CN116618065B - Preparation method and application of biochar composite material for in-situ remediation of organic contaminated sites - Google Patents
Preparation method and application of biochar composite material for in-situ remediation of organic contaminated sites Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 78
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 44
- 238000005067 remediation Methods 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 48
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims abstract description 47
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims abstract description 30
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims abstract description 30
- 235000005822 corn Nutrition 0.000 claims abstract description 30
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 27
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims abstract description 22
- 235000019345 sodium thiosulphate Nutrition 0.000 claims abstract description 22
- 230000003197 catalytic effect Effects 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000001816 cooling Methods 0.000 claims abstract description 11
- 238000001704 evaporation Methods 0.000 claims abstract description 11
- 230000008020 evaporation Effects 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 105
- 239000002689 soil Substances 0.000 claims description 74
- 240000008042 Zea mays Species 0.000 claims description 28
- 239000003673 groundwater Substances 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 22
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 19
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000010902 straw Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 14
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 12
- 239000011790 ferrous sulphate Substances 0.000 claims description 12
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 238000002347 injection Methods 0.000 claims description 6
- 239000007924 injection Substances 0.000 claims description 6
- 239000003344 environmental pollutant Substances 0.000 claims description 5
- 231100000719 pollutant Toxicity 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 4
- 150000001555 benzenes Chemical class 0.000 claims description 3
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 claims description 3
- HFZWRUODUSTPEG-UHFFFAOYSA-N 2,4-dichlorophenol Chemical compound OC1=CC=C(Cl)C=C1Cl HFZWRUODUSTPEG-UHFFFAOYSA-N 0.000 claims description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 2
- 229960002089 ferrous chloride Drugs 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- 241000894007 species Species 0.000 claims description 2
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 2
- 229910052799 carbon Inorganic materials 0.000 claims 2
- 230000008439 repair process Effects 0.000 abstract description 13
- 239000003575 carbonaceous material Substances 0.000 abstract description 3
- 230000015556 catabolic process Effects 0.000 abstract description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 2
- 241000209149 Zea Species 0.000 abstract 2
- 239000003610 charcoal Substances 0.000 abstract 1
- 238000002474 experimental method Methods 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 6
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- 229920005372 Plexiglas® Polymers 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 238000001514 detection method Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 230000004913 activation Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Classifications
-
- 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
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C2101/00—In situ
-
- 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
- C02F2101/34—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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/06—Contaminated groundwater or leachate
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Materials Engineering (AREA)
- Soil Sciences (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention relates to a preparation method and application of a biochar composite material for in-situ remediation of an organic contaminated site. According to the method, corn stalks, ferrous salt and sodium thiosulfate are used as raw materials, the ferrous salt and the sodium thiosulfate are firstly dissolved in water, then a certain amount of corn stalks are added, and the charcoal composite material capable of efficiently catalyzing persulfate to repair an organic pollution site in situ is prepared through evaporation, drying, roasting and cooling. Compared with iron-doped biochar, the biochar composite material provided by the invention has long-acting catalytic activity, and can realize efficient degradation of organic pollutants under the condition that the addition amount of the carbon material is reduced by 20% -50%, so that the in-situ repair cost is remarkably reduced.
Description
Technical Field
The invention belongs to the technical field of organic pollution site restoration, and particularly relates to a preparation method and application of a biochar composite material for in-situ restoration of an organic pollution site.
Background
Organic pollution in the field is always a focus of attention at home and abroad due to the harm of the organic pollution to the ecological environment and human health. The in-situ remediation technology has the advantages of good economy, low pollutant diffusion risk and small soil property change because no polluted soil is required to be dug out, and is widely applied to the field of organic pollution site remediation. Common in-situ repair techniques include in-situ resistance heating thermal desorption techniques, in-situ microorganism techniques, in-situ chemical oxidation/reduction techniques, and the like. The Persulfate (PS) chemical oxidation technology has the advantages of high oxidation efficiency, mild reaction conditions, easy transportation and storage of PS and the like, and is widely used for in-situ oxidation repair of organic pollution sites.
The key to PS oxidation technology is the generation of strongly oxidative free radicals by activation. Fe (II) is a common catalyst for activating PS, and has the advantages of low price, wide sources, safety, no toxicity and the like. However, the pH application range of the PS catalyzed by directly using Fe (II) is acidic (pH 3-4), and for near-neutral and alkaline organic pollution sites, fe (II) and OH can be mixed - The generation of precipitate greatly reduces the catalytic capability, and organic pollutants in the field are difficult to effectively remove. The research shows that the biochar loaded Fe (II) has good catalytic activation on PS because: 1) Fe (II) is loaded on the biochar, so that leaching and precipitation losses of the Fe (II) can be reduced, and PS can be catalyzed in a wider pH range (pH 3-9); 2) The oxygen-containing functional groups on the surface of the biochar have a synergistic catalytic effect on PS.
When the single Fe (II) -loaded biochar is applied, the Fe (II) on the biochar reacts with PS to generate SO 4 - At the same time, fe (II) is converted into Fe (III), and Fe (III) has a reduced ability to provide electron-activated PS, so that the catalytic activity of the catalyst is difficult to be sustained. Therefore, developing a catalyst activated PS with long-acting catalytic activity has become a research hotspot for PS in situ oxidation remediation of organic contaminated sites.
Disclosure of Invention
The invention provides a preparation method of a biochar composite material for in-situ remediation of an organic contaminated site and application of the biochar composite material in-situ remediation of the organic contaminated site. The sulfur is loaded on the iron-doped biochar to increase the conductivity of the biochar material, and meanwhile, fe (III) generated in the reaction process can be reduced to Fe (II), so that the biochar composite material has good catalytic performance on PS for a long time.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the preparation method of the biochar composite material for repairing the organic pollution site in situ comprises the steps of taking corn straw, ferrous salt and sodium thiosulfate as raw materials, firstly dissolving the ferrous salt and the sodium thiosulfate in water, then adding a certain amount of corn straw, and preparing the biochar composite material capable of catalyzing PS in situ to repair the organic pollution site in high efficiency by evaporation, drying, roasting and cooling; the evaporation is stirring evaporation under the water bath heating condition, and the roasting condition is as follows: in CO 2 Heating to 350-450 ℃ in the atmosphere, maintaining for 0.5-2h, heating to 550-800 ℃ and roasting for 0.5-2h.
The ferrous salt is water-soluble ferrous salt, such as ferrous sulfate or at least one of ferrous chloride and ferrous nitrate.
Wherein the mass percentages of the components of the preferable raw materials are as follows: 70-85% of corn stalks, 5-20% of ferrous salt and 10% of sodium thiosulfate.
The preparation method of the biochar composite material for in-situ remediation of the organic contaminated site comprises the following specific steps:
1) Mixing the raw materials: dissolving ferrous salt and sodium thiosulfate which are 5% -20% of the total mass of the raw materials into enough deionized water to obtain a mixed solution; crushing corn stalks, sieving the crushed corn stalks with a sieve of 80-200 meshes, adding the sieved corn stalks into the mixed solution, wherein the adding amount of the corn stalks is 70-85%, and stirring the mixture to form a solid-liquid mixture;
the sufficient deionized water can completely dissolve ferrous salt and sodium thiosulfate, and can fully impregnate the added corn stalks to form a solid-liquid mixture;
2) And (3) evaporation: heating and stirring in a water bath to fully evaporate water in the solid-liquid mixture to be nearly dry, wherein the temperature of the water bath heating is set to enable the water to be rapidly evaporated and simultaneously enable iron species in a system to mainly exist in a Fe (II) form and have a small amount of Fe (III);
3) And (3) drying: placing the evaporated substance in an oven at 60 ℃ to remove residual moisture to constant weight;
4) Roasting: roasting the material with water removed, and adding the material into CO 2 Heating to 350-450 ℃ in the atmosphere, keeping 0.5-2h, heating to 550-800 ℃ and continuously roasting 0.5-2h;
5) And (3) cooling: stopping roasting, and cooling 6-12 h to obtain the biochar composite material.
Preferably, CO 2 The temperature rising rate under the atmosphere is 5-15 ℃/min, and CO 2 The temperature of the atmosphere is 600-800 ℃ at the end of temperature rise, including but not limited to 650 ℃, 700 ℃, 750 ℃, 780 ℃ and the like.
Preferably, the water bath heating temperature in the step 2) is 50-70 ℃;
the method comprises the steps of utilizing the biochar composite material to catalyze PS to repair organic contaminated soil in situ, mixing deionized water and the biochar composite material into homogenate, preparing oxidant PS into solution, and injecting the solution into the organic contaminated soil. And reacting for 5-10 days, taking a soil sample to extract organic pollutants therein, and calculating the content of the residual organic pollutants in the soil through analysis and detection. The concentration of organic pollutants in the soil is 50-500 mg/kg, the concentration of the biochar composite material added into the soil is 1-5 g/kg (the mass of the biochar composite material added into 1kg of the soil is 1-5 g), the concentration of the persulfate solution is 1-5 g/L, the injection rate of the medicament (the biochar composite material and PS) is 5 mL/min, and the mass ratio of the biochar composite material to the PS is preferably 1:1-1:1.7.
The organic pollution underground water is repaired in situ by utilizing the biochar composite material, the catalyst biochar composite material and the oxidant PS are added into the organic pollution underground water, the mixture is uniformly mixed and then reacted for 24-48 hours, a water sample after the reaction is taken, and the content of the residual organic pollutants in the water body is calculated after detection and analysis. The concentration of organic pollutants in groundwater is 50-500 mg/L, the concentration of the biochar composite material added into water is 0.3-1.5 g/L, the concentration of the oxidant PS is 0.2-2 g/L, the biochar composite material has good catalytic performance on PS in 24 h, and the mass ratio of the biochar composite material to the PS is preferably 1:2-1:2.5.
The organic contaminated soil is soil contaminated by benzene series (such as benzene and toluene) or chlorinated hydrocarbon (such as 1, 2-dichloroethane and trichloroethylene), and the organic contaminated groundwater is groundwater contaminated by phenol type pollutants (such as phenol and 2, 4-dichlorophenol).
Compared with the prior art, the invention has the beneficial effects that:
1) The biochar composite material has long-acting catalytic activity. The biochar composite material prepared by the invention overcomes the limitation that new Fe (II) is difficult to circularly generate after Fe (II) is used for catalyzing PS to generate Fe (III) in the past, and the catalytic effect is difficult to continuously maintain. Anaerobic decomposition of sodium thiosulfate to S in the first stage of roasting 2- ，S 2- Can reduce Fe (III) into Fe (II), thereby improving the catalytic activity of the biochar composite material. In addition, S on the surface of the biochar composite material 2- Can combine with Fe (II), and in the process of catalytic reaction, the Fe (II) is slowly released to react with PS to generate SO 4 - The catalysis performance of the biochar composite material for catalyzing PS for a long time is obviously improved.
2) The biochar composite material can obviously reduce in-situ repair cost. Compared with iron-doped biochar, the biochar composite material prepared by the method can realize the efficient degradation of organic pollutants in soil under the condition that the addition amount of the biochar composite material is reduced by 20% -50%, and the in-situ repair cost is remarkably reduced.
Detailed Description
For a better understanding of the present invention, the present invention will be further described with reference to the following embodiments, but the examples are not intended to limit the scope of the present invention.
According to the invention, ferrous salt and sodium thiosulfate are used as raw materials, doping modification is carried out on the carbon-based material, the catalyst consumption can be reduced on the premise of greatly improving the PS catalytic efficiency, the repairing cost is obviously reduced, and the biochar composite material can continuously catalyze PS in a long time. Experiments show that the performance of the biochar composite material for catalyzing PS to remove organic pollutants is obviously stronger than that of PS alone, and the catalytic effect of the biochar composite material is obviously better than that of a single iron-or sulfur-doped carbon-based material under the same condition.
Example 1: (1) The preparation method of the biochar composite material for in-situ remediation of the organic pollution site in the embodiment is a method for preparing the biochar composite material by taking corn straw, ferrous sulfate and sodium thiosulfate as raw materials, and comprises the following specific preparation steps:
1) Mixing the raw materials: dissolving ferrous sulfate and sodium thiosulfate which are 10% of the total mass of the raw materials into 100 mL deionized water to obtain a mixed solution, crushing corn straw, sieving the crushed corn straw with a sieve of 80-200 meshes, adding the sieved corn straw into the mixed solution, wherein the adding amount of the corn straw is 80% (the mass ratio of the corn straw to the ferrous sulfate to the sodium thiosulfate is 8:1:1), and uniformly stirring to obtain a solid-liquid mixture;
2) And (3) evaporation: heating and stirring the mixture in a water bath of a constant-temperature water bath kettle to fully evaporate the water in the solid-liquid mixture to be nearly dry, wherein the water bath temperature is 60 ℃;
3) And (3) drying: placing the evaporated substance in an oven at 60 ℃ to remove residual moisture to constant weight;
4) Roasting: roasting the material with water removed, and adding the material into CO 2 Heating to 350 ℃ under the atmosphere, keeping 1 h, heating to 600 ℃ and continuously roasting 1 h;
5) And (3) cooling: stopping roasting, and cooling 6 h to obtain the biochar composite material.
(2) Experiment for in situ remediation of organic contaminated soil:
the biochar composite material is used for repairing toluene contaminated soil. The experimental process comprises the following specific steps:
in the toluene contaminated soil according to the embodiment of the present invention, the concentration of toluene was 250 mg/kg.
The method comprises the steps of utilizing the biochar composite material to repair toluene contaminated soil in situ, adding 1.5 g biochar composite material into 200 mL deionized water, mixing to obtain homogenate, and adding 1.5 g sodium persulfate into 200 mL deionized water to prepare a solution for later use. The biochar composite material was first injected into a plexiglass column (inner diameter of plexiglass column 8 cm, height 30 cm) containing 1kg toluene contaminated soil at an injection rate of 5 mL/min. And then the sodium persulfate solution is injected into the polluted soil at the injection rate of 5 mL/min. Standing to react 120 h, taking a soil sample every 12 h to extract toluene therein, analyzing and detecting, and calculating the concentration of the residual toluene in the soil.
The result showed that the toluene concentration remained in the soil after 120. 120 h reached the end of the reaction was 21.8 mg/kg, and the removal rate of toluene in the soil was 91.3%.
Example 2: the preparation method of the biochar composite material for in-situ remediation of an organic contaminated site in the embodiment is the same as that in the embodiment 1, and is different in that the mass ratio of the corn stalk to the ferrous sulfate to the sodium thiosulfate is 7:2:1.
The biochar composite material is used for repairing toluene contaminated soil. In the toluene contaminated soil according to the example of the present invention, the toluene concentration was 250 mg/kg, and the experimental procedure was the same as in example 1.
The result showed that the toluene concentration in the soil was 53.7 mg/kg after 120. 120 h reached the end of the reaction, and the toluene removal rate from the soil was 78.5%.
Example 3: (1) The preparation method of the biochar composite material takes corn straw, ferrous sulfate and sodium thiosulfate as raw materials, and specifically comprises the following steps:
1) Mixing the raw materials: dissolving ferrous sulfate and 10% sodium thiosulfate which are equivalent to the total mass of the raw materials in 100 mL deionized water to obtain a mixed solution, crushing corn straw, sieving with a 80-200 mesh sieve, adding the sieved corn straw into the mixed solution, wherein the adding amount of the corn straw is 85% (the mass ratio of the corn straw to the ferrous sulfate to the sodium thiosulfate is 17:1:2), and stirring uniformly to obtain a solid-liquid mixture;
2) And (3) evaporation: heating and stirring the mixture in a water bath of a constant-temperature water bath kettle to fully evaporate the water in the solid-liquid mixture to be nearly dry, wherein the water bath temperature is 60 ℃;
3) And (3) drying: placing the evaporated material in an oven at 60 ℃ to remove residual moisture to constant weight;
4) Roasting: will remove waterRoasting the separated material in CO 2 Heating to 350 ℃ under the atmosphere, keeping 1 h, heating to 600 ℃ and continuously roasting 2h;
5) And (3) cooling: stopping roasting, and cooling 6 h to obtain the biochar composite material.
(2) Experiment for in situ remediation of organic contaminated soil:
the biochar composite material is used for repairing toluene contaminated soil. In the toluene contaminated soil according to the example of the present invention, the toluene concentration was 250 mg/kg, and the experimental procedure was the same as in example 1.
The result showed that the toluene concentration in the soil was 43.8 mg/kg after 120. 120 h reached the end of the reaction, and the toluene removal rate from the soil was 82.5%.
Example 4: this example uses the biochar composite of example 1 for in situ remediation of 1, 2-dichloroethane contaminated soil.
In the 1, 2-dichloroethane-polluted soil according to the embodiment of the invention, the concentration of 1, 2-dichloroethane is 250 mg/kg.
The biochar composite material is used for in-situ remediation of 1, 2-dichloroethane contaminated soil, 1.5 g biochar composite material is added into 200 mL deionized water to be mixed into homogenate, and 1.5 g sodium persulfate is added into 200 mL deionized water to be prepared into solution for standby. The homogenate of the biochar composite catalytic material was injected into a plexiglass column (inner diameter of plexiglass column is 8 cm, height is 30 cm) filled with 1kg of 1, 2-dichloroethane contaminated soil at an injection rate of 5 mL/min. And then the sodium persulfate solution is injected into the polluted soil at the injection rate of 5 mL/min. Standing to react 120 h, taking a soil sample every 12 h to extract 1, 2-dichloroethane therein, analyzing and detecting, and calculating the concentration of the residual 1, 2-dichloroethane in the soil.
The results showed that the 1, 2-dichloroethane remaining in the soil after 120. 120 h had reached the end of the reaction at a concentration of 11.5. 11.5 mg/kg gave a removal rate of 1, 2-dichloroethane in the soil of 95.4%.
Example 5: in this example, the biochar composite material of example 2 was used for in situ remediation of 1, 2-dichloroethane contaminated soil.
In the 1, 2-dichloroethane-polluted soil according to the embodiment of the invention, the concentration of 1, 2-dichloroethane is 250 mg/kg. The experimental procedure was the same as in example 4.
The results showed that the 1, 2-dichloroethane remaining in the soil after 120. 120 h had reached the end of the reaction had a concentration of 61.0 mg/kg, and the removal rate of 1, 2-dichloroethane in the soil was 75.6%.
Example 6: in this example, the biochar composite material of example 3 was used for in situ remediation of 1, 2-dichloroethane contaminated soil.
In the 1, 2-dichloroethane-polluted soil according to the embodiment of the invention, the concentration of 1, 2-dichloroethane is 250 mg/kg. The experimental procedure was the same as in example 4.
The results showed that after 120 h reached the end of the reaction, the residual 1, 2-dichloroethane concentration in the soil was 38.3 mg/kg, and the removal rate of 1, 2-dichloroethane in the soil was 84.7%.
Example 7: the biochar composite material in the embodiment 1 is used for in-situ remediation of organic contaminated groundwater, and is particularly used for removing phenol in the groundwater.
The embodiment of the invention is used for treating the underground water polluted by phenol, and the concentration of the phenol is 50 mg/L. The specific experimental steps are as follows:
20 mg biochar composite material and 50 mg persulfate are added into phenol-polluted groundwater with the concentration of 50 mg/L of 100 mL, and stirred for reaction 24 h, and samples are taken at 1 h, 3 h, 6 h, 12 h and 24 h respectively. Through analysis and detection, the concentration of residual phenol in the groundwater is calculated.
The result shows that after 24 h reaches the end of the reaction, the residual phenol concentration in the groundwater is 3.8 mg/L, and the removal rate of phenol in the groundwater is 92.4%.
Example 8: in this example, the biochar composite material of example 2 was used to repair phenol-contaminated groundwater in situ.
In the phenol-contaminated groundwater according to the example of the present invention, the phenol concentration was 50 mg/L. The experimental procedure was the same as in example 7.
The result showed that the residual phenol concentration in the groundwater was 9.4 mg/L after 24. 24 h reached the end of the reaction, and the removal rate of phenol in the groundwater was 81.2%.
Example 9: in this example, the biochar composite material of example 3 was used to repair phenol-contaminated groundwater in situ.
In the phenol-contaminated groundwater according to the example of the present invention, the phenol concentration was 50 mg/L. The experimental procedure was the same as in example 7.
The result shows that after 24. 24 h reaches the reaction end point, the residual phenol concentration in the groundwater is 32.5 mg/L, and the removal rate of phenol in the groundwater is 85.1%.
To more intuitively display the data changes in examples 1-6, the data are shown in Table 1:
the initial concentrations of toluene and 1, 2-dichloroethane in the contaminated soil were: 250 mg/kg, the concentration of the biochar composite material added into the soil is as follows: 1.5 g/kg, the concentration of the sodium persulfate solution is as follows: 7.5 g/L, reaction time 5 d.
To more intuitively display the data changes in examples 7-9, the data are shown in Table 2:
the initial concentration of phenol in the groundwater is 50 mg/L, and the concentration of the biochar composite material added with the groundwater is as follows: 0.2 The concentration of the sodium persulfate solution at g/L is as follows: 0.5 g/L, reaction time 24 h.
Comparative example 1: the biochar composite material in example 1 was replaced with a ferrous sulfate doped biochar material and the conditions in example 1 were followed for in situ remediation of toluene contaminated soil, i.e. sodium thiosulfate was not added in this comparative example, and the remaining steps were the same as in example 1.
The result showed that 48 h was reached at the end of the reaction, and the residual toluene concentration in the soil was 73. 73 mg/kg, resulting in a removal rate of 60.8%.
Comparative example 2: the biochar composite material in example 1 was replaced with a sodium thiosulfate-doped biochar material, and the conditions in example 1 were used to repair toluene contaminated soil in situ, i.e., no ferrous sulfate was added to this comparative example, and the remaining steps were the same as in example 1.
The result showed that 48 h was reached at the end of the reaction, and the residual toluene concentration in the soil was 211.5 mg/kg, resulting in a removal rate of 15.4%.
Comparative example 3: the firing atmosphere in example 1 was changed to N 2 Other conditions were the same as in example 1, and the conditions in example 1 were used for in situ remediation of toluene contaminated soil.
The result showed that the toluene concentration remained in the soil was 180.3 mg/kg after 120. 120 h reached the end of the reaction, and the removal rate of toluene in the soil was 72.1%.
Comparative example 4: the calcination conditions in example 1 were changed to CO 2 The conditions were otherwise the same as in example 1 except that the temperature was raised directly to 600℃and maintained at 2h without stage roasting in the atmosphere, and the conditions in example 1 were used to repair toluene contaminated soil in situ.
The result showed that the reaction was terminated after 72. 72 h, the concentration of toluene remained in the soil was 117.3 mg/kg, and the removal efficiency of toluene in the soil was 53.1%.
Comparative example 5: step 2) of example 1 was modified to be stirred with a magnetic stirrer for 6 h and then dried in an oven at 60℃under the same conditions as in example 1, and toluene contaminated soil was restored in situ according to the conditions of example 1.
The result showed that the toluene concentration remained in the soil was 96.5 mg/kg and the toluene removal efficiency from the soil was 61.4% after 120 h reached the end of the reaction.
According to the invention, corn straw, ferrous sulfate and sodium thiosulfate are selected as raw materials, and under a specific method, the low-cost, environment-friendly and efficient biochar composite material for catalyzing PS in-situ remediation of the organic pollution site is prepared. Experimental results show that the biochar composite material can effectively remove organic pollutants in soil and underground water, the effective catalytic duration of the catalyst on PS in the soil is 120 h, the effective catalytic duration of the catalyst on PS in the underground water is 24 h, and the pollutant removal efficiency of the process operation within a given parameter range is obviously improved under the same condition.
The invention is applicable to the prior art where it is not described.
Claims (8)
1. The application of the biochar composite material in catalyzing persulfate in-situ remediation of the organic pollution site is characterized in that corn straw, ferrous salt and sodium thiosulfate are used as raw materials, the ferrous salt and the sodium thiosulfate are dissolved in water, then the corn straw is added, and the biochar composite material for catalyzing persulfate in-situ remediation of the organic pollution site is prepared through evaporation, drying, roasting and cooling; the evaporation is stirring evaporation under the water bath heating condition, and the roasting condition is as follows: in CO 2 Heating to 350-450 ℃ in the atmosphere, maintaining for 0.5-2h, heating to 550-800 ℃ and roasting for 0.5-2h;
the raw materials comprise the following components in percentage by mass: 70-85% of corn stalks, 5-20% of ferrous salt and 10% of sodium thiosulfate.
2. The use according to claim 1, wherein the ferrous salt is at least one of ferrous sulfate, ferrous chloride or ferrous nitrate.
3. The use according to claim 1, characterized in that the specific steps of the preparation method are:
1) Mixing the raw materials: dissolving ferrous salt and sodium thiosulfate which are 5% -20% of the total mass of the raw materials into enough deionized water to obtain a mixed solution; crushing corn stalks, sieving the crushed corn stalks with a sieve of 80-200 meshes, adding the sieved corn stalks into the mixed solution, and uniformly stirring the mixture to form a solid-liquid mixture, wherein the adding amount of the corn stalks is 70-85%;
2) And (3) evaporation: heating and stirring in a water bath to fully evaporate water in the solid-liquid mixture, wherein the water bath temperature is set to enable water to be rapidly evaporated and enable iron species in a system to exist in a Fe (II) form;
3) And (3) drying: placing the evaporated substance in an oven at 50-70 ℃ to remove residual moisture to constant weight;
4) Roasting: roasting the material with water removed, and adding the material into CO 2 Heating to 350-450 ℃ in the atmosphere, keeping for 0.5-2h, heating to 550-800 ℃ and continuously roasting for 0.5-2h;
5) And (3) cooling: stopping roasting, and cooling for 6-12 h to obtain the biochar composite material.
4. A method of preparation according to claim 3, wherein the CO 2 The temperature rising rate under the atmosphere is 5-15 ℃/min, and CO 2 The temperature of the atmosphere at the temperature of 550-700 ℃ after the temperature rise; the heating temperature of the water bath is 50-70 ℃.
5. Use of the biochar composite material according to claim 1 for in situ remediation of organically contaminated soil by means of persulfates catalyzed by said biochar composite material: mixing deionized water and the biochar composite material into homogenate, preparing persulfate into solution, and injecting the solution into organic contaminated soil; reacting for 5-10 days, taking a soil sample to extract organic pollutants in the soil, and calculating the concentration of the residual organic pollutants in the soil;
the concentration of organic pollutants in the soil is 50-500 mg/kg, the concentration of the biochar composite material added into the soil is 1-5 g/kg, the concentration of the persulfate solution is 1-5 g/L, and the injection rate of the biochar composite material and the persulfate is 5 mL/min.
6. The use according to claim 5, wherein the mass ratio of the biochar composite material to the persulfate is 1:1-1:1.7; the organic contaminated soil is soil contaminated by benzene series or chlorinated hydrocarbon, the benzene series is at least one of benzene and toluene, and the chlorinated hydrocarbon is at least one of 1, 2-dichloroethane and trichloroethylene.
7. Use of the biochar composite material according to claim 1 for in situ remediation of organically contaminated groundwater with the biochar composite material: adding the biochar composite material and persulfate into organic pollution groundwater, uniformly mixing and reacting for 24-48 hours, taking a water sample after the reaction, and calculating the concentration of residual organic pollutants in the groundwater;
the concentration of organic pollutants in the underground water is 50-500 mg/L, the concentration of the biological carbon composite material added into the underground water is 0.3-1.5 g/L, the concentration of persulfate is 0.2-2 g/L, and the biological carbon composite material has good catalytic performance on the persulfate in 24-h.
8. The application of claim 7, wherein the mass ratio of the biochar composite material to the persulfate is 1:2-1:2.5; the organic polluted groundwater is groundwater polluted by phenolic pollutants, and the phenolic pollutants are at least one of phenol and 2, 4-dichlorophenol.
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| JP2004359726A (en) * | 2003-06-02 | 2004-12-24 | Ishihara Sangyo Kaisha Ltd | Organic compound decomposition agent |
| CN109999768A (en) * | 2019-05-05 | 2019-07-12 | 河北工业大学 | A kind of stalk base composite absorbent purified for chlorinated aromatic hydrocarbons in incineration flue gas |
| CN113426449A (en) * | 2021-06-07 | 2021-09-24 | 中南大学 | Preparation and application of high-activation biochar based on thermal and cobalt complex modification |
| CN113856621A (en) * | 2021-08-13 | 2021-12-31 | 广东工业大学 | Preparation and application of iron-sulfur co-doped biochar material for simultaneously removing lead-arsenic composite pollution |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2004359726A (en) * | 2003-06-02 | 2004-12-24 | Ishihara Sangyo Kaisha Ltd | Organic compound decomposition agent |
| CN109999768A (en) * | 2019-05-05 | 2019-07-12 | 河北工业大学 | A kind of stalk base composite absorbent purified for chlorinated aromatic hydrocarbons in incineration flue gas |
| CN113426449A (en) * | 2021-06-07 | 2021-09-24 | 中南大学 | Preparation and application of high-activation biochar based on thermal and cobalt complex modification |
| CN113856621A (en) * | 2021-08-13 | 2021-12-31 | 广东工业大学 | Preparation and application of iron-sulfur co-doped biochar material for simultaneously removing lead-arsenic composite pollution |
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