CN115722251A - Preparation method and application of hetero-atom-doped algae-based biochar loaded nano zero-valent metal catalyst - Google Patents
Preparation method and application of hetero-atom-doped algae-based biochar loaded nano zero-valent metal catalyst Download PDFInfo
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- CN115722251A CN115722251A CN202211598201.7A CN202211598201A CN115722251A CN 115722251 A CN115722251 A CN 115722251A CN 202211598201 A CN202211598201 A CN 202211598201A CN 115722251 A CN115722251 A CN 115722251A
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- algae
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- 241000195493 Cryptophyta Species 0.000 title claims abstract description 82
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 55
- 239000002184 metal Substances 0.000 title claims abstract description 53
- 239000003054 catalyst Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 23
- 239000002351 wastewater Substances 0.000 claims abstract description 14
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 11
- 239000011574 phosphorus Substances 0.000 claims abstract description 11
- 239000005416 organic matter Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 76
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- 239000007787 solid Substances 0.000 claims description 28
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 25
- 239000012498 ultrapure water Substances 0.000 claims description 25
- 239000000843 powder Substances 0.000 claims description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
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- 238000006243 chemical reaction Methods 0.000 claims description 19
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- 238000001035 drying Methods 0.000 claims description 9
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- 238000007873 sieving Methods 0.000 claims description 9
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- 238000004729 solvothermal method Methods 0.000 claims description 6
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
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- GJYJYFHBOBUTBY-UHFFFAOYSA-N alpha-camphorene Chemical compound CC(C)=CCCC(=C)C1CCC(CCC=C(C)C)=CC1 GJYJYFHBOBUTBY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 4
- 238000000197 pyrolysis Methods 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- 238000010407 vacuum cleaning Methods 0.000 claims description 4
- 238000003828 vacuum filtration Methods 0.000 claims description 4
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 3
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- 238000003763 carbonization Methods 0.000 claims description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- 229910001381 magnesium hypophosphite Inorganic materials 0.000 claims description 3
- SEQVSYFEKVIYCP-UHFFFAOYSA-L magnesium hypophosphite Chemical compound [Mg+2].[O-]P=O.[O-]P=O SEQVSYFEKVIYCP-UHFFFAOYSA-L 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- 229910001380 potassium hypophosphite Inorganic materials 0.000 claims description 3
- CRGPNLUFHHUKCM-UHFFFAOYSA-M potassium phosphinate Chemical compound [K+].[O-]P=O CRGPNLUFHHUKCM-UHFFFAOYSA-M 0.000 claims description 3
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 3
- WYXIGTJNYDDFFH-UHFFFAOYSA-Q triazanium;borate Chemical compound [NH4+].[NH4+].[NH4+].[O-]B([O-])[O-] WYXIGTJNYDDFFH-UHFFFAOYSA-Q 0.000 claims description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- 150000000703 Cerium Chemical class 0.000 claims description 2
- FFEARJCKVFRZRR-UHFFFAOYSA-N L-Methionine Natural products CSCCC(N)C(O)=O FFEARJCKVFRZRR-UHFFFAOYSA-N 0.000 claims description 2
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- 235000013878 L-cysteine Nutrition 0.000 claims description 2
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 claims description 2
- 229930195722 L-methionine Natural products 0.000 claims description 2
- 239000012448 Lithium borohydride Substances 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 2
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
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- 239000011668 ascorbic acid Substances 0.000 claims description 2
- RJTANRZEWTUVMA-UHFFFAOYSA-N boron;n-methylmethanamine Chemical compound [B].CNC RJTANRZEWTUVMA-UHFFFAOYSA-N 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 150000001868 cobalt Chemical class 0.000 claims description 2
- 150000001879 copper Chemical class 0.000 claims description 2
- BRWIZMBXBAOCCF-UHFFFAOYSA-N hydrazinecarbothioamide Chemical compound NNC(N)=S BRWIZMBXBAOCCF-UHFFFAOYSA-N 0.000 claims description 2
- 150000002505 iron Chemical class 0.000 claims description 2
- 229960004452 methionine Drugs 0.000 claims description 2
- 150000002751 molybdenum Chemical class 0.000 claims description 2
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- 239000012286 potassium permanganate Substances 0.000 claims description 2
- KOUKXHPPRFNWPP-UHFFFAOYSA-N pyrazine-2,5-dicarboxylic acid;hydrate Chemical compound O.OC(=O)C1=CN=C(C(O)=O)C=N1 KOUKXHPPRFNWPP-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
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- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 2
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- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 6
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- JOCJYBPHESYFOK-UHFFFAOYSA-K nickel(3+);phosphate Chemical compound [Ni+3].[O-]P([O-])([O-])=O JOCJYBPHESYFOK-UHFFFAOYSA-K 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
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- 229910019142 PO4 Inorganic materials 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- QCJQWJKKTGJDCM-UHFFFAOYSA-N [P].[S] Chemical compound [P].[S] QCJQWJKKTGJDCM-UHFFFAOYSA-N 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
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- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
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- 241000206751 Chrysophyceae Species 0.000 description 1
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- ZFBUHAMJIRQEOU-UHFFFAOYSA-N [Ce++].[O-][N+]([O-])=O.[O-][N+]([O-])=O Chemical compound [Ce++].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZFBUHAMJIRQEOU-UHFFFAOYSA-N 0.000 description 1
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- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
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- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
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Abstract
The invention discloses a preparation method of a heteroatom-doped algae-based biochar loaded nano zero-valent metal catalyst, which comprises the steps of pretreatment of algae organisms, preparation of heteroatom-doped algae-based biochar, preparation of phosphorus and heteroatom co-doped algae-based biochar, loading of nano zero-valent metal and the like to obtain the heteroatom-doped algae-based biochar loaded nano zero-valent metal catalyst, and application of the catalyst in treatment of heavy metal-organic matter composite polluted wastewater.
Description
Technical Field
The invention belongs to the technical field of non-ferrous metal industrial wastewater treatment; in particular to a preparation method of a high-activity composite catalyst of heteroatom doped algae-based biochar loaded nanometer zero-valent metal for efficiently treating non-ferrous metal industrial wastewater, and a method for activating an oxidant by utilizing the composite catalyst material to treat heavy metal-organic matter composite polluted wastewater in the non-ferrous metal industrial wastewater.
Background
The pollution caused by the non-ferrous metal industrial wastewater is mainly organic oxygen consuming substance pollution, inorganic suspended solid pollution, heavy metal pollution, petroleum pollution, alcohol pollution, acid-base pollution, heat pollution and the like. If the waste water generated in the nonferrous metal industry is directly discharged into the environment, not only can serious pollution be caused to water bodies or other environmental factors, the ecological environment is influenced, but also the resource waste is caused. Therefore, how to efficiently and stably treat the colored industrial wastewater and recover valuable elements from the colored industrial wastewater obviously becomes a difficult problem which needs to be solved urgently in the treatment of the colored industrial wastewater at present.
SO generated by activating persulphates 4 - Higher standard reduction potential (2.5-3.1 eV), longer active time (30-40 μ s) and broader pH reactivity and stability than hydroxyl radical (. OH) generated by the conventional Fenton technique, which makes the sulfate radical-based advanced oxidation technique in wasteThe field of water treatment is widely applied. The nano zero-valent metal material taking nano zero-valent iron, nickel and the like as representatives has the advantages of environmental friendliness, low price, high catalytic activity, strong reducibility and the like, is widely applied to the field of environmental remediation such as sewage treatment and the like, and is especially used as an effective heterogeneous catalyst in a sulfate radical-based advanced oxidation technology to strengthen and degrade pollutants in wastewater. However, the nanometer zero-valent metal has the problems of easy oxidation, easy agglomeration and easy loss in the water treatment process due to small particle size, high chemical activity and the like. In addition, when the nano zero-valent metal acts with a target pollutant, most electrons generated by the nano zero-valent metal cannot be effectively transferred to a reaction group but are transferred to hydrogen ions or dissolved oxygen in a water phase, so that the effective electron utilization rate is reduced, and the reaction activity of the nano zero-valent metal in a pollutant-containing water body and the pollutant removal efficiency are influenced.
Disclosure of Invention
Aiming at the problems that the nano zero-valent metal is easy to oxidize and agglomerate in the wastewater treatment process, the invention provides a preparation method of a hetero-atom-doped algae-based charcoal-loaded nano zero-valent metal catalyst which can stably exist in a wastewater solution and has high reaction activity, low economic cost and environmental friendliness.
The preparation method of the heteroatom doped algae-based biochar loaded nano zero-valent metal catalyst comprises the following steps:
(1) Collecting algae, cleaning, drying, crushing, sieving, adding glutaraldehyde solution with volume concentration of 2.5-5%, mixing and stirring for 10-15 h, after solid-liquid separation, washing the solid with ultrapure water for 4-6 times, sequentially soaking the algae in ethanol solutions with volume concentrations of 70%, 90% and 100%, respectively soaking in 0.5h, carrying out solid-liquid separation, and drying to obtain pretreated algae;
the algae is one or more of chlorella, blue algae, diatom, green algae, chrysophyceae and dinoflagellate;
pulverizing and sieving to obtain powder with particle size below 0.4 mm;
(2) Placing the pretreated algae organisms into an extracting solution, ultrasonically dispersing for 0.5-1.0 h at 50-70 ℃, after solid-liquid separation, washing the solid with ultrapure water until the pH is 9.5-10, placing the washed product into an heteroatom precursor solution for solvothermal reaction, after the reaction is finished, carrying out solid-liquid separation, alternately washing the solid with ultrapure water and an absolute ethyl alcohol solution until the pH is neutral, and carrying out vacuum drying until the weight is constant to obtain heteroatom-doped algae-based biochar;
the extracting solution is prepared by mixing 3-5% of lauryl sodium sulfate solution and 2-4% of sodium hydroxide solution according to the volume ratio of 1:1-3; the heteroatomic precursor is one of a nitrogen source, a boron source and a sulfur source, the concentration of the heteroatomic precursor solution is 0.3-0.9 mol/L, wherein the nitrogen source is one or more of ammonium chloride, ammonium persulfate, melamine, urea and ammonium bicarbonate; the boron source is one or more of boric acid, ammonium borate and dimethylamine borane; the sulfur source is one or more of thioacetic acid, thiourea, thiosemicarbazide, thioacetamide, L-cysteine and L-methionine; the hydrothermal reaction temperature is 180-210 ℃, and the reaction time is 3-8 h;
(3) Under inert atmosphere, mixing the heteroatom-doped algae-based biochar with hypophosphite, and putting the mixture into a tubular furnace for pyrolysis and carbonization to obtain phosphorus and heteroatom-doped algae-based biochar;
mixing the heteroatom-doped algae-based biochar and hypophosphite according to the mass ratio of (2-4): 1, heating to 250-350 ℃ at the speed of 1-5 ℃/min, and keeping the temperature at 0.5-1 h to promote the gradual decomposition of solid hypophosphite to generate phosphine gas to continuously fumigate the algae-based biochar, wherein under the atmosphere condition, the phosphine gas generates selective corrosion on the heteroatom-doped algae-based biochar, and the phosphine gas enters cell walls of the biochar to occupy vacant sites; then heating to 500-800 ℃ at the speed of 6-12 ℃/min, pyrolyzing for 1.5-5 h, generating phosphine gas to provide an additional phosphorus source, and uniformly doping phosphorus into the heteroatom-doped algae-based biochar in the process of generating mesopores on the surface of the heteroatom-doped algae-based biochar along with the increase of the pyrolysis temperature; the hypophosphite is one or more of sodium hypophosphite, potassium hypophosphite, ammonium hypophosphite and magnesium hypophosphite;
(4) Under the nitrogen atmosphere, putting the phosphorus and heteroatom co-doped algae-based biochar into 0.025-0.1 g/mL metal salt solution, stirring for 0.5h, slowly dropwise adding a reducing agent solution, continuously stirring for 0.5h after dropwise adding is finished, carrying out solid-liquid separation, sequentially carrying out vacuum filtration and cleaning on the solid by ultrapure water and an absolute ethanol solution for 3-6 times, and carrying out vacuum drying to obtain the phosphorus and heteroatom co-doped algae-based biochar loaded nano zero-valent metal catalyst;
the metal salt is one or two of iron salt, molybdenum salt, cobalt salt, nickel salt, cerium salt, zinc salt and copper salt; when the metal salt is two, the mass ratio of the bimetallic salt is 1:5-5:1; the reducing agent is one of potassium borohydride, sodium borohydride, lithium borohydride, ascorbic acid and tea polyphenol, and the molar ratio of the metal salt to the reducing agent is 1:5-1.
The invention also aims to apply the heteroatom-doped algae-based biochar loaded nano zero-valent metal catalyst prepared by the method in the treatment of heavy metal-organic matter composite polluted wastewater, and the heteroatom-doped algae-based biochar loaded nano zero-valent metal catalyst, persulfate (PS) and peroxide (hydrogen peroxide H) 2 O 2 Calcium peroxide CP, peracetic acid (PAA), potassium permanganate (KMnO) 4 ) One or more of them are used simultaneously.
The method not only reduces the preparation cost and simplifies the operation procedure, but also effectively prevents the oxidation and agglomeration of the nano zero-valent metal particles in the wastewater treatment process on the basis of no secondary pollution to the environment, and effectively improves the surface activity and stability of the nano zero-valent metal particles; the invention also opens up a new way for resource utilization of the waste algae biomass and development of a low-cost, high-activity and green catalyst.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention firstly proposes to use the algae to prepare the heteroatom-doped mesoporous biochar material with high reaction activity and low economic cost, the algae used in the invention has wide sources, the harmful algae can be prepared into the high-value environment functional material by a simple preparation method, the resource value of the algae is utilized while the harmful algae is removed, and the method is environment-friendly and is easy for large-scale production and popularization;
(2) The hetero-atom-doped mesoporous biochar material is prepared by the modes of hetero-atom doping, morphology regulation and the like, and the alga-based biochar rich in functional groups is obtained by regulating and controlling the hydrothermal reaction conditions;
(3) On the basis that solid hypophosphite is easy to decompose under a heated condition to generate phosphine, the solid hypophosphite is skillfully introduced into the heteroatom-doped algae-based biochar, the heteroatom-doped algae-based biochar is fumigated at a medium temperature under a heating condition, phosphine gas generated in the process can controllably corrode the heteroatom-doped algae-based biochar under a closed condition, and the phosphorus and heteroatom-doped mesoporous algae-based biochar composite material is obtained after further medium-temperature carbonization; the intermediate-temperature fumigation of phosphine steam is innovatively utilized, so that the biochar material is endowed with a high mesoporous structure, and diatom co-doping is realized in the process that phosphorus is uniformly doped into heteroatom-doped biochar, so that the efficiency of the biochar material in electron transmission and mass transfer can be greatly improved. In addition, the diatom co-doping in the biochar material enhances the chemical adsorption of pollutants and the activation efficiency of high-activity oxidants, reduces the catalytic activation barrier, and improves the reaction kinetic efficiency through the synergistic regulation of defects and diatom doping;
(4) By regulating the structure of the algae-based biochar, and subsequently introducing nano zero-valent metal into the hetero atom-doped mesoporous algae-based biochar by using a liquid phase reduction precipitation method to form a high-activity composite reaction material of the hetero atom-doped mesoporous algae-based biochar loaded with the nano zero-valent metal, the mass transfer distance between an active center species (a nano zero-valent metal core and a free radical) and a target pollutant is greatly shortened, the rapid diffusion dynamics is promoted to ensure the effective contact of the active center species and the target pollutant, the overall effect of a reaction system is enhanced, and the defects of poor electron selectivity and easy agglomeration of the nano zero-valent metal and the defects of free radical self-quenching or ineffective oxidation reaction (such as reaction with water molecules) are overcome;
(4) According to the invention, the hetero-atom doped mesoporous algae-based biochar is obtained in a novel, green and sustainable manner, and due to the existence of magnetic metal elements such as nano zero-valent iron, nickel and cobalt in the algae-based biochar material, the composite material can be simply recovered, the loss of the composite material is avoided, and the composite material has a good large-scale application prospect.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of the nano zero-valent iron in comparative example 1;
FIG. 2 is a Scanning Electron Microscope (SEM) image of the nitrogen and phosphorus co-doped algae-based charcoal supported nano zero-valent iron catalyst in example 1.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments thereof, it being understood that the scope of the invention is not limited to the details shown.
Example 1
(1) Collecting chlorella, cleaning, crushing and sieving to obtain powder with the particle size of less than or equal to 0.4mm, adding glutaraldehyde solution with the volume concentration of 2.5% into the chlorella powder, stirring for 10 hours, filtering, washing filter residues with ultrapure water for 5 times, sequentially soaking in ethanol solutions with the volume concentrations of 70%, 90% and 100% for 0.5 hour respectively, performing suction filtration, and drying the solid at the temperature of 80 ℃ to obtain pretreated chlorella powder;
(2) Placing 3g of pretreated chlorella powder into an extracting solution (prepared by mixing a sodium dodecyl sulfate solution with the mass volume concentration of 3% and a sodium hydroxide solution with the mass concentration of 2.9% according to the volume ratio of 1:1), ultrasonically dispersing for 0.5h at 60 ℃, performing suction filtration, washing a solid with ultrapure water until the pH is 9.5-10, placing the washed product into a 0.3mol/L melamine solution, performing solvothermal reaction for 6h at 180 ℃, filtering after the reaction is finished, alternately washing the solid with ultrapure water and an absolute ethyl alcohol solution until the pH is neutral, and performing vacuum drying at 80 ℃ to constant weight to obtain nitrogen-doped chlorella-based charcoal;
(3) Mixing nitrogen-doped chlorella-based biochar and sodium hypophosphite according to the mass ratio of 2:1 in a nitrogen atmosphere, placing the mixture in a tubular furnace, heating to 250 ℃ at the speed of 2 ℃/min, keeping for 1h, heating to 600 ℃ at the speed of 7 ℃/min, and pyrolyzing for 5h to obtain nitrogen-phosphorus co-doped chlorella-based biochar;
(4) Under the nitrogen atmosphere, placing nitrogen-phosphorus co-doped chlorella charcoal into a 0.025g/mL ferric chloride solution, stirring for 0.5h, slowly dropwise adding a tea polyphenol solution (the molar ratio of ferric chloride to tea polyphenol is 1.
Comparative example 1: slowly dripping a tea polyphenol solution (the molar ratio of ferric chloride to tea polyphenol is 1.
Example 2
(1) Collecting blue algae, cleaning, crushing and sieving to obtain powder with the particle size of less than or equal to 0.4mm, adding glutaraldehyde solution with the volume concentration of 3.5% into the blue algae powder, stirring to treat 12 h, filtering, washing filter residues with ultrapure water for 5 times, sequentially soaking with ethanol solutions with the volume concentrations of 70%, 90% and 100%, respectively soaking for 0.5h, performing suction filtration, and drying the solid at 70 ℃ to obtain pretreated blue algae powder;
(2) Placing 5g of pretreated cyanobacteria powder into an extracting solution (prepared by mixing a lauryl sodium sulfate solution with the mass volume concentration of 4% and a sodium hydroxide solution with the mass concentration of 3.0% according to the volume ratio of 1:1), ultrasonically dispersing for 1h at 50 ℃, carrying out suction filtration, washing a solid with ultrapure water until the pH is 9.5-10, placing the washed product into a 0.9mol/L L-methionine solution, carrying out solvothermal reaction for 5h at 190 ℃, filtering after the reaction is finished, alternately washing the solid with ultrapure water and an anhydrous ethanol solution until the pH is neutral, and carrying out vacuum drying at 85 ℃ to constant weight to obtain the sulfur-doped cyanobacteria-based biochar;
(3) Under the nitrogen atmosphere, mixing sulfur-doped cyanobacteria-based biochar and potassium hypophosphite 5363 in a mass ratio of 3:1, placing the mixture in a tube furnace, heating to 300 ℃ at a speed of 3 ℃/min, keeping the temperature for 0.8h, heating to 700 ℃ at a speed of 8 ℃/min, and pyrolyzing for 4h to obtain sulfur-phosphorus-doped cyanobacteria-based biochar;
(4) Under the nitrogen atmosphere, the sulfur-phosphorus co-doped blue-green algae biochar is placed in 0.05g/mL nickel phosphate solution, stirred for 0.5h, slowly dropwise added with sodium borohydride solution (the molar ratio of nickel phosphate to sodium borohydride is 1:6), continuously stirred for 0.5h after dropwise addition is finished, suction filtration is carried out, filter residues are sequentially subjected to vacuum filtration and cleaning by ultrapure water and absolute ethyl alcohol solution for 5 times, and the filter residues are respectively cleaned for 5 times and dried under vacuum at 60 ℃ for 8h, so that the sulfur-phosphorus co-doped blue-green algae biochar loaded nano zero-valent nickel catalyst is obtained.
Comparative example 2: slowly dropwise adding a sodium borohydride solution (the molar ratio of nickel phosphate to sodium borohydride is 1:6) into a 0.05g/mL nickel phosphate solution, continuously stirring for 0.5h after dropwise adding is finished, performing suction filtration, sequentially performing vacuum filtration and cleaning on filter residues by using ultrapure water and an absolute ethyl alcohol solution for 5 times, and performing vacuum drying at 60 ℃ for 8h to obtain the nano zero-valent nickel catalyst.
Example 3
(1) Collecting diatom, cleaning, crushing and sieving to obtain powder with the particle size of less than or equal to 0.4mm, adding glutaraldehyde solution with the volume concentration of 4.0% into the diatom powder, stirring to treat 14h, filtering, washing filter residues with ultrapure water for 5 times, sequentially soaking with ethanol solutions with the volume concentrations of 70%, 90% and 100%, soaking for 0.5h respectively, performing suction filtration, and drying the solid at 75 ℃ to obtain pretreated diatom powder;
(2) Placing 5g of pretreated diatom powder into an extracting solution (prepared by mixing a sodium dodecyl sulfate solution with the mass volume concentration of 4% and a sodium hydroxide solution with the mass concentration of 3.5% according to the volume ratio of 1:2), ultrasonically dispersing for 0.5h at 70 ℃, performing suction filtration, washing a solid with ultrapure water until the pH is 9.5-10, placing the washed product into a 0.6 mol/L boric acid solution, performing solvothermal reaction for 3h at 200 ℃, filtering after the reaction is finished, alternately washing the solid with ultrapure water and an absolute ethyl alcohol solution until the pH is neutral, and performing vacuum drying at 85 ℃ to constant weight to obtain boron-doped diatom-based biochar;
(3) Mixing boron-doped diatom-based biochar and ammonium hypophosphite according to the mass ratio of 4:1 in a nitrogen atmosphere, placing the mixture in a tubular furnace, heating to 350 ℃ at the speed of 4 ℃/min, keeping the temperature for 0.5h, heating to 750 ℃ at the speed of 9 ℃/min, and pyrolyzing for 2h to obtain boron-phosphorus co-doped diatom biochar;
(4) Under the nitrogen atmosphere, placing boron-phosphorus co-doped algae-based biochar in 0.08g/mL copper chloride solution, stirring for 0.5h, slowly dropwise adding potassium borohydride solution (the molar ratio of nickel phosphate to potassium borohydride is 1;
comparative example 3: slowly dropwise adding a potassium borohydride solution (the molar ratio of nickel phosphate to potassium borohydride is 1.
Example 4
(1) Collecting chlorella, cleaning, crushing and sieving to obtain powder with the particle size of less than or equal to 0.4mm, adding glutaraldehyde solution with the volume concentration of 3% into the chlorella powder, stirring to treat the powder with 15 h, filtering, washing filter residues with ultrapure water for 4 times, sequentially soaking the filter residues with ethanol solutions with the volume concentrations of 70%, 90% and 100%, respectively soaking the filter residues with 0.5h, performing suction filtration, and drying the solid at the temperature of 80 ℃ to obtain pretreated chlorella powder;
(2) Placing 5g of pretreated chlorella powder into an extracting solution (prepared by mixing a sodium dodecyl sulfate solution with the mass volume concentration of 4% and a sodium hydroxide solution with the mass concentration of 4% according to the volume ratio of 1:3), performing ultrasonic (320W) dispersion for 1h at 55 ℃, performing suction filtration, washing a solid with ultrapure water until the pH is 9.5-10, placing the washed product into a 0.6 mol/L ammonium chloride solution, performing solvothermal reaction for 4h at 200 ℃, filtering after the reaction is finished, alternately washing the solid with ultrapure water and an absolute ethyl alcohol solution until the pH is neutral, and performing vacuum drying at 85 ℃ until the constant weight is obtained, thus obtaining the nitrogen-doped chlorella-based charcoal;
(3) Under the nitrogen atmosphere, mixing nitrogen-doped chlorella-based biochar and magnesium hypophosphite according to the mass ratio of 3:1, putting the mixture into a tube furnace, heating to 350 ℃ at the speed of 5 ℃/min, keeping 0.5h, heating to 800 ℃ at the speed of 10 ℃/min, and pyrolyzing for 1.5h to obtain nitrogen-phosphorus co-doped chlorella biochar;
(4) Under the nitrogen atmosphere, placing nitrogen-phosphorus co-doped chlorella biochar in 0.1g/mL iron phosphate-nickel phosphate (mass ratio of 1:5) solution, stirring 0.5h, slowly dropwise adding potassium borohydride solution (the molar ratio of phosphate to potassium borohydride is 1.
Comparative example 4: slowly dropwise adding a potassium borohydride solution (the molar ratio of phosphate to potassium borohydride is 1.
Example 5
(1) Collecting blue algae, cleaning, crushing and sieving to obtain powder with the particle size of less than or equal to 0.4mm, adding glutaraldehyde solution with the volume concentration of 3.0% into the blue algae powder, stirring for 14 hours, filtering, washing filter residues with ultrapure water for 6 times, sequentially soaking the filter residues with ethanol solutions with the volume concentrations of 70%, 90% and 100% for 0.5 hour respectively, performing suction filtration, and drying the solid at the temperature of 80 ℃ to obtain pretreated blue algae powder;
(2) Placing 5g of pretreated cyanobacteria powder into an extracting solution (prepared by mixing a sodium dodecyl sulfate solution with the mass volume concentration of 3% and a sodium hydroxide solution with the mass concentration of 3% according to the volume ratio of 1:2), ultrasonically dispersing at 60 ℃ for 0.5h (320W), carrying out suction filtration, washing a solid with ultrapure water until the pH is 9.5-10, placing the washed product into a 0.5mol/L ammonium borate solution, carrying out solvent thermal reaction at 185 ℃ for 7h, filtering after the reaction is finished, alternately washing the solid with ultrapure water and an absolute ethyl alcohol solution until the pH is neutral, and carrying out vacuum drying at 85 ℃ until the constant weight is obtained, thus obtaining the boron-doped cyanobacteria charcoal;
(3) Under the nitrogen atmosphere, mixing boron-doped blue-green algae biochar and ammonium hypophosphite according to the mass ratio of 3:1, placing the mixture in a tubular furnace, heating to 300 ℃ at the speed of 1 ℃/min, keeping the temperature for 0.6h, heating to 700 ℃ at the speed of 7 ℃/min, and pyrolyzing for 3h to obtain boron-phosphorus co-doped blue-green algae biochar;
(4) Under the nitrogen atmosphere, placing boron-phosphorus co-doped cyanobacteria charcoal in 0.08g/mL ferric nitrate-cerium nitrate (mass ratio 1:2) solution, stirring for 0.5h, slowly dropwise adding sodium borohydride solution (the molar ratio of nitrate to sodium borohydride is 1.
Comparative example 5: slowly dropwise adding a sodium borohydride solution (the molar ratio of nitrate to sodium borohydride is 1.
Example 6: the catalyst prepared in the embodiment is used for treating smelting wastewater in a certain non-ferrous metal smelting workshop, 1000mL of the workshop wastewater is collected, the pH value of a water sample is 6.5 +/-0.5, and the initial dosage of pollutants is shown in Table 1;
weighing 0.27g of sodium persulfate, putting the sodium persulfate into a 250mL conical flask containing 50mL of water sample, then adjusting the pH value of the water sample to 3.5 +/-0.2, respectively putting 0.5g of the catalyst prepared in the examples 1-5 and the comparative examples 1-5 into the 250mL conical flask, putting the conical flask into a constant temperature water bath shaker, shaking for 1h at 25 ℃, taking the supernatant for filtering, measuring the concentration of heavy metal ions by using an inductively coupled plasma spectrometer (ICP-OES), measuring the COD value by using a spectrophotometry method, calculating the removal amount according to the difference of the concentrations of the heavy metal ions before and after the reaction, wherein the dosage unit is mg/L, and the test results are shown in Table 1.
TABLE 1
Example 7: the catalyst prepared in the embodiment is used for treating smelting wastewater in a non-ferrous metal smelting workshop, 1000mL of the workshop wastewater is collected, the pH value of a water sample is 6.5 +/-0.5, and the initial dosage of pollutants is shown in a table 2;
0.54g of peracetic acid was put into a 250mL conical flask containing 50mL of water sample, the pH of the water sample was adjusted to 3.5. + -. 0.2, 0.5g of the catalysts prepared in examples 1-5 and comparative examples 1-5 were weighed, respectively, and put into the above 250mL conical flask, the conical flask was put into a constant temperature water bath shaker at 25 ℃ and shaken for 1h, then the supernatant was filtered, the concentration of heavy metal ions was measured by an inductively coupled plasma spectrometer (ICP-OES), the COD value was measured by spectrophotometry, the removal amount was calculated from the difference between the concentrations of heavy metal ions before and after the reaction, the dosage unit was mg/L, and the test results were shown in Table 2.
TABLE 2
As can be seen from tables 1 and 2, the heteroatom-doped algae-based biochar-supported nano zero-valent metal catalyst prepared by the method has a good treatment effect on smelting wastewater; the concentration and COD value of heavy metal ions contained in the treated wastewater both meet the discharge requirements of the discharge standard of lead and zinc industrial pollutants (GB 25466-2010), while the concentration and COD value of heavy metal ions contained in the wastewater treated by the comparative catalyst do not meet the discharge requirements of the discharge standard of lead and zinc industrial pollutants (GB 25466-2010).
In conclusion, the method of the invention prepares the harmful algae into the heteroatom-doped mesoporous algae-based biochar material with high reaction activity and low economic cost, removes the harmful algae and simultaneously utilizes the resource value of the algae. By regulating and controlling the structural characteristics of the hetero-atom-doped mesoporous algae-based biochar, the nano zero-valent metal is introduced into the hetero-atom-doped mesoporous algae-based biochar by using a liquid phase reduction method to form the high-activity composite catalyst of the hetero-atom-doped mesoporous algae-based biochar loaded with the nano zero-valent metal, so that the mass transfer distance between an active center species (the nano zero-valent metal and a free radical) and a target pollutant is greatly shortened, the effective contact between the active center species and the target pollutant is ensured, and the overall effect of a catalytic reaction system is enhanced, thereby simultaneously solving the defects of the passivation and the agglomeration of the nano zero-valent metal and the defect of the self-quenching or ineffective oxidation reaction (such as the reaction with water molecules) of the free radical, realizing the large-scale simple recovery of the composite material due to the existence of magnetic metal elements such as nano zero-valent iron, nickel, cerium and the like in the material, avoiding the loss of the composite material, and proving the good application prospect thereof.
Claims (10)
1. A preparation method of a hetero-atom doped algae-based biochar loaded nano zero-valent metal catalyst is characterized by comprising the following steps:
(1) Collecting algae, cleaning, drying, crushing, sieving, adding glutaraldehyde solution with volume concentration of 2.5-5%, mixing and stirring for 10-15 h, after solid-liquid separation, washing the solid with ultrapure water for 4-6 times, sequentially soaking the algae in ethanol solutions with volume concentrations of 70%, 90% and 100%, respectively soaking in 0.5h, carrying out solid-liquid separation, and drying the solid to obtain pretreated algae;
(2) Placing the pretreated algae organisms into an extracting solution, ultrasonically dispersing for 0.5-1.0 h at 50-70 ℃, after solid-liquid separation, washing the solid with ultrapure water until the pH is 9.5-10, placing the washed product into an heteroatom precursor solution for solvothermal reaction, after the reaction is finished, carrying out solid-liquid separation, alternately washing the solid with ultrapure water and an absolute ethyl alcohol solution until the pH is neutral, and carrying out vacuum drying until the weight is constant to obtain heteroatom-doped algae-based biochar;
(3) Under inert atmosphere, mixing the heteroatom-doped algae-based biochar with hypophosphite, and putting the mixture into a tubular furnace for pyrolysis and carbonization to obtain phosphorus and heteroatom-doped algae-based biochar;
(4) Under the nitrogen atmosphere, putting the phosphorus and heteroatom co-doped algae-based biochar into 0.025-0.1 g/mL metal salt solution, stirring for 0.5h, slowly dropwise adding a reducing agent solution, continuously stirring for 0.5h after dropwise adding is finished, carrying out solid-liquid separation, sequentially carrying out vacuum filtration and cleaning on the solid by ultrapure water and an absolute ethanol solution, respectively cleaning for 3-6 times, and carrying out vacuum drying to obtain the heteroatom co-doped algae-based biochar loaded nano zero-valent metal catalyst.
2. The preparation method of the hetero-atom doped algae-based biochar supported nano zero-valent metal catalyst according to claim 1, which is characterized in that: and (2) crushing and sieving the algae in the step (1) to obtain powder with the particle size of less than or equal to 0.4 mm.
3. The preparation method of the hetero-atom doped algae-based biochar supported nano zero-valent metal catalyst according to claim 1, which is characterized in that: the heteroatom precursor in the step (2) is one of a nitrogen source, a boron source and a sulfur source, and the concentration of the heteroatom precursor solution is 0.3-0.9 mol/L; wherein the nitrogen source is one or more of ammonium chloride, ammonium persulfate, melamine, urea and ammonium bicarbonate; the boron source is one or more of boric acid, ammonium borate and dimethylamine borane; the sulfur source is one or more of thioacetic acid, thiourea, thiosemicarbazide, thioacetamide, L-cysteine and L-methionine.
4. The preparation method of the hetero-atom doped algae-based biochar supported nano zero-valent metal catalyst according to claim 1, which is characterized in that: in the step (2), the extracting solution is prepared by mixing 3-5% mass volume concentration sodium dodecyl sulfate solution and 2-4% mass concentration sodium hydroxide solution according to the volume ratio of 1:1-3.
5. The preparation method of the hetero-atom doped algae-based biochar supported nano zero-valent metal catalyst according to claim 1, which is characterized in that: the hydrothermal reaction temperature is 180-210 ℃, and the reaction time is 3-8 h.
6. The preparation method of the heteroatom-doped algae-based biochar supported nano zero-valent metal catalyst according to claim 1, characterized in that: in the step (3), the heteroatom-doped algae-based biochar and hypophosphite are mixed according to the mass ratio of (2-4) to 1, the temperature is raised to 250-350 ℃ at the speed of 1-5 ℃/min, the mixture is kept for 0.5-1 h, then the temperature is raised to 500-800 ℃ at the speed of 6-12 ℃/min, and the pyrolysis is carried out for 1.5-5 h.
7. The preparation method of the hetero-atom doped algae-based biochar supported nano zero-valent metal catalyst according to claim 5, which is characterized in that: the hypophosphite is one or more of sodium hypophosphite, potassium hypophosphite, ammonium hypophosphite and magnesium hypophosphite.
8. The preparation method of the hetero-atom doped algae-based biochar supported nano zero-valent metal catalyst according to claim 1, which is characterized in that: the metal salt is one or two of iron salt, molybdenum salt, cobalt salt, nickel salt, cerium salt, zinc salt and copper salt; when the two metal salts are used, the mass ratio of the bimetallic salt is 1:5-5:1.
9. The preparation method of the hetero-atom doped algae-based biochar supported nano zero-valent metal catalyst according to claim 1, which is characterized in that: the reducing agent is one of potassium borohydride, sodium borohydride, lithium borohydride, ascorbic acid and tea polyphenol, and the molar ratio of the metal salt to the reducing agent is 1:5-1.
10. The application of the heteroatom-doped algae-based biochar-supported nano zero-valent metal catalyst prepared by the preparation method of the heteroatom-doped algae-based biochar-supported nano zero-valent metal catalyst as claimed in any one of claims 1 to 9 in the treatment of heavy metal-organic matter combined pollution wastewater, which is characterized in that: the heteroatom-doped algae-based charcoal-supported nano zero-valent metal catalyst is used together with one or more of persulfate, peroxide, peroxyacetic acid and potassium permanganate.
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| CN116408128B (en) * | 2023-06-09 | 2023-08-04 | 西南林业大学 | Method for preparing Cu-N doped gum carbon catalyst by adopting bitter cherry gum and application |
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