CN112023975B - Doped photocatalyst for treating landfill leachate and preparation method and application thereof - Google Patents
Doped photocatalyst for treating landfill leachate and preparation method and application thereof Download PDFInfo
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- CN112023975B CN112023975B CN202010829281.7A CN202010829281A CN112023975B CN 112023975 B CN112023975 B CN 112023975B CN 202010829281 A CN202010829281 A CN 202010829281A CN 112023975 B CN112023975 B CN 112023975B
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- Prior art keywords
- photocatalyst
- lafeo
- catalyst
- landfill leachate
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 41
- 239000000149 chemical water pollutant Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 229910017771 LaFeO Inorganic materials 0.000 claims abstract description 38
- 229910052755 nonmetal Inorganic materials 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 8
- 229910052796 boron Inorganic materials 0.000 claims abstract description 7
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 7
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 4
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 4
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 44
- 239000000843 powder Substances 0.000 claims description 35
- 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 claims description 32
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 28
- 239000002243 precursor Substances 0.000 claims description 23
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 21
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 21
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 18
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 14
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 14
- 238000000227 grinding Methods 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 229910021536 Zeolite Inorganic materials 0.000 claims description 10
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 10
- 239000010457 zeolite Substances 0.000 claims description 10
- 239000004202 carbamide Substances 0.000 claims description 9
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 9
- 239000002270 dispersing agent Substances 0.000 claims 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 claims description 6
- 239000011651 chromium Substances 0.000 claims description 6
- 239000008139 complexing agent Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000002808 molecular sieve Substances 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 6
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 6
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 6
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- 229960000892 attapulgite Drugs 0.000 claims description 5
- 239000004927 clay Substances 0.000 claims description 5
- 229910052625 palygorskite Inorganic materials 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 5
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 3
- 229940010552 ammonium molybdate Drugs 0.000 claims description 3
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 3
- 239000011609 ammonium molybdate Substances 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- 230000000593 degrading effect Effects 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- 238000003672 processing method Methods 0.000 claims 2
- 239000003054 catalyst Substances 0.000 abstract description 85
- 230000001699 photocatalysis Effects 0.000 abstract description 24
- 230000015556 catabolic process Effects 0.000 abstract description 22
- 238000006731 degradation reaction Methods 0.000 abstract description 22
- 238000007254 oxidation reaction Methods 0.000 abstract description 22
- 230000003647 oxidation Effects 0.000 abstract description 21
- 239000003344 environmental pollutant Substances 0.000 abstract description 8
- 231100000719 pollutant Toxicity 0.000 abstract description 8
- 230000008878 coupling Effects 0.000 abstract description 7
- 238000010168 coupling process Methods 0.000 abstract description 7
- 238000005859 coupling reaction Methods 0.000 abstract description 7
- 230000006798 recombination Effects 0.000 abstract description 4
- 238000005215 recombination Methods 0.000 abstract description 4
- 230000001105 regulatory effect Effects 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 description 34
- 239000012153 distilled water Substances 0.000 description 22
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 14
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 238000001514 detection method Methods 0.000 description 11
- 239000002351 wastewater Substances 0.000 description 11
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 239000005995 Aluminium silicate Substances 0.000 description 9
- 235000012211 aluminium silicate Nutrition 0.000 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 description 9
- 239000005909 Kieselgur Substances 0.000 description 7
- 239000003153 chemical reaction reagent Substances 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- 230000007547 defect Effects 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 229910052724 xenon Inorganic materials 0.000 description 6
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 6
- 238000004128 high performance liquid chromatography Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 238000002798 spectrophotometry method Methods 0.000 description 5
- 239000006228 supernatant Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 238000010170 biological method Methods 0.000 description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 238000000053 physical method Methods 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 239000010813 municipal solid waste Substances 0.000 description 2
- 238000010525 oxidative degradation reaction Methods 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Inorganic materials [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 1
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 230000000249 desinfective effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
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- B01J29/00—Catalysts comprising molecular sieves
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- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/86—Chromium
- B01J23/862—Iron and chromium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/049—Sulfides with chromium, molybdenum, tungsten or polonium with iron group metals or platinum group metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/076—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J37/03—Precipitation; Co-precipitation
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
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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
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- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
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- 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
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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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/06—Contaminated groundwater or leachate
-
- 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
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- 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)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Dispersion Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a doped photocatalyst for treating landfill leachate and a preparation method and application thereof, wherein the photocatalyst adopts a general formula of A-B-LaFeO 3 Y represents, A is Mn, mo, co or Cr, B is N, B, F or S, laFeO 3 Is active component, Y is porous carrier, A, B and LaFeO 3 The mass ratio of (1-4:2-8) is as follows 3 The mass ratio of Y to Y is 30-40. The catalyst disclosed by the invention is modified by codoping of a specific metal component and a nonmetal component, so that the electronic structure of the catalyst is effectively regulated and controlled, the recombination of photo-generated electron-hole pairs is inhibited, and the photocatalytic efficiency is improved; by utilizing the catalyst to perform ultrasonic coupling photocatalytic oxidation, the photocatalytic efficiency is improved, the problems of low treatment efficiency and long period of the existing photocatalytic oxidation technology are solved, and the pollutant degradation efficiency is obviously improved.
Description
Technical Field
The invention relates to a catalyst, a preparation method and application thereof, in particular to a doped photocatalyst for treating landfill leachate, and a preparation method and application thereof.
Background
With the rapid development of economy and the continuous improvement of living standard, the amount of domestic garbage and industrial solid waste is increased rapidly, and the harm of the generated landfill leachate to the environment is increasingly serious. Landfill leachate generally refers to high-concentration wastewater formed by processes such as fermentation, surface water and underground water soaking, rainfall leaching and the like in the process of garbage stacking and landfill, and the components of the wastewater are very complex, and most of the wastewater are confirmed to be three substances, such as aniline, phthalate and phenols with high content in the wastewater, which are listed in a list of important pollutants. Because of the characteristics of complex components, high COD value, poor biodegradability, high ammonia nitrogen content, high chromaticity and the like, the landfill leachate is one of the internationally recognized wastewater treatment difficulties.
The current methods for treating landfill leachate are mainly classified into physical methods, biological methods and advanced oxidation methods. The physical method mainly comprises an adsorption method, an extraction method and a membrane separation method, but the physical method is only a physical transfer process and is not really degraded, and secondary pollution is easily caused if the subsequent treatment is improper. The biological method is to transfer or convert organic matters in the wastewater into simple inorganic matters by utilizing the life activities of microorganisms, however, the B/C ratio of the landfill leachate is low, and the landfill leachate contains a large amount of pollutants having toxic action on the microorganisms, so that the traditional biological method treatment process is difficult to realize the efficient degradation of the landfill leachate. The advanced oxidation method mainly comprises the following steps: (1) ozone oxidation, namely, the purpose of degrading organic matters is achieved through the reaction of ozone molecules or OH and the organic matters, but the method has the defects of high energy consumption, low efficiency, incapability of continuously disinfecting, possibility of generating carcinogenic bromate and the like; (2) wet catalytic oxidation, in which oxygen is used as an oxidant at high temperature and high pressure to realize the oxidative degradation of organic matters, but the further application of the organic matters is limited due to the operating conditions of the high temperature and the high pressure; (3) the electrochemical method is that the electrochemical method,the catalytic degradation of pollutants is realized through the electrode reaction with activation on the interface of an electrode and a solution, but the prior electrode material with excellent performance is lacked, and the defect of high energy consumption exists; (4) fenton oxidation method, the essence of which is Fe 2+ And H 2 O 2 Chain reaction between them to generate OH, which can further oxidize and degrade organic pollutants, however, the Fenton system has a narrow pH range and H 2 O 2 The utilization rate is not high, and secondary pollution of iron mud is generated; (5) the photocatalytic oxidation is carried out, an electron-hole pair generated by electron transition of a semiconductor under illumination is utilized to initiate an oxidation reaction, an oxidant is not required to be added, and the reaction is carried out at normal temperature and normal pressure, but the problem of low oxidation efficiency exists.
In conclusion, the photocatalytic oxidation method has the advantages of no need of additional oxidant, mild conditions, low energy consumption, wide application range, no secondary pollution and the like, and is a wastewater treatment method with a very promising prospect. However, the photocatalytic oxidation at the present stage has the limitations of low oxidation efficiency, long treatment period, difficulty in treating high-concentration organic wastewater and the like.
Disclosure of Invention
The invention aims to: the first purpose of the invention is to provide an economical and efficient doped photocatalyst for treating landfill leachate, the second purpose of the invention is to provide a preparation method of the doped photocatalyst, and the third purpose of the invention is to provide a method for realizing the synergistic degradation of the landfill leachate by utilizing the doped photocatalyst through ultrasonic coupling photocatalytic oxidation.
The technical scheme is as follows: the invention relates to a doped photocatalyst for treating landfill leachate, which adopts a general formula of A-B-LaFeO 3 Y represents, wherein A is a metal doping element Mn, mo, co or Cr, B is a non-metal doping element N, B, F or S, laFeO 3 Is active component, Y is porous carrier, doped component A, B and LaFeO 3 1-4:2-8, laFeO 3 The mass ratio of Y to Y is 30-40.
Preferably, the metal doping element A is Cr, the nonmetal doping element B is N or F, the electronic structure of the prepared doping type photocatalyst is effectively regulated, the service lives of photoproduction electrons and holes are obviously prolonged, the photoresponse range is obviously widened, and the catalytic performance is the most excellent.
The porous carrier Y is natural porous carrier, such as zeolite powder, molecular sieve raw powder, diatomite, montmorillonite or high-viscosity attapulgite clay powder.
The preparation method of the photocatalyst is a sol-gel method, and comprises the following steps: dissolving ferric nitrate and lanthanum nitrate in water, adding urea, boric acid, trifluoroacetic acid or thiourea, manganese nitrate, ammonium molybdate, cobalt nitrate or chromium nitrate, a dispersing agent and a porous carrier, mixing to obtain an M liquid, dissolving a complexing agent in water to obtain an N liquid, adding the N liquid into the M liquid, heating and stirring to obtain a reactant, drying and grinding the reactant to obtain precursor powder, and calcining the precursor powder to obtain the photocatalyst A-B-LaFeO 3 -Y。
Wherein the dispersant is one of sodium carboxymethylcellulose, PEG-10000 or PVA 1799.
The complexing agent is one of citric acid, tartaric acid, EDTA, oxalic acid or acetic acid; preferably, when the complexing agent is citric acid or acetic acid, the prepared doped photocatalyst crystal is not easy to agglomerate, and the catalytic performance is the most excellent.
Wherein the molar ratio of the ferric nitrate to the lanthanum nitrate is 1:1.
The mass ratio of the dispersing agent to the ferric nitrate is 0.1-0.3, the molar ratio of the complexing agent to the ferric nitrate is 1-3:1, and the prepared doped photocatalyst crystal is not easy to agglomerate, regular in shape, uniform in size distribution, large in active surface and excellent in catalytic performance.
The invention adds the N liquid into the M liquid, heats and stirs to obtain the reactant, preferably under the heating condition of 60-100 ℃, the M liquid is slowly dripped into the N liquid with stirring, wherein, the heating is preferably water bath heating.
Wherein, the N liquid and the M liquid react for 2 to 6 hours to obtain a yellow brown gel, the yellow brown gel is dried at the temperature of between 80 and 100 ℃ overnight and then ground to obtain precursor powder, and the precursor powder is calcined at the temperature of between 500 and 700 ℃ for 2 to 4 hours to obtain the photocatalyst A-B-LaFeO 3 -Y。
The treatment method for degrading the landfill leachate by using the photocatalyst is to add the photocatalyst into the landfill leachate to carry out photocatalytic degradation reaction and simultaneously carry out ultrasonic treatment.
Wherein the mass ratio of the photocatalyst to the landfill leachate is 0.01-0.03, the reaction temperature is 20-50 ℃, and the pH value is 5.0-9.0; the ultrasonic frequency is 30-90KHz, and the ultrasonic power is 40-80W.
Preferably, the landfill leachate and the A-B-LaFeO are added into the photoreaction device 3 Y doping type photocatalyst, and carrying out photocatalytic degradation on the photoreaction device under a 400W-600W xenon lamp.
Has the advantages that: compared with the prior art, the invention has the following remarkable advantages:
(1) According to the doped photocatalyst disclosed by the invention, the electronic structure of the catalyst is effectively regulated and controlled through co-doping modification of the specific metal component and the nonmetal component, the recombination of photo-generated electron-hole pairs is inhibited, the photoresponse range is widened, and the photocatalytic efficiency is improved; the synergistic effect is achieved by reasonably blending the types and the proportions of the doped metal elements and the doped non-metal elements, so that the catalytic activity is obviously improved; by loading the catalyst on a natural porous carrier, the specific surface area of the catalyst is increased, the photocatalytic degradation and carrier adsorption synergistic effect is achieved, and the treatment efficiency is improved.
(2) According to the preparation method of the doped photocatalyst, the dispersing agent added in the preparation process can effectively inhibit the agglomeration of crystal grains, realize the nanoscale regulation and control, increase the active surface of the catalyst, and solve the problem of LaFeO in the prior art 3 The problem of unsatisfactory catalytic activity caused by easy agglomeration of crystal grains in the preparation process is solved, and the activity of the obtained catalyst photocatalyst is obviously improved; meanwhile, the catalyst is simple to prepare, is beneficial to recovery, can be repeatedly used, and has good industrial prospect.
(3) By utilizing the catalyst of the invention to carry out photocatalytic oxidation and couple ultrasonic waves, on one hand, the ultrasonic itself has a bond breaking effect on pollutants, on the other hand, the ultrasonic enables the catalyst to be uniformly dispersed in a solution, and the ultrasonic cavitation effect enables the photocatalytic efficiency to be improved, thereby solving the problems of low treatment efficiency and long period of the existing photocatalytic oxidation technology and obviously improving the pollutant degradation efficiency.
(4) The method has the advantages of simple process, no need of additional reagent, low energy consumption, realization of high-efficiency degradation of the high-concentration landfill leachate under mild conditions, better removal rate of COD and ammonia nitrogen by the combined oxidation process, more thorough degradation of pollutants, and excellent removal effect particularly on aniline and phthalate pollutants with higher content.
Detailed Description
The technical solution of the present invention is further explained below.
Example 1
Catalyst 1: 2.165g of lanthanum nitrate and 2.02g of ferric nitrate are weighed, added into 100mL of distilled water to be dissolved in a three-necked bottle, added with 0.146g of trifluoroacetic acid, added with 0.158g of manganese nitrate, added with 0.202g of sodium carboxymethylcellulose, added with 4.05g of zeolite powder and stirred uniformly to obtain M liquid. 1.92g of citric acid was dissolved in 100mL of distilled water and mixed well to obtain N solution. Slowly dropping N solution into M solution under stirring in 60 deg.C water bath, reacting for 6 hr to obtain yellow brown gel, drying at 100 deg.C overnight, grinding to obtain precursor powder, calcining the precursor powder at 500 deg.C for 4 hr to obtain 4% Mn-2%F-LaFeO 3 -a zeolite catalyst.
Catalyst 2: 2.165g of lanthanum nitrate and 2.02g of ferric nitrate are weighed, added into 100mL of distilled water and dissolved in a three-necked bottle, 0.146g of trifluoroacetic acid is added, 0.625g of ammonium molybdate and 0.404g of PVA1799 are added, 3.04g of kaolin is added, and the mixture is stirred uniformly to obtain M solution. 1.92g of citric acid was dissolved in 100mL of distilled water, and mixed well to obtain an N solution. Slowly dropping N solution into M solution under stirring at 60 deg.C in water bath for 6 hr to obtain brown gel, drying at 100 deg.C overnight, grinding to obtain precursor powder, and calcining at 500 deg.C for 4 hr to obtain 4% of Mo-2%F-LaFeO 3 -a zeolite catalyst.
Catalyst 3: 2.165g of lanthanum nitrate and 2.02g of ferric nitrate are weighed, added into 100mL of distilled water to be dissolved in a three-necked bottle, added with 0.146g of trifluoroacetic acid, added with 0.240g of cobalt nitrate, added with 0.202g of sodium carboxymethylcellulose, added with 4.05g of zeolite powder and stirred uniformly to obtain M liquid. 1.92g of citric acid was dissolved in 100mL of distilled water and mixed well to obtain N solution. Slowly dropping N solution into M solution under stirring in 60 deg.C water bath, reacting for 6 hr to obtain yellow brown gel, and heating at 100 deg.CDrying overnight, grinding to obtain precursor powder, calcining the precursor powder at 500 deg.C for 4h to obtain 4% of Co-2%F-LaFeO 3 -a zeolite catalyst.
Catalyst 4: 2.165g of lanthanum nitrate and 2.02g of ferric nitrate are weighed, added into 100mL of distilled water to be dissolved in a three-necked bottle, added with 0.146g of trifluoroacetic acid, added with 0.223g of chromium nitrate, added with 0.202g of sodium carboxymethylcellulose, added with 4.05g of zeolite powder and stirred uniformly to obtain M liquid. 1.92g of citric acid was dissolved in 100mL of distilled water, and mixed well to obtain an N solution. Slowly dropping N solution into M solution under stirring at 60 deg.C in water bath, reacting for 6 hr to obtain yellow brown gel, drying at 100 deg.C overnight, grinding to obtain precursor powder, calcining the precursor powder at 500 deg.C for 4 hr to obtain 4% of Cr-2%F-LaFeO 3 -a zeolite catalyst.
100mL of landfill leachate with the COD value of 8000mg/L and 1.0g of photocatalyst are added into a photoreaction device, and the photoreaction device is subjected to photocatalytic degradation under a 500W xenon lamp, the reaction temperature is controlled to be 50 ℃, and the pH value is 5.0. And (3) inserting a 30KHz ultrasonic amplitude transformer with the power of 40W into the wastewater while carrying out photocatalytic degradation, reacting for 4h, centrifuging a water sample, and taking supernatant for detection. The COD rapid determinator is adopted to detect COD values before and after catalytic degradation, the spectrophotometry method is adopted to detect ammonia nitrogen concentrations before and after catalytic degradation, and the high performance liquid chromatography method is adopted to detect the concentrations of each index before and after catalytic degradation. The results are shown in Table 1.
TABLE 1 Effect of different Metal component dopings on catalytic Activity
As can be seen from table 1, the catalysts doped with different metal components all exhibit excellent catalytic performance and catalytic activity: catalyst 4 > catalyst 1 > catalyst 3 > catalyst 2. This is because of the perovskite type ABO 3 In the photocatalyst, the ionic radius, electronegativity, electronic structure, electronic configuration and the like of the B site have obvious influence on the catalytic activity, so that the B site doping of metal ions can obviously improve the catalytic efficiency; the research finds thatLaFeO 3 The catalytic activity is improved most obviously when the B site of the catalyst is doped with Cr, because ABO is doped with Cr compared with Mn, mo and Co 3 The catalyst has the most stable perovskite structure, cr ions are coupled with Fe ions, and the inhibition effect on the spiral spinning structure exists, so that the conductivity of the catalyst is reduced, and the service life of photo-generated electrons and holes is effectively prolonged due to the reduction of current density.
Example 2
Catalyst 1: 2.165g of lanthanum nitrate and 2.02g of ferric nitrate are weighed, added into 100mL of distilled water and dissolved in a three-necked bottle, 0.312g of urea is added, 0.112g of chromium nitrate is added, 0.404g of PVA1799 is added, 3.04g of kaolin is added, and the mixture is stirred uniformly to obtain M solution. 0.90g of oxalic acid is dissolved in 100mL of distilled water and mixed uniformly to obtain an N solution. Slowly dropping N solution into M solution under stirring at 80 deg.C in water bath, reacting for 4 hr to obtain yellow brown gel, drying at 100 deg.C overnight, grinding to obtain precursor powder, and calcining at 700 deg.C for 2 hr to obtain 2% Cr-6%N-LaFeO 3 -a kaolin catalyst.
Catalyst 2: 2.165g of lanthanum nitrate and 2.02g of ferric nitrate are weighed, added into 100mL of distilled water and dissolved in a three-neck flask, 0.417g of boric acid is added, 0.112g of chromium nitrate is added, 0.404g of PVA1799 is added, 3.04g of kaolin is added, and the mixture is stirred uniformly to obtain M solution. 0.90g of oxalic acid is dissolved in 100mL of distilled water and mixed uniformly to obtain an N solution. Slowly dropping N solution into M solution under stirring at 80 deg.C in water bath, reacting for 4 hr to obtain yellow brown gel, drying at 100 deg.C overnight, grinding to obtain precursor powder, and calcining at 700 deg.C for 2 hr to obtain 2% Cr-6%B-LaFeO 3 -a kaolin catalyst.
Catalyst 3: 2.165g of lanthanum nitrate and 2.02g of ferric nitrate are weighed, added into 100mL of distilled water to be dissolved in a three-necked bottle, added with 0.146g of trifluoroacetic acid, added with 0.112g of chromium nitrate, added with 0.404g of PVA1799 and then added with 3.04g of kaolin, and stirred uniformly to obtain M solution. 0.90g of oxalic acid is dissolved in 100mL of distilled water and mixed uniformly to obtain an N solution. Slowly dripping N liquid into M liquid under the condition of water bath at 80 deg.C with stirring, reacting for 4 hr to obtain yellow brown gel, drying at 100 deg.C overnight, and grinding to obtain precursor powderCalcining the precursor powder at 700 ℃ for 2h to obtain 2% of Cr-6%F-LaFeO 3 -a kaolin catalyst.
Catalyst 4: 2.165g of lanthanum nitrate and 2.02g of ferric nitrate are weighed, added into 100mL of distilled water to be dissolved in a three-necked bottle, 0.173g of thiourea is added, 0.112g of chromium nitrate is added, 0.404g of PVA1799 is added, 3.04g of kaolin is added, and the mixture is stirred uniformly to obtain M solution. 0.90g of oxalic acid is dissolved in 100mL of distilled water and mixed uniformly to obtain an N solution. Slowly dropping N solution into M solution under stirring at 80 deg.C water bath condition, reacting for 4 hr to obtain brown gel, drying at 100 deg.C overnight, grinding to obtain precursor powder, calcining at 700 deg.C for 2 hr to obtain 2% of Cr-6%S-LaFeO 3 -a kaolin catalyst.
100mL of landfill leachate with the COD value of 8000mg/L and 2.0g of photocatalyst are added into a light reaction device, the light reaction device is subjected to photocatalytic degradation under a 600W xenon lamp, the reaction temperature is controlled to be 20 ℃, and the pH value is controlled to be 9.0. When photocatalytic degradation is carried out, a 90KHz ultrasonic amplitude transformer with the power of 80W is inserted into the wastewater, and after 4 hours of reaction, a water sample is centrifuged, and supernatant is taken for detection. The COD rapid determinator is adopted to detect COD values before and after catalytic degradation, the spectrophotometry is adopted to detect ammonia nitrogen concentrations before and after catalytic degradation, and the high performance liquid chromatography is adopted to detect the concentrations of indexes before and after catalytic degradation. The results are shown in Table 2.
TABLE 2 Effect of doping of different non-metallic Components on catalytic Activity
For LaFeO 3 The non-metal doping is carried out to LaFeO 3 O-site doping is carried out, and the optical response range is widened by regulating and controlling the energy band structure, so that the photocatalytic activity is improved. From the results in Table 2, it is clear that the value for LaFeO is 3 N or F doping is most effective because N, FThe ionic radius of ions is closest to that of O ions, partial lattice oxygen is replaced by doping, so that the forbidden bandwidth is reduced, and the forbidden bandwidth is further reduced by the orbital hybridization between N, F and Fe, so that the photoresponse range is widened finally, and the photocatalytic activity is improved.
Example 3
Catalyst 1: 2.165g of lanthanum nitrate and 2.02g of ferric nitrate are weighed, added into 100mL of distilled water to be dissolved in a three-necked bottle, added with 0.417g of urea, added with 0.056g of chromium nitrate, then added with 3.04g of diatomite and 0.606g of PEG-10000, and stirred uniformly to obtain M liquid. 0.75g of tartaric acid was dissolved in 100mL of distilled water and mixed well to obtain N solution. Slowly dropping N solution into M solution under stirring in 100 deg.C water bath, reacting for 2 hr to obtain yellow brown gel, drying at 100 deg.C overnight, grinding to obtain precursor powder, calcining the precursor powder at 700 deg.C for 3 hr to obtain 1% Cr-8%N-LaFeO 3 -a diatomaceous earth catalyst.
Catalyst 2, catalyst 3, catalyst 4 were prepared in a similar manner to catalyst 1 by controlling the amount of chromium nitrate added to obtain catalysts of different doping contents, catalyst 2 was 2% by volume cr-8%N-LaFeO 3 Diatomaceous earth, catalyst 3: 3% Cr-8%N-LaFeO 3 Diatomaceous earth, catalyst 4% Cr-8%N-LaFeO 3 -diatomaceous earth.
100mL of landfill leachate with the COD value of 8000mg/L and 3.0g of photocatalyst are added into a photoreaction device, and the photoreaction device is subjected to photocatalytic degradation under a 400W xenon lamp, the reaction temperature is controlled to be 30 ℃, and the pH value is 7.0. When photocatalytic degradation is carried out, a 60KHz ultrasonic amplitude transformer with the power of 60W is inserted into the wastewater, and after reaction for 4 hours, a water sample is centrifuged, and supernatant is taken for detection. The COD rapid determinator is adopted to detect COD values before and after catalytic degradation, the spectrophotometry is adopted to detect ammonia nitrogen concentrations before and after catalytic degradation, and the high performance liquid chromatography is adopted to detect the concentrations of indexes before and after catalytic degradation. The results are shown in Table 3.
TABLE 3 influence of different doping levels of the metal components on the catalytic activity
As can be seen from Table 3, the catalyst activity is optimum when the doping content is 2% to 3%. It was found that the reasons for this result were mainly: for perovskite type ABO 3 The catalyst has the oxygen vacancy which is gradually increased along with the increase of the doping amount, so that the adsorbed oxygen amount can be increased, and the photocatalytic activity can be obviously improved; on the other hand, lattice defects caused by doping introduce a local energy level between the conduction band and the valence band, which increases the photoresponse of the semiconductor to improve the photocatalytic activity, and these lattice defects become traps for electrons or holes to extend their lifetimes to reduce e - /h + The recombination rate of the compound improves the photocatalytic reaction efficiency; however, defects caused by doping may also become recombination centers of electron-hole to lower reactivity, and thus there is a suitable doping content and an optimal doping content.
Example 4
Catalyst 1: 2.165g of lanthanum nitrate and 2.02g of ferric nitrate are weighed, added into 100mL of distilled water to be dissolved in a three-necked bottle, added with 0.104g of urea, added with 0.167g of chromium nitrate, then added with 3.04g of molecular sieve raw powder and 0.606g of carboxymethyl cellulose, and stirred uniformly to obtain the M solution. 2.92g of EDTA was dissolved in 100mL of distilled water and mixed well to obtain N solution. Slowly dropping N solution into M solution under stirring in 80 deg.C water bath, reacting for 4 hr to obtain yellow brown gel, drying at 100 deg.C overnight, grinding to obtain precursor powder, calcining at 600 deg.C for 3.5 hr to obtain 3% Cr-2%N-LaFeO 3 -a molecular sieve catalyst.
Catalyst 2, catalyst 3, catalyst 4 were prepared in a similar manner to catalyst 1 by controlling the amount of urea added to obtain catalysts of different doping levels, catalyst 2 was 3% by volume cr-4%N-LaFeO 3 Molecular sieves, catalyst 3: 3% Cr-6%N-LaFeO 3 Molecular sieves, catalyst 43% Cr-8%N-LaFeO 3 -a molecular sieve.
100mL of landfill leachate with the COD value of 18000mg/L and 2.0g of photocatalyst are added into a photoreaction device, and the photoreaction device is subjected to photocatalytic degradation under a 500W xenon lamp, the reaction temperature is controlled to be 40 ℃, and the pH value is 7.0. And (3) inserting a 40KHz ultrasonic amplitude transformer with the power of 50W into the wastewater while carrying out photocatalytic degradation, reacting for 4h, centrifuging a water sample, and taking supernatant for detection. The COD rapid determinator is adopted to detect COD values before and after catalytic degradation, the spectrophotometry is adopted to detect ammonia nitrogen concentrations before and after catalytic degradation, and the high performance liquid chromatography is adopted to detect the concentrations of indexes before and after catalytic degradation. The results are shown in Table 4.
TABLE 4 influence of different doping levels of the non-metallic components on the catalytic activity
It can be seen from table 4 that the photocatalytic activity of the catalyst gradually increases with the increase of the doping content of the non-metal component, and when the doping amount reaches 6%, the doping content is increased, and the catalytic activity cannot be further increased. Researches show that although the O-site doping of the non-metal component can widen the photoresponse range and improve the photocatalytic activity, when the doping content is excessive, excessive crystal defects are introduced, so that the service life of photo-generated electron holes is shortened, and therefore, the appropriate doping content and the optimal doping content exist.
Example 5
Catalyst 1: 2.165g of lanthanum nitrate and 2.02g of ferric nitrate are weighed, added into 100mL of distilled water to be dissolved in a three-necked bottle, added with 0.312g of urea, added with 0.167g of chromium nitrate, then added with 4.05g of high-viscosity attapulgite clay powder and 0.606g of carboxymethyl cellulose, and stirred uniformly to obtain M liquid. 0.90g of acetic acid was dissolved in 100mL of distilled water, and mixed well to obtain an N solution. Slowly dropping N solution into M solution under stirring in 100 deg.C water bath, reacting for 2 hr to obtain yellow brown gel, drying at 100 deg.C overnight, grinding to obtain precursor powder, calcining the precursor powder at 700 deg.C for 3 hr to obtain 3% of carboxymethyl cellulose dispersion, and making into 3% Cr-6%N-LaFeO 3 -high viscosity attapulgite clay powder catalyst.
The preparation methods of the catalyst 2 and the catalyst 3 are similar to the catalyst 1, and the catalysts prepared by different dispersion systems are obtained by changing the types of the added dispersing agents, wherein the catalyst 2 is a PEG-10000 dispersion system, and the catalyst 3 is a PVA1799 dispersion system.
100mL of landfill leachate with the COD value of 8000mg/L and 1.0g of photocatalyst are added into a photoreaction device, and the photoreaction device is subjected to photocatalytic degradation under a 500W xenon lamp, the reaction temperature is controlled to be 50 ℃, and the pH value is 5.0. And (3) inserting a 30KHz ultrasonic amplitude transformer with the power of 40W into the wastewater while carrying out photocatalytic degradation, reacting for 4h, centrifuging a water sample, and taking supernatant for detection. The COD rapid determinator is adopted to detect COD values before and after catalytic degradation, the spectrophotometry is adopted to detect ammonia nitrogen concentrations before and after catalytic degradation, and the high performance liquid chromatography is adopted to detect the concentrations of indexes before and after catalytic degradation. The results are shown in Table 5.
TABLE 5 Effect of different dispersions on catalytic Activity
As can be seen from Table 5, the catalysts prepared in the three dispersion systems of sodium carboxymethyl cellulose, PEG-10000 and PVA1799 all have excellent catalytic activity. This is because the addition of the dispersing agent in the preparation process effectively inhibits the agglomeration of the crystal grains, thereby realizing the nano-scale control and increasing the active surface of the catalyst.
Comparative example 1
In this comparative example, no urea and chromium nitrate were added during the catalyst preparation to produce undoped LaFeO 3 Zeolite catalyst, other operating steps, reagents, apparatus and detection method are the same as in example 1.
After the landfill leachate with the COD value of 8000mg/L is degraded synergistically by ultrasonic coupling photocatalytic oxidation, the COD removal rate is 62.45%, the ammonia nitrogen removal rate is 56.76%, the aniline removal rate is 58.43% and the dibutyl phthalate removal rate is 59.84%.
Comparative example 2
In this comparative example, no chromium nitrate was added during the catalyst preparation to produce a single non-metal doped 8%N-LaFeO 3 Kieselguhr catalyst, other operating steps, reagents, apparatus and detection method were the same as in example 3.
After the landfill leachate with the COD value of 8000mg/L is degraded synergistically by ultrasonic coupling photocatalytic oxidation, the COD removal rate is 67.37%, the ammonia nitrogen removal rate is 62.14%, the aniline removal rate is 62.93%, and the dibutyl phthalate removal rate is 63.84%.
Comparative example 3
In this comparative example, no urea was added during the catalyst preparation to obtain a monometallically doped 3% Cr-LaFeO 3 Molecular sieve catalyst, other operating steps, reagents, apparatus and detection method are the same as in example 4.
After the landfill leachate with the COD value of 8000mg/L is degraded synergistically by ultrasonic coupling photocatalytic oxidation, the removal rate of COD is 71.45%, the removal rate of ammonia nitrogen is 66.38%, the removal rate of aniline is 67.64%, and the removal rate of dibutyl phthalate is 66.92%.
Comparative example 4
In this comparative example, 3% of Al-6%N-LaFeO was obtained by replacing chromium nitrate with aluminum nitrate, copper nitrate, and cadmium nitrate, respectively, in the course of catalyst preparation 3 Diatomaceous earth catalyst (catalyst 1), 3% Cu-6%N-LaFeO 3 Diatomaceous earth catalyst (catalyst 2), 3% Cd-6%N-LaFeO 3 Diatomaceous earth catalyst (catalyst 3), other operating steps, reagents, apparatus and detection method were the same as in example 3.
The landfill leachate with the COD value of 8000mg/L is degraded synergistically by ultrasonic coupling photocatalytic oxidation.
Comparative example 5
Comparative exampleIn the catalyst preparation process, no dispersant was added, and 3% of Cr-6%N-LaFeO was obtained 3 The catalyst of high-viscosity attapulgite clay powder, and other operation steps, reagents, devices and detection methods are the same as those of example 5.
After the landfill leachate with the COD value of 8000mg/L is degraded synergistically by ultrasonic coupling photocatalytic oxidation, the removal rate of COD is 70.23%, the removal rate of ammonia nitrogen is 64.75%, the removal rate of aniline is 66.18%, and the removal rate of dibutyl phthalate is 66.86%.
Comparative example 6
In this comparative example, catalyst 1 in example 5 was used as a photocatalyst, and no ultrasonic wave was introduced in the photocatalytic degradation stage, and the other operation steps, reagents, apparatus, and detection method were the same as those in example 5.
After the landfill leachate with the COD value of 8000mg/L is subjected to photocatalytic oxidative degradation, the COD removal rate is 68.24%, the ammonia nitrogen removal rate is 63.78%, the aniline removal rate is 64.12%, and the dibutyl phthalate removal rate is 66.07%.
Claims (10)
1. A doped photocatalyst for treating landfill leachate is characterized in that: the photocatalyst adopts a general formula of A-B-LaFeO 3 Y represents, wherein A is a metal doping element Mn, mo, co or Cr, B is a non-metal doping element N, B, F or S, laFeO 3 Is active component, Y is porous carrier, doped component A, B and LaFeO 3 1-4:2-8, laFeO 3 The mass ratio of Y to Y is 30-40.
2. The photocatalyst as set forth in claim 1, wherein: when A is Cr, B is N or F.
3. The photocatalyst as set forth in claim 1, wherein: and Y is a natural porous carrier.
4. The photocatalyst according to claim 3, characterized in that: the natural porous carrier is one of zeolite powder, molecular sieve raw powder, diatomite, montmorillonite or high-viscosity attapulgite clay powder.
5. A method for preparing the photocatalyst of claim 1, comprising the steps of: dissolving ferric nitrate and lanthanum nitrate in water, adding urea, boric acid, trifluoroacetic acid or thiourea, manganese nitrate, ammonium molybdate, cobalt nitrate or chromium nitrate, a dispersing agent and a porous carrier, mixing to obtain an M liquid, dissolving a complexing agent in water to obtain an N liquid, adding the N liquid into the M liquid, heating and stirring to obtain a reactant, drying and grinding the reactant to obtain precursor powder, and calcining the precursor powder to obtain the photocatalyst A-B-LaFeO 3 -Y。
6. The method for preparing a photocatalyst according to claim 5, characterized in that: the dispersing agent is one of sodium carboxymethylcellulose, PEG-10000 or PVA 1799.
7. The method for preparing a photocatalyst according to claim 5, characterized in that: the complexing agent is one of citric acid, tartaric acid, EDTA, oxalic acid or acetic acid.
8. A treatment method for degrading landfill leachate by using the photocatalyst of claim 1, which is characterized in that: adding a photocatalyst into the landfill leachate to perform photocatalytic degradation reaction, and simultaneously performing ultrasonic treatment.
9. The processing method according to claim 8, characterized in that: the mass ratio of the photocatalyst to the landfill leachate is 0.01-0.03, the reaction temperature is 20-50 ℃, and the pH value is 5.0-9.0.
10. The processing method according to claim 8, characterized in that: the ultrasonic frequency is 30-90KHz, and the ultrasonic power is 40-80W.
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| CN110270349A (en) * | 2019-07-29 | 2019-09-24 | 宜兴国际环保城科技发展有限公司 | A kind of composite catalyst for landfill leachate treatment |
| CN111036285A (en) * | 2019-12-16 | 2020-04-21 | 东南大学 | Photocatalyst of nitrogen modified perovskite composite molecular sieve and preparation method and application method thereof |
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