CN111646632B - Green energy-saving photoelectrocatalysis water treatment system and water treatment method thereof - Google Patents
Green energy-saving photoelectrocatalysis water treatment system and water treatment method thereof Download PDFInfo
- Publication number
- CN111646632B CN111646632B CN202010390583.9A CN202010390583A CN111646632B CN 111646632 B CN111646632 B CN 111646632B CN 202010390583 A CN202010390583 A CN 202010390583A CN 111646632 B CN111646632 B CN 111646632B
- Authority
- CN
- China
- Prior art keywords
- boron
- doped diamond
- electrode
- layer
- gradient
- 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.)
- Active
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 131
- 238000000034 method Methods 0.000 title abstract description 28
- 229910003460 diamond Inorganic materials 0.000 claims abstract description 86
- 239000010432 diamond Substances 0.000 claims abstract description 86
- 230000015556 catabolic process Effects 0.000 claims abstract description 62
- 238000006731 degradation reaction Methods 0.000 claims abstract description 62
- 239000002245 particle Substances 0.000 claims abstract description 28
- 239000011941 photocatalyst Substances 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 17
- 238000003860 storage Methods 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 238000010248 power generation Methods 0.000 claims abstract description 12
- 244000005700 microbiome Species 0.000 claims abstract description 7
- 239000007789 gas Substances 0.000 claims description 61
- 239000000758 substrate Substances 0.000 claims description 41
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 32
- 229910052796 boron Inorganic materials 0.000 claims description 31
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 30
- 238000000151 deposition Methods 0.000 claims description 23
- 239000010936 titanium Substances 0.000 claims description 23
- 230000008021 deposition Effects 0.000 claims description 21
- 238000001514 detection method Methods 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- 229910052799 carbon Inorganic materials 0.000 claims description 15
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 12
- 229910052719 titanium Inorganic materials 0.000 claims description 12
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 10
- 239000010439 graphite Substances 0.000 claims description 9
- 229910002804 graphite Inorganic materials 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 7
- 238000002347 injection Methods 0.000 claims description 7
- 239000007924 injection Substances 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 238000005273 aeration Methods 0.000 claims description 6
- 238000005137 deposition process Methods 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000011159 matrix material Substances 0.000 claims description 5
- 239000012782 phase change material Substances 0.000 claims description 5
- 239000000725 suspension Substances 0.000 claims description 5
- 230000007704 transition Effects 0.000 claims description 5
- 239000004484 Briquette Substances 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 229910052755 nonmetal Inorganic materials 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 238000009736 wetting Methods 0.000 claims description 4
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 3
- 230000000813 microbial effect Effects 0.000 claims description 3
- 238000003491 array Methods 0.000 claims description 2
- 238000005234 chemical deposition Methods 0.000 claims description 2
- 238000013329 compounding Methods 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 239000013081 microcrystal Substances 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims description 2
- 239000002159 nanocrystal Substances 0.000 claims description 2
- 239000004065 semiconductor Substances 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 abstract description 13
- 238000007254 oxidation reaction Methods 0.000 abstract description 13
- 238000006056 electrooxidation reaction Methods 0.000 abstract description 8
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 7
- 238000012545 processing Methods 0.000 abstract description 6
- 238000005868 electrolysis reaction Methods 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 230000001699 photocatalysis Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 19
- 230000008569 process Effects 0.000 description 15
- 239000002351 wastewater Substances 0.000 description 14
- 239000000919 ceramic Substances 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000010408 film Substances 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000007772 electrode material Substances 0.000 description 7
- 239000006260 foam Substances 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 230000001276 controlling effect Effects 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- -1 polypropylene Polymers 0.000 description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 4
- 229920000742 Cotton Polymers 0.000 description 3
- 239000006004 Quartz sand Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000004043 dyeing Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 230000006911 nucleation Effects 0.000 description 3
- 238000010899 nucleation Methods 0.000 description 3
- 239000012188 paraffin wax Substances 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 230000003115 biocidal effect Effects 0.000 description 2
- 229910000085 borane Inorganic materials 0.000 description 2
- 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 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 238000012886 linear function Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000010815 organic waste Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 150000005846 sugar alcohols Chemical class 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 230000005428 wave function Effects 0.000 description 2
- BDKLKNJTMLIAFE-UHFFFAOYSA-N 2-(3-fluorophenyl)-1,3-oxazole-4-carbaldehyde Chemical compound FC1=CC=CC(C=2OC=C(C=O)N=2)=C1 BDKLKNJTMLIAFE-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 235000012255 calcium oxide Nutrition 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 238000004050 hot filament vapor deposition Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000010813 municipal solid waste Substances 0.000 description 1
- 239000002113 nanodiamond Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000005120 petroleum cracking Methods 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229940087562 sodium acetate trihydrate Drugs 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000000979 synthetic dye Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000000427 thin-film deposition Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
Images
Classifications
-
- 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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
- C02F1/325—Irradiation devices or lamp constructions
-
- 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
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
-
- 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
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
-
- 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
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
-
- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
- C02F2001/46138—Electrodes comprising a substrate and a coating
- C02F2001/46142—Catalytic coating
-
- 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
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46152—Electrodes characterised by the shape or form
-
- 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
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46152—Electrodes characterised by the shape or form
- C02F2001/46171—Cylindrical or tubular shaped
-
- 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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/06—Contaminated groundwater or leachate
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- 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
- C02F2103/343—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 pharmaceutical industry, e.g. containing antibiotics
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/009—Apparatus with independent power supply, e.g. solar cells, windpower, fuel cells
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/32—Details relating to UV-irradiation devices
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/32—Details relating to UV-irradiation devices
- C02F2201/322—Lamp arrangement
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
- C02F2201/461—Electrolysis apparatus
- C02F2201/46105—Details relating to the electrolytic devices
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/02—Aerobic processes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/28—Anaerobic digestion processes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/30—Aerobic and anaerobic processes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/30—Aerobic and anaerobic processes
- C02F3/301—Aerobic and anaerobic treatment in the same reactor
-
- 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
Abstract
The invention discloses a green energy-saving photoelectrocatalysis water treatment system and a method for treating water by the same, wherein the system comprises a liquid storage tank, a particle filter plate, a degradation tank and a microorganism treatment module; the intelligent temperature control module and the solar energy-electricity-heat intelligent conversion module; the degradation tank consists of a plurality of processing units, and any one processing unit comprises an anode, a cathode and a stirring device; the anode is a boron-doped diamond electrode loaded with a photocatalyst, the anode and the cathode are connected with a power supply through leads, and the power supply is connected with a solar power generation unit; the degradation tank also comprises a plurality of ultraviolet lamps, and the ultraviolet lamps directly irradiate the anode; the method obviously improves the removal rate of organic pollutants and reduces the electrolysis energy consumption by organically combining photocatalytic oxidation and electrochemical oxidation, has mild reaction conditions, is environment-friendly, is simple to operate, and is suitable for water body treatment under various water quality conditions.
Description
Technical Field
The invention relates to an environment-friendly energy-saving photoelectrocatalysis water treatment system and a water treatment method thereof, belonging to the technical field of water treatment.
Background
The scientific technology is a double-edged sword. On the one hand, the development of science and technology enriches our lives and improves work efficiency, and on the other hand, the development of science and technology also brings a series of safety problems, such as environmental destruction and the like. According to the investigation of the world authoritative institution, with the rapid development of modern social economy and the comprehensive progress of science and technology, thousands of tons of complex man-made organic chemicals are consumed and discharged to the water environment to become environmental organic pollutants every year around the world. The water consumption of the printing and dyeing industry is large, and the water consumption of the textile is 100-200t per 1t of printing and dyeing processing, wherein 80-90% of the water is discharged as printing and dyeing wastewater. The papermaking wastewater mainly comes from two production processes of pulping and papermaking in the production of the papermaking industry, and a large amount of wastewater is discharged in the two processes. The industrial departments such as coking plants, gas plants, petrochemical plants, insulating material plants and the like, and the production processes of ethylene, synthetic phenol, polyamide fiber, synthetic dye, organic pesticide and phenolic resin by petroleum cracking all discharge a large amount of phenol-containing wastewater, and the treatment difficulty is very large. These industrial waste waters contain a large amount of organic pollutants and are of a wide variety of types and treatment methods. In consideration of feasibility, efficiency, cost and other factors, the traditional physical, chemical, biological and other water treatment technologies have difficulty meeting the treatment requirements of modern life and industrial wastewater. The electrochemical advanced oxidation method is considered as an environment-friendly technology capable of effectively degrading various organic environmental pollutants in recent years, electrons are used as an oxidant in the electrochemical oxidation process, no additional chemical reagent is required to be added, the electrochemical oxidation method is green and pollution-free, simple to operate, strong in controllability, simple in equipment, small in occupied area, capable of achieving the effects of disinfection, flocculation and air flotation and good in combinability with other technologies, and is carried out at normal temperature and normal pressure. However, the high energy consumption and the low degradation rate are still the technical difficulties and the research focus of the electrochemical advanced oxidation method in the practical industrial application.
Solar energy is regarded as an inexhaustible green renewable energy source, the prior art can efficiently utilize solar energy for power generation and heat supply, the solar energy is converted into electric energy through photovoltaic power generation, and the electric energy can supply power for electrochemical oxidation degradation of organic wastewater and can also supply electric energy for maintaining the operation of the whole wastewater treatment system. In addition, the organic wastewater can be directly degraded by light, organic pollutants can absorb partial near ultraviolet light (290-400 nm) in the natural environment, and strong photochemical reaction can be generated in the presence of active substances, so that the organic wastewater is degraded, and the organic wastewater has the advantages of environmental friendliness, wide treatment range and the like. However, the ultraviolet radiation in sunlight usually only accounts for about 5% of the total emission energy, and the sunlight cannot be directly utilized to carry out photocatalytic degradation on organic wastewater.
Disclosure of Invention
Aiming at the problems of the traditional electrochemical oxidation technology, the invention provides a green energy-saving photoelectrocatalysis water treatment system and a water treatment method thereof by fully utilizing green clean solar energy and taking a boron-doped diamond electrode loaded with a photocatalyst as an anode.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention relates to a green energy-saving photoelectrocatalysis water treatment system, which comprises a liquid storage tank, a particle filter plate, a degradation tank and a microorganism treatment module, wherein the particle filter plate is arranged in the liquid storage tank; the intelligent temperature control module and the solar energy photo-electricity-heat intelligent conversion module; the outlet of the liquid storage tank is provided with a particle filter plate and is connected to the degradation tank through a pipeline, and the outlet of the degradation tank is connected to the microbial treatment module;
the intelligent temperature control module is used for controlling the temperature of water in the degradation tank to be 5-80 ℃;
the solar energy light-electricity-heat intelligent conversion module comprises a solar power generation unit and a solar heating unit;
the degradation tank comprises a plurality of treatment units, and any one treatment unit comprises an anode, a cathode and a stirring device; the anode is a boron-doped diamond electrode loaded with a photocatalyst, the anode and the cathode are connected with a power supply through leads, and the power supply is connected with a solar power generation unit;
the degradation tank also comprises a plurality of ultraviolet lamps, and the ultraviolet lamps directly irradiate the anode.
The invention relates to a green energy-saving photoelectrocatalysis water treatment system, wherein any one treatment unit also comprises a stirring device.
The invention relates to a green energy-saving photoelectrocatalysis water treatment system, wherein a particle filter plate is at least one selected from a quartz sand filter plate, a PP (polypropylene) cotton filter plate and a microporous foam ceramic plate with porosity of more than 35 PPI.
The microporous foamed ceramic plate with the porosity of more than 35PPI is preferably microporous foamed Al with the porosity of more than 35PPI 2 O 3 Ceramic plate, microporous foam ZrO with porosity greater than 35PPI 2 One of a ceramic plate, a microporous foam SiC ceramic plate having a porosity greater than 35 PPI.
The particle filter plate is used for filtering particle impurities such as silt, rust, suspended matters, colloid and the like in the water body.
The invention relates to a green energy-saving photoelectrocatalysis water treatment system, wherein the wall of a degradation tank contains a phase-change material.
The phase-change material can be any one commonly used in the prior art, such as paraffin, escapement alditol, sodium sulfate, sodium acetate trihydrate, calcium oxide, fatty acid, polyalcohol, disodium hydrogen phosphate, layered perovskite and the like.
The invention relates to a green energy-saving photoelectrocatalysis water treatment system, wherein an anode and a cathode are formed by matching one or more groups of plate electrodes which are parallel to each other but not in contact with each other, or formed by matching a cylindrical electrode and a cylindrical electrode which are coaxial in the center but not in contact with each other, or formed by matching two groups of coaxial cylindrical electrode arrays with different diameters, or formed by matching a honeycomb briquette structure and a cylindrical array, or formed by matching a three-dimensional continuous network structure and a two-dimensional continuous network structure, or formed by matching a two-dimensional closed plate structure and a two-dimensional continuous network structure.
In the invention, the honeycomb briquette structure and the cylindrical array are matched, namely the anode material is a porous structure of the honeycomb briquette structure, namely a plurality of straight holes are arrayed in a cylinder, and the cathode is a rod-shaped material and can be inserted into the pore canal of the anode material to realize the effect of an electrolytic cell.
The invention relates to a green energy-saving photoelectrocatalysis water treatment system, wherein a cathode is selected from one of graphite, stainless steel and a titanium electrode.
The invention relates to a green energy-saving photoelectrocatalysis water treatment system, wherein a photocatalyst bagContaining TiO 2 Further, the photocatalyst is doped modified TiO 2 The doping modification is selected from one of metal ion doping, metal doping, non-metal doping, metal-non-metal co-doping and semiconductor compounding, preferably metal doping, and the metal is preferably Au. TiO 2 2 The morphology of (a) may be one or more of tubular, rod-like, spherical, or powdered.
The invention relates to a green energy-saving photoelectrocatalysis water treatment system.A preparation method of a boron-doped diamond electrode loaded with a photocatalyst is selected from one of a CVD method, a sol-gel-dip coating method and a hydrothermal method;
preferably, the invention relates to a green energy-saving photoelectrocatalysis water treatment system, and the CVD method comprises the following specific processes: titanium tetraisopropoxide or titanium tetrachloride as a titanium source, N 2 As carrier gas, water vapor or O 2 TiO is deposited on the surface of the BDD electrode as a carrier gas and a reaction gas 2 Photocatalyst, tiO 2 The preparation of (A) is carried out in a CVD reactor, and after the deposition is finished, the mixture is calcined in a muffle furnace at 300-600 ℃ for 1-3h.
Preferably, the sol gel-dip coating method comprises the specific processes of adding tetrabutyl titanate or titanium isopropoxide or titanium tetrachloride serving as a titanium source into a solvent to obtain a mixed solution, adding nitric acid into the mixed solution to perform hydrolysis and polycondensation reactions to prepare uniform and transparent sol gel, coating the sol gel on a prepared BDD electrode, coating a layer, drying once, repeating the steps for 3-5 times, calcining at 500 ℃ in a muffle furnace for 0.5 hour, coating, drying, and calcining at 300-600 ℃ in the muffle furnace for 1-3 hours.
Preferably, the invention relates to a green energy-saving photoelectrocatalysis water treatment system, and the specific process of the hydrothermal method comprises the following steps: placing a BDD electrode in a polytetrafluoroethylene lining stainless steel autoclave, adding the BDD electrode into a mixed aqueous solution containing a titanium source, and performing hydrothermal synthesis at 150-180 ℃ for 6-20h; the mixed aqueous solution of the titanium-containing precursor is a mixed aqueous solution of 0.15M titanium trichloride and 3M sodium chloride, or a mixed aqueous solution of titanium trichloride and 3M sodium chloride according to the formula (1-3): 60 volume percent tetrabutyl titanate was dissolved in the dehydrohydrochloric acid precipitation solution.
In the actual operation process, when a hydrothermal method is adopted, a magnetron sputtering technology can be firstly adopted to deposit a ZnO buffer layer with the thickness of 10-20nm on the surface of the BDD electrode or not deposit the buffer layer,
in addition, when the photocatalyst is metal-doped TiO 2 In the preparation process, the alkoxide of the relevant doped metal is added when the titanium source is added.
The invention relates to a green energy-saving photoelectrocatalysis water treatment system.A working electrode layer of a boron-doped diamond electrode is a boron-doped diamond layer with micropores and/or pointed cones distributed on the surface.
Preferably, the boron-doped diamond electrode is a gradient boron-doped diamond electrode, and the wetting angle theta of the gradient boron-doped diamond electrode is less than 40 degrees; the electrode working layer of the gradient boron-doped diamond electrode is a gradient boron-doped diamond layer; the gradient boron-doped diamond layer sequentially comprises a gradient boron-doped diamond bottom layer, a gradient boron-doped diamond middle layer and a gradient boron-doped diamond top layer, wherein the boron content of the gradient boron-doped diamond bottom layer is increased in a gradient manner;
in the gradient boron-doped diamond bottom layer, the B/C is 3333-33333 ppm according to the atomic ratio; preferably 3333 to 10000ppm; in the gradient boron-doped diamond middle layer, the B/C is 10000-33333 ppm by atomic ratio; preferably 13332-20000 ppm; in the gradient boron-doped diamond top layer, the B/C is 16666-50000 ppm according to the atomic ratio; preferably from 26664 to 50000ppm.
The degradation mechanism of the electrochemical oxidative degradation module is generally divided into two ways, namely direct oxidation of organic pollutants on the surface of an electrode and indirect oxidation of pollutants by active substances with strong oxidizing property (such as hydroxyl radicals, active chlorine, active sulfuric acid groups and the like) generated on the surface of the electrode, wherein the indirect oxidation is taken as the dominant way. The degradation efficiency is therefore greatly influenced by the intrinsic properties (specific surface area, sp) of the electrode material 3 /sp 2 Boron doping concentration, etc.) due to intrinsic electrode material characteristicsYield of active substance. The invention integrates the advantages of the electrode material by adopting the gradient boron-doped electrode material with high specific surface area, and can greatly improve the degradation and mineralization efficiency of the electrochemical degradation module.
In the invention, the boron doping content is gradually increased from the bottom to the top of the film, and the bottom high-adhesion layer adopts extremely low boron doping concentration to ensure the film associativity and stability, because the bottom layer is directly contacted with the electrode substrate, diamond phase nucleation is easy in the early deposition stage, defects are few, and sp is 2 The phase is less carbon. Capable of further lifting sp of the nucleation plane 3 The middle layer is used for resisting corrosion, the middle boron content (namely the boron content is higher than that of the bottom layer and lower than that of the top layer) is adopted, the sp3 phase purity (namely the diamond is compact and continuous) can be ensured due to the fact that the boron content in the middle layer is still low, and meanwhile, the conductivity of the middle layer can be ensured due to the fact that the middle layer has a certain boron doping amount. The doping content of boron in the top layer is high, so that the conductivity and the electrochemical activity of the material can be improved, the potential window of the top layer is wide, the oxygen evolution potential is high, the background current is low, and the electrocatalytic activity and the degradation efficiency of the electrode can be greatly improved by the diamond top layer; meanwhile, the hydrophilicity is improved along with the increase of the boron content, and the oxidation efficiency of the electrode in the electrochemical oxidation process can be greatly improved by the improvement of the hydrophilicity. In a word, the electrode material with high catalytic activity and long service life, which is composed of the bottom high-adhesion layer, the middle high-density corrosion-resistant layer and the top high-boron doping concentration catalyst layer, can effectively reduce the degradation efficiency and the maintenance cost in the practical application process of the system.
The invention relates to a green energy-saving photoelectrocatalysis water treatment system, wherein the thickness of a gradient boron-doped diamond layer is 5 mu m-2 mm; the thickness of the middle layer of the gradient boron-doped diamond accounts for 50% -90% of the thickness of the gradient boron-doped diamond layer; the thickness of the gradient boron-doped diamond top layer accounts for less than or equal to 40% of that of the gradient boron-doped diamond layer.
Because the gradient boron-doped diamond bottom layer, the gradient boron-doped diamond middle layer and the gradient boron-doped diamond top layer have different work division, the bottom layer and the top layer respectively play a role in lifting the substrateThe film has high binding property, high electrochemical activity (high catalytic performance) and improved hydrophilicity. Therefore, the main body part of the film material is the middle corrosion-resistant layer which plays the roles of electric conduction, corrosion resistance and the like in the service process, so the thickness of the film material needs to account for more than half of the thickness of the gradient boron-doped diamond layer, and the thickness of the top layer is controlled to account for less than or equal to 40 percent of the thickness of the gradient boron-doped diamond layer, because sp is introduced along with the increase of the boron content 2 The phase carbon (graphite phase carbon) is increased, and the invention can avoid introducing excessive sp by controlling the thickness of the top layer within 40 percent 2 And the phase carbon can improve the hydrophilicity and ensure the hydrophilicity and high catalytic activity of the material.
The invention relates to a green energy-saving photoelectrocatalysis water treatment system, wherein micropores and/or pointed cones are distributed on the surface of a gradient boron-doped diamond layer, the diameter of each micropore is 500 nm-0.5 mm, and the diameter of each pointed cone is 1 mu m-30 mu m.
The invention relates to a green energy-saving photoelectrocatalysis water treatment system.A gradient boron-doped diamond electrode directly takes a substrate as an electrode substrate; or the surface of the substrate is provided with a transition layer to be used as an electrode matrix, and then the surface of the electrode matrix is provided with a gradient boron-doped diamond layer. Wherein the gradient boron doped diamond layer is an electrode working layer.
In the present invention, there is no limitation on the choice of substrate materials, and any substrate materials reported in the prior art are suitable as the substrate of the present invention.
Preferably, the substrate material is selected from one of metal nickel, niobium, tantalum, copper, titanium, cobalt, tungsten, molybdenum, chromium, iron or one of metal alloys; or the electrode substrate material is selected from ceramics A1 2 O 3 、ZrO 2 、SiC、Si 3 N 4 、BN、B 4 C、AlN、WC、Cr 7 C 3 、Ti 2 GeC、Ti 2 AlC and Ti 2 AlN、Ti 3 SiC 2 、Ti 3 GeC 2 、Ti 3 AlC 2 、Ti 4 AlC 3 、BaPO 3 One or a doped ceramic therein; or the electrode substrate material is selected from one of the above-mentioned composite materials consisting of metal and ceramic, orThe substrate material is selected from diamond or Si.
Further preferably, the substrate material is selected from one of titanium, nickel and silicon.
The transition layer is made of at least one of titanium, tungsten, molybdenum, chromium, tantalum, platinum, silver, aluminum, copper and silicon, and the thickness of the transition layer is 50 nm-10 mu m.
Further preferably, when the substrate material is nickel, the transition layer material is titanium.
The invention relates to a green energy-saving photoelectrocatalysis water treatment system, and a preparation method of a gradient boron-doped diamond electrode comprises the following steps:
step one, pretreatment of an electrode substrate
Placing the electrode substrate in a suspension containing mixed nano-crystalline and/or micro-crystalline diamond particles; ultrasonic treatment and drying; obtaining an electrode substrate with the surface adsorbing nano-crystal and/or micro-crystal diamond;
step two, depositing a gradient boron-doped diamond layer
Placing the electrode substrate obtained in the step one in a chemical deposition furnace, sequentially carrying out three-stage deposition on the surface of the electrode substrate to obtain a gradient boron-doped diamond layer, and controlling the mass flow of carbon-containing gas accounting for 1-5% of the total gas in the furnace in the first-stage deposition process; the mass flow percentage of the boron-containing gas in the total gas in the furnace is 0.005-0.05%; controlling the mass flow percentage of the carbon-containing gas in the furnace to be 1-5% in the second-stage deposition process; the mass flow percentage of the boron-containing gas in the total gas in the furnace is 0.015-0.05%; controlling the mass flow percentage of the carbon-containing gas in the third stage of deposition process to be 1-5 percent of the total gas in the furnace; the mass flow percentage of the boron-containing gas in the total gas in the furnace is 0.025-0.075%;
step three, high temperature treatment
Carrying out heat treatment on the electrode substrate with the deposited gradient boron-doped diamond layer, wherein the heat treatment temperature is 400-1200 ℃, and the treatment time is 5-110 min; the pressure intensity in the furnace is 10 Pa-10 5 Pa。
In the actual operation process, when the substrate is directly used as an electrode base body, the substrate is firstly placed in acetone for ultrasonic treatment for 5-20 min to remove oil stains on the surface of the substrate material, then deionized water and/or absolute ethyl alcohol are used for washing the substrate material, and drying is carried out for later use.
In the first step, the mass fraction of the diamond mixed particles in the suspension containing the nano-crystalline and/or micro-crystalline diamond mixed particles is 0.01-0.05%.
In the first step, the particle size of the diamond mixed particles is 5-30 nm, and the purity is more than or equal to 97%.
In the first step, the ultrasonic treatment time is 5-30 min. And after the ultrasonic treatment is finished, taking out the electrode substrate, washing the electrode substrate by using deionized water and/or absolute ethyl alcohol, and drying the electrode substrate.
In the second step, the furnace gas comprises boron-containing gas, carbon-containing gas and hydrogen.
In the actual operation process, after the three-section deposition is finished, firstly closing the boron-containing gas and the boron-containing gas, and continuously introducing the hydrogen for a period of time to etch the graphite phase on the surface of the gradient boron-doped diamond.
The boron source can be one of solid, gas and liquid boron source, and the gasification treatment is carried out when the solid or liquid boron source is selected.
Preferably, the boron-containing gas is B 2 H 6 The carbon-containing gas is CH 4 。
In the second step; the deposition temperature of the first section is 600-1000 ℃, and the air pressure is 10 3 ～10 4 Pa, the time is 1-3 h; the temperature of the second stage deposition is 600-1000 ℃, and the air pressure is 10 3 ～10 4 Pa for 3-48 h; the temperature of the third stage deposition is 600-1000 ℃, and the air pressure is 10 3 ～10 4 Pa; the time is 1 to 12 hours.
In the third step, the heat treatment temperature is 500-800 ℃, and the treatment time is 15-40 min.
Through the doping and heat treatment of the top layer with high boron content, the oxygen evolution potential of the boron-doped diamond layer is larger than 2.3V, the potential window is larger than 3.0V, the electrocatalytic oxidation performance of the surface of the electrode is improved, and meanwhile, the electrode has excellent hydrophilicity (the wetting angle theta is smaller than 40 degrees)
The invention relates to a green energy-saving photoelectrocatalysis water treatment system, wherein a power supply is selected from one of a linearly-adjustable direct-current stabilized power supply, an intermediate-frequency power supply and a pulse power supply, preferably the linearly-adjustable direct-current stabilized power supply, the current of the linearly-adjustable direct-current stabilized power supply can be set according to data provided by a water quality online detection module by taking time as a variable and combining a linear function, a sine function or a square wave function, and energy configuration is optimized, energy consumption is reduced and current efficiency is improved by power supply modulation.
The invention relates to a green energy-saving photoelectrocatalysis water treatment system.
The solar power generation unit can be used for supplying power for electrolysis in the degradation tank, supplying power for the ultraviolet lamp tube and maintaining the power supply for the operation of the whole wastewater treatment system.
The invention relates to a green energy-saving photoelectrocatalysis water treatment system, wherein a solar heating unit is used for providing heat for a degradation tank and concentrating or evaporating and crystallizing recovered water reaching the standard to recover inorganic salt in the water.
The invention relates to a green energy-saving photoelectrocatalysis water treatment system, wherein a microorganism treatment module comprises an anaerobic organism treatment module and an aerobic organism treatment module, the aerobic organism treatment module is provided with an aeration pipeline, and strains in the anaerobic organism treatment module and the aerobic organism treatment module are fixed on an activated carbon bed.
The invention relates to a green energy-saving photoelectrocatalysis water treatment system, which further comprises a water quality online detection module and a water flow control module. The water quality on-line detection module and the water flow control module can monitor and control the whole water treatment system in real time, parameters measurable by the water quality on-line detection system comprise temperature, pH, dissolved oxygen, conductivity, chemical oxygen demand, biological oxygen demand, ammonia nitrogen, total organic carbon and the like, water quality change is tracked in time, and functions of early warning, forecasting and feedback decision making are realized.
The invention relates to a green energy-saving photoelectrocatalysis water treatment system, which also comprises a gas control module, wherein the gas control module consists of a gas injection unit and a gas collection unit, the gas injection unit is used for introducing aeration to an aerobic biological treatment module, and the gas collection unit is used for tail gas collection and treatment.
The invention relates to a method for treating water by using an environment-friendly energy-saving photoelectrocatalysis water treatment system.
The invention relates to a method for treating water by a green energy-saving photoelectrocatalysis water treatment system, which comprises the following steps: the water to be treated firstly enters a liquid storage tank, is filtered by a particle filter plate in the liquid storage tank, enters a degradation tank after being filtered, is subjected to photoelectrocatalysis oxidation treatment, enters a microorganism treatment module after being subjected to photoelectrocatalysis oxidation treatment, and is sequentially subjected to anaerobic biological treatment and aerobic biological treatment, namely the water reaching the standard is discharged or recycled; in the aerobic biological treatment process, aerating is introduced into the aerobic biological treatment module by the gas injection unit; COD in the supernatant is less than or equal to 2000mg/L;
in the photoelectrocatalysis oxidation treatment process, the temperature of the water body in the degradation tank is controlled to be 5-80 ℃ through the intelligent temperature control module, the anode is irradiated by an ultraviolet lamp, and the irradiation intensity of the ultraviolet lamp is 20-100MJ m -2 。
Advantageous effects
1) The method obviously improves the removal rate of organic pollutants and reduces the electrolysis energy consumption by organically combining photocatalytic oxidation and electrochemical oxidation, has mild reaction conditions, is environment-friendly, is simple to operate, and is suitable for water bodies under various water quality conditions.
2) The photocatalyst used in the invention is TiO with non-toxicity, low cost and strong acid and alkali corrosion resistance 2 And the catalyst is loaded on the currently known most ideal electrochemical oxidation anode BDD, so that the problems that the traditional suspended photocatalyst is difficult to recycle and the particle-loaded nano TiO is difficult to recycle are solved 2 Easily fall off, etc., toAnd the boron-doped diamond electrode with high order and large specific surface area is used as a load matrix of the photoelectric catalyst, so that the degradation of organic pollutants by the photoelectric catalytic synergistic effect is effectively utilized.
3) According to the invention, green renewable solar energy is fully utilized through the solar energy-electricity-heat intelligent conversion system, solar energy is efficiently utilized for power generation and heat supply, the solar energy is converted into electric energy, and the electric energy is utilized for performing photoelectric degradation on organic wastewater and maintaining the electricity consumption of the water treatment system in operation; the solar energy is converted into heat energy, the temperature of the photoelectric degradation tank can be controlled through the phase change energy storage material, and the waste heat can also be used for concentrating water reaching the standard or evaporating, crystallizing and recovering inorganic salt in the water reaching the standard. The solar energy is fully utilized, the maximum utilization of the solar energy is realized, and the solar energy-saving device is green, energy-saving, environment-friendly and efficient, and can possibly generate great social benefit and economic benefit.
Drawings
FIG. 1 is a schematic structural diagram of a green energy-saving high-efficiency photoelectrocatalysis water treatment system of the invention; in the figure: 1. a liquid storage tank; 2. a particle filter plate; 3. a pipeline; 4. a degradation tank; 5. an anode; 6. a cathode; 7. a photocatalyst; 8. an ultraviolet lamp; 9. a stirring device; 10. a power source; 11. a microbial treatment module; 12. a solar energy photo-electricity-heat intelligent conversion module; 13. a water quality online detection module; 14. a gas control module; 15. and a water flow control module.
Detailed Description
As shown in fig. 1, the green energy-saving high-efficiency photoelectrocatalysis organic wastewater treatment system comprises a liquid storage tank 1 and a degradation tank 4; the outlet of the liquid storage tank 1 is provided with a particle filter plate 2 and is connected to a degradation tank 4 through a pipeline 3, and the outlet of the degradation tank 4 is connected to a microorganism treatment module 11 (an anaerobic organism treatment module and an aerobic organism treatment module);
the particle filter plate 2 is selected from Maifanitum filter plate, activated carbon filter plate, quartz sand filter plate, PP cotton filter plate, and microporous foam ceramic plate with porosity of more than 35PPI (Al) 2 O 3 、ZrO 2 SiC foam ceramic). The degradation tank 4 contains a plurality of treatment units (only 1 treatment unit is shown in the figure); any one of the processing unitsComprises an anode 5 and a cathode 6, wherein the anode 5 is formed by loading TiO on a boron-doped diamond film 2 Or doped modified TiO 2 Photocatalyst 7 (TiO) 2 BDD), the cathode 6 can be graphite, stainless steel, titanium or other base metal materials, the distance between the anode and the cathode is 5-50mm, and the current density is controlled at 50mA cm -2 The following; an ultraviolet lamp 8 is arranged on the anode 5, the light can be generated by sunlight or an ultraviolet lamp, the ultraviolet lamp directly irradiates the anode, and the irradiation intensity of the ultraviolet lamp group is 20-100MJ m -2 (ii) a The anode 5 and the cathode 6 are connected with a power supply 10 through leads, the power supply is selected from one of a linearly-adjustable direct-current stabilized power supply, an intermediate-frequency power supply and a pulse power supply, preferably the linearly-adjustable direct-current stabilized power supply, the current can be combined and configured according to a linear function, a sine function or a square wave function by taking time as a variable according to data provided by the water quality online detection module; the power supply 10 is connected with a solar energy photoelectric-thermal intelligent conversion module 12, the solar energy photoelectric-thermal intelligent conversion module comprises a photovoltaic power generation unit and a photovoltaic heating unit, and can realize the intelligent conversion between light, electricity and heat, the photovoltaic power generation unit comprises a solar cell panel, a controller and an inverter, and can be used for supplying power for electrolysis in a degradation tank, supplying power for an ultraviolet lamp tube and supplying power for maintaining the operation of the whole water treatment system, and the photovoltaic heating unit can be used for supplying heat to the degradation tank and also can be used for concentrating or evaporating and crystallizing the water reaching the standard to recover inorganic salts in the water reaching the standard; the degradation tank 4 is connected with an anaerobic and aerobic process module 11 through a pipeline, the anaerobic and aerobic process module contains high-efficiency activated sludge and high-activity strains, and COD passing through the degradation tank is reduced to 2000mg L -1 The following organic waste water is firstly treated by anaerobic organisms and then enters aerobic organisms, the aerobic fluidized bed is provided with a corresponding aeration device, all organic matter degradation organism bacterial colonies are fixed on an activated carbon bed, and the organic waste water after reaching the standard through biochemical treatment can be directly discharged or can be recycled subsequently. In addition, the invention is also provided with a water quality online detection module 13 and a gas control module 14; the water flow control module 14, wherein the water quality on-line detection module and the water flow control module can perform real-time monitoring and control on the whole water treatment system, and the measurable parameters of the water quality on-line detection system compriseTemperature, pH, dissolved oxygen, conductivity, chemical oxygen demand, biological oxygen demand, ammonia nitrogen and total organic carbon etc. in time track the quality of water change, realize the function of early warning forecast and feedback decision-making, water flow control module is located reservoir 1, degradation tank 4 and other delivery ports and pipelines for the water flow of detection pipeline and delivery port, gas control module 14 constitute by gas injection unit and gas collection unit, gas injection unit be used for letting in the aeration to aerobic biological treatment module, gas collection unit is used for tail gas collection and processing.
Example 1
In this example 1, the anode is a boron-doped diamond electrode (BDD electrode), the cathode is a graphite electrode, and the preparation method of the boron-doped diamond electrode is as follows:
1.1 pretreatment of the substrate Material
Firstly, taking cylindrical foam Ti as a substrate, and polishing the cylindrical foam Ti by using 600#, 800#, 1000# metallographic abrasive paper; the polished foamed Ti substrate was then immersed in acetone (CH) 3 COCH 3 ) Anhydrous ethanol (C) 2 H 5 OH) ultrasonic oscillation for 10min; and then placing the Ti substrate in the nano-diamond suspension, and planting seed crystals for 30min by ultrasonic to enhance the nucleation effect. Finally, washing with deionized ultrapure water and drying for later use.
1.2BDD thin film deposition
(1) As used herein, a hot wire is
The straight tungsten wire is completely covered above the substrate, then the pretreated substrate is placed in a HFCVD equipment cavity, and the hot wire-substrate distance (10 mm) is adjusted. After the installation is finished, the cabin door is closed, the cabin door is vacuumized, and then hydrogen, methane and borane (diborane used for the experiment is B) are introduced according to the concentration ratio of the air source set by the experiment 2 H 6 :H 2 =5, 95) and when the reaction gas sources are uniformly mixed, closing the air extraction valve, and adjusting the fine adjustment valve to adjust the air pressure in the cavity to be the set pressure. Then turning on the power supply to regulate current, heating the hot wire to a set temperature, and observing the air pressure in the deposition chamber if necessaryAnd the change needs to be continuously adjusted by a fine adjustment valve, and finally, the boron-doped diamond film is deposited. After the deposition is finished, the temperature of the deposition chamber is regulated and controlled by regulating the current to reduce the temperature, and CH is required to be closed at the moment 4 And B 2 H 6 Using only H 2 To etch the graphite phase of the diamond surface. The BDD electrode material deposition parameters used in this example were three deposition runs: the first stage gas flow rate ratio is H 2 :B 2 H 6 :CH 4 = 97sccm. Second stage gas flow ratio H 2 :B 2 H 6 :CH 4 = 97sccm. Third stage gas flow Rate H 2 :B 2 H 6 :CH 4 =97sccm, 1.0sccm, deposition pressure of 2kPa, deposition time of 12h, and deposition temperature of 850 ℃. Stopping introducing borane and methane after the deposition is finished, etching with hydrogen at 850 ℃ for 30min to remove a graphite phase formed on the surface, cooling with the furnace, taking out, cleaning the surface with absolute ethyl alcohol, and then placing into the furnace to continuously deposit the other surface according to the operation;
high temperature oxidation treatment of 1.3BDD films
The BDD electrode material obtained after deposition was placed in a crucible. Setting a temperature rise program of the tube furnace, wherein the temperature rise rate is 10 ℃/min, the atmosphere is air, the temperature is raised to 800 ℃, and the temperature is kept for 35 min. Pushing the crucible containing the BDD material into the resistance heating area, starting timing, enabling the processing time to reach 30 minutes, pushing the crucible to the outer side of the tube furnace, and cooling at room temperature to obtain a BDD electrode finished product. The wetting angle of the BDD electrode was 36.52 °.
The system is used for treating garbage percolate at a certain position of Nanjing, 1L of water sample is treated, a water sample firstly enters a liquid storage tank, then is filtered by a particle filter plate in the liquid storage tank and then enters a degradation tank, wherein the particle filter plate is selected from a quartz sand filter plate, the wall of the degradation tank contains medium paraffin (phase change material), the temperature of water in the degradation tank is controlled to be 40 ℃, two groups of counter electrodes are arranged in the degradation tank, the distance between every two groups of electrodes is 10mm, and the current density is 50mA cm -2 The power supply is a linear adjustable DC stabilized power supply, and the light intensity of the ultraviolet lamp is 50MJ m -2 (ii) a With TiO as a carrier 2 Is a photocatalyst, the size of the catalyst is 0.2-2 μm; after the wastewater is treated in a degradation tank for 48 hours at a stirring speed of 500r/min, detecting that TOC of a water body in the degradation tank is reduced from 3582mg/L to 1899mg/L, COD value is reduced from 20071mg/L to 1624mg/L and the color of the water is changed from dark brown to close to clarification by a water quality online module; then the degraded water passes through the anaerobic biological treatment module and the aerobic biological treatment module in sequence to obtain the water which reaches the standard and is discharged outside. The standard reaching water meets the first level discharge standard requirement (COD is less than or equal to 100 mg/L) in the integrated wastewater discharge standard.
Example 2
The other conditions were the same as in example 1 except that the photocatalyst was changed to Au-doped TiO 2 After the treatment is carried out for 48 hours at the stirring speed of 500r/min, the TOC of the water in the degradation tank is reduced from 3582mg/L to 1269mg/L, the COD value is reduced from 20071mg/L to 1138mg/L, and the color of the water is changed from dark brown to clear through the detection of a water quality on-line module.
Comparative example 1
The other conditions are the same as the example 1, only a stirring device is not arranged in the degradation tank, after 48 hours of treatment, the TOC of the water in the degradation tank is detected to be reduced from 3582mg/L to 2122mg/L by a water quality on-line module, the COD value is reduced from 20071mg/L to 5346mg/L, and the water color is changed from dark brown to transparent light brown.
Comparative example 2
The other conditions are the same as the example 1, only the degradation tank changes the ultraviolet lamp into sunlight irradiation, after 48 hours of treatment at the stirring speed of 500r/min, the TOC of the water body in the degradation tank is reduced from 3582mg/L to 2063mg/L, the COD value is reduced from 20071mg/L to 3095mg/L, and the water color is changed from dark brown to nearly clear through the detection of a water quality online module.
Example 3
When the system is used for treating the actual chemical pharmaceutical wastewater, the water composition is complex and contains antibiotic residues, antibiotic intermediates, unreacted raw materials, organic solvents and the like. Treating 1L of water sample, feeding the water sample into a liquid storage tank, filtering the water sample by a particle filter plate in the liquid storage tank, and feeding the water sample into a degradation tank, wherein the particles pass throughThe filter plate is selected from a PP cotton filter plate, the wall of the degradation tank contains medium paraffin (phase change material), the temperature of water in the degradation tank is 45 ℃, 3 pairs of electrodes are arranged in the degradation tank, wherein an anode 5 adopts a boron-doped diamond electrode (BDD electrode), and a cathode 6 adopts a graphite electrode; the distance between every two electrodes is 10mm, and the current density is 50mA cm -2 The light intensity of the ultraviolet lamp is 50MJ m -2 (ii) a With TiO 2 Is a photocatalyst, the size of the catalyst is 0.2-2 μm; after 48 hours of treatment at a stirring speed of 500r/min, the TOC of the water in the degradation tank is reduced from 6113mg/L to 852mg/L, the COD value is reduced from 22334mg/L to 1998mg/L, and the color of the water is changed from dark brown to nearly colorless through the detection of a water quality on-line module.
Example 4
The other conditions were the same as in example 3 except that the photocatalyst was changed to Au-doped TiO 2 After the wastewater is treated for 48 hours at a stirring speed of 500r/min, the TOC of the water in the degradation tank is reduced from 6113mg/L to 237mg/L, the COD value is reduced from 22334mg/L to 1226mg/L, and the color of the water is changed from dark brown to clear through the detection of an online water quality module.
Comparative example 3
The TOC of the treated mixture was reduced from 6113mg/L to 2256mg/L, the COD of the treated mixture was reduced from 22334mg/L to 3367mg/L, and the color of the water was changed from dark brown to transparent light brown, all the conditions being the same as in example 1, except that no stirring device was provided.
Comparative example 4
The other conditions are the same as the example 1, except that the ultraviolet lamp is changed into sunlight irradiation, after 48 hours of treatment at the stirring speed of 500r/min, the TOC of the water body in the degradation tank is reduced from 6113mg/L to 1965mg/L, the COD value is reduced from 22334mg/L to 2463mg/L, and the color of the water is changed from dark brown to nearly clear through the online detection of the water quality module.
Claims (6)
1. The utility model provides a green energy-conserving photoelectrocatalysis water treatment system which characterized in that: the device comprises a liquid storage tank, a particle filter plate, a degradation tank, a microorganism treatment module, an intelligent temperature control module and a solar photo-electricity-heat intelligent conversion module; the outlet of the liquid storage tank is provided with a particle filter plate and is connected to the degradation tank through a pipeline, and the outlet of the degradation tank is connected to the microbial treatment module;
the intelligent temperature control module is used for controlling the temperature of water in the degradation tank to be 5-80 ℃;
the solar energy light-electricity-heat intelligent conversion module comprises a solar power generation unit and a solar heating unit;
the degradation tank comprises a plurality of treatment units, and any one treatment unit comprises an anode, a cathode and a stirring device; the anode is a boron-doped diamond electrode loaded with a photocatalyst, the anode and the cathode are connected with a power supply through leads, and the power supply is connected with a solar power generation unit;
the degradation tank also comprises a plurality of ultraviolet lamps, and the ultraviolet lamps directly irradiate the anode;
the boron doped diamond electrode is a gradient boron doped diamond electrode having a wetting angle θ <40 °; the electrode working layer of the gradient boron-doped diamond electrode is a gradient boron-doped diamond layer; the gradient boron-doped diamond layer sequentially comprises a gradient boron-doped diamond bottom layer, a gradient boron-doped diamond middle layer and a gradient boron-doped diamond top layer, wherein the boron content of the gradient boron-doped diamond bottom layer is increased in a gradient manner;
in the gradient boron-doped diamond bottom layer, the B/C ratio is 3333 to 33333ppm in terms of atomic ratio; in the gradient boron-doped diamond middle layer, B/C is 10000 to 33333ppm in terms of atomic ratio; in the gradient boron-doped diamond top layer, the B/C ratio is 16666 to 50000ppm according to the atomic ratio;
the thickness of the gradient boron-doped diamond layer is 5 micrometers-2 mm; the thickness of the gradient boron-doped diamond middle layer accounts for 50% -90% of that of the gradient boron-doped diamond layer; the thickness of the gradient boron-doped diamond top layer accounts for less than or equal to 40% of that of the gradient boron-doped diamond layer;
the gradient boron-doped diamond electrode directly takes a substrate as an electrode base body; or arranging a transition layer on the surface of the substrate to serve as an electrode matrix, and arranging a gradient boron-doped diamond layer on the surface of the electrode matrix;
the preparation method of the gradient boron-doped diamond electrode comprises the following steps:
step one, pretreatment of an electrode substrate
Placing the electrode substrate in a suspension containing mixed nano-crystalline and/or micro-crystalline diamond particles; ultrasonic treatment and drying; obtaining an electrode substrate with the surface adsorbing nano-crystal and/or micro-crystal diamond;
step two, depositing a gradient boron-doped diamond layer
Placing the electrode substrate obtained in the step one in a chemical deposition furnace, sequentially performing three-stage deposition on the surface of the electrode substrate to obtain a gradient boron-doped diamond layer, and controlling the mass flow of carbon-containing gas accounting for 1% -5% of the total gas in the furnace in the first-stage deposition process; the mass flow percentage of the boron-containing gas in the total gas in the furnace is 0.005% -0.05%; controlling the mass flow percentage of the carbon-containing gas in the second-stage deposition process to be 1-5% of the total gas in the furnace; the mass flow percentage of the boron-containing gas in the total gas in the furnace is 0.015-0.05%; controlling the mass flow percentage of the carbon-containing gas in the third-stage deposition process to be 1-5% of the total gas in the furnace; the mass flow percentage of the boron-containing gas in the total gas in the furnace is 0.025-0.075%;
step three, high temperature treatment
Carrying out heat treatment on the electrode substrate on which the gradient boron-doped diamond layer is deposited, wherein the heat treatment temperature is 400-1200 ℃, and the treatment time is 5-110min; the pressure in the furnace is from 10Pa to 10Pa 5 Pa；
In the first step, in the suspension containing the nanocrystalline and/or microcrystalline diamond mixed particles, the mass fraction of the diamond mixed particles is 0.01-0.05%; in the first step, the particle size of the diamond mixed particles is 5 to 30nm, the purity is more than or equal to 97 percent,
in the first step, the ultrasonic treatment time is 5-30 min;
in the second step, the furnace gas comprises boron-containing gas, carbon-containing gas and hydrogen;
in the second step; the deposition temperature of the first stage is 600 to 1000 ℃, and the air pressure is 10 3 ~10 4 Pa, the time is 1 to 3h; the temperature of the second-stage deposition is 600 to 1000 ℃, and the air pressure is 10 3 ~10 4 Pa, the time is 3 to 48h; the temperature of the third stage deposition is 600 to 1000 ℃, and the air pressure is 10 3 ~10 4 Pa; the time is 1 to 12h;
in the third step, the heat treatment temperature is 500 to 800 ℃, and the heat treatment time is 15 to 40min.
2. The green energy-saving photoelectrocatalysis water treatment system according to claim 1, wherein: the wall of the degradation tank contains phase-change materials.
3. The green energy-saving photoelectrocatalysis water treatment system according to claim 1, wherein: the anode and the cathode are formed by matching one or more groups of plate electrodes which are parallel to each other but not in contact with each other, or formed by matching cylindrical electrodes and cylindrical electrodes which are coaxial in the center but not in contact with each other, or formed by matching two groups of coaxial cylindrical electrode arrays with different diameters, or formed by matching a honeycomb briquette structure and a cylindrical array, or formed by matching a three-dimensional continuous network structure and a two-dimensional continuous network structure, or formed by matching a two-dimensional closed plate structure and a two-dimensional continuous network structure;
the cathode is selected from one of graphite, stainless steel and titanium electrodes;
the electrode working layer of the boron-doped diamond electrode is a boron-doped diamond layer with micropores and/or pointed cones distributed on the surface.
4. The green energy-saving photoelectrocatalysis water treatment system according to claim 1, wherein:
the photocatalyst comprises TiO 2 Preferably, the photocatalyst is doped modified TiO 2 The doping modification is selected from one of metal ion doping, metal doping, nonmetal doping, metal-nonmetal co-doping and semiconductor compounding.
5. The green energy-saving photoelectrocatalysis water treatment system according to claim 1, which is characterized in that:
the power supply is selected from one of a linearly-adjustable direct-current stabilized power supply, an intermediate-frequency power supply and a pulse power supply, and preferably is a linearly-adjustable direct-current stabilized power supply;
the solar power generation unit comprises a solar panel, a controller and an inverter;
the solar heating unit is used for providing heat for the degradation tank and concentrating or evaporating and crystallizing the recovered water reaching the standard to recover inorganic salt in the water.
6. The green energy-saving photoelectrocatalysis water treatment system according to claim 1, which is characterized in that:
the microorganism treatment module comprises an anaerobic organism treatment module and an aerobic organism treatment module, the aerobic organism treatment module is provided with an aeration pipeline, and strains in the anaerobic organism treatment module and the aerobic organism treatment module are fixed on the activated carbon bed;
the water treatment system also comprises a water quality online detection module and a water flow control module;
the water treatment system also comprises a gas control module, wherein the gas control module consists of a gas injection unit and a gas collection unit, the gas injection unit is used for introducing aeration to the aerobic biological treatment module, and the gas collection unit is used for collecting and treating tail gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010390583.9A CN111646632B (en) | 2020-05-11 | 2020-05-11 | Green energy-saving photoelectrocatalysis water treatment system and water treatment method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010390583.9A CN111646632B (en) | 2020-05-11 | 2020-05-11 | Green energy-saving photoelectrocatalysis water treatment system and water treatment method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111646632A CN111646632A (en) | 2020-09-11 |
| CN111646632B true CN111646632B (en) | 2022-11-04 |
Family
ID=72352262
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010390583.9A Active CN111646632B (en) | 2020-05-11 | 2020-05-11 | Green energy-saving photoelectrocatalysis water treatment system and water treatment method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111646632B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113024040A (en) * | 2021-03-19 | 2021-06-25 | 哈尔滨工业大学 | Green photoelectric wastewater treatment device and method using sunlight as driving force |
| CN113003670A (en) * | 2021-04-08 | 2021-06-22 | 南京环保产业创新中心有限公司 | Safe and efficient electrochemical wastewater treatment device and method |
| CN113149153A (en) * | 2021-05-13 | 2021-07-23 | 中国十七冶集团有限公司 | Building site drinking water treatment facilities |
| CN114349147A (en) * | 2021-12-15 | 2022-04-15 | 北京博纳晶科科技有限公司 | Advanced oxidation treatment method and equipment for phosphorus-containing flame retardant wastewater |
| CN115007598A (en) * | 2022-05-10 | 2022-09-06 | 嘉兴市绿能环保科技有限公司 | Kitchen waste pretreatment method |
| CN115572012A (en) * | 2022-10-21 | 2023-01-06 | 广西博世科环保科技股份有限公司 | Treatment equipment and method for full-scale treatment of landfill leachate |
| CN115594355B (en) * | 2022-10-31 | 2023-08-29 | 江西科技师范大学 | In-situ pollutant degradation photoelectrocatalysis water purification treatment system and method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010022689A1 (en) * | 2008-08-29 | 2010-03-04 | Institute Of Physics As Cr, V. V. I. | Method of doping diamond using charge transfer from organic dyes |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8591856B2 (en) * | 1998-05-15 | 2013-11-26 | SCIO Diamond Technology Corporation | Single crystal diamond electrochemical electrode |
| US20090314711A1 (en) * | 2008-02-11 | 2009-12-24 | Barry Terence P | PHOTOELECTROCATALYTIC OXIDIZER DEVICE HAVING COMPOSITE NANOPOROUS TiO2 COATED Ti PHOTOANODE AND METHOD OF REMOVING AMMONIA FROM WATER IN AQUARIA AND RECIRCULATION AQUACULTURE SYSTEMS |
| CN101555082B (en) * | 2008-04-09 | 2011-05-25 | 中国科学院理化技术研究所 | Wastewater treatment method and device combining electrochemical degradation and photocatalysis oxidation technologies |
| SI23987A (en) * | 2012-02-01 | 2013-08-30 | ENVIT, okoljske tehnologije in inženiring d.o.o. | Mass occurence prevention of harmful cyanobacteria |
| CN102603037A (en) * | 2012-04-01 | 2012-07-25 | 南京工业大学 | Organic wastewater treatment film reactor utilizing sunlight-assisted electro-catalysis |
| CN104047019A (en) * | 2013-03-11 | 2014-09-17 | 同济大学 | Artificial antibody type titanium dioxide (TiO2)/ boron-doped diamond (BDD) membrane electrode and preparation method thereof |
| CN103643219A (en) * | 2013-11-29 | 2014-03-19 | 吉林大学 | Preparation method of boron-doped diamond film electrode taking porous titanium as matrix |
| SG11201809429YA (en) * | 2016-05-06 | 2018-11-29 | Nat Univ Singapore | A photoelectrochemical cell for wastewater treatment and method of fabricating the photoelectrochemical cell |
| CN110526344A (en) * | 2019-09-24 | 2019-12-03 | 河南省功能金刚石研究院有限公司 | Landscape water pollution controlling device |
-
2020
- 2020-05-11 CN CN202010390583.9A patent/CN111646632B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010022689A1 (en) * | 2008-08-29 | 2010-03-04 | Institute Of Physics As Cr, V. V. I. | Method of doping diamond using charge transfer from organic dyes |
Non-Patent Citations (1)
| Title |
|---|
| 高导热金刚石/铜电子封装材料:制备技术、性能影响因素、界面结合改善方法;赵龙等;《材料导报》;20180610(第11期);全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111646632A (en) | 2020-09-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111646632B (en) | Green energy-saving photoelectrocatalysis water treatment system and water treatment method thereof | |
| CN111646634B (en) | Ultrasonic coupling photoelectric Fenton activated persulfate water treatment system and water treatment method | |
| CN104505529B (en) | The collaborative environmental microbiological fuel cell of phycomycete and the method utilizing its water purification to produce electricity | |
| CN111646611B (en) | Ultrasonic ozone coupling photoelectrocatalysis water treatment system and water treatment method | |
| WO2020215846A1 (en) | Biofilm electrochemical reactor for simultaneously removing nitrate nitrogen and trace organic matters in water | |
| CN101831462B (en) | Anaerobic-fermentation hydrogen production method by pretreating and electrochemically strengthening sludge | |
| CN103241910B (en) | Treatment method of tobacco sheet production wastewater | |
| Keruthiga et al. | Sugar industry waste-derived anode for enhanced biohydrogen production from rice mill wastewater using artificial photo-assisted microbial electrolysis cell | |
| CN101591769A (en) | A kind of C, the co-doped nano TiO that N content is adjustable 2The preparation method of film | |
| CN109928584B (en) | Method for simultaneously removing nitric acid nitrogen and trace organic matters in water | |
| CN111675417B (en) | Magnetic adsorption assisted photoelectrocatalysis oxidation water treatment system and water treatment method | |
| CN103241912B (en) | Method for processing waste water generated in production of tobacco sheet | |
| CN103241909B (en) | Process device for waste water generated in tobacco sheet production | |
| CN109395759B (en) | Fe with core-shell structure3C nano particle and preparation method and application thereof | |
| CN111635067B (en) | Ultraviolet-assisted ultrasonic coupling electrocatalytic oxidation water treatment system and water treatment method | |
| CN111646633B (en) | Efficient energy-saving three-dimensional electrode organic water treatment system and water treatment method thereof | |
| Pouramini et al. | Enhancing PFC ability to dye removal and power generation simultaneously via conductive spheres in the anodic chamber | |
| CN106745676A (en) | A kind of ecological many negative electrode urine processing devices and method | |
| Bosu et al. | Influence of nanomaterials in biohydrogen production through photo fermentation and photolysis-Review on applications and mechanism | |
| CN103241911B (en) | Treatment device for tobacco sheet production wastewater | |
| CN113019417A (en) | B-doped g-C3N4/BiVO4Photocatalyst and preparation and application thereof | |
| TWI520427B (en) | Microbial fuel cell with calcined zinc oxide photocatalyst | |
| CN209537276U (en) | A kind of photoelectrocatalysis microorganism electrolysis cell device | |
| CN111825271B (en) | Solar electricity-biology energy-saving water treatment system and water treatment method | |
| CN207800767U (en) | A kind of microbiological fuel cell electricity production hydrogen generating system |
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 |