CN116618072A - Preparation method and application of calcium-rich biochar reinforced double-reaction center Fenton-like catalyst - Google Patents
Preparation method and application of calcium-rich biochar reinforced double-reaction center Fenton-like catalyst Download PDFInfo
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- CN116618072A CN116618072A CN202310521693.8A CN202310521693A CN116618072A CN 116618072 A CN116618072 A CN 116618072A CN 202310521693 A CN202310521693 A CN 202310521693A CN 116618072 A CN116618072 A CN 116618072A
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- biochar
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- 239000003054 catalyst Substances 0.000 title claims abstract description 81
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 229910052791 calcium Inorganic materials 0.000 title claims abstract description 78
- 239000011575 calcium Substances 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims description 19
- 239000010949 copper Substances 0.000 claims abstract description 46
- 229910052751 metal Inorganic materials 0.000 claims abstract description 30
- 239000002184 metal Substances 0.000 claims abstract description 30
- 239000010842 industrial wastewater Substances 0.000 claims abstract description 5
- 239000002028 Biomass Substances 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 239000002699 waste material Substances 0.000 claims description 16
- 230000009471 action Effects 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 12
- 239000000725 suspension Substances 0.000 claims description 12
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 11
- 239000002351 wastewater Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 150000001879 copper Chemical class 0.000 claims description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 10
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 9
- 235000007164 Oryza sativa Nutrition 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 239000008103 glucose Substances 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- 235000009566 rice Nutrition 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 8
- 238000003760 magnetic stirring Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000003344 environmental pollutant Substances 0.000 claims description 7
- 231100000719 pollutant Toxicity 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000007873 sieving Methods 0.000 claims description 6
- 238000003837 high-temperature calcination Methods 0.000 claims description 5
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 4
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 abstract description 26
- 229910000019 calcium carbonate Inorganic materials 0.000 abstract description 13
- 239000013078 crystal Substances 0.000 abstract description 11
- 239000003446 ligand Substances 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 9
- 229910052782 aluminium Inorganic materials 0.000 abstract description 8
- 229910052802 copper Inorganic materials 0.000 abstract description 7
- 239000007790 solid phase Substances 0.000 abstract description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 6
- 230000005540 biological transmission Effects 0.000 abstract description 6
- 230000002950 deficient Effects 0.000 abstract description 4
- 125000000524 functional group Chemical group 0.000 abstract description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 3
- 239000011148 porous material Substances 0.000 abstract description 3
- 230000033116 oxidation-reduction process Effects 0.000 abstract description 2
- 230000001737 promoting effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 15
- 239000000047 product Substances 0.000 description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 230000008569 process Effects 0.000 description 9
- 241000209094 Oryza Species 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- 239000012535 impurity Substances 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 229910017767 Cu—Al Inorganic materials 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 229910001385 heavy metal Inorganic materials 0.000 description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 238000003763 carbonization Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 230000027756 respiratory electron transport chain Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 150000004696 coordination complex Chemical group 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 239000010431 corundum Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000010525 oxidative degradation reaction Methods 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- KHOMMWHGIAOVKF-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetic acid;nickel Chemical compound [Ni].OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KHOMMWHGIAOVKF-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- CXOFVDLJLONNDW-UHFFFAOYSA-N Phenytoin Chemical compound N1C(=O)NC(=O)C1(C=1C=CC=CC=1)C1=CC=CC=C1 CXOFVDLJLONNDW-UHFFFAOYSA-N 0.000 description 1
- OHVGNSMTLSKTGN-BTVCFUMJSA-N [C].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O Chemical compound [C].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O OHVGNSMTLSKTGN-BTVCFUMJSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 229940106691 bisphenol a Drugs 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000000149 chemical water pollutant Substances 0.000 description 1
- 229960003405 ciprofloxacin Drugs 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical compound C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 description 1
- 229960000520 diphenhydramine Drugs 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229960002036 phenytoin Drugs 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/232—Carbonates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
-
- 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
- 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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
Abstract
The application discloses a calcium-rich biochar reinforced double-reaction center Fenton-like catalyst, which constructs a heterogeneous Fenton-like catalytic system with calcium-rich biochar as a solid phase ligand, inorganic metal aluminum as a main crystal and copper as a doping component. The oxidation-reduction effect of the electron-rich region and the electron-deficient region caused by the electronegativity difference of metal atoms is further enhanced by introducing the calcium-rich biochar, and meanwhile, the key performance advantages of the calcium-rich biochar carrier, such as rich organic functional groups on the surface, developed pore structures, electron transmission promoting functions of calcium carbonate components and the like, are fully exerted, so that the treatment effect of heavy metal-organic complexes in industrial wastewater is improved to the greatest extent.
Description
Technical Field
The application relates to the technical field of water treatment catalytic materials, in particular to a preparation method and application of a calcium-rich biochar reinforced double-reaction center Fenton-like catalyst.
Background
Fenton oxidation is a high-grade oxidation technology for carrying out nonselective oxidative degradation and mineralization on refractory pollutants in water environment based on a hydroxyl radical reaction principle, and is generally suitable for pretreatment or advanced treatment of various sewage/wastewater such as dye wastewater, phenolic wastewater, landfill leachate, pharmaceutical wastewater and the like. In the practical application process, fenton oxidation exists, the reaction pH application range is narrow, the catalyst is difficult to recycle, and H 2 O 2 The problems of high consumption, high iron-containing sludge production and the like limit the further popularization and application of the sludge. In order to make up for the technical defects of the traditional Fenton oxidation, the development of a high-efficiency stable heterogeneous Fenton-like catalyst has become a research hot spot in the field of environmental catalysis.
From the electron distribution polarization theory, a heterogeneous Fenton-like catalyst with double reaction centers is constructed by utilizing a crystalline phase doping technology, and electron transmission is enhanced by an organic functional group ligand, so that the method is an effective way for solving the technical problem of traditional Fenton oxidation. For example, in the known technology, "an in-situ doped cobalt Fenton catalyst and its synthesis method and application" discloses adding cobalt source into precursor such as melamine, dicyandiamide or urea, and then synthesizing the in-situ doped cobalt Fenton catalyst through the in-situ doped roasting process. A surface ligand enhanced Fenton catalyst is prepared through baking the metal solution of precursor to form xerogel, calcining at high temp, and calcining with aqueous solution of urea. Although the heterogeneous Fenton-like catalyst has catalytic activity, catalytic stability and H 2 O 2 Effective utilization, pollutant removal and the like have obvious advantages, but the catalyst has limitations in the aspects of catalyst preparation process, pollutant treatment objects, surface solid ligand types and the like. Patent CN 107930694A discloses a surface solid phase enhanced Fenton catalyst, and a preparation method and application thereof, wherein the preparation process is relatively complicated and the control is carried outThe steps are relatively more; secondly, the existing catalyst has limited applicable pollutant types, and most of the existing catalysts are aromatic organic matters such as bisphenol A, diphenhydramine, ciprofloxacin, phenytoin, 2-chlorophenol and the like; in addition, the existing catalyst uses relatively few solid-phase ligand types, and still takes materials such as nitrogen carbide, graphene quantum dots and the like as main materials. How to further develop heterogeneous Fenton-like catalysts with simple preparation process, more excellent comprehensive performance and wide solid-phase ligand sources has become the aim pursued by current scientific researchers.
Disclosure of Invention
Aiming at the prior art, the application aims to provide a preparation method and application of a calcium-rich biochar reinforced double-reaction center Fenton-like catalyst, wherein calcium-rich biomass waste is used as a carbonaceous precursor, and the efficient and stable heterogeneous Fenton-like catalyst is prepared by methods of ultrasonic blending, hydrothermal carbonization, high-temperature calcination and the like.
In order to achieve the above purpose, the application adopts the following technical scheme:
the application provides a preparation method of a calcium-rich biochar reinforced double-reaction center Fenton-like catalyst, which comprises the following steps:
s1: sequentially dissolving inorganic metal salt and glucose in deionized water, adding a calcium-rich biomass waste raw material under the action of ultrasound to obtain a suspension system with uniformly dispersed particles, and carrying out hydrothermal reaction on the obtained suspension system under the condition of magnetic stirring;
s2: after the reaction kettle is naturally cooled to room temperature, washing and drying the product obtained in the step S1;
s3: and (3) calcining the dried product in the step (S2) at high temperature, cooling, grinding and sieving to obtain the calcium-enriched biochar reinforced double-reaction center Fenton-like catalyst.
Preferably, in the step S1, the mass ratio of the inorganic metal salt, the glucose and the calcium-rich biomass waste raw material is (6-7): 3-8): 1.
Preferably, the inorganic metal salt is a metal aluminum salt and a metal copper salt, and the metal aluminum salt is Al (NO 3 ) 3 The metallic copper salt is Cu (NO) 3 ) 2 Or CuCl 2 The method comprises the steps of carrying out a first treatment on the surface of the The mass ratio of the metal aluminum salt to the metal copper salt is 10:1.
More preferably, the calcium-rich biomass waste material is calcium-rich rice hull powder, the calcium content of the calcium-rich biomass waste material is 10-15%, and the particle size of the calcium-rich biomass waste material is 500-1000 meshes.
Preferably, in step S1, the ultrasonic frequency is 30-50kHz and the time is 20-40min.
Preferably, in step S1, the hydrothermal temperature is 150-250 ℃, the reaction time is 15-25h, and the stirring speed is 300-500rpm.
Preferably, in the step S3, the high-temperature calcination temperature is 550 ℃, the calcination time is 3-5h, the heating rate is 5 ℃/min, and the grinding granularity is 100 meshes.
The second aspect of the application provides the calcium-enriched biochar reinforced double-reaction center Fenton-like catalyst obtained by the preparation method.
The third aspect of the present application provides an application of the calcium-enriched biochar-enhanced dual-reaction-center Fenton-like catalyst in pretreatment or deep treatment of heavy metal-organic complex in industrial wastewater, wherein the calcium-enriched biochar-enhanced dual-reaction-center Fenton-like catalyst is added under the action of magnetic stirring aiming at heavy metal-organic complex wastewater with pH value of 3-8, and then H is added dropwise 2 O 2 The solution is reacted for 60-120min.
Preferably, the heavy metal-organic complex wastewater is complex pollutant wastewater formed by coordination of Ni and EDTA; the addition amount of the Fenton-like catalyst of the calcium-rich biochar reinforced double reaction center is 1-3g/L, H 2 O 2 The addition amount is 0.05-0.1mol/L.
The calcium-enriched biochar reinforced double-reaction center Fenton-like catalyst prepared by ultrasonic blending, hydrothermal carbonization and high-temperature calcination processes is mostly irregularly spherical, the surface of the catalyst is composed of Al, O, C, cu, ca, si, mg and other elements, and all the elements are uniformly distributed. Al is mainly Al in the catalyst 3+ And Al 3+ Delta form exists, and Cu element is mainly Cu 2+ And Cu + In the form of Cu + Most. The calcium-rich biochar can be introduced while the Al-O-Cu bond is constructed by crystal phase dopingTo complex with Cu within the crystal framework and more Cu oxide can be immobilized on the catalyst surface by forming C-O-Cu bonds. The electron polarization distribution generated under the action promotes the formation of an electron-rich high-density region with Cu as a center and an electron-deficient low-density region with Al and C (namely an aromatic ring structure) as a center, and compared with the electron-donating ability of Al to Cu, the electron-donating ability of pi system in the aromatic ring structure to Cu is stronger.
In the preparation process, copper salt, aluminum salt and glucose are blended in advance to form a complexing system, then under the condition of adding calcium-rich biomass, the absorption of the calcium-rich biomass to copper is promoted by ultrasonic action, so that the copper can form more Cu-O-C bonds on the surface of biochar while realizing crystalline phase doping in an aluminum oxide crystalline phase structure, and the Cu loading capacity is improved. In the hydrothermal reaction process, glucose firstly reacts through dehydration condensation and the like to form glucose carbon microspheres, aluminum salt is adsorbed on the surfaces of the carbon microspheres to form pseudo-boehmite, and calcium-rich biomass is carbonized in the process and introduced with oxygen-containing functional groups, so that the calcium-rich biomass is more prone to pore filling distribution and is tightly combined with copper during the process; part of the glucose derived carbon and rice hull biochar are converted into carbon dioxide during the calcination process, and pseudo-boehmite on the surface of the carbon is converted into gamma-Al 2 O 3 The aromatic ring of the biochar is connected with Cu through a C-O-Cu bond, caCO 3 The decomposition temperature of (C) is high (> 600 ℃), so that the structure is not changed in the preparation process. After the reaction, aluminum is used as a main core, copper is used as a core and is directly distributed on the surface of the catalyst to be combined with C, and more C and calcium carbonate are covered on the surface in a homogeneous distribution mode. It can also be said that the present application utilizes the processes of ultrasonic blending, hydrothermal carbonization and calcination at 550 deg.c to ensure the retention of original calcium carbonate in rice husk.
The catalyst is accompanied by graphite and CaCO 3 Crystalline phase structure. Conduction band electrons in the graphite structure can freely move in crystal planes, have high electron mobility and conductivity, and are favorable for electron transfer between pi and Cu. The calcium carbonate not only can adsorb and remove heavy metals, but also has good ionization and conductivity, can promote the transmission of electrons and holes, and quickens the speedAnd (3) carrying out oxidative degradation reaction of the pollutants. There are only a few documents concerning the action of calcium carbonate and their use in photocatalysts, which differ from the materials according to the application, as far as their mechanism of action is not yet clear.
The research of the double-reaction-center catalyst at the present stage focuses on the construction of metal systems with different electronegativity differences, or the construction of electron transfer systems of non-carbon materials, and the catalysis efficiency and principle, and the research related to the reinforcement of carbonaceous materials is relatively few; because the biochar composition system and performance are relatively complex to regulate and control, the composition and structure influence the catalytic efficiency of the catalyst, so that difficulty exists in biomass screening; and the solid phase ligand species adopted in the existing catalyst preparation is limited, so the application uses the calcium-rich biochar as a solid phase ligand to realize the widening of the ligand species.
In the application, the action principle of the calcium-enriched biochar is divided into the following aspects: (1) C-O-Cu bond is constructed, and electron transmission between pi and Cu is realized; (2) The electron transport is further enhanced by the synergistic effect of the Al-O-Cu bond; (3) The load combines more Cu, which can be separated from Al 2 O 3 The crystal structure is scattered on the surface of the biochar; (4) More importantly, the calcium carbonate coexisting in the biochar plays a role in electron transfer, and absorbs and removes heavy metals while oxidizing and damaging the heavy metal complex structure. The calcium carbonate is not formed by the post reaction but is present as a raw material itself. Wherein (3) and (4) are different from the previous researches or have not been reported in the previous researches.
In the prior art, because of the many impurities present in biochar, the biochar is pickled to remove the impurities and improve the catalytic performance. In the initial stage of the experiment, the method does not adopt an acid washing means, and the main purposes are (1) to reduce the pretreatment step in the earlier stage, (2) to remove impurities by simple water washing from the industrial application point of view, so that the cost is saved. In order to study the reaction principle in the reaction process, particularly the action of biochar and coexisting impurities thereof, the biochar is pickled, and the unexpected technical effect is obtained by unexpectedly finding that calcium carbonate originally existing in biomass has strengthening effect on catalysis in the reaction process.
The application has the beneficial effects that:
the heterogeneous Fenton-like catalytic system is constructed by taking calcium-rich biochar as a solid-phase ligand, inorganic metal aluminum as a main crystal and copper as a doping component. The oxidation-reduction effect of the electron-rich region and the electron-deficient region caused by the electronegativity difference of metal atoms is further enhanced by introducing the calcium-rich biochar, and meanwhile, the key performance advantages of the calcium-rich biochar carrier, such as rich organic functional groups on the surface, developed pore structures, electron transmission promoting functions of calcium carbonate components and the like, are fully exerted, so that the treatment effect of heavy metal-organic complexes in industrial wastewater is improved to the greatest extent.
After the catalyst is treated for 90min under the condition of an initial pH value of 3-8, the complex breaking efficiency of the heavy metal complex can reach more than 91%, the Cu leaching amount is lower than 0.2mg/L, and the catalyst has a wider pH application range and excellent catalytic reaction characteristics.
Drawings
Fig. 1: SEM-EDS diagram of a calcium-enriched biochar-enhanced double-reaction-center Fenton-like catalyst in example 1;
fig. 2: XPS full spectrum of the calcium-rich biochar enhanced double-reaction center Fenton-like catalyst and fine spectrum of Cu and Al elements in the embodiment 1;
fig. 3: XRD patterns of the three different double-site Fenton-like catalysts in example 1, comparative examples 1-2;
fig. 4: comparative graphs of the removal effect of heavy metal-organic complexes under three different catalyst conditions in example 1 and comparative examples 1 to 2.
Detailed Description
It should be noted that the following detailed description is illustrative and is intended to provide further explanation of the application. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
As described in the background art, based on the method, the application provides a calcium-rich biochar reinforced double-reaction center Fenton-like catalyst, which is prepared by the following steps:
s1: sequentially dissolving inorganic metal salt and glucose in deionized water according to a proportion, adding calcium-rich biomass waste raw materials, obtaining a suspension system with uniformly dispersed particles under the ultrasonic action of 30-50kHz for 20-40min, carrying out hydrothermal reaction on the suspension system under the magnetic stirring condition of 300-500rpm, wherein the hydrothermal temperature is 150-250 ℃, and the reaction time is 15-25h;
the mass ratio of the inorganic metal salt to the glucose to the calcium-rich biomass waste raw material is (6-7): 3-8): 1.
The inorganic metal salt is metal aluminum salt and metal copper salt, and the metal aluminum salt is Al (NO) 3 ) 3 The metallic copper salt is Cu (NO) 3 ) 2 Or CuCl 2 The method comprises the steps of carrying out a first treatment on the surface of the The ratio of the metal aluminum salt to the metal copper salt is 10:1; the raw material of the calcium-rich biomass waste is calcium-rich rice hull powder, the calcium content of the calcium-rich biomass waste is 10-15%, and the particle size of the calcium-rich biomass waste is 500-1000 meshes;
s2: after the reaction kettle is naturally cooled to room temperature, washing and drying the product obtained in the step S1;
s3: and (3) placing the dried product obtained in the step (S2) in a muffle furnace, calcining at a high temperature of 550 ℃ for 3-5 hours, wherein the heating rate is 5 ℃/min, cooling, grinding to 100 meshes, and sieving to obtain the calcium-enriched biochar reinforced double-reaction center Fenton-like catalyst.
In order to enable those skilled in the art to more clearly understand the technical scheme of the present application, the technical scheme of the present application will be described in detail with reference to specific embodiments.
The test materials used in the examples of the present application are all conventional in the art and are commercially available. The calcium-enriched rice hull powder used in the following examples and comparative examples of the present application was purchased from a deep processing plant of agricultural products in the Jiangsu-yun harbor Bifeng.
Example 1
The preparation method of the Fenton-like catalyst with the calcium-rich biochar reinforced double reaction centers comprises the following steps:
step S1, 7.5g of Al (NO) 3 ) 3 ·9H 2 O、0.75g Cu(NO 3 ) 2 ·3H 2 O and 5.0. 5.0g C 6 H 12 O 6 According toDissolving in 55mL deionized water, adding 1.325g of 1000-mesh calcium-rich rice hull powder with the calcium content of 13.28%, performing ultrasonic action at 40kHz for 30min to obtain a suspension system with uniformly dispersed particles, transferring the suspension system into a 100mL hydrothermal reaction kettle, and performing hydrothermal reaction for 20h under the conditions of magnetic stirring and 200 ℃;
s2, after the reaction kettle is naturally cooled to room temperature, washing the obtained product for a plurality of times, and drying the product in a blast drying oven at 80 ℃;
and S3, transferring the dried product obtained in the step S2 into a corundum boat, covering, calcining for 4 hours at a high temperature of 550 ℃ in a muffle furnace, wherein the heating rate is 5 ℃/min, cooling, grinding and sieving with a 100-mesh sieve to obtain the calcium-enriched biochar reinforced double-reaction center Fenton-like catalyst.
The prepared calcium-enriched biochar reinforced double-reaction center Fenton-like catalyst is mostly irregularly spherical (shown in figure 1) through ultrasonic blending, hydrothermal carbonization and high-temperature calcination processes, the surface of the catalyst is composed of Al, O, C, cu, ca, si, mg and other elements, and all the elements are uniformly distributed. XPS results (shown in FIG. 2) indicate that the Al in the catalyst is mainly Al 3+ And Al 3+ Delta form exists, and Cu element is mainly Cu 2+ And Cu + In the form of Cu + Most. The calcium-rich biochar is introduced while the Al-O-Cu bond is constructed by crystal phase doping, so that the calcium-rich biochar can be complexed with Cu in a crystal framework, and more Cu oxide can be fixed on the surface of the catalyst by forming a C-O-Cu bond. The electron polarization distribution generated under the action promotes the formation of an electron-rich high-density region with Cu as a center and an electron-deficient low-density region with Al and C (namely an aromatic ring structure) as a center, and compared with the electron-donating ability of Al to Cu, the electron-donating ability of pi system in the aromatic ring structure to Cu is stronger. XRD analysis showed (as shown in FIG. 3) that the catalyst was accompanied by graphite and CaCO 3 Crystalline phase structure. Conduction band electrons in the graphite structure can freely move in a crystal plane, so that the graphite structure has high electron mobility and conductivity, and is beneficial to electron transfer between pi and Cu; the calcium carbonate not only can adsorb and remove heavy metals, but also has good ionization and conductivity, can promote the transmission of electrons and holes and accelerate the oxidation of pollutantsAnd (3) carrying out degradation reaction.
Comparative example 1
A preparation method of a biochar reinforced double-reaction center Fenton-like catalyst comprises the following steps:
step S1, 1.325g of calcium-rich rice hull powder is placed in 50mL of HCl solution with the concentration of 1mol/L, magnetically stirred for 24 hours, and then washed with deionized water until the pH value of the supernatant is neutral;
step S2, 7.5g of Al (NO) 3 ) 3 ·9H 2 O、0.75g Cu(NO 3 ) 2 ·3H 2 O and 5.0. 5.0g C 6 H 12 O 6 Sequentially dissolving in 55mL of deionized water, adding the acid-washed rice hull powder in the step S1, performing ultrasonic action at 40kHz for 30min to obtain a suspension system with uniformly dispersed particles, transferring the suspension system into a 100mL hydrothermal reaction kettle, and performing hydrothermal reaction for 20h under the conditions of magnetic stirring and 200 ℃;
s3, after the reaction kettle is naturally cooled to room temperature, washing the obtained product for a plurality of times, and drying the product in a blast drying oven at 80 ℃;
s4, transferring the dried product obtained in the step S3 into a corundum boat, covering, calcining for 4 hours at a high temperature of 550 ℃ in a muffle furnace, heating at a speed of 5 ℃/min, cooling, grinding and sieving with a 100-mesh sieve to obtain the biochar reinforced double-reaction-center Fenton-like catalyst Cu-Al 2 O 3 -ABC。
In this comparative example, the calcium-enriched biochar was subjected to acid washing, and the rest was the same as in example 1.
XRD analysis results showed (as shown in FIG. 3) that compared with Cu-Al 2 O 3 Catalyst Cu-Al 2 O 3 The graphite crystal structure is present in ABC, but CaCO is absent 3 The crystal phase structure shows that the graphite structure in the biochar can promote electron cloud polarization distribution on the surface of the catalyst, so that the efficiency of the double-reaction-center catalyst is enhanced.
Comparative example 2
A preparation method of a double-reaction-center Fenton-like catalyst comprises the following steps:
step S1, 7.5g of Al (NO) 3 ) 3 ·9H 2 O、0.75g Cu(NO 3 ) 2 ·3H 2 O and 5.0. 5.0g C 6 H 12 O 6 Sequentially dissolving in 55mL of deionized water, performing ultrasonic action at 40kHz for 30min to obtain a suspension system with uniformly dispersed particles, transferring the suspension system into a 100mL hydrothermal reaction kettle, and performing hydrothermal reaction for 20h under the conditions of magnetic stirring and 200 ℃;
s2, after the reaction kettle is naturally cooled to room temperature, washing the obtained product for a plurality of times, and drying the product in a blast drying oven at 80 ℃;
step S3, transferring the dried product in the step S2 into a corundum boat, covering, calcining for 4 hours at a high temperature of 550 ℃ in a muffle furnace, heating at a speed of 5 ℃/min, cooling, grinding and sieving with a 100-mesh sieve to obtain the double-reaction center Fenton-like catalyst Cu-Al 2 O 3 。
In this comparative example, no calcium-enriched biochar was added, and the rest was the same as in example 1.
Experimental example
The catalysts prepared in example 1 and comparative examples 1-2 were subjected to catalytic oxidation comparative experiments to further illustrate the performance advantages of the calcium-enriched biochar-enhanced dual-reaction center Fenton-like catalyst, which comprises the following specific steps:
50mL of Ni-EDTA simulated wastewater (10 mg/L in Ni) 2+ Ion concentration meter) in the reactor, then 2g/L of catalyst and 75mmol/L H are added in sequence 2 O 2 The reaction is carried out. During the reaction, 1mL of the sample is periodically sampled in a colorimetric tube, and then a proper amount of Na is added 2 SO 3 And NaOH to terminate the reaction and remove free Ni from the solution 2+ . The sample was diluted and filtered through a 0.45 μm microporous filter membrane, and its Ni was detected 2+ Concentration. The results are shown in FIG. 4, cu-Al 2 O 3 BC is the catalyst prepared in example 1, cu-Al 2 O 3 ABC is the catalyst prepared in comparative example 1, cu-Al 2 O 3 The catalyst prepared in comparative example 2.
After 90min treatment at an initial pH of 5, the complex breaking efficiency of the heavy metal complex of example 1 reaches 96.7%, and the Cu leaching amount is lower than 0.2mg/L.
As can be seen from FIG. 4, the double reaction center Fenton-like catalyst Cu-Al of comparative example 2 after 90min of catalytic oxidation reaction 2 O 3 The decomplexing efficiency of (2) is only 22.5%, which is far lower than that of Fenton-like catalyst (Cu-Al) under the doping condition of the calcium-rich biochar of example 1 2 O 3 -BC), i.e. the strengthening effect of the calcium-rich biochar on the double-reaction-center Fenton-like catalyst.
In the initial stage of the experiment, the method does not adopt an acid washing means, and the main purposes are (1) to reduce the pretreatment step in the earlier stage, (2) to remove impurities by simple water washing from the industrial application point of view, so that the cost is saved. In order to clarify the reaction principle in the reaction process, particularly the action of biochar and coexisting impurities thereof, the biochar was subjected to acid washing, namely comparative example 1, and it was unexpectedly found that calcium carbonate originally present in biomass has an enhanced effect on catalysis in the reaction process.
Comparative example 1 after removal of impurities, especially calcium carbonate, from biochar by acid washing, catalyst (cu—al 2 O 3 -ABC) is reduced to 69.3%, which shows that calcium carbonate in the biochar has a synergistic effect on Fenton-like catalyst performance.
The above description is only of the preferred embodiments of the present application and is not intended to limit the present application, but various modifications and variations can be made to the present application by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (10)
1. The preparation method of the calcium-rich biochar reinforced double-reaction center Fenton-like catalyst is characterized by comprising the following steps of:
s1: sequentially dissolving inorganic metal salt and glucose in deionized water, adding a calcium-rich biomass waste raw material under the action of ultrasound to obtain a suspension system with uniformly dispersed particles, and carrying out hydrothermal reaction on the obtained suspension system under the condition of magnetic stirring;
s2: after the reaction kettle is naturally cooled to room temperature, washing and drying the product obtained in the step S1;
s3: and (3) calcining the dried product in the step (S2) at high temperature, cooling, grinding and sieving to obtain the calcium-enriched biochar reinforced double-reaction center Fenton-like catalyst.
2. The preparation method of the calcium-enriched biochar reinforced double-reaction-center Fenton-like catalyst according to claim 1, wherein in the step S1, the mass ratio of the inorganic metal salt to the glucose to the calcium-enriched biomass waste raw materials is (6-7): 3-8): 1.
3. The method for preparing the calcium-enriched biochar-enhanced double-reaction-center Fenton-like catalyst according to claim 1, wherein the inorganic metal salt is a metal aluminum salt and a metal copper salt, and the metal aluminum salt is Al (NO 3 ) 3 The metallic copper salt is Cu (NO) 3 ) 2 Or CuCl 2 The method comprises the steps of carrying out a first treatment on the surface of the The mass ratio of the metal aluminum salt to the metal copper salt is 10:1.
4. The method for preparing the Fenton-like catalyst of the calcium-rich biochar reinforced double reaction center according to claim 3, wherein the raw material of the calcium-rich biomass waste is calcium-rich rice hull powder, the calcium content of the calcium-rich biomass waste is 10-15%, and the particle size of the calcium-rich biomass waste is 500-1000 meshes.
5. The method for preparing the calcium-enriched biochar-enhanced double-reaction-center Fenton-like catalyst according to claim 1, wherein in the step S1, the ultrasonic frequency is 30-50kHz, and the time is 20-40min.
6. The method for preparing the calcium-enriched biochar-enhanced double-reaction-center Fenton-like catalyst according to claim 1, wherein in the step S1, the hydrothermal temperature is 150-250 ℃, the reaction time is 15-25h, and the stirring rotation speed is 300-500rpm.
7. The method for preparing the calcium-enriched biochar reinforced double-reaction-center Fenton-like catalyst according to claim 1, wherein in the step S3, the high-temperature calcination temperature is 550 ℃, the calcination time is 3-5h, the heating rate is 5 ℃/min, and the grinding granularity is 100 meshes.
8. The calcium-enriched biochar-enhanced double-reaction-center Fenton-like catalyst obtained by the preparation method of any one of claims 1 to 7.
9. The use of the calcium-enriched biochar-enhanced double-reaction-center Fenton-like catalyst according to claim 8 in pretreatment or deep treatment of heavy metal-organic complex in industrial wastewater, wherein the calcium-enriched biochar-enhanced double-reaction-center Fenton-like catalyst is added under the action of magnetic stirring for heavy metal-organic complex wastewater with pH value of 3-8, and then H is added dropwise 2 O 2 The solution is reacted for 60-120min.
10. The application of the calcium-enriched biochar-enhanced double-reaction-center Fenton-like catalyst in pretreatment or deep treatment of heavy metal-organic complex in industrial wastewater, wherein the heavy metal-organic complex wastewater is complex pollutant wastewater formed by coordination of Ni and EDTA; the addition amount of the Fenton-like catalyst of the calcium-rich biochar reinforced double reaction center is 1-3g/L, H 2 O 2 The addition amount is 0.05-0.1mol/L.
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