CN115845791B - Preparation method and application of Ca/La-based perovskite adsorption material - Google Patents
Preparation method and application of Ca/La-based perovskite adsorption material Download PDFInfo
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Abstract
The invention relates to a preparation method and application of Ca/La-based perovskite adsorption material, comprising the following steps: adding anhydrous calcium chloride and lanthanum nitrate hexahydrate into deionized water to form a solution a; sequentially adding manganese nitrate tetrahydrate, absolute ethyl alcohol and water into the solution a; keeping the high temperature in the high-pressure reaction kettle for a certain time and then cooling to room temperature; drying the extracted solid, calcining at high temperature, and cooling to room temperature to obtain Ca x La 1‑x MnO 3 And (3) powder. According to the invention, ca/La-based perovskite adsorption material is synthesized by adopting a solvothermal method, ca is used as an A-site metal to partially replace La to be doped into perovskite, so that the structure and morphology of lanthanum-based perovskite are effectively changed, the mesoporous quantity is increased, the pore volume is increased, the oxygen vacancy content is increased, the generation of dominant morphology is beneficial to the adsorption of phosphate, and in addition, through long-term adsorption and repeated adsorption tests, the Ca/La-based perovskite adsorption material is verified to be capable of continuously adsorbing phosphate, can be repeatedly utilized under the condition of no desorption, and has good application and popularization values.
Description
Technical Field
The invention relates to the technical field of adsorption materials, in particular to a preparation method and application of a Ca/La-based perovskite adsorption material.
Background
Phosphorus (P) is a resource guarantee for sustainable development of modern agriculture, however, excessive discharge of phosphate into runoff from point sources such as urban sewage and non-point sources such as agricultural runoff is one of the main factors of water eutrophication. Eutrophication is a global problem, and therefore, phosphorus removal is critical to reducing eutrophic water and improving water environment quality.
Currently, methods for removing phosphate from water bodies include biological methods, chemical precipitation methods, adsorption methods and the like. Among them, the adsorption method is widely used for removing phosphate because it is not easy to produce secondary pollution, and has high efficiency and high selectivity to phosphate. In recent years, common dephosphorizing adsorption materials include metal modified biochar, metal oxides/hydroxides, layered double metal hydroxides and metal organic framework compounds, wherein the combination of metal cations and phosphate anions increases the affinity of phosphate, and it is not difficult to find that metal cations become necessary conditions for the preparation of the adsorption materials. Among the commonly used metals (such as La, ca, mg and Fe), la is relatively abundant as a rare earth element metal in the crust, and has been proved to have a high affinity with phosphate due to its small product precipitation equilibrium constant (Ksp) of reaction with phosphate, which is a research hotspot for metal-based adsorption materials.
Perovskite oxide of the formula ABO 3 (A-rare earth elements such as La, nd and Sm; B-transition metals such as Fe, mn, co, al, cr), the research of lanthanum-based perovskite at present mainly focuses on substances such as adsorption dye and pesticide, and the like, and the lanthanum-based perovskite has better affinity to oxyanions (such as phosphate), but still has poorer adsorption capacity, so that the removal rate of phosphate in water is low, and the perovskite is difficult to reuse, and therefore, the development of novel perovskite materials with phosphorus removal advantage structures becomes an important research point.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects in the prior art and provide a preparation method and application of Ca/La-based perovskite adsorption material.
The invention is realized by the following technical scheme:
a preparation method of Ca/La-based perovskite adsorption material comprises the following steps:
s1, adding anhydrous calcium chloride and lanthanum nitrate hexahydrate into deionized water to form a solution a;
s2, sequentially adding manganese nitrate tetrahydrate, absolute ethyl alcohol, ethylene glycol and water into the solution a;
s3, maintaining the high temperature in the high-pressure reaction kettle for a certain time, and cooling to room temperature;
s4, drying the extracted solid, calcining at high temperature, and cooling to room temperature to obtain Ca x La 1-x MnO 3 And (3) powder.
According to the above technical scheme, in step S1, 0.4439g anhydrous calcium chloride and 6.9280g lanthanum nitrate hexahydrate, namely Ca, are added to 20mL deionized water 0.2 La 0.8 MnO 3 。
According to the above technical scheme, in step S1, 0.8879g anhydrous calcium chloride and 5.1960g lanthanum nitrate hexahydrate, namely Ca, are added to 20mL deionized water 0.4 La 0.6 MnO 3 。
According to the above technical scheme, in step S1, 1.5537g anhydrous calcium chloride and 2.5980g lanthanum nitrate hexahydrate, namely Ca, are added to 20mL deionized water 0.7 La 0.3 MnO 3 。
According to the above technical solution, preferably, in step S2, 5.325mL of manganese nitrate tetrahydrate, 80mL of absolute ethanol, 20mL of ethylene glycol and 20mL of water are sequentially added into the solution a;
according to the above technical scheme, in step S3, it is preferable to cool to room temperature after maintaining at 120-200 ℃ for 24 hours.
According to the above technical scheme, in step S4, preferably, the drying temperature is 60-120 ℃, the calcination is performed for 2 hours in air at 400 ℃, and the temperature is raised to 600-1000 ℃ and the calcination is performed for 4 hours in air.
The patent also discloses an application of the Ca/La-based perovskite adsorption material, and a preparation method based on the Ca/La-based perovskite adsorption material, wherein the Ca x La 1-x MnO 3 The surface morphology of the powder can form a structure with mesopores inside micron-sized macropores, and the structure is used for adsorbing phosphate in water.
According to the above technical scheme, preferably, the Ca x La 1-x MnO 3 The powder can be reused to adsorb phosphate without desorption.
The beneficial effects of the invention are as follows:
according to the invention, ca/La-based perovskite adsorption material is synthesized by adopting a solvothermal method, ca is used as an A-site metal to partially replace La to be doped into perovskite, so that the structure and morphology of lanthanum-based perovskite are effectively changed, the mesoporous quantity is increased, the pore volume is increased, the oxygen vacancy content is increased, the generation of dominant morphology is beneficial to the adsorption of phosphate, and in addition, through long-term adsorption and repeated adsorption tests, the Ca/La-based perovskite adsorption material is verified to be capable of continuously adsorbing phosphate, can be repeatedly utilized under the condition of no desorption, and has good application and popularization values.
Drawings
FIG. 1 is an XRD analysis of samples LMO, CLMO-1, CLMO-2, and CLMO-3 of the present invention.
FIG. 2 is a sample of the LMO, CLMO-1, CLMO-2, and CLMO-3 of the present invention N 2 Adsorption and desorption curves and pore size distribution plots.
FIG. 3 is a schematic graph of specific surface area, average pore size and average pore volume of samples LMO, CLMO-1, CLMO-2, and CLMO-3 of the present invention.
Fig. 4 is a surface topography of LMO samples under SEM scanning electron microscopy.
FIG. 5 is a surface topography of a CLMO-1 sample under SEM scanning electron microscopy.
FIG. 6 is a surface topography of a CLMO-2 sample under SEM scanning electron microscopy.
FIG. 7 is a surface topography of a CLMO-3 sample under SEM scanning electron microscopy.
FIG. 8 is a Langmuir isothermal fit of phosphorus adsorption for samples LMO, CLMO-1, CLMO-2, and CLMO-3 of the present invention.
FIG. 9 is a Freundlich isothermal fit of samples of LMO, CLMO-1, CLMO-2, and CLMO-3 of the present invention adsorbing phosphorus.
FIG. 10 is a graph of Langmuir, freundlich fitting parameters for phosphorus adsorption for samples of LMO, CLMO-1, CLMO-2, and CLMO-3 of the present invention.
FIG. 11 is a schematic illustration of the dephosphorization performance of samples LMO, CLMO-1, CLMO-2, and CLMO-3 of the present invention in a simulated water body with low concentration.
FIG. 12 is a schematic view of the phosphorous removal performance of the CLMO-2 sample of the present invention in a water body with low phosphorous concentration by repeated adsorption without desorption.
FIG. 13 is a schematic diagram showing the dephosphorization performance of the CLMO-2 sample of the present invention in a water body with low phosphorus concentration by long-term adsorption under the condition of no desorption.
Description of the embodiments
The present invention will be described in further detail below with reference to the drawings and preferred embodiments, so that those skilled in the art can better understand the technical solutions of the present invention. All other embodiments, based on the embodiments of the invention, which would be apparent to one of ordinary skill in the art without making any inventive effort are intended to be within the scope of the invention.
Example 1 the invention comprises the steps of:
s1, adding anhydrous calcium chloride and lanthanum nitrate hexahydrate into deionized water to form a solution a. Wherein, 0.444g and 6.928g of anhydrous calcium chloride and lanthanum nitrate hexahydrate are respectively added, and then Ca is obtained 0.2 La 0.8 MnO 3 Powder, noted CLMO-1; 0.8879g and 5.196g of anhydrous calcium chloride and lanthanum nitrate hexahydrate are added respectively, and Ca is obtained 0.4 La 0.6 MnO 3 Powder, noted CLMO-2; 1.5537g and 2.598g of anhydrous calcium chloride and lanthanum nitrate hexahydrate are added respectively, and Ca is obtained 0.7 La 0.3 MnO 3 The powder was designated CLMO-3. In addition, in order to compare the technical effects of the Ca/La-based perovskite adsorption material prepared by the technical scheme, a control group is arranged at the same time, namely anhydrous calcium chloride is not added, 8.660g of lanthanum nitrate hexahydrate is added into deionized water, other steps are consistent, and LaMnO is obtained 3 The powder was designated LMO.
S2, sequentially adding manganese nitrate tetrahydrate, absolute ethyl alcohol and water into the solution a, and adding 5.325mL of manganese nitrate tetrahydrate, 80mL of absolute ethyl alcohol, 20mL of ethylene glycol and 20mL of water in the example. The concentration of the tetrahydrated manganese nitrate is 98%, the concentration range can be expanded to 80% -99%, the concentration of the absolute ethyl alcohol can be expanded to 75% -99% of the ethyl alcohol solution, the concentration of the ethylene glycol is 98%, the concentration can be expanded to 75% -99%, and the reagents are all analytically pure.
S3, cooling to room temperature after keeping the high temperature in the high-pressure reaction kettle for a certain time, specifically, transferring the obtained solution into a polytetrafluoroethylene stainless steel high-pressure reaction kettle, and cooling to room temperature after keeping the temperature at 180 ℃ for 24 hours.
S4, placing the extracted solid into an oven, drying and grinding at 80 ℃, placing the dried solid into a tube furnace, setting the heating rate of the tube furnace to be 5 ℃/min, calcining the solid in air at 400 ℃ for 2 hours, heating the solid to air at 600 ℃ for calcining the solid for 4 hours, and cooling the solid to room temperature to obtain powdery samples which are LMO, CLMO-1, CLMO-2 and CLMO-3 samples respectively.
To study the crystal structure of the sample, XRD analysis was performed on the sample, and the data was processed through the jade 9.0, as shown in fig. 1, as the Ca doping concentration was increased, the characteristic peak was shifted to the right as a whole, since the ionic radius of Ca was slightly smaller than the La radius, vacancies were generated, resulting in lattice contraction, and thus a gradual shift of diffraction peaks toward a large angle was observed. XRD diffraction peaks of LMO samples belong to a hexagonal system structure of perovskite, XRD diffraction peaks of samples after Ca doping belong to an orthorhombic system structure, and the difference is that a space group of a CLMO-1 sample is Cmcm, PDF cards #97-008-9997 are met, space groups of CLMO-2 and CLMO-3 samples are Pnma, and PDF cards #97-018-7700 are met. The crystal structure of LMO is obviously changed while generating vacancies after Ca doping, and the doping proportion is different, and the space groups are also different.
The N2 adsorption and desorption curves and pore size distribution are shown in figures 2 and 3, the isotherm of the sample belongs to type IV, and a typical H3 hysteresis loop exists, which shows that the adsorbent belongs to mesoporous adsorption materials with irregular pore structures. Specific surface area of CLMO-1 30.61m 2 /g＞27.58m 2/ g（CLMO-2）＞22.94m 2 /g（LMO）＞13.35m 2 /g (CLMO-3). As is known from the pore size distribution, with the doping of Ca, the microporous structure is gradually replaced by mesopores and macropores, compared with CLMO-1, CLMO-2 is increased in mesogen Kong Zhanbi, the pore structure is more developed, and when the Ca doping proportion is further increased, micropores and mesopores of the CLMO-3 are gradually replaced by macropores, and the pore development degree is reduced.
The surface morphology of the sample was observed by SEM and found that LMO was mostly spheres 15-25 μm in size, on which there were a large number of concave-convex surfaces caused by holes (fig. 4), and the surface structure of the sample changed greatly after Ca doping. The surface of the CLMO-1 sample is smooth and takes a branch-like structure (figure 5), an obvious pore structure appears on the surface of the CLMO-2 sample, a large number of mesopores exist in a micron-sized macropore (figure 6), and the surface of the CLMO-3 sample is similar to the CLMO-2, but the mesoporous and microporous structures are hardly seen by the CLMO-3 because the grains in the macropores are densely packed (figure 7). Surface element analysis by SEM-EDS shows that the sample surface mainly comprises La, mn and O, and Ca element identification shows that Ca atoms are successfully introduced into the crystal lattice of the sample and uniformly distributed on the sample surface. Combine XRD and N 2 Adsorption-desorption isothermal curves and poresThe diameter distribution result shows that the difference of the calcium doping proportion causes the change of the crystal structure and further affects the pore diameter distribution and the surface morphology of the sample, and the proper proportion of calcium doping lanthanum-based perovskite causes the change of the crystal lattice shrinkage and the crystal structure, thereby promoting the mesoporous development of the material and improving the specific surface area.
As shown in fig. 8-10, the adsorption behavior of the samples was fitted by Langmuir and Freundlich isotherm models. The results show that when four samples adsorb phosphate, the adsorption capacity of the four samples to the phosphate is more in accordance with a Langmuir isotherm model, and the fitting result shows that the adsorption capacity of the four samples to the phosphate is as follows: CLMO-2 (63.01 mg P/g) > CLMO-1 (54.98 mg P/g) > LMO (38.52 mg P/g) > CLMO-3 (18.37 mg P/g); the maximum adsorption capacity of the sample at CLMO-2 was increased by 160% compared to when undoped. Along with the increase of the calcium doping content, the adsorption capacity of the phosphate shows a trend of increasing and then decreasing, which shows that the change of the morphology and structure of the sample by the calcium doping influences the adsorption capacity of the sample, and the increase of the mesoporous number and the increase of the oxygen vacancy content are known according to the difference of the adsorption capacity, and the generation of the dominant morphology is favorable for the adsorption of the phosphate.
Example 2 this patent also discloses the use of a Ca/La-based perovskite adsorption material, based on the above-mentioned method for producing Ca/La-based perovskite adsorption material, the Ca x La 1-x MnO 3 The surface morphology of the powder can form a structure with mesopores inside micro-scale macropores, and the structure is used for adsorbing phosphate in water body and Ca x La 1-x MnO 3 The powder can be reused to adsorb phosphate without desorption.
(1) Low concentration test:
0.02g of samples (CLMO-1, CLMO-2, CLMO-3) were weighed into a conical flask and 50mL of KH of varying concentrations (1,2,3,4,5,6,8, 10mg P/L, pH=7) were added 2 PO 4 A solution. Then the solution was shaken in a constant temperature shaking incubator at a temperature of 25.+ -. 0.5 ℃ and a rotational speed of 180rpm for 24 hours, and the sample was taken out. The supernatant was passed through a 0.45 μm microporous filter membrane, and the phosphorus concentration was measured by ammonium molybdate spectrophotometry, and the test was repeated 3 times.
FIG. 11 is fourSeed sample in low concentration simulated water body (C) 0 =1 to 10mg P/L) of the residual concentration after adsorption. The result shows that the residual concentration of CLMO-1 and CLMO-2 is less than 0.02mg/L under the condition of the initial phosphate concentration of 1-10 mg/L, wherein the CLMO-2 has higher removal rate to the phosphate of the water body, and the residual concentration after LMO treatment is within 0.04mg/L, and can reach the standard of below United States Environmental Protection Agency (USEPA) regulated by 0.05mg/L. Thus combining adsorption performance and cost considerations, ca 0.4 La 0.6 MnO 3 The sample is more suitable for treating water bodies with the actual concentration lower than 5mg P/L, the application range of CLMO-2 is wider, and the sample has good dephosphorization effect on water bodies within the range of 1-10 mg P/L.
(2) Long-term adsorption and repeated adsorption test:
to verify the adsorption of CLMO-2 to low concentration phosphate (initial ph=7, sampling time=1, 2,3,4, 6,8, 10, 12, 15 days). The initial low-concentration simulated wastewater (400 mL,3mg P/L phosphate) was placed in a 500mL Erlenmeyer flask. CLMO-2 (0.4 g/L) was added to the flask and the reaction flask was shaken at 180rpm for 24h. After 60 minutes of standing, the solution was separated and fresh phosphate (400 mL,3mg P/L) was added again at low concentration without the need to add CLMO-2 sample again. These procedures were repeated eight times to investigate the ability of CLMO-2 samples to manage phosphate for long periods without desorption. In addition, conditions of dynamic adsorption in rivers were also simulated. These processes lasted 25 days (sampling times of day 1, day 2, day 3, day 5, day 7, day 10, day 13, day 18 and day 25). In a typical experiment, CLMO-2 (0.4. 0.4 g/L) was placed in 400mL of initial phosphate simulated wastewater (5 mg P/L) on a shaker at 180rpm, and the supernatant was intermittently extracted for analysis. Then, the phosphate of high concentration was dropped into a triangular flask to keep the phosphate at 5mg P/L. This procedure was repeated seven times, CLMO-2 was always immersed in the reaction solution, and the extracted solution was filtered through a 0.45 μm filter membrane for analysis, and the test was repeated 3 times.
The lanthanum-based perovskite has high selectivity on phosphate, can be widely applied to the treatment of various phosphorus-containing water bodies, and has excellent performance under the condition of low phosphorus concentration. And evaluating that lanthanum-based perovskite repeatedly adsorbs or adsorbs low-concentration phosphate water bodies for a long time under the condition of not desorbing has more important practical significance.
As a result, CLMO-2 can adsorb phosphate several times without desorption, as shown in FIG. 12. CLMO-2 can reach the maximum adsorption amount of phosphate in the previous 4 rounds of adsorption. The adsorption capacity of each round is reduced to a certain extent, and the adsorption is carried out after 8 rounds of adsorption under the condition of no desorption. The blank group accumulated about 24 mg/L, and the cumulative removal rate of CLMO-2 reached 87.9%.
The long-term adsorption test for 24 days proves that the lanthanum-based perovskite has the capacity of long-term phosphate management as shown in figure 13, and the result shows that the CLMO-2 has good adsorption effect on phosphate, and the residual phosphate in each round is less than 0.05mg/L. After 9 high concentration phosphate cycles, the blank group accumulated about 45mg/L of phosphate, and the accumulated removal rate of CLMO-2 reached 98.8%. Comprehensive repeated adsorption and long-term adsorption test results show that CLMO-2 still has good adaptability and adsorption capacity under the condition of no desorption, and the problem of unsatisfactory adsorption and desorption effects of lanthanum-based materials is solved to a certain extent.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (7)
1. The application of the Ca/La-based perovskite adsorption material is characterized in that the preparation method of the Ca/La-based perovskite adsorption material comprises the following steps:
s1, adding anhydrous calcium chloride and lanthanum nitrate hexahydrate into deionized water to form a solution a;
s2, sequentially adding manganese nitrate tetrahydrate, absolute ethyl alcohol, ethylene glycol and water into the solution a;
s3, keeping the temperature in a high-pressure reaction kettle at 120-200 ℃ for 24 hours, and cooling to room temperature;
s4, drying the extracted solid, calcining at 400-1000 ℃, and cooling to room temperature to obtain Ca x La 1-x MnO 3 A powder;
the Ca is x La 1-x MnO 3 The surface morphology of the powder can form a structure with mesopores inside micron-sized macropores, and the structure is used for adsorbing phosphate in water.
2. Use of a Ca/La based perovskite adsorption material according to claim 1, wherein in step S1 0.4439g anhydrous calcium chloride and 6.9280g lanthanum nitrate hexahydrate are added to 20mL deionized water, respectively.
3. Use of a Ca/La based perovskite adsorption material according to claim 1, wherein in step S1 0.8879g anhydrous calcium chloride and 5.1960g lanthanum nitrate hexahydrate are added to 20mL deionized water, respectively.
4. Use of a Ca/La based perovskite adsorption material according to claim 1, wherein in step S1 1.5537g anhydrous calcium chloride and 2.5980g lanthanum nitrate hexahydrate are added to 20mL deionized water, respectively.
5. Use of the Ca/La based perovskite adsorption material according to any one of claims 2 to 4, wherein 5.325mL of manganese nitrate tetrahydrate, 80mL of absolute ethanol, 20mL of ethylene glycol and 20mL of water are added in this order to the solution a in step S2.
6. The use of a Ca/La based perovskite adsorption material according to claim 1, wherein in step S4, the drying temperature is 60-120 ℃, the calcination is performed in air at 400 ℃ for 2 hours, and the calcination is performed in air at 600-1000 ℃ for 4 hours.
7. Use of a Ca/La based perovskite adsorption material according to claim 1, wherein the Ca x La 1- x MnO 3 The powder can be reused to adsorb phosphate without desorption.
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