CN114984931B - Aminated magnetic hydrothermal carbon-MOFs adsorbent and preparation method and application thereof - Google Patents
Aminated magnetic hydrothermal carbon-MOFs adsorbent and preparation method and application thereof Download PDFInfo
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 92
- 239000003463 adsorbent Substances 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 47
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 41
- 238000001179 sorption measurement Methods 0.000 claims abstract description 40
- 238000002156 mixing Methods 0.000 claims abstract description 30
- 238000005406 washing Methods 0.000 claims abstract description 28
- 238000001035 drying Methods 0.000 claims abstract description 27
- 239000000243 solution Substances 0.000 claims abstract description 22
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 17
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 21
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical group NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 18
- 244000026873 Alternanthera philoxeroides Species 0.000 claims description 12
- 241000196324 Embryophyta Species 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- 238000009210 therapy by ultrasound Methods 0.000 claims description 11
- 239000011148 porous material Substances 0.000 claims description 8
- 150000001412 amines Chemical class 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 6
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical group NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- 229920000877 Melamine resin Chemical group 0.000 claims description 3
- 230000005389 magnetism Effects 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical group NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- 239000000356 contaminant Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 11
- 239000003344 environmental pollutant Substances 0.000 abstract description 5
- 231100000719 pollutant Toxicity 0.000 abstract description 5
- 238000005576 amination reaction Methods 0.000 abstract description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 20
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- 239000002131 composite material Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 7
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 241000428811 Alternanthera Species 0.000 description 5
- 239000002689 soil Substances 0.000 description 5
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- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000002048 multi walled nanotube Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 239000013206 MIL-53 Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000007792 addition Methods 0.000 description 3
- 239000003610 charcoal Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 3
- 241000759905 Camptotheca acuminata Species 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 241000201912 Suaeda Species 0.000 description 2
- 230000000274 adsorptive effect Effects 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 229940088710 antibiotic agent Drugs 0.000 description 2
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 2
- 230000035558 fertility Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 2
- 229940043267 rhodamine b Drugs 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 230000009919 sequestration Effects 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
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- 241000223600 Alternaria Species 0.000 description 1
- 235000014466 Douglas bleu Nutrition 0.000 description 1
- 241000282412 Homo Species 0.000 description 1
- 208000005374 Poisoning Diseases 0.000 description 1
- 240000001416 Pseudotsuga menziesii Species 0.000 description 1
- 235000005386 Pseudotsuga menziesii var menziesii Nutrition 0.000 description 1
- 244000272264 Saussurea lappa Species 0.000 description 1
- 235000006784 Saussurea lappa Nutrition 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
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- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
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- 231100000739 chronic poisoning Toxicity 0.000 description 1
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- 238000010586 diagram Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
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- 239000004009 herbicide Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229920000592 inorganic polymer Polymers 0.000 description 1
- 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 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000003211 malignant effect Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
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- 238000001556 precipitation Methods 0.000 description 1
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- 230000009467 reduction Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 239000003516 soil conditioner Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
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
- B01J20/28—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
-
- 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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
-
- 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
- B01J20/28014—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 form
- B01J20/28026—Particles within, immobilised, dispersed, entrapped in or on a matrix, e.g. a resin
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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- 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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- 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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- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to an aminated magnetic hydrothermal carbon-MOFs adsorbent and a preparation method and application thereof, and belongs to the technical field of heavy metal adsorption materials. The preparation method of the aminated magnetic hydrothermal carbon-MOFs adsorbent comprises the following steps: uniformly mixing ferric trichloride with a 2-amino terephthalic acid and DMF solution to obtain a mixture 1; uniformly mixing the mixture 1 with modified biochar to obtain a mixture 2; and (3) reacting the mixture 2 at 130-150 ℃ for 12-14.5 h, washing and drying to obtain the aminated magnetic hydrothermal carbon-MOFs adsorbent. The preparation method of the amination magnetic hydrothermal carbon-MOFs adsorbent heavy metal adsorption material is simple, efficient, green, energy-saving, emission-reducing and low in cost, the prepared adsorbent is easy to disperse in aqueous solution, does not agglomerate, can efficiently adsorb various heavy metals, has great advantages on the adsorption of various heavy metal mixed pollutants, is easy to recycle, and solves the problem of flooding of invasive plants.
Description
Technical Field
The invention relates to an aminated magnetic hydrothermal carbon-MOFs adsorbent and a preparation method and application thereof, and belongs to the technical field of heavy metal adsorption materials.
Background
Heavy metals can interact with proteins and various enzymes in human bodies strongly, so that the proteins and the enzymes in human bodies lose activity, and can be enriched in certain organs of human bodies, if the tolerance limit of the human bodies is exceeded, acute poisoning, subacute poisoning, chronic poisoning and the like of the human bodies can be caused, and the human bodies can be greatly harmed,
heavy metals are not biodegradable, but are bioaccumulative and can directly threaten higher organisms, including humans.
Biochar is a low-cost and environment-friendly material, has great potential in separating heavy metals from water, and has better effect in effectively removing toxic heavy metals from water than other materials. Biochar is becoming an effective soil conditioner with a variety of functions including carbon sequestration, soil fertility enhancement and contaminated soil remediation for sustainable carbon sequestration while improving soil quality.
The camptotheca acuminata and the common suaeda herb are the most widely distributed malignant invasive species, and are wild, so that the camptotheca acuminata and the common suaeda herb have strong adaptability, strong transmissibility and strong fertility and destroy biological diversity. Currently, the treatment methods mainly include chemical methods (herbicide spraying) and physical methods (mechanical or manual cutting). However, these methods are very limited and consume a lot of manpower and financial resources.
Performance, kinetics and mechanism publications, envi Pollut Res (2022), discloses an amine functionalized magnetic biochar extracted from the invasive plant Alternaria alternifolia for enhanced efficient removal of Cr (VI): performance, kinetics and mechanism studies. However, the adsorption performance thereof is to be further improved. And the dispersion is poor, and the ultrasonic wave, stirring, shaking and the like are needed to disperse the water in the water body.
Navarathna C M,Dewage N B,Karunanayake AG,et al.Rhodamine B Adsorptive Removal and Photocatalytic Degradation on MIL-53-Fe MOF/Magnetic Magnetite/Biochar Composites[J]Journal of Inorganic and Organometallic Polymers and Materials,2020,30 (1): 214-229. An adsorption and photocatalytic degradation of rhodamine B by MIL-53-Fe MOF/magnetic magnetite/biochar composite is disclosed, which first prepares MBC as a matrix for MIL-53-Fe MOF. Then, about 50g of a Costus douglas fir charcoal (Black Owl, biochar Supreme Inc.) was added to the water (particle size sieve to 1-2mm, surface area 687m 2 Permeability of 0.251cm 3 /g) and homogenized with a mixed solution of ferric trichloride (about 18 g) and ferric sulfate (about 36.6 g) (total of about 1950mL water). Then, magnetite precipitation onto biochar was triggered by dropwise addition of 10M NaOH, and the pH was maintained at 10 for about 24 hours. Filtering the obtained Fe 3 O 4 Magnetized Biochar (MBC), which is used as a matrix, deposits and nucleates MIL-53-Fe MOF during the synthesis of the MOF, however, its adsorptivity to heavy metals is poor, and the synthesis process is cumbersome and complicated.
Xiong W,Zeng Z,Xin L,et al.Multi-walled carbon nanotube/amino-functionalized MIL-53(Fe)composites:Remarkable adsorptive removal of antibiotics from aqueous solutions[J]Chemosphere,2018,210 (NOV.): 1061-1069 discloses a walled carbon nanotube&Amino-functionalized MILs-53 (Fe) composite: significant adsorption removal of antibiotics in aqueous solutions: a typical synthesis procedure is as follows: 0.674g of ferric chloride hexahydrate, 0.4572 g of 2-aminoterephthalic acid and 56mL of DMF solution were mixed by stirring at room temperature and then transferred to 100mL of polytetrafluoroethylene liningStainless steel autoclave. Thereafter, the autoclave was heated at 170℃for 24 hours. The product was washed with DMF and ethanol, filtered and dried. To synthesize multi-wall carbon nano tube/NH 2 MIL-53 (Fe) composite material with purified multi-walled carbon nanotubes (PR China) dispersed in NH 2 -MILs-53 (Fe) precursor mixture. The rest of the synthesis steps are the same as those of NH2-MIL-53 (Fe). An appropriate amount of purified multi-walled carbon nanotubes was introduced into DMF and then mixed with ferric chloride hexahydrate, 2-amino terephthalic acid, and DMF. The resulting mixture was stirred at room temperature, then transferred to a 100mL polytetrafluoroethylene liner in a stainless steel autoclave and heated at 170 ℃ for 24 hours. The powder was collected by centrifugation, washing and drying. However, the adsorption of heavy metals is also very poor, the required temperature is high and the reaction time is long.
In order to improve the environmental heavy metal pollution as soon as possible, an adsorption material with good dispersibility and good heavy metal adsorption is provided, the heavy metal pollution treatment efficiency is improved, the treatment cost is reduced, and the technical problem which is urgent to be solved in the field is solved.
Disclosure of Invention
The first object of the invention is to provide a preparation method of an aminated magnetic hydrothermal carbon-MOFs adsorbent.
To achieve the first object of the present invention, the preparation method of the aminated magnetic hydrothermal carbon-MOFs adsorbent of the present invention comprises:
a. uniformly mixing ferric trichloride with 2-amino terephthalic acid and DMF solution to obtain a mixture 1
b. Uniformly mixing the mixture 1 with modified biochar to obtain a mixture 2;
c. reacting the mixture 2 at 130-150 ℃ for 12-14.5 h, washing and drying to obtain the aminated magnetic hydrothermal carbon-MOFs adsorbent;
wherein, the ratio of the ferric trichloride to the 2-amino terephthalic acid, the DMF solution and the modified biochar is as follows: 1.8 to 2.2mmol:1.8 to 2.2mmol:40mL: 0.1-1.5 g;
the preparation method of the modified biochar in the step b comprises the following steps: plant powder, organic amine, ferric trichloride and water are mixed according to the mass ratio of 4-5: 2.5 to 3:2.5 to 3: and (3) uniformly mixing 35-45, reacting at 200-230 ℃ for 12-14.5 h, washing and drying to obtain the product.
And c, the reaction temperature in the step is too high, so that the structure of the biochar can be damaged.
In a specific embodiment, the uniform mixing in the step a is ultrasonic for 5-15 min.
In a specific embodiment, the organic amine in the step b is hexamethylenediamine, ethylenediamine or melamine; and b, uniformly mixing the materials in the step (b) preferably ultrasonic for 15-30 min.
In a specific embodiment, in the preparation method of the modified biochar, the uniform mixing is stirring for 15-30 min.
In one embodiment, the mixture 2 of step c is reacted at 130-140 ℃ for 12-14 hours; the washing and drying in the step c preferably comprises: washing with methanol solution in 7000-9000 rpm centrifuge for 3-4 times, and stoving at 70-120 deg.c.
In one embodiment, the washing and drying in the preparation method of the modified biochar comprises the following steps: washing with pure water for 3-5 times and drying at 70-120 ℃.
In a specific embodiment, in the preparation method of the modified biochar, the plant powder is alternanthera philoxeroides, and the particle size of the plant powder is preferably 60-80 meshes.
It is a second object of the present invention to provide an aminated magnetic hydrothermal carbon-MOFs adsorbent.
To achieve the second object of the present invention, the aminated magnetic hydrothermal carbon-MOFs adsorbent is prepared by the method as described above.
In a specific embodiment, the aminated magnetic hydrothermal carbon-MOFs adsorbent has magnetism, contains-NH and C-N, C = N, C =O groups on the surface, and has a specific surface area of preferably 60-70 m 2 /g; more preferably, the average pore size is 9 to 10nm, and the pore volume is 0.14 to 0.15cm 3 /kg; it is further preferred that MOFs are supported on the surface of the aminated magnetic hydrothermal carbon-MOFs adsorbent.
The third object of the invention is to provide the aminated magnetic hydrothermal carbon-MOFs adsorbent prepared by the method or the application of the aminated magnetic hydrothermal carbon-MOFs adsorbent in heavy metal adsorption; the heavy metal is preferably at least one of Pb (II), cr (VI), zn (II), cu (II), cd (II) and Ni (II); more preferably two or more of Pb (II), cr (VI), zn (II), cu (II), cd (II), and Ni (II); further preferably, the application method is that the aminated magnetic hydrothermal carbon-MOFs adsorbent and the pollutant containing heavy metal are adsorbed in an aqueous solution; the pH of the adsorption is preferably 2-7, the temperature is 25-30 ℃, and the heavy metal concentration is 25-500 mg/L.
The beneficial effects are that:
(1) The preparation method of the amination magnetic hydrothermal carbon-MOFs adsorbent heavy metal adsorption material is simple, and has the characteristics of high efficiency, environment friendliness, energy conservation, emission reduction and low cost.
(2) The aminated magnetic hydrothermal carbon-MOFs adsorbent has the characteristics of easy dispersion in aqueous solution, no agglomeration, rich functional groups and extremely high specific surface area, can efficiently adsorb various heavy metals, can adsorb Pb (II) and Cr (VI) to be up to 153.82mg/g and 144.24mg/g, and can remove more than 50% of other heavy metals.
(3) The existing adsorbent can only adsorb single heavy metal, has poor adsorption effect on various heavy metal mixed pollutants, can adsorb two or more heavy metals at the same time, has good adsorption effect, and has great advantages on the adsorption of various heavy metal mixed pollutants.
(4) The aminated magnetic hydrothermal carbon-MOFs adsorbent can be recycled through magnetic substances, so that the manual recycling cost and secondary pollution are sufficiently reduced.
(5) The raw material used in the invention is the invasive plant, so that the problem of invasive plant flooding is solved, and the preparation process is mild, safe and environment-friendly.
Drawings
FIG. 1 is a graph of dispersion versus graph; a is the aminated magnetic hydrothermal carbon-MOFs adsorbent of example 1, B is the aminated magnetic hydrothermal carbon of comparative example 1, and C is the original biochar of comparative example 2;
FIG. 2 is a graph of contact angle measurements; a is the original biochar of comparative example 2, B is the aminated magnetic hydrothermal carbon of comparative example 1, C is the aminated magnetic hydrothermal carbon-MOFs adsorbent of example 1;
FIG. 3 is an XRD pattern for the aminated magnetic hydrothermal carbon-MOFs adsorbent of example 1 and comparative example 4, NM-53 being comparative example 4;
FIG. 4 is a FT-IR chart of examples 1-5 aminated magnetic hydrothermal carbon-MOFs adsorbents and comparative example 4, NM-53 is comparative example 4;
FIG. 5 is an SEM image of an aminated magnetic hydrothermal carbon-MOFs adsorbent before and after heavy metal adsorption, a is before adsorption, and b is after mixed adsorption of Pb (II), cr (VI), zn (II), ni (II), cu (II) and Cd (II); c. d, h, f, g, e adsorbing Pb (II), cr (VI), zn (II), ni (II), cu (II) and Cd (II);
FIG. 6 is an adsorption kinetics plot of the aminated magnetic hydrothermal carbon-MOFs adsorbent of example 1;
FIG. 7 is an adsorption isotherm curve of the aminated magnetic hydrothermal carbon-MOFs adsorbent of example 1.
Fig. 8 is a graph of the magnetic tape of example 1.
Detailed Description
To achieve the first object of the present invention, the preparation method of the aminated magnetic hydrothermal carbon-MOFs adsorbent of the present invention comprises:
a. uniformly mixing ferric trichloride with 2-amino terephthalic acid and DMF solution to obtain a mixture 1
b. Uniformly mixing the mixture 1 with modified biochar to obtain a mixture 2;
c. reacting the mixture 2 at 130-150 ℃ for 12-14.5 h, washing and drying to obtain the aminated magnetic hydrothermal carbon-MOFs adsorbent;
wherein, the ratio of the ferric trichloride to the 2-amino terephthalic acid, the DMF solution and the modified biochar is as follows: 1.8 to 2.2mmol:1.8 to 2.2mmol:40mL: 0.1-1.5 g;
the preparation method of the modified biochar in the step b comprises the following steps: plant powder, organic amine, ferric trichloride and water are mixed according to the mass ratio of 4-5: 2.5 to 3:2.5 to 3: and (3) uniformly mixing 35-45, reacting at 200-230 ℃ for 12-14 h, washing and drying to obtain the product.
And c, the reaction temperature in the step is too high, so that the structure of the biochar can be damaged.
In a specific embodiment, the uniform mixing in the step a is ultrasonic for 5-15 min.
In a specific embodiment, the organic amine in the step b is hexamethylenediamine, ethylenediamine or melamine; and b, uniformly mixing the materials in the step (b) preferably ultrasonic for 15-30 min.
In a specific embodiment, in the preparation method of the modified biochar, the uniform mixing is stirring for 15-30 min.
In one embodiment, the mixture 2 of step c is reacted at 130-140 ℃ for 12-14 hours; the washing and drying in the step c preferably comprises: washing with methanol solution in 7000-9000 rpm centrifuge for 3-4 times, and stoving at 70-120 deg.c.
In one embodiment, the washing and drying in the preparation method of the modified biochar comprises the following steps: washing with pure water for 3-5 times and drying at 70-120 ℃.
In a specific embodiment, in the preparation method of the modified biochar, the plant powder is alternanthera philoxeroides, and the particle size of the plant powder is preferably 60-80 meshes.
To achieve the second object of the present invention, the aminated magnetic hydrothermal carbon-MOFs adsorbent is prepared by the method as described above.
In a specific embodiment, the aminated magnetic hydrothermal carbon-MOFs adsorbent has magnetism, contains-NH and C-N, C = N, C =O groups on the surface, and has a specific surface area of preferably 60-70 m 2 /g; more preferably, the average pore size is 9 to 10nm, and the pore volume is 0.14 to 0.15cm 3 /kg; it is further preferred that MOFs are supported on the surface of the aminated magnetic hydrothermal carbon-MOFs adsorbent.
The third object of the invention is to provide the aminated magnetic hydrothermal carbon-MOFs adsorbent prepared by the method or the application of the aminated magnetic hydrothermal carbon-MOFs adsorbent in heavy metal adsorption; the heavy metal is preferably at least one of Pb (II), cr (VI), zn (II), cu (II), cd (II) and Ni (II); more preferably two or more of Pb (II), cr (VI), zn (II), cu (II), cd (II), and Ni (II); further preferably, the application method is that the aminated magnetic hydrothermal carbon-MOFs adsorbent and the pollutant containing heavy metal are adsorbed in an aqueous solution; the pH of the adsorption is preferably 2-7, the temperature is 25-30 ℃, and the heavy metal concentration is 25-500 mg/L.
The following describes the invention in more detail with reference to examples, which are not intended to limit the invention thereto.
Example 1
Cutting the collected alligator alternanthera into small sections of 3cm, washing soil with clean water, drying at 80 ℃ for 24 hours, drying to constant weight, crushing the dried alligator alternanthera by a crusher, sieving with a 60-mesh filter screen, finally mixing 4.5g of alligator alternanthera powder with 38mL of pure water, sequentially adding 2.7g of ferric trichloride and 2.8g of hexamethylenediamine, stirring for 30 minutes at 3000 revolutions per minute by a magnetic stirrer, placing into a reaction kettle, reacting at 210 ℃ for 12 hours, washing with pure water for 3 times, and drying at 70 ℃. Obtaining the hexamethylenediamine aminated alternanthera philoxeroides magnetic hydrothermal carbon.
Mixing 2mmol of ferric trichloride with 2mmol of 2-amino terephthalic acid and 40 mM of LDMF solution, and carrying out ultrasonic treatment for 10min to obtain a mixture 1;
mixing the mixture 1 with 1g of hexamethylenediamine aminated alternanthera philoxeroides magnetic hydrothermal carbon, and carrying out ultrasonic treatment for 30min to obtain a mixture 2;
the mixture 2 is reacted for 12 hours at 150 ℃, washed 3 times by methanol solution in a 8000-turn centrifuge, and dried at 70 ℃ to obtain the aminated magnetic hydrothermal carbon-MOFs adsorbent.
Fig. 2 is a graph of contact angle measurements of aminated magnetic hydrothermal carbon-MOFs adsorbents, which can be found to change materials from hydrophobic to hydrophilic. FIG. 3 shows XRD patterns of the aminated magnetic hydrothermal carbon-MOFs adsorbent, and the loading MOFs can be found, and the XRD patterns show characteristic peaks of the MOFs, which indicate that the MOFs are successfully loaded on the aminated magnetic hydrothermal carbon without damaging the crystal form of the biochar. FIG. 4 is a FT-IR diagram of an aminated magnetic hydrothermal carbon-MOFs adsorbent, showing that the introduction of MOFs adds more functional groups. Fig. 5 is an SEM image of the aminated magnetic hydrothermal carbon-MOFs adsorbent before and after adsorbing heavy metals, and the MOFs are found to be loaded on the surface of biochar in the form of small particles, and the number of particles disappears after adsorption, indicating that the surface of the MOFs undergoes corresponding chemical reaction. Fig. 6 is an adsorption kinetics curve of the aminated magnetic hydrothermal carbon-MOFs adsorbent, and fig. 7 is an adsorption isotherm curve of the aminated magnetic hydrothermal carbon-MOFs adsorbent.
Table 1 shows that the adsorption capacity of the aminated magnetic hydrothermal carbon-MOFs adsorbent is best compared with the adsorption capacity of different heavy metals of the original biochar, the aminated magnetic biochar and the MOFs, and the adsorption capacity of the aminated magnetic hydrothermal carbon-MOFs adsorbent can reach more than 100 mg/g. The concentration of all heavy metals is 200mg/L, the reaction temperature is 25 ℃, the reaction time is 24 hours, and the pH (Pb (II), cr (VI), zn (II), cu (II), cd (II) and Ni (II) are respectively 5, 2, 5, 4, 6 and 6.
TABLE 1 comparison of adsorption values for different adsorbents
Table 2 shows the adsorption data of the aminated magnetic hydrothermal carbon-MOFs adsorbent of example 1 for adsorption of mixed metals and single metals, and the adsorption was found to be significantly reduced, indicating that competitive adsorption occurred.
TABLE 2 adsorption effect of aminated magnetic hydrothermal carbon-MOFs adsorbents in Mixed heavy Metal solutions
TABLE 3 regeneration Performance of the adsorption of aminated magnetic hydrothermal carbon-MOFs adsorbents
Examples 2 to 5
Examples 2-5 are similar to example 1, except that hexamethylenediamine aminated alternanthera magnetic hydrothermal charcoal was added at 0.1g, 0.3g, 0.7g, 1.5g, respectively. Examples 1 to 5 adsorption effects of different modified biochar additions on Cr (VI) and Pb (II) are shown in Table 4. Table 4 adsorption effects of different modified biochar additions of examples 1 to 5
Comparative example 1
The hexamethylenediamine aminated alternanthera philoxeroides magnetic hydrothermal carbon of example 1 is a modified hydrothermal carbon.
Comparative example 2
Is pure hydrothermal carbon: cutting the collected alternanthera philoxeroides into small sections of 3cm, washing soil with clean water, drying at 80 ℃ for 24 hours, drying to constant weight, crushing the dried alternanthera philoxeroides by a crusher, sieving with a 60-mesh filter screen, finally mixing 4.5g of alternanthera philoxeroides powder with 38mL of pure water, stirring for 30 minutes at 3000 rpm, placing into a reaction kettle, reacting at 210 ℃ for 12 hours, washing with pure water for 3 times, and drying at 70 ℃. The alligator alternanthera hydrothermal charcoal.
Comparative example 3
Are pure MOFs: mixing 2mmol of ferric trichloride with 2mmol of terephthalic acid and 40 mM LDMF solution, performing ultrasonic treatment for 10min to obtain a mixture, reacting the mixture at 150 ℃ for 12h, washing the mixture with methanol solution in a 8000-turn centrifuge for 3 times, and drying the mixture at 70 ℃ to obtain the pure MOFs.
Comparative example 4
For modified MOFs: otherwise the same as in comparative example 3, except that 2, amino terephthalic acid was used in place of phthalic acid in comparative example 4.
Comparative example 5
Is pure water thermal carbon composite pure MOFs:
mixing 2mmol of ferric trichloride with 2mmol of terephthalic acid and 40 mM DMF solution, and performing ultrasonic treatment for 10min to obtain a mixture 1;
mixing the mixture 1 with the alternanthera philoxeroides hydrothermal carbon of the comparative example 2, and carrying out ultrasonic treatment for 30min to obtain a mixture 2;
and (3) reacting the mixture 2 at 150 ℃ for 12 hours, washing the mixture with a methanol solution in a 8000-turn centrifuge for 3 times, and drying the mixture at 70 ℃ to obtain the pure water thermal carbon composite pure MOFs adsorbent.
Comparative example 6
Is pure water thermal carbon composite modified MOFs:
mixing 2mmol of ferric trichloride with 2mmol of 2, amino terephthalic acid and 40 mM DMF solution, and performing ultrasonic treatment for 10min to obtain a mixture 1;
mixing the mixture 1 with the alternanthera philoxeroides hydrothermal carbon of the comparative example 2, and carrying out ultrasonic treatment for 30min to obtain a mixture 2;
and (3) reacting the mixture 2 at 150 ℃ for 12 hours, washing the mixture with a methanol solution in a 8000-turn centrifuge for 3 times, and drying the mixture at 70 ℃ to obtain the pure water thermal carbon composite modified MOFs adsorbent.
Comparative example 7
The modified hydrothermal carbon composite pure MOFs:
mixing 2mmol of ferric trichloride with 2mmol of terephthalic acid and 40 mM DMF solution, and performing ultrasonic treatment for 10min to obtain a mixture 1;
mixing the mixture 1 with hexamethylenediamine aminated alternanthera philoxeroides magnetic hydrothermal carbon of the comparative example 1, and carrying out ultrasonic treatment for 30min to obtain a mixture 2;
and (3) reacting the mixture 2 at 150 ℃ for 12 hours, washing the mixture with a methanol solution in a 8000-turn centrifuge for 3 times, and drying the mixture at 70 ℃ to obtain the modified hydrothermal carbon composite pure MOFs adsorbent.
TABLE 5 adsorbent specific surface area, pore size and pore volume
Claims (17)
1. A method for preparing an aminated magnetic hydrothermal carbon-MOFs adsorbent, the method comprising:
a. uniformly mixing ferric trichloride with a 2-amino terephthalic acid and DMF solution to obtain a mixture 1;
b. uniformly mixing the mixture 1 with modified biochar to obtain a mixture 2;
c. reacting the mixture 2 at 130-150 ℃ for 12-14.5-h, washing and drying to obtain the aminated magnetic hydrothermal carbon-MOFs adsorbent;
wherein, the ratio of the ferric trichloride to the 2-amino terephthalic acid, the DMF solution and the modified biochar is as follows: 1.8 to 2.2mmol:1.8 to 2.2mmol:40mL:0.1 to 1.5. 1.5g;
the preparation method of the modified biochar in the step b comprises the following steps: plant powder, organic amine, ferric trichloride and water are mixed according to the mass ratio of 4-5: 2.5 to 3:2.5 to 3: after being uniformly mixed with 35-45 ℃, reacting at 200-230 ℃ for 12-14 h, washing and drying to obtain the modified biochar, wherein the plant powder is alternanthera philoxeroides.
2. The preparation method of the aminated magnetic hydrothermal carbon-MOFs adsorbent according to claim 1, wherein the uniform mixing in the step a is carried out for 5-15 min by ultrasonic treatment.
3. The method for preparing the aminated magnetic hydrothermal carbon-MOFs adsorbent according to claim 1 or 2, wherein the organic amine in the step b is hexamethylenediamine, ethylenediamine or melamine.
4. The preparation method of the aminated magnetic hydrothermal carbon-MOFs adsorbent according to claim 1 or 2, wherein the uniform mixing in the step b is carried out for 15-30 min by ultrasonic treatment.
5. The method for preparing an aminated magnetic hydrothermal carbon-MOFs adsorbent according to claim 1 or 2, wherein the uniformly mixing in the method for preparing the modified biochar is stirring for 15-30 min.
6. The method for preparing an aminated magnetic hydrothermal carbon-MOFs adsorbent according to claim 1 or 2, wherein the mixture 2 of step c is reacted at 130-140 ℃ for 12-14 h.
7. The method for preparing an aminated magnetic hydrothermal carbon-MOFs adsorbent according to claim 1 or 2, wherein the washing and drying in the step c comprises: washing with methanol solution in 7000-9000 rpm centrifuge for 3-4 times, and stoving at 70-120 deg.c.
8. The method for preparing an aminated magnetic hydrothermal carbon-MOFs adsorbent according to claim 1 or 2, wherein the washing and drying in the method for preparing a modified biochar comprises: washing with pure water for 3-5 times and drying at 70-120 ℃.
9. The method for producing an aminated magnetic hydrothermal carbon-MOFs adsorbent according to claim 1 or 2, wherein the particle size of the plant powder is 60 to 80 mesh.
10. An aminated magnetic hydrothermal carbon-MOFs adsorbent, which is characterized in that the aminated magnetic hydrothermal carbon-MOFs adsorbent is prepared by the method of any one of claims 1 to 9; the aminated magnetic hydrothermal carbon-MOFs adsorbent has magnetism, and the surface of the adsorbent contains-NH and C-N, C = N, C =O groups.
11. The aminated magnetic hydrothermal carbon-MOFs adsorbent according to claim 10, wherein the specific surface area of the aminated magnetic hydrothermal carbon-MOFs adsorbent is 60 to 70m 2 /g。
12. The aminated magnetic hydrothermal carbon-MOFs adsorbent according to claim 11, wherein the aminated magnetic hydrothermal carbon-MOFs adsorbent has an average pore size of 9 to 10nm and a pore volume of 0.14 to 0.15cm 3 /g。
13. The aminated magnetic hydrothermal carbon-MOFs adsorbent according to claim 11, wherein MOFs of the aminated magnetic hydrothermal carbon-MOFs adsorbent are supported on a surface of the aminated magnetic hydrothermal carbon-MOFs adsorbent.
14. The use of an aminated magnetic hydrothermal carbon-MOFs adsorbent prepared according to any one of claims 1 to 9 or according to any one of claims 10 to 13 for adsorption of heavy metals.
15. The use of an aminated magnetic hydrothermal carbon-MOFs adsorbent according to claim 14 for adsorbing heavy metals, the heavy metals being at least one of Pb (II), cr (VI), zn (II), cu (II), cd (II), ni (II).
16. The use of the aminated magnetic hydrothermal carbon-MOFs adsorbent according to claim 15, wherein the heavy metal is two or more of Pb (II), cr (VI), zn (II), cu (II), cd (II), ni (II).
17. The use of the aminated magnetic hydrothermal carbon-MOFs adsorbent according to claim 14 for adsorbing heavy metals by adsorbing the aminated magnetic hydrothermal carbon-MOFs adsorbent with heavy metal-containing contaminants in an aqueous solution; the pH value of the adsorption is 2-7, the temperature is 25-30 ℃, and the heavy metal concentration is 25-500 mg/L.
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