CN115722251B - Preparation method and application of heteroatom doped algae-based biochar loaded nano zero-valent metal catalyst - Google Patents
Preparation method and application of heteroatom doped algae-based biochar loaded nano zero-valent metal catalyst Download PDFInfo
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- CN115722251B CN115722251B CN202211598201.7A CN202211598201A CN115722251B CN 115722251 B CN115722251 B CN 115722251B CN 202211598201 A CN202211598201 A CN 202211598201A CN 115722251 B CN115722251 B CN 115722251B
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- 241000195493 Cryptophyta Species 0.000 title claims abstract description 87
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 55
- 239000002184 metal Substances 0.000 title claims abstract description 53
- 239000003054 catalyst Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 125000005842 heteroatom Chemical group 0.000 title claims description 15
- 239000002351 wastewater Substances 0.000 claims abstract description 14
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 11
- 239000011574 phosphorus Substances 0.000 claims abstract description 11
- 150000002902 organometallic compounds Chemical class 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 86
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 41
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 33
- 239000012498 ultrapure water Substances 0.000 claims description 33
- 238000005406 washing Methods 0.000 claims description 28
- 239000007787 solid Substances 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 25
- 239000000843 powder Substances 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000001291 vacuum drying Methods 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000002791 soaking Methods 0.000 claims description 13
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 239000011591 potassium Substances 0.000 claims description 10
- 229910052700 potassium Inorganic materials 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 10
- 239000012279 sodium borohydride Substances 0.000 claims description 10
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 10
- 238000004140 cleaning Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 9
- 238000003828 vacuum filtration Methods 0.000 claims description 9
- 235000019441 ethanol Nutrition 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 238000007873 sieving Methods 0.000 claims description 8
- 238000004729 solvothermal method Methods 0.000 claims description 8
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 7
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 7
- 230000007935 neutral effect Effects 0.000 claims description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- 241001122767 Theaceae Species 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 150000008442 polyphenolic compounds Chemical class 0.000 claims description 6
- 235000013824 polyphenols Nutrition 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 238000000197 pyrolysis Methods 0.000 claims description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- GJYJYFHBOBUTBY-UHFFFAOYSA-N alpha-camphorene Chemical compound CC(C)=CCCC(=C)C1CCC(CCC=C(C)C)=CC1 GJYJYFHBOBUTBY-UHFFFAOYSA-N 0.000 claims description 4
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 3
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- 238000003763 carbonization Methods 0.000 claims description 3
- 229910001381 magnesium hypophosphite Inorganic materials 0.000 claims description 3
- SEQVSYFEKVIYCP-UHFFFAOYSA-L magnesium hypophosphite Chemical compound [Mg+2].[O-]P=O.[O-]P=O SEQVSYFEKVIYCP-UHFFFAOYSA-L 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- 229910001380 potassium hypophosphite Inorganic materials 0.000 claims description 3
- CRGPNLUFHHUKCM-UHFFFAOYSA-M potassium phosphinate Chemical compound [K+].[O-]P=O CRGPNLUFHHUKCM-UHFFFAOYSA-M 0.000 claims description 3
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 3
- WYXIGTJNYDDFFH-UHFFFAOYSA-Q triazanium;borate Chemical compound [NH4+].[NH4+].[NH4+].[O-]B([O-])[O-] WYXIGTJNYDDFFH-UHFFFAOYSA-Q 0.000 claims description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- 150000000703 Cerium Chemical class 0.000 claims description 2
- FFEARJCKVFRZRR-UHFFFAOYSA-N L-Methionine Natural products CSCCC(N)C(O)=O FFEARJCKVFRZRR-UHFFFAOYSA-N 0.000 claims description 2
- 239000004201 L-cysteine Substances 0.000 claims description 2
- 235000013878 L-cysteine Nutrition 0.000 claims description 2
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 claims description 2
- 229930195722 L-methionine Natural products 0.000 claims description 2
- 239000012448 Lithium borohydride Substances 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 2
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- RJTANRZEWTUVMA-UHFFFAOYSA-N boron;n-methylmethanamine Chemical compound [B].CNC RJTANRZEWTUVMA-UHFFFAOYSA-N 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 150000001868 cobalt Chemical class 0.000 claims description 2
- 150000001879 copper Chemical class 0.000 claims description 2
- 238000011010 flushing procedure Methods 0.000 claims description 2
- BRWIZMBXBAOCCF-UHFFFAOYSA-N hydrazinecarbothioamide Chemical compound NNC(N)=S BRWIZMBXBAOCCF-UHFFFAOYSA-N 0.000 claims description 2
- 229960004452 methionine Drugs 0.000 claims description 2
- 150000002751 molybdenum Chemical class 0.000 claims description 2
- 150000002815 nickel Chemical class 0.000 claims description 2
- 150000002978 peroxides Chemical class 0.000 claims description 2
- 239000012286 potassium permanganate Substances 0.000 claims description 2
- KOUKXHPPRFNWPP-UHFFFAOYSA-N pyrazine-2,5-dicarboxylic acid;hydrate Chemical compound O.OC(=O)C1=CN=C(C(O)=O)C=N1 KOUKXHPPRFNWPP-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 150000003751 zinc Chemical class 0.000 claims description 2
- 241000195649 Chlorella <Chlorellales> Species 0.000 description 19
- 238000000967 suction filtration Methods 0.000 description 19
- 238000001914 filtration Methods 0.000 description 17
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000003344 environmental pollutant Substances 0.000 description 13
- 231100000719 pollutant Toxicity 0.000 description 13
- 230000000694 effects Effects 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000002131 composite material Substances 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 229910001385 heavy metal Inorganic materials 0.000 description 7
- 239000010842 industrial wastewater Substances 0.000 description 7
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 7
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 6
- GDFCWFBWQUEQIJ-UHFFFAOYSA-N [B].[P] Chemical compound [B].[P] GDFCWFBWQUEQIJ-UHFFFAOYSA-N 0.000 description 6
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 229910000159 nickel phosphate Inorganic materials 0.000 description 6
- JOCJYBPHESYFOK-UHFFFAOYSA-K nickel(3+);phosphate Chemical compound [Ni+3].[O-]P([O-])([O-])=O JOCJYBPHESYFOK-UHFFFAOYSA-K 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000003723 Smelting Methods 0.000 description 5
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- 238000010298 pulverizing process Methods 0.000 description 5
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- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 241000894007 species Species 0.000 description 4
- 229910052684 Cerium Inorganic materials 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- -1 sulfate radicals Chemical class 0.000 description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- ZFBUHAMJIRQEOU-UHFFFAOYSA-N [Ce++].[O-][N+]([O-])=O.[O-][N+]([O-])=O Chemical compound [Ce++].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZFBUHAMJIRQEOU-UHFFFAOYSA-N 0.000 description 2
- QCJQWJKKTGJDCM-UHFFFAOYSA-N [P].[S] Chemical compound [P].[S] QCJQWJKKTGJDCM-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- LCFKXCNZLIBDOX-UHFFFAOYSA-L dihydrogen phosphate;nickel(2+) Chemical compound [Ni+2].OP(O)([O-])=O.OP(O)([O-])=O LCFKXCNZLIBDOX-UHFFFAOYSA-L 0.000 description 2
- 238000003958 fumigation Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 2
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
- 238000002798 spectrophotometry method Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000010407 vacuum cleaning Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 239000004343 Calcium peroxide Substances 0.000 description 1
- 241000195628 Chlorophyta Species 0.000 description 1
- 241000206751 Chrysophyceae Species 0.000 description 1
- FFEARJCKVFRZRR-SCSAIBSYSA-N D-methionine Chemical compound CSCC[C@@H](N)C(O)=O FFEARJCKVFRZRR-SCSAIBSYSA-N 0.000 description 1
- 241000199914 Dinophyceae Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 235000019402 calcium peroxide Nutrition 0.000 description 1
- LHJQIRIGXXHNLA-UHFFFAOYSA-N calcium peroxide Chemical compound [Ca+2].[O-][O-] LHJQIRIGXXHNLA-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
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- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
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- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000036284 oxygen consumption Effects 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
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- 238000005303 weighing Methods 0.000 description 1
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Abstract
The invention discloses a preparation method of an heteroatomic doped algae-based biochar loaded nano zero-valent metal catalyst, which is used for preparing the heteroatomic doped algae-based biochar, preparing the phosphorus and the heteroatomic co-doped algae-based biochar, loading nano zero-valent metal and the like to obtain the heteroatomic doped algae-based biochar loaded nano zero-valent metal catalyst, and the catalyst is applied to the treatment of heavy metal-organic compound polluted wastewater.
Description
Technical Field
The invention belongs to the technical field of nonferrous metal industrial wastewater treatment; in particular to a preparation method of a high-activity composite catalyst for efficiently treating non-ferrous metal industrial wastewater by using heteroatomic doped algae-based biochar loaded nano zero-valent metal, and a treatment method for heavy metal-organic compound polluted wastewater in the non-ferrous metal industrial wastewater by using the composite catalyst material to activate an oxidant.
Background
The pollution caused by the nonferrous metal industrial wastewater is mainly organic oxygen consumption substance pollution, inorganic solid suspended matter pollution, heavy metal pollution, petroleum pollution, alcohol pollution, acid-base pollution, heat pollution and the like. If the wastewater generated in nonferrous metal industry is directly discharged into the environment, serious pollution can be caused to water bodies or other environmental factors, the ecological environment is influenced, and resource waste can be caused. Therefore, how to efficiently and stably treat the colored industrial wastewater and recover the valuable elements from the colored industrial wastewater is obviously a problem which is urgently needed to be solved in the current colored industrial wastewater treatment.
SO produced by activating persulfate 4 - Has a higher standard reduction potential (2.5-3.1 eV) than the hydroxyl radical (.oh) generated by the conventional Fenton technique, a longer activity time (30-40 μs) and a wider pH reactivity and stability, which makes advanced oxidation techniques based on sulfate radicals widely used in the field of wastewater treatment. The nano zero-valent metal material with nano zero-valent iron, nickel and the like as representative has the advantages of environmental protection, low price, high catalytic activity, strong reducibility and the like, and is widely applied to the field of environmental remediation such as sewage treatment and the like, and is particularly used as an effective heterogeneous catalyst in the advanced oxidation technology based on sulfate radical so as to strengthen and degrade pollutants in wastewater. However, nano zero-valent metal has the problems of easy oxidation, easy agglomeration and easy loss in the water treatment process due to small particle size, high chemical activity and the like. In addition, when the nano zero-valent metal reacts with the target pollutant, most of electrons generated by the nano zero-valent metal cannot be effectively transferred to the reactive group, but are transferred to hydrogen ions or dissolved oxygen in the water phase, so that the effective electron utilization rate is reduced, and the reactivity of the nano zero-valent metal in the pollutant-containing water body and the pollutant removal efficiency are influenced.
Disclosure of Invention
Aiming at the problem that nano zero-valent metal is easy to oxidize and agglomerate in the wastewater treatment process, the invention provides the preparation method of the heteroatomic doped algae-based biochar supported nano zero-valent metal catalyst which can stably exist in the wastewater solution and has high reaction activity, low economic cost and environmental friendliness.
The preparation method of the heteroatom doped algae-based biochar loaded nano zero-valent metal catalyst comprises the following steps:
(1) Cleaning algae, drying, crushing and sieving, adding glutaraldehyde solution with volume concentration of 2.5-5%, mixing and stirring to treat 10-15, h, after solid-liquid separation, flushing the solid with ultrapure water for 4-6 times, soaking algae in ethanol solution with volume concentration of 70%, 90% and 100% in sequence, soaking 0.5-h respectively, solid-liquid separation, and drying to obtain pretreated algae;
the algae is one or more of chlorella, blue algae, diatom, green algae, golden algae and dinoflagellate;
pulverizing, sieving to obtain powder with particle diameter below 0.4 mm;
(2) Placing pretreated algae organisms into an extracting solution, performing ultrasonic dispersion at 50-70 ℃ for 0.5-1.0 h, performing solid-liquid separation, washing the solid with ultrapure water until the pH value is 9.5-10, placing the washed product into a heteroatomic precursor solution for solvothermal reaction, performing solid-liquid separation after the reaction is finished, alternately washing the solid with ultrapure water and absolute ethyl alcohol solution until the pH value is neutral, and performing vacuum drying until the constant weight is obtained to obtain heteroatomic doped algae-based biochar;
the extracting solution is prepared by mixing a sodium dodecyl sulfate solution with the mass volume concentration of 3-5% and a sodium hydroxide solution with the mass concentration of 2-4% according to the volume ratio of 1:1-3; the heteroatomic precursor is one of a nitrogen source, a boron source and a sulfur source, the concentration of the heteroatomic precursor solution is 0.3-0.9 mol/L, wherein the nitrogen source is one or more of ammonium chloride, ammonium persulfate, melamine, urea and ammonium bicarbonate; the boron source is one or more of boric acid, ammonium borate and dimethylamine borane; the sulfur source is one or more of thioacetic acid, thiourea, thiosemicarbazide, thioacetamide, L-cysteine and L-methionine; the hydrothermal reaction temperature is 180-210 ℃ and the reaction time is 3-8 h;
(3) Under inert atmosphere, mixing the heteroatomic doped algae-based biochar and hypophosphite, and then placing the mixture in a tube furnace for pyrolysis carbonization to obtain phosphorus and heteroatomic co-doped algae-based biochar;
mixing the heteroatomic doped algae-based biochar and hypophosphite according to the mass ratio of (2-4) 1, heating to 250-350 ℃ at the speed of 1-5 ℃/min, and keeping the temperature at 0.5-1 h so as to promote the gradual decomposition of the solid hypophosphite to generate phosphine gas for continuously fumigating the heteroatomic doped algae-based biochar, wherein under the atmosphere condition, the phosphine gas selectively corrodes the heteroatomic doped algae-based biochar, and the phosphine gas enters the cell wall of the biochar to occupy the vacancy; then heating to 500-800 ℃ at the speed of 6-12 ℃/min, pyrolyzing 1.5-5 h, generating phosphine gas to provide an additional phosphorus source, and uniformly doping phosphorus into the heteroatomic doped algae-based biochar in the process that mesopores appear on the surface of the heteroatomic doped algae-based biochar along with the increase of the pyrolysis temperature; the hypophosphite is one or more of sodium hypophosphite, potassium hypophosphite, ammonium hypophosphite and magnesium hypophosphite;
(4) Placing phosphorus and heteroatomic codoped algae-based biochar in 0.025-0.1 g/mL metal salt solution under nitrogen atmosphere, stirring for 0.5h, slowly dropwise adding a reducing agent solution, continuously stirring for 0.5h after dropwise adding, separating solid from liquid, sequentially vacuum-pumping, filtering and washing the solid by ultrapure water and absolute ethanol solution, respectively cleaning for 3-6 times, and vacuum-drying to obtain the phosphorus and heteroatomic codoped algae-based biochar loaded nano zero-valent metal catalyst;
the metal salt is one or two of ferric salt, molybdenum salt, cobalt salt, nickel salt, cerium salt, zinc salt and copper salt; when the metal salts are two, the mass ratio of the bimetallic salts is 1:5-5:1; the reducing agent is one of potassium borohydride, sodium borohydride, lithium borohydride, ascorbic acid and tea polyphenol, and the molar ratio of the metal salt to the reducing agent is 1:5-1:15.
The invention also aims to apply the heteroatomic doped algae-based biochar loaded nano zero-valent metal catalyst prepared by the method to the treatment of heavy metal-organic compound polluted wastewater, wherein the heteroatomic doped algae-based biochar loaded nano zero-valent metal catalyst, persulfates (PS) and peroxides (hydrogen peroxide H) 2 O 2 Calcium peroxide CP), peracetic acid (PAA), potassium permanganate (KMnO) 4 ) One or more of them are used simultaneously.
The method not only reduces the preparation cost and simplifies the operation procedure, but also effectively prevents the oxidation and agglomeration of the nano zero-valent metal particles in the wastewater treatment process on the basis of no secondary pollution to the environment, and effectively improves the surface activity and stability of the nano zero-valent metal particles; the invention also opens up a new way for the resource utilization of waste algae biomass and the development of low-cost, high-activity and green catalysts.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention provides the preparation of the heteroatomic doped mesoporous biochar material with high reactivity and low economic cost by using the algae organisms for the first time, the algae used by the invention has wide sources, and the harmful algae can be prepared into the high-value environment functional material by a simple preparation method, so that the resource value of the algae is utilized while the harmful algae is removed, and the method is environment-friendly and easy for mass production and popularization;
(2) The invention prepares the hetero-atom doped mesoporous biochar material through the modes of hetero-atom doping, morphology regulation and the like, and obtains the algae-based biochar rich in functional groups by regulating and controlling the hydrothermal reaction conditions;
(3) The invention utilizes solid hypophosphite which is easy to decompose under the heating condition to generate phosphine, and then skillfully introduces the solid hypophosphite into the heteroatomic doped algae-based biochar, and carries out medium-temperature fumigation on the heteroatomic doped algae-based biochar under the heating condition, wherein the generated phosphine gas can carry out controllable corrosion on the heteroatomic doped algae-based biochar under the sealing condition, and then further carries out medium-temperature carbonization to obtain the phosphorus and heteroatomic co-doped medium Kong Zaoji biochar composite material; the medium-temperature fumigation of phosphine vapor is innovatively utilized, so that the high mesoporous structure of the biochar material is endowed, and the co-doping of double atoms is realized in the process that phosphorus is uniformly doped into the hetero-atom doped biochar, so that the efficiency of the biochar material in electron transmission and mass transfer can be greatly improved. In addition, the co-doping of the diatomic in the biochar material enhances the chemical adsorption of pollutants and the activation efficiency of high-activity oxidants, reduces the catalytic activation barrier, and the synergistic adjustment of the defects and the diatomic doping improves the reaction kinetic efficiency;
(4) By regulating and controlling the structure of the algae-based biochar, the nano zero-valent metal is introduced into the hetero-atom doped medium Kong Zaoji biochar by a liquid-phase reduction precipitation method to form a high-activity composite reaction material of the hetero-atom doped medium Kong Zaoji biochar loaded with the nano zero-valent metal, so that the mass transfer distance between active center species (nano zero-valent metal cores and free radicals) and target pollutants is greatly shortened, rapid diffusion kinetics are promoted to ensure effective contact between the active center species and the target pollutants, the overall effect of a reaction system is enhanced, and the defects of poor electron selectivity and easy agglomeration of the nano zero-valent metal and the defects of free radical self-quenching or ineffective oxidation reaction (such as reaction with water molecules) are overcome;
(4) According to the invention, the hetero-atom doped medium Kong Zaoji biochar is obtained in a novel, green and sustainable manner, and the simple recovery of the composite material can be realized due to the existence of magnetic metal elements such as nano zero-valent iron, nickel, cobalt and the like in the algae-based biochar material, so that the loss of the composite material is avoided, and the composite material has a good large-scale application prospect.
Drawings
FIG. 1 is a drawing of a nano zero-valent iron Scanning Electron Microscope (SEM) of comparative example 1;
fig. 2 is a Scanning Electron Microscope (SEM) image of the nitrogen and phosphorus co-doped algae-based biochar supported nano zero-valent iron catalyst in example 1.
Detailed Description
The invention will be described in further detail with reference to the following specific embodiments, with the understanding that the scope of the invention is not limited to what is shown.
Example 1
(1) Cleaning Chlorella, pulverizing, sieving to obtain powder with particle diameter less than or equal to 0.4mm, adding glutaraldehyde solution with volume concentration of 2.5% into Chlorella powder, stirring for 10 hr, filtering, washing the residue with ultrapure water for 5 times, sequentially soaking with 70%, 90% and 100% ethanol solution for 0.5 hr, vacuum filtering, and drying at 80deg.C to obtain pretreated Chlorella powder;
(2) 3g of pretreated chlorella powder is placed in an extracting solution (prepared by mixing a sodium dodecyl sulfate solution with the mass volume concentration of 3% and a sodium hydroxide solution with the mass concentration of 2.9% according to the proportion of 1:1), ultrasonic (320W) dispersion is carried out for 0.5h at the temperature of 60 ℃, suction filtration is carried out, the solid is washed to pH value of 9.5-10 by ultrapure water, the washed product is placed in a melamine solution with the concentration of 0.3mol/L for solvothermal reaction at the temperature of 180 ℃ for 6h, after the reaction is finished, filtration is carried out, the solid is alternately washed to pH value of neutral by ultrapure water and absolute ethyl alcohol solution, and vacuum drying is carried out at the temperature of 80 ℃ until the constant weight is obtained, thus obtaining the nitrogen-doped chlorella biochar;
(3) Mixing nitrogen-doped chlorella-based biochar and sodium hypophosphite according to the mass ratio of 2:1 in a nitrogen atmosphere, then placing the mixture in a tube furnace, heating to 250 ℃ at the speed of 2 ℃/min, keeping for 1h, heating to 600 ℃ at the speed of 7 ℃/min, and pyrolyzing for 5h to obtain nitrogen-phosphorus co-doped chlorella-based biochar;
(4) Placing the nitrogen-phosphorus co-doped chlorella biochar in 0.025g/mL ferric chloride solution under nitrogen atmosphere, stirring for 0.5h, slowly dropwise adding tea polyphenol solution (the molar ratio of ferric chloride to tea polyphenol is 1:15), continuously stirring for 0.5h after the dropwise adding is completed, carrying out suction filtration, sequentially carrying out vacuum filtration and cleaning on filter residues by using ultrapure water and absolute ethyl alcohol solution, respectively cleaning for 4 times, and carrying out vacuum drying at 60 ℃ for 8h to obtain the nitrogen-phosphorus co-doped chlorella biochar loaded nano zero-valent iron catalyst (shown in figure 2).
Comparative example 1: slowly dropwise adding a tea polyphenol solution (the molar ratio of ferric chloride to tea polyphenol is 1:15) into 0.025g/mL ferric chloride solution, continuously stirring for 0.5h after the dropwise adding is completed, carrying out suction filtration, sequentially carrying out vacuum filtration and cleaning on filter residues by using ultrapure water and absolute ethyl alcohol solution, carrying out vacuum drying for 8h at 60 ℃ for 4 times to obtain the nano zero-valent iron catalyst (figure 1), wherein the nano zero-valent iron particles are in a chain aggregate state, and the agglomeration is very serious.
Example 2
(1) Collecting blue algae, cleaning, crushing and sieving to obtain powder with the particle diameter less than or equal to 0.4mm, adding glutaraldehyde solution with the volume concentration of 3.5% into the blue algae powder, stirring for 12-h, filtering, washing filter residues with ultrapure water for 5 times, sequentially soaking the filter residues with ethanol solutions with the volume concentrations of 70%, 90% and 100%, respectively soaking for 0.5h, carrying out suction filtration, and drying at the solid temperature of 70 ℃ to obtain pretreated blue algae powder;
(2) 5g of pretreated blue algae powder is placed in an extracting solution (prepared by mixing a dodecyl sodium sulfate solution with the mass volume concentration of 4% and a sodium hydroxide solution with the mass concentration of 3.0% according to the proportion of 1:1), ultrasonic (320W) dispersion is carried out for 1h at 50 ℃, suction filtration is carried out, the solid is washed by ultrapure water until the pH value is 9.5-10, the washed product is placed in a 0.9mol/L L-methionine solution for solvothermal reaction for 5h at 190 ℃, after the reaction is finished, filtration is carried out, the solid is alternately washed by ultrapure water and an absolute ethanol solution until the pH value is neutral, and vacuum drying is carried out at 85 ℃ until the constant weight, thus obtaining the sulfur-doped blue algae-based biochar;
(3) Under the nitrogen atmosphere, mixing the sulfur-doped blue algae-based biochar and potassium hypophosphite according to the mass ratio of 3:1, then placing the mixture in a tube furnace, heating to 300 ℃ at the speed of 3 ℃/min, keeping for 0.8h, heating to 700 ℃ at the speed of 8 ℃/min, and pyrolyzing for 4h to obtain the sulfur-phosphorus-doped blue algae-based biochar;
(4) And (3) placing the sulfur-phosphorus co-doped blue algae biochar in a nickel phosphate solution with the concentration of 0.05g/mL under the nitrogen atmosphere, stirring for 0.5h, slowly dropwise adding a sodium borohydride solution (the molar ratio of the nickel phosphate to the sodium borohydride is 1:6), continuously stirring for 0.5h after the dropwise adding is completed, carrying out suction filtration, sequentially carrying out vacuum filtration and washing on filter residues by using ultrapure water and an absolute ethyl alcohol solution, carrying out washing for 5 times, and carrying out vacuum drying at 60 ℃ for 8h to obtain the sulfur-phosphorus co-doped blue algae biochar loaded nano zero-valent nickel catalyst.
Comparative example 2: slowly dropwise adding a sodium borohydride solution (the molar ratio of the nickel phosphate to the sodium borohydride is 1:6) into 0.05g/mL of nickel phosphate solution, continuously stirring for 0.5h after the dropwise adding is completed, carrying out suction filtration, sequentially carrying out vacuum filtration and washing on filter residues by using ultrapure water and an absolute ethanol solution, carrying out washing 5 times respectively, and carrying out vacuum drying at 60 ℃ for 8h to obtain the nano zero-valent nickel catalyst.
Example 3
(1) Collecting diatom, cleaning, pulverizing, sieving to obtain powder with particle diameter less than or equal to 0.4mm, adding glutaraldehyde solution with volume concentration of 4.0% into the diatom powder, stirring for 14-h, filtering, washing the filter residue with ultrapure water for 5 times, sequentially soaking with ethanol solutions with volume concentrations of 70%, 90% and 100%, soaking for 0.5h, suction filtering, and drying at solid at 75deg.C to obtain pretreated diatom powder;
(2) 5g of pretreated diatom powder is placed in an extracting solution (prepared by mixing a dodecyl sodium sulfate solution with the mass volume concentration of 4% and a sodium hydroxide solution with the mass concentration of 3.5% according to the volume ratio of 1:2), ultrasonic (320W) dispersion is carried out for 0.5h at the temperature of 70 ℃, suction filtration is carried out, the solid is washed by ultrapure water until the pH value is 9.5-10, the washed product is placed in a boric acid solution with the concentration of 0.6 mol/L for solvothermal reaction for 3h at the temperature of 200 ℃, after the reaction is finished, filtration is carried out, the solid is alternately washed by ultrapure water and an absolute ethyl alcohol solution until the pH value is neutral, and vacuum drying is carried out at the temperature of 85 ℃ until the constant weight is obtained, thus obtaining the boron doped diatom-based biochar;
(3) Mixing boron-doped diatom-based biochar and ammonium hypophosphite according to a mass ratio of 4:1 in a nitrogen atmosphere, then placing the mixture in a tube furnace, heating to 350 ℃ at a speed of 4 ℃/min, keeping for 0.5h, heating to 750 ℃ at a speed of 9 ℃/min, and carrying out pyrolysis for 2h to obtain boron-phosphorus co-doped diatom-based biochar;
(4) Placing boron-phosphorus co-doped algae-based biochar in 0.08g/mL copper chloride solution under nitrogen atmosphere, stirring for 0.5h, slowly dropwise adding potassium borohydride solution (the molar ratio of nickel phosphate to potassium borohydride is 1:10), continuously stirring for 0.5h after the dropwise adding is completed, carrying out suction filtration, sequentially carrying out vacuum filtration and washing on filter residues by using ultrapure water and absolute ethyl alcohol solution, carrying out washing for 5 times respectively, and carrying out vacuum drying at 60 ℃ for 8h to obtain the boron-phosphorus co-doped diatomite-based biochar loaded nano zero-valent copper catalyst;
comparative example 3: slowly dropwise adding a potassium borohydride solution (the molar ratio of nickel phosphate to potassium borohydride is 1:10) into a copper chloride solution with the concentration of 0.08g/mL, continuously stirring for 0.5: 0.5h after the dropwise adding, carrying out suction filtration, sequentially carrying out vacuum filtration and washing on filter residues by using ultrapure water and an absolute ethyl alcohol solution, washing for 5 times respectively, and carrying out vacuum drying at 60 ℃ for 8: 8h to obtain the nano zero-valent copper catalyst.
Example 4
(1) Cleaning Chlorella, pulverizing, sieving to obtain powder with particle diameter less than or equal to 0.4mm, adding glutaraldehyde solution with volume concentration of 3% into Chlorella powder, stirring for 15-h, filtering, washing the residue with ultrapure water for 4 times, sequentially soaking with ethanol solutions with volume concentrations of 70%, 90% and 100%, soaking respectively in 0.5h, vacuum filtering, and drying at 80deg.C to obtain pretreated Chlorella powder;
(2) 5g of pretreated chlorella powder is placed in an extracting solution (prepared by mixing a sodium dodecyl sulfate solution with the mass volume concentration of 4% and a sodium hydroxide solution with the mass concentration of 4% according to the proportion of 1:3), ultrasonic (320W) dispersion is carried out for 1h at 55 ℃, suction filtration is carried out, the solid is washed by ultrapure water until the pH value is 9.5-10, the washed product is placed in an ammonium chloride solution with the concentration of 0.6 mol/L for solvothermal reaction for 4h at 200 ℃, after the reaction is finished, filtration is carried out, the solid is alternately washed by ultrapure water and an absolute ethyl alcohol solution until the pH value is neutral, and vacuum drying is carried out at 85 ℃ until the constant weight is achieved, thus obtaining the nitrogen-doped chlorella biochar;
(3) Mixing nitrogen-doped chlorella biochar and magnesium hypophosphite according to the mass ratio of 3:1 in a nitrogen atmosphere, then placing the mixture in a tube furnace, heating to 350 ℃ at the speed of 5 ℃/min, keeping the temperature at 0.5h, heating to 800 ℃ at the speed of 10 ℃/min, and pyrolyzing the mixture for 1.5 hours to obtain the nitrogen-phosphorus co-doped chlorella biochar;
(4) Placing the nitrogen-phosphorus co-doped chlorella biochar in 0.1g/mL of ferric phosphate-nickel phosphate (mass ratio is 1:5) solution under the nitrogen atmosphere, slowly dropwise adding a potassium borohydride solution (the molar ratio of phosphate to potassium borohydride is 1:15) after stirring 0.5: 0.5h, continuously stirring 0.5: 0.5h after the dropwise adding is completed, carrying out suction filtration, sequentially carrying out vacuum suction filtration and washing on filter residues by using ultrapure water and absolute ethyl alcohol solution, respectively washing 5 times, and carrying out vacuum drying at 60 ℃ for 8h to obtain the nitrogen-phosphorus co-doped chlorella biochar loaded nano zero-valent iron-nickel catalyst.
Comparative example 4: slowly dripping potassium borohydride solution (the molar ratio of phosphate to potassium borohydride is 1:12) into 0.1g/mL of ferric phosphate-nickel phosphate (the mass ratio is 1:5), continuously stirring for 0.5: 0.5h after dripping, carrying out suction filtration, sequentially carrying out vacuum suction filtration and washing on filter residues by using ultrapure water and absolute ethyl alcohol solution, washing for 5 times respectively, and carrying out vacuum drying at 60 ℃ for 8h to obtain the nano zero-valent iron-nickel catalyst.
Example 5
(1) Collecting blue algae, cleaning, pulverizing, sieving to obtain powder with particle diameter less than or equal to 0.4mm, adding glutaraldehyde solution with volume concentration of 3.0% into blue algae powder, stirring for 14h, filtering, washing the filter residue with ultrapure water for 6 times, sequentially soaking with ethanol solutions with volume concentrations of 70%, 90% and 100%, soaking for 0.5h, suction filtering, and drying at 80deg.C to obtain pretreated blue algae powder;
(2) 5g of pretreated blue algae powder is placed in an extracting solution (prepared by mixing a dodecyl sodium sulfate solution with the mass volume concentration of 3% and a sodium hydroxide solution with the mass concentration of 3% according to the proportion of 1:2), ultrasonic (320W) dispersion is carried out for 0.5h at the temperature of 60 ℃, suction filtration is carried out, the solid is washed by ultrapure water until the pH value is 9.5-10, the washed product is placed in an ammonium borate solution with the concentration of 0.5mol/L for solvothermal reaction for 7h at the temperature of 185 ℃, after the reaction is finished, filtration is carried out, the solid is alternately washed by ultrapure water and an absolute ethanol solution until the pH value is neutral, and vacuum drying is carried out at the temperature of 85 ℃ until the weight is constant, thus obtaining boron-doped blue algae biochar;
(3) Mixing boron-doped blue algae biochar and ammonium hypophosphite according to a mass ratio of 3:1 in a nitrogen atmosphere, then placing the mixture in a tube furnace, heating to 300 ℃ at a speed of 1 ℃/min, keeping for 0.6h, heating to 700 ℃ at a speed of 7 ℃/min, and carrying out pyrolysis for 3h to obtain boron-phosphorus co-doped blue algae biochar;
(4) And (3) placing the boron-phosphorus co-doped blue algae biochar in 0.08g/mL ferric nitrate-cerium nitrate (mass ratio of 1:2) solution under nitrogen atmosphere, stirring for 0.5h, slowly dropwise adding sodium borohydride solution (the molar ratio of nitrate to sodium borohydride is 1:12), continuously stirring for 0.5h after dropwise adding, carrying out suction filtration, sequentially carrying out vacuum filtration and washing on filter residues by using ultrapure water and absolute ethyl alcohol solution, carrying out vacuum filtration and washing for 5 times respectively, and carrying out vacuum drying at 60 ℃ for 8h to obtain the boron-phosphorus co-doped blue algae biochar loaded nano zero-valent iron cerium catalyst.
Comparative example 5: slowly dropwise adding a sodium borohydride solution (the molar ratio of nitrate to sodium borohydride is 1:12) into 0.08g/mL of ferric nitrate-cerium nitrate (mass ratio is 1:2), continuously stirring for 0.5h after the dropwise adding is completed, carrying out suction filtration, sequentially carrying out vacuum suction filtration and washing on filter residues by using ultrapure water and an absolute ethyl alcohol solution, washing for 5 times respectively, and carrying out vacuum drying at 60 ℃ for 8h to obtain the phosphorus-doped algae-based biochar-loaded nano zero-valent iron cerium catalyst.
Example 6: the catalyst prepared in the embodiment is used for treating smelting wastewater of a nonferrous metal smelting workshop, 1000mL of the workshop wastewater is collected, the pH value of a water sample is 6.5+/-0.5, and the initial dosage of pollutants is shown in table 1;
weighing 0.27g of sodium persulfate, putting the sodium persulfate into a 250mL conical flask containing 50mL of water sample, then adjusting the pH of the water sample to 3.5+/-0.2, putting 0.5g of the catalyst prepared in examples 1-5 and comparative examples 1-5 into the 250mL conical flask respectively, putting the conical flask into a constant temperature water bath shaker, shaking for 1h at 25 ℃, taking supernatant, filtering, measuring the concentration of heavy metal ions by using an inductively coupled plasma spectrometer (ICP-OES), measuring the COD value by using a spectrophotometry, calculating the removal amount according to the difference value of the concentration of the heavy metal ions before and after the reaction, and measuring the dosage unit as mg/L, wherein the test result is shown in a table 1.
TABLE 1
。
Example 7: the catalyst prepared in the embodiment is used for treating smelting wastewater of a nonferrous metal smelting workshop, 1000mL of the workshop wastewater is collected, the pH value of a water sample is 6.5+/-0.5, and the initial dosage of pollutants is shown in Table 2;
0.54g of peracetic acid is put into a 250mL conical flask containing 50mL of water sample, the pH of the water sample is adjusted to 3.5+/-0.2, 0.5g of the catalysts prepared in examples 1-5 and comparative examples 1-5 are respectively weighed and respectively put into the 250mL conical flask, the conical flask is placed into a constant temperature water bath shaking table for 1h at 25 ℃, the supernatant is taken for filtration, the concentration of heavy metal ions is measured by an inductively coupled plasma spectrometer (ICP-OES), the COD value is measured by a spectrophotometry, the removal amount is calculated according to the difference of the concentration of the heavy metal ions before and after the reaction, the dosage unit is mg/L, and the test result is shown in Table 2.
TABLE 2
From tables 1 and 2, the heteroatom doped algae-based biochar loaded nano zero-valent metal catalyst prepared by the method has good treatment effect on smelting wastewater; the concentration and COD value of the heavy metal ions contained in the treated wastewater meet the emission requirements of emission standards of industrial pollutants of lead and zinc (GB 25466-2010), and the concentration and COD value of the heavy metal ions contained in the wastewater treated by the catalyst of the comparative example do not meet the emission requirements of emission standards of industrial pollutants of lead and zinc (GB 25466-2010).
In conclusion, the method prepares the harmful algae into the heteroatomic doping medium Kong Zaoji biochar material with high reactivity and low economic cost, and the resource value of the algae is utilized while the harmful algae is removed. By regulating the structural characteristics of the hetero-atom doped medium Kong Zaoji biochar, the nano zero-valent metal is introduced into the hetero-atom doped medium Kong Zaoji biochar by utilizing a liquid phase reduction method, so that the hetero-atom doped medium Kong Zaoji biochar loaded nano zero-valent metal high-activity composite catalyst is formed, the mass transfer distance between an active center species (nano zero-valent metal and free radicals) and target pollutants is greatly shortened, the effective contact between the active center species and the target pollutants is ensured, and the integral effect of a catalytic reaction system is enhanced, thereby simultaneously solving the defects of passivation and agglomeration of the nano zero-valent metal and the defects of free radical self-quenching or ineffective oxidation reaction (such as reaction with water molecules), realizing simple recovery of composite materials and avoiding loss of the composite materials due to the existence of magnetic metal elements such as nano zero-valent iron, nickel and cerium in the materials, and proving good large-scale application prospect.
Claims (10)
1. The preparation method of the heteroatom doped algae-based biochar loaded nano zero-valent metal catalyst is characterized by comprising the following steps:
(1) Cleaning algae, drying, crushing and sieving, adding glutaraldehyde solution with volume concentration of 2.5-5%, mixing and stirring to treat 10-15 h, after solid-liquid separation, flushing the solid with ultrapure water for 4-6 times, soaking the algae in ethanol solution with volume concentration of 70%, 90% and 100% in sequence, soaking 0.5h respectively, solid-liquid separation, and drying the solid to obtain pretreated algae;
(2) Placing pretreated algae organisms into an extracting solution, performing ultrasonic dispersion at 50-70 ℃ for 0.5-1.0 h, performing solid-liquid separation, washing the solid with ultrapure water until the pH value is 9.5-10, placing the washed product into a heteroatomic precursor solution for solvothermal reaction, performing solid-liquid separation after the reaction is finished, alternately washing the solid with ultrapure water and absolute ethyl alcohol solution until the pH value is neutral, and performing vacuum drying until the constant weight is obtained to obtain heteroatomic doped algae-based biochar;
(3) Under inert atmosphere, mixing the heteroatomic doped algae-based biochar and hypophosphite, and then placing the mixture in a tube furnace for pyrolysis carbonization to obtain phosphorus and heteroatomic co-doped algae-based biochar;
(4) Placing phosphorus and heteroatomic codoped algae-based biochar in 0.025-0.1 g/mL metal salt solution under nitrogen atmosphere, stirring for 0.5h, slowly dropwise adding a reducing agent solution, continuously stirring for 0.5h after dropwise adding, separating solid from liquid, sequentially carrying out vacuum filtration and washing on the solid by using ultrapure water and absolute ethanol solution, respectively washing for 3-6 times, and carrying out vacuum drying to obtain the heteroatomic codoped algae-based biochar loaded nano zero-valent metal catalyst;
the heteroatomic precursor is one of a nitrogen source, a boron source and a sulfur source.
2. The method for preparing the heteroatomic doped algae-based biochar supported nano zero-valent metal catalyst according to claim 1, which is characterized in that: the algae in the step (1) are crushed and sieved to obtain powder with the particle size less than or equal to 0.4 mm.
3. The method for preparing the heteroatomic doped algae-based biochar supported nano zero-valent metal catalyst according to claim 1, which is characterized in that: the concentration of the heteroatomic precursor solution in the step (2) is 0.3-0.9 mol/L; wherein the nitrogen source is one or more of ammonium chloride, ammonium persulfate, melamine, urea and ammonium bicarbonate; the boron source is one or more of boric acid, ammonium borate and dimethylamine borane; the sulfur source is one or more of thioacetic acid, thiourea, thiosemicarbazide, thioacetamide, L-cysteine and L-methionine.
4. The method for preparing the heteroatomic doped algae-based biochar supported nano zero-valent metal catalyst according to claim 1, which is characterized in that: the extracting solution in the step (2) is prepared by mixing sodium dodecyl sulfate solution with the mass volume concentration of 3-5% and sodium hydroxide solution with the mass concentration of 2-4% according to the volume ratio of 1:1-3.
5. The method for preparing the heteroatomic doped algae-based biochar supported nano zero-valent metal catalyst according to claim 1, which is characterized in that: the solvothermal reaction temperature is 180-210 ℃ and the reaction time is 3-8 h.
6. The method for preparing the heteroatomic doped algae-based biochar supported nano zero-valent metal catalyst according to claim 1, which is characterized in that: in the step (3), the heteroatomic doped algae-based biochar and hypophosphite are mixed according to the mass ratio of (2-4): 1, the temperature is raised to 250-350 ℃ at the speed of 1-5 ℃/min, the temperature is raised to 500-800 ℃ at the speed of 6-12 ℃/min after the temperature is kept for 0.5-1 h, and the pyrolysis is carried out for 1.5-5 h.
7. The method for preparing the heteroatomic doped algae-based biochar supported nano zero-valent metal catalyst according to claim 5, wherein the method is characterized by comprising the following steps of: the hypophosphite is one or more of sodium hypophosphite, potassium hypophosphite, ammonium hypophosphite and magnesium hypophosphite.
8. The method for preparing the heteroatomic doped algae-based biochar supported nano zero-valent metal catalyst according to claim 1, which is characterized in that: the metal salt is one or two of ferric salt, molybdenum salt, cobalt salt, nickel salt, cerium salt, zinc salt and copper salt; when the metal salts are two, the mass ratio of the bimetallic salts is 1:5-5:1.
9. The method for preparing the heteroatomic doped algae-based biochar supported nano zero-valent metal catalyst according to claim 1, which is characterized in that: the reducing agent is one of potassium borohydride, sodium borohydride, lithium borohydride, ascorbic acid and tea polyphenol, and the molar ratio of the metal salt to the reducing agent is 1:5-1:15.
10. The application of the heteroatom-doped algae-based biochar-supported nano zero-valent metal catalyst prepared by the preparation method of the heteroatom-doped algae-based biochar-supported nano zero-valent metal catalyst in the treatment of heavy metal-organic compound complex polluted wastewater, which is characterized in that: the heteroatom doped algae-based biochar loaded nano zero-valent metal catalyst is used together with one or more of persulfates, peroxides and potassium permanganate.
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