CN112547021A - Biomass-based hydroxyapatite composite material and preparation method and application thereof - Google Patents
Biomass-based hydroxyapatite composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a biomass-based hydroxyapatite composite material and a preparation method and application thereof, the composite material takes a biomass material as a substrate, after water washing, drying, crushing, screening, alkali washing, acid washing, alcohol washing and drying pretreatment, a pretreated biomass material is prepared, the pretreated biomass material is firstly added into a phosphate solution to load phosphate radicals, then is added into a calcium salt solution with alkaline pH for in-situ precipitation reaction, and finally is aged, filtered and dried to prepare the biomass-based hydroxyapatite composite material, the solid loading amount of the hydroxyapatite is 1 to 20 percent, the preparation process is simple, the cost is low, no secondary pollution is caused, the prepared composite material combines the high adsorption reaction activity and the exclusive adsorption property of the hydroxyapatite with the agglomeration prevention and convenient operation properties of a carrier, and has higher fluorine adsorption amount in a fluorine-polluted water body, thereby providing an effective way for the comprehensive utilization of agricultural waste resources, and simultaneously provides reliable technical support for the deep removal of the fluorine ions in the water.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, and particularly relates to a biomass-based hydroxyapatite composite material and a preparation method and application thereof.
Background
Fluorine is one of the essential elements in the earth's system that are involved in the metabolic processes of organisms, however, excessive fluorine intake has adverse effects on animals, plants and humans. Fluoride contamination in groundwater threatens millions of people worldwide, however, it is difficult for conventional precipitation or coagulation methods to reduce fluoride below the world health organization specified fluorine standard (1.5 mg/L) in a cost-effective manner. For example, due to CaF2The solubility of the fluoride is higher, and the fluoride is difficult to reduce below 8mg/L by calcium salt precipitation; while coagulation requires a large amount of aluminum salt (up to 1200 mg/L) to reduce fluoride to below 1.5mg/L and pH<5, the acid environment can accelerate the dissolution of aluminum into the water environment, thus posing a threat to human health.
At present, the treatment method for removing fluoride in water mainly comprises the following steps: precipitation-coagulation, membrane filtration, ion exchange and adsorption (J. Hazard. Mater. 2006, 137 (1), 456-. Among them, the adsorption method is widely used because of its advantages of high efficiency, low cost, easy operation, environmental protection, etc. The most commonly used defluorinating adsorbents are metal oxides such as activated alumina, zirconia, etc., or porous materials such as activated carbon, clays, zeolites, etc. The adsorbents such as active carbon, clay, zeolite and the like usually enrich fluorine ions through self-rich pore channel structures, and the adsorption effect is nonspecific. While metal inorganic oxides such as activated alumina, zirconia and the like can form coordination bonds and complexes with fluoride ions through Lewis acid-base complexation (J. Am. chem. Soc., 1965, 87(16), 3571-3577), so that specific binding is realized, however, the stability of the activated alumina under acidic and alkaline conditions is poor, and the adsorption of the zirconia to fluoride is highly dependent on acidic pH, so that the practical application is influenced.
Hydroxyapatite (HAP) is used as a main component of human bones and teeth, has good biocompatibility, is a calcium phosphate salt with a pH value of 4-12 and very stable at normal temperature, and is widely applied to the fields of medical treatment, environmental protection and the like. HAP is ubiquitous in nature and fluoride ions in groundwater can be adsorbed thereon to form thermodynamically more stable Fluorapatite (FAP). Owing to the special crystal structure and surface characteristics of HAP, HAP has effective adsorption and selectivity to fluorine ions and heavy metal ions, and has attracted much attention in recent years. However, HAP usually exists in the form of ultrafine particles, and has the problems of easy agglomeration and inactivation, large pressure drop of water, difficult separation and recovery, difficult desorption and regeneration and the like in water, so that the application of HAP in the actual water treatment process is greatly limited. The composite material prepared by fixing HAP on large-particle carriers with rich pore channels, such as activated carbon, carbon nanotubes, zeolite, high-molecular resin, biomass and the like, is an effective way for solving the problems. For example, in the 2017 scholars' paper of souqing, the preparation, characterization and defluorination performance research of hydroxyapatite and composite materials thereof is disclosed, the activated carbon-hydroxyapatite composite material and carbon nanotube-hydroxyapatite are synthesized in situ by a chemical precipitation method and applied and defluorination research is carried out, however, the preparation process of the raw materials of the activated carbon and the carbon nanotube is complex, the cost is high, and the carbon nanotube also has certain toxicity. For example, CN110252261A discloses a resin-based nano-hydroxyapatite composite material, a preparation method thereof, and an application thereof in the treatment of fluorine-contaminated water, wherein a polymer resin is selected as a carrier, and nano-hydroxyapatite particles are immobilized in polymer resin pores to prepare the composite material, however, a large amount of toxic organic reagents are used in the synthesis of the polymer material, the synthesis process is complex, the preparation cost is high, and toxic intermediate byproducts are generated, which causes serious secondary pollution.
In recent years, agricultural waste resource utilization is widely concerned, and on one hand, the agricultural waste can be used as a high-quality carrier and can be directly or after modification used for adsorbing pollution ions in wastewater due to large area, high physical structure porosity and large amount of active groups; on the other hand, the traditional adsorbent has low efficiency and high cost when treating low-concentration fluorine-polluted wastewater, and is easy to cause secondary pollution, and the agricultural wastes have the characteristics of low cost, wide sources, reproducibility and the like, so that the defects can be well remedied.
Disclosure of Invention
The invention aims to solve the technical problems of the prior art and provides a biomass-based hydroxyapatite composite material and a preparation method and application thereof, the biomass-based hydroxyapatite composite material takes agricultural waste biomass materials as a carrier, hydroxyapatite is immobilized on a biomass substrate by an in-situ precipitation method to prepare the biomass-based hydroxyapatite composite material, so that the high adsorption reaction activity and the special adsorption characteristic of hydroxyapatite are combined with the characteristics of agglomeration prevention and convenient operation of the carrier, the technical defects of low adsorption efficiency, high preparation cost, easy secondary pollution, poor selectivity and the like of the traditional defluorination adsorbent are effectively solved, the problems of easy agglomeration and inactivation, large pressure drop of water, difficult separation and recovery, difficult desorption and regeneration and the like of hydroxyapatite particles in water are solved, and an effective way is provided for the comprehensive utilization of agricultural waste resources, and simultaneously provides reliable technical support for the deep removal of the fluorine ions in the water.
In order to achieve the technical purpose, the technical scheme adopted by the invention is as follows: a preparation method of a biomass-based hydroxyapatite composite material comprises the following steps:
step S1, taking a certain amount of biomass material, cleaning the biomass material by distilled water, drying the biomass material to constant weight, crushing the biomass material by a vibration crusher, and sieving the crushed biomass material by a sieve of 10-60 meshes for later use;
step S2, carrying out alkali washing swelling on the biomass material obtained by screening in the step S1, and washing with water until the effluent is neutral;
step S3, fully pickling and oxidizing the biomass material obtained after alkali washing swelling and water washing in the step S2, filtering, and washing with water until the effluent is neutral;
step S4, washing the biomass material obtained after acid washing, oxidation and water washing in the step S3 with ethanol, and then drying the biomass material at 100 ℃ for 24 hours to obtain a pretreated biomass material;
step S5, carrying out phosphorylation addition on the pretreated biomass material obtained in the step S4, and then filtering and drying to obtain a phosphorylated biomass material;
step S6, adding the phosphorylated biomass material obtained in the step S5 into a calcium salt solution with alkaline pH for in-situ precipitation reaction, and standing and aging at room temperature after the reaction is finished;
and S7, filtering the biomass material aged in the step S6, washing with water until the effluent is neutral, then leaching with ethanol, and drying at 40-60 ℃ for 24h to obtain the biomass-based hydroxyapatite composite material.
Further, in step S1, the biomass material is one of bagasse, orange peel, corncob, peanut shell, rice hull, walnut shell, wood dust and bamboo dust, wherein the bagasse, orange peel, corncob and peanut shell have high content of holocellulose, so that a rich pore structure is provided, the solid content of hydroxyapatite is favorably improved, the peanut shell, rice hull, walnut shell, wood dust and bamboo dust have high content of lignin, the peanut shell, rice hull, walnut shell, wood dust and bamboo dust are endowed with rigidity and are not easy to rot, the recycling and the reusing of the adsorbent are favorably realized, and the particle size of the sieved biomass material is between 0.25mm and 2 mm.
Further, in the step S2, the alkali washing swelling method includes soaking the biomass material obtained by screening in the step S1 in an alkali solution at normal temperature for 3-6 hours, wherein the solute of the alkali solution is sodium hydroxide or potassium hydroxide, the concentration of the alkali solution is 1-2M, and the adding ratio of the biomass material in the alkali solution is 20 g/L.
In step S3, the acid washing and oxidizing method includes soaking the biomass material obtained after the alkali washing and swelling and water washing in step S2 for 3-6 hours at normal temperature with a permanganate solution, wherein the mixing mass ratio of the biomass material and the permanganate is 100: 0.5-2, and the permanganate is any one of potassium permanganate and sodium permanganate.
Further, in step S5, the phosphorylation addition reaction method includes adding the pretreated biomass material into a phosphate solution with a concentration of 0.3-1M, mixing and stirring at a speed of 200-400 rpm at 25-60 ℃, and reacting for 12-24 hours, wherein a ratio of a mass of the pretreated biomass material in g to a volume of the phosphate solution in mL is 1:25, the phosphate solution is one of a trisodium phosphate solution, a disodium hydrogen phosphate solution, and a diammonium hydrogen phosphate solution, filtering after the reaction is finished, and drying for 12 hours at 40-60 ℃ to obtain the phosphorylated biomass material.
Further, in step S6, the phosphorylated biomass material obtained in step S5 is slowly added into a calcium ion solution with a concentration of 0.5-1.67M, the pH of the reaction system is maintained at 10-11 with ammonia water, the mixture is stirred at a speed of 200-400 rpm at 25-60 ℃, the reaction is performed for 1-2 hours, and then the mixture is left to stand and aged for 12-24 hours at room temperature, wherein the ratio of the mass of the biomass material in g to the volume of the calcium ion solution in mL is 1:25, and the calcium ion solution is one of a calcium chloride solution or a calcium nitrate solution.
The invention also provides a biomass-based hydroxyapatite composite material prepared by the preparation method.
The invention also provides application of the biomass-based hydroxyapatite composite material in adsorption treatment of fluorine ions in fluorine-polluted water, wherein the fluorine-polluted water comprises fluorine-polluted water containing strong competitive ions, and the strong competitive ions are ions having strong competitive adsorption with the fluorine ions.
Further, the adsorbed biomass-based hydroxyapatite composite material is desorbed and regenerated through an alkali salt mixed solution, wherein the alkali in the alkali salt mixed solution is sodium hydroxide or potassium hydroxide, the salt is sodium chloride or potassium chloride, and the mass concentrations of the alkali and the salt are both 2-15%.
Compared with the prior art, the invention has the beneficial effects that:
1) the invention provides a biomass-based hydroxyapatite composite material, which takes a biomass material as a substrate, avoids the problem of easy agglomeration of ultrafine particle hydroxyapatite due to the limited domain effect of rich pore structure, is derived from original agricultural wastes, has the characteristics of simple raw material preparation, low cost, wide source and the like compared with carriers such as activated carbon, carbon nano tubes, resin and the like, can effectively reduce the environmental pollution problem caused by random accumulation and incineration of the biomass material as an adsorbent raw material while saving the cost, realizes the resource utilization of the agricultural wastes, and has certain social and economic values;
2) the biomass-based hydroxyapatite composite material uses a biomass material as a matrix, hydroxyapatite particles are loaded on the surface of the biomass and in a pore channel through liquid-phase in-situ precipitation, the composite material combines the high adsorption reaction activity and the exclusive adsorption property of the hydroxyapatite with the characteristics of carrier agglomeration prevention and convenient operation, and has higher fluorine adsorption capacity in a fluorine-polluted water body, the composite material carries out deep treatment on the fluorine-polluted water body, can reduce the concentration of fluorine ions in a certain amount of the fluorine-polluted water body to below 1.5mg/L, has high fluorine removal efficiency, still keeps higher adsorption capacity on the fluorine ions in a strong competitive ion system, and has specific adsorption;
3) the biomass-based hydroxyapatite composite material takes biomass materials as a matrix to immobilize the hydroxyapatite in the preparation process, the modifier and inorganic matters used in the preparation are nontoxic and harmless, secondary pollution can not be caused, the preparation cost is low, the process is simple, the prepared composite material can be recycled and regenerated, the resource utilization rate is high, and the biomass-based hydroxyapatite composite material is suitable for treating actual fluorine-polluted wastewater and is suitable for large-scale preparation and application.
Detailed Description
In order to make those skilled in the art better understand the technical solution of the present invention, the following detailed description will be made with reference to some embodiments.
The experimental procedures used in the examples below are, unless otherwise specified, conventional procedures and the reagents, methods and equipment used are, unless otherwise specified, conventional in the art.
The invention provides a biomass-based hydroxyapatite composite material, which is prepared by immobilizing hydroxyapatite by taking a biomass material as a matrix, combines the high adsorption reaction activity and the special adsorption property of the hydroxyapatite with the characteristics of carrier agglomeration prevention and convenient operation, has higher fluorine adsorption capacity in a fluorine-polluted water body, and has specific adsorption on fluorine ions in a strong competitive ion system.
The preparation method of the biomass-based hydroxyapatite composite material comprises the following steps:
step S1: taking a certain amount of biomass material, cleaning the biomass material by using distilled water, drying the biomass material to constant weight, crushing the biomass material by using a vibration crusher, and sieving the biomass material by using a sieve with 10-60 meshes for later use; the biomass material is one of bagasse, orange peel, corncob, peanut shell, rice hull, walnut shell, wood chip and bamboo chip, wherein the bagasse, orange peel, corncob and peanut shell have high content of holocellulose, so that a rich pore structure is provided, the solid loading amount of hydroxyapatite is favorably improved, the lignin content of the peanut shell, the rice hull, walnut shell, wood chip and bamboo chip is higher, rigidity is provided, the peanut shell, the rice hull, the walnut shell, the wood chip and the bamboo chip are not easy to rot, the recycling of an adsorbent is favorably realized, and the particle size of screened particles is between 0.25 and 2 mm;
step S2: carrying out alkali washing swelling on the biomass material obtained by screening in the step S1, soaking the biomass material for 3-6 hours at normal temperature by using an alkali solution, and washing the biomass material to be neutral by using water after the soaking is finished, wherein the solute of the alkali solution is sodium hydroxide or potassium hydroxide, and the adding ratio of the biomass material to the alkali solution is 20g/L, wherein the concentration of the alkali solution is 1-2M;
step S3: carrying out acid washing oxidation on the biomass material obtained by swelling in the step S2, soaking the biomass material for 3-6 hours at normal temperature by using a permanganate solution, and washing the biomass material to be neutral by using water after the soaking is finished; wherein the mass ratio of the biomass material in g to the permanganate in g is 100: 0.5-2; wherein the permanganate is potassium permanganate or sodium permanganate;
step S4: leaching the biomass material oxidized in the step S3 with ethanol, and drying at 100 ℃ for 24h to obtain a pretreated biomass material;
step S5: adding the pretreated biomass material obtained in the step S4 into a phosphate solution with the concentration of 0.3-1M for phosphorylation addition reaction, mixing and stirring at the speed of 200-400 rpm at 25-60 ℃, reacting for 12-24 h, wherein the ratio of the mass of the biomass material in g to the volume of the phosphate solution in mL is 1:25, filtering after the reaction is finished, and drying at 40-60 ℃ for 12h to obtain a phosphorylated biomass material; wherein the phosphate ion solution is one of trisodium phosphate solution, disodium hydrogen phosphate solution or diammonium hydrogen phosphate solution;
step S6: slowly adding the phosphorylated biomass material obtained in the step S5 into a calcium ion solution with the concentration of 0.5-1.67M, maintaining the pH value of a reaction system at 10-11 by using ammonia water, mixing and stirring at the speed of 200-400 rpm at 25-60 ℃, reacting for 1-2 h, and then standing and aging for 12-24 h at room temperature, wherein the ratio of the mass of the biomass material in g to the volume of the calcium ion solution in mL is 1: 25; the calcium ion solution is one of calcium chloride solution or calcium nitrate solution;
step S7: and (4) filtering the biomass material aged in the step S6, washing with water until the effluent is neutral, then leaching with ethanol, and drying at 40-60 ℃ for 24h to obtain the biomass-based hydroxyapatite composite material.
The prepared biomass-based hydroxyapatite composite material is used for treating fluorine-polluted water, the initial concentration of fluorine in water is 10mg/L, the adding amount of an adsorbent is 0.5g/L, and the adsorption amount of fluorine (the average adsorption amount of fluorine per gram calculated by the composite material) is 2-6 mg under the conditions that the reaction temperature is 25 ℃ and the pH = 7.
Further, when the fluorine-polluted water body comprises a fluorine-polluted water body containing strong competitive ions, and the strong competitive ions are ions having a strong competitive adsorption effect with fluorine ions, the prepared biomass-based hydroxyapatite composite material is used for treating the fluorine-polluted water body containing the strong competitive ions (containing 1g/L sulfate ions), the initial concentration of fluorine in water is 10mg/L, the adding amount of an adsorbent is 0.5g/L, the reaction temperature is 25 ℃, and the adsorption amount of fluorine is 1-3 mg/g under the condition of pH = 7.
Further, the adsorbed biomass-based hydroxyapatite composite material is desorbed and regenerated through an alkali salt mixed solution, the elution time is 12-24 hours, preferably 12 hours, wherein the alkali in the alkali salt mixed solution is sodium hydroxide or potassium hydroxide, the salt is sodium chloride or potassium chloride, and the mass concentrations of the alkali and the salt are both 2% -15%.
Example 1
The biomass-based hydroxyapatite composite material is prepared by taking a biomass material as a carrier and immobilizing hydroxyapatite on the biomass substrate through an in-situ precipitation method.
The specific preparation method of the biomass-based hydroxyapatite composite material comprises the following steps:
step S1: taking fresh biomass material bagasse, cleaning with distilled water, drying to constant weight, crushing with a vibration crusher, and sieving with a 18-mesh sieve for later use, wherein the average particle size is 2 mm;
step S2: and (3) soaking the biomass material obtained by screening in the step (S1) in 1M sodium hydroxide solution at normal temperature for 3h, wherein the adding ratio of the biomass material is 20g/L (20 g of biomass material is added in each liter of sodium hydroxide solution), the biomass material is fully washed by alkali and swelled, then filtered, and washed by water until the effluent is neutral.
Step S3: and (3) soaking the biomass material obtained after the alkali washing swelling and water washing in the step S2 in 0.1g/L potassium permanganate solution for 3h at normal temperature, wherein the adding ratio of the biomass material is 20g/L, filtering the biomass material after full acid washing oxidation, and washing with water until the effluent is neutral.
Step S4: carrying out ethanol leaching on the biomass material obtained after acid washing oxidation and water washing in the step S3, and then drying for 24h at 100 ℃ to obtain a pretreated biomass material;
step S5: adding the pretreated biomass material obtained in the step S4 into trisodium phosphate solution with the concentration of 0.5M for phosphorylation addition reaction, mixing and stirring at the speed of 200rpm at 40 ℃, reacting for 12 hours, wherein the ratio of the mass of the biomass material in g to the volume of the phosphate solution in mL is 1:25, filtering after the reaction is finished, and drying for 12 hours at 40 ℃ to obtain a phosphorylated biomass material;
step S6: slowly adding the phosphorylated biomass material obtained in the step S5 into a calcium chloride solution with the concentration of 1.67M, adjusting the pH value of a reaction system to be 10-11 by using ammonia water, mixing and stirring at the speed of 200rpm at 40 ℃, reacting for 1h, and standing and aging for 24h at room temperature, wherein the ratio of the mass of the biomass material in g to the volume of the calcium ion solution in mL is 1: 25;
step S7: and (4) filtering the biomass material aged in the step (S6), washing with water until the effluent is neutral, then leaching with ethanol, and drying at 60 ℃ for 24h to obtain the biomass-based hydroxyapatite composite material, wherein the solid loading of hydroxyapatite is 15%.
The biomass-based hydroxyapatite composite material of the embodiment is applied to the treatment of a fluorine-polluted water body, the initial concentration of fluorine ions in water is 10mg/L, the dosage of the biomass-based hydroxyapatite composite material (hereinafter, "adsorbent" refers to "biomass-based hydroxyapatite composite material") is 0.5g/L, the reaction temperature is 25 ℃, and the adsorption amount of fluorine is 4.9mg/g under the condition of pH = 7.
And (3) eluting the adsorbent after adsorbing the fluoride ions for 12h by using an alkali salt mixed solution of 5wt% of sodium hydroxide and 5wt% of sodium chloride, continuously using the desorbed adsorbent for next cycle adsorption, wherein the addition amount of the regenerated adsorbent is 0.5g/L, the reaction temperature is 25 ℃, and the adsorption amount of fluorine is 4.0mg/g under the condition of pH = 7.
The biomass-based hydroxyapatite composite material of the embodiment is applied to a fluorine-polluted water body with strong competitive ions (containing 1g/L of sulfate ions) for treatment, the initial concentration of fluorine in the water is 10mg/L, the dosage of the adsorbent is 0.5g/L, the reaction temperature is 25 ℃, and the adsorption amount of fluorine is 1.8mg/g under the condition of pH = 7.
Example 2
Step S1: cleaning fresh biomass material peanut shells with distilled water, drying to constant weight, crushing by using a vibration crusher, and sieving with a 40-mesh sieve for later use, wherein the average particle size of the peanut shells is 0.5 mm;
step S2: and (4) soaking the biomass material obtained by screening in the step S1 in 1.5M sodium hydroxide solution for 3h at normal temperature, wherein the adding ratio of the biomass material is 20g/L, the biomass material is fully washed by alkali and swelled, then filtered, and washed by water until the effluent is neutral.
Step S3: and (4) soaking the biomass material obtained by swelling in the step (S2) in 0.2g/L potassium permanganate solution for 3h at normal temperature, wherein the adding ratio of the biomass material is 20g/L, filtering after the biomass material is sufficiently acid-washed and oxidized, and washing with water until the effluent is neutral.
Step S4: leaching the biomass material oxidized in the step S3 with ethanol, and drying at 100 ℃ for 24h to obtain a pretreated biomass material;
step S5: adding the pretreated biomass material obtained in the step S4 into a diammonium hydrogen phosphate solution with the concentration of 0.6M for phosphorylation addition reaction, mixing and stirring at the speed of 300rpm at 50 ℃, reacting for 12 hours, wherein the ratio of the mass of the biomass material in g to the volume of a phosphate solution in mL is 1:25, filtering after the reaction is finished, and drying for 12 hours at 50 ℃ to obtain a phosphorylated biomass material;
step S6: slowly adding the phosphorylated biomass material obtained in the step S5 into a calcium nitrate solution with the concentration of 1M, adjusting the pH value of a reaction system to be 10-11 by using ammonia water, mixing and stirring at the speed of 300rpm at 50 ℃, reacting for 1.5h, and standing and aging for 24h at room temperature, wherein the ratio of the mass of the biomass material in g to the volume of the calcium ion solution in mL is 1: 25;
step S7: and (4) filtering the biomass material aged in the step (S6), washing with water until the effluent is neutral, then leaching with ethanol, and drying at 60 ℃ for 24h to obtain the biomass-based hydroxyapatite composite material, wherein the solid loading of the hydroxyapatite is 18%.
The biomass-based hydroxyapatite composite material of the embodiment is applied to the treatment of fluorine-polluted water, the initial concentration of fluorine in water is 10mg/L, the addition amount of the adsorbent is 0.5g/L, and the adsorption amount of fluorine is 5.6 mg/g under the conditions that the reaction temperature is 25 ℃ and the pH = 7.
And (3) eluting the adsorbent after adsorbing the fluoride ions for 12h by using an alkali salt mixed solution of 5wt% of sodium hydroxide and 5wt% of sodium chloride, continuously using the desorbed adsorbent for next cycle adsorption, wherein the addition amount of the regenerated adsorbent is 0.5g/L, the reaction temperature is 25 ℃, and the adsorption amount of fluorine is 4.2mg/g under the condition of pH = 7.
The biomass-based hydroxyapatite composite material of the embodiment is applied to a fluorine-polluted water body with strong competitive ions (containing 1g/L of sulfate ions) for treatment, the initial concentration of fluorine in the water is 10mg/L, the dosage of the adsorbent is 0.5g/L, the reaction temperature is 25 ℃, and the adsorption amount of fluorine is 2.9mg/g under the condition of pH = 7.
Example 3
Step S1: cleaning fresh bamboo scraps of a biomass material by using distilled water, drying to constant weight, crushing by using a vibration crusher, and sieving by using a 60-mesh sieve for later use, wherein the average particle size of the bamboo scraps is 0.25 mm;
step S2: and (4) soaking the biomass material obtained by screening in the step S1 in 2M sodium hydroxide solution at normal temperature for 3h, wherein the adding ratio of the biomass material is 20g/L, the biomass material is fully washed by alkali and swelled, then filtered, and washed by water until the effluent is neutral.
Step S3: and (4) soaking the biomass material obtained by swelling in the step (S2) in 0.4g/L potassium permanganate solution for 3h at normal temperature, wherein the adding ratio of the biomass material is 20g/L, filtering after the biomass material is sufficiently acid-washed and oxidized, and washing with water until the effluent is neutral.
Step S4: leaching the biomass material oxidized in the step S3 with ethanol, and drying at 100 ℃ for 24h to obtain a pretreated biomass material;
step S5: adding the pretreated biomass material obtained in the step S4 into a disodium hydrogen phosphate solution with the concentration of 1M for phosphorylation addition reaction, mixing and stirring at the speed of 300rpm at 60 ℃, reacting for 24 hours, wherein the ratio of the mass of the biomass material in g to the volume of a phosphate solution in mL is 1:25, filtering after the reaction is finished, and drying at 50 ℃ for 12 hours to obtain a phosphorylated biomass material;
step S6: slowly adding the phosphorylated biomass material obtained in the step S5 into a calcium chloride solution with the concentration of 1.67M, adjusting the pH value of a reaction system to be 10-11 by using ammonia water, mixing and stirring at the speed of 300rpm at 50 ℃, reacting for 2 hours, and standing and aging for 24 hours at room temperature, wherein the ratio of the mass of the biomass material in g to the volume of the calcium ion solution in mL is 1: 25;
step S7: and (4) filtering the biomass material aged in the step (S6), washing with water until the effluent is neutral, then leaching with ethanol, and drying at 60 ℃ for 24h to obtain the biomass-based hydroxyapatite composite material, wherein the solid loading of hydroxyapatite is 8%.
The biomass-based hydroxyapatite composite material is applied to the treatment of fluorine-polluted water, the initial concentration of fluorine in water is 10mg/L, the adding amount of an adsorbent is 0.5g/L, the adsorption amount of fluorine is 2.5mg/g under the conditions that the reaction temperature is 25 ℃ and the pH = 7.
And (3) eluting the adsorbent after adsorbing the fluoride ions for 12h by using an alkali salt mixed solution of 5wt% of sodium hydroxide and 5wt% of sodium chloride, continuously using the desorbed adsorbent for next cycle adsorption, wherein the addition amount of the regenerated adsorbent is 0.5g/L, the reaction temperature is 25 ℃, and the adsorption amount of fluorine is 1.7mg/g under the condition of pH = 7.
The biomass-based hydroxyapatite composite material is applied to a fluorine-polluted water body with strong competitive ions (containing 1g/L of sulfate ions) for treatment, the initial concentration of fluorine in the water is 10mg/L, the addition amount of the adsorbent is 0.5g/L, and the adsorption amount of the adsorbent to fluorine is 1.0 mg/g.
Example 4
The biomass-based hydroxyapatite composite material can be used for inspecting the fluorine treatment capacity of the material through a column adsorption dynamic test. Taking examples 1-3 as examples, the specific experimental steps are as follows:
preparing simulated fluorine-containing sewage: f−Concentration of 5mg/L, HCO3 −/SO4 2−/ Cl−/ NO3 −/ Ca2+/ Mg2+The concentration is respectively 150mg/L, 100mg/L, 8mg/L, 15mg/L and 5mg/L, the pH of the inlet solution is 8.1 +/-0.2, the wet volume dosage of the adsorbent is 5mL, the flow rate is 15-30min/BV, and the effluent fluorine ion concentration meeting the standard is F−<1.5mg/L, the standard treatment capacity of the adsorbent prepared according to the embodiments 1-3 of the invention to the fluorine-containing sewage is 72 BV, 100 BV and 52BV respectively, and the standard treatment capacity of the pretreatment biomass material to the fluorine under the same conditions is 8 BV. And (3) eluting the adsorbent adsorbing the fluorine ions by using an alkali salt mixed solution of 5wt% of sodium hydroxide and 5wt% of sodium chloride, continuously using the desorbed adsorbent for next cycle adsorption, and respectively setting the fluorine treatment capacity of 40BV, 68 BV and 36BV of the adsorbent prepared in the examples 1-3 after regenerating for 5 times.
In addition, as a result of a comparison document (journal of the university of Segan building science and technology (Nature science edition), 2002, 34(004): 325-−In a competitive-free ion dynamic column test with the concentration of 5mg/L and the pH of the entering solution of 7.5 +/-0.2, the treatment capacity of zeolite to fluorine-containing sewage is 15-30 BVThe treatment capacity of the fluoride-containing sewage by the alumina is 200-240 BV; when the biomass-based hydroxyapatite composite material prepared by the invention is used for defluorination research, higher defluorination efficiency can be achieved, and the combination of a specific adsorbent (hydroxyapatite) and an excellent carrier (biomass material) can effectively improve the adsorption effect and the recovery and regeneration performance of the composite material.
The above is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above-mentioned embodiments, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention. It should be noted that modifications and embellishments within the scope of the invention may be made by those skilled in the art without departing from the principle of the invention.
Claims (10)
1. A preparation method of a biomass-based hydroxyapatite composite material is characterized by comprising the following steps:
step S1, a certain amount of biomass material is taken, cleaned by distilled water, dried to constant weight, then crushed and sieved by a sieve with 10-60 meshes for later use;
step S2, carrying out alkali washing swelling on the biomass material obtained by screening in the step S1, and washing with water until the effluent is neutral;
step S3, fully pickling and oxidizing the biomass material obtained after alkali washing swelling and water washing in the step S2, filtering, and washing with water until the effluent is neutral;
step S4, sequentially carrying out ethanol leaching and drying on the biomass material obtained after acid washing oxidation and water washing in the step S3 to obtain a pretreated biomass material;
step S5, carrying out phosphorylation addition on the pretreated biomass material obtained in the step S4, and then filtering and drying to obtain a phosphorylated biomass material;
step S6, adding the phosphorylated biomass material obtained in the step S5 into a calcium salt solution with alkaline pH for in-situ precipitation reaction, and standing and aging at room temperature after the reaction is finished;
and S7, filtering the biomass material aged in the step S6, washing with water until the effluent is neutral, and then sequentially leaching with ethanol and drying to obtain the biomass-based hydroxyapatite composite material.
2. The method for preparing the biomass-based hydroxyapatite composite material according to claim 1, characterized in that: in the step S1, the biomass material is one of bagasse, orange peel, corncob, peanut shell, rice hull, walnut shell, wood chip, and bamboo dust, and the particle size of the sieved biomass material is 0.25-2 mm.
3. The method for preparing the biomass-based hydroxyapatite composite material according to claim 1, characterized in that: and in the step S2, the alkali washing swelling method comprises the step of soaking the biomass material obtained by screening in the step S1 in an alkali solution at normal temperature for 3-6 hours, wherein the solute of the alkali solution is sodium hydroxide or potassium hydroxide, the concentration of the alkali solution is 1-2M, and the adding ratio of the biomass material in the alkali solution is 20 g/L.
4. The method for preparing the biomass-based hydroxyapatite composite material according to claim 1, characterized in that: in the step S3, the acid washing oxidation method comprises the step of soaking the biomass material obtained after the alkali washing swelling and water washing in the step S2 for 3-6 hours at normal temperature by using a permanganate solution, wherein the mixing mass ratio of the biomass material to the permanganate is 100: 0.5-2, and the permanganate is any one of potassium permanganate and sodium permanganate.
5. The method for preparing the biomass-based hydroxyapatite composite material according to claim 4, characterized in that: in the step S5, the phosphorylation addition reaction method comprises the steps of adding the pretreated biomass material into a phosphate solution with the concentration of 0.3-1M, mixing and stirring at the speed of 200-400 rpm at the temperature of 25-60 ℃, and reacting for 12-24 hours, wherein the mass consumption of the pretreated biomass material and the volume ratio of the phosphate solution are 0.04g/mL, and the phosphate solution is one of a trisodium phosphate solution, a disodium hydrogen phosphate solution and a diammonium hydrogen phosphate solution.
6. The method for preparing the biomass-based hydroxyapatite composite material according to claim 5, characterized in that: in the step S6, the phosphorylated biomass material obtained in the step S5 is slowly added into a calcium ion solution with the concentration of 0.5-1.67M, ammonia water is used for maintaining the pH value of a reaction system at 10-11, the materials are mixed and stirred at the speed of 200-400 rpm at the temperature of 25-60 ℃, the reaction is carried out for 1-2 hours, then the mixture is kept stand and aged for 12-24 hours at room temperature, wherein the mass consumption of the biomass material and the volume ratio of the calcium ion solution are 0.04g/mL, and the calcium ion solution is one of a calcium chloride solution or a calcium nitrate solution.
7. A biomass-based hydroxyapatite composite material, characterized by being prepared by the method for preparing the biomass-based hydroxyapatite composite material according to any one of claims 1 to 6.
8. Use of the biomass-based hydroxyapatite composite material according to claim 7 for the adsorptive treatment of fluoride ions in a fluorine-contaminated water body.
9. Use according to claim 8, characterized in that: the fluorine-polluted water body comprises a fluorine-polluted water body containing strong competitive ions, and the strong competitive ions are ions having strong competitive adsorption with fluorine ions.
10. Use according to claim 8, characterized in that: the adsorbed biomass-based hydroxyapatite composite material is desorbed and regenerated through an alkali salt mixed solution, wherein the alkali in the alkali salt mixed solution is sodium hydroxide or potassium hydroxide, the salt is sodium chloride or potassium chloride, and the mass concentrations of the alkali and the salt are both 2-15%.
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