CN116282326A - Method for adsorbing heavy metal ions - Google Patents
Method for adsorbing heavy metal ions Download PDFInfo
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- CN116282326A CN116282326A CN202211571840.4A CN202211571840A CN116282326A CN 116282326 A CN116282326 A CN 116282326A CN 202211571840 A CN202211571840 A CN 202211571840A CN 116282326 A CN116282326 A CN 116282326A
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- heavy metal
- biochar
- metal ions
- shaddock
- shaddock ped
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- 150000002500 ions Chemical class 0.000 title claims abstract description 92
- 238000000034 method Methods 0.000 title claims abstract description 68
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- 235000001759 Citrus maxima Nutrition 0.000 claims abstract description 94
- 238000001179 sorption measurement Methods 0.000 claims abstract description 70
- 238000012986 modification Methods 0.000 claims abstract description 39
- 230000004048 modification Effects 0.000 claims abstract description 39
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000011777 magnesium Substances 0.000 claims abstract description 24
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 19
- 238000000227 grinding Methods 0.000 claims abstract description 10
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 3
- 239000000843 powder Substances 0.000 claims description 39
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 25
- 239000007788 liquid Substances 0.000 claims description 18
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- 239000001606 7-[(2S,3R,4S,5S,6R)-4,5-dihydroxy-6-(hydroxymethyl)-3-[(2S,3R,4R,5R,6S)-3,4,5-trihydroxy-6-methyloxan-2-yl]oxyoxan-2-yl]oxy-5-hydroxy-2-(4-hydroxyphenyl)chroman-4-one Substances 0.000 claims description 17
- DFPMSGMNTNDNHN-ZPHOTFPESA-N naringin Chemical compound O[C@@H]1[C@H](O)[C@@H](O)[C@H](C)O[C@H]1O[C@H]1[C@H](OC=2C=C3O[C@@H](CC(=O)C3=C(O)C=2)C=2C=CC(O)=CC=2)O[C@H](CO)[C@@H](O)[C@@H]1O DFPMSGMNTNDNHN-ZPHOTFPESA-N 0.000 claims description 17
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- KZEVSDGEBAJOTK-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[5-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CC=1OC(=NN=1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O KZEVSDGEBAJOTK-UHFFFAOYSA-N 0.000 description 2
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- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
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- 206010007269 Carcinogenicity Diseases 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
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- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- 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
-
- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—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 surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
-
- 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
- B01J2220/4887—Residues, wastes, e.g. garbage, municipal or industrial sludges, compost, animal manure; fly-ashes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention provides a method for adsorbing heavy metal ions, which comprises the following steps: (1) Pretreating, modifying magnesium, drying, pyrolyzing and grinding the shaddock peel to obtain shaddock peel biochar; (2) Mixing the shaddock ped biochar obtained in the step (1) with a solution containing heavy metal ions to finish the adsorption of the heavy metal ions; the temperature of the mixing in the step (2) is 15-35 ℃; the heavy metal ion includes Pb 2+ And/or Cd 2+ . The invention takes the pomelo peel as the raw material, has wide sources and low cost, endows the obtained pomelo peel biochar with developed pore channels and higher specific surface area, and increases the adsorption area; after the modification treatment of magnesium, the surface of the obtained shaddock ped biochar contains more magnesium ions, and the shaddock ped biochar can be precipitated through ion exchange or mineralsHeavy metal ions are adsorbed in a mode, and Pb is adsorbed by the shaddock ped biochar obtained by the method 2+ And Cd 2+ The maximum adsorption amounts were 1499mg/g and 950mg/g, respectively.
Description
Technical Field
The invention belongs to the technical field of water treatment, relates to a treatment method of heavy metal ions, and particularly relates to a method for adsorbing heavy metal ions.
Background
Biochar is an aromatic compound with rich carbon elements and porous physical structure, which is produced by slow pyrolysis of biomass at low temperature under the condition of limiting oxygen. The internal pores of the biochar are developed, have larger specific surface area and can be used as an adsorption material; meanwhile, the surface of the carbon has rich oxygen-containing functional groups and a graphite-like structure inside the carbon, so that the biochar has certain conductivity and is used as a catalytic material for degrading pollutants; biochar has become a research hot spot in the field of environmental remediation due to the advantages of wide sources, environmental friendliness, strong reproducibility and the like.
CN115138334a discloses a nitrogen-doped biochar, a preparation method thereof and application thereof in carbon dioxide adsorption, wherein straw, biogas slurry and sodium sulfate are mixed, and the mixture undergoes hydrothermal reaction to obtain nitrogen-doped hydrothermal carbon; and mixing the nitrogen-doped hydrothermal carbon with potassium hydroxide, and activating in a nitrogen atmosphere to obtain the nitrogen-doped biochar. According to the technical scheme, the nitrogen-doped biochar can be prepared in a green mode, high doping efficiency is guaranteed, the resource treatment of straw and biogas slurry is realized, and the obtained nitrogen-doped biochar has good adsorption performance on carbon dioxide.
CN115055515a discloses a microbial remediation method for plastics in refuse contaminated soil, the microbial remediation method comprising: the microorganisms on the plastic surface in the garbage polluted site are amplified and cultured by using a liquid culture medium, and the obtained bacterial liquid is transferred into a selective inorganic salt culture medium for enrichment culture, so that functional bacterial groups with plastic degradation capability are obtained through enrichment; mixing and adsorbing the bacterial suspension with biomass charcoal, and freezing and drying to obtain microorganism immobilized biomass charcoal; and adding the microorganism immobilized biomass charcoal into the mixed solution of carboxymethyl cellulose and sodium alginate, uniformly stirring, then dropwise adding into a calcium chloride solution for crosslinking reaction to obtain biomass charcoal-based microorganism immobilized particles, adding into garbage contaminated soil, and carrying out in-situ restoration on the garbage contaminated soil. According to the technical scheme, the problems of difficult degradation of plastics in garbage polluted soil and migration and removal of microplastic are solved.
Besides the soil problems, water pollution is an environmental pollution problem to be solved urgently at present, and repair is difficult due to various pollution sources, complex components and the like, and CN115069215A discloses a novel functionalized magnetic porous biochar material, a preparation method and application thereof. In the technical scheme, loofah sponge is used as a raw material, a surface modification technology doped with N and Fe is used for modifying and modifying a substrate material, potassium hydroxide is used as an activating agent, and a high-temperature carbonization mode is used for synthesis, so that the novel functional magnetic porous biochar material is prepared. The modified material has multiple pores, large specific surface area, increased adsorption sites and excellent adsorption performance, can complete enrichment and recovery in water, reduces the use of organic solvents, is efficient and convenient, and has good adsorption performance on fluoroquinolone antibiotics in water.
Heavy metals are dangerous wastes with teratogenicity, carcinogenicity and mutation, can be deposited on a riverbed but are easily dissolved in water again, can migrate along with water, can be transferred along a food chain and are enriched in animals and plants, and have increasingly significant harm to the environment and human health. With the continuous development and optimization of water pollution remediation technology and materials, various methods such as precipitation, ion exchange, microorganism, membrane treatment, adsorption and the like are used for heavy metal pollution remediation. The adsorption method is considered to be an excellent one of a plurality of repair methods because of the advantages of rapidness, high efficiency, simple operation, low cost, easy availability, environmental friendliness and the like. Common adsorbents include attapulgite, zeolite, molecular sieve or zero-valent iron, but the actual requirements cannot be met due to the defects of low adsorption capacity, poor selectivity, poor reusability and the like.
In this regard, the invention provides a method for adsorbing heavy metal ions in water by using the shaddock ped biochar, which improves the adsorption capacity and the adsorption selectivity, reduces the heavy metal pollution and purifies the water environment.
Disclosure of Invention
The invention aims to provide a method for adsorbing heavy metal ions, which can reduce cost, improve the adsorption quantity of the heavy metal ions and purify the water environment by utilizing shaddock peel biochar to adsorb the heavy metal ions. In order to achieve the aim of the invention, the invention adopts the following technical scheme:
the invention provides a method for adsorbing heavy metal ions, which comprises the following steps:
(1) Pretreating, modifying magnesium, drying, pyrolyzing and grinding the shaddock peel to obtain shaddock peel biochar;
(2) Mixing the shaddock ped biochar obtained in the step (1) with a solution containing heavy metal ions to finish the adsorption of the heavy metal ions;
the temperature of the mixing in the step (2) is 15-35 ℃;
the heavy metal ion includes Pb 2+ And/or Cd 2+ ；
The shaddock ped biochar obtained in the step (1) of the invention has the following effect on Pb 2+ And Cd 2+ The maximum adsorption amount is 1499mg/g and 950mg/g respectively.
The invention takes the pomelo peel as the raw material, has wide sources and low cost, endows the obtained pomelo peel biochar with developed pore channels and higher specific surface area, and increases the adsorption area; after the modification treatment of magnesium, the surface of the obtained shaddock ped biochar contains more magnesium ions, and heavy metal ions can be adsorbed by ion exchange or mineral precipitation, and the shaddock ped biochar obtained in the step (1) has the following advantages of no pollution, low cost and low cost 2+ And Cd 2+ The maximum adsorption capacity can reach 1499mg/g and 950mg/g respectively.
The temperature of the mixing in step (2) in the present invention is 15 to 35℃and may be, for example, 15℃ 20℃25℃ 30℃or 35℃but is not limited to the values recited, and other values not recited in the numerical range are equally applicable. According to the invention, as the mixing temperature is increased, the maximum adsorption amount of the shaddock ped charcoal to heavy metal ions gradually decreases, and the shaddock ped charcoal is in exothermic reaction with the adsorption of the heavy metal ions, so that the increased temperature is unfavorable for the adsorption of the heavy metal ions.
Preferably, the water content of the shaddock ped in the step (1) is 40-85wt%, for example, 40wt%, 50wt%, 60wt%, 70wt%, 80wt% or 85wt%, but is not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
Preferably, the pretreatment of step (1) comprises: and cutting, cleaning, drying and crushing the shaddock peel to obtain shaddock peel powder.
Preferably, the temperature of the drying is 60-80 ℃, for example, 60 ℃, 65 ℃, 70 ℃, 75 ℃ or 80 ℃, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the drying time is 12-48h, for example, 12h, 24h, 36h or 48h, but not limited to the recited values, and other non-recited values in the range are equally applicable.
Preferably, the D80 particle size of the powdered pomelo peel obtained after crushing is 40-100 mesh, for example, 40 mesh, 50 mesh, 60 mesh, 70 mesh, 80 mesh, 90 mesh or 100 mesh, but not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
Preferably, the modifier used in the modification of the magnesium in step (1) comprises a magnesium chloride solution and/or a magnesium nitrate solution, preferably a magnesium chloride solution.
Preferably, the concentration of the magnesium chloride solution is 0.1-2mol/L, for example, 0.1mol/L, 0.3mol/L, 0.5mol/L, 0.8mol/L, 1mol/L, 1.2mol/L, 1.5mol/L, 1.8mol/L or 2mol/L, but not limited to the recited values, and other non-recited values within the numerical range are equally applicable.
Preferably, the method of magnesium modification comprises dip modification and/or spray modification, preferably dip modification.
Preferably, in the impregnation modification, the solid-to-liquid ratio (1-5): 100 of the shaddock ped powder to the magnesium chloride solution can be, for example, 1:100, 2:100, 3:100, 4:100 or 5:100, but is not limited to the recited values, and other non-recited values in the numerical range are equally applicable, wherein the unit of the solid-to-liquid ratio is g/mL.
Preferably, the temperature of the impregnation modification is 25-30 ℃, for example, 25 ℃, 26 ℃, 27 ℃, 28 ℃, 29 ℃ or 30 ℃, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the time for the impregnation modification is 0.5 to 3 hours, for example, 0.5 hours, 1 hour, 1.5 hours, 2 hours, 2.5 hours or 3 hours, but not limited to the recited values, other non-recited values within the range of values are equally applicable.
Preferably, the impregnation modification is accompanied by stirring.
Preferably, the stirring speed is 550-850r/min, for example, 550r/min, 600r/min, 650r/min, 700r/min, 750r/min, 800r/min or 850r/min, but the stirring speed is not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
Preferably, the drying temperature in step (1) is 60-80 ℃, for example 60 ℃, 65 ℃, 70 ℃, 75 ℃ or 80 ℃, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the drying time in step (1) is 12-48 hours, for example, 12 hours, 24 hours, 36 hours or 48 hours, but not limited to the recited values, and other non-recited values in the range of values are equally applicable.
Preferably, the pyrolysis temperature in step (1) is 350-450 ℃, and may be, for example, 350 ℃, 360 ℃, 370 ℃, 380 ℃, 390 ℃, 400 ℃, 410 ℃, 420 ℃, 430 ℃, 440 ℃, or 450 ℃, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the pyrolysis time in step (1) is 1-2h, and may be, for example, 1h, 1.1h, 1.2h, 1.3h, 1.4h, 1.5h, 1.6h, 1.7h, 1.8h, 1.9h or 2h, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the heating rate of the pyrolysis in the step (1) is 5-10 ℃/min, for example, 5 ℃/min, 6 ℃/min, 7 ℃/min, 8 ℃/min, 9 ℃/min or 10 ℃/min, but the heating rate is not limited to the recited values, and other values not listed in the numerical range are equally applicable.
Preferably, the pyrolysis of step (1) is carried out under a protective atmosphere.
Preferably, the protective atmosphere comprises nitrogen and/or argon.
Preferably, the D80 particle size of the pomelo peel biochar obtained after grinding in the step (1) is less than or equal to 100 mesh, for example, 100 mesh, 120 mesh, 140 mesh, 160 mesh or 180 mesh, but is not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
Preferably, pb in the solution containing heavy metal ions in the step (2) 2+ The concentration of (C) is 300-1500mg/L, and may be, for example, 300mg/L, 500mg/L, 800mg/L, 1000mg/L, 1200mg/L or 1500mg/L, but is not limited to the values recited, and other values not recited in the numerical range are equally applicable.
Preferably, step (2) is performed by adding Cd to the solution containing the medium metal ions 2+ For example, 300mg/L, 500mg/L, 700mg/L, 900mg/L, 1100mg/L, 1300mg/L or 1500mg/L, but not limited to the values recited, other values not recited in the numerical range are equally applicable.
Preferably, the pH of the solution containing heavy metal ions in step (2) is 2-5, and may be, for example, 2, 2.5, 3, 3.5, 4, 4.5 or 5, but is not limited to the values recited, and other values not recited in the range of values are equally applicable.
Preferably, the solid-to-liquid ratio of the shaddock ped biochar to the solution containing heavy metal ions in step (2) is 1 (1-50), for example, may be 1:1, 1:5, 1:10, 1:20, 1:30, 1:40 or 1:50, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable, wherein the unit of the solid-to-liquid ratio is g/L.
Preferably, the mixing of step (2) is accompanied by stirring and/or shaking.
Preferably, the stirring speed is 150-250r/min, for example 150r/min, 180r/min, 200r/min, 230r/min or 250r/min, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the oscillation rate is 150-250r/min, and may be 150r/min, 180r/min, 200r/min, 230r/min or 250r/min, for example, but not limited to, the recited values, and other values not recited in the numerical range are equally applicable.
As a preferred technical solution of the method according to the invention, the method comprises the steps of:
(a) Cutting, cleaning, drying and crushing the shaddock peel to obtain shaddock peel powder with the D80 particle size of 40-100 meshes;
(b) Immersing and modifying the shaddock ped powder obtained in the step (a) in a magnesium chloride solution with the concentration of 0.1-2mol/L at the temperature of 25-30 ℃ for 0.5-3h, wherein the solid-to-liquid ratio of the shaddock ped powder to the magnesium chloride solution is (1-5), wherein the immersing and modifying is carried out with stirring at the stirring speed of 550-850r/min, drying at the temperature of 60-80 ℃ for 12-48h, heating to 350-450 ℃ at the speed of 5-10 ℃/min, carrying out pyrolysis for 1-2h under a protective atmosphere, and grinding until the D80 particle size is less than or equal to 100 meshes to obtain shaddock ped biochar;
(c) The shaddock ped biochar obtained in the step (b) is prepared by mixing the shaddock ped biochar with Pb containing powder according to the solid-to-liquid ratio of 1 (1-50) g/L 2+ And Cd 2+ The solution of heavy metal ions is mixed at 15-35 ℃, and stirring is carried out during mixing until the adsorption balance of the heavy metal ions is reached.
Compared with the prior art, the invention has the following beneficial effects:
the invention takes the pomelo peel as the raw material, has wide sources and low cost, endows the obtained pomelo peel biochar with developed pore channels and higher specific surface area, and increases the adsorption area; after the modification treatment of magnesium, the surface of the obtained shaddock ped biochar contains more magnesium ions, and heavy metal ions can be adsorbed by ion exchange or mineral precipitation, so that the shaddock ped biochar prepared by the invention has the advantages of high Pb content and low cost 2+ And Cd 2+ The maximum adsorption amounts were 1499mg/g and 950mg/g, respectively.
Drawings
FIG. 1 is an SEM image of the naringin biochar obtained in example 1;
FIG. 2 is an SEM image of the naringin biochar obtained without magnesium modification of comparative example 1;
FIG. 3 shows Pb adsorption using shaddock peel, navel orange peel and Wo Ganpi as raw materials in example 1, comparative example 2 and comparative example 3, respectively 2+ Curve comparison graph;
FIG. 4 shows the naringin biomass obtained in example 1Carbon adsorption of Pb 2+ XRD contrast patterns before and after;
FIG. 5 is a graph showing the adsorption of Cd from shaddock ped, navel orange peel and Wo Ganpi, respectively, in example 8, comparative example 5 and comparative example 6 2+ Curve comparison graph;
FIG. 6 shows the adsorption of Cd by the charcoal of naringin obtained in example 8 2+ XRD contrast patterns before and after.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof. The shaddock peel used in the specific embodiment of the invention comes from Jiangxi province to Shang city.
Example 1
The embodiment provides a method for adsorbing heavy metal ions, which comprises the following steps:
(a) Cutting and cleaning pericarpium Citri Grandis, oven drying at 60deg.C, and pulverizing to obtain 50 mesh D80 pericarpium Citri Grandis powder;
(b) Carrying out dipping modification on the shaddock ped powder obtained in the step (a) in a magnesium chloride solution with the concentration of 0.5mol/L at the temperature of 25 ℃ for 2.5h, wherein the solid-to-liquid ratio of the shaddock ped powder to the magnesium chloride solution is 5:100g/mL, the dipping modification is carried out with stirring, the stirring speed is 700r/min, the shaddock ped powder is dried at the temperature of 70 ℃ for 36h, then the shaddock ped powder is heated to 400 ℃ at the speed of 10 ℃/min, pyrolysis is carried out for 2h in a nitrogen atmosphere, and the grain diameter D80 after grinding is less than or equal to 100 meshes, thus obtaining the shaddock ped biochar;
(c) The shaddock ped biochar obtained in the step (b) contains 1500mg/L Pb according to the solid-to-liquid ratio of 1:1g/L 2+ Mixing the heavy metal ion solution with the pH value of 4 at 25 ℃, and stirring until the adsorption balance of the heavy metal ions is reached.
Example 2
The embodiment provides a method for adsorbing heavy metal ions, which comprises the following steps:
(a) Cutting and cleaning pericarpium Citri Grandis, oven drying at 70deg.C, and pulverizing to obtain 40 mesh powder with D80 particle diameter;
(b) Carrying out dipping modification on the shaddock ped powder obtained in the step (a) in a magnesium chloride solution with the concentration of 0.5mol/L at the temperature of 28 ℃ for 1h, wherein the solid-to-liquid ratio of the shaddock ped powder to the magnesium chloride solution is 2.5:100g/mL, the dipping modification is carried out with stirring, the stirring speed is 550r/min, the shaddock ped powder is dried at the temperature of 60 ℃ for 48h, then the shaddock ped powder is heated to 350 ℃ at the speed of 8 ℃/min, pyrolysis is carried out for 1.5h in an argon atmosphere, and the grain size of D80 after grinding is less than or equal to 100 meshes, thus obtaining the shaddock ped biochar;
(c) The shaddock ped biochar obtained in the step (b) contains 1500mg/L Pb according to the solid-to-liquid ratio of 1:1g/L 2+ Mixing the heavy metal ion solution with the pH value of 5 at 25 ℃, and stirring until the adsorption balance of the heavy metal ions is reached.
Example 3
The embodiment provides a method for adsorbing heavy metal ions, which comprises the following steps:
(a) Cutting and cleaning the shaddock peel, drying at 80 ℃, and crushing to obtain shaddock peel powder with the D80 particle size of 100 meshes;
(b) Carrying out dipping modification on the shaddock ped powder obtained in the step (a) in a magnesium chloride solution with the concentration of 0.5mol/L at the temperature of 30 ℃ for 1h, wherein the solid-to-liquid ratio of the shaddock ped powder to the magnesium chloride solution is 1:100g/mL, the dipping modification is carried out with stirring, the stirring speed is 850r/min, the shaddock ped powder is dried at the temperature of 80 ℃ for 12h, the temperature is increased to 450 ℃ at the speed of 5 ℃/min, pyrolysis is carried out for 1h in a nitrogen atmosphere, and the D80 particle size after grinding is less than or equal to 100 meshes, so that the shaddock ped biochar is obtained;
(c) The shaddock ped biochar obtained in the step (b) contains 1500mg/L Pb according to the solid-to-liquid ratio of 1:1g/L 2+ Mixing the heavy metal ion solution with the pH value of 4 at 25 ℃, and stirring until the adsorption balance of the heavy metal ions is reached.
Example 4
This example provides a method for adsorbing heavy metal ions, which is the same as example 1 except that the temperature of the mixture in step (c) is 15 ℃.
Example 5
This example provides a method for adsorbing heavy metal ions, which is the same as example 1 except that the temperature of the mixture in step (c) is 35 ℃.
Example 6
This example provides a method for adsorbing heavy metal ions, wherein the method is the same as example 1 except that the pH of the heavy metal ion solution in step (c) is 3.
Example 7
This example provides a method for adsorbing heavy metal ions, wherein the method is the same as example 1 except that the pH of the heavy metal ion solution in step (c) is 2.
Example 8
The embodiment provides a method for adsorbing heavy metal ions, wherein the heavy metal ion solution in the step (c) contains 1000mg/L Cd 2+ And does not contain Pb 2+ Except for this, the procedure was the same as in example 1.
Example 9
The embodiment provides a method for adsorbing heavy metal ions, wherein the heavy metal ion solution in the step (c) contains 1000mg/L Cd 2+ And does not contain Pb 2+ Except for this, the procedure was the same as in example 2.
Example 10
The embodiment provides a method for adsorbing heavy metal ions, wherein the heavy metal ion solution in the step (c) contains 1000mg/L Cd 2+ And does not contain Pb 2+ Except for this, the procedure was the same as in example 3.
Example 11
This example provides a method for adsorbing heavy metal ions, which is the same as example 8 except that the temperature of the mixture in step (c) is 15 ℃.
Example 12
This example provides a method for adsorbing heavy metal ions, which is the same as example 8 except that the temperature of the mixture in step (c) is 35 ℃.
Example 13
This example provides a method for adsorbing heavy metal ions, wherein the method is the same as example 8 except that the pH of the heavy metal ion solution in step (c) is 3.
Example 14
This example provides a method for adsorbing heavy metal ions, wherein the method is the same as example 8 except that the pH of the heavy metal ion solution in step (c) is 2.
Example 15
The present embodiment provides a method for adsorbing heavy metal ions, wherein Pb in the heavy metal ion solution in the step (c) is removed 2+ And Cd 2+ The concentrations of (2) are 1500mg/L and 300mg/L, respectively, namely Pb 2+ And Cd 2+ Except that the concentration ratio of (C) was 5:1, the rest was the same as in example 1.
Example 16
The present embodiment provides a method for adsorbing heavy metal ions, wherein Pb in the heavy metal ion solution in the step (c) is removed 2+ And Cd 2+ The concentration of (C) is 1500mg/L and 1500mg/L, respectively, namely Pb 2+ And Cd 2+ Except that the concentration ratio of (C) was 1:1, the rest was the same as in example 1.
Example 17
The present embodiment provides a method for adsorbing heavy metal ions, wherein Pb in the heavy metal ion solution in the step (c) is removed 2+ And Cd 2+ The concentration of (A) is 300mg/L and 1500mg/L, respectively, namely Pb 2+ And Cd 2+ Except that the concentration ratio of (C) was 1:5, the rest was the same as in example 1.
Comparative example 1
This comparative example provides a method for adsorbing heavy metal ions, which is the same as example 1 except that the naringin powder in step (b) is not subjected to magnesium modification.
Comparative example 2
This comparative example provides a method for adsorbing heavy metal ions, wherein the same procedure as in example 1 is used except that the citrus grandis peel used in step (a) is replaced with navel orange peel to obtain orange peel powder, the orange peel powder obtained in step (a) is used in step (b) to prepare orange peel biochar, and the orange peel biochar obtained in step (b) is used in step (c) to adsorb heavy metal ions, and the navel orange peel used in this comparative example is from Jiangzhuzhou city, jiangxi province.
Comparative example 3
This comparative example provides a method for adsorbing heavy metal ions, in which the same procedure as in example 1 was used except that the pomelo peel used in step (a) was replaced with a citrus peel powder, the citrus peel powder obtained in step (a) was used in step (b) to prepare citrus peel biochar, and the citrus peel biochar obtained in step (b) was used in step (c) to adsorb heavy metal ions, and the citrus peel powder used in this comparative example was from Gangzhou city, jiangxi province.
Comparative example 4
This comparative example provides a method for adsorbing heavy metal ions, which is the same as example 8 except that the naringin powder in step (b) is not subjected to magnesium modification.
Comparative example 5
This comparative example provides a method for adsorbing heavy metal ions, wherein the same procedure as in example 8 is used except that the citrus grandis peel used in step (a) is replaced with navel orange peel to obtain orange peel powder, the orange peel powder obtained in step (a) is used in step (b) to prepare orange peel biochar, and the orange peel biochar obtained in step (b) is used in step (c) to adsorb heavy metal ions, and the navel orange peel used in this comparative example is from Jiangzhuzhou city, jiangxi province.
Comparative example 6
This comparative example provides a method for adsorbing heavy metal ions, in which the same procedure as in example 8 was used except that the pomelo peel used in step (a) was replaced with a citrus peel powder, the citrus peel powder obtained in step (a) was used in step (b) to prepare citrus peel biochar, and the citrus peel biochar obtained in step (b) was used in step (c) to adsorb heavy metal ions, and the citrus peel powder used in this comparative example was from Gangzhou city, jiangxi province.
Performance testing
Pb in the heavy metal ion solution after adsorption was tested by the methods provided in examples 1 to 17 and comparative examples 1 to 6 2+ 、Cd 2 + Further evaluating the adsorption effect, the specific test method comprises: extracting 10mL of supernatant of heavy metal ion solution after adsorption with 10mL syringe, installing 0.45 μm filter membrane, filtering, arranging three parallel samples for each experiment, and measuring Pb by inductively coupled plasma atomic emission spectrometry (ICP-AES) 2+ 、Cd 2+ The experimental results obtained from the concentration of (1) and the concentration of (2) in the three groups of dataValues.
The surface morphology of the shaddock ped biochar before and after magnesium modification is observed by adopting a German Zeiss Sigma 300 Scanning Electron Microscope (SEM); testing the functional groups on the surface of the biochar by adopting a Sieimer femto 5 Fourier infrared spectrum analyzer; detecting information such as valence state and composition of the element on the surface of the biochar by adopting an X-ray photoelectron spectroscopy (XPS) with the model number of K-alpha+ of Thermo Scientific; the resulting product crystal structure was examined using an X-ray powder diffraction analyzer (XRD) model D8 Advance, bruke AXS, germany.
As can be seen from the above embodiments, the heavy metal ion solutions in examples 1 to 7 and comparative examples 1 to 3 contain Pb 2+ The heavy metal ion solutions in examples 8 to 14 and comparative examples 4 to 6 contain Cd 2+ The heavy metal ion solutions in examples 15 to 17 contain Pb 2 + And Cd 2+ . For Pb 2+ And or Cd 2+ The adsorption results of (2) are shown in tables 1 to 3, respectively.
Table 1 shows Pb in heavy metal ion solutions of examples 1 to 7 and comparative examples 1 to 3 2+ Is not limited, and the adsorption result of the (a) is obtained.
TABLE 1
Examples 1 to 7 and comparative examples 1 to 3 for Pb 2+ The adsorption results of the present invention are shown in Table 1, and it can be seen that the naringin biochar prepared by the present invention has a specific adsorption effect on Pb 2+ The adsorption capacity of the catalyst can reach 1499mg/g.
As is clear from a comparison of example 4, example 5 and example 1, the mixing temperature of the naringin and the heavy metal ion solution increases, and the naringin is responsible for Pb 2+ The adsorption amount of Pb was slightly decreased because of Pb 2+ Is exothermic.
As is clear from a comparison of example 6, example 7 and example 1, heavy metals were reduced during mixingpH of ionic solution, and Pb is reacted by shaddock ped biochar 2+ Because stable compound precipitates are more likely to form under higher pH conditions.
From comparison of comparative example 1 and example 1, it is understood that the naringin biochar obtained without magnesium modification has a pH of=4 against Pb 2+ No adsorption capacity; the magnesium content of the shaddock ped biochar obtained before and after the magnesium modification is tested by utilizing a microwave digestion and ICP method, and the magnesium content in the shaddock ped biochar obtained before and after the modification is respectively 3.42mg/g and 226.35mg/g, which indicates that the magnesium modification is successful; the SEM images of the shaddock ped biochar obtained in example 1 and comparative example 1 respectively in fig. 1 and 2 show that the surface of the shaddock ped biochar without magnesium modification contains small particles, the surface of the shaddock ped biochar after magnesium modification is smooth, the small particles disappear, and the morphology is obviously changed.
Comparative examples 2 and 3 were respectively preparation of orange peel biochar and orange peel biochar from navel orange peel and Wo Ganpi as raw materials, and used for adsorption of Pb 2+ The obtained orange peel biochar and orange peel biochar pair Pb 2+ The adsorption amounts of (C) are 1082mg/g and 1165mg/g, respectively. FIG. 3 shows Pb adsorption using shaddock peel, navel orange peel and Wo Ganpi as raw materials in example 1, comparative example 2 and comparative example 3, respectively 2+ The curve comparison shows that the adsorption equilibrium time of the three materials is almost consistent, but the adsorption amount of the shaddock ped biochar is maximum, so that the shaddock ped is selected as the raw material of the biochar for adsorbing Pb 2+ 。
FIG. 4 shows Pb adsorption by the charcoal of naringin obtained in example 1 2+ The XRD contrast patterns of the front and back can show that the magnesium is successfully loaded on the biochar and Pb 2+ Pb by 3 (CO 3 ) 2 (OH) 2 The precipitated form of the compound is present on the shaddock ped biochar.
Table 2 shows the Cd content of the heavy metal ion solutions of examples 8-14 and comparative examples 4-6 2+ Is not limited, and the adsorption result of the (a) is obtained.
TABLE 2
| Cd 2+ Maximum adsorption capacity (mg/g) | Cd 2+ Adsorption Rate (%) | |
| Example 8 | 519 | 51.90 |
| Example 9 | 590 | 59.00 |
| Example 10 | 950 | 95.00 |
| Example 11 | 651 | 65.10 |
| Example 12 | 444 | 44.40 |
| Example 13 | 433 | 43.30 |
| Example 14 | 246 | 24.60 |
| Comparative example 4 | 0 | 0.00 |
| Comparative example 5 | 649 | 64.90 |
| Comparative example 6 | 543 | 54.30 |
Examples 8-14 and comparative examples 4-6 for Cd 2+ The adsorption results of the invention are shown in Table 2, and it can be seen that the shaddock ped biochar prepared by the invention has the effect on Cd 2+ The maximum adsorption capacity of the catalyst can reach 950mg/g.
As can be seen from a comparison of examples 11, 12 and 8, the temperature of the mixture of the naringin and the heavy metal ion solution was increased, and the naringin was effective to Cd 2+ The adsorption amount of (2) is slightly reduced because of Cd 2+ Is exothermic.
As can be seen from a comparison of examples 13, 14 and 8, the pH of the heavy metal ion solution was lowered during the mixing, and the shaddock ped charcoal was effective to Cd 2+ Because stable compound precipitates are more likely to form under higher pH conditions.
As can be seen from comparison of comparative example 4 and example 8, at pH=4, the shaddock ped biochar obtained without magnesium modification was effective against Cd 2+ There is little adsorption capacity.
Comparative example 5 and comparative example 6 were respectively preparation of orange peel biochar and orange peel biochar from navel orange peel and Wo Ganpi as raw materials, and were used for adsorption of Cd 2+ The obtained orange peel biochar and orange peel biochar pair Cd 2+ The maximum adsorption amounts of (C) were 649mg/g and 543mg/g. FIG. 5 is a graph showing the adsorption of Cd from shaddock ped, navel orange peel and Wo Ganpi, respectively, in example 8, comparative example 5 and comparative example 6 2+ The graph is compared to see the three pairs Cd 2+ The maximum adsorption amount of the orange peel biochar is not different, but the equilibrium is achievedThe time is 2 times of that of the shaddock ped biochar, and Cd in practical application 2+ The pollution concentration is generally low, and the shaddock ped biochar is comprehensively considered.
FIG. 6 shows the adsorption of Cd by the charcoal of naringin obtained in example 8 2+ The XRD contrast patterns of the front and back can show that magnesium is successfully loaded on the shaddock ped biochar and Cd 2+ By CdCO 3 The precipitated form of the compound is present on the shaddock ped biochar.
Table 3 shows the various proportions of Pb in the heavy metal solutions of the naringin biochar obtained in example 1, examples 15-17 and example 8 2+ And Cd 2+ Is not limited, and the adsorption result of the (a) is obtained.
TABLE 3 Table 3
As can be seen from Table 3, pb was contained in a different proportion 2+ And Cd 2+ In the heavy metal ion solution of (1), the obtained shaddock ped biochar has a specific effect on Pb 2+ The adsorption rate of the catalyst reaches more than 80 percent and is close to the maximum adsorption quantity; cd in the solution 2+ When the concentration is increased from 300mg/L to 1500mg/L, the shaddock ped charcoal pair Cd 2+ Still not exceeding 5%. It is speculated that when a sufficient amount of Pb is present in the solution 2+ When the shaddock ped biochar is used, the shaddock ped biochar hardly adsorbs Cd 2+ The method comprises the steps of carrying out a first treatment on the surface of the When Pb 2+ When the concentration of 300mg/L can not meet the adsorption capacity of the obtained shaddock ped biochar, part of Cd can be adsorbed 2+ But Pb in solution 2+ Is close to 100% and is specific to Cd 2+ The adsorption rate of (2) is only about 20%. In Pb-containing 2+ And Cd 2+ In the mixed solution, two heavy metal ions are competitively adsorbed on the shaddock ped biochar, and the shaddock ped biochar can preferentially adsorb Pb 2+ Probably due to the difference in metal properties and affinity for adsorption sites.
In summary, the invention provides a method for adsorbing heavy metal ions, which takes the pomelo peel as a raw material, has wide sources and low cost, endows the obtained pomelo peel biochar with developed pore channels and higher specific surface area, and increases the adsorption area; and modifying the obtained pomelo peel with magnesiumThe surface of the biological carbon contains more magnesium ions, and heavy metal ions can be adsorbed by ion exchange or mineral precipitation, and the shaddock ped biological carbon obtained by the invention has the advantages of Pb resistance 2+ And Cd 2+ The maximum adsorption amounts were 1499mg/g and 950mg/g, respectively.
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that fall within the technical scope of the present invention disclosed herein are within the scope of the present invention.
Claims (10)
1. A method of adsorbing heavy metal ions, the method comprising the steps of:
(1) Pretreating, modifying magnesium, drying, pyrolyzing and grinding the shaddock peel to obtain shaddock peel biochar;
(2) Mixing the shaddock ped biochar obtained in the step (1) with a solution containing heavy metal ions until the adsorption balance of the heavy metal ions is achieved;
the temperature of the mixing in the step (2) is 15-35 ℃;
the heavy metal ion includes Pb 2+ And/or Cd 2+ 。
2. The method of claim 1, wherein the moisture content of the pomelo peel of step (1) is 40-85wt%;
preferably, the pretreatment of step (1) comprises: cutting, cleaning, drying and crushing the shaddock peel to obtain shaddock peel powder;
preferably, the temperature of the drying is 60-80 ℃;
preferably, the drying time is 12-48 hours;
preferably, the D80 particle size of the pomelo peel powder obtained after crushing is 40-100 meshes.
3. The method according to claim 1, wherein the modifier used in the modification of the magnesium in step (1) comprises a magnesium chloride solution and/or a magnesium nitrate solution, preferably a magnesium chloride solution;
preferably, the concentration of the magnesium chloride solution is 0.1-2mol/L.
4. A method according to claim 3, wherein the method of magnesium modification of step (1) comprises dip modification and/or spray modification, preferably dip modification;
preferably, in the impregnation modification, the solid-to-liquid ratio of the shaddock ped powder to the magnesium chloride solution is (1-5): 100, and the unit of the solid-to-liquid ratio is g/mL;
preferably, the temperature of the impregnation modification is 25-30 ℃;
preferably, the time for the impregnation modification is 0.5 to 3 hours;
preferably, the impregnation modification is accompanied by stirring;
preferably, the stirring speed is 550-850r/min.
5. The method of any one of claims 1-4, wherein the drying of step (1) is at a temperature of 60-80 ℃;
preferably, the drying time of step (1) is 12-48 hours.
6. The method of any one of claims 1-5, wherein the temperature of the pyrolysis of step (1) is 350-450 ℃;
preferably, the pyrolysis of step (1) takes 1 to 2 hours;
preferably, the heating rate of the pyrolysis in the step (1) is 5-10 ℃/min;
preferably, the pyrolysis of step (1) is carried out under a protective atmosphere;
preferably, the protective atmosphere comprises nitrogen and/or argon.
7. The method of any one of claims 1-6, wherein the D80 particle size of the naringin biochar obtained after grinding in step (1) is less than or equal to 100 mesh.
8. The method according to any one of claims 1 to 7, wherein Pb in the solution containing heavy metal ions in step (2) 2+ The concentration of (2) is 300-1500mg/L;
preferably, step (2) is performed by adding Cd to the solution containing the medium metal ions 2+ The concentration of (2) is 300-1500mg/L;
preferably, the pH of the solution containing heavy metal ions in step (2) is 2-5.
9. The method according to any one of claims 1 to 8, wherein the solid to liquid ratio of the naringin biochar to the solution containing the heavy metal ions is 1 (1 to 50) in g/L at the time of the mixing in the step (2);
preferably, the mixing of step (2) is accompanied by stirring and/or shaking;
preferably, the stirring speed is 150-250r/min;
preferably, the rate of oscillation is 150-250r/min.
10. The method according to any one of claims 1-9, characterized in that the method comprises the steps of:
(a) Cutting, cleaning, drying and crushing the shaddock peel to obtain shaddock peel powder with the D80 particle size of 40-100 meshes;
(b) Immersing and modifying the shaddock ped powder obtained in the step (a) in a magnesium chloride solution with the concentration of 0.1-2mol/L at the temperature of 25-30 ℃ for 0.5-3h, wherein the solid-to-liquid ratio of the shaddock ped powder to the magnesium chloride solution is (1-5), wherein the immersing and modifying is carried out with stirring at the stirring speed of 550-850r/min, drying at the temperature of 60-80 ℃ for 12-48h, heating to 350-450 ℃ at the speed of 5-10 ℃/min, carrying out pyrolysis for 1-2h under a protective atmosphere, and grinding until the D80 particle size is less than or equal to 100 meshes to obtain shaddock ped biochar;
(c) The shaddock ped biochar obtained in the step (b) is prepared by mixing the shaddock ped biochar with Pb containing powder according to the solid-to-liquid ratio of 1 (1-50) g/L 2+ And Cd 2+ The solution of heavy metal ions is mixed at 15-35 ℃, and stirring is carried out during mixing until the adsorption balance of the heavy metal ions is reached.
Priority Applications (1)
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