CN116116374B - La (La)2O3Preparation method and application of BNNFs composite adsorbent - Google Patents
La (La)2O3Preparation method and application of BNNFs composite adsorbent Download PDFInfo
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 51
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000001179 sorption measurement Methods 0.000 claims abstract description 29
- 239000000843 powder Substances 0.000 claims abstract description 26
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 21
- 238000002360 preparation method Methods 0.000 claims abstract description 20
- 239000008367 deionised water Substances 0.000 claims abstract description 16
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 13
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000004202 carbamide Substances 0.000 claims abstract description 12
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000004327 boric acid Substances 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 9
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 239000006185 dispersion Substances 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 14
- 229910002422 La(NO3)3·6H2O Inorganic materials 0.000 claims description 13
- 238000000137 annealing Methods 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 8
- 239000002351 wastewater Substances 0.000 claims description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- 238000004065 wastewater treatment Methods 0.000 claims description 3
- 238000005352 clarification Methods 0.000 claims 1
- 238000000967 suction filtration Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 11
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052582 BN Inorganic materials 0.000 abstract description 7
- 125000000129 anionic group Chemical group 0.000 abstract description 4
- 239000003344 environmental pollutant Substances 0.000 abstract description 4
- 231100000719 pollutant Toxicity 0.000 abstract description 4
- 125000000524 functional group Chemical group 0.000 description 11
- 230000004048 modification Effects 0.000 description 9
- 238000012986 modification Methods 0.000 description 9
- 150000001450 anions Chemical class 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000011737 fluorine Substances 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- -1 fluorine ions Chemical class 0.000 description 5
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 238000001914 filtration Methods 0.000 description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical group [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 229940088710 antibiotic agent Drugs 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000009297 electrocoagulation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- YXEUGTSPQFTXTR-UHFFFAOYSA-K lanthanum(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[La+3] YXEUGTSPQFTXTR-UHFFFAOYSA-K 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009827 uniform distribution Methods 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0259—Compounds of N, P, As, Sb, Bi
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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
- B01J20/28014—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
- B01J20/28023—Fibres or filaments
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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
- B01J20/28054—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
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
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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
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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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
- C02F2101/30—Organic compounds
- C02F2101/306—Pesticides
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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
- C02F2101/30—Organic compounds
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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- Water Treatment By Sorption (AREA)
Abstract
The invention relates to a preparation method and application of La 2O3/BNNFs composite adsorbent. The method comprises the following steps: (1): mixing melamine and boric acid, adding the mixture into deionized water, and heating and stirring to obtain BNNFs powder; (2) Adding BNNFs powder obtained in the previous step into urea solution to obtain dispersion liquid; (3) The preparation method is simple in preparation condition, and the yield is high, and the obtained adsorbent has high specific surface area and porosity, so that the removal capacity of the boron nitride material to anionic pollutants is obviously improved, and has better adsorption performance to fluoride in water.
Description
Technical Field
The invention relates to the field of adsorbent preparation, in particular to a preparation method and application of La 2O3/BNNFs composite adsorbent.
Background
There are many methods for removing fluoride from water, including chemical precipitation, electrocoagulation, adsorption, membrane technology, ion exchange, and the like. These methods have advantages and disadvantages, such as secondary pollution, complex ion exchange method and high cost, and the adsorption method is to adsorb fluorine ions on the surface of the adsorbent material through the function groups and active sites on the surface of the adsorbent through ligand exchange or complexation, so as to remove the fluorine ions in water. It is generally more efficient than other techniques. In recent years, therefore, the use of adsorption to remove fluoride ions from water has been the focus of research by scholars at home and abroad. However, the conventional adsorbent material generally has the characteristics of narrow adsorption range and poor stability, so that the preparation of an adsorbent material with excellent stability and cycle performance becomes a hot spot of current research.
Hexagonal boron nitride (h-BN) has a structure similar to graphite, which is also called "white graphite", and has the advantages of high chemical stability, good high temperature resistance, oxidation resistance and the like, wherein the porous boron nitride fiber (BNNFs) has the advantages of h-BN material, and also has high specific surface area, rich pore structure and rich functional groups, so that the porous boron nitride fiber has been widely paid attention to the adsorption field. Porous BN is currently commonly used for the treatment of antibiotics in water (patent CN 109833847), heavy metals (environ. Res.,2020,183,109240), organic dyes (chem. Eng. Com., 2022,209,1111-1129), etc., whereas few reports are relevant for the treatment of anions in water, such as fluoride.
In general, pore size distribution, the number of functional groups, surface charge properties, and the like have a great influence on porous BN adsorption. However, the original porous BNNFs has a surface that is negatively charged and has poor affinity for anions, which prevents its adsorption of anions. Thus, the porous BNNFs is subjected to a modification treatment to enhance its affinity for anions. The Al (III) modified boron nitride nano-sheet (BNNSs) is reported to be used for removing fluoride (J.alloys Compd.,2019,793,512-518) in water at present, but compared with BNNFs materials, the prepared adsorbent has smaller specific surface area, fewer pore structures, relatively fewer surface active sites and functional groups and poorer fluoride removing capability. Therefore, finding a proper modification method, the invention is particularly important to invent the porous BN which has a surface containing a large amount of functional groups and pore structures and has good affinity to fluoride.
Disclosure of Invention
The invention aims at overcoming the defects in the prior art and provides a preparation method and application of a La 2O3/BNNFs composite adsorbent. The method utilizes lanthanum oxide and nitrogen-containing functional groups to carry out compound modification on BNNFs at the same time to realize the efficient removal of anions in the BNNFs material; meanwhile, the preparation flow is optimized, and the annealing process reduces the cost. The preparation method provided by the invention has the advantages of simple preparation conditions and high yield, and the obtained adsorbent has high specific surface area and porosity, so that the removal capability of the boron nitride material on anionic pollutants is obviously improved, and the adsorbent has better adsorption performance on fluoride in water.
The technical scheme adopted by the invention is as follows:
A preparation method of La 2O3/BNNFs composite adsorbent comprises the following steps:
(1) Preparation BNNFs of powder: mixing melamine and boric acid, adding the mixture into deionized water, heating and stirring the mixture to 70-90 ℃, preserving heat for 4-8 hours after clarifying the solution to obtain flocculent precipitate, filtering the flocculent precipitate, drying the flocculent precipitate at 60-70 ℃ to obtain a precursor, placing the precursor into a tube furnace, heating the precursor to 900-1100 ℃ at a speed of 2-5 ℃/min under an N 2 atmosphere, and preserving heat for 2-4 hours to obtain BNNFs powder;
Wherein, the mole ratio of melamine to boric acid is 1:2; adding 0.1-0.5 mol boric acid into every 500-1000 mL water;
(2) Adding BNNFs powder obtained in the previous step into urea solution, and stirring for 12-24h to obtain dispersion;
Wherein, 0.02mol BNNFs powder is added into each 100-300 mL urea solution; the concentration range of the urea solution is 5-15g/l;
(3) Dissolving La (NO 3)3·6H2 O) in deionized water, adding the dispersion liquid obtained in the step (2), and fully stirring for 12-24 hours to obtain a mixed liquid;
Wherein, 0.0002-0.005mol La (NO 3)3·6H2 O; BNNFs powder to La (NO 3)3·6H2 O molar ratio is 1:0.01-0.25) is added into every 5ml deionized water;
(4) Centrifuging and cold drying the mixed solution obtained in the step (3) to obtain La (III) @ BNNFs;
(5) And (3) carrying out annealing treatment on the product La (III) @ BNNFs obtained in the step (4) in a muffle furnace, wherein the annealing temperature is 200-500 ℃, and the annealing time is 0.5-3h, so as to obtain the La 2O3/BNNFs composite adsorbent, namely La 2O3/BNNFs.
The application of the composite adsorbent prepared by the method is used for treating fluoride-containing wastewater.
The method specifically comprises the following steps: adding La 2O3/BNNFs composite adsorbent into fluoride-containing wastewater, stirring for 120-720 minutes, and then completing adsorption.
The concentration of fluoride in the fluoride-containing wastewater is 5-100 mg/l; 5-15 mg of composite adsorbent is added into each 25mL of wastewater.
The invention has the substantial characteristics that:
in the prior art, the surface of the boron nitride material is electronegative, and is commonly used for removing heavy metal ion pollution (lead, cadmium, mercury, cobalt and the like) and organic pollution (antibiotics, paint, pesticides and the like), but the surface of the boron nitride material is not ideal in anion removal, and the problem of easy agglomeration when pure-phase lanthanum oxide (lanthanum hydroxide) material is used as an adsorbent. In the prior art, the modification is mostly simple metal oxide modification, and the high-efficiency removal of the anionic pollutants cannot be realized due to the limitation of the number of positively charged functional groups on the surface and insufficient active adsorption sites.
Aiming at the problems, the invention provides a preparation method and application of La 2O3/BNNFs composite adsorbent. On the one hand, la (NO 3)3·6H2 O and urea) are used for simultaneously modifying BNNFs and the annealing technology is improved, compared with the prior pure oxide modification (chem. Eng. J,2020,394,124985) and annealing conditions (Colloids surf. A,2022,632,127749) in an N 2 atmosphere, the annealing in a muffle furnace greatly reduces the production cost, and simultaneously improves the number of nitrogen-containing functional groups and active sites on the surface of the adsorbent, which is more beneficial to the adsorption of anions.
The beneficial effects of the invention are as follows:
(1) The invention uses the dipping curing method, has simple preparation process and large yield, does not need harsh experimental conditions, and greatly shortens the process flow.
(2) Boric acid and melamine are used as raw materials to prepare BNNFs with high specific surface area. And then La (NO 3)3·6H2 O and urea are used for carrying out composite modification on BNNFs, compared with the prior pure oxide modification, the method increases the quantity of nitrogen-containing functional groups on the surface of BNNFs, and simultaneously ensures that La 2O3 small particles are uniformly dispersed on the surface of BNNFs, and the small particles and the nitrogen-containing functional groups can be used as active sites, so that the adsorption performance of the composite modified La has high specific surface area and porosity (482.974 m 2 g-1 and 0.392cm 3 g-1) while changing the surface charge of BNNFs.
(3) The adsorbent of the invention has better adsorption performance on fluoride in water, which is far higher than that of original BNNFs, the optimal adsorption capacity reaches 80.04mg/g, and the optimal adsorption capacity of original BNNFs is only 26.64mg/g.
(4) The adsorbent of the invention not only avoids the agglomeration or excessive consumption of rare earth elements, but also overcomes the defect of BNNFs that the capability of removing anionic pollutants in water is poor. The water treatment agent has high stability, can be reused, and has important significance in water treatment.
Drawings
The invention will be further described with reference to the drawings and examples.
FIG. 1 is a flow chart of the preparation process of the La 2O3/BNNFs composite adsorbent of the present invention.
FIG. 2 is an X-ray diffraction pattern of BNNFs and La 2O3/BNNFs composite adsorbent prepared in example 1.
FIG. 3 is an infrared spectrum of La 2O3/BNNFs composite adsorbent prepared in example 1.
FIG. 4 is a scanning electron microscope image of the La 2O3/BNNFs complex adsorbent prepared in example 1
FIG. 5 is a nitrogen adsorption-desorption isotherm of BNNFs and La 2O3/BNNFs composite adsorbent prepared in example 1.
FIG. 6 is a graph showing the effect of BNNFs and La 2O3/BNNFs composite adsorbent prepared in example 1 on treatment of 10mg/l fluorine-containing wastewater.
FIG. 7 is a recycling chart of the La 2O3/BNNFs composite adsorbent prepared in example 1.
Detailed Description
Embodiments of the present invention are further described below with reference to the accompanying drawings.
Example 1
A preparation method of La 2O3/BNNFs composite adsorbent comprises the following specific steps (as shown in figure 1):
Step one: dispersing 0.15mol of melamine and 0.3mol of boric acid in 800ml of deionized water, heating to 90 ℃ in a water bath kettle, stirring at constant temperature for 8 hours after the solution is clarified, naturally cooling to room temperature after the reaction is finished to obtain flocculent precipitate, filtering and drying to obtain a precursor, and then placing the precursor in a tube furnace in N 2 atmosphere, heating to 1050 ℃ for cracking reaction for 4 hours to obtain BNNFs powder for later use;
Step two: 1g of urea was dissolved in 200ml of deionized water, and 0.02mol BNNFs powder was added thereto, and stirred at room temperature for 24 hours, which was designated as a mixed solution A. Then 0.001mol of La (NO 3)3·6H2 O, dissolved in 5ml of deionized water) is taken and added into the mixed solution A, and the mixture is fully stirred for 24 hours at room temperature, so that the adsorption balance of La (III) on BNNFs is ensured;
Step three: centrifuging the mixed solution, and performing cold drying treatment to obtain powder La (III) @ BNNFs;
Step four: the powder La (III) @ BNNFs was placed in a muffle furnace and annealed at 500℃for 2h to give a modified La 2O3/BNNFs adsorbent designated La 2O3 (0.001)/BNNFs.
FIG. 2 is an X-ray diffraction pattern of BNNFs and La 2O3 (0.001)/BNNFs composite adsorbents prepared in example 1, from which it can be seen that the pure BNNFs sample is slightly shifted and diffraction peaks widened compared to the h-BN standard card (JCPDS No. 34-0421). This is because BNNFS is prepared with low crystallinity and a large amount of impurity oxygen elements and defects, which helps to increase the specific surface area, bringing more adsorption sites. In addition to this, la 2O3 (0.001)/BNNFs had no distinct other peaks, indicating that La 2O3 loaded on BNNFs was amorphous. The peak intensity of BNNFs was reduced after modification, which may be caused by La 2O3 coating the BNNFs surface.
FIG. 3 is an infrared spectrum of La 2O3 (0.001)/BNNFs composite adsorbent in example 1, and it can be seen that the surface thereof contains a large number of functional groups such as amino groups, hydroxyl groups, etc., which can have a favorable effect on adsorption.
FIG. 4 is a scanning analysis chart of La 2O3 (0.001)/BNNFs composite adsorbent in example 1, and it was found that the modified adsorbent still remained in a coarse fibrous state of BNNFs, but the surface became more rough and uniformly supported La 2O3 particles.
Fig. 5 is a nitrogen adsorption-desorption isotherm of BNNFs and La 2O3 (0.001)/BNNFs composite adsorbent, and it is known that the samples all belong to type iv isotherm with H4 hysteresis loop, which shows that micropores and slit holes exist on the surface of the adsorbent, and the specific surface area of the composite material is slightly reduced compared with BNNFs, which is caused by that La 2O3 small clusters occupy the pore structure on the surface of BNNFs, but still have larger specific surface area and porosity (482.974 m 2 g-1 and 0.392cm 3 g-1).
And (3) measuring the performance of adsorbing fluorine ions:
The powder BNNFs and La 2O3 (0.001)/BNNFs obtained in example 1 were each taken and put into a sodium fluoride solution (25 ml) having an initial concentration of 5 to 100mg/l, respectively, and stirred well to adsorption equilibrium. The standard curve and the fluoride ion selective electrode are used for measuring the concentration of fluorine, when the initial concentration of the fluoride ion solution is 10mg/l, the obtained wastewater treatment result is shown in figure 6, the adsorption capacity is respectively 5.36mg/g and 11.61mg/g, and the adsorption capacity is improved by 2.17 times compared with BNNFs. The adsorbent prepared by the invention has high specific surface area, rich nitrogen-containing functional groups, la 2O3 small particles with uniform distribution and the like, and the active adsorption sites can be used together, so that the removal capacity of La 2O3 (0.001)/BNNFs powder of the invention on fluoride ions in water is obviously higher than BNNFs.
The obtained La 2O3 (0.001)/BNNFs composite adsorbent was subjected to a cycle ability test, first using a 0.1M NaOH solution as a desorbent, and then calcining in a muffle furnace for 2 hours. The results are shown in fig. 7, which shows that: the adsorbent has slightly reduced adsorption performance after 5 times of circulation, but still can maintain higher adsorption capacity. The La 2O3 (0.001)/BNNFs composite adsorbent is a reusable adsorbent, and has wide application prospect in the field of environmental remediation.
Example 2
Step one: dispersing 0.15mol of melamine and 0.3mol of boric acid in 800ml of deionized water, heating to 90 ℃ in a water bath kettle, stirring at constant temperature for 6 hours after the solution is clarified, naturally cooling to room temperature after the reaction is finished to obtain white flocculent precipitate, filtering and drying to obtain a precursor, and then placing the precursor in a tube furnace in N 2 atmosphere, heating to 900 ℃ for cracking reaction for 4 hours to obtain BNNFs powder for later use;
step two: 1g of urea was dissolved in 200ml of ionized water, and 0.02mol BNNFs powder was added thereto, followed by stirring at room temperature for 24 hours, and designated as a mixed solution A. Then 0.001mol of La (NO 3)3·6H2 O, dissolved in 5ml of deionized water) is taken and added into the mixed solution A, and the mixture is fully stirred for 24 hours at room temperature, so that the adsorption balance of La (III) on BNNFs is ensured;
Step three: centrifuging the mixed solution, and performing cold drying treatment to obtain powder La (III) @ BNNFs;
step four: and (3) placing the powder La (III) @ BNNFs in a muffle furnace, and annealing at 500 ℃ for 2 hours to obtain the modified La 2O3/BNNFs adsorbent.
Example 3
Step one: dispersing 0.15mol of melamine and 0.3mol of boric acid in 800ml of deionized water, heating to 90 ℃ in a water bath kettle, stirring at constant temperature for 6 hours after the solution is clarified, naturally cooling to room temperature after the reaction is finished to obtain flocculent precipitate, filtering and drying to obtain a precursor, and then placing the precursor in a tube furnace in N 2 atmosphere, heating to 900 ℃ and carrying out cracking reaction for 4 hours to obtain BNNFs powder for later use;
Step two: 1g of urea is taken and dissolved in a proper amount of 200ml of deionized water, 0.02mol BNNFs of powder is added, and the mixture is stirred for 24 hours at room temperature and is marked as a mixed solution A. Then 0.001mol of La (NO 3)3·6H2 O, dissolved in 5ml of deionized water) is taken and added into the mixed solution A, and the mixture is fully stirred for 24 hours at room temperature, so that the adsorption balance of La (III) on BNNFs is ensured;
Step three: centrifuging the mixed solution, and performing cold drying treatment to obtain powder La (III) @ BNNFs;
Step four: and (3) placing the powder La (III) @ BNNFs in a muffle furnace, and annealing at 200 ℃ for 3 hours to obtain the modified La 2O3/BNNFs adsorbent.
Examples 4, 5 and 6
Based on example 1, the amount of La (NO 3)3·6H2 O was adjusted.
The La (NO 3)3·6H2 O addition amounts are respectively changed to 0.00025mol, 0.0005mol and 0.0015 mol) in example 1, and the operations are the same as in example 1, and the obtained product is similar to example 1, the effect of the obtained product on fluoride removal is shown in FIG. 6, and compared with BNNFs, the adsorption performance is improved, wherein the preferable addition amount is 0.001-0.0015mol, namely BNNFs and La (NO 3)3·6H2 O molar ratio is 1:0.05-0.075).
The foregoing is merely illustrative of some embodiments of the invention, and it will be apparent to those skilled in the art that various modifications and improvements can be made without departing from the inventive concept.
The invention is not a matter of the known technology.
Claims (3)
1. The preparation method of the La 2O3/BNNFs composite adsorbent for fluoride-containing wastewater treatment is characterized by comprising the following steps:
(1) Preparation BNNFs of powder: mixing melamine and boric acid, adding the mixture into deionized water, heating and stirring the mixture to 70-90 ℃, preserving heat for 4-8 h after solution clarification to obtain flocculent precipitate, carrying out suction filtration, drying the flocculent precipitate at 60-70 ℃ to obtain a precursor, placing the precursor into a tube furnace, heating the precursor to 900-1100 ℃ in an N 2 atmosphere, and preserving heat for 2-4 h to obtain BNNFs powder;
wherein, the mole ratio of melamine to boric acid is 1:2; adding 0.1-0.5 mol of boric acid into every 500-1000 mL of deionized water;
(2) Adding BNNFs powder obtained in the previous step into urea solution, and stirring for 12-24: 24 h to obtain dispersion;
Wherein, 0.02 mol BNNFs powder is added into each 100-300 mL urea solution; the concentration range of the urea solution is 5-15 g/L;
(3) Dissolving La (NO 3)3·6H2 O in deionized water, adding the dispersion liquid obtained in the step (2), and fully stirring 12-24 h to obtain a mixed liquid;
Wherein, every 5ml deionized water is added with 0.0002-0.005 mol La (NO 3)3·6H2 O; BNNFs powder and La (the mol ratio of NO 3)3·6H2 O is 1:0.01-0.25);
(4) Centrifuging and cold drying the mixed solution obtained in the step (3) to obtain trivalent La@BNNFs;
(5) And (3) carrying out annealing treatment on the trivalent La@BNNFs obtained in the step (4) in a muffle furnace, wherein the annealing temperature is 200-500 ℃, and the annealing time is 0.5-3 h, so that the La 2O3/BNNFs composite adsorbent, namely La 2O3/BNNFs, is obtained.
2. The use of the composite adsorbent prepared by the preparation method according to claim 1, which is characterized by being used for fluoride-containing wastewater treatment.
3. The use according to claim 2, characterized in that it comprises in particular the following steps: adding La 2O3/BNNFs composite adsorbent into fluoride-containing wastewater, stirring for 120-720 minutes, and then completing adsorption;
The concentration of fluoride in the fluoride-containing wastewater is 5-100 mg/L; 5-15 mg of the composite adsorbent is added into each 25 mL fluoride-containing wastewater.
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