CN112892476A - Biochar composite material and preparation method and application thereof - Google Patents
Biochar composite material and preparation method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 147
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 239000000843 powder Substances 0.000 claims abstract description 113
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 89
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 74
- 239000010452 phosphate Substances 0.000 claims abstract description 72
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 64
- 229910052742 iron Inorganic materials 0.000 claims abstract description 50
- 241000238017 Astacoidea Species 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 35
- 239000007788 liquid Substances 0.000 claims abstract description 20
- 239000002028 Biomass Substances 0.000 claims abstract description 17
- 238000000926 separation method Methods 0.000 claims abstract description 11
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 7
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 238000000197 pyrolysis Methods 0.000 claims description 18
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 9
- 238000007873 sieving Methods 0.000 claims description 8
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 claims description 3
- 229960002089 ferrous chloride Drugs 0.000 claims description 3
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 3
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 3
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 66
- 230000009467 reduction Effects 0.000 abstract description 10
- 230000001360 synchronised effect Effects 0.000 abstract description 9
- 239000002910 solid waste Substances 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 4
- 241000238030 Procambarus clarkii Species 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 37
- 230000000694 effects Effects 0.000 description 28
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 18
- 239000011148 porous material Substances 0.000 description 12
- 229910001448 ferrous ion Inorganic materials 0.000 description 11
- -1 iron ions Chemical class 0.000 description 11
- 239000003610 charcoal Substances 0.000 description 9
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 9
- 239000000706 filtrate Substances 0.000 description 9
- 239000012528 membrane Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 238000005070 sampling Methods 0.000 description 8
- 238000002798 spectrophotometry method Methods 0.000 description 8
- 239000003344 environmental pollutant Substances 0.000 description 7
- 229960004887 ferric hydroxide Drugs 0.000 description 7
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 7
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 description 7
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 7
- 231100000719 pollutant Toxicity 0.000 description 7
- 238000010668 complexation reaction Methods 0.000 description 6
- 239000003446 ligand Substances 0.000 description 6
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 239000003463 adsorbent Substances 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 229910001424 calcium ion Inorganic materials 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000010806 kitchen waste Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 102000020897 Formins Human genes 0.000 description 1
- 108091022623 Formins Proteins 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
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- 239000012535 impurity Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000000644 propagated effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—Magnetic properties
-
- 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
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- 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
- C02F1/48—Treatment of water, waste water, or sewage with magnetic or electric fields
- C02F1/488—Treatment of water, waste water, or sewage with magnetic or electric fields for separation of magnetic materials, e.g. magnetic flocculation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4875—Sorbents characterised by the starting material used for their preparation the starting material being a waste, residue or of undefined composition
- B01J2220/4881—Residues from shells, e.g. eggshells, mollusk shells
-
- 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
- C02F2101/105—Phosphorus compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Water Treatment By Sorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a biochar composite material and a preparation method and application thereof, wherein the procambarus clarkii shell powder is mixed with an iron-containing solution and then reacts; then carrying out solid-liquid separation on the reaction liquid to obtain the iron-carrying biomass; and finally, pyrolyzing the iron-loaded biomass in a nitrogen atmosphere to obtain the biochar composite material. The biochar composite material prepared by the method can realize the reduction treatment and resource utilization of the solid waste crayfish shells on the one hand, and can realize the efficient single and synchronous adsorption removal of Cr (VI) and phosphate radicals in a water body on the other hand, has special significance for pollution control and treatment, and has the advantages of simple preparation method, wide raw material source and low cost.
Description
Technical Field
The invention belongs to the field of solid waste disposal and resource utilization and composite environmental pollution treatment, and particularly relates to a biochar composite material and a preparation method and application thereof.
Background
With the development of social economy and the rapid increase of population, the water pollution situation is increased year by year, and most of water sources contain various pollutants, such as heavy metals, dissolved inorganic matters, organic matters and the like. In particular, the waste water containing Cr (VI) is extremely toxic, is difficult to degrade in the environment, can be enriched in organisms through a food chain, and seriously threatens the health safety of human beings. Meanwhile, the over-standard phosphorus content can cause water eutrophication, and algae can be rapidly propagated, so that the survival of aquatic organisms is damaged, and the ecological safety of the environment is threatened. Therefore, the treatment of water polluted by heavy metal or/and phosphorus has been receiving more and more extensive attention, and the common treatment methods thereof include biological methods, chemical precipitation methods and the like, but still have greater limitations. In recent years, new adsorbents have been widely used in wastewater treatment processes due to their advantages of high efficiency and simple operation.
It is well known that biochar, a novel adsorbent, is a carbon-rich product obtained by pyrolysis of biomass under oxygen-limited conditions. The biochar has a developed pore structure and a developed specific surface area, and the surface of the biochar is rich in functional groups, so that the biochar is a good adsorbent. However, the adsorption effect of raw biochar on pollutants is not ideal. Therefore, the existing novel adsorbents are in need of improvement.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, the invention aims to provide a biochar composite material and a preparation method and application thereof, the biochar composite material prepared by the method can realize the reduction treatment and resource utilization of solid waste crayfish shells on the one hand, and the obtained biochar composite material can realize the efficient single and synchronous adsorption removal of Cr (VI) and phosphate radical in water on the other hand, and has special significance for pollution control and treatment, and the preparation method is simple, the raw material source is wide, and the cost is low.
In one aspect of the invention, a method of making a biochar composite is presented. According to an embodiment of the invention, the method comprises:
(1) mixing crayfish shell powder with an iron-containing solution and then reacting;
(2) carrying out solid-liquid separation on the reaction liquid obtained in the step (1) so as to obtain iron-carrying biomass;
(3) and pyrolyzing the iron-carrying biomass in a nitrogen atmosphere to obtain the biochar composite material.
According to the method for preparing the biochar composite material, the crawfish shell powder and the iron-containing solution are mixed and then react, because the crawfish shell powder has a pore structure and a high specific surface area, iron ions and/or ferrous ions in the iron-containing solution are embedded into pores of the crawfish shell powder, and part of the iron ions and/or ferrous ions are hydrolyzed to generate ferric hydroxide and/or ferrous hydroxide; then carrying out solid-liquid separation on the reaction liquid to obtain iron-carrying biomass; and finally, carrying out pyrolysis on the iron-carrying biomass in a nitrogen atmosphere, wherein in the pyrolysis process, the crayfish shells are converted into biochar, and meanwhile, iron ions and/or ferrous ions and part of ferric hydroxide and/or ferrous hydroxide which are embedded into pores of the biochar shells are converted into ferric oxide, ferroferric oxide and the like, namely, the iron in the biochar exists in the forms of ferric oxide, ferroferric oxide and the like. The biochar composite material in the application removes Cr (VI), and has the functions of reduction, complexation and precipitation besides the basic physical adsorption function compared with other biochar materials. The biochar is an electron donor and an electron shuttle, and the biochar composite material has stronger electron donating capability, so that the reducing power to Cr (VI) is enhanced, and the removal rate to Cr (VI) is improved. In the removal of phosphate ions, the adsorption of the biochar composite material to phosphate is mainly electrostatic attraction, ligand exchange and surface complexation. The biochar composite material contains a large amount of calcium ions, phosphate ions can be removed through precipitation, positive charges are carried on the surface of the biochar composite material, the phosphate ions can be effectively adsorbed, and ligand exchange effect can be generated between acidic ferrous oxide and the phosphate ions generated on the surface of the biochar, so that the removal rate is improved. The biochar composite material has large specific surface area and porosity, provides attachment points for iron oxide, and can accelerate the removal of pollutants through surface adsorption. Meanwhile, due to the magnetic property of ferroferric oxide, the biochar composite material can be well separated from the water phase, so that the biochar composite material can be rapidly recovered. Therefore, the biochar composite material prepared by the method can realize the reduction treatment and resource utilization of the solid waste crayfish shells on the one hand, and can realize the efficient single and synchronous adsorption removal of Cr (VI) and phosphate radicals on the other hand, and has special significance for pollution control and treatment, and the preparation method is simple, the raw material source is rich, and the cost is low.
In addition, the biochar composite according to the above embodiment of the invention may also have the following additional technical features:
in some embodiments of the present invention, in the step (1), the particle size of the crayfish shell powder is 200 to 400 μm. Therefore, the obtained biochar composite material has high specific surface area and good adsorption effect.
In some embodiments of the present invention, in step (1), the iron-containing solution comprises at least one of ferric chloride, ferric sulfate, ferric nitrate, ferric acetate, ferrous chloride, ferrous sulfate, ferrous nitrate, and ferrous acetate.
In some embodiments of the present invention, in the step (1), the concentration of the iron-containing solution is 1 to 2 mol.L-1. Therefore, the prepared biochar composite material is good in adsorption effect.
In some embodiments of the invention, in step (1), the solid-to-liquid ratio of the crayfish shell powder to the iron-containing solution is (5-15) g: (25-200) mL. Therefore, on one hand, the crayfish shell powder and the iron-containing solution can be ensured to be fully reacted; on the other hand, the increase of the loss of the iron-containing solution and the load of the subsequent solid-liquid separation can be avoided.
In some embodiments of the invention, in step (3), the pyrolysis has a temperature rise rate of 5-15 ℃ min-1And carrying out pyrolysis at 400-600 ℃ for 90-120 min. Therefore, the prepared biochar composite material is good in adsorption effect.
In a second aspect of the invention, a biochar composite is provided. According to the embodiment of the invention, the biochar composite material is prepared by the method. Therefore, on one hand, the reduction treatment and resource utilization of the solid waste crayfish shells can be realized, on the other hand, the obtained biochar composite material can realize the efficient single and synchronous adsorption removal of Cr (VI) and phosphate radicals in the water body, and has special significance for pollution control and treatment.
In a third aspect of the invention, a method of treating a body of water containing cr (vi) and/or phosphate is provided. According to an embodiment of the invention, the method comprises:
a. grinding, sieving, washing and drying the biochar composite material to obtain biochar composite material powder; b. and mixing and reacting the biochar composite powder with a water body containing Cr (VI) and/or phosphate. Therefore, on one hand, the reduction treatment and resource utilization of the solid waste crayfish shells can be realized, on the other hand, the obtained biochar composite material powder can realize the efficient single and synchronous adsorption removal of Cr (VI) and phosphate radicals in the water body, and has special significance for pollution control and treatment.
In addition, the method for treating the water body containing the Cr (VI) and/or the phosphate radical according to the embodiment of the invention can also have the following additional technical characteristics:
in some embodiments of the present invention, in the step a, the particle size of the biocoke composite powder is 120 to 150 μm.
In some embodiments of the present invention, in the step b, the concentration of Cr (VI) in the water body is 20-100 mg.L-1The concentration of the phosphate radical is 2-8 mg.L-1。
In some embodiments of the invention, in step b, the adding amount of the biochar composite powder is 0.5-4.0 g based on 1L of the water body. Thereby, the removal rate of Cr (VI) and/or phosphate in the water body can be improved.
In some embodiments of the invention, the pH of the water body is 2.00-9.00. Therefore, the adsorption effect of the biochar composite powder can be ensured.
In some embodiments of the present invention, the temperature of the mixing reaction is 30 to 50 ℃, and the reaction time is 150 to 180 min. Therefore, the adsorption effect of the biochar composite powder can be ensured.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
FIG. 1 is a schematic flow diagram of a method of making a biochar composite according to one embodiment of the invention;
FIG. 2 is the single adsorption effect of biochar composite powder on Cr (VI) and phosphate under different pH conditions in example 1;
FIG. 3 is the single adsorption effect of different biochar composite powder dosages on Cr (VI) and phosphate in example 2;
FIG. 4 is the single adsorption effect of biochar composite powder on Cr (VI) and phosphate at different contaminant concentrations in example 3;
FIG. 5 shows the effect of simultaneous adsorption of Cr (VI) and phosphate by the biochar composite powder in example 4;
fig. 6 is an SEM image of the biochar composite in example 1.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
In one aspect of the invention, a method of making a biochar composite is presented. According to an embodiment of the invention, with reference to fig. 1, the method comprises:
s100: mixing crayfish shell powder and iron-containing solution for reaction
In this step, the preparation of crayfish shell powder is first carried out: cleaning collected kitchen waste crayfish shells, placing the cleaned shells in an oven, drying the shells at 115-125 ℃ and preferably at 120 ℃, crushing the shells, and sieving the crushed shells to obtain crayfish shell powder; and then mixing the crayfish shell powder with the iron-containing solution and then reacting to obtain a reaction liquid. The inventor finds that because the crayfish shell powder has a pore structure and a high specific surface area, iron ions and/or ferrous ions in the iron-containing solution are embedded into pores of the crayfish shell powder in the reaction process, and part of the iron ions and/or ferrous ions are hydrolyzed to generate ferric hydroxide and/or ferrous hydroxide, and the ferrous hydroxide is oxidized into ferric hydroxide by oxygen.
Further, the particle size of the crayfish shell powder is 200-400 μm. The particle size of the crayfish shell powder in the range of the application is adopted in the biochar composite material, so that the prepared biochar composite material has a strong adsorption effect.
Further, the concentration of the iron-containing solution is 1-2 mol.L-1Preferably 1 mol. L-1. The inventor finds that if the concentration of the iron-containing solution is too high, redundant iron ions and/or ferrous ions can form a large amount of iron-containing particles on the surface of the biochar to block the pores of the biochar, so that the adsorption capacity is reduced; if the concentration of the iron-containing solution is too low, the crayfish shells cannot be treatedEnough iron ions and/or ferrous ions are embedded into the pores of the powder, so that the prepared biochar composite material has poor adsorption effect. Therefore, the concentration of the iron-containing solution within the range of the application can ensure that the prepared biochar composite material has a strong adsorption effect. It should be noted that the specific type of the iron-containing solution can be selected by those skilled in the art according to actual needs, for example, the iron-containing solution includes at least one of ferric chloride, ferric sulfate, ferric nitrate, ferric acetate, ferrous chloride, ferrous sulfate, ferrous nitrate and ferrous acetate.
Further, the solid-to-liquid ratio of the crayfish shell powder to the iron-containing solution is (5-15) g: (25-200) mL, preferably (5-15) g: (50-150) mL. The inventor finds that if the solid-liquid ratio is too high, the contact between the crayfish shell powder and the iron-containing solution is insufficient, and the adsorption effect of the biochar composite material is affected; and if the solid-liquid ratio is too low, the loss of the iron-containing solution and the load of subsequent solid-liquid separation are increased. Therefore, by adopting the solid-liquid ratio in the range of the application, on one hand, the biochar composite material has a better adsorption effect; on the other hand, the increase of the loss of the iron-containing solution and the load of the subsequent solid-liquid separation can be avoided.
S200: subjecting the reaction solution obtained in step S100 to solid-liquid separation
In this step, the iron-loaded biomass can be obtained by subjecting the reaction solution obtained in step S100 to solid-liquid separation. The solid-liquid separation method is not particularly limited, and may be, for example, centrifugation.
S300: carrying out pyrolysis on iron-loaded biomass in nitrogen atmosphere
In the step, the iron-carrying biomass is heated and heated in the nitrogen atmosphere to cause the decomposition of molecules to produce the biochar composite material. Specifically, during the pyrolysis process, the crayfish shells are converted into biochar, and iron ions and/or ferrous ions and part of ferric hydroxide and/or ferrous hydroxide embedded in the pores of the crayfish shells are converted into ferric oxide, ferroferric oxide and the like, namely the iron in the biochar exists in the forms of ferric oxide, ferroferric oxide and the like. The biochar composite material in the application removes Cr (VI), and has the functions of reduction, complexation and precipitation besides the basic physical adsorption function compared with other biochar materials. The biochar is an electron donor and an electron shuttle, and the biochar composite material has stronger electron donating capability, so that the reducing power to Cr (VI) is enhanced, and the removal rate to Cr (VI) is improved. In the removal of phosphate ions, the adsorption of the biochar composite material to phosphate is mainly electrostatic attraction, ligand exchange and surface complexation. The biochar composite material contains a large amount of calcium ions, phosphate ions can be removed through precipitation, positive charges are carried on the surface of the biochar composite material, the phosphate ions can be effectively adsorbed, and ligand exchange effect can be generated between acidic ferrous oxide and the phosphate ions generated on the surface of the biochar, so that the removal rate is improved. The biochar composite material has large specific surface area and porosity, provides attachment points for iron oxide, and can accelerate the removal of pollutants through surface adsorption. Meanwhile, due to the magnetic property of ferroferric oxide, the biochar composite material can be well separated from the water phase, so that the biochar composite material can be rapidly recovered.
Further, the heating rate of the pyrolysis is 5-15 ℃ min-1Preferably 5 to 10 ℃ per min-1(ii) a The pyrolysis is carried out at 400-600 ℃, preferably 500-600 ℃ for 90-120 min, preferably 110-120 min. The inventor finds that if the pyrolysis temperature is too high, carbonization is excessive, and ash content is increased sharply; if the pyrolysis time is too short, pyrolysis is insufficient; and if the pyrolysis time is too long, the carbonization is serious, and the oxygen-containing functional group is invalid. Therefore, the iron-loaded biomass can be moderately carbonized by adopting the pyrolysis conditions of the application.
The inventor finds that by mixing the crayfish shell powder with the iron-containing solution and then carrying out the reaction, because the crayfish shell powder has a pore structure and a high specific surface area, iron ions and/or ferrous ions in the iron-containing solution are embedded into pores of the crayfish shell powder, and part of the iron ions and/or ferrous ions are hydrolyzed to generate ferric hydroxide and/or ferrous hydroxide; then carrying out solid-liquid separation on the reacted liquid to obtain iron-loaded biomass; and finally, carrying out pyrolysis on the iron-carrying biomass in a nitrogen atmosphere, wherein in the pyrolysis process, the crayfish shells are converted into biochar, and meanwhile, iron ions and/or ferrous ions and part of ferric hydroxide and/or ferrous hydroxide which are embedded into pores of the biochar shells are converted into ferric oxide, ferroferric oxide and the like, namely, the iron in the biochar exists in the forms of ferric oxide, ferroferric oxide and the like. The biochar composite material in the application removes Cr (VI), and has the functions of reduction, complexation and precipitation besides the basic physical adsorption function compared with other biochar materials. The biochar is an electron donor and an electron shuttle, and the biochar composite material has stronger electron donating capability, so that the reducing power to Cr (VI) is enhanced, and the removal rate to Cr (VI) is improved. In the removal of phosphate ions, the adsorption of the biochar composite material to phosphate is mainly electrostatic attraction, ligand exchange and surface complexation. The biochar composite material contains a large amount of calcium ions, phosphate ions can be removed through precipitation, positive charges are carried on the surface of the biochar composite material, the phosphate ions can be effectively adsorbed, and ligand exchange effect can be generated between acidic ferrous oxide and the phosphate ions generated on the surface of the biochar, so that the removal rate is improved. The biochar composite material has large specific surface area and porosity, provides attachment points for iron oxide, and can accelerate the removal of pollutants through surface adsorption. Meanwhile, due to the magnetic property of ferroferric oxide, the biochar composite material can be well separated from the water phase, so that the biochar composite material can be rapidly recovered. Therefore, the biochar composite material prepared by the method can realize the reduction treatment and resource utilization of the solid waste crayfish shells on the one hand, and can realize the efficient single and synchronous adsorption removal of Cr (VI) and phosphate radicals in a water body on the other hand, and has special significance for pollution control and treatment, and the preparation method is simple, the raw material source is rich, and the cost is low.
In a second aspect of the invention, a biochar composite is provided. According to the embodiment of the invention, the biochar composite material is prepared by the method. Therefore, on one hand, the reduction treatment and resource utilization of the solid waste crayfish shells can be realized, on the other hand, the obtained biochar composite material can realize the efficient single and synchronous adsorption removal of Cr (VI) and phosphate radicals in the water body, and has special significance for pollution control and treatment. It should be noted that the features and advantages described above for the method of preparing the biochar composite are also applicable to the biochar composite and will not be described herein again.
In a third aspect of the invention, a method of treating a body of water containing cr (vi) and/or phosphate is provided. According to an embodiment of the invention, the method comprises:
sa: grinding, sieving, washing and drying the biochar composite material
In the step, the biochar composite material is ground, sieved and washed, so that impurities on the surface of the biochar are washed away, and the ground and sieved biochar composite material can be uniformly dispersed in a water body, so that the adsorption efficiency is improved. Cleaning, placing in an oven, and drying at 115-125 ℃, preferably 120 ℃ to constant weight to obtain biochar composite material powder with the particle size of 120-150 mu m.
Sb: mixing and reacting biochar composite powder with water containing Cr (VI) and/or phosphate radical
In the step, Cr (VI) in the water body is CrO4 2-、HCrO4 -And Cr2O7 2-Is present in the form of at least one of the following, the phosphate being present as H3PO4、HPO4 2-、H2PO4 -And PO4 3-By mixing and reacting the obtained biochar composite powder with a water body containing Cr (VI); or mixing and reacting the biochar composite powder with water containing phosphate radicals; or the biochar composite powder is mixed with water containing Cr (VI) and phosphate radical for reaction, and the biochar composite powder has positive charges on the surface and negative charges on Cr (VI) and/or phosphate radical in the water, so that the biochar composite powder can carry out reaction on Cr (VI) and/or phosphate radical in the waterThe adsorption realizes the efficient single and synchronous adsorption removal of Cr (VI) and phosphate radical in the water body, and has special significance for pollution control and treatment. It should be noted that the features and advantages described above for the biochar composite and the preparation method thereof are also applicable to the method for treating the water body containing cr (vi) and/or phosphate radical, and are not described herein again.
Furthermore, whether the water body is a single water body only containing Cr (VI) or phosphate radical or a mixed water body simultaneously containing Cr (VI) and phosphate radical, the concentration of Cr (VI) in the water body is 20-100 mg.L-1(ii) a The concentration of the phosphate radical is 2-8 mg.L-1. The inventor finds that the adsorption capacity of the biochar composite powder to Cr (VI) and/or phosphate in a water body is increased along with the increase of the concentration, and if the concentration of Cr (VI) and/or phosphate in the water body is too low, the adsorption capacity of the biochar composite powder is reduced; if the concentration of Cr (VI) and/or phosphate radical in the water body is too high, the adsorption capacity of the biochar composite material powder cannot be obviously increased along with the increase of the concentration, and the removal rate is low. Therefore, by adopting the Cr (VI) and/or phosphate radical concentration in the range, the biochar composite material powder can have higher adsorption capacity and higher removal rate of Cr (VI) and/or phosphate radical in the water body.
Further, based on 1L of the water body, the adding amount of the biochar composite powder is 0.5-4.0 g. The inventor finds that if the adding amount of the biochar composite powder is too small, the removal rate of Cr (VI) and/or phosphate radical in the water body is low; if the adding amount of the biochar composite powder is too large, although the removal rate is correspondingly improved, the effective adsorption sites are increased along with the increase of the adding amount, and when enough effective adsorption sites exist but the reactant concentration is low, the adsorption is unsaturated, so that the adsorption capacity of the biochar composite powder is reduced. Therefore, by adopting the adding amount within the range of the application, the biochar composite powder can have higher adsorption capacity and higher removal rate of Cr (VI) and/or phosphate radical in the water body.
Further, the pH value of the water body is 2.00-9.00. The inventor finds that if the pH is too high, the adsorption effect of the biochar composite material powder is poor under the condition of the too high pH; if the pH is too low, too low pH will produce an inhibitory effect, which will also result in poor adsorption effect of the biochar composite powder. Therefore, the adsorption capacity of the biochar composite powder is better by adopting the pH value in the range of the application.
Further, the temperature of the mixing reaction is 30-50 ℃, and preferably 30 ℃; the reaction time is 150-180 min, preferably 180 min. The inventors found that if the reaction temperature is too high, energy consumption is increased; on the other hand, if the reaction temperature is too low, adsorption may be insufficient and the removal rate may be low. Meanwhile, if the reaction time is too short, the reaction is insufficient, and the removal rate is low; if the reaction time is too long, the biochar composite material powder reaches adsorption saturation, the reaction time is continuously prolonged, the removal rate cannot be improved, and the efficiency is reduced. Thus, the adsorption can be sufficiently performed by using the reaction temperature and time within the range of the present application, and the increase of energy consumption and the decrease of efficiency can be avoided.
The following embodiments of the present invention are described in detail, and it should be noted that the following embodiments are exemplary only, and are not to be construed as limiting the present invention. In addition, all reagents used in the following examples are commercially available or can be synthesized according to methods herein or known, and are readily available to those skilled in the art for reaction conditions not listed, if not explicitly stated.
Example 1
The preparation method of the biochar composite powder comprises the following steps:
step 1: cleaning collected kitchen waste crayfish shells, placing the cleaned shells in an oven to be dried at 120 ℃, crushing the shells, sieving the crushed shells with a 20-mesh sieve, placing the crushed shells in a self-sealing bag, and placing the self-sealing bag in the drying oven for storage to obtain crayfish shell powder (the particle size is about 300 mu m); 10g of crawfish shell powder was mixed with 100mL of ferric chloride solution (concentration 1 mol. L)-1) According to the solid-liquid ratio of 1 g: 10mL of the mixture is mixed and reacted (the reaction temperature is 30 ℃ and the reaction time is 180min) to obtain reaction liquid；
Step 2: centrifuging the reaction solution to obtain iron-loaded biomass;
and step 3: transferring the iron-loaded biomass to a crucible, placing the crucible in a tubular furnace, introducing nitrogen at room temperature for 10min, and introducing nitrogen at 10 ℃ for min under the protection of nitrogen-1Heating to 600 ℃, pyrolyzing for 120min, cooling to room temperature, taking out to obtain the biochar composite, taking out a sample, grinding, sieving with a 100-mesh sieve, and washing with a solid-to-liquid ratio of 1 g: 50mL, centrifuging, drying at 120 ℃ to constant weight to obtain biochar composite powder with the particle size of about 130 mu m, and sealing and storing.
The biochar composite material powder singly adsorbs Cr (VI) in water:
taking 0.08g (based on 1L of water body, the adding amount of the biochar composite material powder is 2.0 g.L)-1) Putting the biochar composite powder into a 50mL centrifuge tube, and adding 40mL of Cr (VI) -containing solution (Cr (VI) with the concentration of 40 mg.L)-1Initial pH of 4.80), the pH was adjusted to 3.00, 5.00, 6.00, 7.00 and 9.00, respectively, and the reaction was stirred at 120rpm without adjusting the pH (4.80) and stirred at 30 ℃ for 180 min. After sampling and filtering with a 0.22 μm filter membrane, the concentration of Cr (VI) in the filtrate is measured by ultraviolet spectrophotometry, and the single adsorption effect of the biochar composite powder on Cr (VI) under different pH conditions is finally obtained as shown in figure 2 and table 1-1.
The biochar composite powder can be used for singly adsorbing phosphate radicals in water:
weighing 0.06g (based on 1L water body, the adding amount of the biochar composite material powder is 1.5 g.L)-1) Placing the biochar composite powder into a 50mL centrifuge tube, and adding 40mL phosphate radical-containing solution (the phosphate radical concentration is 4 mg. L)-1Initial pH 5.86), the pH was adjusted to 2.00, 3.00, 5.00, 7.00 and 9.00, respectively, and the reaction was shaken at 30 ℃ for 180min without adjusting the pH (5.86) under stirring at 120 rpm. After sampling and filtering with a 0.22-micron filter membrane, measuring the concentration of phosphate radicals in the filtrate by adopting an ultraviolet spectrophotometry, wherein the single adsorption effect of the biochar composite powder on the phosphate radicals under different pH conditions is finally obtained as shown in figure 2 and tables 1-2.
TABLE 1-1 Single adsorption Rate of biochar composite powder to Cr (VI) under different pH conditions
TABLE 1-2 Single adsorption Rate of biochar composite powder to phosphate radical under different pH conditions
Example 2
The procedure for preparing the biocoke composite powder was the same as in example 1;
the biochar composite material powder singly adsorbs Cr (VI) in water:
the adding amount of the biochar composite powder is adjusted to be 0.02g, 0.04g, 0.08g, 0.12g and 0.16g (based on 1L of water body, the adding amount of the biochar composite powder is respectively 0.5 g.L-1、1.0g·L-1、2.0g·L-1、3.0g·L-1And 4.0 g.L-1) And respectively placing the solution in a 50mL centrifuge tube, and adding 40mL of Cr (VI) -containing solution (Cr (VI) with the concentration of 40 mg.L-1Initial pH was 4.80), the pH was adjusted, and the reaction was stirred at 120rpm and 30 ℃ for 180min with shaking. After sampling and filtering with a 0.22 μm filter membrane, the concentration of Cr (VI) in the filtrate is determined by ultraviolet spectrophotometry, and the single adsorption effect of different amounts of biochar composite powder on Cr (VI) is shown in FIG. 3 and Table 2-1.
The biochar composite powder can be used for singly adsorbing phosphate radicals in water:
the adding amount of the biochar composite powder is adjusted to be 0.02g, 0.04g, 0.06g, 0.08g and 0.12g (based on 1L of water body, the adding amount of the biochar composite powder is respectively 0.5 g.L-1、1.0g·L-1、1.5g·L-1、2.0g·L-1And 3.0 g.L-1) And respectively placing the solution in a 50mL centrifuge tube, and then adding 40mL phosphate radical-containing solution (the phosphate radical concentration is 4 mg. L)-1Initial pH 5.86), not adjustedThe reaction was carried out at 30 ℃ for 180min with stirring at 120 rpm. After sampling and filtering with a 0.22 mu m filter membrane, measuring the concentration of phosphate radicals in the filtrate by adopting an ultraviolet spectrophotometry, wherein the single adsorption effect of the finally obtained different biochar composite material powder dosage on the phosphate radicals is shown in figure 3 and table 2-2.
TABLE 2-1 Single adsorption Rate for Cr (VI) under different dosages of biochar composite powder
TABLE 2-2 Single adsorption Rate for phosphate radical under different biochar composite powder dosage conditions
Example 3
The procedure for preparing the biocoke composite powder was the same as in example 1;
the biochar composite material powder singly adsorbs Cr (VI) in water:
weighing 0.08g (based on 1L water body, the adding amount of the biochar composite material powder is 2.0 g.L)-1) Putting the biochar composite powder into a 50mL centrifuge tube, adding 40mL of Cr (VI) -containing solution (the concentration of Cr (VI) is adjusted to 20 mg.L respectively)-1、40mg·L-1、60mg·L-1、80mg·L-1、100mg·L-1) The reaction was carried out without adjusting pH and with stirring at 120rpm and shaking at 30 ℃ for 180 min. After sampling and filtering with a 0.22 μm filter membrane, the concentration of Cr (VI) in the filtrate is determined by ultraviolet spectrophotometry, and the single adsorption effect of the biochar composite powder on Cr (VI) under different pollutant concentrations is finally obtained as shown in fig. 4 and table 3-1.
The biochar composite powder can be used for singly adsorbing phosphate radicals in water:
weighing 0.06g (based on 1L water body, the adding amount of the biochar composite material powder is 1.5 g.L)-1) Putting the biochar composite powder into a 50mL centrifuge tube,then, 40mL of a solution containing phosphate radicals (the concentration of phosphate radicals was adjusted to 2 mg. multidot.L, respectively) was added-1、4mg·L-1、6mg·L-1、8mg·L-1) The reaction was carried out without adjusting pH and with stirring at 120rpm and shaking at 30 ℃ for 180 min. After sampling and filtering with a 0.22-micron filter membrane, measuring the concentration of phosphate radicals in the filtrate by using an ultraviolet spectrophotometry, wherein the single adsorption effect of the biochar composite material powder on the phosphate radicals under different pollutant concentrations is finally obtained as shown in figure 4 and a table 3-2.
TABLE 3-1 Single adsorption Rate of biochar composite powder to Cr (VI) under different contaminant concentration conditions
TABLE 3-2 Single adsorption Rate of biochar composite powder to phosphate radical under different contaminant concentration conditions
Example 4
The procedure for preparing the biocoke composite powder was the same as in example 1;
the biochar composite powder synchronously adsorbs Cr (VI) and phosphate radical in water:
weighing 0.08g (based on 1L water body, the adding amount of the biochar composite material powder is 2.0 g.L)-1) Putting the biochar composite powder into a 50mL centrifuge tube, and adding 40mL of mixed solution (Cr (VI)) containing Cr (VI) and phosphate radical, wherein the concentration of the mixed solution (Cr (VI)) is 40 mg.L-1The concentration of phosphate radical was adjusted to 2 mg. L, respectively-1、4mg·L-1、6mg·L-1、8mg·L-1) The reaction was carried out without adjusting pH and with stirring at 120rpm and shaking at 30 ℃ for 180 min. After sampling and filtering with a filter membrane of 0.22 mu m, the concentrations of Cr (VI) and phosphate radical in the filtrate are measured by adopting an ultraviolet spectrophotometry. The synchronous adsorption effect of the finally obtained biochar composite powder on Cr (VI) and phosphate radical is shown in figure 5 respectively. Adsorption removal effect of biochar composite powder on chromiumThe decrease was observed with increasing phosphate concentration, but the decrease was not significant. When the concentration of phosphate radical is less than or equal to 8 mg.L-1In this case, the removal rate of Cr (VI) was kept at about 95%, and the removal rate of phosphorus was 64.13%. The result shows that Cr (VI) and phosphate radical can be removed in the biochar composite powder singly and synchronously and efficiently.
Comparative example
The preparation steps of the unmodified charcoal powder are as follows:
step 1: cleaning collected kitchen waste crayfish shells, placing the cleaned shells in an oven to be dried at 120 ℃, crushing the shells, sieving the crushed shells with a 20-mesh sieve, placing the crushed shells in a self-sealing bag, and placing the self-sealing bag in the drying oven for storage to obtain crayfish shell powder (the particle size is 300 mu m);
step 2: transferring the crayfish shell powder to a crucible, placing the crucible in a tube furnace, introducing nitrogen for 10min at room temperature, and introducing nitrogen at 10 ℃ min under the protection of nitrogen-1Heating to 600 ℃, pyrolyzing for 120min, cooling to room temperature, taking out, washing, and sieving with a 100-mesh sieve to obtain unmodified biochar. Sorting, washing and drying the unmodified charcoal to obtain unmodified charcoal powder with the particle size of 120-150 mu m.
The unmodified charcoal powder singly adsorbs Cr (VI) in the water body:
weighing 0.08g (based on 1L water, the adding amount of the unmodified charcoal powder is 2.0 g.L)-1) Placing unmodified charcoal powder in 50mL centrifuge tube, adding 40mL Cr (VI) -containing solution (Cr (VI)) with concentration of 40 mg.L-1Initial pH was 4.80), the pH was adjusted, and the reaction was stirred at 120rpm and 30 ℃ for 180min with shaking. After the sample was filtered through a 0.22 μm filter membrane, the concentration of Cr (VI) in the filtrate was measured by UV spectrophotometry. The removal rate of the finally obtained unmodified biochar to Cr (VI) is only 1.71 percent, and the corresponding adsorption quantity is 0.34mg g-1。
The unmodified charcoal powder singly adsorbs phosphate radicals in water:
weighing 0.06g (based on 1L water, the adding amount of unmodified charcoal powder is 1.5 g.L)-1) Placing unmodified charcoal powder in 50mLTo the heart tube, 40mL of a solution containing phosphate (phosphate concentration 4 mg. L.) was added-1Initial pH 5.86), the reaction was carried out without pH adjustment and with stirring at 120rpm and shaking at 30 ℃ for 180 min. After sampling and filtering with a 0.22 mu m filter membrane, measuring the concentration of phosphate radical in the filtrate by adopting an ultraviolet spectrophotometry, wherein the removal rate of the phosphate radical by the finally obtained unmodified biochar is only 40.34 percent, and the corresponding adsorption quantity is 1.08mg g-1。
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. A method of making a biochar composite, comprising:
(1) mixing crayfish shell powder with an iron-containing solution and then reacting;
(2) carrying out solid-liquid separation on the reaction liquid obtained in the step (1) so as to obtain iron-carrying biomass;
(3) and pyrolyzing the iron-carrying biomass in a nitrogen atmosphere to obtain the biochar composite material.
2. The method as claimed in claim 1, wherein in the step (1), the crawfish shell powder has a particle size of 200 to 400 μm;
optionally, in step (1), the iron-containing solution comprises at least one of ferric chloride, ferric sulfate, ferric nitrate, ferric acetate, ferrous chloride, ferrous sulfate, ferrous nitrate, and ferrous acetate;
optionally, in the step (1), the concentration of the iron-containing solution is 1-2 mol.L-1；
Optionally, in the step (1), the solid-to-liquid ratio of the crayfish shell powder to the iron-containing solution is (5-15) g: (25-200) mL.
3. The method of claim 1, wherein in step (3), the pyrolysis is carried out at a temperature increase rate of 5-15 ℃ min-1And carrying out pyrolysis at 400-600 ℃ for 90-120 min.
4. A biochar composite, characterized in that it is prepared by the method according to any one of claims 1 to 3.
5. A method of treating a body of water containing cr (vi) and/or phosphate comprising:
a. grinding, sieving, washing and drying the biochar composite material as claimed in claim 4 to obtain biochar composite material powder;
b. and mixing and reacting the biochar composite powder with a water body containing Cr (VI) and/or phosphate.
6. The method according to claim 5, wherein in the step a, the particle size of the biochar composite powder is 120-150 μm.
7. The method according to claim 5, wherein in the step b, the concentration of Cr (VI) in the water body is 20-100 mg-L-1Concentration of said phosphate radical2 to 8 mg.L-1。
8. The method according to claim 5, wherein in the step b, the biochar composite powder is added in an amount of 0.5-4.0 g based on 1L of the water body.
9. The method of claim 5, wherein the pH of the body of water is 2.00 to 9.00.
10. The method according to claim 5, wherein the temperature of the mixing reaction is 30 to 50 ℃.
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| CN110327898A (en) * | 2019-07-01 | 2019-10-15 | 河南城建学院 | A kind of shrimp shell base magnetism multi-stage porous carbon surface imprinted material and its preparation method and application |
| CN114950429A (en) * | 2022-05-07 | 2022-08-30 | 湖南大学 | Low-temperature iron-carbon composite material and preparation method and application thereof |
| CN115337905A (en) * | 2022-08-19 | 2022-11-15 | 重庆大学 | Nano-iron modified biochar composite material and preparation method and application thereof |
| CN115337905B (en) * | 2022-08-19 | 2023-09-19 | 重庆大学 | Nano-iron modified biochar composite material and preparation method and application thereof |
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Application publication date: 20210604 |