CN117417525B - Poly-N-phenylglycine@biochar composite material and preparation method and application thereof - Google Patents
Poly-N-phenylglycine@biochar composite material and preparation method and application thereof Download PDFInfo
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- CN117417525B CN117417525B CN202311374576.XA CN202311374576A CN117417525B CN 117417525 B CN117417525 B CN 117417525B CN 202311374576 A CN202311374576 A CN 202311374576A CN 117417525 B CN117417525 B CN 117417525B
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- NPKSPKHJBVJUKB-UHFFFAOYSA-N N-phenylglycine Chemical compound OC(=O)CNC1=CC=CC=C1 NPKSPKHJBVJUKB-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 239000002131 composite material Substances 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 239000000243 solution Substances 0.000 claims abstract description 37
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 30
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 27
- 239000011259 mixed solution Substances 0.000 claims abstract description 25
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 23
- 239000000178 monomer Substances 0.000 claims abstract description 23
- 239000010902 straw Substances 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 20
- 241000209140 Triticum Species 0.000 claims abstract description 17
- 235000021307 Triticum Nutrition 0.000 claims abstract description 17
- 239000002028 Biomass Substances 0.000 claims abstract description 12
- 239000003463 adsorbent Substances 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000001179 sorption measurement Methods 0.000 claims description 30
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 239000003610 charcoal Substances 0.000 claims description 4
- 239000010802 sludge Substances 0.000 claims description 4
- -1 hair Substances 0.000 claims description 3
- 239000010868 animal carcass Substances 0.000 claims description 2
- FAWGZAFXDJGWBB-UHFFFAOYSA-N antimony(3+) Chemical compound [Sb+3] FAWGZAFXDJGWBB-UHFFFAOYSA-N 0.000 claims description 2
- 239000010806 kitchen waste Substances 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 239000010828 animal waste Substances 0.000 claims 1
- 230000000630 rising effect Effects 0.000 claims 1
- 238000000197 pyrolysis Methods 0.000 abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 19
- 239000000463 material Substances 0.000 abstract description 7
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- IFBHRQDFSNCLOZ-IIRVCBMXSA-N 4-nitrophenyl-α-d-galactoside Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@@H]1OC1=CC=C([N+]([O-])=O)C=C1 IFBHRQDFSNCLOZ-IIRVCBMXSA-N 0.000 abstract 2
- 238000010438 heat treatment Methods 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 239000000843 powder Substances 0.000 description 16
- 238000003756 stirring Methods 0.000 description 16
- 230000004048 modification Effects 0.000 description 9
- 238000012986 modification Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 239000012298 atmosphere Substances 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 239000000706 filtrate Substances 0.000 description 8
- 238000000227 grinding Methods 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000010453 quartz Substances 0.000 description 8
- 238000007873 sieving Methods 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 238000000967 suction filtration Methods 0.000 description 8
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 7
- 238000011010 flushing procedure Methods 0.000 description 7
- 238000009210 therapy by ultrasound Methods 0.000 description 7
- 210000003608 fece Anatomy 0.000 description 5
- 239000010871 livestock manure Substances 0.000 description 5
- 229910052787 antimony Inorganic materials 0.000 description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 229920001940 conductive polymer Polymers 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000004043 dyeing Methods 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000009920 chelation Effects 0.000 description 2
- 238000007385 chemical modification Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 229920000767 polyaniline Polymers 0.000 description 2
- 229920000128 polypyrrole Polymers 0.000 description 2
- 125000004151 quinonyl group Chemical group 0.000 description 2
- IRLPACMLTUPBCL-KQYNXXCUSA-N 5'-adenylyl sulfate Chemical compound C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](COP(O)(=O)OS(O)(=O)=O)[C@@H](O)[C@H]1O IRLPACMLTUPBCL-KQYNXXCUSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000002154 agricultural waste Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 1
- 150000001463 antimony compounds Chemical class 0.000 description 1
- WSXIMVDZMNWNRF-UHFFFAOYSA-N antimony;ethane-1,2-diol Chemical compound [Sb].OCCO WSXIMVDZMNWNRF-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009990 desizing Methods 0.000 description 1
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 206010035653 pneumoconiosis Diseases 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000241 respiratory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 208000017520 skin disease Diseases 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/10—Alpha-amino-carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- 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
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/04—Preparatory processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Polyamides (AREA)
Abstract
The invention belongs to the technical field of preparation of functionalized biochar materials, and particularly relates to a poly-N-phenylglycine@biochar composite material, and a preparation method and application thereof. The method comprises the following steps: biomass is used as a raw material to prepare biochar; dispersing N-phenylglycine monomer in isopropanol, adding biochar into the isopropanol, uniformly mixing to obtain a mixed solution, dropwise adding ammonium persulfate solution into the mixed solution, carrying out polymerization reaction of the N-phenylglycine monomer, washing and drying after polymerization is finished to obtain the poly-N-phenylglycine@biochar composite material. The invention takes wheat straw as biomass raw material, adopts oxygen-limited high-temperature pyrolysis method to prepare biochar, then uses in-situ polymerization method to successfully prepare poly-N-phenylglycine@biochar composite material, is marked as BC/PNPG composite material, and uses the BC/PNPG composite material as adsorbent to remove Sb (III) in water.
Description
Technical Field
The invention belongs to the technical field of preparation of functionalized biochar materials, and particularly relates to a poly-N-phenylglycine@biochar composite material, and a preparation method and application thereof.
Background
Along with the rapid development of the printing and dyeing industry in China, printing and dyeing wastewater becomes one of the heavy-point pollution sources of water environment pollution. In textile and printing, antimony compounds such as antimony acetate, ethylene glycol antimony and antimony trioxide enter waste water along with desizing and alkali reduction procedures, so that a large amount of antimony (Sb) pollutants are contained in printing and dyeing waste water. Sb poisoning may cause respiratory irritation, pneumoconiosis, skin diseases, and may also have carcinogenic effects, so reducing antimony pollution is significant for human health. The conventional methods for treating the Sb-containing wastewater at present comprise a coagulation method, an adsorption method, an electrochemical method and a membrane separation technology, wherein the adsorption method is considered to be an effective Sb treatment method because of low cost, simple operation, high efficiency and possibility of adsorbent regeneration.
Biochar, which is an inexpensive adsorption material, has the characteristics of environmental friendliness, high stability and the like, is considered as a material with great development prospects in wastewater treatment, however, the original biochar is poor in heavy metal ion adsorption capacity due to limited surface area, poor pore structure and fewer functional groups, and various methods are adopted for modifying the biochar. The common methods comprise chemical modification and physical modification, wherein the physical modification mainly comprises two modes of steam and gas purging and mainly aims at the pore structure of the biochar; the chemical modification method is the most widely used modification method at present, and mainly comprises acid modification, alkali modification, metal salt or oxide modification, conductive polymer modification, other inorganic material modification and the like. Conductive polymers are considered as excellent adsorbents because of their diverse functional groups, large active surfaces and other characteristics, with polyaniline and polypyrrole being most widely used, but the targets of adsorption of polyaniline and polypyrrole are mainly Cu (II), co (II), cd (II), ni (II), pb (II), zn (II) and Fe (III), both of which have poor adsorption properties for antimony (Sb) pollutants.
There is a need for an adsorbent that can adsorb against antimony (Sb) contaminants to address the shortcomings of the prior art.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a poly-N-phenylglycine@charcoal composite material, a preparation method and application thereof.
In order to achieve the above purpose, the technical scheme adopted by the application is as follows:
A preparation method of a poly-N-phenylglycine@biochar composite material comprises the following steps:
biomass is used as a raw material to prepare biochar, and theoretically all the biochar can be applied to the application;
Dispersing N-phenylglycine monomer in isopropanol, adding biochar into the isopropanol, uniformly mixing to obtain a mixed solution, dropwise adding ammonium persulfate solution into the mixed solution, taking ammonium persulfate as an initiator, carrying out polymerization reaction of the N-phenylglycine monomer, and washing and drying after polymerization is finished to obtain the poly-N-phenylglycine@biochar composite material.
Preferably, the biomass comprises straw, hair, kitchen waste, animal carcasses, animal manure, municipal sludge.
Preferably, the straw is selected from wheat straw, and the wheat straw is used as biomass for carbonization treatment to obtain the biochar with a porous structure, so that the biochar has a large specific surface area and more Sb (III) adsorption active sites; in addition, the wheat straw is mainly selected as the raw material of the biochar in the experiment, because the main crop in the Shaanxi Guanzhong area is wheat, and the wheat straw can be used as agricultural waste in a recycling way.
Preferably, the biochar is prepared according to the following steps:
Pyrolyzing biomass in nitrogen atmosphere at a heating rate of 5-10 ℃/min for 2-4h at 400-800 ℃; if straw is used as biomass, the conditions are: pyrolyzing at 800 ℃ for 4h at a heating rate of 10 ℃/min.
Preferably, the mass ratio of the N-phenylglycine monomer to the biochar is 0.1-0.5:0.5.
Preferably, the molar ratio of the N-phenylglycine monomer to the ammonium persulfate is 1:1-2, the concentration of ammonium persulfate is 1.25mol/L.
Preferably, the polymerization conditions are: at room temperature, the ammonium persulfate solution is added dropwise and then stirred continuously for 12-24 hours.
Preferably, the polymerization reaction can also be carried out under acidic conditions, in particular: dispersing N-phenylglycine monomer in isopropanol, adding biochar into the isopropanol and uniformly mixing to obtain a mixed solution, firstly dripping sulfuric acid solution into the mixed solution, then dripping ammonium persulfate solution, carrying out polymerization reaction of the N-phenylglycine monomer, and washing and drying after polymerization is finished to obtain the poly-N-phenylglycine@biochar composite material;
Wherein the concentration of the H 2SO4 solution is 1mol/L.
The invention also protects the poly-N-phenylglycine@biochar composite material prepared by the preparation method.
The invention also protects the application of the poly-N-phenylglycine@biochar composite material in preparing the trivalent antimony adsorbent, and the application method comprises the following steps:
The composite material is added into 50mL of Sb (III) solution with the concentration of 55 mg.L -1 according to the dosage of 1-3 g.L -1 for adsorption, and the adsorption reaction is carried out in a water bath constant temperature oscillator with the temperature of 25 ℃ and the speed of 150 rpm.
Compared with the prior art, the application has the beneficial effects that:
1. The application provides a brand new material for adsorbing Sb (III) in water, namely a poly-N-phenylglycine@biochar composite material, and the application firstly discloses an adsorption principle of adsorbing Sb (III) in water by using poly-N-phenylglycine and the poly-N-phenylglycine, and after the poly-N-phenylglycine is compounded with the biochar, the problem of high price of the poly-N-phenylglycine is solved, and the adsorption performance of the biochar to Sb (III) in water is improved; in the application, the poly-N-phenylglycine@biochar composite material is prepared by taking wheat straw as a biomass raw material and performing low-temperature oxygen-limited pyrolysis at 800 ℃ to prepare original Biochar (BC), and then the poly-N-phenylglycine@biochar composite material is successfully prepared by an in-situ polymerization method and is recorded as BC/PNPG composite material;
2. According to the invention, the poly-N-phenylglycine@biochar composite material is used as an adsorbent to effectively remove Sb (III) in water, the mass ratio of the N-phenylglycine to the biochar is examined in detail, the influence of the synthetic environment on the adsorption of the Sb (III) by the BC/PNPG composite material is examined, and the adsorption mechanism is explored by combining characterization means such as SEM, XPS and FTIR;
The interaction mechanism of BC/PNPG with Sb (III) can be summarized as: the biochar has an adsorption effect, carboxyl on the biochar can be complexed with Sb 3+ to generate Sb (OH) 3 sediment, poly-N-phenylglycine is attached to the biochar, and the interaction mechanism of the poly-N-phenylglycine and Sb (III) is as follows: the protonated dual-polarized ion on poly-N-phenylglycine and Sb (III) generate oxidation-reduction reaction to generate neutral anilino and Sb (V), part of Sb 3+ is combined with N atoms on anilino through chelation, generated anilino is further removed from Sb 3+ through chelation, and part of Sb 3+ is combined with carboxyl on poly-N-phenylglycine through covalent bond, part of Sb 3+ is oxidized into Sb 5+ by an adsorbent, so that Sb 5+ appears in the solution, and generated Sb 5+ is electrostatically adsorbed in a form of Sb (OH) 6 -.
Drawings
FIG. 1 is an equation for polymerizing N-phenylglycine (NPG) monomers to poly-N-phenylglycine (PNPG);
FIG. 2 is an SEM image of the biochar of example 1, the poly-N-phenylglycine@biochar composite material BC/PNPG-1:5, BC/PNPG-3:5, BC/PNPG-5:5 of examples 1-3 of the present invention;
FIG. 3 is a FTIR graph of the biochar of example 1, the poly-N-phenylglycine@biochar composite BC/PNPG-1:5, BC/PNPG-3:5, BC/PNPG-5:5 of examples 1-3 of the present invention;
FIG. 4 is an XPS diagram of the biochar of example 1, the poly-N-phenylglycine@biochar composite material BC/PNPG-1:5, BC/PNPG-3:5, BC/PNPG-5:5 of examples 1-3 of the present invention;
FIG. 5 is a graph showing the effect of the adsorption of Sb (III) by the biochar of example 1, the poly-N-phenylglycine@biochar composites BC/PNPG-1:5, BC/PNPG-3:5, BC/PNPG-5:5, and BC/PNPG-5:5-S of examples 4 according to the present invention.
Detailed Description
The following detailed description of embodiments of the invention is, therefore, to be taken in conjunction with the accompanying drawings, and it is to be understood that the scope of the invention is not limited to the specific embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The raw materials used in the invention are not specific to manufacturers, and are conventional products which can be purchased commercially.
In order to make the contents of the present invention more easily understood, the technical scheme of the present invention will be further described with reference to the specific embodiments, but the present invention is not limited thereto.
The application further improves the adsorption performance of the biological carbon adsorbent by modifying the biological carbon by adopting the poly-N-phenylglycine;
The conductive polymer has the advantages of large surface area, adjustable surface chemical property and the like, can provide a large number of adsorption sites for metal ions, is a novel conductive polymer with high-density functional groups, is prepared by compounding poly-N-phenylglycine and biochar for the first time, is used for removing Sb (III), and is controlled in reaction conditions to obtain the high-efficiency functional biochar composite adsorbent, so that the novel material for efficiently removing Sb (III) is provided.
Example 1
A preparation method of a poly-N-phenylglycine@biochar composite material comprises the following steps:
(1) Preparation of Biochar (BC):
Cleaning wheat straw, drying in an oven at 80 ℃ for 12 hours, and preparing the biochar by adopting an oxygen-limited pyrolysis method, wherein the method comprises the following steps: placing a quartz boat containing wheat straw in a tube furnace, setting the pyrolysis temperature to be 800 ℃, heating to a target temperature at a heating rate of 10 ℃/min under nitrogen (400 mL/min) atmosphere, continuously pyrolyzing for 4 hours, cooling to room temperature after pyrolysis is finished, taking out, grinding and sieving a product into 100-200 mesh powder, and marking the prepared biochar as BC;
(2) Preparation of poly-N-phenylglycine@biochar composite material (BC/PNPG composite material):
and (3) carrying out ultrasonic treatment on 0.1g of N-phenylglycine monomer in 7mL of isopropanol for 1h to form a uniform solution, adding 0.5g of the biochar obtained in the step (1), stirring for 12h to obtain a mixed solution, dripping an APS solution (1 mL,1.25 mol/L) into the mixed solution at a speed of 5 s/drop, carrying out NPG polymerization reaction, continuing stirring for 12h after the dripping is finished, carrying out suction filtration, flushing the obtained powder with deionized water until the filtrate becomes colorless, and then drying in an oven at 60 ℃ for 12h to obtain the composite material BC/PNPG-1:5 composite material.
Example 2
A preparation method of a poly-N-phenylglycine@biochar composite material comprises the following steps:
(1) Preparation of Biochar (BC):
Cleaning wheat straw, drying in an oven at 80 ℃ for 12 hours, and preparing the biochar by adopting an oxygen-limited pyrolysis method, wherein the method comprises the following steps: placing a quartz boat containing wheat straw in a tube furnace, setting the pyrolysis temperature to be 800 ℃, heating to a target temperature at a heating rate of 10 ℃/min under nitrogen (400 mL/min) atmosphere, continuously pyrolyzing for 4 hours, cooling to room temperature after pyrolysis is finished, taking out, grinding and sieving a product into 100-200 mesh powder, and marking the prepared biochar as BC;
(2) Preparation of poly-N-phenylglycine@biochar composite material (BC/PNPG composite material):
And (3) carrying out ultrasonic treatment on 0.3g of N-phenylglycine monomer in 20mL of isopropanol for 1h to form a uniform solution, adding 0.5g of the biochar obtained in the step (1) into the uniform solution, stirring for 12h to obtain a mixed solution, dripping an APS solution (3 mL,1.25 mol/L) into the mixed solution at a speed of 5 s/drop, carrying out NPG polymerization reaction, continuing stirring for 12h after the dripping is finished, carrying out suction filtration, flushing the obtained powder with deionized water until the filtrate becomes colorless, and then drying in an oven at 60 ℃ for 12h to obtain the composite BC/PNPG-3:5 composite.
Example 3
A preparation method of a poly-N-phenylglycine@biochar composite material comprises the following steps:
(1) Preparation of Biochar (BC):
Cleaning wheat straw, drying in an oven at 80 ℃ for 12 hours, and preparing the biochar by adopting an oxygen-limited pyrolysis method, wherein the method comprises the following steps: placing a quartz boat containing wheat straw in a tube furnace, setting the pyrolysis temperature to be 800 ℃, heating to a target temperature at a heating rate of 10 ℃/min under nitrogen (400 mL/min) atmosphere, continuously pyrolyzing for 4 hours, cooling to room temperature after pyrolysis is finished, taking out, grinding and sieving a product into 100-200 mesh powder, and marking the prepared biochar as BC;
(2) Preparation of poly-N-phenylglycine@biochar composite material (BC/PNPG composite material):
And (3) carrying out ultrasonic treatment on 0.5g of N-phenylglycine monomer in 33mL of isopropanol for 1h to form a uniform solution, adding 0.5g of the biochar obtained in the step (1) into the uniform solution, stirring for 12h to obtain a mixed solution, dripping an APS solution (5 mL,1.25 mol/L) into the mixed solution at a speed of 5 s/drop, carrying out NPG polymerization reaction, continuing stirring for 12h after the dripping is finished, carrying out suction filtration, flushing the obtained powder with deionized water until the filtrate becomes colorless, and then drying in an oven at 60 ℃ for 12h to obtain the composite BC/PNPG-5:5 composite.
Example 4
A preparation method of a poly-N-phenylglycine@biochar composite material comprises the following steps:
(1) Preparation of Biochar (BC):
Cleaning wheat straw, drying in an oven at 80 ℃ for 12 hours, and preparing the biochar by adopting an oxygen-limited pyrolysis method, wherein the method comprises the following steps: placing a quartz boat containing wheat straw in a tube furnace, setting the pyrolysis temperature to be 800 ℃, heating to a target temperature at a heating rate of 10 ℃/min under nitrogen (400 mL/min) atmosphere, continuously pyrolyzing for 4 hours, cooling to room temperature after pyrolysis is finished, taking out, grinding and sieving a product into 100-200 mesh powder, and marking the prepared biochar as BC;
(2) Preparation of poly-N-phenylglycine@biochar composite material (BC/PNPG composite material):
0.5g of N-phenylglycine monomer is ultrasonically treated in 33mL of isopropanol for 1h to form a uniform solution, 0.5g of the biochar obtained in the step (1) is added, and then the mixture is stirred for 12h, so that a mixed solution is obtained, 10mL of 1mol/LH 2SO4 is added, and stirring is continued for 30min. The APS solution (5 ml,1.25 m) was added dropwise to the mixture at a rate of one drop per 5 seconds, and after stirring for 12 hours, suction filtration was performed, and the resulting powder was rinsed with deionized water until the filtrate became colorless. And then dried in an oven at 60 ℃ for 12 hours to obtain a composite material which is named as BC/PNPG-5:5-S composite material.
Example 5
A preparation method of a poly-N-phenylglycine@biochar composite material comprises the following steps:
(1) Preparation of Biochar (BC):
Drying municipal sludge in an oven at 80 ℃ for 12 hours, placing a quartz boat containing the municipal sludge in a tube furnace, setting the pyrolysis temperature to 600 ℃, heating to a target temperature at a heating rate of 5 ℃/min under nitrogen (400 mL/min) atmosphere, continuously pyrolyzing for 3 hours, cooling to room temperature after pyrolysis is finished, taking out, grinding and sieving a product into 100-200 mesh powder, and marking the prepared biochar as BC;
(2) Preparation of poly-N-phenylglycine@biochar composite material (BC/PNPG composite material):
And (3) carrying out ultrasonic treatment on 0.2g of N-phenylglycine monomer in 14mL of isopropanol for 1h to form a uniform solution, adding 0.5g of the biochar obtained in the step (1) into the uniform solution, stirring for 12h to obtain a mixed solution, dripping an APS solution (1 mL,0.625 mol/L) into the mixed solution at a speed of 5 s/drop, carrying out NPG polymerization reaction, continuing stirring for 18h after the dripping is finished, carrying out suction filtration, flushing the obtained powder with deionized water until the filtrate becomes colorless, and then drying in an oven at 60 ℃ for 12h to obtain the poly N-phenylglycine@biochar composite material.
Example 6
A preparation method of a poly-N-phenylglycine@biochar composite material comprises the following steps:
(1) Preparation of Biochar (BC):
Washing hair, drying in an oven at 80 ℃ for 12 hours, placing a quartz boat containing the hair in a tube furnace, setting the pyrolysis temperature to 400 ℃, heating to a target temperature at a heating rate of 10 ℃/min under nitrogen (400 mL/min) atmosphere, continuously pyrolyzing for 3 hours, cooling to room temperature after pyrolysis is finished, taking out, grinding and sieving the product into 100-200 mesh powder, and marking the prepared biochar as BC;
(2) Preparation of poly-N-phenylglycine@biochar composite material (BC/PNPG composite material):
and (3) carrying out ultrasonic treatment on 0.1g of N-phenylglycine monomer in 7mL of isopropanol for 1h to form a uniform solution, adding 0.5g of the biochar obtained in the step (1), stirring for 12h to obtain a mixed solution, dripping an APS solution (1 mL,1 mol/L) into the mixed solution at a speed of 5 s/drop, carrying out NPG polymerization reaction, continuing stirring for 24h after the dripping is finished, carrying out suction filtration, flushing the obtained powder with deionized water until the filtrate becomes colorless, and then drying in an oven at 60 ℃ for 12h to obtain the poly N-phenylglycine@biochar composite material.
Example 7
A preparation method of a poly-N-phenylglycine@biochar composite material comprises the following steps:
(1) Preparation of Biochar (BC):
Drying animal manure in an oven at 80 ℃ for 12 hours, placing a quartz boat containing the animal manure in a tube furnace, setting the pyrolysis temperature to 400 ℃, heating to a target temperature at a heating rate of 5 ℃/min under nitrogen (400 mL/min) atmosphere, continuously pyrolyzing for 2 hours, cooling to room temperature after pyrolysis is finished, taking out, grinding and sieving a product into 100-200 mesh powder, and marking the prepared biochar as BC;
(2) Preparation of poly-N-phenylglycine@biochar composite material (BC/PNPG composite material):
And (3) carrying out ultrasonic treatment on 0.1g of N-phenylglycine monomer in 7mL of isopropanol for 1h to form a uniform solution, adding 0.5g of the biochar obtained in the step (1), stirring for 12h to obtain a mixed solution, dripping an APS solution (1 mL,0.8 mol/L) into the mixed solution at a speed of 3 s/drop, carrying out NPG polymerization reaction, continuing stirring for 24h after dripping, carrying out suction filtration, flushing the obtained powder with deionized water until the filtrate becomes colorless, and then drying in an oven at 60 ℃ for 12h to obtain the poly N-phenylglycine@biochar composite material.
Example 8
A preparation method of a poly-N-phenylglycine@biochar composite material comprises the following steps:
(1) Preparation of Biochar (BC):
drying animal manure in an oven at 80 ℃ for 12 hours, placing a quartz boat containing the animal manure in a tube furnace, setting the pyrolysis temperature to be 600 ℃, heating to a target temperature at a heating rate of 5 ℃/min under nitrogen (400 mL/min) atmosphere, continuously pyrolyzing for 4 hours, cooling to room temperature after pyrolysis is finished, taking out, grinding and sieving a product into 100-200 mesh powder, and marking the prepared biochar as BC;
(2) Preparation of poly-N-phenylglycine@biochar composite material (BC/PNPG composite material):
And (3) carrying out ultrasonic treatment on 0.5g of N-phenylglycine monomer in 33mL of isopropanol for 1h to form a uniform solution, adding 0.5g of the biochar obtained in the step (1) into the uniform solution, stirring for 12h to obtain a mixed solution, dripping an APS solution (5 mL,1.25 mol/L) into the mixed solution at a speed of 3 s/drop, carrying out NPG polymerization reaction, continuing stirring for 24h after the dripping is finished, carrying out suction filtration, flushing the obtained powder with deionized water until the filtrate becomes colorless, and then drying in an oven at 60 ℃ for 12h to obtain the poly N-phenylglycine@biochar composite material.
The poly N-phenylglycine@charcoal composite materials with excellent Sb adsorption performance are prepared in examples 1-8, the poly N-phenylglycine@charcoal composite materials prepared in examples 1-4 are taken as examples, and compared with the charcoal prepared in example 1, the specific research method and the specific result are as follows:
the polymerization of N-phenylglycine (NPG) is carried out in situ at room temperature under the action of ammonium persulfate as an initiator, as shown in FIG. 1.
When the wheat straw is used as biomass to prepare the biochar, volatile organic matters generated in the pyrolysis process of the biochar quickly escape, so that the wall of the biochar is gradually thinned to form a pore structure shown in figure 2, the obtained biochar has a large specific surface area, the adsorption sites of Sb (III) are increased, and the attachment quantity of N-phenylglycine is increased.
FIG. 3 is a FTIR graph of the biochar of example 1, the poly-N-phenylglycine@biochar composite BC/PNPG-1:5, BC/PNPG-3:5, BC/PNPG-5:5 of examples 1-3 of the present invention; a stretching vibration peak of-OH is arranged at 3437cm -1; the peak at -1 cm 2850-2920 cm is caused by C-H vibration; characteristic peaks at 1590cm -1 and 1499cm -1 are attributed to the tensile vibration of c=c on the quinone ring and benzene ring, respectively; at 1310cm -1 is a characteristic peak of C-N bonds in aniline; the 1236cm -1 band is associated with C-O-C stretching vibrations; the peak at 1050cm -1 is caused by the stretching vibration of C-O; peaks at 1145cm -1 and 827cm -1, respectively, belong to the quinone ring and 1,4 (p) substituted phenyl ring structures, and infrared signatures indicate successful polymerization of PNPG on BC.
As can be seen from the XPS spectrum of FIG. 4, after PNPG particles are attached to the biochar, the content of N element on BC/PNPG-1:5, BC/PNPG-3:5 and BC/PNPG-5:5 is obviously increased.
The following adsorption experiments of Sb (iii) were performed using the biochar samples of examples 1-4 and example 1, and the adsorption experiments were specifically operated as: the BC/PNPG composite material was subjected to adsorption in an amount of 2 g.L -1 to 50mL of Sb (III) solution with a concentration of 55 mg.L -1, the adsorption reaction was carried out in a water bath constant temperature shaker at 25℃and 150rpm, after 24 hours, the solution was filtered through a 0.45 μm filter membrane, and the concentration of Sb (III) remaining in the solution was measured by ICP-OES.
FIG. 5 shows that the adsorption capacity of the poly N-phenylglycine@charcoal composite material prepared under different environmental conditions to Sb (III) is increased, the adsorption capacity of BC/PNPG-5:5-S is increased from 12.07 mg.g -1 to 17.65 mg.g -1, and the element content is basically unchanged (FIG. 4), which shows that under the acidic condition, a plurality of hydrogen ions and APS in water compete for electrons in water together, so that the electron-obtaining capacity of the APS as an oxidant is enhanced, the polymerization reaction of PNPG on charcoal is promoted, more PNPG particles are loaded on the charcoal, and more adsorption sites are provided for adsorption of Sb (III). After the polymerization reaction is finished, the aqueous solution is still acidic, and conditions are created for protonation of functional groups such as carboxyl groups, so that the surface of the material is positively charged, and Sb (OH) 6 - in water can be removed through electrostatic action; in addition, the adsorption experiment proves that the adsorption capacity of the BC/PNPG composite material to Sb (III) is effectively improved compared with BC.
It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims (8)
1. The preparation method of the poly-N-phenylglycine@biochar composite material is characterized by comprising the following steps of:
biomass is used as a raw material to prepare biochar;
Dispersing N-phenylglycine monomer in isopropanol, adding biochar into the isopropanol and uniformly mixing to obtain a mixed solution, dropwise adding ammonium persulfate solution into the mixed solution, carrying out polymerization reaction of the N-phenylglycine monomer, and washing and drying after polymerization to obtain the poly-N-phenylglycine@biochar composite material;
The mass ratio of the N-phenylglycine monomer to the biochar is 0.1-0.5:0.5;
The molar ratio of the N-phenylglycine monomer to the ammonium persulfate is 1:1-2, the concentration of ammonium persulfate is 1.25mol/L.
2. The method for preparing the poly-N-phenylglycine@charcoal composite material according to claim 1, wherein the biomass comprises straw, hair, kitchen waste, animal carcasses, animal wastes and municipal sludge.
3. The method for preparing the poly-N-phenylglycine@biochar composite material according to claim 2, wherein the straw is selected from wheat straws.
4. The method for preparing the poly-N-phenylglycine@charcoal composite material according to claim 1, wherein the charcoal is prepared by the following steps:
The biomass is pyrolyzed for 2 to 4 hours at the temperature rising rate of 5 to 10 ℃/min under the nitrogen atmosphere at the temperature of 400 to 800 ℃.
5. The method for preparing the poly-N-phenylglycine@biochar composite material according to claim 1, wherein the polymerization reaction conditions are as follows: at room temperature, the ammonium persulfate solution is added dropwise and then stirred continuously for 12-24 hours.
6. The method for preparing the poly-N-phenylglycine@biochar composite material according to claim 1, wherein the polymerization reaction can be further performed under acidic conditions, specifically: dispersing N-phenylglycine monomer in isopropanol, adding biochar into the isopropanol and uniformly mixing to obtain a mixed solution, firstly dripping sulfuric acid solution into the mixed solution, then dripping ammonium persulfate solution, carrying out polymerization reaction of the N-phenylglycine monomer, and washing and drying after polymerization is finished to obtain the poly-N-phenylglycine@biochar composite material;
Wherein the concentration of the H 2SO4 solution is 1mol/L.
7. A poly N-phenylglycine @ biochar composite material made by the method of any one of claims 1-6.
8. Use of the poly-N-phenylglycine@biochar composite material according to claim 7 in the preparation of a trivalent antimony adsorbent, characterized in that the application method comprises the following steps:
The composite material is added into 50mL of Sb (III) solution with the concentration of 55 mg.L -1 according to the addition amount of 1-3 g.L -1 for adsorption.
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| JP2006281212A (en) * | 2006-06-02 | 2006-10-19 | Bridgestone Corp | Ozone decomposition type gas adsorbent, filter medium using this adsorbent, method for regenerating it, and recycled article |
| CN106890624A (en) * | 2017-03-20 | 2017-06-27 | 湖南大学 | A kind of shitosan/anhydride modified biological carbon composite and preparation method thereof and purposes |
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| CN110548483A (en) * | 2019-05-25 | 2019-12-10 | 北京化工大学 | preparation method and application of biochar/nano ferroferric oxide composite material |
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| JP2006281212A (en) * | 2006-06-02 | 2006-10-19 | Bridgestone Corp | Ozone decomposition type gas adsorbent, filter medium using this adsorbent, method for regenerating it, and recycled article |
| CN106890624A (en) * | 2017-03-20 | 2017-06-27 | 湖南大学 | A kind of shitosan/anhydride modified biological carbon composite and preparation method thereof and purposes |
| CN110015742A (en) * | 2019-04-30 | 2019-07-16 | 生态环境部华南环境科学研究所 | A kind of water hyacinth charcoal load nano zero-valence iron composite material and preparation and application |
| CN110548483A (en) * | 2019-05-25 | 2019-12-10 | 北京化工大学 | preparation method and application of biochar/nano ferroferric oxide composite material |
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