CN112121822A - Preparation method of biochar/pyrite composite granular Fenton oxidation catalyst - Google Patents
Preparation method of biochar/pyrite composite granular Fenton oxidation catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 38
- 230000003647 oxidation Effects 0.000 title claims abstract description 37
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 37
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910052683 pyrite Inorganic materials 0.000 title claims abstract description 30
- 239000011028 pyrite Substances 0.000 title claims abstract description 30
- 239000002131 composite material Substances 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000007864 aqueous solution Substances 0.000 claims abstract description 14
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000001768 carboxy methyl cellulose Substances 0.000 claims abstract description 13
- 239000002245 particle Substances 0.000 claims abstract description 13
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims abstract description 13
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 238000000227 grinding Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 239000008247 solid mixture Substances 0.000 claims abstract description 7
- 230000004913 activation Effects 0.000 claims abstract description 6
- 238000009736 wetting Methods 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 238000000197 pyrolysis Methods 0.000 claims description 7
- 239000002028 Biomass Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 claims description 2
- NFMAZVUSKIJEIH-UHFFFAOYSA-N bis(sulfanylidene)iron Chemical compound S=[Fe]=S NFMAZVUSKIJEIH-UHFFFAOYSA-N 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- 229910000339 iron disulfide Inorganic materials 0.000 claims description 2
- 229910052569 sulfide mineral Inorganic materials 0.000 claims description 2
- 239000002351 wastewater Substances 0.000 abstract description 28
- 238000006243 chemical reaction Methods 0.000 abstract description 22
- 230000000694 effects Effects 0.000 abstract description 10
- 239000003242 anti bacterial agent Substances 0.000 abstract description 3
- 229940088710 antibiotic agent Drugs 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 9
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 8
- 239000003344 environmental pollutant Substances 0.000 description 7
- 231100000719 pollutant Toxicity 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000004065 wastewater treatment Methods 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 238000001125 extrusion Methods 0.000 description 5
- 239000010841 municipal wastewater Substances 0.000 description 5
- 239000010902 straw Substances 0.000 description 5
- 238000010525 oxidative degradation reaction Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000003115 biocidal effect Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
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- 239000000356 contaminant Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 235000010575 Pueraria lobata Nutrition 0.000 description 1
- 241000219781 Pueraria montana var. lobata Species 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
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- 239000011148 porous material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/343—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the pharmaceutical industry, e.g. containing antibiotics
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
-
- 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
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
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Abstract
The invention discloses a preparation method of a biochar/pyrite composite granular Fenton oxidation catalyst, which comprises the following steps: mixing biochar and pyrite in a mass ratio of 3: 1-5: 1, performing mechanical grinding and activation to obtain a solid mixture, then adding sodium carboxymethylcellulose aqueous solution for wetting, stirring and mixing uniformly, granulating, heating and curing at 200-250 ℃, and cooling to obtain a granular Fenton oxidation catalyst with the particle size of 2-5 mm. The granular Fenton oxidation catalyst prepared by the preparation method is easy to recycle after reaction, and has obvious effect when the catalytic Fenton oxidation method is used for treating organic wastewater such as dye, antibiotics and the like.
Description
Technical Field
The invention relates to the field of wastewater treatment agents, in particular to a preparation method of a biochar/pyrite composite granular Fenton oxidation catalyst.
Background
The Fenton (Fenton) oxidation method is a commonly used advanced oxidation technology for treating organic wastewater, and comprises the following stepsUsing Fe (II)/Fe (III) and H2O2Chain reaction between them to generate hydroxyl radical with strong oxidizing power (·OH)(Eθ(·OH/H2O) ═ 2.73V), which can degrade organic pollutants in water without selectivity. However, the slow conversion rate of Fe (III) to Fe (II) in the chain reaction limits the efficiency of Fenton oxidation for contaminant degradation. Therefore, in the conventional Fenton oxidation technology, the pH value of a medium needs to be adjusted in advance, and high-concentration Fe (II) needs to be added, so that a large amount of hazardous waste iron mud is generated in the subsequent process steps. In order to solve the problem, many researches adopt physical fields such as light, electricity, ultrasonic waves and the like to strengthen the Fenton reaction (Yulisu and the like, chemical reports, 2017,68: 297-; in recent years, researchers have focused on the catalysis of multiphase Fenton reactions by using cheap natural iron-containing minerals (such as pyrite, magnetite, etc.) (Fangjia et al, Proc. environmental science 2015,35: 3529-.
≡Fe(II)+H2O2→≡Fe(III)+·OH+OH- (1)
≡Fe(III)+H2O2→≡Fe(II)+HO2 ·+H+ (2)
Biochar (Biochar) is a high carbon-containing material obtained by high-temperature pyrolysis of waste biomass under an oxygen-limited condition, and has good application prospects in a plurality of fields such as carbon fixation and emission reduction, soil improvement, environmental remediation, carrier materials and the like. The biochar has the advantages of wide raw material source, simple preparation, developed pore structure, large specific surface area and rich surface functional groups, and can adsorb or fix various organic and heavy metal pollutants (Kudzuvine super-high grade, ecological and rural environmental bulletin, 2016,32: 168-doped 172) in soil and water. Recent researches have found that biochar is rich in electrons, has strong electron donating capability, and can accelerate the conversion of Fe (III) to Fe (II) in a Fenton reaction system (Wang et al, Chemical Engineering Journal,2019,362: 561-; meanwhile, the biochar can promote hydrogen peroxide (H)2O2) Decompose and improve·OH yield, which in turn accelerates the oxidative degradation of organic contaminants (Xiao et al, Chemical Engineering Journal,2020,391: 123605). However, the powdered biochar adopted in the existing research is difficult to separate and recycle from the wastewater after reaction, so that the application of the powdered biochar in the actual wastewater treatment engineering is restricted.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of a biochar/pyrite composite granular Fenton oxidation catalyst, the granular Fenton oxidation catalyst obtained by the preparation method is easy to recycle after reaction, and the effect is obvious when organic wastewater such as dye, antibiotics and the like is treated by a catalytic Fenton oxidation method.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a biochar/pyrite composite granular Fenton oxidation catalyst comprises the following steps: mixing biochar and pyrite in a mass ratio of 3: 1-5: 1, performing mechanical grinding and activation to obtain a solid mixture, then adding sodium carboxymethylcellulose aqueous solution for wetting, stirring and mixing uniformly, granulating, heating and curing at 200-250 ℃, and cooling to obtain a granular Fenton oxidation catalyst with the particle size of 2-5 mm.
The biochar is a solid obtained by pyrolysis of biomass serving as a raw material at 700-900 ℃. Biomass includes straw, wood chips, and the like.
The pyrite is a natural iron sulfide mineral with the mass content of iron disulfide being more than 95%.
The particle size of the solid mixture obtained by mechanical grinding and activation is below 50 μm. The mechanical grinding activation improves the reactivity of solid particles, and meanwhile, an oxide passivation layer on the surface of the pyrite can be effectively removed, so that the reactivity is further improved.
The concentration of the sodium carboxymethylcellulose aqueous solution is 3 wt%.
The dosage ratio of the sodium carboxymethylcellulose aqueous solution to the solid mixture is 1 mL-g-1～1.5mL·g-1. By the above-mentioned configurationThe sodium carboxymethyl cellulose can achieve the best wetting and bonding effect on solid substances (biochar and pyrite).
The product after granulation is cylindrical particles with the diameter of 2-3 mm and the length of 3-5 mm.
The invention has the beneficial effects that:
(1) the catalyst is granular, and is convenient to recycle from the treated wastewater.
(2) The biochar used by the catalyst is cheap and easily available, and can accelerate the conversion of Fe (III) to Fe (II) and promote H2O2Decomposition to produce·OH, and further improving the treatment effect on organic wastewater such as dye, antibiotics and the like.
(3) The pyrite used in the catalyst of the present invention can react with Fe (III), dissolved oxygen, etc. to release Fe (II) continuously, and simultaneously, the pH of the reaction system is maintained to be in an acidic state required by Fenton reaction.
(4) The catalyst of the invention can ensure that the Fenton oxidation method can maintain the degradation capability of organic wastewater in a wider pH range through the combination of the biochar and the pyrite.
Detailed Description
The following specific embodiments further describe the invention:
preparation of the catalyst
The preparation conditions of the particulate fenton oxidation catalyst are shown in table 1.
TABLE 1
Example 1
80g of biochar prepared by pyrolyzing straw as a raw material at 800 ℃ and 20g of pyrite (FeS) were weighed2Content is more than or equal to 95wt percent), and grinding the mixture in a ball mill until the grain diameter is less than 50 mu m. Taking out, adding 120mL of sodium carboxymethylcellulose aqueous solution with the mass content of 3%, stirring and mixing uniformly, and putting into an extrusion granulator to prepare cylindrical particles with the diameter of 2mm and the length of 3-4 mm. Then putting the mixture into an oven to be heated and cured at 230 DEG CAnd cooling to obtain the No. 1 granular Fenton oxidation catalyst.
Example 2
75g of biochar obtained by pyrolysis of straw at 800 ℃ and 15g of pyrite (FeS) were weighed according to the procedure of example 12Content is more than or equal to 95wt percent), and grinding the mixture in a ball mill until the grain diameter is less than 50 mu m. Taking out, adding 135mL of sodium carboxymethylcellulose aqueous solution with the mass content of 3%, stirring and mixing uniformly, and putting into an extrusion granulator to prepare cylindrical particles with the diameter of 2mm and the length of 3-4 mm. And then putting the mixture into an oven to be heated and solidified at 250 ℃, and cooling to obtain the No. 2 granular Fenton oxidation catalyst.
Example 3
75g of biochar obtained by pyrolysis of straw at 800 ℃ and 25g of pyrite (FeS) were weighed according to the procedure of example 12Content is more than or equal to 95wt percent), and grinding the mixture in a ball mill until the grain diameter is less than 50 mu m. Taking out, adding 100mL of sodium carboxymethylcellulose aqueous solution with the mass content of 3%, stirring and mixing uniformly, and putting into an extrusion granulator to prepare cylindrical particles with the diameter of 3mm and the length of 4-5 mm. And then putting the mixture into an oven to be heated and solidified at the temperature of 200 ℃, and cooling the mixture to obtain the No. 3 granular Fenton oxidation catalyst.
Example 4
80g of biochar obtained by pyrolysis of straw as a starting material at 700 ℃ and 20g of pyrite (FeS) were weighed according to the procedure described in example 12Content is more than or equal to 95wt percent), and grinding the mixture in a ball mill until the grain diameter is less than 50 mu m. Taking out, adding 120mL of sodium carboxymethylcellulose aqueous solution with the mass content of 3%, stirring and mixing uniformly, and putting into an extrusion granulator to prepare cylindrical particles with the diameter of 2mm and the length of 3-4 mm. And then putting the mixture into an oven to be heated and solidified at 230 ℃, and cooling to obtain the No. 4 granular Fenton oxidation catalyst.
Example 5
75g of biochar obtained by pyrolysis of wood chips at 900 ℃ and 15g of pyrite (FeS) were weighed out as described in example 12Content is more than or equal to 95wt percent), and grinding the mixture in a ball mill until the grain diameter is less than 50 mu m. Taking out, adding sodium carboxymethylcellulose with mass content of 3%And (3) uniformly stirring and mixing 117mL of the aqueous solution, and then putting the aqueous solution into an extrusion granulator to prepare cylindrical particles with the diameter of 2mm and the length of 3-4 mm. And then putting the mixture into an oven to be heated and solidified at 220 ℃, and cooling to obtain the 5# granular Fenton oxidation catalyst.
Verification implementation effect for treating organic wastewater
The effect of various catalysts on the catalytic Fenton oxidative degradation of organic wastewater is shown in Table 2.
TABLE 2
The Chemical Oxygen Demand (COD) in 1L is 450 mg.L-13g of granular Fenton oxidation catalysts No. 1, No. 2 and No. 3 prepared in examples 1, 2 and 3 were added to the dye wastewater of (1) & lt, & gt mol & L, and after stirring the mixture uniformly-120mL of the aqueous solution of hydrogen peroxide is used for starting the reaction, and after the reaction is carried out for 80min, the COD in the wastewater is respectively reduced to 35 mg.L, 43 mg.L and 33 mg.L by sampling and measuring-1The concentration of the wastewater is lower than the allowable discharge concentration (50 mg. L) of the first class A standard in GB18918-2002 discharge Standard of pollutants for municipal wastewater treatment plants-1)。
The Chemical Oxygen Demand (COD) in 1L is 260mgL-12g of the No. 4 and No. 5 granular Fenton oxidation catalyst prepared in examples 4 and 5 was added to the antibiotic wastewater of (1) and stirred uniformly, and then the solution was added to the reactor at a concentration of 1 mol. L-1The reaction is started by 10mL of aqueous hydrogen peroxide solution, and after the reaction is carried out for 120min, the COD in the wastewater is respectively reduced to 41 mg/L and 30 mg/L by sampling and measuring-1The allowable discharge concentration (50 mg. L) is lower than the first class A standard in GB18918-2002 discharge Standard of pollutants for municipal wastewater treatment plants-1)。
The Chemical Oxygen Demand (COD) in 1L is 450 mg.L-1Adding 3g of pyrite into the dye wastewater, stirring uniformly, and adding the 1 mol/L-concentration-120mL of the aqueous hydrogen peroxide solution is used for starting the reaction, and after the reaction is carried out for 80min, the COD in the wastewater is reduced to 162 mg.L by sampling-1The allowable discharge concentration (50 m) of the pollutant discharge concentration exceeds the first class A standard in GB18918-2002 discharge Standard of pollutants for municipal wastewater treatment plantsgL-1). Compared with the effect of treating the organic wastewater by the catalysts prepared in examples 1, 2 and 3, the granular Fenton oxidation catalyst prepared by the invention has better effect on the oxidative degradation of the organic wastewater.
Chemical Oxygen Demand (COD) at 1L is 260 mg.L-1Adding 2g of pyrite into the antibiotic wastewater, stirring uniformly, and adding the antibiotic wastewater with the concentration of 1 mol.L-1The reaction is started by 10mL of aqueous hydrogen peroxide solution, and after the reaction is carried out for 120min, the COD in the wastewater is reduced to 127 mg.L by sampling-1The allowable discharge concentration (50 mgL) of the first class A standard in GB18918-2002 discharge Standard of pollutants for municipal wastewater treatment plants-1). Compared with the effect of treating the organic wastewater by the catalysts prepared in examples 4 and 5, the granular Fenton oxidation catalyst prepared by the invention has better effect on the oxidative degradation of the organic wastewater.
The Chemical Oxygen Demand (COD) in 1L is 450 mg.L-1The initial pH of the waste water was adjusted to 3.0, 5.0, 7.0, 9.0 and 11.0 with dilute sulfuric acid or dilute sodium hydroxide solution, respectively, 3g of the granular Fenton oxidation catalyst No. 1 prepared in example 1 was added thereto, and after stirring the mixture uniformly, the mixture was added to the reactor at a concentration of 1 mol. L-1After the reaction is carried out for 80min, the pH of the wastewater is respectively 2.9, 3.1, 3.6 and 4.3 by sampling and measuring, and the COD in the wastewater is respectively reduced to 27, 32, 33, 45 and 62 mg.L-1. Except for the strong alkaline condition with the initial pH of 11.0, the COD of the wastewater treated under other conditions is lower than the allowable discharge concentration (50 mg. L) of the primary A standard in GB18918-2002 pollutant discharge Standard of municipal wastewater treatment plant-1). The granular Fenton oxidation catalyst prepared by the invention has wider application range on the pH value of organic wastewater.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (7)
1. A preparation method of a biochar/pyrite composite granular Fenton oxidation catalyst is characterized by comprising the following steps: the method comprises the following steps: mixing biochar and pyrite in a mass ratio of 3: 1-5: 1, performing mechanical grinding and activation to obtain a solid mixture, then adding sodium carboxymethylcellulose aqueous solution for wetting, stirring and mixing uniformly, granulating, heating and curing at 200-250 ℃, and cooling to obtain a granular Fenton oxidation catalyst with the particle size of 2-5 mm.
2. The method for preparing the biochar/pyrite composite granular Fenton oxidation catalyst according to claim 1, characterized by comprising the following steps: the biochar is a solid obtained by pyrolysis of biomass serving as a raw material at 700-900 ℃.
3. The method for preparing the biochar/pyrite composite granular Fenton oxidation catalyst according to claim 1, characterized by comprising the following steps: the pyrite is a natural iron sulfide mineral with the mass content of iron disulfide being more than 95%.
4. The method for preparing the biochar/pyrite composite granular Fenton oxidation catalyst according to claim 1, characterized by comprising the following steps: the particle size of the solid mixture obtained by mechanical grinding and activation is below 50 μm.
5. The method for preparing the biochar/pyrite composite granular Fenton oxidation catalyst according to claim 1, characterized by comprising the following steps: the concentration of the sodium carboxymethylcellulose aqueous solution is 3 wt%.
6. The method for preparing the biochar/pyrite composite granular Fenton oxidation catalyst according to claim 1, characterized by comprising the following steps: the dosage ratio of the sodium carboxymethylcellulose aqueous solution to the solid mixture is 1 mL-g-1～1.5mL·g-1。
7. The method for preparing the biochar/pyrite composite granular Fenton oxidation catalyst according to claim 1, characterized by comprising the following steps: the product after granulation is cylindrical particles with the diameter of 2-3 mm and the length of 3-5 mm.
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| CN112897624A (en) * | 2021-01-26 | 2021-06-04 | 南开大学 | Pyrite/biochar composite material and preparation method and application thereof |
| CN113426448A (en) * | 2021-06-04 | 2021-09-24 | 浙江科技学院 | Preparation method and application of novel biochar-based tar cracking catalyst |
| CN114192106A (en) * | 2021-11-29 | 2022-03-18 | 山东鲁抗中和环保科技有限公司 | Preparation method and application of iron-loaded bentonite |
| CN114653332A (en) * | 2022-03-24 | 2022-06-24 | 湖南大学 | Method for degrading antibiotics in water body by using pyrite modified charcoal |
| CN115041197A (en) * | 2022-07-27 | 2022-09-13 | 广西民族大学 | Ferrous disulfide/tungsten disulfide composite catalyst and preparation method and application thereof |
| CN116078350A (en) * | 2022-12-30 | 2023-05-09 | 四川师范大学 | Pyrite-biochar composite material and preparation and application thereof |
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| CN112897624A (en) * | 2021-01-26 | 2021-06-04 | 南开大学 | Pyrite/biochar composite material and preparation method and application thereof |
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| CN114653332B (en) * | 2022-03-24 | 2023-08-15 | 湖南大学 | Method for degrading antibiotics in water body by pyrite modified biochar |
| CN115041197A (en) * | 2022-07-27 | 2022-09-13 | 广西民族大学 | Ferrous disulfide/tungsten disulfide composite catalyst and preparation method and application thereof |
| CN115041197B (en) * | 2022-07-27 | 2023-09-19 | 广西民族大学 | Ferrous disulfide/tungsten disulfide composite catalyst and preparation method and application thereof |
| CN116078350A (en) * | 2022-12-30 | 2023-05-09 | 四川师范大学 | Pyrite-biochar composite material and preparation and application thereof |
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Application publication date: 20201225 |