CN113617378A - Magnetic composite photocatalyst, preparation method, special system and method - Google Patents
Magnetic composite photocatalyst, preparation method, special system and method Download PDFInfo
- Publication number
- CN113617378A CN113617378A CN202111035409.3A CN202111035409A CN113617378A CN 113617378 A CN113617378 A CN 113617378A CN 202111035409 A CN202111035409 A CN 202111035409A CN 113617378 A CN113617378 A CN 113617378A
- Authority
- CN
- China
- Prior art keywords
- tank
- solution
- electrode plate
- wastewater
- magnetic composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 44
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000002351 wastewater Substances 0.000 claims abstract description 100
- 239000003054 catalyst Substances 0.000 claims abstract description 63
- 150000003839 salts Chemical class 0.000 claims abstract description 55
- 230000003197 catalytic effect Effects 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 77
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 66
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 59
- 238000013032 photocatalytic reaction Methods 0.000 claims description 47
- 238000003756 stirring Methods 0.000 claims description 47
- 239000000543 intermediate Substances 0.000 claims description 40
- 238000006243 chemical reaction Methods 0.000 claims description 37
- 238000011033 desalting Methods 0.000 claims description 35
- 238000001035 drying Methods 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 26
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 239000012266 salt solution Substances 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 21
- 238000003860 storage Methods 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 20
- 239000011259 mixed solution Substances 0.000 claims description 19
- 239000002243 precursor Substances 0.000 claims description 18
- 239000004094 surface-active agent Substances 0.000 claims description 16
- 238000001354 calcination Methods 0.000 claims description 15
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 15
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 14
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 14
- 239000012450 pharmaceutical intermediate Substances 0.000 claims description 14
- 230000035484 reaction time Effects 0.000 claims description 14
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 14
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 14
- 238000001291 vacuum drying Methods 0.000 claims description 14
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 13
- 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 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 11
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 11
- 229910017604 nitric acid Inorganic materials 0.000 claims description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 9
- 239000002585 base Substances 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 239000011593 sulfur Substances 0.000 claims description 9
- 239000004202 carbamide Substances 0.000 claims description 8
- 230000001699 photocatalysis Effects 0.000 claims description 8
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 8
- 229910052724 xenon Inorganic materials 0.000 claims description 8
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 238000007599 discharging Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 4
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 239000005416 organic matter Substances 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 4
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- CKQBSDUWDZEMJL-UHFFFAOYSA-N [W].[Br] Chemical compound [W].[Br] CKQBSDUWDZEMJL-UHFFFAOYSA-N 0.000 claims description 3
- 229940043279 diisopropylamine Drugs 0.000 claims description 3
- 239000012467 final product Substances 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 3
- 239000004966 Carbon aerogel Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 238000012544 monitoring process Methods 0.000 claims description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 18
- 238000013329 compounding Methods 0.000 abstract description 5
- 239000003344 environmental pollutant Substances 0.000 abstract description 4
- 230000005307 ferromagnetism Effects 0.000 abstract description 4
- 231100000719 pollutant Toxicity 0.000 abstract description 4
- 238000012546 transfer Methods 0.000 abstract description 3
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 31
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 20
- 238000003760 magnetic stirring Methods 0.000 description 15
- 238000012360 testing method Methods 0.000 description 14
- 239000000203 mixture Substances 0.000 description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 12
- 229910052760 oxygen Inorganic materials 0.000 description 12
- 239000001301 oxygen Substances 0.000 description 12
- 239000002244 precipitate Substances 0.000 description 12
- 150000001555 benzenes Chemical class 0.000 description 10
- 239000011780 sodium chloride Substances 0.000 description 10
- 238000005303 weighing Methods 0.000 description 10
- 239000004809 Teflon Substances 0.000 description 9
- 229920006362 Teflon® Polymers 0.000 description 9
- 238000007664 blowing Methods 0.000 description 9
- 239000012299 nitrogen atmosphere Substances 0.000 description 9
- 239000003513 alkali Substances 0.000 description 8
- 150000001448 anilines Chemical class 0.000 description 8
- 229910016951 Fe0.5Ni0.5 Inorganic materials 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000011049 filling Methods 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 238000010612 desalination reaction Methods 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 6
- 150000008282 halocarbons Chemical class 0.000 description 6
- 229910021645 metal ion Inorganic materials 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- -1 aniline series compounds Chemical class 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 230000001276 controlling effect Effects 0.000 description 5
- 230000005684 electric field Effects 0.000 description 5
- 150000002989 phenols Chemical class 0.000 description 5
- 230000010287 polarization Effects 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 230000006798 recombination Effects 0.000 description 4
- 238000005215 recombination Methods 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 231100000086 high toxicity Toxicity 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 230000005389 magnetism Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000012028 Fenton's reagent Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000003851 biochemical process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method 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
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000005621 ferroelectricity Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000001139 pH measurement Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000009279 wet oxidation reaction Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- B01J35/33—Electric or magnetic 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
-
- 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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/32—Hydrocarbons, e.g. oil
- C02F2101/322—Volatile compounds, e.g. benzene
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Catalysts (AREA)
Abstract
The inventionDiscloses a magnetic composite photocatalyst, a preparation method, a special system and a special method thereof, wherein the magnetic composite photocatalyst is Bi5Fe1‑xNixTi3‑yCoyO15/S‑g‑C3N4Wherein x is 0.1-0.5, and y is 0.3-0.9. In Bi5FeTi3O15Doping Ni at the middle Fe position and doping Co at the Ti position to obtain Bi5Fe1‑xNixTi3‑yCoyO15g-C doped with S3N4The magnetic composite photocatalyst which has high catalytic efficiency and high visible light utilization rate and can be recycled is obtained by compounding. The magnetic composite catalyst and the special matched treatment system fully utilize visible light to induce and generate strong oxidizing free radicals so as to effectively degrade pollutants in the medical intermediate wastewater and recover salt in the pollutants, the loss in the material transfer process is avoided by utilizing the ferromagnetism of the catalyst, the treatment process is clean and energy-saving, and no secondary pollution is caused.
Description
Technical Field
The invention relates to a magnetic photocatalyst, a preparation method, a special system and a special method, in particular to a composite photocatalyst which has high catalytic efficiency and high visible light utilization rate, can be recycled and is used for degrading medical intermediate wastewater, a preparation method, special equipment and a method.
Background
The medical intermediate is a chemical raw material or a chemical product used in the process of synthesizing the medicine, is a key raw material for producing chemical bulk drugs, is used as an important component in fine chemical engineering, and gradually becomes the key point and core for developing chemical industry in various countries. The pharmaceutical intermediate industry in China has formed a relatively complete system from research and development to production and sale, and the pharmaceutical intermediate market in China will grow continuously in the background of new product research and development and medicine demand in the future. In the process of producing the medical intermediate or synthesizing other medicines, a large amount of waste water is generated, and the waste water of the medical intermediate has the characteristics of high toxicity, high salt and high-concentration organic matters due to the benzene series, the aniline compounds, the phenolic compounds and the halogenated hydrocarbon solvent contained in the waste water. And the production process involves multiple acid-base adjusting processes, and the increase of sodium ions and chloride ions brings high salinity. The medical intermediate wastewater has complex components and high treatment difficulty, has the characteristics of biological inhibition, toxicity and the like of different degrees, and has poor biodegradability, so that the wastewater is difficult to treat by directly utilizing a biochemical process.
The existing methods for treating the high-toxicity, high-salt and high-concentration organic wastewater mainly comprise a chemical oxidation method, a Fenton reagent oxidation method, a wet oxidation method, an activated carbon adsorption method and the like. The conventional method faces the problems of high cost, low efficiency, secondary pollution and the like of the medical intermediate wastewater with complex water quality.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a magnetic composite photocatalyst which has high catalytic efficiency on medical intermediate wastewater under visible light and can be recycled; the second purpose of the invention is to provide a preparation method of the magnetic composite photocatalyst; the third purpose of the invention is to provide the application of the magnetic composite photocatalyst in the treatment of medical intermediate wastewater; the fourth purpose of the invention is to provide a special system for treating medical intermediate wastewater by using the magnetic composite photocatalyst; the fifth purpose of the invention is to provide a method for treating medical intermediate wastewater by using the special system and the magnetic composite photocatalyst.
The technical scheme is as follows: the magnetic composite photocatalyst of the invention is Bi5Fe1-xNixTi3-yCoyO15/S-g-C3N4Wherein x is 0.1-0.5, y is 0.3-0.9, Bi5Fe1-xNixTi3-yCoyO15Is in Bi5FeTi3O15Middle Fe position doped with Ni and Ti position doped with Co for modification, S-g-C3N4Is obtained by doping S in the graphite carbon nitride for modification.
The preparation method of the magnetic composite photocatalyst comprises the following steps:
(1) dissolving bismuth nitrate, ferric nitrate, nickel nitrate, cobalt nitrate and tetrabutyl titanate in dilute nitric acid to obtain a mixed solution, dropwise adding a mineralizer into the mixed solution to obtain solution A, and dissolving a surfactant in water to obtain solution B. Mixing the solution A and the solution B under stirring, thermally reacting, cooling, centrifugally separating, washing with water, washing with ethanol, drying, and grinding to obtain a product Bi5Fe1-xNixTi3O15；
(2) Dissolving nitrogen-rich organic matter and sulfur source in water to obtain precursor gel, and calcining the precursor gel to obtain S-g-C3N4From S-g-C3N4And Bi5Fe1-xNixTi3-yCoyO15Dissolving in water, stirring and mixing evenly, and vacuum drying to obtain the final product Bi5Fe1-xNixTi3-yCoyO15/S-g-C3N4。
Further, in the step (1), the surfactant is one or two of a fluorocarbon surfactant, sodium dodecyl sulfate, cetyltrimethylammonium bromide and polyvinyl alcohol.
Further, in the step (1), the mineralizer is one of tetramethylammonium hydroxide, triethylenediamine, quaternary ammonium base and diisopropylamine.
Further, in the step (1), the molar ratio of bismuth nitrate, ferric nitrate, nickel nitrate, cobalt nitrate and tetrabutyl titanate is 1: 0.1-0.18: 0.02-0.1: 0.06-0.18: 0.42-0.54, the concentration of the mineralizer is 1.2-1.6mol/L, and the liquid-solid ratio of the mineralizer to the cobalt nitrate is 200-: 1 mL/g; the mass ratio of the nickel nitrate to the surfactant is 1: 20-25.
Further, in the step (1), the stirring and mixing time is 45-60 min; the temperature of the thermal reaction is 150-220 ℃, and the reaction time is 24-72 h.
Further, in the step (2), the nitrogen-rich organic substance is one of urea, dicyandiamide and melamine.
Further, in the step (2), the sulfur source is one of thiourea, thioacetamide and sodium thiosulfate.
Further, in the step (2), the mass ratio of the nitrogen-rich organic matter to the sulfur source is 1: 0.1-0.2; the Bi5Fe1-xNixTi3-yCoyO15With S-g-C3N4The mass ratio of (1): 0.1-0.5.
Further, in the step (2), the calcination temperature is 450-550 ℃, and the calcination time is 4-6.5 h; the stirring and mixing time is 45-60 min.
Further, in the step (2), the temperature of the vacuum drying is 90-100 ℃, and the time of the vacuum drying is 8-12 h.
The invention relates to an application of a magnetic composite photocatalyst in treating medical intermediate wastewater.
Further, the medical intermediate wastewater comprises organic wastewater of benzene series, aniline compounds, phenolic compounds and halogenated hydrocarbon solvents.
Furthermore, the COD value of the medical intermediate wastewater is 39000-42000mg/L, and the salt content is 20000-23000 mg/L.
The special system for treating the medical intermediate wastewater by using the magnetic composite photocatalyst comprises a pH adjusting tank, a photocatalytic reaction tank, a desalting tank and a salt solution storage tank, wherein the pH adjusting tank is connected with the photocatalytic reaction tank; a liquid level meter is arranged on the upper side of the side wall of the photocatalytic reaction tank, an electromagnetic system and a light source are arranged in the photocatalytic reaction tank, and a first stirring paddle is arranged at the bottom of the photocatalytic reaction tank; an anode electrode plate and a cathode electrode plate are arranged in the desalting tank; the photocatalytic reaction tank is respectively connected with the pH adjusting tank and the desalting tank, and the desalting tank is connected with the salt liquid storage tank.
The method for treating the medical intermediate wastewater by using the special system comprises the following steps: injecting the medical intermediate wastewater into a pH adjusting tank, adjusting pH, then feeding the wastewater into a photocatalytic reaction tank filled with the magnetic composite photocatalyst as defined in claim 1, monitoring the liquid level by a liquid level meter, stopping feeding the liquid, opening a first stirring paddle and a light source at the bottom of the photocatalytic reaction tank to perform photocatalytic oxidation reaction, closing the light source and the first stirring paddle after the reaction is finished, opening an electromagnetic system to adsorb the magnetic composite photocatalyst, discharging the wastewater after the catalytic oxidation treatment into a desalting tank, electrifying an anode electrode plate and a cathode electrode plate of the desalting tank to remove salt, and discharging the treated liquid after the desalting from a device. And (3) filling clear water into the desalting tank, powering off the anode electrode plate and the cathode electrode plate, short-circuiting the two electrode plates, dissolving salt on the anode electrode plate and the cathode electrode plate in the clear water to obtain a salt solution, and conveying the salt solution into a salt solution storage tank.
Further, the solid-to-liquid ratio of the magnetic composite photocatalyst to the medical intermediate wastewater is 1-5:1 g/L.
Further, the pH is 5 to 8.
Further, the light source is one of a xenon lamp, a modified LED lamp and a bromine tungsten lamp.
Further, the positive electrode plate and the negative electrode plate are made of carbon aerogel materials, and the voltage between the positive electrode plate and the negative electrode plate is 1.2-1.4V.
Furthermore, the stirring paddles are all electric stirring paddles.
The magnetic composite catalyst widens the photoresponse range of the magnetic composite catalyst by the double doping synergistic effect of Ni and Co, and has higher absorption capacity in a visible light region because the doping narrows the band gap of the catalyst and red shift of an absorption band occurs. The strength of the internal ferroelectric polarization electric field is improved after Bi-system layered perovskite used as ferroelectrics is doped with Ni and Co bimetallic elements, and the photocatalytic capability is enhanced. The doping of Ni and Co bimetallic ions in low valence state causes surface lattice oxygen defect, the generation of oxygen vacancy can provide more active sites, and negatively charged ions and radicals can be adsorbed. The doped introduced magnetic ions also enable the ferromagnetism of the catalyst to be enhanced. At the same time, the oxygen vacancy introduced into the surface by ion doping promotes the porous S-g-C3N4And compounding to form the S-shaped heterojunction. The separation efficiency of a photon-generated carrier is improved through a unique stepped charge transfer mode of an S-type heterojunction, a photon-generated hole with higher oxidation potential and a photon-generated electron with lower reduction potential are reserved under the excitation of visible light, and the photo-generated hole and the photon-generated electron cooperate with high-activity free radicals to react with specific groups of benzene series, aniline series compounds, phenol series compounds and halogenated hydrocarbon solvent contained in the medical intermediate wastewater, so that a stronger oxidation effect can be obtained under the irradiation of light, and the efficient degradation of organic matters such as the benzene series, the aniline series compounds, the phenol series compounds, the halogenated hydrocarbon solvent and the like which are difficult to degrade in the medical intermediate wastewater is realized.
According to the invention, by controlling the components and the dosage of the surfactant and the mineralizer, Ni and Co metal ions can be successfully doped into the layered perovskite at the same time, and a byproduct metal oxide (BiFeO) is avoided3NiO, CoO, etc.) to improve the yield of the target catalyst. The addition of the surfactant is beneficial to the crystal growth of the nano-scale catalyst, and the selection of the low-concentration organic base as the mineralizer can provide a mild reaction environment for the crystal growth process, thereby being beneficial to the growth of the crystalThe catalyst has controllable form, narrow particle size distribution and high purity.
The special system of the invention is provided with the pH adjusting tank in front of the catalytic reaction tank for pH value adjustment, thereby avoiding the influence on the catalyst when directly adjusting the pH value in the catalytic reaction system and prolonging the service life of the catalyst. The method adopts the direct filling of the powdery catalyst aiming at the characteristic of high chroma of the medical intermediate wastewater, and solves the problem that the high chroma wastewater influences the light absorption performance of the photocatalyst. Set up electromagnetic system in catalytic reaction jar, can switch on before going out water and produce magnetism and keep catalyst powder, increased the filter screen in the pipeline simultaneously for in keeping the photocatalytic reaction jar, avoid catalyst powder along with the problem that goes out water loss, also avoid the catalyst to produce secondary pollution along with going out water, satisfy the requirement of repetitious usage for a long time. Particularly, the method adopts the steps of placing the desalting agent in the photocatalytic reaction, reducing the content of organic matters in the medical intermediate wastewater, then recovering the salt, recycling resources, solving the problem of secondary pollution caused by waste salt, and reducing the salinity of the effluent water, and also continuously entering a coupling biochemical pool for reaction, thereby reducing the cost.
Has the advantages that: compared with the prior art, the invention has the following remarkable advantages:
(1) the magnetic composite photocatalyst of the invention is doped with Ni and Co bimetallic ions and introduced with oxygen vacancies on the surface to promote the reaction with porous S-g-C3N4The S-shaped heterojunction formed by compounding effectively improves the capability of the photocatalyst in treating the medical intermediate wastewater. The removal rate of COD in the degraded water reaches more than 70 percent. The salt content of the desalted wastewater is below 7000mg/L, and the NaCl content in the salt recovered from the salt solution storage tank reaches above 90%, so that the biodegradability of the wastewater is improved.
(2) The preparation method of the magnetic composite catalyst is simple to operate, the raw materials are easy to obtain, and the cost is low; the method has the advantages of simple required equipment and flexible process, and in the preparation process, by controlling the components and the dosage of the surfactant and the mineralizer, Ni and Co metal ions can be successfully doped into the layered perovskite simultaneously, so that a byproduct metal oxide (BiFeO) is avoided3NiO, CoO, etc.) to improve the yield of the target catalyst.
(3) The matched special treatment system for treating the medical intermediate wastewater by using the magnetic composite photocatalyst can effectively prolong the service life of the catalyst, ensure that the catalyst can fully absorb a light source and be recycled, avoid secondary pollution caused by the catalyst, recycle resources by recycling salt, solve the problem of secondary pollution caused by waste salt, and is green and environment-friendly.
Drawings
FIG. 1 is a process flow diagram of the present invention for treating medical intermediate wastewater by using a magnetic composite catalyst;
FIG. 2 shows Bi obtained in example 15Fe0.8Ni0.2Ti2.5Co0.5O15A drawing;
FIG. 3 shows Bi obtained in example 15Fe0.8Ni0.2Ti2.5Co0.5O15/S-g-C3N4Figure (a).
Detailed Description
Example 1
As shown in figure 1, the special system for treating the medical intermediate wastewater by using the magnetic composite photocatalyst comprises a pH adjusting module, a photocatalytic reaction module and a desalting module, wherein the modules are connected through a pipeline, and a filter screen is arranged in the pipeline. Wherein, pH adjusting module includes pH adjusting tank 1, acid-base liquid storage pot 3 and first measuring pump 6, and 1 upper portion of pH adjusting tank is equipped with pH inductor 2, and the bottom is equipped with first stirring rake 28, and acid-base liquid storage pot 3 divide into acid liquor district and alkali lye district, and acid liquor district bottom is equipped with acid liquor valve 4, and alkali lye district is equipped with alkali lye valve 5, and acid liquor valve 4 and alkali lye valve 5 link to each other with pH adjusting tank 1 through first measuring pump 6. The photocatalytic reaction module includes first check valve 7, second measuring pump 8 and photocatalytic reaction jar 13, photocatalytic reaction jar 13 top is equipped with governing valve 9, manometer 12 and first drum valve 26, photocatalytic reaction jar 13 top is equipped with electromagnetic system 10 and light source 11 from the last downwardly extending, photocatalytic reaction jar 13 lateral wall upper portion is equipped with level gauge 14, the middle part is equipped with temperature-sensing ware 15, be equipped with second stirring rake 17 in the photocatalytic reaction jar 13 bottom, photocatalytic reaction jar 13 bottom is equipped with sample valve 27 outward. The photocatalytic reaction tank 13 is filled with a magnetic composite catalyst 16. The pH adjusting tank 1 is communicated with a photocatalytic reaction tank 13 through a first check valve 7 and a second metering pump 8. The desalination district module includes second check valve 18, desalination jar 19, third check valve 22 and salt solution storage tank 24, and 19 tops of desalination jar are equipped with water filling port 23 and second air blast valve 25, and 19 top both sides of desalination jar are equipped with anode electrode board 20 and cathode electrode board 21 from the upper downward extension, and desalination jar 19 links to each other with salt solution storage tank 24 through third check valve 22. The photocatalytic reaction tank 13 is connected with a desalting tank 19 through a second check valve 18. The light source 11 is 4 xenon lamps of 500w, and the electromagnetic system 10 is 4 spiral electromagnet coils. The light sources 11 and the electromagnetic systems 10 are alternately and evenly distributed in the photocatalytic reaction tank 13.
Example 1
(1)Bi5Fe0.8Ni0.2Ti2.5Co0.5O15Preparation of
According to a molar ratio of 1: 0.16: 0.04: 0.1: 0.5 respectively weighing 2.91g of bismuth nitrate, 0.39g of ferric nitrate, 0.07g of nickel nitrate, 0.18g of cobalt nitrate and 1.02g of tetrabutyl titanate, dissolving in 20mL of dilute nitric acid of 4mol/L, and magnetically stirring for 0.5h until the mixture is completely dissolved to obtain a mixed solution. 54mL of 1.2mol/L quaternary ammonium base solution is added into the mixed solution dropwise until the pH value of the mixed solution is about 8, gray precipitate is gradually generated, stirring is continued for 1h to obtain solution A, and 1.4g of sodium dodecyl sulfate is dissolved in 5mL of water to obtain solution B. And mixing the solution A and the solution B for 0.75h under magnetic stirring to obtain a turbid solution. The cloudy solution was transferred to a teflon lined autoclave to a volume of 80% of the autoclave. And continuously carrying out thermal reaction in an air-blowing drying oven, wherein the reaction temperature is 185 ℃, and the reaction time is 48 h. Centrifuging the precipitate after reaction, washing with water for three times, washing with ethanol for three times, drying, and grinding to obtain Bi5Fe0.8Ni0.2Ti2.5Co0.5O15As shown in FIG. 2, the powder was pale yellow
(2)Bi5Fe0.8Ni0.2Ti2.5Co0.5O15/S-g-C3N4Preparation of
According to the mass ratio of 1: 0.2 weighing 15g of urea and 3g of thiourea, completely dissolving in warm water at 50 ℃, then continuing to magnetically stir for 1.5h to obtain precursor gel, transferring the precursor gel into a tube furnace, and calcining for 5h at 500 ℃ in a nitrogen atmosphere. According to the mass ratio of 1: 0.1 calcining the resulting powder S-g-C3N4And Bi5Fe0.8Ni0.2Ti2.5Co0.5O15Mixed in 30mL water, magnetically stirred for 0.8h and then transferred to a vacuum drying oven for drying at 90 ℃ for 12 h. Drying to obtain the final powder product Bi5Fe0.8Ni0.2Ti2.5Co0.5O15/S-g-C3N4As shown in fig. 3, the powder appeared black.
(3) Catalyst Bi5Fe0.8Ni0.2Ti2.5Co0.5O15/S-g-C3N4Treatment of pharmaceutical intermediate organic wastewater
As shown in figure 1, 20L of wastewater containing benzene series and aniline compounds, the pH value is 1, the COD is 42000mg/L, the salt content is 23000mg/L, the pH adjusting tank 1 is filled with alkali liquor, the alkali liquor is quantitatively fed into the pH adjusting tank 1 through a first metering pump 6 by controlling an alkali liquor valve 5 of an acid-alkali liquor storage tank 3, and the acid liquor is quantitatively fed into the pH adjusting tank 1 through the first metering pump 6 by controlling an acid liquor valve 4 if the wastewater stock solution is alkaline. The pH value in the pH adjusting tank 1 is monitored in real time through the pH sensing probe 2, the first stirring paddle 28 is opened for stirring, and after the pH value of the wastewater in the pH adjusting tank 1 is adjusted to 8, the lye valve 5 and the first metering pump 6 are closed. And opening the first one-way valve 7, opening the second metering pump 8, and enabling the wastewater in the pH adjusting tank 1 to flow into the photocatalytic reaction tank 13 from the upper end of the photocatalytic reaction tank 13. The photocatalytic reaction tank 13 is pre-filled with a magnetic composite catalyst 16, and the catalyst is 20g of powder Bi5Fe0.8Ni0.2Ti2.5Co0.5O15/S-g-C3N4When the liquid level meter 14 detects that the liquid level reaches three fifths (L2) of the height of the photocatalytic reaction tank 13, the liquid feeding is stopped, and the second metering pump 8 is closed. The second stirring paddle 17 at the bottom of the photocatalytic reaction tank 13 is opened to start stirring, so that the magnetic composite catalyst 16 powder Bi5Fe0.8Ni0.2Ti2.5Co0.5O15/S-g-C3N4Fully dispersed in the wastewater, a light source 11 is turned on, the light source 11 is a 500W xenon lamp, the photocatalytic oxidation reaction lasts for 5 hours under the irradiation of the light source 11, and the temperature of the liquid in the catalytic reaction tank 13 is monitored by a temperature sensor 15. After the reaction time is reached, the light source 11 is turned off first, then the second stirring paddle 17 is turned off, the electromagnetic system 10 is turned on, the electromagnetic adsorption process lasts for 5min, and then the magnetic composite catalyst 16 powder Bi is obtained5Fe0.8Ni0.2Ti2.5Co0.5O15/S-g-C3N4Are magnetically attracted to the surface of the electromagnetic system 10. And opening a sampling valve 27 at the bottom of the photocatalytic reaction tank 13 for sampling analysis, and continuing the reaction if the COD does not reach the standard. And if the COD reaches the standard, opening the second one-way valve 18, opening the first air blowing valve 26, discharging all the wastewater subjected to catalytic oxidation treatment into the desalting tank 19 by using the air compressor, and then closing the air compressor, the first air blowing valve 26 and the second one-way valve 18. And opening the regulating valve 9 at the top of the photocatalytic reaction tank 13 for pressure relief treatment, and closing the regulating valve 9 when the reading of the pressure gauge 12 is zero. And (3) turning on an external 1.4V direct-current power supply, electrifying the anode electrode plate 20 and the cathode electrode plate 21, and separating anions and cations in the wastewater by using an electric field generated between the anode electrode plate 20 and the cathode electrode plate 21 to achieve the aim of desalting. And opening the second air blowing valve 25 after the desalting process lasts for 0.5h, and discharging the desalted treatment liquid by utilizing an external air compressor. The air compressor, second air blast valve 25, is turned off after the desalination tank 19 is emptied. Utilize water filling port 23 to pour into the clear water to the two-thirds of desalting tank 19 volume, close the external power supply of plate electrode this moment, with anode plate electrode 20 and cathode plate electrode 21 short circuit, originally adsorb the ion on anode plate electrode 20 and cathode plate electrode 21 and get back to the aquatic again, the clear water in desalting tank 19 becomes the salt solution that organic matter content is low. And opening the third one-way valve 22, opening the second air blowing valve 25, and using an external air compressor to flow the salt solution into the salt solution storage tank 24 to wait for recycling of salt. And after the desalting tank 19 is emptied, the air compressor, the second air blowing valve 25 and the third one-way valve 22 are closed, and primary wastewater treatment is completed.
The COD test and the salt content test of the water treated by the experiment show that the removal rate of COD reaches 75.3 percent when the magnetic composite catalyst and the special system thereof are used for treating the medical intermediate wastewater. The salt content of the desalted wastewater is 6125mg/L, and the NaCl content in the salt recovered from the salt solution storage tank 24 reaches 95.1%. The addition of the preferred surfactant and mineralizer can enable metal ions to be successfully doped into the interior of the layered perovskite, and the generation of a byproduct metal oxide is avoided. The photoresponse range of the catalyst is widened by double doping of Ni and Co, and the doping narrows the band gap of the catalyst, so that the absorption band is red-shifted, and the catalyst has higher absorption capacity in a visible light region. The electric field intensity of the ferroelectric polarization can be improved to a certain extent, and the photocatalytic capability can be enhanced.
Example 2
(1)Bi5Fe0.9Ni0.1Ti2.7Co0.3O15Preparation of
According to a molar ratio of 1: 0.18: 0.02: 0.06: 0.54 respectively weighing 3.64g of bismuth nitrate, 0.55g of ferric nitrate, 0.05g of nickel nitrate, 0.13g of cobalt nitrate and 1.38g of tetrabutyl titanate, dissolving in 20mL of dilute nitric acid of 4mol/L, and magnetically stirring for 0.5h until the mixture is completely dissolved to obtain a mixed solution. 65mL of 1.4mol/L triethylenediamine solution was added dropwise to the mixed solution until the pH of the mixed solution became about 8, and stirring was continued for 1 hour to obtain solution A, and 1g of cetyltrimethylammonium bromide was dissolved in 5mL of water to obtain solution B. And mixing the solution A and the solution B for 1 hour under magnetic stirring to obtain a turbid solution. The cloudy solution was transferred to a teflon lined autoclave to a volume of 80% of the autoclave. And continuously carrying out thermal reaction in an air-blast drying oven, wherein the reaction temperature is 180 ℃, and the reaction time is 48 h. Centrifuging the precipitate after reaction, washing with water for three times, washing with ethanol for three times, drying, and grinding to obtain Bi5Fe0.9Ni0.1Ti2.7Co0.3O15。
(2)Bi5Fe0.9Ni0.1Ti2.7Co0.3O15/S-g-C3N4Preparation of
According to the mass ratio of 1: 0.1 weight of 15g dicyanodiamide and 1.5g sodium thiosulfate, after complete dissolution in warm water at 50 ℃ continue magnetic stirringAnd (5) obtaining a precursor gel after 1.5 h. Transferring the precursor gel into a tube furnace, calcining for 6.5h at 450 ℃ in nitrogen atmosphere to obtain powder S-g-C3N4. According to the mass ratio of 1: 0.5 mixing the powder S-g-C3N4And Bi5Fe0.9Ni0.1Ti2.7Co0.3O15Mixed in 30mL water, magnetically stirred for 2h, and then transferred to a vacuum drying oven for drying at 100 ℃ for 8 h. Drying to obtain the final powder product Bi5Fe0.9Ni0.1Ti2.7Co0.3O15/S-g-C3N4。
(3) Catalyst Bi5Fe0.9Ni0.1Ti2.7Co0.3O15/S-g-C3N4Treatment of pharmaceutical intermediate organic wastewater
The procedure of the treatment process was the same as in example 1, wherein the pH of the wastewater was adjusted to 5 in the pH adjusting tank 1, and the magnetic composite catalyst 16Bi was contained in the photocatalytic reaction tank 135Fe0.9Ni0.1Ti2.7Co0.3O15/S-g-C3N4100g is pre-filled, a modified LED lamp is selected as a light source 11, and a direct current power supply of 1.2V is externally connected to an electrode plate. 20L of wastewater containing the benzene series and the halogenated hydrocarbon solvent has the pH value of 1, the COD of 39000mg/L and the salt content of 20000 mg/L. After single treatment, a COD test and a salt content test show that when the magnetic composite catalyst and the special system thereof are used for treating medical intermediate wastewater, the removal rate of COD reaches 72.5%, and the salt content of the wastewater after desalting is 6079 mg/L. The NaCl content in the salt recovered from the salt solution storage tank 24 reaches 94.1 percent. The ferroelectric polarization brought by the ferroelectricity of the magnetic composite catalyst can form a polarization electric field in the material, and under the action of the electric field in the ferroelectric polarization, the moving directions of electrons and holes are opposite, so that the separation of photon-generated carriers is promoted, the service lives of the electrons and the holes are prolonged, and the generation of high-oxidizing free radicals and the degradation of organic pollutants in wastewater are facilitated.
Example 3
(1)Bi5Fe0.5Ni0.5Ti2.1Co0.9O15Preparation of
According toThe molar ratio is 1: 0.1: 0.1: 0.18: 0.42 respectively weighing 3.4g of bismuth nitrate, 0.28g of ferric nitrate, 0.21g of nickel nitrate, 0.37g of cobalt nitrate and 1g of tetrabutyl titanate, dissolving in 20mL of dilute nitric acid of 4mol/L, and magnetically stirring for 0.5h until the mixture is completely dissolved. 74mL of a 1.6mol/L tetramethylammonium hydroxide solution was added dropwise to the mixture until the pH of the solution became about 8, and stirring was continued for 1 hour to obtain solution A, and 5.25g of polyvinyl alcohol was dissolved in 5mL of water to obtain solution B. And mixing the solution A and the solution B for 0.75h under magnetic stirring to obtain a turbid solution. The cloudy solution was transferred to a teflon lined autoclave to a volume of 80% of the autoclave. And continuously carrying out thermal reaction in an air-blowing drying oven, wherein the reaction temperature is 220 ℃, and the reaction time is 24 hours. Centrifuging the precipitate after reaction, washing with water for three times, washing with ethanol for three times, drying, and grinding to obtain Bi5Fe0.5Ni0.5Ti2.1Co0.9O15。
(2)Bi5Fe0.5Ni0.5Ti2.1Co0.9O15/S-g-C3N4Preparation of
According to the mass ratio of 1: 0.15 g of melamine and 2.25g of thioacetamide were weighed out and after complete dissolution in warm water at 50 ℃ magnetic stirring was continued for 1.5 h. The precursor obtained after stirring is transferred to a tubular furnace and calcined for 4h at 550 ℃ in the nitrogen atmosphere. According to the mass ratio of 1: 0.3 calcining the resulting powder S-g-C3N4And Bi5Fe0.5Ni0.5Ti2.1Co0.9O15Mixed in 30mL water, magnetically stirred for 2h, and then transferred to a vacuum drying oven for drying at 95 ℃ for 12 h. Drying to obtain the final powder product Bi5Fe0.5Ni0.5Ti2.1Co0.9O15/S-g-C3N4。
(3) Catalyst Bi5Fe0.5Ni0.5Ti2.1Co0.9O15/S-g-C3N4Treatment of pharmaceutical intermediate organic wastewater
The procedure of the treatment process was the same as in example 1, wherein the pH of the wastewater was adjusted to 6 in the pH adjusting tank 1, and the magnetic composite catalyst 16Bi was contained in the photocatalytic reaction tank 135Fe0.5Ni0.5Ti2.1Co0.9O1560g of materials are pre-filled, a light source 11 adopts a bromine tungsten lamp, and an electrode plate is externally connected with a 1.3V direct current power supply. 20L of wastewater containing aniline compounds and phenolic compounds, the pH value is 1, the COD is 41500mg/L, and the salt content is 21500 mg/L. After single treatment, through COD test and salt content test, the removal rate of the catalyst and the special equipment thereof to the medical intermediate wastewater COD reaches 74.1%. The salt content of the wastewater after the desalting is 6743mg/L, and the NaCl content in the salt recovered from the salt solution storage tank 24 reaches 92.9 percent. The doping of the metal ions in the lower valence state causes oxygen defects in the surface lattice, the creation of oxygen vacancies can provide more active sites, and negatively charged ions and radicals can be adsorbed. Oxygen vacancy at the surface promotes the reaction with porous g-C3N4The S-shaped heterojunction formed by compounding improves the separation efficiency of photon-generated carriers, avoids excessive oxygen vacancies caused by doping, and further improves the photocatalytic capability.
Example 4
(1)Bi5Fe0.7Ni0.3Ti2.4Co0.6O15Preparation of
According to a molar ratio of 1: 0.14: 0.06: 0.12: 0.48 respectively weighing 3.88g of bismuth nitrate, 0.46g of ferric nitrate, 0.14g of nickel nitrate, 0.28g of cobalt nitrate and 1.31g of tetrabutyl titanate, dissolving in 20mL of dilute nitric acid of 4mol/L, and magnetically stirring for 0.5h until the mixture is completely dissolved. 70mL of 1.6mol/L diisopropylamine solution is added into the mixed solution dropwise until the pH value of the solution is about 8, stirring is continued for 1h to obtain solution A, and 3.15g of fluorocarbon surfactant is dissolved in 5mL of water to obtain solution B. And mixing the solution A and the solution B for 0.85h under magnetic stirring to obtain a turbid solution. The cloudy solution was transferred to a teflon lined autoclave to a volume of 80% of the autoclave. And continuously carrying out thermal reaction in an air-blowing drying oven, wherein the reaction temperature is 150 ℃, and the reaction time is 72 h. Centrifuging the precipitate after reaction, washing with water for three times, washing with ethanol for three times, drying, and grinding to obtain Bi5Fe0.7Ni0.3Ti2.4Co0.6O15。
(2)Bi5Fe0.7Ni0.3Ti2.4Co0.6O15/S-g-C3N4Preparation of
According to the mass ratio of 1: 0.1 weight 15g of urea and 1.5g of thiourea, after complete dissolution in warm water at 50 ℃ the magnetic stirring was continued for 1.5 h. The precursor obtained after stirring is transferred to a tubular furnace and calcined for 5.5h at 500 ℃ in the nitrogen atmosphere. According to the mass ratio of 1: 0.2 calcining the resulting powder S-g-C3N4And Bi5Fe0.7Ni0.3Ti2.4Co0.6O15Mixed in 30mL water, magnetically stirred for 2h, and then transferred to a vacuum drying oven for drying at 90 ℃ for 12 h. Drying to obtain the final powder product Bi5Fe0.7Ni0.3Ti2.4Co0.6O15/S-g-C3N4。
(3) Catalyst Bi5Fe0.7Ni0.3Ti2.4Co0.6O15/S-g-C3N4Treatment of pharmaceutical intermediate organic wastewater
The procedure of the treatment process was the same as in example 1, wherein the pH of the wastewater was adjusted to 7 in the pH adjusting tank 1, and the magnetic composite catalyst 16Bi was contained in the photocatalytic reaction tank 135Fe0.7Ni0.3Ti2.4Co0.6O15/S-g-C3N4And pre-filling 45g, wherein a 500W xenon lamp is selected as the light source 11, and a 1.4V direct-current power supply is externally connected to the electrode plate. The pharmaceutical intermediate organic wastewater is 20L, the pH is 1, the COD is 41232mg/L, and the salt content is 21119 mg/L. After single treatment, through a COD test and a salt content test, the removal rate of the catalyst and the special equipment thereof to the COD of the medical intermediate wastewater reaches 73.2 percent. The salt content of the wastewater after the desalting is 6524mg/L, and the NaCl content in the salt recovered from the salt solution storage tank 24 reaches 93 percent. The invention adopts the method that the desalting device is arranged after the photocatalytic reaction, thereby solving the problem of secondary pollution caused by waste salt, because a large amount of organic matters can be attached to the salt obtained by desalting, which belongs to dangerous waste, and the invention can firstly reduce the content of the organic matters in the medical intermediate wastewater and then recover the salt by arranging the desalting device behind the photocatalytic reaction tank, thereby recycling resources. The salinity of the effluent can be reduced, and the effluent can also continuously enter a biochemical pool for reaction, so that the cost is reduced.
Example 5
(1)Bi5Fe0.9Ni0.1Ti2.7Co0.3O15Preparation of
According to a molar ratio of 1: 0.18: 0.02: 0.06: 0.54 respectively weighing 3.64g of bismuth nitrate, 0.55g of ferric nitrate, 0.05g of nickel nitrate, 0.13g of cobalt nitrate and 1.38g of tetrabutyl titanate, dissolving in 20mL of dilute nitric acid of 4mol/L, and magnetically stirring for 0.5h until the mixture is completely dissolved. 65mL of a 1.3mol/L triethylenediamine solution was added dropwise to the mixture until the pH of the solution became about 8, and stirring was continued for 1 hour to obtain solution A, and 1g of cetyltrimethylammonium bromide was dissolved in 5mL of water to obtain solution B. And mixing the solution A and the solution B for 1 hour under magnetic stirring to obtain a turbid solution. The cloudy solution was transferred to a teflon lined autoclave to a volume of 80% of the autoclave. And continuously carrying out thermal reaction in an air-blast drying oven, wherein the reaction temperature is 200 ℃, and the reaction time is 36 h. Centrifuging the precipitate after reaction, washing with water for three times, washing with ethanol for three times, drying, and grinding to obtain Bi5Fe0.9Ni0.1Ti2.7Co0.3O15。
(2)Bi5Fe0.9Ni0.1Ti2.7Co0.3O15/S-g-C3N4Preparation of
According to the mass ratio of 1: 0.1 weight 15g of urea and 1.5g of thiourea, after complete dissolution in warm water at 50 ℃ the magnetic stirring was continued for 1.5 h. The precursor obtained after stirring is transferred to a tubular furnace and calcined for 6.5h at 450 ℃ in nitrogen atmosphere. According to the mass ratio of 1: 0.2 calcining the resulting powder S-g-C3N4And Bi5Fe0.9Ni0.1Ti2.7Co0.3O15Mixed in 30mL water, magnetically stirred for 2h, and then transferred to a vacuum drying oven for drying at 100 ℃ for 8 h. Drying to obtain the final powder product Bi5Fe0.9Ni0.1Ti2.7Co0.3O15/S-g-C3N4。
(3) Catalyst Bi5Fe0.9Ni0.1Ti2.7Co0.3O15/S-g-C3N4Treatment of pharmaceutical intermediate organic wastewater
The procedure of the treatment process was the same as in example 1, wherein the pH of the wastewater was adjusted to 6.5 in the pH adjusting tank 1, and the magnetic composite catalyst 16Bi was contained in the photocatalytic reaction tank 135Fe0.9Ni0.1Ti2.7Co0.3O15/S-g-C3N470g of pre-filling, wherein a 500W xenon lamp is selected as the light source 11, and a 1.25V direct-current power supply is externally connected to the electrode plate. 20L of waste water containing phenolic compounds and halogenated hydrocarbon solvent has pH of 1, COD of 41232mg/L and salt content of 21119 mg/L. Samples were taken up until 2h, 3h, 4h, 5h, 6h, and 7h after the photocatalytic reaction proceeded, and the COD removal rate at each sampling was determined as shown in Table 1.
TABLE 1
| Time/h | 2 | 3 | 4 | 5 | 6 | 7 |
| COD/(mg/L) | 27035.6 | 20316 | 15050.3 | 10806.4 | 9195.3 | 8016.4 |
| COD removal Rate/%) | 31.2 | 48.3 | 61.7 | 72.5 | 76.6 | 79.6 |
As can be seen from the results in Table 1, when the same batch of wastewater is continuously treated, the COD removal rate is continuously improved along with the prolonging of the photocatalytic reaction time, the cost can be saved while the degradation rate is ensured by controlling the single reaction time to be 5h, and the method is economical and efficient.
Example 6
(1)Bi5Fe0.9Ni0.1Ti2.7Co0.3O15Preparation of
According to a molar ratio of 1: 0.18: 0.02: 0.06: 0.54 respectively weighing 3.64g of bismuth nitrate, 0.55g of ferric nitrate, 0.05g of nickel nitrate, 0.13g of cobalt nitrate and 1.38g of tetrabutyl titanate, dissolving in 20mL of dilute nitric acid of 4mol/L, and magnetically stirring for 0.5h until the mixture is completely dissolved. A solution of 65mL of 1.4mol/L triethylenediamine was added dropwise to the mixture until the pH of the solution became about 8, and stirring was continued for 1 hour to obtain solution A, and 1g of cetyltrimethylammonium bromide was dissolved in 5mL of water to obtain solution B. And mixing the solution A and the solution B for 1 hour under magnetic stirring to obtain a turbid solution. The cloudy solution was transferred to a teflon lined autoclave to a volume of 80% of the autoclave. And continuously carrying out thermal reaction in an air-blast drying oven, wherein the reaction temperature is 200 ℃, and the reaction time is 36 h. Centrifuging the precipitate after reaction, washing with water for three times, washing with ethanol for three times, drying, and grinding to obtain Bi5Fe0.9Ni0.1Ti2.7Co0.3O15。
(2)Bi5Fe0.9Ni0.1Ti2.7Co0.3O15/S-g-C3N4Preparation of
According to the mass ratio of 1: 0.1 weight 15g of urea and 1.5g of thiourea, after complete dissolution in warm water at 50 ℃ the magnetic stirring was continued for 1.5 h. The precursor obtained after stirring is transferred to a tubular furnace and calcined for 6.5h at 450 ℃ in nitrogen atmosphere. According to the mass ratio of 1: 0.2 calcining the resulting powder S-g-C3N4And Bi5Fe0.9Ni0.1Ti2.7Co0.3O15Mixed in 30mL water, magnetically stirred for 2h, and then transferred to a vacuum drying oven for drying at 100 ℃ for 8 h. Drying to obtain the final powder product Bi5Fe0.9Ni0.1Ti2.7Co0.3O15/S-g-C3N4。
The procedure of the apparatus treatment was the same as that of example 1, wherein the pH of the wastewater was adjusted to 6.5 in the pH adjusting tank 1, and the magnetic composite catalyst 16Bi was contained in the photocatalytic reaction tank 135Fe0.9Ni0.1Ti2.7Co0.3O15/S-g-C3N470g of pre-filling, wherein a 500W xenon lamp is selected as the light source 11, and a 1.25V direct-current power supply is externally connected to the electrode plate. The wastewater containing the benzene series and the aniline series compounds was treated in batches in sequence, the initial pH was 1, the COD was 42000mg/L, the salt content was 21500mg/L, and the amount of wastewater per batch was 20L, and the results are shown in Table 2.
TABLE 2
As can be seen from table 2, the catalyst in the reaction system is in the form of powder and highly dispersed in the wastewater, and can fully contact the pollutants in the wastewater and fully utilize the light energy provided by the light source. The electromagnetic system 10 in the photocatalytic reaction tank 13 is electrified before water outlet to generate magnetism to retain catalyst powder, so that the catalyst can be reused, loss is reduced, and secondary pollution of the catalyst along with water outlet is avoided. Meanwhile, a pipeline filter screen is added, so that the photocatalyst can be kept in the photocatalytic reaction tank, the loss is avoided, and the requirement of repeated use for a long time is met.
Comparative example 1
(1)S-g-C3N4Preparation of
According to the mass ratio of 1: 0.2 weigh 15g of urea and 3g of thiourea, and after complete dissolution in warm water at 50 ℃, the precursor gel is obtained by continuing magnetic stirring for 1.5 h. The precursor gel was transferred to a tube furnace and calcined at 500 ℃ for 5h under nitrogen atmosphere. The light yellow powder obtained after calcination is the final product S-g-C3N4。
(2)S-g-C3N4Treatment of pharmaceutical intermediate organic wastewater
The treatment process was the same as that of example 1, 20L of waste water containing aniline compounds and phenol compounds, pH was 1, COD was 41000mg/L, and salt content was 21110 mg/L. After single treatment, the COD test and the salt content test show that only S-g-C is utilized3N4The special system provided by the invention is used for treating the medical intermediate wastewater, and the removal rate of COD is only 12.1%. The salt content of the wastewater after the desalting is 10521 mg/L. The content of NaCl in the salt recovered from the salt solution storage tank 24 is 47%. Description of monomers S-g-C3N4The degradation effect on the waste water of the aniline medical intermediate is not good, and g-C doped with sulfur3N4Although the light absorption band can be widened to the visible region, there is no problem of improving the high coincidence rate of photo-generated charges and holes. And due to the monomers S-g-C3N4The catalyst does not have any ferromagnetism, so the catalyst is seriously lost when the treatment solution flows out of the catalytic reaction tank.
Comparative example 2
(1)Bi5Fe0.8Ni0.2Ti2.5Co0.5O15Preparation of
According to a molar ratio of 1: 0.16: 0.04: 0.5: 0.1 respectively weighing 2.91g of bismuth nitrate, 0.39g of ferric nitrate, 0.07g of nickel nitrate, 0.18g of cobalt nitrate and 1.02g of tetrabutyl titanate, dissolving in 54mL of 20mL of 4mol/L dilute nitric acid, and magnetically stirring for 0.5h until the mixture is completely dissolved to obtain a mixed solution. Dripping 1.2mol/L quaternary ammonium base solution into the mixed solution untilUntil the pH of the mixed solution reaches about 8, gray precipitate is gradually generated, the stirring is continued for 1 hour to obtain solution A, and 1.4g of cetyltrimethylammonium bromide is dissolved in 5mL of water to obtain solution B. And mixing the solution A and the solution B for 1 hour under magnetic stirring to obtain a turbid solution. The cloudy solution was transferred to a teflon lined autoclave to a volume of 80% of the autoclave. And continuously carrying out thermal reaction in an air-blowing drying oven, wherein the reaction temperature is 185 ℃, and the reaction time is 48 h. Centrifuging the precipitate after reaction, washing with water for three times, washing with ethanol for three times, drying, and grinding to obtain Bi5Fe0.8Ni0.2Ti2.5Co0.5O15。
(2)Bi5Fe0.8Ni0.2Ti2.5Co0.5O15Treatment of pharmaceutical intermediate organic wastewater
The treatment process is the same as that of example 1, 20L of wastewater containing benzene series and aniline compounds, the pH is 1, the COD is 41000mg/L, and the salt content is 21000 mg/L. After single treatment, the results of COD test and salt content test show that only Bi is utilized5Fe0.8Ni0.2Ti2.5Co0.5O15The special system provided by the invention is used for treating the medical intermediate wastewater, the removal rate of COD is only 28.7%, and the salt content of the wastewater after desalting is 9210 mg/L. The content of NaCl in the salt recovered from the salt solution storage tank 24 is 61%. Description of the monomer Bi5Fe0.8Ni0.2Ti2.5Co0.5O15After the doping of the multi-metal ions, the ferromagnetism is enhanced, but excessive surface oxygen vacancies become composite sites of photon-generated carriers, so that the utilization rate of visible light is reduced, and the catalytic effect is reduced. The auxiliary effect of the surfactant is lost, metal ions are more difficult to be doped into the catalyst structure, and more metal oxide byproducts are generated, so that the photocatalytic effect is greatly reduced.
Comparative example 3
(1)Bi5Fe0.8Ni0.2Ti2.5Co0.5O15Preparation of
According to a molar ratio of 1: 0.16: 0.04: 0.5: 0.1 weighing 2.91g bismuth nitrate, 0.39g ferric nitrate, 0.07g nickel nitrate, 0.18g nitric acidCobalt, 1.02g tetrabutyl titanate, was dissolved in 20mL of dilute nitric acid of 4mol/L, and magnetically stirred for 0.5h until the mixture was completely dissolved to obtain a mixed solution. Adding 54mL of 1.2mol/L quaternary ammonium base solution dropwise into the mixed solution until the pH of the solution is about 8, gradually generating gray precipitate, continuing stirring for 1h to obtain solution A, and dissolving 1.4g of cetyltrimethylammonium bromide in 5mL of water to obtain solution B. And mixing the solution A and the solution B for 1 hour under magnetic stirring to obtain a turbid solution. The cloudy solution was transferred to a teflon lined autoclave to a volume of 80% of the autoclave. The thermal reaction is carried out in a forced air drying oven, the reaction temperature is 185 ℃, and the reaction time is 48 h. Centrifuging, washing with ethanol, drying and grinding the precipitate to obtain Bi5Fe0.8Ni0.2Ti2.5Co0.5O15。
(2)Bi5Fe0.8Ni0.2Ti2.5Co0.5O15/g-C3N4Preparation of
15g of urea was weighed out and dissolved completely in warm water at 50 ℃ and magnetic stirring was continued for 1.5 h. And (3) stirring to obtain precursor gel, transferring the precursor gel into a tubular furnace, and calcining for 5 hours at 500 ℃ in a nitrogen atmosphere to obtain powder. According to the mass ratio of 1: 0.2 mixing the powders g to C3N4And Bi5Fe0.8Ni0.2Ti2.5Co0.5O15Mixed in 30mL water, magnetically stirred for 2h, and then transferred to a vacuum drying oven for drying at 90 ℃ for 12 h. Drying to obtain the final powder product Bi5Fe0.8Ni0.2Ti2.5Co0.5O15/g-C3N4。
(3)Bi5Fe0.8Ni0.2Ti2.5Co0.5O15/g-C3N4Treatment of pharmaceutical intermediate organic wastewater
The treatment process is the same as that of example 1, 20L of wastewater containing benzene series and aniline compounds, the pH is 1, the COD is 41000mg/L, and the salt content is 21000 mg/L. After single treatment, the results of COD test and salt content test show that only Bi is utilized5Fe0.8Ni0.2Ti2.5Co0.5O15/g-C3N4The special system provided by the invention is used for treating the medical intermediate wastewater, the removal rate of COD is only 39.6%, and the salt content of the wastewater after desalting is 9252 mg/L. The NaCl content in the salt recovered from the salt solution storage tank 24 is 72%. Description will be given of Bi5Fe0.8Ni0.2Ti2.5Co0.5O15-eAnd g-C undoped with sulfur element3N4Direct recombination results in inefficient recombination, and the absence of bridging between elemental sulfur and oxygen vacancies results in more physical recombination predominating and a lower proportion of heterojunctions formed.
Comparative example 4
(1)Bi5Fe0.9Ni0.1Ti2.7Co0.3O15Preparation of
According to a molar ratio of 1: 0.18: 0.02: 0.06: 0.54 respectively weighing 3.64g of bismuth nitrate, 0.55g of ferric nitrate, 0.05g of nickel nitrate, 0.13g of cobalt nitrate and 1.38g of tetrabutyl titanate, dissolving in 20mL of dilute nitric acid of 4mol/L, and magnetically stirring for 0.5h until the mixture is completely dissolved to obtain a mixed solution. 65mL of 4.5mol/L triethylenediamine solution was added dropwise to the mixed solution until the pH of the mixed solution became about 8, and stirring was continued for 1 hour to obtain solution A, and 1g of cetyltrimethylammonium bromide was dissolved in 5mL of water to obtain solution B. And mixing the solution A and the solution B for 0.75h under magnetic stirring to obtain a turbid solution. The cloudy solution was transferred to a teflon lined autoclave to a volume of 80% of the autoclave. And continuously carrying out thermal reaction in an air-blast drying oven, wherein the reaction temperature is 180 ℃, and the reaction time is 48 h. Centrifuging the precipitate after reaction, washing with water for three times, washing with ethanol for three times, drying, and grinding to obtain Bi5Fe0.9Ni0.1Ti2.7Co0.3O15。
(2)Bi5Fe0.9Ni0.1Ti2.7Co0.3O15/S-g-C3N4Preparation of
According to the mass ratio of 15: 1 weigh 15g of dicyanodiamine and 1g of sodium thiosulfate, completely dissolve in warm water at 50 ℃, and then continue to magnetically stir for 1.5h to obtain a precursor gel. Transferring the precursor gel to a tubeCalcining the mixture for 5 hours at 500 ℃ in a nitrogen atmosphere in a furnace to obtain powder S-g-C3N4. According to the mass ratio of 1: 0.5 mixing the powder S-g-C3N4And Bi5Fe0.9Ni0.1Ti2.7Co0.3O15Mixed in 30mL water, magnetically stirred for 2h, and then transferred to a vacuum drying oven for drying at 90 ℃ for 12 h. Drying to obtain the final powder product Bi5Fe0.9Ni0.1Ti2.7Co0.3O15/S-g-C3N4。
(3)Bi5Fe0.9Ni0.1Ti2.7Co0.3O15/S-g-C3N4Treatment of pharmaceutical intermediate organic wastewater
The treatment process is carried out in a 40L open container, 4 xenon lamps of 500W are used as light sources, the catalyst is recovered by magnetite, and the wastewater containing the benzene series and the aniline compounds is treated in turn in batches, wherein the initial pH is 1, the COD is 41232mg/L, the salt content is 21119mg/L, and the quantity of each batch of wastewater is 20L. The treated wastewater was desalted by evaporation, and the results are shown in Table 3.
TABLE 3
| Time/h | First batch | Second batch | Third batch | Fourth batch |
| COD/(mg/L) | 23121 | 29752 | 35811 | 39240 |
| COD removal Rate/%) | 43.9 | 38.6 | 13.1 | 4.8 |
| Salt content/(mg/L) of the treatment fluid | 21086 | 21108 | 21091 | 21102 |
| Salinity NaCl content/%) | 33 | 34 | 33.2 | 31.5 |
As can be seen from table 3, when the catalyst is directly used for photocatalytic treatment of medical intermediate wastewater without using the dedicated system, the catalyst directly contacts with the wastewater with strong acidity, so that the activity of the catalyst is reduced, the recycling capability of the catalyst is remarkably reduced, and the content of salt and organic matters in the wastewater is high, so that the wastewater cannot be recycled.
In conclusion, Bi with different doping ratios is prepared by adopting surfactants of sodium dodecyl sulfate, hexadecyl trimethyl ammonium bromide, polyvinyl alcohol, fluorocarbon surfactant, mineralizer of tetramethyl ammonium hydroxide, triethylene diamine, quaternary ammonium base and diisopropylamine5Fe1-xNixTi3-yCoyO15g-C doped with sulfur3N4The magnetic composite photocatalyst obtained by compounding can utilize Bi5Fe1- xNixTi3-yCoyO15The oxygen vacancy on the surface forms an S-type heterojunction, and the oxygen vacancy concentration on the surface of the catalyst can be regulated and controlled through the doped S, so that the generation of new recombination sites of electron holes is avoided. The unique charge transfer mode of the S-type heterojunction reserves holes and electrons with higher oxidation-reduction potential, so that the composite catalyst has stronger capability of degrading benzene, aniline and ester pollutants in medical intermediate wastewater, and the removal rate of COD can reach more than 70%. The salt content of the wastewater after desalting is below 7000 mg/L. The NaCl content in the salt recovered from the salt solution storage tank 24 is over 90 percent. The dispersive catalyst powder can fully utilize light energy, efficiently degrade organic matters, fully avoid the loss of the catalyst powder by utilizing a simple electromagnetic attraction effect and avoid the generation of secondary pollution. The activity of the catalyst is hardly reduced after the catalyst is recycled, the catalytic efficiency is high, and the cost is saved.
Claims (10)
1. The magnetic composite photocatalyst is characterized in that the catalyst is Bi5Fe1-xNixTi3-yCoyO15/S-g-C3N4Wherein x is 0.1-0.5, y is 0.3-0.9, Bi5Fe1-xNixTi3-yCoyO15Is in Bi5FeTi3O15Middle Fe position doped with Ni and Ti position doped with Co for modification, S-g-C3N4Is obtained by doping S in the graphite carbon nitride for modification.
2. The preparation method of the magnetic composite photocatalyst of claim 1, characterized by comprising the steps of:
(1) dissolving bismuth nitrate, ferric nitrate, nickel nitrate, cobalt nitrate and tetrabutyl titanate in dilute nitric acid to obtain a mixed solution, dropwise adding a mineralizer into the mixed solution to obtain solution A, and dissolving a surfactant in water to obtain solution B. Mixing the solution A and the solution B under stirring, thermally reacting, cooling, centrifugally separating, washing with water, washing with ethanol, drying, and grinding to obtain a product Bi5Fe1-xNixTi3O15；
(2) Dissolving nitrogen-rich organic matter and sulfur source in water to obtain precursor gel, and calcining the precursor gel to obtain S-g-C3N4From S-g-C3N4And Bi5Fe1-xNixTi3-yCoyO15Dissolving in water, stirring and mixing evenly, and vacuum drying to obtain the final product Bi5Fe1- xNixTi3-yCoyO15/S-g-C3N4。
3. The preparation method according to claim 2, wherein in the step (1), the surfactant is one or two of a fluorocarbon surfactant, sodium dodecyl sulfate, cetyltrimethylammonium bromide and polyvinyl alcohol; the mineralizer is one of tetramethylammonium hydroxide, triethylenediamine, quaternary ammonium base and diisopropylamine.
4. The preparation method according to claim 2, wherein in the step (1), the molar ratio of the bismuth nitrate, the ferric nitrate, the nickel nitrate, the cobalt nitrate and the tetrabutyl titanate is 1: 0.1-0.18: 0.02-0.1: 0.06-0.18: 0.42-0.54, the concentration of the mineralizer is 1.2-1.6mol/L, and the liquid-solid ratio of the mineralizer to the cobalt nitrate is 200-: 1 mL/g; the mass ratio of the nickel nitrate to the surfactant is 1: 20-25; the stirring and mixing time is 45-60 min; the temperature of the thermal reaction is 150-220 ℃, and the reaction time is 24-72 h.
5. The method according to claim 2, wherein in step (2), the nitrogen-rich organic substance is one of urea, dicyanodiamine and melamine; the sulfur source is one of thiourea, thioacetamide and sodium thiosulfate.
6. The method according to claim 2, wherein in the step (2), the mass ratio of the nitrogen-rich organic substance to the sulfur source is 1: 0.1-0.2; the Bi5Fe1-xNixTi3-yCoyO15With S-g-C3N4The mass ratio of (1): 0.1-0.5; the calcination temperature is 450-550 ℃, and the calcination time is 4-6.5 h; the stirring and uniformly mixing time is 45-60 min; the temperature of the vacuum drying is 90-100 ℃, and the time of the vacuum drying is 8-12 h.
7. The use of the magnetic composite photocatalyst of claim 1 in the treatment of medical intermediate wastewater.
8. The special system for treating the medical intermediate wastewater by using the magnetic composite photocatalyst as claimed in claim 1, wherein the special system comprises a pH adjusting tank (1), a photocatalytic reaction tank (13), a desalting tank (19) and a salt solution storage tank (24); a liquid level meter (14) is arranged on the upper side of the side wall of the photocatalytic reaction tank (13), an electromagnetic system (10) and a light source (11) are arranged in the photocatalytic reaction tank (13), and a first stirring paddle (17) is arranged at the bottom of the photocatalytic reaction tank (13); an anode electrode plate (20) and a cathode electrode plate (21) are arranged in the desalting tank (19); the photocatalytic reaction tank (13) is respectively connected with the pH adjusting tank (1) and the desalting tank (19), and the desalting tank (19) is connected with the salt liquid storage tank (24).
9. The method for treating pharmaceutical intermediate wastewater by using the special system as claimed in claim 8, characterized by comprising the following steps: injecting the medical intermediate wastewater into a pH adjusting tank (1), adjusting pH, then sending the medical intermediate wastewater into a photocatalytic reaction tank (13) filled with the magnetic composite photocatalyst (16) as defined in claim 1, monitoring the liquid level height by a liquid level meter (14) to stop liquid inlet, opening a first stirring paddle (17) and a light source (11) at the bottom of the photocatalytic reaction tank (13) to perform photocatalytic oxidation reaction, closing the light source (11) and the first stirring paddle (17) after the reaction is finished, opening an electromagnetic system (10) to adsorb the magnetic composite photocatalyst, discharging the wastewater after catalytic oxidation treatment into a desalting tank (19), electrifying an anode electrode plate (20) and a cathode electrode plate (21) of the desalting tank (19) to remove salt, and discharging the treated liquid after desalting out of the device. Clean water is injected into the desalting tank (19), the anode electrode plate (20) and the cathode electrode plate (21) are powered off, the two electrode plates are in short circuit, salt on the anode electrode plate (20) and the salt on the cathode electrode plate (21) are dissolved in the clean water to obtain salt solution, and the salt solution is sent into the salt solution storage tank (24).
10. The method as claimed in claim 9, wherein the solid-to-liquid ratio of the magnetic composite photocatalyst (16) to the pharmaceutical intermediate wastewater is 1-5:1 g/L; the pH is 5-8; the light source (11) is one of a xenon lamp, a modified LED lamp and a bromine tungsten lamp; the anode electrode plate (20) and the cathode electrode plate (21) are made of carbon aerogel materials, and the voltage between the anode electrode plate (20) and the cathode electrode plate (21) is 1.2-1.4V.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111035409.3A CN113617378B (en) | 2021-09-03 | 2021-09-03 | Magnetic composite photocatalyst, preparation method, special system and method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111035409.3A CN113617378B (en) | 2021-09-03 | 2021-09-03 | Magnetic composite photocatalyst, preparation method, special system and method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113617378A true CN113617378A (en) | 2021-11-09 |
| CN113617378B CN113617378B (en) | 2023-10-10 |
Family
ID=78389117
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111035409.3A Active CN113617378B (en) | 2021-09-03 | 2021-09-03 | Magnetic composite photocatalyst, preparation method, special system and method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113617378B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114570410A (en) * | 2022-03-31 | 2022-06-03 | 浙江大学 | g-C3N4/TiO2/C nano heterojunction photocatalyst and in-situ preparation method thereof |
| CN114832846A (en) * | 2022-05-06 | 2022-08-02 | 东南大学 | Magnetic core-shell structure composite catalyst for degrading nitrogen heterocyclic pollutants, preparation method, treatment system and treatment method |
| CN115805095A (en) * | 2022-12-12 | 2023-03-17 | 东南大学 | High-specific-surface-area porous composite photocatalyst, preparation method, integrated treatment system and treatment method |
| CN116809106A (en) * | 2023-06-25 | 2023-09-29 | 重庆工商大学 | Microwave-assisted oxygen-enriched vacancy Co@NC for efficiently degrading organic pollutants X A aerogel catalyst |
| CN116809106B (en) * | 2023-06-25 | 2024-05-28 | 重庆工商大学 | Microwave-assisted oxygen-enriched vacancy Co@NC for efficiently degrading organic pollutantsXA aerogel catalyst |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101214441A (en) * | 2007-12-28 | 2008-07-09 | 中国科学院上海硅酸盐研究所 | Preparation method of titanium barium ferrum series photocatalyst |
| CN101607818A (en) * | 2009-07-06 | 2009-12-23 | 扬州大学 | Has laminate structure ferrotianium cobalt acid bismuth stupalith of multi-ferrum property and preparation method thereof |
| CN105688970A (en) * | 2016-02-29 | 2016-06-22 | 湖南大学 | g-C3N4 modified self-doping Bi2WO6 composite photocatalyst and preparation method and application thereof |
| CN106994349A (en) * | 2017-05-11 | 2017-08-01 | 中国科学院新疆理化技术研究所 | A kind of Preparation method and use of the laminated perovskite photochemical catalyst iron titanate bismuth of hierarchy |
| CN111482190A (en) * | 2020-04-24 | 2020-08-04 | 杜桂芳 | Bi2WO6-g-C3N4Heterojunction photocatalytic hydrogen production material and preparation method thereof |
-
2021
- 2021-09-03 CN CN202111035409.3A patent/CN113617378B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101214441A (en) * | 2007-12-28 | 2008-07-09 | 中国科学院上海硅酸盐研究所 | Preparation method of titanium barium ferrum series photocatalyst |
| CN101607818A (en) * | 2009-07-06 | 2009-12-23 | 扬州大学 | Has laminate structure ferrotianium cobalt acid bismuth stupalith of multi-ferrum property and preparation method thereof |
| CN105688970A (en) * | 2016-02-29 | 2016-06-22 | 湖南大学 | g-C3N4 modified self-doping Bi2WO6 composite photocatalyst and preparation method and application thereof |
| CN106994349A (en) * | 2017-05-11 | 2017-08-01 | 中国科学院新疆理化技术研究所 | A kind of Preparation method and use of the laminated perovskite photochemical catalyst iron titanate bismuth of hierarchy |
| CN111482190A (en) * | 2020-04-24 | 2020-08-04 | 杜桂芳 | Bi2WO6-g-C3N4Heterojunction photocatalytic hydrogen production material and preparation method thereof |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114570410A (en) * | 2022-03-31 | 2022-06-03 | 浙江大学 | g-C3N4/TiO2/C nano heterojunction photocatalyst and in-situ preparation method thereof |
| CN114570410B (en) * | 2022-03-31 | 2023-02-03 | 浙江大学 | g-C 3 N 4 /TiO 2 /C nano heterojunction photocatalyst and in-situ preparation method thereof |
| CN114832846A (en) * | 2022-05-06 | 2022-08-02 | 东南大学 | Magnetic core-shell structure composite catalyst for degrading nitrogen heterocyclic pollutants, preparation method, treatment system and treatment method |
| CN114832846B (en) * | 2022-05-06 | 2024-02-02 | 东南大学 | Magnetic core-shell structure composite catalyst for degrading nitrogen heterocyclic pollutants, preparation method, treatment system and treatment method |
| CN115805095A (en) * | 2022-12-12 | 2023-03-17 | 东南大学 | High-specific-surface-area porous composite photocatalyst, preparation method, integrated treatment system and treatment method |
| CN115805095B (en) * | 2022-12-12 | 2024-02-06 | 东南大学 | High specific surface area porous composite photocatalyst, preparation method, integrated treatment system and treatment method |
| CN116809106A (en) * | 2023-06-25 | 2023-09-29 | 重庆工商大学 | Microwave-assisted oxygen-enriched vacancy Co@NC for efficiently degrading organic pollutants X A aerogel catalyst |
| CN116809106B (en) * | 2023-06-25 | 2024-05-28 | 重庆工商大学 | Microwave-assisted oxygen-enriched vacancy Co@NC for efficiently degrading organic pollutantsXA aerogel catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113617378B (en) | 2023-10-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113617378B (en) | Magnetic composite photocatalyst, preparation method, special system and method | |
| CN101752564B (en) | Hydrothermal synthesis method of LiFePO4 of anode material of lithium ion battery with one-dimensional nanometer structure | |
| CN105289693B (en) | A kind of Zn0.5Co0.5Fe2O4/g‑C3N4The preparation method of composite photo-catalyst | |
| EP3410526B1 (en) | System and method for preparing high-activity specific-valence-state electrolyte of all-vanadium flow battery | |
| CN103606694A (en) | Preparation method for commercial vanadium battery electrolyte | |
| CN103165878A (en) | Preparation method of spherical nickel-manganese binary material | |
| CN101982421B (en) | Preparation method of nano cobalt oxide | |
| CN103682323A (en) | Lithium nickel manganese oxide cathode material, precursor thereof and preparation method thereof | |
| EP3401991B1 (en) | System and method for producing 3.5-valent highly pure vanadium electrolyte | |
| CN105375078B (en) | A kind of method that spherical nickel-cobalt mangaic acid lithium is prepared by based lithium-ion battery positive plate circulation | |
| EP3410527A1 (en) | System and method for preparing high purity vanadium electrolyte | |
| CN104098201B (en) | A kind of starch wastewater treatment method | |
| CN1890183A (en) | Process for making nickel hydroxide | |
| US10868325B2 (en) | System and method for preparing vanadium battery high-purity electrolyte | |
| CN103936082B (en) | A kind of synthetic method of cobalt acid samarium nano-powder | |
| CN101830537B (en) | Method for degrading organic components in ore-dressing wastewater of sulphide ores by catalysis under visible light | |
| KR102361906B1 (en) | Reuse System of Wastewater | |
| US4525254A (en) | Process and apparatus for purifying effluents and liquors | |
| CN113663697A (en) | Heterojunction type Fenton-like catalyst, preparation method, special system and method | |
| CN105390691A (en) | Method for preparing spherical nickel cobalt lithium manganate by liquid phase template method | |
| CN112607785A (en) | MnFe2O4/C nano composite microsphere and preparation method thereof | |
| CN102659215A (en) | Polarization modified iron-carbon micro-electrolysis material and preparation method thereof | |
| CN110512225B (en) | Preparation method of zinc oxide powder | |
| CN207918452U (en) | A kind of system preparing cobalt carbonate | |
| CN216513245U (en) | Pretreatment system of phosphorus-containing and ammonia-containing wastewater |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |