CN116116374A - La (La) 2 O 3 Preparation method and application of BNNFs composite adsorbent - Google Patents
La (La) 2 O 3 Preparation method and application of BNNFs composite adsorbent Download PDFInfo
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 56
- 239000002131 composite material Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000001179 sorption measurement Methods 0.000 claims abstract description 30
- 239000000843 powder Substances 0.000 claims abstract description 27
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 19
- 229910021193 La 2 O 3 Inorganic materials 0.000 claims abstract description 19
- 239000008367 deionised water Substances 0.000 claims abstract description 16
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 14
- 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
- 238000003756 stirring Methods 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
- 238000000137 annealing Methods 0.000 claims abstract description 10
- 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
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 239000006185 dispersion Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000011259 mixed solution Substances 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 10
- 239000002351 wastewater Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 238000000643 oven drying Methods 0.000 claims description 3
- 238000004065 wastewater treatment Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 12
- 229910052582 BN Inorganic materials 0.000 abstract description 8
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 abstract description 8
- 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
- 239000000203 mixture Substances 0.000 abstract 1
- 125000000524 functional group Chemical group 0.000 description 11
- 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 10
- 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 8
- 230000004048 modification Effects 0.000 description 8
- 238000012986 modification Methods 0.000 description 8
- 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
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- -1 fluorine ions Chemical class 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
- 239000000835 fiber Substances 0.000 description 3
- 230000008569 process Effects 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
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 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
- 238000005342 ion exchange Methods 0.000 description 2
- YXEUGTSPQFTXTR-UHFFFAOYSA-K lanthanum(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[La+3] YXEUGTSPQFTXTR-UHFFFAOYSA-K 0.000 description 2
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical class [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 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
- 230000009286 beneficial effect Effects 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
- 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
- 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
- 150000002222 fluorine compounds Chemical class 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
- 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
- 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
- 239000000047 product 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
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- 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
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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
- B01J20/0203—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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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- 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
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Abstract
The invention relates to La 2 O 3 Preparation method and application of BNFs 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 BNFFs powder; (2) Adding the BNFs powder obtained in the previous step into urea solution to obtain dispersion liquid; (3) La (the powder of La)NO 3 ) 3 ·6H 2 O is dissolved in deionized water, and then the obtained dispersion liquid is added to obtain a mixed liquid; (4) obtaining La (III) @ BNNFs after centrifugal and cold drying treatment; (5) Annealing in a muffle furnace to obtain La 2 O 3 BNFs composite adsorbent. 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.
Description
Technical Field
The invention relates to the field of adsorbent preparation, in particular to a La 2 O 3 Preparation method and application of BNFs 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", has advantages of high chemical stability, good high temperature resistance, oxidation resistance and the like, wherein porous boron nitride fibers (BNNFs) have advantages of h-BN material, and also have high specific surface area, abundant pore structure and abundant functional groups, so that the porous boron nitride fibers are widely focused in 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 surface of the original porous BNNFs is electronegative and has poor affinity for anions, which prevents its adsorption of anions. Therefore, the porous BNNFs are subjected to certain modification treatment to enhance the affinity of the porous BNNFs to anions. The use of Al (III) modified boron nitride nanoplates (BNSs) for removing fluorides (J.alloys Compd.,2019,793,512-518) in water has been reported 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 removal 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 existing in the prior art and providing a La 2 O 3 Preparation method and application of BNFs composite adsorbent. The method utilizes lanthanum oxide and nitrogen-containing functional groups to carry out composite modification on BNFs simultaneously so as to realize the efficient removal of anions in water by the BNFs 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:
la (La) 2 O 3 A preparation method of the BNFs composite adsorbent comprises the following steps:
(1) Preparing BNFs powder: mixing melamine and boric acid, adding into deionized water, heating and stirring to 70-90deg.C, clarifying, maintaining the temperature for 4-8 hr to obtain flocculent precipitate, vacuum filtering, oven drying at 60-70deg.C to obtain precursor, placing the precursor in a tube furnace, and adding into N 2 Heating to 900-1100deg.C at a rate of 2-5deg.C/min under atmosphereThe temperature time is 2-4h, and BNFs powder is obtained;
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 the BNFs powder obtained in the previous step into urea solution, and stirring for 12-24 hours to obtain dispersion liquid;
wherein, 0.02mol BNFs powder is added into each 100-300 mL urea solution; the concentration range of the urea solution is 5-15g/l;
(3) La (NO) 3 ) 3 ·6H 2 After O is dissolved 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) is added per 5ml deionized water 3 ) 3 ·6H 2 O; bnfs powder and La (NO) 3 ) 3 ·6H 2 The mol ratio of O is 1:0.01-0.25;
(4) Centrifuging and cold drying the mixed solution obtained in the step (3) to obtain La (III) @ BNNFs;
(5) Annealing the La (III) @ BNNFs obtained in the step (4) in a muffle furnace at 200-500 ℃ for 0.5-3h to obtain La 2 O 3 BNNFs composite adsorbent, i.e. La 2 O 3 /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: la addition to fluoride containing wastewater 2 O 3 And (3) stirring the BNFs composite adsorbent for 120-720 minutes to finish the 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.
The present invention addresses the above problems by providing a La 2 O 3 Preparation method and application of BNFs composite adsorbent. On the one hand La (NO) 3 ) 3 ·6H 2 O and urea simultaneously modify BNNFs and improve the annealing technique. This is compared with the prior simple oxide modification (chem. Eng. J,2020,394,124985), and N 2 Annealing conditions under atmosphere (Colloids surf. A,2022,632,127749), annealing in a muffle furnace greatly reduces production costs and simultaneously increases the number of nitrogen-containing functional groups and active sites on the adsorbent surface, which is more conducive to anion adsorption. On the other hand, lanthanum oxide is uniformly dispersed on the surface of boron nitride, so that the problem that pure-phase lanthanum oxide (lanthanum hydroxide) material is easy to agglomerate when being used as an adsorbent and excessively consumed in the adsorption process is solved.
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) The invention prepares BNNFs with high specific surface area by taking boric acid and melamine as raw materials. Further utilize La (NO) 3 ) 3 ·6H 2 The complex modification of BNFs by O and urea increases the number of nitrogen-containing functional groups on the surface of BNFs and simultaneously leads La to the fact that compared with the prior pure oxide modification 2 O 3 The small particles are more uniformly dispersed on the surface of BNNFs. Both these small particles and nitrogen-containing functional groups can be active sites, with high specific surface area and porosity (482.974 m) while altering BNNFs surface charge 2 g -1 And 0.392cm 3 g -1 ) The adsorption performance is obviously improved.
(3) The adsorbent of the invention has better adsorption performance on fluoride in water, which is far higher than that of original BNFs, the optimal adsorption capacity reaches 80.04mg/g, and the optimal adsorption capacity of original BNFs 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 poor capability of BNNFs for removing anionic pollutants in water. 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 shows La of the present invention 2 O 3 Preparation process flow diagram of BNFs composite adsorbent.
FIG. 2 shows BNFs and La prepared in example 1 2 O 3 X-ray diffraction pattern of BNFs composite adsorbent.
FIG. 3 shows La prepared in example 1 2 O 3 Infrared spectrogram of BNFs composite adsorbent.
FIG. 4 shows La prepared in example 1 2 O 3 Scanning electron microscope image of BNFs composite adsorbent
FIG. 5 shows BNFs and La prepared in example 1 2 O 3 Nitrogen adsorption-desorption isotherms of the BNNFs composite adsorbent.
FIG. 6 shows BNFs and La prepared in example 1 2 O 3 Comparison graph of the effect of BNFs composite adsorbent on 10mg/l fluorine-containing wastewater treatment.
FIG. 7 is a diagram of La prepared in example 1 2 O 3 And (3) a recycling chart of the BNFs composite adsorbent.
Detailed Description
Embodiments of the present invention are further described below with reference to the accompanying drawings.
Example 1
La (La) 2 O 3 The preparation method of the BNFs composite adsorbent comprises the following specific steps (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, and naturally cooling after the reaction is finishedCooling to room temperature to obtain flocculent precipitate, filtering, oven drying to obtain precursor, and placing the precursor in N 2 Heating to 1050 ℃ in a tube furnace in atmosphere to carry out cracking reaction for 4 hours to obtain BNFs powder for later use;
step two: 1g of urea was dissolved in 200ml of deionized water, and 0.02mol of BNFs powder was added thereto, and stirred at room temperature for 24 hours, which was designated as a mixed solution A. Then 0.001mol La (NO) 3 ) 3 ·6H 2 O is dissolved in 5ml of deionized water, added into the mixed solution A, and 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 carrying out cold drying treatment to obtain powder La (III) @ BNNFs;
step four: placing powder La (III) @ BNNFs in a muffle furnace, and annealing at 500 ℃ for 2h to obtain modified La 2 O 3 BNNFs adsorbent named La 2 O 3 (0.001)/BNNFs。
FIG. 2 is BNFs and La prepared in example 1 2 O 3 The X-ray diffraction pattern of the (0.001)/BNFs composite adsorbent shows that the pure BNFs sample has a slight shift and broad diffraction peak compared with the h-BN standard card (JCPDS No. 34-0421). This is because the BNNFS prepared has 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 La 2 O 3 (0.001)/BNFs has no obvious other peaks, indicating La carried on BNFs 2 O 3 Is of an amorphous structure. Modified BNFs peak intensity is reduced, which may be La 2 O 3 Covering on the surface of BNNFs.
FIG. 3 is La in example 1 2 O 3 The infrared spectrogram of the (0.001)/BNFs composite adsorbent can show that the surface of the composite adsorbent contains a large amount of functional groups such as amino groups, hydroxyl groups and the like, and the adsorption can be favorably influenced.
FIG. 4 is La in example 1 2 O 3 As a result of scanning analysis of the (0.001)/BNFs composite adsorbent, it was found that the modified adsorbent still maintained the crude fiber state of BNFs, but the surface became coarser and was uniformly supported with La 2 O 3 Small particles.
FIG. 5 is BNNFs and La 2 O 3 The nitrogen adsorption-desorption isotherm of the (0.001)/BNFs composite adsorbent shows that the samples all belong to an IV-type 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 BNFs due to La 2 O 3 The small clusters occupy the pore structure of the BNNFs surface, but still have a large 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:
BNNFs and La were obtained in example 1 2 O 3 10mg of (0.001)/BNFs powder was added to 5-100mg/l of sodium fluoride solution (25 ml) 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 BNFs. This is because the adsorbent prepared by the invention has high specific surface area, rich nitrogen-containing functional groups and La with uniform distribution 2 O 3 Small particles, etc., which act together as active adsorption sites, so that La of the present invention 2 O 3 The (0.001)/BNFs powder has obviously higher fluorine ion removal capability than BNFs.
For La obtained 2 O 3 The (0.001)/BNFs composite adsorbent was tested for its ability to circulate by first using a 0.1M NaOH solution as the 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. Indicating La 2 O 3 The (0.001)/BNFs 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, and adding in a water bath kettleHeating to 90 ℃, stirring for 6 hours at constant temperature 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 N 2 Heating to 900 ℃ in a tube furnace in atmosphere to carry out cracking reaction for 4 hours to obtain BNFs powder for later use;
step two: 1g of urea was dissolved in 200ml of ionized water, and 0.02mol of BNFs powder was added thereto, and stirred at room temperature for 24 hours, which was designated as a mixed solution A. Then 0.001mol La (NO) 3 ) 3 ·6H 2 O is dissolved in 5ml of deionized water, added into the mixed solution A, and 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 carrying out cold drying treatment to obtain powder La (III) @ BNNFs;
step four: placing powder La (III) @ BNNFs in a muffle furnace, and annealing at 500 ℃ for 2h to obtain modified La 2 O 3 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 placing the precursor in N 2 Heating to 900 ℃ in a tube furnace in atmosphere to carry out cracking reaction for 4 hours to obtain BNFs powder for later use;
step two: 1g of urea was dissolved in a suitable amount of 200ml of deionized water, and 0.02mol of BNFs powder was added thereto, and stirred at room temperature for 24 hours, which was designated as a mixed solution A. Then 0.001mol La (NO) 3 ) 3 ·6H 2 O is dissolved in 5ml of deionized water, added into the mixed solution A, and 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 carrying out cold drying treatment to obtain powder La (III) @ BNNFs;
step four: placing powder La (III) @ BNNFs in a muffle furnace, and annealing at 200 ℃ for 3h to obtain modified La 2 O 3 BNNFs adsorbent.
Examples 4, 5 and 6
Based on example 1, la (NO 3 ) 3 ·6H 2 The amount of O added.
La (NO) in example 1 3 ) 3 ·6H 2 The addition amounts of O were changed to 0.00025mol, 0.0005mol and 0.0015mol, respectively, and the other operations were the same as in example 1, and the obtained product was similar to example 1, and the effect of the addition of O on fluoride removal was shown in FIG. 6, and the adsorption performance was improved as compared with BNFs, wherein the addition amount was preferably 0.001-0.0015mol, namely BNFs and La (NO 3 ) 3 ·6H 2 The molar ratio of O 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 (4)
1. La (La) 2 O 3 The preparation method of the BNFs composite adsorbent is characterized by comprising the following steps:
(1) Preparing BNFs powder: mixing melamine and boric acid, adding into deionized water, heating and stirring to 70-90deg.C, clarifying, maintaining the temperature for 4-8 hr to obtain flocculent precipitate, vacuum filtering, oven drying at 60-70deg.C to obtain precursor, placing the precursor in a tube furnace, and adding into N 2 Heating to 900-1100 ℃ under atmosphere, and keeping the temperature for 2-4h to obtain BNFs 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 the BNFs powder obtained in the previous step into urea solution, and stirring for 12-24 hours to obtain dispersion liquid;
wherein, 0.02mol BNFs powder is added into each 100-300 mL urea solution; the concentration range of the urea solution is 5-15g/L;
(3) La (NO) 3 ) 3 ·6H 2 After O is dissolved in deionized water, adding the dispersion liquid obtained in the step (2)Fully stirring for 12-24h to obtain a mixed solution;
wherein 0.0002-0.005mol La (NO) is added per 5ml deionized water 3 ) 3 ·6H 2 O; bnfs powder and La (NO) 3 ) 3 ·6H 2 The mol ratio of O is 1:0.01-0.25;
(4) Centrifuging and cold drying the mixed solution obtained in the step (3) to obtain La (III) @ BNNFs;
(5) Annealing the La (III) @ BNNFs obtained in the step (4) in a muffle furnace at 200-500 ℃ for 0.5-3h to obtain La 2 O 3 BNNFs composite adsorbent, i.e. La 2 O 3 /BNNFs。
2. La according to claim 1 2 O 3 The preparation method of the BNFs composite adsorbent is characterized in that the heating rate is 2-5 ℃/min.
3. The use of the composite adsorbent prepared by the method of claim 1, characterized by being used for fluoride-containing wastewater treatment.
4. The use according to claim 4, characterized in that it comprises in particular the following steps: la addition to fluoride containing wastewater 2 O 3 BNFs composite adsorbent, stirring for 120-720 min, and then finishing 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.
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