CN108975504A - The method that bismuthic acid copper-fullerene photochemical catalyst removes nitrite and ammonia nitrogen simultaneously - Google Patents
The method that bismuthic acid copper-fullerene photochemical catalyst removes nitrite and ammonia nitrogen simultaneously Download PDFInfo
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- CN108975504A CN108975504A CN201810855410.2A CN201810855410A CN108975504A CN 108975504 A CN108975504 A CN 108975504A CN 201810855410 A CN201810855410 A CN 201810855410A CN 108975504 A CN108975504 A CN 108975504A
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- Prior art keywords
- fullerene
- nitrite
- acid copper
- bismuthic acid
- photochemical catalyst
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- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 239000002253 acid Substances 0.000 title claims abstract description 87
- 229910003472 fullerene Inorganic materials 0.000 title claims abstract description 86
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 title claims abstract description 74
- 239000003054 catalyst Substances 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 51
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 68
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 32
- 239000010865 sewage Substances 0.000 claims abstract description 22
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 11
- 230000008569 process Effects 0.000 claims abstract description 7
- 230000005855 radiation Effects 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 239000010949 copper Substances 0.000 claims description 24
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 23
- 229910052802 copper Inorganic materials 0.000 claims description 23
- JVMRPSJZNHXORP-UHFFFAOYSA-N ON=O.ON=O.ON=O.N Chemical compound ON=O.ON=O.ON=O.N JVMRPSJZNHXORP-UHFFFAOYSA-N 0.000 claims description 21
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 claims description 20
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 20
- 239000011259 mixed solution Substances 0.000 claims description 17
- 229910002651 NO3 Inorganic materials 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 14
- 150000001621 bismuth Chemical class 0.000 claims description 13
- 150000001879 copper Chemical class 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 9
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 5
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 5
- 238000002306 biochemical method Methods 0.000 claims description 4
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims 3
- 239000000243 solution Substances 0.000 description 31
- 238000006243 chemical reaction Methods 0.000 description 30
- 239000000463 material Substances 0.000 description 16
- MMDJDBSEMBIJBB-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] MMDJDBSEMBIJBB-UHFFFAOYSA-N 0.000 description 15
- 239000002131 composite material Substances 0.000 description 13
- 239000004065 semiconductor Substances 0.000 description 13
- 230000015556 catabolic process Effects 0.000 description 12
- 238000006731 degradation reaction Methods 0.000 description 12
- 238000002835 absorbance Methods 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 7
- -1 nitrite anions Chemical class 0.000 description 7
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 description 6
- 229940124530 sulfonamide Drugs 0.000 description 6
- 244000005700 microbiome Species 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 230000000813 microbial effect Effects 0.000 description 4
- GQPLMRYTRLFLPF-UHFFFAOYSA-N nitrous oxide Inorganic materials [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- HCFPRFJJTHMING-UHFFFAOYSA-N ethane-1,2-diamine;hydron;chloride Chemical compound [Cl-].NCC[NH3+] HCFPRFJJTHMING-UHFFFAOYSA-N 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- 238000011953 bioanalysis Methods 0.000 description 2
- 238000004737 colorimetric analysis Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 2
- 125000001477 organic nitrogen group Chemical group 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 238000005375 photometry Methods 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 238000002798 spectrophotometry method Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 2
- 235000002906 tartaric acid Nutrition 0.000 description 2
- 239000011975 tartaric acid Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 206010017993 Gastrointestinal neoplasms Diseases 0.000 description 1
- 108010054147 Hemoglobins Proteins 0.000 description 1
- 102000001554 Hemoglobins Human genes 0.000 description 1
- 206010020772 Hypertension Diseases 0.000 description 1
- 108010061951 Methemoglobin Proteins 0.000 description 1
- 241001495402 Nitrococcus Species 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000009360 aquaculture Methods 0.000 description 1
- 244000144974 aquaculture Species 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 210000003743 erythrocyte Anatomy 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 208000032839 leukemia Diseases 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007483 microbial process Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229940005654 nitrite ion Drugs 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- XKLJHFLUAHKGGU-UHFFFAOYSA-N nitrous amide Chemical compound ON=N XKLJHFLUAHKGGU-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000006213 oxygenation reaction Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- VZOPRCCTKLAGPN-ZFJVMAEJSA-L potassium;sodium;(2r,3r)-2,3-dihydroxybutanedioate;tetrahydrate Chemical compound O.O.O.O.[Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O VZOPRCCTKLAGPN-ZFJVMAEJSA-L 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000985 reflectance spectrum Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 229940074446 sodium potassium tartrate tetrahydrate Drugs 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/30—Aerobic and anaerobic processes
- C02F3/301—Aerobic and anaerobic treatment in the same reactor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—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
- B01J23/843—Arsenic, antimony or bismuth
- B01J23/8437—Bismuth
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
- C02F2101/166—Nitrites
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Biodiversity & Conservation Biology (AREA)
- Microbiology (AREA)
- Catalysts (AREA)
- Physical Water Treatments (AREA)
Abstract
The invention discloses a kind of methods that bismuthic acid copper-fullerene photochemical catalyst removes nitrite and ammonia nitrogen simultaneously.The described method includes: bismuthic acid copper-fullerene photochemical catalyst is added into the sewage containing nitrite and ammonia nitrogen, it is passed through nitrogen, obtained mixed system is irradiated with ultraviolet-visible later, to remove nitrite and ammonia nitrogen therein simultaneously；It is passed through air again later, continues to irradiate mixed system with ultraviolet-visible, realize thorough denitrogenation.The present invention creatively combines removing nitrite with removal of ammonia and nitrogen together, remove nitrite and ammonia nitrogen simultaneously under the radiation of sunlight, it changes traditional denitrogenation and removes the process flow of nitrite, the operating condition time is shortened, time cost is reduced, saves economic cost, and removal rate is high.
Description
Technical field
The present invention relates to a kind of sewage water treatment methods, in particular to a kind of to be urged using bismuthic acid copper-fullerene photochemical catalyst light
The method changed while removing nitrite and ammonia nitrogen, belongs to photocatalysis technology field.
Background technique
Water is predominantly in the form of organic nitrogen and inorganic nitrogen.Organic nitrogen can be converted under the action of microorganism
Inorganic nitrogen.Therefore, the inorganic nitrogen in water body is removed, there is important application value for sewage treatment.Inorganic nitrogen is in water body master
It will be with ammonia nitrogen (NH3- N), nitrate nitrogen (NO3 -- N) and nitrite nitrogen (NO2 -- N) three kinds of existence forms.
Due to being excessively used of agrochemical, a large amount of discharges of trade effluent and sanitary sewage, ammonia nitrogen is usually exceeded.Ammonia nitrogen
Under aerobic condition, nitrococcus can be translated into nitrite anions (NO2 -), further oxidable is nitrate anion (NO3 -).Water
The content of ammonia nitrogen is often larger in body, and the toxicity of nitrite anions is then three kinds of maximum one kind of form Poisoning.Nitrite anions
In conjunction with hemoglobin, ferrihemoglobin is formed in vivo, reduces the oxygen carrying capacity of red blood cell.Moreover, nitrite anions and nitre
Acid group can also be converted into nitrosamine in human body, cause various diseases such as human primary gastrointestinal cancers, leukaemia, hypertension etc..Therefore, how to drop
Low water body Nitrite and ammonia nitrogen are the important topics put in face of the research staff of this field.
Existing technology is often handled nitrite anions with ammonia nitrogen respectively.For example, number of patent application is
The Chinese patent of CN99100739.5 eliminates the pollution problem of nitrite in drinking water using bioanalysis；Number of patent application
For the Chinese patent of CN200510112131.X, a kind of microorganism nitrite degradation agent and production method are disclosed；Patent Shen
Please number be CN200610023388.2 Chinese patent, describe it is a kind of using granule sludge carry out nitrite denitrification side
Method.These above-mentioned methods belong to microbial process.And in chemical method, number of patent application is the China of CN200710144384.4
Patent realizes high concentration nitrite wastewater denitrification using the method for microwave-assisted processing；Number of patent application is
The Chinese patent of CN200910060734.8 realizes Nitrite in aquaculture as reagent using sulfamic acid and drops
Solution；Ren Xianghong etc. (Ren Xianghong, Fan grasp peace sulphite removal nitro oxidizer waste water in nitrite, chemistry world,
2000,11:575-581) it reports a kind of using sodium sulfite as the nitrite waste water treatment process of reagent.Chinese patent " catalysis
Iron and biological coupling short-cut denitrification technique " (number of patent application: CN201510187814.5) realizes sewage using iron as reducing agent
Denitrogenation.The utility model patent of Patent No. CN201620767248.5 discloses a kind of Ozone flue gas desulfurization and denitrification purification system
Recirculated water nitrogen rejection facility in system.Chinese patent CN201010603906.4 discloses a kind of anti-using sulphite and nitrite
Answer the technical matters of denitration.Although these documents disclose the method for removing nitrite ion (nitrite), do not relate to
And the method for removal of ammonia and nitrogen simultaneously.
In terms of ammonia nitrogen removal, denitrogenation method has microbial method and physical-chemical process.Microbial method is in nitrifier elder generation
It is nitrite anions and nitrate anion by mineralized nitrogen, is then put nitrate anion and transforming nitrite for nitrogen by denitrifying bacterium
Out.Application number be respectively CN201611242635.8, CN201611242599.5, CN201610632670.4,
CN201610632620.6、CN201610632354.7、CN201610632666.8、CN201610633033.9、
The patents such as CN201510007561.9 disclose the method for photocatalysis removal of ammonia and nitrogen.But these methods are not related to removing Asia simultaneously
The technology of nitrate anion and ammonia nitrogen.
Bioanalysis denitrogenation has more drawback, it is necessary to strict control microorganism growing environment and condition, it is necessary to artificially add
Carbon source, influence of the nitric efficiency vulnerable to season and weather temperature.The activity of microorganism, which significantly reduces, under low temperature even inactivates, high temperature
Lower microorganism is possible " being burnt to death ".
Summary of the invention
In order to overcome above-mentioned existing deficiency, we have proposed following inventions.
The purpose of the present invention is to provide a kind of bismuthic acid copper-fullerene photochemical catalysts to remove nitrite and ammonia nitrogen simultaneously
Method, to overcome deficiency in the prior art.
For realization aforementioned invention purpose, the technical solution adopted by the present invention includes:
A kind of bismuthic acid copper-fullerene photochemical catalyst is provided in the embodiment of the present invention while removing nitrite and ammonia nitrogen
Method comprising:
Bismuthic acid copper-fullerene photochemical catalyst is added into the sewage containing nitrite and ammonia nitrogen, later first anaerobism item
With the mixed system of ultraviolet-visible irradiation nitrite and ammonia nitrogen under aerobic condition after part, to remove nitrous therein simultaneously
Hydrochlorate and ammonia nitrogen.
Further, which comprises adjust the mixed system to being in alkalinity, be passed through nitrogen, then with UV, visible light
Light irradiates the mixed system, removes while realizing Nitrite In Polluted Water nitrate and ammonia nitrogen.
Further, the method also includes: be to irradiate the mixed system under condition of nitrogen gas with ultraviolet-visible
Step is completed and then is passed through air into the mixed system, irradiates the mixed system again later with ultraviolet-visible, real
The thorough removing of existing Nitrite In Polluted Water nitrate and ammonia nitrogen.
A kind of bismuthic acid copper-fullerene photochemical catalyst is additionally provided in the embodiment of the present invention while removing nitrite and ammonia nitrogen
Method comprising: oxidation processes or Biochemical method are carried out to the sewage containing ammonia nitrogen, turn some of ammonia nitrogens
Nitrite nitrogen is turned to, bismuthic acid copper-fullerene photochemical catalyst is added later, letting nitrogen in and deoxidizing creates anaerobic condition, then with UV, visible light
Light irradiates obtained mixed system, to remove nitrite and ammonia nitrogen therein simultaneously.
A kind of bismuthic acid copper-fullerene photochemical catalyst is additionally provided in the embodiment of the present invention while removing nitrite and ammonia nitrogen
Method comprising: the sewage containing ammonia nitrogen is mixed with the sewage containing nitrite, later be added bismuthic acid copper-fullerene
Photochemical catalyst, letting nitrogen in and deoxidizing creates anaerobic condition, then obtained mixed system is irradiated with ultraviolet-visible, to remove it simultaneously
In nitrite and ammonia nitrogen.
In some exemplary embodiments, which comprises adjust the mixed system to being in alkalinity, then with UV, visible light
Light irradiates the mixed system, removes while realizing Nitrite In Polluted Water nitrate and ammonia nitrogen.
Further, the method that the bismuthic acid copper-fullerene photochemical catalyst removes nitrite and ammonia nitrogen simultaneously include: to
Bismuthic acid copper-fullerene photochemical catalyst is added in sewage containing nitrite and ammonia nitrogen, with UV, visible light illumination after letting nitrogen in and deoxidizing
Obtained mixed system is penetrated, and, it is oxygenated into the mixed system, then irradiated with ultraviolet-visible, makes the ammonia nitrogen in water body
It is degraded to N completely2, to remove nitrite and ammonia nitrogen therein simultaneously.
Compared with prior art, the present invention creatively combines removing nitrite with removal of ammonia and nitrogen together, in the sun
Nitrite and ammonia nitrogen are removed simultaneously under the radiation of light, the process flow of removing nitrite and traditional denitrogenation is changed, shortens
The operating condition time reduces time cost, saves economic cost, and removal rate is high, there is significant skill compared with prior art
Art progress；And the preparation method of bismuthic acid copper-fullerene photochemical catalyst of the present invention is simple, low in raw material price, item
Part is easily-controllable.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
The some embodiments recorded in invention, for those of ordinary skill in the art, without creative efforts,
It is also possible to obtain other drawings based on these drawings.
Fig. 1 is that bismuthic acid copper-fullerene photochemical catalyst prepares reaction unit schematic diagram in the embodiment of the present invention 1.
Fig. 2 is that fullerene in the embodiment of the present invention 1, bismuthic acid copper, bismuthic acid copper-fullerene composite semiconductor material XRD spread out
Penetrate spectrogram.
Fig. 3 is fullerene in the embodiment of the present invention 1, bismuthic acid copper, bismuthic acid copper-fullerene composite semiconductor material Raman light
Spectrogram.
Fig. 4 a- Fig. 4 d is fullerene in the embodiment of the present invention 1, bismuthic acid copper-fullerene composite semiconductor material, bismuthic acid respectively
Copper and bismuthic acid copper-fullerene composite semiconductor material TEM figure.
Fig. 5 is that bismuthic acid copper, the bismuthic acid copper-fullerene composite semiconductor material UV, visible light in the embodiment of the present invention 1 are unrestrained
Reflectance spectrum figure.
Fig. 6 is nitrite nitrogen and ammonia in bismuthic acid copper in the embodiment of the present invention 1-fullerene composite semiconductor material reaction process
The change curve schematic diagram of nitrogen.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, with reference to the accompanying drawing to specific reality of the invention
The mode of applying is described in detail.The example of these preferred embodiments is illustrated in the accompanying drawings.Shown in attached drawing and according to
The embodiments of the present invention of attached drawing description are only exemplary, and the present invention is not limited to these embodiments.
Here, it should also be noted that, in order to avoid having obscured the present invention because of unnecessary details, in the accompanying drawings only
Show with closely related structure and/or processing step according to the solution of the present invention, and be omitted little with relationship of the present invention
Other details.
The one aspect of the embodiment of the present invention provides a kind of bismuthic acid copper-fullerene photochemical catalyst while removing nitrite
With the method for ammonia nitrogen comprising: bismuthic acid copper-fullerene photochemical catalyst is added into the sewage containing nitrite and ammonia nitrogen, it
The mixed system for irradiating nitrite and ammonia nitrogen after first anaerobic condition under aerobic condition with ultraviolet-visible afterwards, to remove simultaneously
Remove nitrite and ammonia nitrogen therein.
In some exemplary embodiments, which comprises the mixed system is adjusted to being in alkalinity, is passed through nitrogen, then
The mixed system is irradiated with ultraviolet-visible, is removed while realizing Nitrite In Polluted Water nitrate and ammonia nitrogen.
Further, the pH value of the mixed system is 9.0-10.5.
Further, the method also includes: be to irradiate the mixed system under condition of nitrogen gas with ultraviolet-visible
Step is completed and then is passed through air into the mixed system, irradiates the mixed system again later with ultraviolet-visible, real
The thorough removing of existing Nitrite In Polluted Water nitrate and ammonia nitrogen.
The other side of the embodiment of the present invention additionally provides a kind of bismuthic acid copper-fullerene photochemical catalyst while removing nitrous
The method of hydrochlorate and ammonia nitrogen comprising: oxidation processes or Biochemical method are carried out to the sewage containing ammonia nitrogen, make part
Ammonia nitrogen be converted into nitrite nitrogen, later be added bismuthic acid copper-fullerene photochemical catalyst, letting nitrogen in and deoxidizing create anaerobic condition (or
Respectively under the conditions of anaerobic and aerobic), then obtained mixed system is irradiated with ultraviolet-visible, to remove Asia therein simultaneously
Nitrate and ammonia nitrogen.
In some exemplary embodiments, which comprises adjust the mixed system to being in alkalinity, then with UV, visible light
Light irradiates the mixed system, removes while realizing Nitrite In Polluted Water nitrate and ammonia nitrogen.
Further, the pH value of the mixed system is 9.0-10.5.
The other side of the embodiment of the present invention additionally provides a kind of bismuthic acid copper-fullerene photochemical catalyst while removing nitrous
The method of hydrochlorate and ammonia nitrogen comprising: the sewage containing ammonia nitrogen is mixed with the sewage containing nitrite, bismuthic acid is added later
Copper-fullerene photochemical catalyst, letting nitrogen in and deoxidizing create anaerobic condition (or respectively under the conditions of anaerobic and aerobic), then with UV, visible light
Light irradiates obtained mixed system, to remove nitrite and ammonia nitrogen therein simultaneously.
In some exemplary embodiments, the bismuthic acid copper-fullerene photochemical catalyst removes nitrite and ammonia nitrogen simultaneously
Method includes: that the mixed system is added in the bismuthic acid copper-fullerene photochemical catalyst, respectively under the conditions of anaerobic and aerobic with
Ultraviolet-visible irradiates the mixed system, while removing nitrite and ammonia nitrogen；And be oxygenated into the mixed system,
It is irradiated again with ultraviolet-visible, the ammonia nitrogen in sewage is made to be degraded to N completely2, realize the same of Nitrite In Polluted Water nitrate and ammonia nitrogen
When remove.
In some exemplary embodiments, which comprises adjust the mixed system to being in alkalinity, respectively in anaerobism and
The mixed system is irradiated with ultraviolet-visible under aerobic condition, is removed while realizing Nitrite In Polluted Water nitrate and ammonia nitrogen.
Further, the pH value of the mixed system is 9.0-10.5.
In some more specifically exemplary embodiments, the method, which may also include that, carries out oxygen to the sewage containing ammonia nitrogen
Change processing or Biochemical method, for example, being converted into some of ammonia nitrogens using the ammonia nitrogen in microbial degradation sewage
Nitrite nitrogen, backward sewage in be added bismuthic acid copper-fullerene photochemical catalyst, respectively under the conditions of anaerobic and aerobic with it is ultraviolet can
The obtained mixed system of light-exposed irradiation, to remove nitrite and ammonia nitrogen therein simultaneously.
Wherein, the technology of microbial degradation ammonia nitrogen can refer to state of the art, as CN107244742A,
CN107974416A, CN106947709A, CN106676038A etc..
In some more specifically exemplary embodiments, the method is specifically included:
A certain amount of aforementioned bismuthic acid copper-fullerene photochemical catalyst is taken, is placed in the mixed reaction solution containing nitrite and ammonia nitrogen,
Reaction solution PH is adjusted in 9.0-10.5 or so with sodium hydroxide.This reaction is divided into two stages: first stage, in confined reaction
Carried out in system, be first passed through nitrogen 20min, then under ultraviolet light irradiation with when removal nitrite and ammonia nitrogen；Second stage,
Air is filled with into reaction solution, then ultraviolet-visible irradiation is to remove the nitrogen that the first stage does not remove.This method can be simultaneously
The nitrogen for removing Nitrite and ammonia nitrogen, and being effectively utilized in sunlight removal water body.The catalyst passes through purple
Outer radiation of visible light, bismuthic acid copper-fulvene compounding material photochemical catalyst remove going for nitrite in water body and ammonia nitrogen simultaneously
Except rate can reach 90% or so.
Further, the content of fullerene is 0.01-10.0wt%, bismuthic acid in the bismuthic acid copper-fullerene photochemical catalyst
The content of copper is 90.00-99.99wt%.
In some exemplary embodiments, the preparation method of the bismuthic acid copper-fullerene photochemical catalyst includes:
Soluble bismuth salt, soluble copper salt are dissolved in solvent with fullerene and are uniformly mixed, adjusts the mixing later
Solution is alkalinity, then the mixed solution is reacted 8h under the conditions of 180 DEG C, and the bismuthic acid copper-fullerene photochemical catalyst is made.
In some exemplary embodiments, the preparation method is specifically included: by soluble bismuth salt, soluble copper salt and fowler
Alkene is dissolved in solvent and is uniformly mixed, and adjusts the mixed solution later for alkalinity, then by the mixed solution in 180 DEG C of conditions
Bismuthic acid copper-fullerene the photochemical catalyst is made in lower reaction 8h.
Further, the soluble bismuth salt and the molar ratio of soluble copper salt are 2:1.
Further, the mass ratio of the fullerene and bismuthic acid copper is 1-9:100.
Further, the soluble bismuth salt includes bismuth nitrate, but not limited to this.
Further, the soluble copper salt includes copper nitrate, but not limited to this.
Further, the solvent includes deionized water, but not limited to this.
Further, the alkaline matter to adjust the mixed solution to alkalinity includes sodium hydroxide, but not limited to this.
Further, the preparation method further include: the mixed solution is placed under conditions of temperature is 180 DEG C and is reacted
8h, is washed with deionized later, filters, and then places it in drying in the baking oven that temperature is 40-60 DEG C and for 24 hours, obtains institute
Bismuthic acid copper-fullerene the photochemical catalyst stated.
By above-mentioned technical proposal, the present invention creatively combines removing nitrite with removal of ammonia and nitrogen together, too
Nitrite and ammonia nitrogen are removed simultaneously under the radiation of sunlight, changes the process flow of removing nitrite and traditional denitrogenation, contracting
The short operating condition time reduces time cost, saves economic cost, and removal rate is high, has compared with prior art significant
Technological progress.
Technology of the invention is further explained below in conjunction with drawings and examples.
Embodiment 1
Using bismuth nitrate and copper nitrate as raw material, according to molar ratio Bi:Cu=2:1 ratio weigh, be dissolved separately in from
In sub- water, uniformly mix.By dry 2 hours 120 DEG C of fullerenes, it is added in mixed liquor according to the 1-9% of bismuthic acid copper mass,
It is 60-90 minutes ultrasonic, it is stirred for 60 minutes.Then a certain amount of sodium hydroxide is added, stirring moves back anti-to high pressure for 60-90 minutes
It answers in kettle, airtight heating 8 hours at 180 DEG C.It is cooled to room temperature to sample, is washed with deionized, filters, by sodium hydroxide
And other electrolyte remove.It is 24 hours dry in 40-60 DEG C of baking oven, bismuthic acid copper-fullerene composite semiconductor material is made.
The bismuthic acid copper for taking a certain amount of above method to be prepared-fullerene photochemical catalyst 0.3750g is put into 250mL containing Asia
(deionized water used in reaction solution leads to nitrogen 30min nitrogen in the reaction solution of nitrate 50mg/L and ammonia nitrogen concentration 100mg/L
Gas removes oxygen in water), suitable NaOH is added, keeps the pH of solution between 9.5-10.0, is placed in light-catalyzed reaction instrument,
Magnetic stirrer carries out light-catalyzed reaction under ultraviolet-visible irradiation.Remaining ammonia nitrogen, nitrous state are measured every 30min
The absorbance of nitrogen, nitrate nitrogen.The response situation of ammonia nitrogen, nitrite nitrogen, nitrate nitrogen is calculated with this.First stage (closed reaction
Device, shown in Figure 1), illumination 5 hours, nitrite nitrogen removal rate was up to 89%, and for ammonia nitrogen removal frank up to 56%, no nitrate nitrogen is raw
At；Second stage (oxygenation) continues illumination 8 hours (totally 13 hours), and nitrite nitrogen removal rate is 90%, and ammonia nitrogen removal frank reaches
83%, no nitrate nitrogen generates.
In reaction process, three kinds of nitrite nitrogen, nitrate nitrogen, ammonia nitrogen substances detect respectively, avoid interfering with each other.Nitrite nitrogen
The measurement of content uses ultraviolet spectrophotometry, ammonia nitrogen using N- (1- how base) ethylenediamine photometry, the measurement of nitrate nitrogen content
Using reagent colorimetric method.It is utilized respectively ultraviolet-uisible spectrophotometer measurement nitrite nitrogen, three kinds of nitrate nitrogen, ammonia nitrogen substances
Trap, the variation of nitrite nitrogen, nitrate nitrogen, ammonia nitrogen in the reaction is tracked with this.
Wherein, ammonia nitrogen degradation rate=(1-Ct/C0) × 100%=(1-At/A0) × 100%
In formula: C0For the initial concentration of ammonia nitrogen in reaction solution, CtIt is the concentration of ammonia nitrogen in reaction solution after degradation t hours, A0For
The initial absorbance of ammonia nitrogen, A in reaction solutiontIt is the absorbance of ammonia nitrogen in reaction solution after degradation t hours.
Nitrite nitrogen degradation rate=(1-Ct/C0) × 100%=(1-At/A0) × 100%
In formula: C0For the initial concentration of nitrite nitrogen in reaction solution, CtNitrite nitrogen in reaction solution after being degradation t hours
Concentration, A0For the initial absorbance of nitrite nitrogen in reaction solution, AtIt is the absorbance of nitrite nitrogen in reaction solution after degradation t hours.
Nitrate nitrogen degradation rate=(1-Ct/C0) × 100%=(1-At/A0) × 100%
In formula: C0For the initial concentration of nitrate nitrogen in reaction solution, CtIt is the concentration of nitrate nitrogen in reaction solution after degradation t hours,
A0For the initial absorbance of nitrate nitrogen in reaction solution, AtIt is the absorbance of nitrate nitrogen in reaction solution after degradation t hours.
A, ammonia nitrogen is measured using reagent colorimetric method:
Specific steps: pipetting 1.0mL reaction solution, moves it into 50mL colorimetric cylinder, is diluted to 50mL, shakes up.It is added
1.0mL sodium potassium tartrate tetrahydrate, shakes up.1.0mL nessler reagent is added, is shaken up.10min is stood, is to measure to inhale at 382nm in wavelength
The removal rate of ammonia nitrogen is calculated with this by above-mentioned formula for luminosity.
The preparation of tartaric acid Ghana: precise tartaric acid Ghana 50g is dissolved in 100mL deionized water, heating
It is cooled to room temperature after boiling, adds water to be settled in 100mL volumetric flask and save.
The preparation of nessler reagent: precise 16g NaOH is dissolved in 50mL deionized water and is sufficiently cooled to room temperature.It is quasi-
It really weighs 10g mercuric iodixde and 7g potassium iodide is dissolved in 20mL deionized water, be denoted as solution A.Solution A is added drop-wise to lasting stirring simultaneously
In the NaOH solution being cooled to room temperature, adds water to be settled in 100mL volumetric flask and save.
B, nitrite nitrogen is measured using N- (1- how base) ethylenediamine photometry:
Specific steps: pipetting 1.0mL reaction solution, moves it into 50mL colorimetric cylinder, is diluted to 50mL, shakes up.It is added
1.0mL10g/L sulfanilamide (SN), shake up.5-8min is stood, N- (the 1- how base) ethylenediamine-hydrochloride for adding 1.0mL 10g/L is molten
Liquid shakes up.10min is stood, absorbance is measured at 540nm, the removal rate of nitrite nitrogen is calculated by above-mentioned formula with this.
The preparation of sulfanilamide (SN): precise 1g sulfanilamide (SN) is dissolved in about 50mL deionized water and 10mL mass fraction is 36% dense salt
In the mixed liquor of acid, adds water to be settled in 100mL volumetric flask and save.
The preparation of N- (1- how base) ethylenediamine-hydrochloride: precise N- (1- how base) ethylenediamine-hydrochloride 0.1g is molten by its
Solution adds water to be settled in 100mL brown volumetric flask and be placed in refrigerator and saves in 50mL deionized water.
C, nitrate nitrogen is measured using ultraviolet spectrophotometry:
Specific steps: pipetting 1.0mL reaction solution, moves it into 50mL colorimetric cylinder, adds the HCl of 1.0mL 1mol/L
With 0.8w% sulfamic acid solution, it is diluted to 50mL, is shaken up.10min is stood, absorbance is measured at 220nm, nitre is obtained with this
State nitrogen generates situation.
Test result:
Referring to fig. 2, fullerene in the embodiment of the present invention 1, bismuthic acid copper, bismuthic acid copper-fullerene composite semiconductor material are shown
The XRD diffraction spectrogram of material.Curve bismuthic acid copper 2 θ=20.90,28.02,29.68,30.82,33.30,34.22,37.38,
42.48,45.12,46.64,47.71,53.01,55.61,60.61,63.77,66.12,68.01,73.07,74.23 and
Diffraction maximum at 78.07 correspond respectively to (200) of bismuthic acid copper, (211), (220), (002), (130), (112), (202),
(400), (330), (141), (420), (123), (332), (521), (530), (413), (204), (451), (314) and
(253), substantially consistent with bismuthic acid copper standard diagram (JCPDS71-1774).
Referring to Fig. 3, fullerene in the embodiment of the present invention 1, bismuthic acid copper, bismuthic acid copper-fullerene composite semiconductor material are shown
The Raman spectrogram of material.
A- Fig. 4 d respectively illustrates fullerene in the embodiment of the present invention 1, bismuthic acid copper-fullerene composite semiconductor referring to fig. 4
Material, bismuthic acid copper, bismuthic acid copper-fullerene composite semiconductor material TEM scheme (wherein, Fig. 4 a. fullerene, Fig. 4 b. bismuthic acid copper-
Fullerene, Fig. 4 c. bismuthic acid copper, Fig. 4 d. bismuthic acid copper-fullerene).
Referring to Fig. 5, bismuthic acid copper, the bismuthic acid copper-fullerene composite semiconductor material purple in the embodiment of the present invention 1 are shown
The outer visible spectrogram that diffuses.
Inventor also to bismuthic acid copper-fullerene photochemical catalyst during the reaction nitrite nitrogen and ammonia nitrogen variation into
Characterization is gone.Wherein, the variation of nitrite nitrogen and ammonia nitrogen can be found in bismuthic acid copper-fullerene composite semiconductor material reaction process
Fig. 6.
It should be appreciated that the technical concepts and features of above-described embodiment only to illustrate the invention, its object is to allow be familiar with this
The personage of item technology cans understand the content of the present invention and implement it accordingly, and it is not intended to limit the scope of the present invention.It is all
Equivalent change or modification made by Spirit Essence according to the present invention, should be covered by the protection scope of the present invention.
Claims (10)
1. a kind of method that bismuthic acid copper-fullerene photochemical catalyst removes nitrite and ammonia nitrogen simultaneously, characterized by comprising: to
Bismuthic acid copper-fullerene photochemical catalyst is added in sewage containing nitrite and ammonia nitrogen, later aerobic item after first anaerobic condition
With the mixed system of ultraviolet-visible irradiation nitrite and ammonia nitrogen under part, to remove nitrite and ammonia therein simultaneously
Nitrogen.
2. according to the method described in claim 1, it is characterised by comprising: adjust the mixed system to be in alkalinity, be passed through nitrogen
Gas, then the mixed system is irradiated with ultraviolet-visible, it is removed while realizing Nitrite In Polluted Water nitrate and ammonia nitrogen；Preferably,
The pH value of the mixed system is 9.0-10.5.
3. according to the method described in claim 1, characterized by further comprising: be to irradiate under condition of nitrogen gas with ultraviolet-visible
The step of mixed system, completes and then is passed through air into the mixed system, is irradiated again with ultraviolet-visible later
The mixed system realizes the thorough removing of Nitrite In Polluted Water nitrate and ammonia nitrogen.
4. according to the method described in claim 1, it is characterized by: fullerene in bismuthic acid copper-fullerene photochemical catalyst
Content is 0.01-10.0wt%, and the content of bismuthic acid copper is 90.00-99.99wt%；
Preferably, the preparation method of the bismuthic acid copper-fullerene photochemical catalyst includes:
Soluble bismuth salt, soluble copper salt are dissolved in solvent with fullerene and are uniformly mixed, adjusts the mixed solution later
For alkalinity, then the mixed solution reacted into 8h under the conditions of 180 DEG C, the bismuthic acid copper-fullerene photochemical catalyst is made；
Preferably, the soluble bismuth salt and the molar ratio of soluble copper salt are 2:1；
Preferably, the mass ratio of the fullerene and bismuthic acid copper is 1-9:100；
Preferably, the soluble bismuth salt includes bismuth nitrate；
Preferably, the soluble copper salt includes copper nitrate；
Preferably, the solvent includes deionized water；
Preferably, the alkaline matter to adjust the mixed solution to alkalinity includes sodium hydroxide；
Preferably, the preparation method further include: the mixed solution is placed under conditions of temperature is 180 DEG C and reacts 8h, it
After be washed with deionized, filter, then place it in the baking oven that temperature is 40-60 DEG C it is dry for 24 hours, obtain the bismuth
Sour copper-fullerene photochemical catalyst.
5. a kind of method that bismuthic acid copper-fullerene photochemical catalyst removes nitrite and ammonia nitrogen simultaneously, characterized by comprising: right
Sewage containing ammonia nitrogen carries out oxidation processes or Biochemical method, and some of ammonia nitrogens is made to be converted into nitrite nitrogen, it
Bismuthic acid copper-fullerene photochemical catalyst is added afterwards, letting nitrogen in and deoxidizing creates anaerobic condition, then obtained mixing is irradiated with ultraviolet-visible
System, to remove nitrite and ammonia nitrogen therein simultaneously.
6. according to the method described in claim 5, it is characterised by comprising: adjusting the mixed system to being in alkalinity, then with purple
Mixed system described in outer radiation of visible light removes while realizing Nitrite In Polluted Water nitrate and ammonia nitrogen；Preferably, the mixture
The pH value of system is 9.0-10.5.
7. according to the method described in claim 5, it is characterized by: fullerene in bismuthic acid copper-fullerene photochemical catalyst
Content is 0.01-10.0wt%, and the content of bismuthic acid copper is 90.00-99.99wt%；
Preferably, the preparation method of the bismuthic acid copper-fullerene photochemical catalyst includes:
Soluble bismuth salt, soluble copper salt are dissolved in solvent with fullerene and are uniformly mixed, adjusts the mixed solution later
For alkalinity, then the mixed solution reacted into 8h under the conditions of 180 DEG C, the bismuthic acid copper-fullerene photochemical catalyst is made；
Preferably, the soluble bismuth salt and the molar ratio of soluble copper salt are 2:1；
Preferably, the mass ratio of the fullerene and bismuthic acid copper is 1-9:100；
Preferably, the soluble bismuth salt includes bismuth nitrate；
Preferably, the soluble copper salt includes copper nitrate；
Preferably, the solvent includes deionized water；
Preferably, the alkaline matter to adjust the mixed solution to alkalinity includes sodium hydroxide；
Preferably, the preparation method further include: the mixed solution is placed under conditions of temperature is 180 DEG C and reacts 8h, it
After be washed with deionized, filter, then place it in the baking oven that temperature is 40-60 DEG C it is dry for 24 hours, obtain the bismuth
Sour copper-fullerene photochemical catalyst.
8. a kind of method that bismuthic acid copper-fullerene photochemical catalyst removes nitrite and ammonia nitrogen simultaneously, characterized by comprising: will
Sewage containing ammonia nitrogen is mixed with the sewage containing nitrite, and bismuthic acid copper-fullerene photochemical catalyst, letting nitrogen in and deoxidizing are added later
Anaerobic condition is created, then irradiates obtained mixed system with ultraviolet-visible, to remove nitrite and ammonia therein simultaneously
Nitrogen.
9. according to the method described in claim 8, it is characterised by comprising: adjusting the mixed system to being in alkalinity, then with purple
Mixed system described in outer radiation of visible light removes while realizing Nitrite In Polluted Water nitrate and ammonia nitrogen；Preferably, the mixture
The pH value of system is 9.0-10.5.
10. according to the method described in claim 8, it is characterized by: fullerene in bismuthic acid copper-fullerene photochemical catalyst
Content is 0.01-10.0wt%, and the content of bismuthic acid copper is 90.00-99.99wt%；
Preferably, the preparation method of the bismuthic acid copper-fullerene photochemical catalyst includes:
Soluble bismuth salt, soluble copper salt are dissolved in solvent with fullerene and are uniformly mixed, adjusts the mixed solution later
For alkalinity, then the mixed solution reacted into 8h under the conditions of 180 DEG C, the bismuthic acid copper-fullerene photochemical catalyst is made；
Preferably, the soluble bismuth salt and the molar ratio of soluble copper salt are 2:1；
Preferably, the mass ratio of the fullerene and bismuthic acid copper is 1-9:100；
Preferably, the soluble bismuth salt includes bismuth nitrate；
Preferably, the soluble copper salt includes copper nitrate；
Preferably, the solvent includes deionized water；
Preferably, the alkaline matter to adjust the mixed solution to alkalinity includes sodium hydroxide；
Preferably, the preparation method further include: the mixed solution is placed under conditions of temperature is 180 DEG C and reacts 8h, it
After be washed with deionized, filter, then place it in the baking oven that temperature is 40-60 DEG C it is dry for 24 hours, obtain the bismuth
Sour copper-fullerene photochemical catalyst.
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