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 PDF

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CN116116374A
CN116116374A CN202310231206.4A CN202310231206A CN116116374A CN 116116374 A CN116116374 A CN 116116374A CN 202310231206 A CN202310231206 A CN 202310231206A CN 116116374 A CN116116374 A CN 116116374A
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CN116116374B (en
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房毅
顾雅欣
唐成春
蔡华宜
严松
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Hebei University of Technology
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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

La (La) 2 O 3 Preparation method and application of BNNFs composite adsorbent
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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