CN112473652A - Preparation method and application of hydrogen peroxide modified biochar containing transition metal - Google Patents
Preparation method and application of hydrogen peroxide modified biochar containing transition metal Download PDFInfo
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- CN112473652A CN112473652A CN202011191437.XA CN202011191437A CN112473652A CN 112473652 A CN112473652 A CN 112473652A CN 202011191437 A CN202011191437 A CN 202011191437A CN 112473652 A CN112473652 A CN 112473652A
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- biochar
- transition metal
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- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 34
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000010949 copper Substances 0.000 claims abstract description 31
- 229910052802 copper Inorganic materials 0.000 claims abstract description 25
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052742 iron Inorganic materials 0.000 claims abstract description 23
- 230000010355 oscillation Effects 0.000 claims abstract description 18
- 238000000967 suction filtration Methods 0.000 claims abstract description 18
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 238000005336 cracking Methods 0.000 claims abstract description 3
- 239000011572 manganese Substances 0.000 claims description 37
- 229910052748 manganese Inorganic materials 0.000 claims description 26
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 17
- 230000008569 process Effects 0.000 claims description 10
- 230000000593 degrading effect Effects 0.000 claims description 6
- 239000002957 persistent organic pollutant Substances 0.000 claims description 6
- 238000000197 pyrolysis Methods 0.000 claims description 6
- 231100000331 toxic Toxicity 0.000 claims description 4
- 230000002588 toxic effect Effects 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 abstract description 27
- 229940043267 rhodamine b Drugs 0.000 abstract description 26
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 14
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 239000003607 modifier Substances 0.000 abstract description 5
- 239000003054 catalyst Substances 0.000 abstract description 3
- 239000003610 charcoal Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 25
- 238000012986 modification Methods 0.000 description 21
- 230000004048 modification Effects 0.000 description 20
- 230000015556 catabolic process Effects 0.000 description 17
- 238000006731 degradation reaction Methods 0.000 description 17
- 229910001385 heavy metal Inorganic materials 0.000 description 12
- 239000003344 environmental pollutant Substances 0.000 description 10
- 231100000719 pollutant Toxicity 0.000 description 10
- 239000000779 smoke Substances 0.000 description 9
- 230000007613 environmental effect Effects 0.000 description 7
- 150000002696 manganese Chemical class 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 239000002028 Biomass Substances 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 230000001699 photocatalysis Effects 0.000 description 5
- 239000002689 soil Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000002505 iron Chemical class 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 150000001879 copper Chemical class 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000002715 modification method Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000003900 soil pollution Methods 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- -1 11.3mg/g) Substances 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 241001494479 Pecora Species 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- IYRDVAUFQZOLSB-UHFFFAOYSA-N copper iron Chemical compound [Fe].[Cu] IYRDVAUFQZOLSB-UHFFFAOYSA-N 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000003588 decontaminative effect Effects 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
- 238000002474 experimental method Methods 0.000 description 1
- 210000003608 fece Anatomy 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000010871 livestock manure Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- AHADSRNLHOHMQK-UHFFFAOYSA-N methylidenecopper Chemical compound [Cu].[C] AHADSRNLHOHMQK-UHFFFAOYSA-N 0.000 description 1
- QMQXDJATSGGYDR-UHFFFAOYSA-N methylidyneiron Chemical compound [C].[Fe] QMQXDJATSGGYDR-UHFFFAOYSA-N 0.000 description 1
- 230000001089 mineralizing effect Effects 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229940109850 royal jelly Drugs 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
Images
Classifications
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- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- 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
- B01J23/72—Copper
-
- 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
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
-
- 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
-
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention discloses a method for producing H2O2A preparation method and application of modified biochar containing transition metal. Taking biochar enriched with transition metals as a raw material, and dehydrating and thermally cracking to obtain a transition metal biochar sample;putting a transition metal biochar sample into a container, and dropwise adding hydrogen peroxide (H)2O2) Covering, leaving air holes on the cover, and placing in a constant temperature oscillation box for oscillation for 12-24 h; and carrying out suction filtration, washing and drying on the obtained sample to obtain the hydrogen peroxide modified transition metal-containing biochar product. The biochar sample enriched with transition metals such as manganese, copper, iron and the like has no catalytic performance, and H is adopted2O2As a modifier, the manganese, copper and iron modified charcoal catalyst with visible light catalytic activity can be prepared and applied to removing rhodamine B (RhB) and Phenol (Phenol) in water.
Description
Technical Field
Aiming at the difficulties that a large amount of biomass materials obtained after the soil or water body polluted by heavy metals such as manganese, copper, iron and the like is treated by a phytoremediation technology and is difficult to convert and recycle, the technology provides a simple hydrogen peroxide modification method, and the biomass materials polluted by the metals are subjected to resource conversion, so that the biomass materials are applied to the reduction and removal of toxic organic pollutants in the water body. The technology belongs to the fields of resource sustainable utilization and pollution treatment.
Background
With the rapid development of mining, ore smelting and industrialization, the soil pollution is increasingly intensified, and the serious heavy metal non-point source pollution is one of the important environmental problems faced by human beings at present. The phytoremediation technology is a novel green, economic and safe soil pollution treatment technology for treating soil heavy metal non-point source pollution at present. The heavy metals in the soil are moved out of the soil body by using plants, and are transferred and enriched in the body, so that the aim of reducing the heavy metals in the soil is fulfilled. Wherein, because manganese, iron and copper are necessary elements in the photosynthesis and growth process of plants, the manganese, iron and copper are more easily enriched in the body by the plants.
However, as the plant repair technology enters the field demonstration and application stage, the post-treatment problem of the repaired plant needs to be solved. If a large amount of plants rich in heavy metals are not properly treated as soon as possible, the heavy metals enriched in the plants can reenter the environment, and the heavy metals in the organisms have higher activity and bring greater harm to the environment. However, transportation and storage of these heavy metal highly enriched biomasses require large space occupation, and they are also potential biomass energy sources, and resource waste can be caused when the heavy metal highly enriched biomasses are not utilized. Therefore, the harmlessness and reclamation of the repaired plant are the research hotspots in the current environmental field.
Biochar (Biochar, BC) is a porous carbonaceous material prepared by carbonizing a biomass raw material by an anoxic pyrolysis or hydrothermal method. The biochar has wide research and application prospects in the fields of energy conversion and storage, agricultural production, environmental protection and the like due to the characteristics of high cost performance, wide availability, eco-friendliness and the like. However, the original biochar has limited adsorption capacity for pollutants and poor performance when used in catalytic materials, and is usually modified for better adsorption and catalytic performance. At present, the main functional groups of the biochar surface modification are acid-base groups, organic functional groups and metal valence state modification. Wherein a green oxidant H is used2O2The oxidation modification is carried out on the biochar, so that the adsorption performance and the catalytic activity of the biochar are improved, and the method is an effective and friendly modification method.
A great number of reports show that the adsorption performance of the biochar and the oxidation mineralization capability of organic pollutants can be enhanced by loading metal oxides on the biochar, for example, royal jelly and other people load lanthanum on sheep manure and then carry out pyrolysis to prepare the biochar, so that the metal lanthanum modified biochar with better phosphorus adsorption effect is obtained; magnesium is loaded in corncobs and then pyrolyzed by dungeon and the like to prepare magnesium modified biochar with good adsorption effect on phosphorus and nitrogen in water; the tube carrying and the like use bismuth tungstate, nitrogen and sulfur to modify the biochar together, and the modified biochar with good photocatalytic performance and adsorption performance is obtained.
Although there are many reports on the metal oxide modified biochar, no report has been made on the research on modifying heavy metal-enriched biochar to provide its decontamination capability. The biochar material enriched with heavy metals is simply modified, so that the oxidizing and mineralizing capability of the biochar material on organic pollutants in the environment can be obviously improved, and the green recycling economy of 'waste by waste' of pollutants is realized.
Disclosure of Invention
Aiming at the technical problems, the invention provides a simpler method for modifying manganese, copper or iron biochar. By means of H2O2Is prepared by a modification methodH2O2Modified manganese/copper/iron biochar.
The method comprises the following specific steps:
(1) taking biochar enriched with transition metals as a raw material, and dehydrating and thermally cracking to obtain a transition metal biochar sample;
(2) putting a transition metal biochar sample into a container, and dropwise adding H2O2Covering, leaving air holes on the cover, and placing in a constant temperature oscillation box for oscillation for 12-24 h;
(3) and (3) carrying out suction filtration, washing and drying on the sample obtained in the step (2) to obtain the hydrogen peroxide modified transition metal-containing biochar product.
The biochar enriched with transition metals in step (1) comprises biochar enriched with one or more of manganese, copper, or iron; wherein the manganese content is more than 10 mg/g, the copper content is more than 14 mg/g, and the iron content is more than 9 mg/g.
In the step (1), the temperature of the pyrolysis process is increased to 300 ℃ and 700 ℃ at the temperature increasing rate of 15-17 ℃/min, and the pyrolysis is carried out for 0.5-2 h.
Step (2) H2O2The mass concentration of the active carbon is 28-30 percent; h with mass concentration of 28-30%2O2The dropping speed of (A) is 60 to 75 drops/min.
H with the mass concentration of 28-30% in the step (2)2O2The ratio of volume (mL) to mass (g) of the transition metal biochar sample is 45-55: 1, preferably 50: 1.
the invention has a technical scheme that the prepared hydrogen peroxide modified transition metal-containing biochar is applied to degradation of toxic organic pollutants.
Toxic organic contaminants include, but are not limited to, rhodamine B and phenol.
The addition amount of the hydrogen peroxide modified biochar containing the transition metal is 250 mg/L.
H2O2Is used as an important chemical in almost all industrial fields and environmental protection fields. In the conventional industries of textile, paper-making, etc., H2O2Generally as bleaching and oxidizing agents, and in recent years H2O2The utilization in the environmental protection field is also developed. H2O2Has a prominent advantage in environmental protection, namely H2O2The reactions involved produce pure water and oxygen.
In the technical scheme of the invention, H2O2As an inexpensive oxidizing agent having good oxidizing ability, the present invention successfully used H2O2The manganese, copper or iron biochar is modified, so that the manganese, copper or iron biochar has the capability of degrading pollutants by visible light catalysis. This patent uses H2O2Manganese biochar with the capability of degrading pollutants by visible light catalysis is successfully prepared as a modifier and applied to removing rhodamine B (RhB) and organic pollutant Phenol (Phenol), and the results show that H2O2The modified manganese biochar has good capacity of removing RhB and Phenol.
The invention has the advantages of cheap raw materials, reliable source, environmental protection, safety, simple and convenient preparation process, easily controlled conditions, adjustable process parameters, good pollutant removal capability and H2O2The modified manganese biochar has good stability. Low cost of H2O2As a modifier, the manganese, copper or iron biochar which originally has no capability of degrading pollutants by visible light catalysis has the capability of degrading pollutants by visible light catalysis. The resource utilization and the applicability of the repair plant are expanded. Through photocatalytic degradation experiments, H is found2O2The modified manganese biochar can degrade RhB and Phenol under the condition of visible light.
The invention aims to provide a simple preparation method of modified Mn, Cu or Fe biochar. Compared with unmodified Mn/Cu/Fe biochar, the unmodified Mn, Cu or Fe biochar has no visible light catalytic capability, so that the pollutant removal efficiency is not ideal mostly. By the appropriate amount of H2O2After modification, 68% of rhodamine B (10 mg/L) can be removed by the copper biochar material after illumination for 3 hours; the manganese biochar material has the capability of removing pollutants, 98% of rhodamine B (10 mg/L) can be removed after 3 hours of illumination, and 52% of Phenol (2mg/L) can be removed after 5 hours of illumination; 63% of rhodamine B (10 mg/L) can be removed by irradiating the iron-copper biochar material for 3 hours.
Drawings
FIG. 1 shows three different carbon materials added with H dropwise during modification2O2The picture of time.
FIG. 2 is H in the preparation of example 42O2Gas chromatography detection of gases produced by the modification process.
FIG. 3 is an SEM photograph of MB-H0 and MB-H5 prepared in example 4.
FIG. 4 is an XRD pattern of MB-H0 and MB-H5 prepared in example 4.
FIG. 5 is an XPS spectrum of MB-H0 and MB-H5 prepared in example 4.
FIG. 6 shows activated charcoal, blank charcoal, H2O2Modified activated carbon and H2O2Kinetics curve of modified blank charcoal degradation RhB.
FIG. 7 is a graph showing the degradation kinetics of MB-H0 prepared in example 1 and MB-H5 manganese biochar prepared in example 4 on RhB.
FIG. 8 is a graph of the degradation kinetics of CuB-H5 versus RhB prepared in example 6.
FIG. 9 is a graph showing the degradation kinetics of FeB-H5 on RhB prepared in example 7.
FIG. 10 is a graph showing the degradation kinetics of MB-H5 versus Phenol prepared in example 4.
Detailed Description
Preparation of H2O2Modified Mn/Cu/Fe biochar, i.e. directly with H2O2Mn, Cu or Fe biochar prepared by a modifier. Nomenclature of biochar (MB-Hx, Mn biochar-H)2O2modifying; x represents H2O2The amount of the modifier is ml, and 0 represents unmodified; Cu-BC represents unmodified copper biochar, CuB-Hx represents modified copper biochar; Fe-BC represents unmodified iron biochar, FeB-Hx represents modified iron biochar).
Example 1
Respectively drying manganese-enriched biochar (Mn, 11.3mg/g), copper biochar (Cu, 14.3mg/g) and iron biochar (Fe, 9.7mg/g) at 60 ℃ for 24h for dehydration, and placing in a tube furnaceIn N2In the atmosphere, the temperature is 300 ℃, the pyrolysis is carried out for 1 h, and the transition metal biochar sample is obtained after being screened by a 100-mesh sieve and marked as a Mn-300 ℃ biochar sample, a Cu-300 ℃ biochar sample and a Fe-300 ℃ biochar sample.
Example 2
Weighing 0.1g of Mn-300 ℃ biochar sample, placing the sample in a 10ml small glass bottle, and dripping H with the initial mass fraction of 28% at the speed of 60-75D/min2O2 2mL, generating a large amount of white smoke with burnt smell in the dripping process, covering after finishing dripping, reserving 2-4 air holes on the cover, and placing the cover in a constant temperature oscillation box for oscillation at 25 ℃ for 12-24 h; carrying out suction filtration treatment on the manganese biochar material after oscillation is finished, washing the manganese biochar material for 3 times during suction filtration, and drying the modified Mn biochar material subjected to suction filtration in a constant-temperature drying oven at 60 ℃ for 12 hours to obtain H2O2The modified Mn biochar is named as MB-H2.
Example 3
Weighing 0.1g of Mn-300 ℃ biochar sample, placing the sample in a 10ml small glass bottle, and dripping H with the initial mass fraction of 30% at the speed of 60-75D/min2O2 5mL, generating a large amount of white smoke with burnt smell in the dripping process, covering after finishing dripping, reserving 2-4 air holes on the cover, and placing the cover in a constant temperature oscillation box for oscillation at 25 ℃ for 12-24 h; carrying out suction filtration treatment on the manganese biochar material after oscillation is finished, washing the manganese biochar material for 3 times during suction filtration, and drying the modified Mn biochar material subjected to suction filtration in a constant-temperature drying oven at 60 ℃ for 12 hours to obtain H2O2The modified Mn biochar is named as MB-H5.
Example 4
Weighing 0.1g of a Cu-300 ℃ biochar sample, placing the sample in a 10ml small glass bottle, and dropwise adding H with the initial mass fraction of 29% at the speed of 60-75D/min2O2 5mL, generating a small amount of smoke in the dripping process, covering after the dripping is finished, reserving 2-4 air holes on the cover, and placing the cover in a constant-temperature oscillation box to oscillate for 12-24 hours at 25 ℃; carrying out suction filtration treatment on the manganese biochar material after oscillation is finished, washing the manganese biochar material for 3 times during suction filtration, and drying the modified Cu biochar material subjected to suction filtration in a constant-temperature drying oven at 60 ℃ for 12 hours to obtain H2O2Modified Cu biocharNamed CuB-H5.
Example 5
Weighing 0.1g of a biochar sample at the temperature of Fe-300 ℃, placing the biochar sample in a 10ml small glass bottle, and dripping H with the initial mass fraction of 30% at the speed of 60-75D/min2O2 5mL, generating a small amount of smoke in the dripping process, covering after the dripping is finished, reserving 2-4 air holes on the cover, and placing the cover in a constant-temperature oscillation box to oscillate for 12-24 hours at 25 ℃; carrying out suction filtration treatment on the manganese biochar material after oscillation is finished, washing the manganese biochar material for 3 times during suction filtration, and drying the modified Fe biochar material subjected to suction filtration in a constant-temperature drying oven at 60 ℃ for 12 hours to obtain H2O2The modified Fe biochar is named as FeB-H5.
Example 6
Weighing 0.1g of blank biochar sample at 300 ℃, placing the blank biochar sample in a 10ml small glass bottle, and dropwise adding H with the initial mass fraction of 29% at 60-75D/min2O2 5mL, after the dropwise addition is finished, covering the container with a cover, reserving 2-4 air holes on the cover, and placing the container in a constant temperature oscillation box to oscillate for 12-24 hours at 25 ℃; after the oscillation is finished, carrying out suction filtration treatment on the blank biochar material, washing the blank biochar material for 3 times during suction filtration, and drying the modified blank biochar material subjected to suction filtration in a constant-temperature drying oven at 60 ℃ for 12 hours to obtain H2O2Modified blank biochar named as H2O2 -blank BC。
Example 7
Removing experimental operation steps: 40mL of different degradation substrates were added to a 70 mL glass tube at initial water concentrations of RhB =10 mg/L or Phenol =2mg/L, 0.010 g of the sample obtained in examples 1-7 was added to the solution, the supernatant was centrifuged at certain reaction time intervals, and Phenol concentration C was determined by HPLCt. The specific conditions of detecting Phenol by high performance liquid chromatography are as follows: agilent 1260 type high performance liquid chromatography, C18 reversed phase chromatographic column, mobile phase 1: 1, the column temperature is kept at 30.00 ℃, and the flow rate is 1.00 mL.min-1Sample introduction volume of 20.00 mu L and detection wavelength lambdamax=220 nm. Measuring the lambda of the RhB removal rate on an ultraviolet-visible spectrophotometermaxAbsorbance value A of =554nmtAnd calculating C from the standard curvet。
FIG. 1 shows that H is added dropwise during modification of three materials of Mn-300 ℃ biochar sample, Activated Carbon (AC) and blank biochar (blank BC) at 300 ℃ in example 42O2The picture of time. It can be seen from the figure that the biochar rich in manganese is added with H2O2A large amount of white smoke is generated sometimes, while the activated carbon and the blank biochar do not generate white smoke. This is because the transition manganese metal element and H in the manganese biochar2O2The gas produced by the reaction takes place. Because the active carbon or the blank biochar does not contain the transition metal element or the content is too low to be compatible with H2O2The reaction produced gas, so no smoke was seen.
FIG. 2 is a gas chromatographic detection of the gas produced in FIG. 1. It can be seen in the figure that the retention time of the white smoke is consistent with that of oxygen, indicating that the main component of the white smoke is oxygen.
FIG. 3 shows SEM pictures of MB-H0 and MB-H5. It can be seen that at the same magnification, particulate particulates were present on the surface of the MB-H0 catalyst and not on the surface of the MB-H5 catalyst, which was much smoother.
FIG. 4 shows XRD patterns of MB-H0 and MB-H5. It can be seen that the MB-H0 sample exhibited characteristic diffraction peaks of KCl (JCPDS nos. 41-1476) at 2 θ =28.3 °, 40.5 °, 50.1 °, 58.6 °, 66.4 °, 73.7 °, indicating that the main species of MB-H0 was KCl. In addition, the diffraction peak at 2 θ =36.3 ° is assigned to MnO2The unmodified MB-H0 sample was shown to be composed primarily of KCl and MnO2. The diffraction peak of the MB-H5 sample at 2 θ =18.8 °, 21.6 ° is assigned to mno (oh), and the diffraction peak at 2 θ =24.5 ° is assigned to SiO2The main components are MnO (OH) and SiO2。
FIG. 5 shows XPS spectra of MB-H0 and MB-H5. As can be seen from FIGS. 5a and 5b, the modified MB-H5 sample has no K, Cl or Ca elements, but has a Si element peak, which is consistent with the results of XRD analysis, as compared with the pre-modified MB-H0 sample. In addition, the Mn2p patterns (FIGS. 5c, 5d) of the MB-H0 and MB-H5 samples show that Mn2p in the MB-H0 sample is a complex valence state in which Mn is +2 and +4, while the valence state of Mn in the MB-H5 sample is +3, which is also consistent with the analysis result in XRD.
FIG. 6 shows Activated Charcoal (AC), blank biochar (blank BC), H2O2Modified activated carbon (H)2O2-AC) and H2O2Modified blank biochar (H)2O2Blank BC) degradation kinetics curve for RhB. It can be seen that neither AC nor blank BC before nor after modification could photocatalytically degrade RhB. This is probably because these two carbon materials do not have transition metal elements or their contents are too low to have visible light catalytic activity, and thus are not capable of photocatalytic degradation of contaminants.
FIG. 7 is a graph of the degradation kinetics of manganese biochar on RhB before and after modification. As can be seen, the manganese biochar (MB-H0) before modification has no photocatalytic activity per se, and passes through H2O2The degradation rates of modified manganese biochar MB-H2, MB-H4, MB-H5 and MB-H6 to RhB are respectively 74%, 79%, 98% and 86%. The results show that H2O2The modification performance improves the photocatalytic activity of the manganese biochar to a certain extent, and H is modified along with the modification process2O2The photocatalytic degradation capability of the manganese biochar is enhanced along with the increase of the adding amount. When H is present2O2When the amount of (2) is 5ml, H is added2O2The ratio of volume (mL) to manganese biochar mass (g) is 50: 1 hour, the prepared manganese biochar MB-H5 sample has the highest reaction activity, and the degradation rate of RhB reaches 98% when the visible light reacts for 3 hours.
FIG. 8 is a graph of the degradation kinetics of copper carbon to RhB before and after modification. As can be seen, the degradation rate of modified copper biochar (CuB-H5) on RhB reaches 68% after 3 hours of photoreaction, which indicates that the copper biochar sample before modification has no photocatalytic activity and is subjected to H2O2The modified RhB has the catalytic capability of degrading RhB under the catalysis of visible light.
FIG. 9 is a graph of the degradation kinetics of iron carbon to RhB before and after modification. As can be seen, the degradation rate of the modified iron biochar (FeB-H5) on RhB reaches 63% after the photoreaction is carried out for 3 hours, which shows that only H passes through2O2The modified iron biochar (FeB-H5) has visible light catalytic performance.
FIG. 10 is a graph of the degradation kinetics of MB-H5 versus Phenol. It can be seen that the removal rate of the MB-H5 sample to Phenol after 5 hours of photoreaction is 52%, which indicates that the modified manganese biochar also has significant visible light catalytic degradation capability to organic colorless small molecule pollutants.
Table 1 shows the contents of manganese, copper and iron in the biochar before and after modification obtained in examples 4, 6 and 7, and it can be seen from the table that the contents of manganese, copper and iron elements in the manganese biochar (MB-H0), copper biochar (Cu-BC) and iron biochar (Fe-BC) are 11.3mg/g, 14.3mg/g and 9.7mg/g, respectively. Through H2O2After modification, the contents of manganese, copper and iron elements in the modified manganese biochar (MB-H5), the modified copper biochar (CuB-H5) and the modified iron biochar (FeB-H5) are respectively 4.4mg/g, 5.7mg/g and 3.1 mg/g. This may be with transition metals and H2O2Forms a ligand, and is the root cause of the photocatalytic activity.
TABLE 1 manganese, copper, iron content in biochar before and after modification of the biochar
| Mn（mg/g） | Cu（mg/g） | Fe（mg/g） | |
| Before modification | 11.3 | 14.3 | 9.7 |
| After modification | 4.4 | 5.7 | 3.1 |
Claims (7)
1. The preparation method of the hydrogen peroxide modified biochar containing the transition metal is characterized by comprising the following steps:
(1) taking biochar enriched with transition metals as a raw material, and dehydrating and thermally cracking to obtain a transition metal biochar sample;
(2) placing a transition metal biochar sample in a container, adding hydrogen peroxide dropwise, covering, leaving air holes on the cover, and placing in a constant-temperature oscillation box for oscillation for 12-24 h;
(3) and (3) carrying out suction filtration, washing and drying on the sample obtained in the step (2) to obtain the hydrogen peroxide modified transition metal-containing biochar product.
2. The method for preparing the hydrogen peroxide modified transition metal-containing biochar according to claim 1, wherein the biochar enriched with the transition metal in the step (1) comprises biochar enriched with one or more of manganese, copper, or iron; wherein the manganese content is more than 10 mg/g, the copper content is more than 14 mg/g, and the iron content is more than 9 mg/g.
3. The method for preparing hydrogen peroxide modified biochar containing transition metals as claimed in claim 1, wherein the pyrolysis process in step (1) is carried out at a temperature rise rate of 15-17 ℃/min to 300-700 ℃ for 0.5-2 h.
4. The process for producing hydrogen peroxide-modified transition metal-containing biochar according to claim 1, wherein H in step (2)2O2The mass concentration of the active carbon is 28-30 percent; h2O2The dropping speed of (A) is 60 to 75 drops/min.
5. The method for preparing hydrogen peroxide modified biochar containing transition metals according to claim 1, wherein the mass concentration of H in the step (2) is 28-30%2O2The ratio of the volume mL-mass g of the transition metal biochar sample to the volume mL-mass g of the transition metal biochar sample is 45-55: 1.
6. use of the hydrogen peroxide modified transition metal-containing biochar prepared according to any one of claims 1-5 for degrading toxic organic pollutants.
7. The use as claimed in claim 6, wherein the hydrogen peroxide modified transition metal-containing biochar is added in an amount of 250 mg/L.
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