CN110639469B - Sulfide reduction modified biochar and preparation method and application thereof - Google Patents
Sulfide reduction modified biochar and preparation method and application thereof Download PDFInfo
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- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 43
- 239000012498 ultrapure water Substances 0.000 claims abstract description 43
- 239000002994 raw material Substances 0.000 claims abstract description 41
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 38
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 37
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 32
- 239000011593 sulfur Substances 0.000 claims abstract description 32
- 239000000725 suspension Substances 0.000 claims abstract description 26
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 19
- 239000001301 oxygen Substances 0.000 claims abstract description 19
- 238000000967 suction filtration Methods 0.000 claims abstract description 18
- 238000012986 modification Methods 0.000 claims abstract description 17
- 230000004048 modification Effects 0.000 claims abstract description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 16
- 239000011368 organic material Substances 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 238000007873 sieving Methods 0.000 claims abstract description 9
- 238000000227 grinding Methods 0.000 claims abstract description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 7
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims description 15
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 14
- 239000002957 persistent organic pollutant Substances 0.000 claims description 14
- 239000012528 membrane Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000002351 wastewater Substances 0.000 claims description 10
- BFPYWIDHMRZLRN-SLHNCBLASA-N Ethinyl estradiol Chemical compound OC1=CC=C2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 BFPYWIDHMRZLRN-SLHNCBLASA-N 0.000 claims description 6
- 239000000356 contaminant Substances 0.000 claims description 6
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 6
- 230000007613 environmental effect Effects 0.000 claims description 4
- 229940011871 estrogen Drugs 0.000 claims description 4
- 239000000262 estrogen Substances 0.000 claims description 4
- 230000002209 hydrophobic effect Effects 0.000 claims description 4
- 235000017060 Arachis glabrata Nutrition 0.000 claims description 3
- 244000105624 Arachis hypogaea Species 0.000 claims description 3
- 235000010777 Arachis hypogaea Nutrition 0.000 claims description 3
- 235000018262 Arachis monticola Nutrition 0.000 claims description 3
- 241000218691 Cupressaceae Species 0.000 claims description 3
- 241000209140 Triticum Species 0.000 claims description 3
- 235000021307 Triticum Nutrition 0.000 claims description 3
- 210000003608 fece Anatomy 0.000 claims description 3
- 239000010871 livestock manure Substances 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 235000020232 peanut Nutrition 0.000 claims description 3
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 claims description 3
- 239000010902 straw Substances 0.000 claims description 3
- 150000003568 thioethers Chemical class 0.000 claims 4
- 238000001914 filtration Methods 0.000 claims 3
- 229930185605 Bisphenol Natural products 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 27
- 150000004763 sulfides Chemical class 0.000 description 24
- 238000001179 sorption measurement Methods 0.000 description 19
- 230000000694 effects Effects 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000005192 partition Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000000872 buffer Substances 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 241001326934 Triarrhena Species 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical group [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical group [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 2
- 229910014033 C-OH Inorganic materials 0.000 description 1
- 241000218645 Cedrus Species 0.000 description 1
- 229910014570 C—OH Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
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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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
- B01J20/0285—Sulfides of compounds other than those provided for in B01J20/045
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- 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
- C02F2101/32—Hydrocarbons, e.g. oil
- C02F2101/327—Polyaromatic Hydrocarbons [PAH's]
-
- 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
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- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Water Treatment By Sorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses sulfide reduction modified biochar and a preparation method and application thereof, wherein the preparation method comprises the following steps: under the condition of limited oxygen, preserving heat of a biological organic material at 300-700 ℃ for 2-4 hours, grinding for at least half an hour, sieving to obtain a biological carbon raw material, adding the biological carbon raw material into ultrapure water, carrying out ultrasonic treatment for at least 30 minutes, introducing nitrogen for at least 30 minutes to obtain a biological carbon suspension, adding the sulfur reduction modification solution obtained in the step 1) into the biological carbon suspension, stirring for at least 5 hours under the condition of introducing nitrogen, and carrying out suction filtration to obtain the sulfide reduction modified biological carbon. The preparation method provided by the invention has the advantages of simple operation steps, mild reaction, high safety and small environmental pollution, and the whole operation process is carried out under the conditions of normal temperature and normal pressure.
Description
Technical Field
The invention belongs to the technical field of environment functional materials, and particularly relates to sulfide reduction modified biochar and a preparation method and application thereof.
Background
As a novel environment functional material, the biochar has a large number of micro-pore structures and a high specific surface area, and shows a good adsorption removal effect on organic pollutants such as environmental estrogen and the like as an adsorbent in a water environment. Researches find that the biochar treated by different reducing agents or oxidizing agents has certain changes in the types and the number of surface functional groups and the size of surface pores, so that a more ideal adsorption effect is achieved. Therefore, many scholars consider the modified biochar as an ideal adsorbent and study the adsorption effect of the modified biochar on various pollutants in the environment.
In prior studies, modified biochar was limited to sulfur reduction modification. For example, patent 201710512326 discloses a triarrhena-based modified biochar material prepared by treating triarrhena-based biochar with potassium hydroxide and hydrochloric acid. Patent 201610530322 nitrifies raw material of biochar in concentrated acid mixed solution of concentrated nitric acid and concentrated sulfuric acid to obtain nitrified biochar, and then reduces the nitrified biochar by a reducing agent to obtain amino biochar; and soaking the obtained amino biochar in a solution containing an iron compound, and adding a reducing agent for reaction to finally obtain the iron-based-amino composite modified biochar material. However, most of the modified biochar prepared by the methods at present is suitable for removing heavy metal ions in wastewater, and the modified biochar for adsorbing organic pollutants in the wastewater is rare.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a sulfide reduction modified biochar which can remove organic pollutants in wastewater.
The invention also aims to provide the preparation method of the sulfide reduction modified biochar, which has the advantages of simple operation, mild reaction, low requirement on temperature and little environmental pollution.
The invention also aims to provide application of the sulfide reduction modified biochar in adsorbing organic pollutants in wastewater.
The purpose of the invention is realized by the following technical scheme.
A preparation method of sulfide reduction modified biochar comprises the following steps:
1) preparing a biochar suspension: under the condition of oxygen limitation, preserving heat of a biological organic material at 300-700 ℃ for 2-4 hours, grinding for at least half an hour, sieving to obtain a biological carbon raw material, adding the biological carbon raw material into ultrapure water, performing ultrasonic treatment for at least 30 minutes, and introducing nitrogen for at least 30 minutes to obtain a biological carbon suspension, wherein the biological organic material is cypress branch sawdust, wheat straw, peanut shell or pig manure, and the ratio of the mass fraction of the biological carbon raw material to the volume fraction of the ultrapure water added into the biological carbon raw material is 1: (200-1000);
preparing a sulfur reduction modified solution: putting sulfide salt into deoxygenated ultrapure water, and stirring until the sulfide salt is completely dissolved to obtain a sulfur reduction modification solution, wherein the concentration of the sulfide salt in the sulfur reduction modification solution is 0.05-1 mol/L;
in the step 1), the sieving mesh number is 50-200 meshes.
In the step 1), the preparation method of the ultrapure water after oxygen removal comprises the following steps: nitrogen gas was introduced into the ultrapure water for at least 30 minutes to discharge dissolved oxygen in the ultrapure water.
In the step 1), the oxygen-limiting condition is protection in a nitrogen atmosphere.
2) Preparing sulfide reduction modified biochar: adding the sulfur reduction modified solution obtained in the step 1) into the biochar suspension, stirring for at least 5 hours under the condition of introducing nitrogen, and performing suction filtration to obtain sulfide reduction modified biochar, wherein the ratio of the mass parts of the biochar raw materials in the biochar suspension to the mass parts of sulfide salts in the sulfur reduction modified solution is 1: (0.0025 to 0.054).
In the step 2), the filter membrane adopted by the suction filtration is a 0.22-0.45 mu m water system filter membrane, and the suction filtration is carried out for at least 4 times by adding ultrapure water.
In the above technical scheme, the unit of the mass fraction is g, the unit of the volume fraction is mL, and the unit of the mass fraction is mol.
The sulfide reduction modified biochar prepared by the preparation method.
The sulfide reduction modified biochar is applied to adsorbing organic pollutants in wastewater.
In the above technical solution, the organic contaminant is a hydrophobic organic contaminant.
In the technical scheme, the hydrophobic organic pollutant is polycyclic aromatic hydrocarbon or environmental estrogen, the polycyclic aromatic hydrocarbon is phenanthrene Phen, and the environmental estrogen is bisphenol A BPA or 17 alpha-ethinyl estradiol EE 2.
Compared with the prior art, the invention has the following advantages:
(1) the preparation method disclosed by the invention is simple in operation steps, mild in reaction, high in safety and small in environmental pollution, and the whole operation process is carried out under the conditions of normal temperature and normal pressure;
(2) for organic pollutants in sewage, the adsorption capacity of the sulfide reduction modified biochar is greatly improved compared with that of biochar raw materials, and the method can be used for removing the organic pollutants in the sewage.
Drawings
FIG. 1(a) is an X-ray photoelectron (XPS) spectrum of a raw material of biochar in example 1;
FIG. 1(b) is an X-ray photoelectron (XPS) spectrum of sulfide-reduced-modified biochar obtained in example 1;
FIG. 2 is a comparison of infrared (FTIR) spectra of sulfide-reducing modified biochar (RBC) obtained in example 1 and raw biochar material (BC) from example 1;
FIG. 3(a) is a Scanning Electron Microscope (SEM) pattern of the biochar raw material in example 1;
FIG. 3(b) is a Scanning Electron Microscope (SEM) pattern of the sulfide-reduced-modified biochar obtained in example 1;
FIG. 4 is a comparison of adsorption isotherms of organic contaminants on the sulfide-reduced modified biochar obtained in example 1 and the biochar raw material in example 1.
Detailed Description
The technical scheme of the invention is further explained by combining specific examples.
In the following examples, the drugs were purchased from shin-shin technology development ltd, Tianjin and were pure in purity. Nitrogen is purchased from the annular gas Co., Ltd, Tianjin, and the purity is more than or equal to 99.999 percent.
In the following examples, reference is made to an apparatus: high Performance Liquid Chromatography (HPLC) Agilent 1200, manufacturer Agilent, usa; the nitrogen muffle BF51732C-1 was manufactured by Thermo corporation of America.
In the following examples, the oxygen-limiting conditions in step 1) were protected under a nitrogen atmosphere. Parts by mass are in g, parts by volume are in mL, parts by mass are in mol.
Example 1
A preparation method of sulfide reduction modified biochar comprises the following steps:
1) preparing a biochar suspension: heating a biological organic material at 300 ℃ for 4 hours under an oxygen-limited condition, grinding for 1 hour, sieving by a 100-mesh sieve to obtain a biological carbon raw material (BC), adding the biological carbon raw material into ultrapure water, performing ultrasonic treatment for 30 minutes, and introducing nitrogen for 30 minutes to obtain a stable biological carbon suspension, wherein the biological organic material is cypress branch sawdust, and the ratio of the mass parts of the biological carbon raw material to the volume parts of the ultrapure water added with the biological carbon raw material is 1: 450, respectively;
preparing a sulfur reduction modified solution: putting sulfide salt into the deoxidized ultrapure water, and stirring until the sulfide salt is completely dissolved to obtain a sulfur reduction modification solution, wherein the concentration of the sulfide salt in the sulfur reduction modification solution is 0.2mol/L, and the sulfide salt is sodium sulfide;
the preparation method of the ultrapure water after oxygen removal comprises the following steps: nitrogen gas was introduced into the ultrapure water for 60 minutes to discharge dissolved oxygen from the ultrapure water.
2) Preparing sulfide reduction modified biochar: adding the sulfur reduction modified solution obtained in the step 1) into the biochar suspension, stirring for 24 hours under the condition of introducing nitrogen, and performing suction filtration to obtain sulfide reduction modified biochar (RBC), wherein the ratio of the mass parts of the biochar raw materials in the biochar suspension to the mass parts of sulfide salts in the sulfur reduction modified solution is 1: 0.01.
in the step 2), the filter membrane adopted by the suction filtration is a water system filter membrane with a filter hole of 0.22 mu m, and ultrapure water is added for suction filtration for 4 times.
The adsorption capacity of the sulfide reduction modified biochar on organic pollutants obtained in the embodiment 1 is greatly improved, and the sulfide reduction modified biochar can be used for removing the organic pollutants in wastewater. As shown in fig. 1(a) and 1(b), it is known from X-ray photoelectron (XPS) spectroscopy that the C ═ C/C-C on the surface of the sulfide reduction-modified biochar is increased, the C-O-C/C-OH content is significantly decreased, and the C ═ O functional group content is slightly decreased, which indicates that the oxygen-containing functional group on the surface of the biochar is reduced, the oxygen content is decreased, and the carbon content is greatly increased. Is favorable for the adsorption of organic pollutants in the wastewater.
As shown in FIG. 2, 1701cm of sulfide-reduced and modified biochar was observed from an infrared (FTIR) spectrum-1C ═ O absorption peak and 1040cm-1The absorption peaks of C-O-C appeared nearby show a weakening trend, which shows that aldehyde groups C ═ O functional groups and epoxy groups C-O-C on the surface of the original biochar are reduced and are broken. 1472cm-1The absorption peak of the C-C bond is gradually enhanced, which shows that the aromatic carbon content on the surface of the biochar is increased after the reduction modification of the sulfide, and the aromaticity is greatly enhanced. Is favorable for the adsorption of organic pollutants in the wastewater.
As shown in fig. 3(a) and 3(b), as can be seen from Scanning Electron Microscope (SEM) spectra, the biochar after sulfide reduction modification is cracked into small fragments, and has a richer microporous structure, so that adsorption sites for pollutants are increased, and adsorption of organic pollutants in wastewater can be greatly improved.
Approximately 10mg of the original cedar branch biochar sample (biochar raw material in example 1) and the sulfide-reduced and modified biochar obtained in example 1 were weighed in sequence, each in a clean brown sample bottle, and approximately 40ml of buffer (composed of 0.58mmol of Na) was added to the 40ml bottle2HPO4、9.42mmol NaH2PO4Prepared buffer solution with pH 6.0, solvent deionized water), add about 20ml of buffer to a 20ml bottle, weigh and record the mass of buffer added. Different volumes and concentrations of the stock solutions of adsorbates (BPA, EE2 or PHEN) were injected with a micropipette, the caps were screwed down and spun in a spinner at 8rpm in the dark for 14 days. And after the adsorption is balanced, taking down the sample bottle and standing for 24 hours to ensure that the biochar is completely precipitated. Finally, 1ml of the supernatant was pipetted into a liquid phase bottle using a pipette, and the sample was measured by High Performance Liquid Chromatography (HPLC), and the calculated adsorption isotherm was shown in FIG. 4.
As shown in FIG. 4, when bisphenol A (BPA) in an aqueous environment is adsorbed, the raw material of biochar is (BPA)BC) adsorption partition coefficient Kd265(BC _ BPA), adsorption partition coefficient K of sulfide-reduced modified biochar (RBC)dWas 43000(RBC _ BPA).
Adsorption distribution coefficient K of biochar raw material (BC) when 17 alpha-ethinyl estradiol (EE2) in water environment is adsorbedd584(BC _ EE2), the adsorption partition coefficient K of the sulfide-reduced modified biochar (RBC)d90000(RBC _ EE 2).
When Phenanthrene (PHEN) in water environment is adsorbed, the adsorption distribution coefficient K of biochar raw material (BC)d47000(BC _ PHEN), adsorption partition coefficient K of sulfide-reduced modified biochar (RBC)d2550000(RBC _ PHEN).
Compared with the original Biochar (BC), the adsorption capacity of the sulfide reduction modified biochar (RBC) is improved by 54-162 times.
Example 2
A preparation method of sulfide reduction modified biochar comprises the following steps:
1) preparing a biochar suspension: heating a biological organic material at 500 ℃ for 2 hours under an oxygen-limited condition, grinding for half an hour, sieving with a 50-mesh sieve to obtain a stable biological carbon raw material, adding the biological carbon raw material into ultrapure water, carrying out ultrasonic treatment for 30 minutes, and introducing nitrogen for 60 minutes to obtain a biological carbon suspension, wherein the biological organic material is wheat straw, and the ratio of the mass part of the biological carbon raw material to the volume part of the ultrapure water added with the biological carbon raw material is 1: 450, respectively;
preparing a sulfur reduction modified solution: putting sulfide salt into the deoxidized ultrapure water, and stirring until the sulfide salt is completely dissolved to obtain a sulfur reduction modification solution, wherein the concentration of the sulfide salt in the sulfur reduction modification solution is 0.1mol/L, and the sulfide salt is potassium sulfide;
the preparation method of the ultrapure water after oxygen removal comprises the following steps: nitrogen gas was introduced into the ultrapure water for 60 minutes to discharge dissolved oxygen from the ultrapure water.
2) Preparing sulfide reduction modified biochar: adding the sulfur reduction modified solution obtained in the step 1) into the biochar suspension, stirring for 24 hours under the condition of introducing nitrogen, and performing suction filtration to obtain sulfide reduction modified biochar, wherein the ratio of the mass parts of the biochar raw material in the biochar suspension to the mass parts of sulfide salt in the sulfur reduction modified solution is 1: 0.005.
in the step 2), the filter membrane adopted by the suction filtration is a water system filter membrane with a filter hole of 0.22 mu m, and ultrapure water is added for suction filtration for 4 times.
Example 3
A preparation method of sulfide reduction modified biochar comprises the following steps:
1) preparing a biochar suspension: under the condition of oxygen limitation, keeping the temperature of a biological organic material at 400 ℃ for 3 hours, grinding for half an hour, sieving with a 200-mesh sieve to obtain a stable biological carbon raw material, adding the biological carbon raw material into ultrapure water, carrying out ultrasonic treatment for 30 minutes, and introducing nitrogen for 60 minutes to obtain a biological carbon suspension, wherein the biological organic material is peanut shells, and the ratio of the mass parts of the biological carbon raw material to the volume parts of the ultrapure water added with the biological carbon raw material is 1: 450, respectively;
preparing a sulfur reduction modified solution: putting sulfide salt into the deoxidized ultrapure water, and stirring until the sulfide salt is completely dissolved to obtain a sulfur reduction modification solution, wherein the concentration of the sulfide salt in the sulfur reduction modification solution is 0.05mol/L, and the sulfide salt is sodium sulfide;
the preparation method of the ultrapure water after oxygen removal comprises the following steps: nitrogen gas was introduced into the ultrapure water for 60 minutes to discharge dissolved oxygen from the ultrapure water.
2) Preparing sulfide reduction modified biochar: adding the sulfur reduction modified solution obtained in the step 1) into the biochar suspension, stirring for 24 hours under the condition of introducing nitrogen, and performing suction filtration to obtain sulfide reduction modified biochar, wherein the ratio of the mass parts of the biochar raw material in the biochar suspension to the mass parts of sulfide salt in the sulfur reduction modified solution is 1: 0.0025.
in the step 2), the filter membrane adopted by the suction filtration is a water system filter membrane with a filter hole of 0.45 mu m, and ultrapure water is added for suction filtration for 4 times.
Example 4
A preparation method of sulfide reduction modified biochar comprises the following steps:
1) preparing a biochar suspension: under the condition of oxygen limitation, keeping the temperature of a biological organic material at 700 ℃ for 2 hours, grinding for 1 hour, sieving with a 100-mesh sieve to obtain a biological carbon raw material, adding the biological carbon raw material into ultrapure water, carrying out ultrasonic treatment for 30 minutes, and introducing nitrogen for 60 minutes to obtain a stable biological carbon suspension, wherein the biological organic material is pig manure, and the ratio of the mass parts of the biological carbon raw material to the volume parts of the ultrapure water added with the biological carbon raw material is 1: 450, respectively;
preparing a sulfur reduction modified solution: putting sulfide salt into the deoxidized ultrapure water, and stirring until the sulfide salt is completely dissolved to obtain a sulfur reduction modification solution, wherein the concentration of the sulfide salt in the sulfur reduction modification solution is 1mol/L, and the sulfide salt is potassium sulfide;
the preparation method of the ultrapure water after oxygen removal comprises the following steps: nitrogen gas was introduced into the ultrapure water for 60 minutes to discharge dissolved oxygen from the ultrapure water.
2) Preparing sulfide reduction modified biochar: adding the sulfur reduction modified solution obtained in the step 1) into the biochar suspension, stirring for 24 hours under the condition of introducing nitrogen, and performing suction filtration to obtain sulfide reduction modified biochar, wherein the ratio of the mass parts of the biochar raw material in the biochar suspension to the mass parts of sulfide salt in the sulfur reduction modified solution is 1: 0.054.
in the step 2), the filter membrane adopted by the suction filtration is a water system filter membrane with a filter hole of 0.22 mu m, and ultrapure water is added for suction filtration for 4 times.
Experiments prove that the technical effects consistent with those of the embodiment 1 can be realized in the embodiments 2 to 4 of the invention.
The method obtains subsidies of a science and research project of the university of Tianjin city (JW1715), an open fund of the Tianjin city water resource and water environment key laboratory and an 'innovation team culture plan' of the high schools of Tianjin city (TD 13-5073).
The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.
Claims (7)
1. The application of the sulfide reduction modified biochar in adsorbing organic pollutants in wastewater is characterized in that the preparation method of the sulfide reduction modified biochar comprises the following steps:
1) preparing a biochar suspension: under the condition of oxygen limitation, preserving heat of a biological organic material at 300-700 ℃ for 2-4 hours, grinding for at least half an hour, sieving to obtain a biological carbon raw material, adding the biological carbon raw material into ultrapure water, performing ultrasonic treatment for at least 30 minutes, and introducing nitrogen for at least 30 minutes to obtain a biological carbon suspension, wherein the biological organic material is cypress branch sawdust, wheat straw, peanut shell or pig manure, and the ratio of the mass fraction of the biological carbon raw material to the volume fraction of the ultrapure water added into the biological carbon raw material is 1: (200-1000);
preparing a sulfur reduction modified solution: putting sulfide salt into deoxygenated ultrapure water, and stirring until the sulfide salt is completely dissolved to obtain a sulfur reduction modification solution, wherein the concentration of the sulfide salt in the sulfur reduction modification solution is 0.05-1 mol/L;
2) preparing sulfide reduction modified biochar: adding the sulfur reduction modified solution obtained in the step 1) into the biochar suspension, stirring for at least 5 hours under the condition of introducing nitrogen, and performing suction filtration to obtain sulfide reduction modified biochar, wherein the ratio of the mass parts of the biochar raw materials in the biochar suspension to the mass parts of sulfide salts in the sulfur reduction modified solution is 1: (0.0025-0.054), the unit of the mass part is g, the unit of the volume part is mL, and the unit of the mass part is mol.
2. The use according to claim 1, wherein in the step 1), the sieving mesh number is 50-200 meshes.
3. The application of claim 2, wherein in the step 1), the preparation method of the ultrapure water after oxygen removal is as follows: nitrogen gas was introduced into the ultrapure water for at least 30 minutes to discharge dissolved oxygen in the ultrapure water.
4. Use according to claim 3, wherein in step 1) the oxygen-limiting conditions are protection under a nitrogen atmosphere.
5. The application of claim 4, wherein in the step 2), the filtration membrane used for suction filtration is a 0.22-0.45 μm water-based filtration membrane, and the filtration is performed at least 4 times by adding ultrapure water.
6. Use according to claim 1, wherein the organic contaminant is a hydrophobic organic contaminant.
7. The use according to claim 6, wherein the hydrophobic organic contaminant is a polycyclic aromatic hydrocarbon which is a phenanthrene or an environmental estrogen which is bisphenol or 17 α -ethinyl estradiol.
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