangue and the like, and meanwhile, the process is accompanied with serious pollution to a site, surface water and underground water. Especially polycyclic aromatic hydrocarbon organic pollutants including phenol, naphthalene, phenanthrene, anthracene, benzopyrene and the like cause serious damage to the ecological environment of industrial areas. Therefore, the treatment and repair of organic pollutants in soil and underground water of a typical polluted site in an aggregation area of coal-related industries are urgent.
The existing organic matter purification treatment technologies such as adsorption, membrane filtration, chemical oxidation, biological treatment and the like have respective limitations, and advanced oxidation technologies are concerned by researchers in recent years due to the advantages of high efficiency, thoroughness, wide application range, no secondary pollution and the like, and particularly are persulfate activation catalysis technologies, which are leading-edge technologies for rapidly and effectively degrading water and site pollutants and are emerging for more than ten years. Persulfate is activated to generate strong oxidizing sulfate radical (SO)4 ·-) Standard oxidation-reduction potential (E) thereof0Higher than hydroxyl radical (OH) (E) (+ 2.5- +3.1V)0The concentration of the water is +1.8 to +2.7V), and the water has longer half-life (30 to 40 mu s, and the half-life of OH is 1 mu s), so that the sustained action time with the target pollutants can be greatly prolonged, and the deep mineralization of the target pollutants is promoted. But at present, the persulfate has low activation efficiency under single thermal, electric, sound and light conditions; and transition metal ion (Co)2+、Ce3+、Ag+、Fe2+、Fe3+、Ni2+、Ru3+、Mn2+Etc.) or transition metal oxides (MnO)2、Co3O4、Fe3O4、ZnFe2O4Etc.) metal ions are introduced or leached in the process of activating persulfate, thereby causing secondary pollution to environmental water or sites; carbon-based materials such as N-doped graphene, N-doped C nanotubes and N-doped biochar face the problems of high energy consumption, high cost, complex preparation, low efficiency and the like, so that the large-scale application of the carbon-based materials in water and field treatment is limited. For example, chinese patent CN201510074018.0 discloses a method for removing endocrine disruptors in water by using cobalt-doped magnetic redox graphene in cooperation with persulfate, chinese patent CN201710301211.2 discloses a method for removing phenolic substances in water by using iron-sulfur-loaded multi-walled carbon nanotubes to reinforce persulfate, chinese patent CN201810234261.8 discloses a method for removing endocrine disruptors in water by using carbon-based magnetic metal composite material to catalytically activate persulfate, and chinese patent CN202010238748.0 discloses a method for degrading sulfonamides in sewage by using ordered mesoporous carbon activated persulfateA method for preparing antibiotic. The carbon-based persulfate activation material has the advantages of high raw material cost, complex preparation and low activation efficiency, and is difficult to use in actual water and site treatment.
Therefore, aiming at the characteristics of difficult treatment, complex components, strong toxicity and the like of organic pollutants in actual water bodies and sites of coal industry gathering areas, the method adopts a waste-to-waste strategy to develop the catalyst which can effectively activate persulfate, is environment-friendly and has industrialization prospect, and has important significance.
Disclosure of Invention
The coal gangue in-situ carbon activation material prepared by the preparation method provided by the invention has the function of degrading organic pollutants, can be used as a catalyst to be applied to treatment of organic pollutant-polluted wastewater, and has high degradation rate.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a coal gangue in-situ carbon activation material, which comprises the following steps:
sequentially carrying out mechanical activation, chemical activation, calcination and functional group grafting treatment on the coal gangue to obtain a coal gangue in-situ carbon activation material; the calcining atmosphere is inert atmosphere; the functional group in the functional group grafting treatment is at least one of hydroxyl, sulfydryl, amino, carboxyl, sulfonic group and amide group.
Preferably, the coal gangue contains 10-30% of carbon and more than 60% of kaolinite by mass.
Preferably, the fineness of the coal gangue after mechanical activation is-100 meshes, and the stripping rate is more than 70%.
Preferably, the chemical activation mode is acid leaching treatment.
Preferably, the acid leaching solution used for the acid leaching treatment is hydrofluoric acid, hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid, and the concentration of the acid leaching solution is 1-12M.
Preferably, the time of the acid leaching treatment is 0.5-24 h, and the temperature of the acid leaching treatment is 20-95 ℃.
Preferably, the calcining temperature is 200-800 ℃, and the calcining time is 0.5-12 h.
Preferably, the functional group grafting treatment is performed in a functional group-containing compound solution, the concentration of the functional group-containing compound solution is 0.1-10M, the time of the functional group grafting treatment is 0.5-72 h, and the temperature of the functional group grafting treatment is 20-95 ℃.
The invention provides the coal gangue in-situ carbon activation material prepared by the preparation method in the technical scheme.
The invention provides application of the coal gangue in-situ carbon activation material in the technical scheme in degradation of organic pollutants.
The invention provides a preparation method of a coal gangue in-situ carbon activation material, which comprises the following steps: sequentially carrying out mechanical activation, chemical activation, calcination and functional group grafting treatment on the coal gangue to obtain a coal gangue in-situ carbon activation material; the calcining atmosphere is inert atmosphere; the functional group in the functional group grafting treatment is at least one of hydroxyl, sulfydryl, amino, carboxyl, sulfonic group and amide group. According to the invention, the gangue is mechanically activated, so that the construction and release of surface/interface active groups of the gangue are realized, the chemical activation promotes the formation and construction of a novel micro-nano pore structure in the gangue, the gangue is calcined in an inert atmosphere, the induced generation of defect sites and the establishment of active points can be realized, and the in-situ grafting of the active groups is realized through the construction of functional groups, so that the persulfate with higher activation efficiency is achieved, and the degradation performance of the activation material on organic pollutants is further improved; the coal gangue serves as a raw material, so that a large amount of coal gangue can be consumed, the pollution of the coal gangue to the environment is reduced, the economic value of the coal gangue can be improved, and the coal gangue solid waste utilization method has important significance for high-value utilization of the coal gangue solid waste and efficient treatment of organic pollutants in actual water bodies and sites of coal industry gathering areas. The results of the examples show that when the addition amount of the coal gangue in-situ carbon activation material prepared by the preparation method provided by the invention is 0.5g/L, the degradation rate of phenol (25mg/L) for 10min exceeds 87%, and the degradation rate of naphthalene (10mg/L) for 10min exceeds 85%.
Detailed Description
The invention provides a preparation method of a coal gangue in-situ carbon activation material, which comprises the following steps:
and sequentially carrying out mechanical activation, chemical activation, calcination and functional group grafting treatment on the coal gangue to obtain the coal gangue in-situ carbon activation material.
In the invention, the carbon content in the coal gangue is preferably 10-30% by mass, and more preferably 15-25%; the kaolinite content in the coal gangue is preferably > 60%, more preferably > 70%. The invention limits the components in the coal gangue in the range, can fully utilize the carbon content of the coal gangue and the aluminosilicate framework structure, and further realizes the in-situ carbon activation of the coal gangue.
In the present invention, the mechanical activation is preferably by crushing and pulverizing. The specific operation mode of the crushing and grinding is not particularly limited, and the crushing and grinding process can be realized by adopting the conventional crushing and grinding process in the field. The invention adopts the crushing and grinding mode to treat the coal gangue, can reduce the size of the coal gangue, improve the specific surface area of the coal gangue, realize the construction and the release of surface/interface active groups of the coal gangue, and facilitate the subsequent chemical activation.
In the invention, the fineness of the coal gangue after mechanical activation is preferably-100 meshes, and more preferably-150 meshes; the stripping rate of the mechanically activated coal gangue is preferably more than 70%, more preferably more than 75%. The invention limits the fineness and the stripping rate of the coal gangue within the range, and can further ensure the construction and the release of surface/interface active groups of the coal gangue.
In the present invention, the chemical activation is preferably performed by acid leaching. In the present invention, the acid leaching solution at the time of the acid leaching treatment is preferably hydrofluoric acid, hydrochloric acid, sulfuric acid, nitric acid, or phosphoric acid, and more preferably hydrochloric acid, sulfuric acid, or nitric acid; the concentration of the acid leaching solution is preferably 1-12M, and more preferably 5-10M. According to the invention, an acid leaching treatment mode is adopted, so that an aluminosilicate framework structure in the coal gangue can be etched, and the formation and construction of a novel micro-nano pore structure are promoted.
In the invention, the time of the acid leaching treatment is preferably 0.5-24 h, more preferably 5-15 h, and most preferably 8-12 h; the temperature of the acid leaching treatment is preferably 20-95 ℃, and more preferably 50-80 ℃. The invention limits the temperature and time of acid leaching treatment in the above range, and can further ensure complete chemical activation.
The specific source of the acid leaching solution is not particularly limited in the present invention, and any commercially available product or self-preparation known to those skilled in the art may be used.
In the invention, the calcination temperature is preferably 200-800 ℃, more preferably 300-600 ℃, and most preferably 400-500 ℃; the calcination time is preferably 0.5-12 h, more preferably 2-8 h, and most preferably 4-6 h. The invention can partially oxidize and activate the organic carbon component in the coal gangue by a calcining mode, thereby leading the coal gangue to obtain rich in-vivo defects and active sites.
In the invention, the heating rate of heating to the calcination temperature is preferably 0.5-20 ℃/min, more preferably 1-15 ℃/min, and most preferably 5-10 ℃/min. In the invention, the cooling rate after calcination is preferably 0.5-20 ℃/min, more preferably 1-15 ℃/min, and most preferably 5-10 ℃/min. According to the invention, by controlling the heating and cooling rates, the damage of the material structure caused by too fast temperature change can be prevented.
In the present invention, the atmosphere of the calcination is an inert atmosphere. In the present invention, the inert atmosphere is preferably nitrogen, argon or helium, more preferably nitrogen or argon; the gas flow rate of the inert atmosphere is preferably 0.05-5 mL/min, more preferably 0.1-3 mL/min, and most preferably 1-2 mL/min. According to the invention, the calcining atmosphere is controlled within the range, and the induction generation of defect sites and the establishment of active sites can be further promoted by regulating and controlling the calcining atmosphere.
In the present invention, the functional group in the functional group grafting treatment is at least one of a hydroxyl group, a mercapto group, an amino group, a carboxyl group, a sulfonic acid group, and an amide group. In the present invention, the functional group grafting treatment is preferably performed in a solution of a compound having a functional group, and the concentration of the compound in the solution of the compound having a functional group is preferably 0.1 to 10M, more preferably 0.5 to 5M, and most preferably 1 to 3M.
In the present invention, when the functional group is a hydroxyl group, the compound having a functional group is preferably at least one of ethylene glycol, glycerol, and hydrogen peroxide; when the functional group is a mercapto group, the compound containing a functional group is preferably at least one of a thiol and a thiophenol; when the functional group is an amino group, the compound containing a functional group is preferably at least one of aniline, ethylenediamine, and an amino acid; when the functional group is a carboxyl group, the compound containing the functional group is preferably at least one of acetic acid, benzoic acid and disodium ethylenediaminetetraacetate; when the functional group is a sulfonic acid group, the compound having a functional group is preferably at least one of 1, 5-naphthalenedisulfonic acid and sodium dodecylbenzenesulfonate; when the functional group is an amide group, the compound having a functional group is preferably at least one of acrylamide and methylolacrylamide. The source of the functional group-containing compound is not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used. According to the invention, the calcined coal gangue is immersed in the solution of the compound, and the functional group in the compound containing the functional group can be combined with the in-vivo defect and the active site of the coal gangue, so that the in-situ grafting of the active group is realized, the higher persulfate activation efficiency is achieved, and the degradation performance of the activated material on organic pollutants is further improved.
In the invention, the time for the functional group grafting treatment is preferably 0.5-72 h, more preferably 1-48 h, and most preferably 12-24 h; the temperature of the functional group grafting treatment is preferably 20-95 ℃, more preferably 40-80 ℃, and most preferably 50-60 ℃. In the present invention, the functional group grafting treatment is preferably performed under stirring conditions. The stirring speed is not particularly limited, and the liquid can be prevented from splashing. The invention realizes the in-situ grafting of the activated group through group construction, thereby achieving higher persulfate activation efficiency.
After the functional group grafting treatment is finished, the product of the functional group grafting treatment is preferably subjected to filtering, washing and drying treatment in sequence to obtain the coal gangue in-situ carbon activation material. The present invention is not particularly limited to the specific operations of the filtration, washing and drying treatment, and those known to those skilled in the art may be used.
The preparation method provided by the invention adopts the coal gangue as a raw material, so that a large amount of coal gangue can be consumed, the pollution of the coal gangue to the environment is reduced, and the economic value of the coal gangue can be improved; the gangue is mechanically activated, so that the surface/interface active groups of the gangue are constructed and released, the chemical activation promotes the formation and construction of a novel micro-nano pore structure in the gangue, the gangue is calcined in inert atmosphere, the induced generation of defect sites and the establishment of active points can be realized, and the in-situ grafting of the active groups is realized through the construction of functional groups, so that the higher persulfate activation efficiency is achieved, and the degradation performance of the activation material on organic pollutants is improved.
The invention provides application of the coal gangue in-situ carbon activation material prepared by the preparation method in the technical scheme in degradation of organic pollutants.
In the invention, the coal gangue in-situ carbon activation material preferably degrades organic pollutants under the condition of keeping out of the sun. The specific application mode of the coal gangue in-situ carbon activation material in the degradation of organic pollutants is not particularly limited, and the conventional mode in the field is adopted. The specific dosage of the coal gangue in-situ carbon activation material in the degradation of the organic pollutants is not specially limited, and can be determined according to the technical common knowledge of the technical personnel in the field.
The coal gangue in-situ carbon activation material prepared by the invention is applied to degrading organic pollutants, and has higher degradation rate for the organic pollutants compared with a catalyst which is not calcined and is not subjected to functional group grafting treatment and commercially available coal dust.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The preparation method of the coal gangue in-situ carbon activation material comprises the following steps:
(1) selecting coal gangue with carbon content of 20% and kaolinite content of more than 60%, primarily crushing the coal gangue, adding the crushed coal gangue into a high-speed dispersion grinder, and grinding and mechanically activating until the fineness is-100 meshes and the stripping rate is more than 70%, thereby obtaining mechanically activated coal gangue;
(2) putting the mechanically activated coal gangue obtained in the step (1) into a 5M hydrochloric acid solution for acid leaching treatment, wherein the temperature of the acid leaching treatment is 60 ℃, and the treatment time is 2 hours, so as to obtain chemically activated coal gangue;
(3) placing the chemically activated coal gangue obtained in the step (2) into a nitrogen atmosphere, controlling the gas flow rate to be 0.5mL/min, heating to 400 ℃ at a heating rate of 5 ℃/min for calcination, wherein the calcination time is 4h, and then cooling to room temperature at a cooling rate of 5 ℃/min to obtain calcined coal gangue;
(4) and (4) placing the calcined coal gangue obtained in the step (3) into a 5M hydrogen peroxide solution, stirring for 24 hours at the temperature of 60 ℃, and then sequentially filtering, washing and drying to obtain the coal gangue in-situ carbon activation material.
Example 2
The preparation method of the coal gangue in-situ carbon activation material comprises the following steps:
(1) selecting coal gangue with the carbon content of 25% and the kaolinite content of more than 60%, primarily crushing the coal gangue, adding the crushed coal gangue into a high-speed dispersion grinder, and grinding and mechanically activating until the fineness is-100 meshes and the stripping rate is more than 70%, so as to obtain mechanically activated coal gangue;
(2) putting the mechanically activated coal gangue obtained in the step (1) into a 5M nitric acid solution for acid leaching treatment, wherein the temperature of the acid leaching treatment is 60 ℃, and the time of the acid leaching treatment is 2 hours, so as to obtain chemically activated coal gangue;
(3) placing the chemically activated coal gangue obtained in the step (2) into a nitrogen atmosphere, controlling the gas flow rate to be 0.5mL/min, heating to 500 ℃ at a heating rate of 5 ℃/min for calcination, wherein the calcination time is 4h, and then cooling to room temperature at a cooling rate of 5 ℃/min to obtain calcined coal gangue;
(4) and (3) placing the calcined coal gangue obtained in the step (3) into a 5M aniline solution (ethanol is used as a solvent), stirring for 24 hours at the temperature of 60 ℃, and then sequentially filtering, washing and drying to obtain the coal gangue in-situ carbon activation material.
Example 3
The preparation method of the coal gangue in-situ carbon activation material comprises the following steps:
(1) selecting coal gangue with carbon content of 15% and kaolinite content of more than 60%, primarily crushing the coal gangue, adding the crushed coal gangue into a high-speed dispersion grinder, and grinding and mechanically activating until the fineness is-100 meshes and the stripping rate is more than 70%, thereby obtaining mechanically activated coal gangue;
(2) putting the mechanically activated coal gangue obtained in the step (1) into a 5M sulfuric acid solution for acid leaching treatment, wherein the temperature of the acid leaching treatment is 60 ℃, and the treatment time is 2 hours, so as to obtain chemically activated coal gangue;
(3) placing the chemically activated coal gangue obtained in the step (2) into a nitrogen atmosphere, controlling the gas flow rate to be 0.5mL/min, heating to 300 ℃ at a heating rate of 5 ℃/min for calcining for 4h, and then cooling to room temperature at a cooling rate of 5 ℃/min to obtain calcined coal gangue;
(4) and (3) placing the calcined coal gangue obtained in the step (3) into a 5M lauryl mercaptan (methanol as a solvent) solution, stirring for 24 hours at the temperature of 60 ℃, and then sequentially filtering, washing and drying to obtain the coal gangue in-situ carbon activation material.
Example 4
The preparation method of the coal gangue in-situ carbon activation material comprises the following steps:
(1) selecting coal gangue with the carbon content of 25% and the kaolinite content of more than 60%, primarily crushing the coal gangue, adding the crushed coal gangue into a high-speed dispersion grinder, and grinding and mechanically activating until the fineness is-100 meshes and the stripping rate is more than 70%, so as to obtain mechanically activated coal gangue;
(2) putting the mechanically activated coal gangue obtained in the step (1) into a 5M nitric acid solution for acid leaching treatment, wherein the temperature of the acid leaching treatment is 60 ℃, and the time of the acid leaching treatment is 2 hours, so as to obtain chemically activated coal gangue;
(3) placing the chemically activated coal gangue obtained in the step (2) into an argon atmosphere, controlling the gas flow rate to be 0.5mL/min, heating to 400 ℃ at a heating rate of 5 ℃/min for calcining for 4h, and then cooling to room temperature at a cooling rate of 5 ℃/min to obtain calcined coal gangue;
(4) and (4) placing the calcined coal gangue obtained in the step (3) into a 5M acetic acid aqueous solution, stirring for 24 hours at the temperature of 60 ℃, and then sequentially filtering, washing and drying to obtain the coal gangue in-situ carbon activation material.
Comparative example 1
Example 1 coal gangue after mechanical activation obtained in step (1).
Comparative example 2
Example 1 coal gangue after chemical activation obtained in step (2).
Example 3
The ash content of the commercial coal powder is 9.8 percent, the fineness of the coal powder is below 200 meshes, and the coal powder is dried at the temperature of 105 ℃.
Application example 1
0.05g of the coal gangue in-situ carbon activation material prepared in the example 1 is mixed with 100mL of phenol solution with the concentration of 25mg/L, after 5min of ultrasonic dispersion, a dark adsorption experiment is started in a dark environment, the dark adsorption time is 60min, then 1mL of potassium monopersulfate composite salt solution with the concentration of 0.1M is added, the reaction lasts for 10min, then a water system filter membrane with the thickness of 0.22 μ M is used for filtration, and finally high performance liquid chromatography is adopted for testing, so that the degradation rate of the coal gangue in-situ carbon activation material prepared in the example 1 on phenol is obtained, and is shown in Table 1.
The phenol solution with the medium concentration of 25mg/L is replaced by a naphthalene solution with the concentration of 10mg/L, and the above operation is repeated, so that the degradation rate of the coal gangue in-situ carbon activation material prepared in example 1 on naphthalene is obtained, as shown in Table 1.
Application examples 2 to 4
The coal gangue in-situ carbon activation material in application example 1 is sequentially replaced with the coal gangue in-situ carbon activation material prepared in examples 2 to 4, and the other conditions are the same as in application example 1, so that the degradation rates of the coal gangue in-situ carbon activation material prepared in examples 2 to 4 on phenol and naphthalene are obtained, and are shown in table 1.
Application example 5
The coal gangue in-situ carbon activation material in the application example 1 is replaced by the coal gangue after mechanical activation provided in the comparative example 1, and other conditions are the same as the application example 1, so that the degradation rates of the coal gangue after mechanical activation to phenol and naphthalene are obtained, and are shown in table 1.
Application example 6
The coal gangue in-situ carbon activation material in the application example 1 is replaced by the coal gangue after chemical activation provided by the comparative example 2, and the other conditions are the same as the application example 1, so that the degradation rate of the coal gangue after chemical activation to phenol and naphthalene is obtained, as shown in table 1.
Application example 7
The coal gangue in-situ carbon activation material in the application example 1 is replaced by the coal powder provided by the comparative example 3, and the degradation rate of the coal powder to phenol and naphthalene is obtained under the same other conditions as the application example 1, as shown in table 1.
Table 1 test results of degradation rates of application examples 1-7 on phenol and naphthalene
| Performance index | Application example 1 | Application example 2 | Application example 3 | Application example 4 | Application example 5 | Application example 6 | Application example 7 |
| Phenol degradation Rate (%) | 94.97 | 99.65 | 87.13 | 92.46 | 1.5 | 30.20 | 0.23 |
| Naphthalene degradation Rate (%) | 88.86 | 98.34 | 85.43 | 87.65 | 0.8 | 17.86 | 0.15 |
As can be seen from Table 1, the coal gangue in-situ carbon activation materials prepared in the embodiments 1 to 4 of the invention have high degradation rate on organic pollutants phenol and naphthalene, while the materials provided in the comparative examples 1 to 3 have low degradation rate on phenol and naphthalene, which indicates that the degradation performance of the coal gangue in-situ carbon activation materials on organic pollutants can be greatly improved after calcination and functional group grafting treatment.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (3)
1. A preparation method of a coal gangue in-situ carbon activation material applied to organic pollutant degradation comprises the following steps:
sequentially carrying out mechanical activation, chemical activation, calcination and functional group grafting treatment on the coal gangue to obtain a coal gangue in-situ carbon activation material; the calcining atmosphere is inert atmosphere; the functional group in the functional group grafting treatment is at least one of hydroxyl, sulfydryl, amino, carboxyl, sulfonic group and amide;
the carbon content in the coal gangue is 10-30%, and the kaolinite content is more than 60%;
the mechanical activation mode is crushing and grinding; the fineness of the coal gangue after mechanical activation is-100 meshes, and the stripping rate is more than 70%;
the chemical activation mode is acid leaching treatment; the acid leaching solution adopted by the acid leaching treatment is hydrofluoric acid, hydrochloric acid, nitric acid or phosphoric acid, and the concentration of the acid leaching solution is 1-12M; the time of the acid leaching treatment is 0.5-24 h, and the temperature of the acid leaching treatment is 20-95 ℃;
the calcining temperature is 200-800 ℃, and the calcining time is 0.5-12 h; the inert atmosphere is nitrogen, argon or helium; the heating rate of heating to the calcining temperature is 0.5-20 ℃/min, and the cooling rate after calcining and sintering is 0.5-20 ℃/min;
the functional group grafting treatment is carried out in a compound solution containing functional groups, the concentration of the compound solution containing functional groups is 0.1-10M, the time of the functional group grafting treatment is 0.5-72 h, and the temperature of the functional group grafting treatment is 20-95 ℃;
when the functional group is a hydroxyl group, the compound containing the functional group is at least one of ethylene glycol, glycerol and hydrogen peroxide; when the functional group is a mercapto group, the compound containing the functional group is at least one of thiol and thiophenol; when the functional group is an amino group, the compound containing a functional group is at least one of aniline, ethylenediamine and an amino acid; when the functional group is carboxyl, the compound containing the functional group is at least one of acetic acid, benzoic acid and disodium ethylene diamine tetraacetate; when the functional group is a sulfonic acid group, the compound containing the functional group is at least one of 1, 5-naphthalene disulfonic acid and sodium dodecyl benzene sulfonate; when the functional group is an amide group, the compound having a functional group is at least one of acrylamide and methylolacrylamide.
2. The coal gangue in-situ carbon activation material prepared by the preparation method of claim 1.
3. The application of the coal gangue in-situ carbon activation material as defined in claim 2 in the degradation of organic pollutants.
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