CN111229171A - Straw-loaded MOF material adsorbent and preparation method and application thereof - Google Patents
Straw-loaded MOF material adsorbent and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a straw-loaded MOF material adsorbent, which is prepared by adding a precursor solution for synthesizing an MOF material into straw powder, carrying out hydrothermal reaction and loading the MOF material on the straw powder. According to the invention, organic ligands, straws and iron salt solution are used as main raw materials, effective loading and particle size regulation of the MOF material on the surface of the straws are synchronously realized through one-step high-temperature hydrothermal reaction, and the obtained straw loaded MOF adsorbent has large adsorption capacity, strong external interference ion resistance and strong adaptability to actual phosphorus-containing sewage variation; the defects of small adsorption capacity, easy agglomeration in the preparation process, low adsorbent yield and the like of the MOF which is used independently can be effectively overcome, and a brand new thought can be provided for the high-efficiency MOF-based adsorption technology.
Description
Technical Field
The invention belongs to the technical field of adsorbent preparation, and particularly relates to a straw-loaded MOF material adsorbent and a preparation method and application thereof.
Background
Phosphorus is one of essential elements for the growth of animals and plants, but excessive phosphorus easily causes environmental pollution, such as eutrophication of water bodies and severe phenomena of 'water bloom' and even 'red tide'. In addition, according to 2016 Chinese water resources bulletin: for 118 lakes, the total is 3.1 km2The water surface is evaluated, the eutrophic lake accounts for 21.4 percent, the eutrophic lake accounts for 78.6 percent, in the eutrophic lake, the light eutrophic lake accounts for 62.0 percent, and the moderate eutrophic lake accounts for 38.0 percent; the water quality evaluation is carried out on 943 water reservoirs, and the evaluation result of the nutrient condition of the water reservoirs shows that the medium nutrient reservoir accounts for 71.2 percent, the eutrophic reservoir accounts for 28.8 percent, the light eutrophic reservoir accounts for 86.3 percent, the medium eutrophic reservoir accounts for 12.9 percent, the heavy eutrophic reservoir accounts for 0.8 percent, the situation is not optimistic, and the management is very urgent. The existing methods for treating phosphate in water bodies comprise a chemical method, an ion exchange method, a membrane technology method, a biological adsorption method and the like, wherein the biological adsorption method becomes a research hotspot in the field due to the advantages of simple preparation, low cost, easy popularization, good adsorption effect, easy biodegradation and the like.
Organic Metal Framework (MOF) is considered to be a class of materials that have good adsorption effects and can remove water pollutants. However, the particle size of the MOF material synthesized at present is often too large, and the adsorption efficiency of the MOF material cannot be fully exerted; and is not conducive to recycling. Therefore, further research and research on the adsorbent which is cheap, has high adsorption capacity, can be repeatedly used and has great research and application significance on the adsorbent with good effect of high-concentration phosphate.
In addition, China is a big agricultural country, according to incomplete statistics, the annual output exceeds 100 billions of tons, straws are main byproducts of crops, at present, the straws in China mainly utilize rich cellulose and are used for papermaking and preparing fertilizers for agricultural product planting, and the like, and some places only burn the straws or even directly discard the straws, so that the COD (chemical oxygen demand) of a water body is easily increased and other adverse phenomena are easily caused while a large amount of biomass resources are wasted, and the ecological environment is damaged; further exploring the high-efficiency resource utilization means of agricultural and sideline products such as straws and the like.
Disclosure of Invention
The invention mainly aims to provide a straw-loaded MOF material adsorbent, and the adsorbent can effectively solve the problems that the existing single MOF material adsorbent is difficult to recover, the adsorption capacity is low, the adsorption effect on high-concentration phosphate is poor, the required addition amount is high and the like by loading an MOF material on the surface of straws, can provide a brand new thought for an efficient MOF-based adsorption technology, can effectively realize the resource utilization of agricultural and sideline products such as straws and the like, and has important economic and environmental benefits.
In order to achieve the purpose, the invention adopts the technical scheme that:
a straw loaded MOF material adsorbent is prepared by adding a precursor solution for synthesizing an MOF material into straw powder, carrying out hydrothermal reaction, and loading the MOF material on the straw powder.
In the scheme, the precursor solution for synthesizing the MOF material comprises metal salt, an organic ligand and an organic solvent, wherein the metal salt is chloride, nitrate or sulfate of metals such as Fe, Al, Co, Cr or Zr.
In the scheme, the organic ligand is terephthalic acid and 2-X-1, 4-terephthalic acid (X is-NH)2-NO2-Cl, -Br or-I), trimesic acid or pyromellitic acid (anhydride); the organic solvent can be N, N-Dimethylformamide (DMF), methanol or ethanol, etc.
In the scheme, the fineness of the straw powder is 50-400 meshes; the particle size of the MOF material is 5-50 nm.
In the scheme, the straws are cellulose-rich agricultural wastes such as cotton stalks, wheat straws, bagasse, corn stalks, rice straws, lotus seedpods or loofah pulp.
The preparation method of the straw-loaded MOF material adsorbent comprises the following steps:
1) adding metal salt and an organic ligand into an organic solvent, preparing a precursor solution of the MOF material with metal as the center, then adding the precursor solution into straw powder, and performing ultrasonic dispersion or magnetic stirring to obtain a reaction solution;
2) heating the reaction solution obtained in the step 1) to carry out hydrothermal reaction, and after the reaction is finished, centrifuging, washing and drying the obtained reaction product to obtain the straw-loaded MOF material adsorbent.
In the scheme, the metal salt is chloride, nitrate or sulfate of Fe, Al, Co, Cr or Zr and other metals; the organic ligand is terephthalic acid, 2-X-1, 4-terephthalic acid (X is-NH)2-NO2-Cl, -Br or-I), trimesic acid or pyromellitic acid (anhydride); the organic solvent is N, N-Dimethylformamide (DMF), methanol or ethanol, etc.
In the scheme, the straw powder is prepared by sequentially removing soluble sugars and other impurities from straws in a steaming and deionized water cleaning mode for 3-5 times, and then drying and crushing, wherein the fineness of the straw powder is 50-400 meshes.
In the scheme, the concentration of the metal ions introduced into the precursor solution in the step 1) is 10-500 mmol/L.
In the scheme, the molar ratio of the metal salt to the organic ligand is (0.25-10): 1.
In the scheme, the dosage ratio of the straw powder to the precursor solution is 1 (100) -1000 g/ml.
In the scheme, the hydrothermal reaction temperature is 100-150 ℃, and the time is 12-108 h.
In the scheme, the ultrasonic dispersion power is 100-; the magnetic stirring speed is 50-300r/min, and the time is 30-240 min.
In the scheme, the centrifugal rotating speed is 4000-.
In the above scheme, the reagent used in the washing step is one or more of DMF, absolute ethanol, and absolute methanol.
In the above scheme, the drying mode can be freeze drying, normal pressure drying, reduced pressure drying and the like; and the drying temperature under normal pressure or reduced pressure is 60-180 ℃.
The straw-loaded MOF material adsorbent is applied to treating phosphate in wastewater, wherein the addition amount of the straw-loaded MOF adsorbent is 0.05-2.0g for 1L of phosphate wastewater with the concentration of 50-500 mg/L.
Compared with the prior art, the invention has the beneficial effects that:
1) the straw-loaded MOF material adsorbent disclosed by the invention takes an organic ligand, straws and an iron salt solution as main raw materials, and the synthesized MOF uniformly grows on the surfaces of the straws through one-step high-temperature hydrothermal reaction; based on the dispersion and electrostatic adsorption of the straws, the method is favorable for realizing the regulation and control of the diameter of the MOF material, preparing the MOF material with smaller particle size and synchronously realizing the effective load of the MOF active components on the straws; the obtained straw-loaded MOF adsorbent has large adsorption capacity, strong external interference ion resistance and strong adaptability to actual phosphorus-containing sewage variation; the defects that the MOF is not large in adsorption amount when used alone, the preparation process is easy to agglomerate, the yield of the adsorbent is not high and the like can be effectively overcome; in addition, the adsorbent can be stored for a long time and recycled for multiple times, and has important research prospect and important practical application value.
2) The preparation method provided by the invention is simple, mild in reaction conditions, convenient to operate, environment-friendly and easy to popularize and apply.
3) The invention has the advantages of wide source of raw materials, low cost, low price and easy obtainment, can realize the resource utilization of the straws, and has important economic benefit and environmental benefit.
Drawings
FIG. 1 is an SEM image of (a) MOF material obtained in comparative example 2 and (b) MOF adsorbent loaded straw obtained in example 1;
FIG. 2 is a TEM image of the straw-loaded MOF adsorbent obtained in example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
A straw-loaded MOF adsorbent takes bagasse as a carrier, and a preparation method thereof comprises the following steps:
1) washing the collected and squeezed bagasse with water, boiling and filtering, repeating the boiling and filtering process for 3-4 times to remove soluble sugars and other impurities, then washing with water, filtering to remove the soluble sugars and other impurities, then drying in an electrothermal blowing drying oven at 80 ℃ for 24 hours, crushing after drying, and collecting 100-mesh 200-mesh bagasse powder;
2) 0.618g of terephthalic acid was added to 50ml of FeCl3FeCl with concentration of 150.0mmol/L3Preparing precursor solution of MOF material in DMF solution, adding 0.05g of bagasse powder, and stirring for 60min at 125r/min by using a magnetic stirrer to obtain reaction solution;
3) putting the obtained reaction solution into a forced air drying oven, heating to 110 ℃, and carrying out heat preservation reaction for 20 hours to obtain a solid product; and centrifuging for 10min at 10000r/min, removing supernatant, washing with DMF and absolute ethanol for 3 times respectively, and drying in a vacuum drying oven at 70 ℃ for 12h to obtain the straw-loaded MOF adsorbent.
In the present example, the bagasse employed had a dry matter content of 90-92%; the dry matter comprises the following components in percentage by mass: 42-50% of cellulose, 25-30% of hemicellulose, 20-25% of lignin, 1.5-2.0% of crude protein, 0.2-0.9% of crude fat and 2-3% of crude ash.
The bagasse-loaded MOF adsorbent obtained in this example was applied to removal of phosphate in wastewater, and the phosphate removal effect was tested, specifically including the following steps: simulating waste water by using 25ml of potassium dihydrogen phosphate solution with the concentration of 100mg/L and the pH value of 5.3, adding 0.01g of the obtained straw-loaded MOF material into the potassium dihydrogen phosphate solution, shaking by a shaking table at 270r/min for 2.5h, standing for 40min, filtering, taking an appropriate amount of filtrate, and detecting the concentration of phosphate in the waste water by adopting an ion chromatography method.
Tests show that the bagasse-loaded MOF material obtained in the embodiment has 172.37mg/g of phosphate adsorption amount and has a large adsorption capacity.
Example 2
A straw-loaded MOF adsorbent takes cotton straws as a carrier, and a preparation method thereof comprises the following steps:
1) washing the collected and squeezed sugarcane residues with water, boiling and filtering, repeating the boiling and filtering process for 3-4 times to remove soluble sugars and other impurities, then washing with water, filtering to remove the soluble sugars and other impurities, drying in an electrothermal blowing drying box at 80 ℃ for 24h, crushing after drying, and respectively collecting cotton stalk powder of 50-100 meshes, 100-mesh and 200-mesh and 400-mesh;
2) 0.532g of p-2-aminophthalic acid was added to 50ml of FeCl3FeCl with concentration of 150.0mmol/L3Preparing precursor solution of MOF material in DMF solution, then respectively adding 0.05g of the cotton stalk powder with different particle sizes, and stirring for 40min at 150r/min by using a magnetic stirrer to obtain reaction solution;
3) putting the obtained reaction solution into a forced air drying oven, heating to 110 ℃, and carrying out heat preservation reaction for 24 hours to obtain a solid product; and centrifuging for 10min at 10000r/min, removing supernatant, washing with DMF and absolute ethanol for 3-5 times respectively, and drying in a vacuum drying oven at 70 ℃ for 10h to obtain the straw-loaded MOF adsorbent with different particle size ranges.
In this example, the dry matter content of the cotton stalk used is 88-93%; the dry matter comprises the following components in percentage by mass: 40-48% of cellulose, 23-30% of hemicellulose, 17-23% of lignin, 1.5-2.0% of crude protein, 0.9-1.9% of crude fat and 3-5% of crude ash.
The method comprises the following steps of respectively applying the cotton stalks with different particle sizes (50-100 meshes, 100-200 meshes and 200-400 meshes) loaded with the MOF and the MOF adsorbent obtained without adding the cotton stalks to remove phosphate in wastewater, and testing the removal effect of the phosphate, wherein the method specifically comprises the following steps: simulating waste water by using 25ml of potassium dihydrogen phosphate solution with the concentration of 100mg/L and the pH value of 5.3, adding 0.01g of cotton stalk loaded MOF material into the potassium dihydrogen phosphate solution, shaking by a shaking table at 270r/min for 2.5h, standing for 40min, filtering, taking an appropriate amount of filtrate, and detecting the concentration of phosphate in the waste water by adopting an ion chromatography method.
Tests show that the MOF material loaded on the cotton stalks of 50-100 meshes, 100-200 meshes and 200-400 meshes and the MOF material not loaded on the cotton stalks obtained in the embodiment respectively have the adsorption capacity of 103.25mg/g, 132.37mg/g and 134.75mg/g for phosphate radical, and the size of the cotton stalks has a certain regulation effect on the adsorption effect of the obtained adsorbent.
Example 3
A straw-loaded MOF adsorbent takes rice straws as a carrier, and the preparation method comprises the following steps:
1) washing collected and squeezed sugarcane residues with water, boiling and filtering, repeating the boiling and filtering process for 3-4 times to remove soluble sugars and other impurities, then washing with water, filtering to remove the soluble sugars and other impurities, drying in an electrothermal blowing drying box at 80 ℃ for 24 hours, crushing after drying, and collecting 200-mesh 400-mesh straw powder;
2) 0.476g of trimesic acid was added to 50ml and FeCl3FeCl with concentration of 150.0mmol/L3Preparing precursor solution of MOF material in DMF solution, then adding 0.025g, 0.05g, 0.075g and 0.01g of rice straw powder respectively, and stirring for 45min at 100r/min by using a magnetic stirrer to obtain reaction solution;
3) putting the obtained reaction solution into a forced air drying oven, heating to 100 ℃, and carrying out heat preservation reaction for 24 hours to obtain a solid product; centrifuging for 10min at 10000r/min, removing supernatant, washing with DMF and anhydrous ethanol for 3-5 times, and drying in a vacuum drying oven at 100 deg.C for 12 hr to obtain straw-loaded MOF adsorbent with different loading effects.
In this example, the dry matter content of the used rice straw is 90-94%; the dry matter comprises the following components in percentage by mass: 40-50% of cellulose, 21-30% of hemicellulose, 18-29% of lignin, 1.0-1.8% of crude protein, 0.1-0.7% of crude fat and 1-3% of crude ash.
The rice straw loaded MOF adsorbents with different loading effects obtained in the embodiment are respectively applied to removing phosphate in wastewater, and the phosphate removal effect is tested, and the method specifically comprises the following steps: simulating waste water by using 25ml of potassium dihydrogen phosphate solution with the concentration of 100mg/L and the pH value of 5.3, adding 0.01g of the obtained rice straw loaded MOF material into the potassium dihydrogen phosphate solution, shaking by a shaking table at 270r/min for 2.5h, standing for 40min, filtering, taking an appropriate amount of filtrate, and detecting the concentration of phosphate in the waste water by adopting an ion chromatography method.
Tests show that when the adding amounts of the rice straws are respectively 0.025g, 0.05g, 0.075g and 0.01g, the obtained rice straw loaded MOF material has 117.33mg/g, 172.37mg/g, 120.35mg/g and 101.35mg/g of phosphate adsorption amount, has larger adsorption capacity, and the introduction amount of the rice straws has a certain regulation and control effect on the loading effect and the adsorption performance.
Example 4
A straw-loaded MOF adsorbent takes bagasse as a carrier, and a preparation method thereof comprises the following steps:
1) washing the collected and squeezed bagasse with water, boiling and filtering, repeating the boiling and filtering process for 3-4 times to remove soluble sugars and other impurities, then washing with water, filtering to remove the soluble sugars and other impurities, freeze-drying, crushing after drying, and collecting 200-mesh 400-mesh bagasse powder;
2) 0.400g of pyromellitic acid was added to 50ml of FeCl3FeCl with concentration of 150.0mmol/L3Preparing precursor solution of MOF material in DMF solution, adding 0.05g of bagasse powder, and stirring for 45min at 100r/min by using a magnetic stirrer to obtain reaction solution;
3) putting the obtained reaction solution into a forced air drying oven, heating to 130 ℃, and carrying out heat preservation reaction for 16 hours to obtain a solid product; centrifuging for 10min at 9000r/min, removing supernatant, washing with DMF and anhydrous ethanol for 3-5 times, and drying in a vacuum drying oven at 150 deg.C for 8 hr to obtain the straw-loaded MOF adsorbent.
In the present example, the bagasse employed had a dry matter content of 90-92%; the dry matter comprises the following components in percentage by mass: 42-50% of cellulose, 25-30% of hemicellulose, 20-25% of lignin, 1.5-2.0% of crude protein, 0.2-0.9% of crude fat and 2-3% of crude ash.
The bagasse-loaded MOF adsorbent obtained in this example was applied to removal of phosphate in wastewater, and the phosphate removal effect was tested under different pH conditions, specifically including the following steps: simulating waste water by 25ml of potassium dihydrogen phosphate solution with the concentration of 100mg/L and the pH values of 2.0, 5.3, 9.0 and 12.5 respectively, adding 0.01g of the obtained straw-loaded MOF material into the potassium dihydrogen phosphate solution, shaking for 2.5 hours by a shaking table at 270r/min, standing for 30 minutes, filtering, taking a proper amount of filtrate, and detecting the concentration of phosphate in the waste water by an ion chromatography method; the test results show that the bagasse-loaded MOF material obtained in the example has the absorption capacity of 159.28mg/g, 142.37mg/g, 129.27mg/g and 78.79mg/g for phosphate under the condition of pH 2.0, 5.3, 9.0 or 12.5, respectively, and the obtained adsorbent can adapt to the influence of wastewater with a wide range of pH values.
The bagasse-loaded MOF adsorbent obtained in the embodiment is applied to removal of phosphate in wastewater, and the phosphate removal effect under the influence of different calcium ions is tested, and the method specifically comprises the following steps: simulating waste water by using 25ml of phosphate solution with the concentration of 100mg/L and simultaneously containing 40mg/L,80mg/L,120mg/L and 160mg/L of calcium ions and pH value of 5.3 respectively, adding 0.01g of straw-loaded MOF material into the phosphate, shaking by a shaking table at 270r/min for 2.5h, standing for 30min, filtering, taking a proper amount of filtrate, and detecting the concentration of the phosphate in the waste water by adopting an ion chromatography method; the test result shows that: in the phosphate respectively containing 40mg/L,80mg/L,120mg/L and 160mg/L calcium ions, the adsorption amounts of the obtained adsorbents to the phosphate are 161.37mg/g, 163.54mg/g, 164.88mg/g and 166.68mg/g respectively, which shows that the bagasse loaded MOF adsorbent of the embodiment can synergistically adsorb phosphate under the action of the calcium ions, and shows that the strong adaptability for treating the actual phosphate-containing sewage is shown.
The bagasse-loaded MOF adsorbent obtained in the embodiment is applied to removal of phosphate in wastewater, and the phosphate removal effect under the influence of different magnesium ions is tested, and the method specifically comprises the following steps: simulating waste water by using 25ml of phosphate solution with the concentration of 100mg/L and simultaneously containing 24mg/L,48mg/L,72mg/L and 96mg/L of magnesium ions and the pH value of 5.3 respectively, adding 0.01g of straw-loaded MOF material into the phosphate, shaking by a shaking table at 270r/min for 2.5h, standing for 30min, filtering, taking a proper amount of filtrate, and detecting the concentration of the phosphate in the waste water by adopting an ion chromatography method; the test result shows that: in phosphate solutions containing 24mg/L,48mg/L,72mg/L and 96mg/L of magnesium ions respectively, the adsorption amounts of the obtained adsorbents to phosphate are 153.43mg/g, 153.59mg/g, 155.26mg/g and 157.70mg/g respectively, which shows that the straw-loaded MOF adsorbent obtained in the embodiment can synergistically adsorb phosphate under the action of strong acidity and the presence of magnesium ions, and the surface of the adsorbent has strong adaptability for treating actual phosphate-containing sewage.
Example 5
A straw-loaded MOF adsorbent takes bagasse as a carrier, and a preparation method thereof comprises the following steps:
1) washing the collected and squeezed bagasse with water, boiling and filtering, repeating the boiling and filtering process for 3-4 times to remove soluble sugars and other impurities, then washing with water, filtering to remove the soluble sugars and other impurities, then drying in vacuum at 45 ℃ for 12-20h, crushing after drying, and collecting bagasse powder of 200 meshes and 400 meshes;
2) 0.675g of 2-aminoterephthalic acid was added to 50ml of FeCl3FeCl with concentration of 150.0mmol/L3Preparing precursor solution of MOF material in DMF solution, adding 0.05g of bagasse powder, and stirring for 45min at 100r/min by using a magnetic stirrer to obtain reaction solution;
3) putting the obtained reaction solution into a forced air drying oven, heating to 130 ℃, and carrying out heat preservation reaction for 16 hours to obtain a solid product; centrifuging for 10min at 9000r/min, removing supernatant, washing with DMF and anhydrous ethanol for 3-5 times, and drying in a vacuum drying oven at 150 deg.C for 8 hr to obtain the straw-loaded MOF adsorbent.
In the present example, the bagasse employed had a dry matter content of 90-92%; the dry matter comprises the following components in percentage by mass: 42-50% of cellulose, 25-30% of hemicellulose, 20-25% of lignin, 1.5-2.0% of crude protein, 0.2-0.9% of crude fat and 2-3% of crude ash.
The bagasse-loaded MOF adsorbent obtained in this example was applied to removal of phosphate in wastewater, and the phosphate removal effect was tested, specifically including the following steps: simulating waste water by using 25ml of potassium dihydrogen phosphate solution with the concentration of 100mg/L and the pH value of 5.3, adding 0.01g of the obtained straw loaded with an MOF material into the potassium dihydrogen phosphate solution, shaking by a shaking table at 270r/min for 2.5h, standing for 30min, filtering, taking a proper amount of filtrate, and detecting the concentration of phosphate in the waste water by adopting an ion chromatography method; the test result shows that the bagasse-loaded MOF material obtained in the example has 197.10mg/g of phosphate adsorption capacity and relatively large adsorption capacity.
Example 6
A straw loaded MOF adsorbent takes vegetable sponge as a carrier, and a preparation method thereof comprises the following steps:
1) collecting loofah pulp, washing with water, boiling and filtering, repeating the boiling and filtering process for 3-4 times to remove soluble saccharides and other impurities, washing with water, filtering to remove the soluble saccharides and other impurities, freeze-drying, crushing after drying, and collecting bagasse powder of 200 meshes and 400 meshes;
2) 0.662g of trimesic acid and FeCl are added in 50ml of trimesic acid and stirred with a magnetic stirrer at 100r/min for 45min3FeCl with concentration of 150.0mmol/L3Preparing precursor solution of MOF material in DMF solution, adding 0.05g of bagasse powder, and stirring for 30min at 120r/min by using a magnetic stirrer to obtain reaction solution;
3) putting the obtained reaction solution into a forced air drying oven, heating to 120 ℃, and carrying out heat preservation reaction for 16 hours to obtain a solid product; centrifuging for 10min at 9000r/min, removing supernatant, washing with DMF and anhydrous ethanol for 3-5 times, and drying in a vacuum drying oven at 150 deg.C for 8 hr to obtain the straw-loaded MOF adsorbent.
In this example, the dry matter content of the vegetable sponge used was 94-97%; the dry matter comprises the following components in percentage by mass: 45-55% of cellulose, 22-30% of hemicellulose, 15-25% of lignin, 0.5-1.2% of crude protein, 0.1-0.5% of crude fat and 1-2% of crude ash.
The loofah sponge MOF-loaded adsorbent obtained in the embodiment is applied to removal of phosphate in wastewater, and the phosphate removal effect is tested, and the method specifically comprises the following steps: simulating waste water by using 25ml of potassium dihydrogen phosphate solution with the concentration of 100mg/L and the pH value of 5.3, adding 0.01g of the obtained straw loaded with an MOF material into the potassium dihydrogen phosphate solution, shaking by a shaking table at 270r/min for 2.5h, standing for 30min, filtering, taking a proper amount of filtrate, and detecting the concentration of phosphate in the waste water by adopting an ion chromatography method; test results show that the sponge gourd loaded MOF material obtained in the embodiment has 173.40mg/g of phosphate radical adsorption amount and has a larger adsorption capacity.
Example 7
A straw-loaded MOF adsorbent takes straws as a carrier, and a preparation method thereof comprises the following steps:
1) collecting wheat straws, washing with water, boiling and filtering, repeating the boiling and filtering process for 3-4 times to remove soluble sugars and other impurities, then washing with water, filtering to dry, further removing the soluble sugars and other impurities, then drying in vacuum at 55 ℃ for 12-20h, crushing after drying is finished, and collecting wheat straw powder of 200 meshes and 400 meshes;
2) 0.4g of pyromellitic acid was added to 50ml of FeCl3FeCl with concentration of 150.0mmol/L3Preparing a precursor solution of the MOF material in a DMF solution, then adding 0.05g of wheat straw powder, and stirring for 30min at 120r/min by using a magnetic stirrer to obtain a reaction solution;
3) putting the obtained reaction solution into a forced air drying oven, heating to 120 ℃, and carrying out heat preservation reaction for 16 hours to obtain a solid product; centrifuging for 10min at 9000r/min, removing supernatant, washing with DMF and anhydrous ethanol for 3-5 times, and drying in a vacuum drying oven at 150 deg.C for 8 hr to obtain the straw-loaded MOF adsorbent.
In the embodiment, the dry matter content of the adopted wheat straw is 89-93%; the dry matter comprises the following components in percentage by mass: 40-51% of cellulose, 22-33% of hemicellulose, 18-25% of lignin, 1.0-2.5% of crude protein, 0.6-1.7% of crude fat and 2-3% of crude ash.
The straw-loaded MOF adsorbent obtained in the embodiment is applied to removal of phosphate in wastewater, and the phosphate removal effect is tested, and the method specifically comprises the following steps: simulating waste water by using 25ml of potassium dihydrogen phosphate solution with the concentration of 100mg/L and the pH value of 5.3, adding 0.01g of the obtained straw loaded with an MOF material into the potassium dihydrogen phosphate solution, shaking by a shaking table at 270r/min for 2.5h, standing for 30min, filtering, taking a proper amount of filtrate, and detecting the concentration of phosphate in the waste water by adopting an ion chromatography method; test results show that the straw-loaded MOF material obtained in the embodiment has 133.29mg/g of phosphate adsorption amount and relatively large adsorption capacity.
Example 8
A straw-loaded MOF adsorbent takes bagasse as a carrier, and a preparation method thereof comprises the following steps:
1) washing the collected and squeezed bagasse with water, boiling and filtering, repeating the boiling and filtering process for 3-4 times to remove soluble sugars and other impurities, then washing with water, filtering to remove the soluble sugars and other impurities, drying in an electrothermal blowing drying oven at 80 ℃ for 24 hours, crushing after drying, and collecting 200-mesh 300-mesh bagasse powder;
2) 0.532g of terephthalic acid and 0.512g of 2-amino-terephthalic acid were added to 50ml of AlCl3AlCl with concentration of 150.0mmol/L3Preparing precursor solution of MOF material in DMF solution, adding 0.05g of bagasse powder, and stirring for 30min at 100r/min by using a magnetic stirrer to obtain reaction solution;
3) putting the obtained reaction solution into a forced air drying oven, heating to 130 ℃, and carrying out heat preservation reaction for 48 hours to obtain a solid product; and centrifuging for 10min at 8000r/min, discarding supernatant, washing with DMF and anhydrous ethanol for 3 times respectively, and drying in a vacuum drying oven at 70 deg.C for 12h to obtain the straw-loaded MOF adsorbent.
In the present example, the bagasse employed had a dry matter content of 90-92%; the dry matter comprises the following components in percentage by mass: 42-50% of cellulose, 25-30% of hemicellulose, 20-25% of lignin, 1.5-2.0% of crude protein, 0.2-0.9% of crude fat and 2-3% of crude ash.
The bagasse-loaded MOF adsorbent obtained in this example was applied to removal of phosphate in wastewater, and the phosphate removal effect was tested, specifically including the following steps: simulating waste water by using 25ml of potassium dihydrogen phosphate solution with the concentration of 100mg/L and the pH value of 5.3, adding 0.01g of the obtained straw-loaded MOF material into the potassium dihydrogen phosphate solution, shaking by a shaking table at 270r/min for 2.5h, standing for 40min, filtering, taking an appropriate amount of filtrate, and detecting the concentration of phosphate in the waste water by adopting an ion chromatography method.
Tests show that the bagasse-loaded MOF material obtained in the embodiment has 152.44mg/g and 187.53mg/g of phosphate adsorption amount, and has a larger adsorption capacity.
The above case is the case of synthesizing MOF-loaded straw material with Fe and Al as the center, and similar conclusions can be obtained after loading straw with other organic ligands and MOF material with Fe, Al, Co, Cr, Zr and other metal centers, which are not listed here.
Comparative example 1
A pure straw-based material is prepared by the following steps:
the method comprises the steps of collecting cotton stalks, wheat straws, bagasse, corn stalks, rice straws, lotus seeds or loofah pulp, boiling and filtering, repeating the boiling and filtering process for 3-4 times to remove soluble sugars and other impurities, then washing with water, filtering to remove the soluble sugars and other impurities, drying for 24 hours in an electrothermal blowing drying oven at 80 ℃, crushing after drying, crushing and collecting 200-mesh 400-mesh straw-based materials.
Comparative example 2
A MOF adsorbent, the preparation method of which comprises the following steps:
0.618g of terephthalic acid was added to 50ml of FeCl3FeCl with concentration of 150.0mmol/L3Preparing a precursor solution of the MOF material in a DMF solution, stirring for 60min at 125r/min by using a magnetic stirrer to obtain a reaction solution, putting the reaction solution into a forced air drying box, heating to 110 ℃, and carrying out heat preservation reaction for 20h to obtain a solid product; and centrifuging for 10min at 10000r/min, removing supernatant, washing with DMF and absolute ethanol for 3 times respectively, and drying in a vacuum drying oven at 70 ℃ for 12h to obtain the straw-loaded MOF adsorbent.
Comparative example 3
A MOF adsorbent, the preparation method of which comprises the following steps:
2) 0.532g of p-2-aminophthalic acid was added to 50ml of FeCl3FeCl with concentration of 150.0mmol/L3Preparing precursor solution of MOF material in DMF solution, and stirring with a magnetic stirrer at 150r/min for 40min to obtain reaction solution; putting the reaction solution into a forced air drying oven, heating to 110 ℃, and carrying out heat preservation reaction for 24 hours to obtain a solid product; and centrifuging for 10min at 10000r/min, removing supernatant, washing with DMF and absolute ethanol for 3-5 times respectively, and drying in a vacuum drying oven at 70 ℃ for 10h to obtain the straw-loaded MOF adsorbent with different particle size ranges.
Comparative example 4
0.476g of trimesic acid was added to 50ml of FeCl3FeCl with concentration of 150.0mmol/L3Preparing precursor solution of MOF material in DMF solution, and stirring for 45min at 100r/min by using a magnetic stirrer to obtain reaction solution; putting the obtained reaction solution into a forced air drying oven, heating to 100 ℃, and carrying out heat preservation reaction for 24 hours to obtain a solid product; centrifuging for 10min at 10000r/min, removing supernatant, washing with DMF and anhydrous ethanol for 3-5 times, and drying in a vacuum drying oven at 100 deg.C for 12 hr to obtain straw-loaded MOF adsorbent with different loading effects.
Comparative example 5
A MOF adsorbent, the preparation method of which comprises the following steps:
0.400g of pyromellitic acid was added to 50ml of FeCl3FeCl with concentration of 150.0mmol/L3Preparing precursor solution of MOF material in DMF solution, and adding 0.05g bagasseStirring the powder for 45min at a speed of 100r/min by using a magnetic stirrer to obtain a reaction solution, putting the reaction solution into a forced air drying oven, heating the reaction solution to 130 ℃, and carrying out heat preservation reaction for 16h to obtain a solid product; centrifuging for 10min at 9000r/min, removing supernatant, washing with DMF and anhydrous ethanol for 3-5 times, and drying in a vacuum drying oven at 150 deg.C for 8 hr to obtain the straw-loaded MOF adsorbent.
FIG. 1 is a scanning electron microscope image of the straw-supported MOF adsorbent obtained in example 1 of the present invention and the MOF adsorbent obtained in comparative example 2, and FIG. 2 is a transmission electron microscope image of the straw-supported MOF adsorbent obtained in example 1 of the present invention; the result shows that the straw is introduced in the synthesis process of the MOF material, so that the effective load of the MOF material on the surface of straw particles is realized, the particle size of the MOF material can be further regulated, and the MOF material with smaller size and better dispersibility is obtained.
The MOF adsorbent obtained in the comparative examples 1-5 is applied to removing phosphate in wastewater, and the phosphate removal effect is tested, and the method specifically comprises the following steps: simulating waste water by 25ml of potassium dihydrogen phosphate solution with the concentration of 100mg/L and the pH value of 5.3, adding 0.01g of MOF material into the potassium dihydrogen phosphate solution, shaking by a shaking table at 270r/min for 2.5h, standing for 40min, filtering, taking a proper amount of filtrate, and detecting the concentration of phosphate in the waste water by an ion chromatography method.
The test result shows that: the absorption amounts of the straw-based material based on cotton stalks, wheat straws, bagasse, corn stalks, rice straws, lotus seeds or loofah pulp obtained in the comparative example 1 to phosphate are respectively 0.07mg/g, 0.02mg/g, 0.03mg/g, 0.03mg/g, 0.01mg/g and 0.05mg/g, which indicates that the straw-based material has poor absorption effect on phosphate radical; the adsorption amounts of the MOF materials obtained in the comparative examples 2-5 to phosphate are 100.37mg/g, 90.77mg/g, 97.67mg/g and 102.32mg/g respectively, which shows that the adsorption performance of the obtained adsorbent can be obviously improved by loading the MOF materials on the surfaces of the straws, the actual dosage of the MOF active materials can be reduced, and a brand new thought can be provided for the preparation of high-performance MOF-based adsorption materials.
The above embodiments are merely examples for clearly illustrating the present invention and do not limit the present invention. Other variants and modifications of the invention, which are obvious to those skilled in the art and can be made on the basis of the above description, are not necessary or exhaustive for all embodiments, and are therefore within the scope of the invention.
Claims (10)
1. A straw-loaded MOF material adsorbent is characterized in that a precursor solution for synthesizing an MOF material is added into straw powder to carry out hydrothermal reaction, and the straw powder is loaded with the MOF material.
2. The straw-loaded MOF material adsorbent of claim 1, wherein a precursor solution of the synthetic MOF material comprises a metal salt, an organic ligand and an organic solvent, wherein the metal salt is a chloride, nitrate or sulfate of Fe, Al, Co, Cr or Zr.
3. The straw-loaded MOF material adsorbent of claim 1, wherein the straw powder has a fineness of 50-400 mesh.
4. The straw-loaded MOF material adsorbent of claim 1, wherein the straw is cotton stalk, wheat straw, bagasse, corn stalk, rice straw, lotus seedpod or loofah.
5. A preparation method of the straw-loaded MOF material adsorbent as claimed in any one of claims 1 to 4, characterized by comprising the following steps:
1) adding metal salt and an organic ligand into an organic solvent to prepare a precursor solution for synthesizing the MOF material, then adding the precursor solution into straw powder, and performing ultrasonic dispersion or magnetic stirring uniformly to obtain a reaction solution;
2) heating the reaction solution obtained in the step 1) to carry out hydrothermal reaction, and after the reaction is finished, centrifuging, washing and drying the obtained reaction product to obtain the straw-loaded MOF material adsorbent.
6. The production method according to claim 5, wherein the metal salt is a chloride, nitrate or sulfate of Fe, Al, Co, Cr or Zr; the organic ligand is terephthalic acid, trimesic acid, pyromellitic anhydride or 2-X-1, 4-terephthalic acid, wherein X is-NH2，-NO2-Cl, -Br or-I.
7. The preparation method according to claim 5, wherein the concentration of the iron ions introduced into the precursor solution in step 1) is 10 to 500 mmol/L; the molar ratio of the metal salt to the organic ligand is (0.25-10): 1.
8. The preparation method as claimed in claim 5, wherein the dosage ratio of the straw powder to the precursor solution is 1 (100) g: ml.
9. The preparation method as claimed in claim 5, wherein the hydrothermal reaction temperature is 100-150 ℃ and the time is 12-108 h.
10. The application of the straw-loaded MOF material adsorbent disclosed by any one of claims 1 to 4 or obtained by the preparation process disclosed by any one of claims 5 to 9 in the field of phosphate in wastewater treatment, is characterized in that the addition amount of the straw-loaded MOF adsorbent is 0.05-2.0g for 1L of wastewater with phosphate concentration of 50-500 mg/L.
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