WO2022088309A1 - 一种生物质基羟基磷灰石复合材料及其制备方法和应用 - Google Patents

一种生物质基羟基磷灰石复合材料及其制备方法和应用 Download PDF

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WO2022088309A1
WO2022088309A1 PCT/CN2020/130008 CN2020130008W WO2022088309A1 WO 2022088309 A1 WO2022088309 A1 WO 2022088309A1 CN 2020130008 W CN2020130008 W CN 2020130008W WO 2022088309 A1 WO2022088309 A1 WO 2022088309A1
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biomass
solution
composite material
biomass material
hydroxyapatite composite
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PCT/CN2020/130008
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English (en)
French (fr)
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叶美晨
胡志超
陈辰
丁长春
梁红超
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南京长三角绿色发展研究院有限公司
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Publication of WO2022088309A1 publication Critical patent/WO2022088309A1/zh

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
    • B01J20/0292—Phosphates of compounds other than those provided for in B01J20/048
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/12—Halogens or halogen-containing compounds
    • C02F2101/14—Fluorine or fluorine-containing compounds

Definitions

  • the invention relates to the technical field of wastewater treatment, in particular to a biomass-based hydroxyapatite composite material and a preparation method and application thereof.
  • Fluorine is one of the essential elements involved in the metabolism of organisms in the earth system.
  • excessive fluoride intake will have adverse effects on animals, plants and humans.
  • Fluoride contamination in groundwater threatens millions of people worldwide, yet traditional precipitation or coagulation methods are difficult to cost-effectively reduce fluoride to below the World Health Organization fluoride standard (1.5mg/L) .
  • CaF2 World Health Organization fluoride standard
  • coagulation requires large amounts of aluminium salts (up to 1200mg/L) to reduce fluoride to 1.5mg/L Below, and the acidic environment of pH ⁇ 5 will accelerate the dissolution of aluminum into the water environment, posing a threat to human health.
  • the treatment methods for removing fluoride in water mainly include: precipitation-coagulation method, membrane filtration method, ion exchange method and adsorption method (J. Hazard. Mater. 2006, 137(1), 456-463).
  • the adsorption method is widely used because of its high efficiency, low cost, easy operation and environmental protection.
  • the most commonly used defluorination adsorbents are metal oxides such as activated alumina, zirconia, etc., or porous substances such as activated carbon, clay, zeolite, etc.
  • adsorbents such as activated carbon, clay, and zeolite often enrich fluoride ions through their own rich pore structure, and the adsorption is non-specific.
  • metal inorganic oxides such as activated alumina, zirconia, etc. can form coordination bonds, complexes with fluoride ions through Lewis acid-base complexation (J.Am.Chem.Soc., 1965, 87(16), 3571-3577).
  • activated alumina under acidic and basic conditions
  • the stability of activated alumina under acidic and basic conditions is poor, and the adsorption of fluoride by zirconia is highly dependent on acidic pH, which affects the practical application.
  • HAP Hydroxyapatite
  • FAP fluoroapatite Due to the special crystal structure and surface characteristics of HAP, HAP has effective adsorption and selectivity for fluoride ions and heavy metal ions, which has attracted extensive attention in recent years.
  • HAP usually exists in the form of ultrafine particles, and has problems such as easy agglomeration and deactivation in water, large pressure drop over water, difficult separation and recovery, and difficulty in desorption and regeneration, which greatly limits its application in practical water treatment processes.
  • the composite materials prepared by immobilizing HAP on large particle carriers with abundant pores, such as activated carbon, carbon nanotubes, zeolites, polymer resins, biomass, etc. are an effective way to solve the above problems.
  • the preparation, characterization and fluoride removal performance of hydroxyapatite and its composites were disclosed, and activated carbon-hydroxyapatite composites, carbon nanotubes, and carbon nanotubes were synthesized in situ by chemical precipitation method.
  • the technical problem to be solved by the present invention is to provide a biomass-based hydroxyapatite composite material and a preparation method and application thereof for the deficiencies of the prior art.
  • the biomass-based hydroxyapatite composite material is made of agricultural waste biomass.
  • the material is used as a carrier, and the hydroxyapatite is immobilized on the biomass matrix by the in-situ precipitation method to prepare a biomass-based hydroxyapatite composite material, so as to combine the high adsorption reactivity and exclusive adsorption characteristics of hydroxyapatite with
  • the combination of the carrier's anti-agglomeration and convenient operation characteristics effectively solves the technical disadvantages of traditional defluorination adsorbents such as low adsorption efficiency, high preparation cost, easy to cause secondary pollution, poor selectivity, etc.
  • the problems of agglomeration and deactivation, large pressure drop over water, difficult separation and recovery, and difficulty in desorption and regeneration provide an effective way for the comprehensive utilization of agricultural waste resources,
  • the technical solution adopted in the present invention is: a preparation method of a biomass-based hydroxyapatite composite material, comprising the following steps:
  • step S1 a certain amount of biomass material is taken, washed with distilled water, dried to constant weight, pulverized by a vibrating pulverizer, and sieved through 10-60 mesh for subsequent use;
  • Step S2 after performing alkaline washing and swelling on the biomass material obtained by screening in step S1, washing with water until the effluent is neutral;
  • Step S3 the biomass material obtained after alkali washing, swelling and water washing in step S2 is fully acid washed and oxidized, then filtered, and washed with water until the effluent is neutral;
  • Step S4 performing ethanol rinsing on the biomass material obtained after acid washing, oxidation and water washing in step S3, and then drying at 100° C. for 24 hours to obtain pretreated biomass material;
  • Step S5 subjecting the pretreated biomass material obtained in step S4 to phosphorylation addition, filtering and drying to obtain phosphorylated biomass material;
  • Step S6 adding the phosphorylated biomass material obtained in step S5 to an in-situ precipitation reaction in a calcium salt solution with an alkaline pH, and then allowing to stand at room temperature for aging after completion of the reaction;
  • step S7 the biomass material after the aging in step S6 is filtered, washed with water until the effluent is neutral, then rinsed with ethanol, and dried at 40-60° C. for 24 hours to obtain a biomass-based hydroxyapatite composite material.
  • the biomass material is one of bagasse, orange peel, corncob, peanut husk, rice husk, walnut husk, sawdust, and bamboo chip, wherein bagasse, orange peel, corncob, Peanut husks have high holocellulose content, which endows them with rich pore structure, which is beneficial to increase the immobilization capacity of hydroxyapatite. It is rigid and not easy to rot, which is beneficial to the recycling and regeneration of adsorbents.
  • the particle size of the sieved biomass material is between 0.25 and 2 mm.
  • step S2 the method for alkali washing and swelling is to soak the biomass material obtained by sieving in step S1 at normal temperature for 3-6 hours, wherein the alkali solution solute is sodium hydroxide or potassium hydroxide , the concentration of the alkaline solution is 1-2M, and the dosing ratio of the biomass material in the alkaline solution is 20g/L.
  • the alkali solution solute is sodium hydroxide or potassium hydroxide
  • the concentration of the alkaline solution is 1-2M
  • the dosing ratio of the biomass material in the alkaline solution is 20g/L.
  • step S3 the method of pickling and oxidation is to soak the biomass material obtained after alkali washing, swelling and water washing in step S2 with a permanganate solution at room temperature for 3-6 hours, wherein the biomass material and high manganese
  • the mixed mass ratio of the acid salt is 100:0.5-2
  • the permanganate is any one of potassium permanganate or sodium permanganate.
  • the phosphorylation addition reaction method is as follows: adding the pretreated biomass material to a phosphate solution with a concentration of 0.3-1M, mixing and stirring at a speed of 200-400rpm at 25-60°C, and reacting. 12-24h, wherein the ratio of the mass of the pretreated biomass material in g to the volume of the phosphate solution in mL is 1:25, and the phosphate solution is trisodium phosphate solution, disodium hydrogen phosphate solution, One of the diammonium hydrogen phosphate solutions is filtered after the reaction is completed, and dried at 40-60° C. for 12 hours to obtain a phosphorylated biomass material.
  • step S6 the phosphorylated biomass material obtained in step S5 is slowly added to the calcium ion solution with a concentration of 0.5-1.67M, and the pH value of the reaction system is maintained at 10-11 with ammonia water, and the pH value of the reaction system is maintained at 25-60° C. Mix and stir at a speed of 200-400 rpm, react for 1-2 hours, and then stand 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, the calcium ion solution is a kind of in calcium chloride solution or calcium nitrate solution.
  • the present invention also provides a biomass-based hydroxyapatite composite material, which is prepared by the above-mentioned preparation method.
  • the present invention also provides the use of the above-mentioned biomass-based hydroxyapatite composite material for adsorbing and treating fluorine ions in fluorine-contaminated water bodies, wherein the fluorine-contaminated water bodies include fluorine-contaminated water bodies containing strong competitive ions, and the strong competitive ions are Fluoride ion has a strong competitive adsorption ion.
  • the adsorbed biomass-based hydroxyapatite composite material is desorbed and regenerated by an alkali-salt mixed solution, wherein the alkali in the alkali-salt mixed solution is sodium hydroxide or potassium hydroxide, and the salt is sodium chloride or chloride. Potassium, and the mass concentration of alkali and salt are both 2% to 15%.
  • the present invention provides a biomass-based hydroxyapatite composite material, the composite material is based on biomass material, and the confinement effect of its rich pore structure avoids the problem of easy agglomeration of ultra-fine particle hydroxyapatite, Moreover, biomass materials are derived from original agricultural wastes. Compared with carriers such as activated carbon, carbon nanotubes, and resins, biomass materials have the characteristics of simple raw material preparation, low cost, and wide sources. As an adsorbent raw material, it can save costs while saving costs. Effectively reduce the environmental pollution caused by random accumulation and incineration, and realize the resource utilization of agricultural waste, which has certain social and economic value;
  • the biomass-based hydroxyapatite composite material of the present invention takes the biomass material as the matrix, and supports the hydroxyapatite particles on the surface of the biomass and inside the pores through in-situ precipitation in the liquid phase. Combining the high adsorption reactivity and exclusive adsorption characteristics of the carrier with the anti-agglomeration and convenient operation characteristics of the carrier, it has a high fluorine adsorption capacity in the fluorine-contaminated water body.
  • the concentration of fluoride ion in the fluorine-polluted water body is reduced to below 1.5mg/L, the fluorine removal efficiency is high, and the fluoride ion still maintains a high adsorption capacity in the strong competitive ion system, and has specific adsorption;
  • the biomass material is used as the matrix to immobilize the hydroxyapatite, and the modifier and inorganic substances used in the preparation are non-toxic and harmless, and will not cause secondary problems. pollution, low preparation cost, simple process, the prepared composite material can be recycled and regenerated, and the resource utilization rate is high.
  • the invention provides a biomass-based hydroxyapatite composite material, which uses biomass material as a matrix to immobilize hydroxyapatite, and the prepared biomass-based hydroxyapatite composite material has high adsorption capacity of hydroxyapatite.
  • the reactivity and exclusive adsorption characteristics are combined with the anti-agglomeration and convenient operation characteristics of the carrier, which has a high fluorine adsorption capacity in fluorine-contaminated water, and has specific adsorption to fluoride ions in a strong competitive ion system.
  • the preparation method of the biomass-based hydroxyapatite composite material of the present invention comprises the following steps:
  • Step S1 take a certain amount of biomass material, clean it with distilled water, dry it to constant weight, pulverize it with a vibrating pulverizer, and sieve it with 10-60 meshes for subsequent use; wherein, the biomass material is bagasse, orange peel, corncob, One of peanut husks, rice husks, walnut husks, wood chips, and bamboo chips.
  • bagasse, orange peel, corn cob, and peanut husks have high cellulose content, giving them a rich pore structure, which is conducive to improving hydroxyapatite
  • the solid load of the stone, the lignin content of peanut husk, rice husk, walnut husk, sawdust and bamboo shavings is high, which gives it rigidity and is not easy to rot, which is conducive to the recycling and regeneration of adsorbents, and the particle size after sieving.
  • Step S2 perform alkaline washing and swelling on the biomass material obtained by screening in step S1, soak it in an alkaline solution at room temperature for 3 to 6 hours, and wash it with water to neutrality after the soaking, wherein the solute of the alkaline solution is sodium hydroxide or potassium hydroxide , the concentration of the alkaline solution is 1-2M, and the dosing ratio of the biomass material in the alkaline solution is 20g/L;
  • Step S3 pickling and oxidizing the swollen biomass material obtained in step S2, soaking it in a permanganate solution at room temperature for 3 to 6 hours, and washing it with water until neutral after soaking; wherein the mass of the biomass material is in g
  • the mass ratio with permanganate in g is 100:0.5 ⁇ 2; wherein permanganate is potassium permanganate or sodium permanganate;
  • Step S4 the biomass material obtained by the oxidation in step S3 is washed with ethanol, and then dried at 100° C. for 24 hours to obtain the pretreated biomass material;
  • Step S5 adding the pretreated biomass material obtained in step S4 into a phosphate solution with a concentration of 0.3-1M for phosphorylation addition reaction, mixing and stirring at a speed of 200-400rpm at 25-60°C, and reacting for 12- 24h, wherein the ratio of the mass of the biomass material in g to the volume of the phosphate solution in mL is 1:25, filter after the reaction is completed, and dry at 40-60 ° C for 12h to obtain 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 add the phosphorylated biomass material obtained in step S5 into the calcium ion solution with a concentration of 0.5-1.67M, maintain the pH value of the reaction system at 10-11 with ammonia water, and keep the pH value of the reaction system at 25-60 °C at 200- Mix and stir at a speed of 400 rpm, react for 1 to 2 hours, and then stand at room temperature for 12 to 24 hours, 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; calcium The ionic solution is one of calcium chloride solution or calcium nitrate solution;
  • Step S7 filter the biomass material after the aging in step S6, wash with water until the effluent is neutral, then rinse with ethanol, and dry at 40-60° C. for 24 hours to obtain a biomass-based hydroxyapatite composite material.
  • the biomass-based hydroxyapatite composite material prepared above was used to treat fluorine-contaminated water bodies.
  • the initial concentration of fluorine in the water was 10 mg/L
  • the dosage of the adsorbent was 0.5 g/L
  • the reaction temperature was 25 °C
  • the fluorine-contaminated water body includes a fluorine-contaminated water body containing strong competitive ions
  • the strong competitive ions are ions that have strong competitive adsorption with fluorine ions
  • the biomass-based hydroxyapatite composite material prepared above is used for The fluorine-contaminated water with strong competing ions (containing 1g/L sulfate ion) is treated.
  • 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°C
  • the pH 7 conditions
  • the adsorption amount of fluorine is 1 to 3 mg/g.
  • the adsorbed biomass-based hydroxyapatite composite material is desorbed and regenerated by the alkali salt mixed solution, and the elution time is 12 to 24 hours, preferably 12 hours, wherein the alkali in the alkali salt mixed solution is sodium hydroxide or hydroxide Potassium and salt are sodium chloride or potassium chloride, and the mass concentrations of alkali and salt are both 2% to 15%.
  • a biomass-based hydroxyapatite composite material is prepared by using biomass material as a carrier to immobilize hydroxyapatite on the biomass substrate by an in-situ precipitation method.
  • Step S1 take the fresh biomass material bagasse, clean it with distilled water, dry to constant weight, pulverize with a vibrating pulverizer, sieve through 18 meshes for later use, and its average particle size is 2mm;
  • Step S2 soak the biomass material obtained by sieving in step S1 in a 1M sodium hydroxide solution for 3h at room temperature, and the biomass material dosage ratio is 20g/L (20g biomass material is put into each liter of sodium hydroxide solution. ), the biomass material is swelled by alkali washing and then filtered, and washed with water until the effluent is neutral.
  • Step S3 immerse the biomass material obtained after alkali washing, swelling and water washing in step S2 in 0.1 g/L potassium permanganate solution for 3 hours at room temperature, the dosage ratio of the biomass material is 20 g/L, and the biomass material is fully After pickling and oxidation, filter, and wash with water until the effluent is neutral.
  • Step S4 performing ethanol leaching on the biomass material obtained after acid washing, oxidation and water washing in step S3, and then drying at 100° C. for 24 hours to obtain pretreated biomass material;
  • Step S5 adding the pretreated biomass material obtained in step S4 into a solution of trisodium phosphate with a concentration of 0.5M for phosphorylation addition reaction, mixing and stirring at a speed of 200 rpm at 40°C, and reacting for 12 hours, wherein the biomass material
  • the ratio of the mass in g to the volume of the phosphate solution in mL is 1:25, after the reaction is completed, filter, and dry at 40 ° C for 12 hours to obtain phosphorylated biomass material;
  • Step S6 Slowly add the phosphorylated biomass material obtained in Step S5 into a calcium chloride solution with a concentration of 1.67M, adjust the pH value of the reaction system with ammonia water to maintain at 10-11, and mix and stir at a speed of 200rpm at 40°C , react for 1h, and then stand 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 filter the biomass material after the aging in step S6, wash with water until the effluent is neutral, then rinse with ethanol, and dry at 60° C. for 24 hours to obtain a biomass-based hydroxyapatite composite material, hydroxyphosphorus
  • the limestone solid loading is 15%.
  • the above adsorbent after adsorbing fluoride ions was eluted with an alkali salt mixed solution of 5wt% sodium hydroxide + 5wt% sodium chloride for 12h, and the adsorbent after desorption was continued to be used for the next cycle adsorption, and the adsorbent after regeneration
  • the dosage is 0.5g/L
  • the reaction temperature is 25°C
  • the adsorption capacity of fluorine is 4.0mg/g.
  • the biomass-based hydroxyapatite composite material of this embodiment was applied to the fluorine-contaminated water body with strong competing ions (containing 1g/L sulfate ion) for treatment.
  • Step S1 take fresh biomass material peanut shells, rinse with distilled water, dry to constant weight, pulverize with a vibrating pulverizer, sieve through 40 meshes for use, and have an average particle size of 0.5 mm;
  • Step S2 Immerse the biomass material obtained by sieving in step S1 in a 1.5M sodium hydroxide solution for 3 hours at room temperature, the biomass material dosage ratio is 20g/L, and the biomass material is fully alkali-washed and swollen and filtered. Wash with water until the water is neutral.
  • Step S3 Immerse the biomass material obtained by swelling in step S2 in a 0.2g/L potassium permanganate solution for 3h at room temperature, the biomass material dosage ratio is 20g/L, and the biomass material is fully pickled and oxidized and then filtered , washed with water until the water is neutral.
  • Step S4 the biomass material obtained by the oxidation in step S3 is washed with ethanol, and then dried at 100° C. for 24 hours to obtain the pretreated biomass material;
  • Step S5 Add the pretreated biomass material obtained in Step S4 into a diammonium hydrogen phosphate solution with a concentration of 0.6M to carry out a phosphorylation addition reaction, mix and stir at a speed of 300rpm at 50°C, and react for 12h, wherein the biomass
  • the ratio of the mass of the material in g to the volume of the phosphate solution in mL is 1:25, and after the reaction is completed, it is filtered and dried at 50 ° C for 12 hours to obtain phosphorylated biomass material;
  • Step S6 slowly add the phosphorylated biomass material obtained in step S5 into a calcium nitrate solution with a concentration of 1M, adjust the pH value of the reaction system with ammonia water to maintain at 10-11, mix and stir at a speed of 300rpm at 50°C, and react. 1.5h, and then stand for 24h at room temperature, wherein the ratio of the mass of biomass material in g to the volume of calcium ion solution in mL is 1:25;
  • Step S7 filter the biomass material after the aging in step S6, wash with water until the effluent is neutral, then rinse with ethanol, and dry at 60° C. for 24 hours to obtain a biomass-based hydroxyapatite composite material, hydroxyphosphorus
  • the limestone solid loading was 18%.
  • the biomass-based hydroxyapatite composite material of this embodiment was applied to the treatment of fluorine-contaminated water bodies.
  • the initial concentration of fluorine in the water was 10 mg/L
  • the dosage of the adsorbent was 0.5 g/L
  • the reaction temperature was 25 °C
  • the pH 7 conditions
  • the adsorption capacity of fluorine was 5.6 mg/g.
  • the above adsorbent after adsorbing fluoride ions was eluted with an alkali salt mixed solution of 5wt% sodium hydroxide + 5wt% sodium chloride for 12h, and the adsorbent after desorption was continued to be used for the next cycle adsorption, and the adsorbent after regeneration
  • the dosage is 0.5g/L
  • the reaction temperature is 25°C
  • the adsorption amount of fluorine is 4.2mg/g.
  • the biomass-based hydroxyapatite composite material of this embodiment was applied to the fluorine-contaminated water body with strong competing ions (containing 1g/L sulfate ion) for treatment.
  • Step S1 take the fresh biomass material bamboo chips, clean them with distilled water, dry to constant weight, pulverize with a vibrating pulverizer, sieve with 60 meshes for subsequent use, and have an average particle size of 0.25mm;
  • Step S2 Immerse the biomass material obtained by screening in step S1 in a 2M sodium hydroxide solution for 3 hours at room temperature, the biomass material dosage ratio is 20g/L, and the biomass material is fully alkali-washed and swollen, filtered, and washed with water. Until the water is neutral.
  • Step S3 Immerse the biomass material obtained by swelling in step S2 in a 0.4g/L potassium permanganate solution for 3h at room temperature, the biomass material dosage ratio is 20g/L, and the biomass material is fully pickled and oxidized and then filtered , washed with water until the water is neutral.
  • Step S4 the biomass material obtained by the oxidation in step S3 is washed with ethanol, and then dried at 100° C. for 24 hours to obtain the pretreated biomass material;
  • Step S5 The pretreated biomass material obtained in step S4 is added to a solution of disodium hydrogen phosphate with a concentration of 1 M to carry out a phosphorylation addition reaction, and the reaction is carried out at a speed of 300 rpm at 60° C. for 24 hours.
  • the ratio of the mass in g to the volume of the phosphate solution in mL is 1:25, after the reaction is completed, filter, and dry at 50 ° C for 12 hours to obtain phosphorylated biomass material;
  • Step S6 Slowly add the phosphorylated biomass material obtained in Step S5 into a calcium chloride solution with a concentration of 1.67M, adjust the pH of the reaction system with ammonia water to maintain a pH value of 10-11, and mix and stir at a speed of 300rpm at 50°C , react for 2h, and then stand 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 filter the biomass material after the aging in step S6, wash with water until the effluent is neutral, then rinse with ethanol, and dry at 60° C. for 24 hours to obtain a biomass-based hydroxyapatite composite material, hydroxyphosphorus
  • the limestone solid loading is 8%.
  • the above biomass-based hydroxyapatite composite material was applied to the treatment of fluorine-contaminated water.
  • the initial concentration of fluorine in the water was 10 mg/L
  • the dosage of the adsorbent was 0.5 g/L
  • the reaction temperature was 25 °C
  • the above adsorbent after adsorbing fluoride ions was eluted with an alkali salt mixed solution of 5wt% sodium hydroxide + 5wt% sodium chloride for 12h, and the adsorbent after desorption was continued to be used for the next cycle adsorption, and the adsorbent after regeneration
  • the dosage is 0.5g/L
  • the reaction temperature is 25°C
  • the adsorption amount of fluorine is 1.7mg/g.
  • the above biomass-based hydroxyapatite composite material was applied to fluorine-contaminated water with strong competing ions (containing 1g/L sulfate ion) for treatment.
  • the initial concentration of fluorine in the water was 10mg/L, and the dosage of the adsorbent was 0.5g. /L, the adsorption amount of fluorine was 1.0 mg/g.
  • the biomass-based hydroxyapatite composite material of the present invention can be used to investigate the ability of the material to treat fluorine through a column adsorption dynamic test. Taking Examples 1 to 3 as examples, the specific experimental steps are as follows:
  • F- concentration is 5mg/L
  • HCO 3 -/SO 4 2 -/Cl-/NO 3 -/Ca 2+ /Mg 2+ / concentration is 150mg/L, 100mg/L, 100mg respectively /L, 8mg/L, 15mg/L, 5mg/L
  • the pH of the settled solution is 8.1 ⁇ 0.2
  • the wet volume dosage of the adsorbent is 5mL
  • the flow rate is 15-30min/BV
  • the fluoride ion concentration in the effluent is F- ⁇ 1.5.
  • the up-to-standard treatment amounts of the adsorbents prepared according to Examples 1 to 3 of the present invention to fluorine-containing sewage are 72, 100, and 52 BV, respectively, while the up-to-standard treatment amounts of pretreated biomass materials to fluorine under the same conditions are 8BV.
  • the above adsorbent after adsorbing fluoride ions is eluted with an alkali salt mixed solution of 5wt% sodium hydroxide + 5wt% sodium chloride, and the desorbed adsorbent is continued to be used for the next cycle adsorption, Examples 1-3
  • the treated amount of fluorine under the same conditions after regeneration of the prepared adsorbent was 40, 68, and 36 BV, respectively.
  • the adsorption capacity of activated alumina is only 0.5 ⁇ 1mg/g, at F-concentration 5mg/L
  • the pH of settled solution In the non-competitive ion dynamic column test of 7.5 ⁇ 0.2, the treatment capacity of zeolite to fluorine-containing sewage is 15-30 BV, and the treatment capacity of activated alumina to fluorine-containing sewage is 200-240 BV; the biomass-based hydroxyl group prepared by the invention is used.
  • the apatite composite material is used for fluorine removal research, it can achieve high fluorine removal efficiency.
  • the combination of specific adsorbent (hydroxyapatite) and excellent carrier (biomass material) can effectively improve the adsorption effect of the composite material. Recycling performance.

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Abstract

一种生物质基羟基磷灰石复合材料及其制备方法和应用，该复合材料以生物质材料为基体，经过水洗、烘干、粉碎、筛分、碱洗、酸洗、醇洗、烘干预处理后，制得预处理生物质材料，预处理生物质材料先加入到磷酸盐溶液中加载磷酸根，再加入到pH为碱性的钙盐溶液中原位沉淀反应，最后经陈化、过滤、干燥后制得生物质基羟基磷灰石复合材料，羟基磷灰石固载量为1%-20%。制备的复合材料将羟基磷灰石的高吸附反应活性、专属吸附特性与载体的防止团聚、操作方便特性相结合，在氟污染水体中具有较高的氟吸附量。

Description

一种生物质基羟基磷灰石复合材料及其制备方法和应用 技术领域
本发明涉及一种废水处理技术领域，具体涉及一种生物质基羟基磷灰石复合材料及其制备方法和应用。
背景技术
氟是地球系统中参与生物体新陈代谢过程不可或缺的主要元素之一，然而过多的氟摄入对动植物和人体都会产生不利的影响。地下水中的氟化物污染威胁着全世界数百万人，然而传统的沉淀或混凝法很难以具有成本效益的方式将氟化物降至世界卫生组织规定的含氟标准(1.5mg/L)以下。例如，由于CaF 2的溶解度较高，钙盐沉淀很难将氟化物降至8mg/L以下；而混凝需要大量的铝盐(高达1200mg/L)，才能将氟化物降至1.5mg/L以下，且pH<5的酸性环境会加快铝溶出到水环境中，对人体健康构成威胁。
目前，去除水体中氟化物的处理方法主要包括：沉淀-混凝法、膜过滤法、离子交换法和吸附法(J.Hazard.Mater.2006,137(1)，456–463)。其中吸附法因其高效率、低成本、易操作和环保等优点而被广泛采用。最常用的除氟吸附剂有金属氧化物如活性氧化铝、氧化锆等，或多孔性物质如活性炭、黏土、沸石等。其中活性炭、黏土、沸石等吸附剂往往是通过自身丰富孔道结构对氟离子进行富集，吸附作用具有非特异性。而金属无机氧化物如活性氧化铝、氧化锆等可通过Lewis酸碱络合(J.Am.Chem.Soc.,1965,87(16),3571-3577)与氟离子形成配位键、络合物，实现特异性结合，然而活性氧化铝在酸性和碱性条件下的稳定性差，氧化锆对氟化物的吸附高度依赖于酸性pH，影响了实际应用。
羟基磷灰石(HAP)作为人体骨骼和牙齿的主要成分，具有良好的生物相容性，是pH值在4～12之间常温下非常稳定的磷酸钙盐，被广泛应用于医疗、环保等领域。HAP普遍存在于自然界中，地下水中的氟离子可被吸附在其上形成热力学更稳定的氟磷灰石(FAP)。由于HAP特殊的晶型结构和表面特性，HAP对氟离子以及重金属离子具有有效的吸附性和选择性，近年来引起了广泛关注。然而HAP通常以超细颗粒存在，在水中具有易团聚失活、过水压降大、难分离回收、脱附再生困难等问题，使其在实际水处理过程中的应用被大大限制。而将HAP进行固载于具有丰富孔道的大颗粒载体如活性炭、碳纳米管、沸石、高分子树脂、生物质等制备的复合材料是解决上述问题的有效途径。如在汤庆子的2017年学士论文中公开了羟基磷灰石及其复合材料的制备、表征和除氟性能研究，其通过化学沉淀法原位合成了活性炭-羟基磷灰石复合材料、碳纳米管-羟基磷灰石并应用与除氟研究，然而活性炭及碳纳米管的原 料制备过程复杂，成本较高，且碳纳米管还具有一定的毒性。又如专利CN110252261A公开了一种树脂基纳米羟基磷灰石复合材料、制备方法及在氟污染水体处理中的应用，通过选用高分子树脂作为载体，将纳米级羟基磷灰石颗粒固载于高分子树脂孔道中制备而得，然而高分子材料合成中会使用到大量有毒有机试剂，合成工艺复杂、制备成本较高，并产生有毒中间副产物，引起二次污染严重。
近年来，农业废弃物资源化利用受到广泛关注，一方面由于其面积较大、物理结构孔隙度高、含有大量的活性基团，可将其作为一种优质的载体，又可将其直接或改性后用于吸附废水中的污染离子；另一方面，传统吸附剂在处理低浓度氟污染废水时效率低、成本高且易造成二次污染，而农业废弃物具有成本低、来源广、可再生等特点，能较好地弥补这些缺陷。
发明内容
本发明所要解决的技术问题是针对现有技术的不足，提供一种生物质基羟基磷灰石复合材料及其制备方法和应用，该生物质基羟基磷灰石复合材料以农业废弃物生物质材料为载体，通过原位沉淀法将羟基磷灰石固载于生物质基体上，制备得到生物质基羟基磷灰石复合材料，从而将羟基磷灰石的高吸附反应活性、专属吸附特性与载体的防止团聚、操作方便特性相结合，有效解决了传统除氟吸附剂吸附效率低、制备成本高、易造成二次污染、选择性差等技术弊端，以及解决了羟基磷灰石颗粒在水中易团聚失活、过水压降大、难分离回收、脱附再生困难等问题，为农业废弃物资源的综合利用提供了有效途径，同时为水中氟离子的深度去除提供可靠的技术支持。
为实现上述技术目的，本发明采取的技术方案为：一种生物质基羟基磷灰石复合材料的制备方法，包括如下步骤：
步骤S1、取一定量生物质材料，经蒸馏水清洗干净后烘干至恒重，采用振动粉碎机粉碎，通过10～60目筛分备用；
步骤S2、将步骤S1筛分得到的生物质材料进行碱洗溶胀后，水洗至出水为中性；
步骤S3、将步骤S2碱洗溶胀、水洗后得到的生物质材料经充分酸洗氧化后过滤，水洗至出水为中性；
步骤S4、将步骤S3酸洗氧化、水洗后得到的生物质材料进行乙醇淋洗，然后在100℃下烘干24h，得到预处理生物质材料；
步骤S5、将步骤S4得到的预处理生物质材料进行磷酸化加成后过滤、烘干，得到磷酸化生物质材料；
步骤S6、将步骤S5得到的磷酸化生物质材料加入到pH为碱性的钙盐溶液中原位沉淀反应，反应结束后于室温下静置陈化；
步骤S7、将步骤S6陈化结束后的生物质材料过滤，水洗至出水为中性，然后乙醇淋洗，在40～60℃下烘干24h，得到生物质基羟基磷灰石复合材料。
进一步地，步骤S1中，所述生物质材料为甘蔗渣、橘子皮、玉米芯、花生壳、稻壳、核桃壳、木屑、竹屑中的一种，其中甘蔗渣、橘子皮、玉米芯、花生壳的综纤维素含量较高，赋予其丰富孔道结构，有利于提高羟基磷灰石的固载量，花生壳、稻壳、核桃壳、木屑、竹屑的木质素含量较高，赋予其刚性并且不容易腐烂，有利于吸附剂的回收再生利用，筛分后的生物质材料颗粒粒径大小介于0.25～2mm之间。
进一步地，步骤S2中，碱洗溶胀的方法为，将步骤S1筛分得到的生物质材料用碱溶液于常温下浸泡3～6h，其中，所述碱溶液溶质为氢氧化钠或氢氧化钾，碱溶液的浓度为1～2M，生物质材料在碱溶液中的投加比为20g/L。
进一步地，步骤S3中，酸洗氧化的方法为，将步骤S2碱洗溶胀、水洗后得到的生物质材料用高锰酸盐溶液于常温下浸泡3～6h，其中，生物质材料与高锰酸盐的混合质量比为100:0.5～2，所述高锰酸盐为高锰酸钾或高锰酸钠中的任一种。
进一步地，步骤S5中，磷酸化加成反应的方法为，预处理生物质材料加入到浓度为0.3～1M的磷酸盐溶液中，在25～60℃下以200～400rpm的速度混合搅拌，反应12～24h，其中预处理生物质材料以g为单位的质量与磷酸盐溶液以mL为单位的体积的比值为1:25，所述磷酸盐溶液为磷酸三钠溶液、磷酸氢二钠溶液、磷酸氢二铵溶液中的一种，待反应结束后过滤，于40～60℃下烘干12h，得到磷酸化生物质材料。
进一步地，步骤S6中，将步骤S5得到的磷酸化生物质材料缓慢加入到浓度为0.5～1.67M的钙离子溶液中，用氨水将反应体系pH值维持在10～11，在25～60℃下以200～400rpm的速度混合搅拌，反应1～2h，然后室温下静置陈化12～24h，其中生物质材料以g为单位的质量与钙离子溶液以mL为单位的体积的比值为1:25，所述钙离子溶液为氯化钙溶液或硝酸钙溶液中的一种。
本发明还提供了一种生物质基羟基磷灰石复合材料，采用上述制备方法制备得到。
本发明还提供了上述生物质基羟基磷灰石复合材料用于吸附处理氟污染水体中氟离子的用途，所述氟污染水体包括含强竞争离子的氟污染水体，所述强竞争离子为与氟离子具有强竞争吸附作用的离子。
进一步地，吸附后的生物质基羟基磷灰石复合材料通过碱盐混合液进行脱附再生，其中碱盐混合溶液中的碱为氢氧化钠或氢氧化钾，盐为氯化钠或氯化钾，且碱、盐的质量浓度均为2％～15％。
与现有技术相比，本发明的有益效果在于：
1)本发明提供了一种生物质基羟基磷灰石复合材料，该复合材料以生物质材料为基体，其丰富孔道结构的限域效应避免了超细颗粒羟基磷灰石易团聚的问题，而且生物质材料来源于原始农业废弃物，相比于活性炭、碳纳米管、树脂等载体，生物质材料具有原料制备简单、成本低、来源广等特点，作为吸附剂原料在节约成本的同时可有效减少其随意堆积和焚烧带来的环境污染问题，并实现农业废弃物的资源化利用，有一定的社会和经济价值；
2)本发明的生物质基羟基磷灰石复合材料以生物质材料为基体，通过液相原位沉淀将羟基磷灰石颗粒负载在生物质表面和孔道内部，该复合材料将羟基磷灰石的高吸附反应活性、专属吸附特性与载体的防止团聚、操作方便特性相结合，在氟污染水体中具有较高的氟吸附量，该复合材料对氟污染水体进行深度处理，能够将一定量的氟污染水体中氟离子的浓度降到1.5mg/L以下，除氟效率高，在强竞争离子体系中对氟离子仍保持较高的吸附量，具有特异性吸附；
3)本发明的生物质基羟基磷灰石复合材料在制备过程中以生物质材料为基体固载羟基磷灰石，制备中使用改性剂和无机物无毒无害，不会造成二次污染，制备成本低，工艺简单，制备的复合材料可回收再生，资源利用率高，适用于实际氟污染废水处理，适合大量制备应用。
具体实施方式
为了使本领域技术领域人员更好地理解本发明的技术方案，下面结合部分实施例对本发明的技术方案作进一步详细描述。
下述实施例中所使用的实验方法，如无特殊说明，均为常规方法，所用的试剂、方法和设备，如无特殊说明，均为本技术领域常规试剂、方法和设备。
本发明提供了一种生物质基羟基磷灰石复合材料，其以生物质材料为基体固载羟基磷灰石，制备得到的生物质基羟基磷灰石复合材料将羟基磷灰石的高吸附反应活性、专属吸附特性与载体的防止团聚、操作方便特性相结合，在氟污染水体中具有较高的氟吸附量，在强竞争离子体系中对氟离子具有特异性吸附。
本发明的生物质基羟基磷灰石复合材料的制备方法，包括以下步骤：
步骤S1：取一定量生物质材料，经蒸馏水清洗干净，烘干至恒重，采用振动粉碎机粉碎， 10～60目筛分备用；其中，生物质材料为甘蔗渣、橘子皮、玉米芯、花生壳、稻壳、核桃壳、木屑、竹屑中的一种，其中甘蔗渣、橘子皮、玉米芯、花生壳的综纤维素含量较高，赋予其丰富孔道结构，有利于提高羟基磷灰石的固载量，花生壳、稻壳、核桃壳、木屑、竹屑的木质素含量较高，赋予其刚性并且不容易腐烂，有利于吸附剂的回收再生利用，筛分后颗粒粒径大小介于0.25～2mm之间；
步骤S2：将步骤S1筛分得到的生物质材料进行碱洗溶胀，用碱溶液于常温下浸泡3～6h，浸泡结束后用水洗至中性，其中碱溶液溶质为氢氧化钠或氢氧化钾，碱溶液的浓度为1～2M生物质材料在碱溶液中的投加比为20g/L；
步骤S3：将步骤S2溶胀得到的生物质材料进行酸洗氧化，用高锰酸盐溶液于常温下浸泡3～6h，浸泡结束后用水洗至中性；其中生物质材料以g为单位的质量与高锰酸盐以g为单位的质量比值为100:0.5～2；其中高锰酸盐为高锰酸钾或高锰酸钠；
步骤S4：将步骤S3氧化得到的生物质材料进行乙醇淋洗，然后在100℃下烘干24h，得到预处理生物质材料；
步骤S5：将步骤S4得到的预处理生物质材料加入到浓度为0.3～1M的磷酸盐溶液中进行磷酸化加成反应，在25～60℃下以200～400rpm的速度混合搅拌，反应12～24h，其中生物质材料以g为单位的质量与磷酸盐溶液以mL为单位的体积的比值为1:25，待反应结束后过滤，于40～60℃下烘干12h，得到磷酸化生物质材料；其中磷酸根离子溶液为磷酸三钠溶液、磷酸氢二钠溶液或磷酸氢二铵溶液中的一种；
步骤S6：将步骤S5得到的磷酸化生物质材料缓慢加入到浓度为0.5～1.67M的钙离子溶液中，用氨水将反应体系pH值维持在10～11，在25～60℃下以200～400rpm的速度混合搅拌，反应1～2h，然后室温下静置陈化12～24h，其中生物质材料以g为单位的质量与钙离子溶液以mL为单位的体积的比值为1:25；钙离子溶液为氯化钙溶液或硝酸钙溶液中的一种；
步骤S7：将步骤S6陈化结束后的生物质材料过滤，水洗至出水为中性，然后乙醇淋洗，在40～60℃下烘干24h，即得到生物质基羟基磷灰石复合材料。
采用上述制备的生物质基羟基磷灰石复合材料对氟污染水体进行处理，水中氟初始浓度为10mg/L，吸附剂投加量为0.5g/L，反应温度25℃条件下，pH＝7条件下，对氟的吸附量(以复合材料计平均每克对氟的吸附量)为2～6mg。
进一步地，当氟污染水体包括含强竞争离子的氟污染水体，所述强竞争离子为与氟离子具有强竞争吸附作用的离子时，采用上述制备的生物质基羟基磷灰石复合材料用于强竞争离子 (含1g/L硫酸根离子)的氟污染水体进行处理，水中氟初始浓度为10mg/L，吸附剂投加量为0.5g/L，反应温度25℃，pH＝7条件下，对氟的吸附量为1～3mg/g。
进一步地，吸附后的生物质基羟基磷灰石复合材料通过碱盐混合液进行脱附再生，洗脱时间12～24h，优选12h，其中碱盐混合溶液中的碱为氢氧化钠或氢氧化钾，盐为氯化钠或氯化钾，且碱、盐的质量浓度均为2％～15％。
实施例1
以生物质材料为载体，通过原位沉淀法将羟基磷灰石固载于该生物质基体上，制备得到一种生物质基羟基磷灰石复合材料。
上述生物质基羟基磷灰石复合材料的具体制备方法如下：
步骤S1：取新鲜生物质材料甘蔗渣，经蒸馏水清洗干净，烘干至恒重，采用振动粉碎机粉碎，经18目筛分备用，其平均粒径为2mm；
步骤S2：将步骤S1筛分得到的生物质材料在常温下于1M的氢氧化钠溶液中浸泡3h，生物质材料投加比为20g/L(每升氢氧化钠溶液中投入20g生物质材料)，生物质材料经充分碱洗溶胀后过滤，水洗至出水为中性。
步骤S3：将步骤S2碱洗溶胀、水洗后得到的生物质材料在常温下于0.1g/L高锰酸钾溶液中浸渍3h，生物质材料投加比为20g/L，生物质材料经充分酸洗氧化后过滤，水洗至出水为中性。
步骤S4：将步骤S3酸洗氧化、水洗后得到的生物质材料进行乙醇淋洗，然后在100℃下烘干24h，得到预处理生物质材料；
步骤S5：将步骤S4得到的预处理生物质材料加入到浓度为0.5M的磷酸三钠溶液中进行磷酸化加成反应，在40℃下以200rpm的速度混合搅拌，反应12h，其中生物质材料以g为单位的质量与磷酸盐溶液以mL为单位的体积的比值为1:25，待反应结束后过滤，于40℃下烘干12h，得到磷酸化生物质材料；
步骤S6：将步骤S5得到的磷酸化生物质材料缓慢加入到浓度为1.67M的氯化钙溶液中，用氨水调节反应体系pH值维持在10～11，在40℃下以200rpm的速度混合搅拌，反应1h，然后室温下静置陈化24h，其中生物质材料以g为单位的质量与钙离子溶液以mL为单位的体积的比值为1:25；
步骤S7：将步骤S6陈化结束后的生物质材料过滤，水洗至出水为中性，然后乙醇淋洗，在60℃下烘干24h，即得到生物质基羟基磷灰石复合材料，羟基磷灰石固载量为15％。
将本实施例的生物质基羟基磷灰石复合材料应用于氟污染水体处理，水中氟离子初始浓度为10mg/L，生物质基羟基磷灰石复合材料(下述“吸附剂”指代“生物质基羟基磷灰石复合材料”)投加量为0.5g/L，反应温度25℃，pH＝7条件下，对氟的吸附量为4.9mg/g。
将上述吸附氟离子后的吸附剂使用5wt％氢氧化钠+5wt％氯化钠的碱盐混合溶液进行洗脱12h，脱附后的吸附剂继续用于下一次的循环吸附，再生后吸附剂投加量为0.5g/L，反应温度25℃，pH＝7条件下，对氟的吸附量为4.0mg/g。
将本实施例的生物质基羟基磷灰石复合材料应用于强竞争离子(含1g/L的硫酸根离子)的氟污染水体进行处理，水中氟初始浓度为10mg/L，吸附剂投加量为0.5g/L，反应温度25℃，pH＝7条件下，对氟的吸附量为1.8mg/g。
实施例2
步骤S1：取新鲜生物质材料花生壳，经蒸馏水清洗干净，烘干至恒重，采用振动粉碎机粉碎，经40目筛分备用，其平均粒径为0.5mm；
步骤S2：将步骤S1筛分得到的生物质材料在常温下于1.5M的氢氧化钠溶液中浸渍3h，生物质材料投加比为20g/L，生物质材料经充分碱洗溶胀后过滤，水洗至出水为中性。
步骤S3：将步骤S2溶胀得到的生物质材料在常温下于0.2g/L高锰酸钾溶液中浸渍3h，生物质材料投加比为20g/L，生物质材料经充分酸洗氧化后过滤，水洗至出水为中性。
步骤S4：将步骤S3氧化得到的生物质材料进行乙醇淋洗，然后在100℃下烘干24h，得到预处理生物质材料；
步骤S5：将步骤S4得到的预处理生物质材料加入到浓度为0.6M的磷酸氢二氨溶液中进行磷酸化加成反应，在50℃下以300rpm的速度混合搅拌，反应12h，其中生物质材料以g为单位的质量与磷酸盐溶液以mL为单位的体积的比值为1:25，待反应结束后过滤，于50℃下烘干12h，得到磷酸化生物质材料；
步骤S6：将步骤S5得到的磷酸化生物质材料缓慢加入到浓度为1M的硝酸钙溶液中，用氨水调节反应体系pH值维持在10～11，在50℃下以300rpm的速度混合搅拌，反应1.5h，然后室温下静置陈化24h，其中生物质材料以g为单位的质量与钙离子溶液以mL为单位的体积的比值为1:25；
步骤S7：将步骤S6陈化结束后的生物质材料过滤，水洗至出水为中性，然后乙醇淋洗，在60℃下烘干24h，即得到生物质基羟基磷灰石复合材料，羟基磷灰石固载量为18％。
将本实施例的生物质基羟基磷灰石复合材料应用于氟污染水体处理，水中氟初始浓度为 10mg/L，吸附剂投加量为0.5g/L，反应温度25℃，pH＝7条件下，对氟的吸附量为5.6mg/g。
将上述吸附氟离子后的吸附剂使用5wt％氢氧化钠+5wt％氯化钠的碱盐混合溶液进行洗脱12h，脱附后的吸附剂继续用于下一次的循环吸附，再生后吸附剂投加量为0.5g/L，反应温度25℃，pH＝7条件下，对氟的吸附量为4.2mg/g。
将本实施例的生物质基羟基磷灰石复合材料应用于强竞争离子(含1g/L的硫酸根离子)的氟污染水体进行处理，水中氟初始浓度为10mg/L，吸附剂投加量为0.5g/L，反应温度25℃，pH＝7条件下，对氟的吸附量为2.9mg/g。
实施例3
步骤S1：取新鲜生物质材料竹屑，经蒸馏水清洗干净，烘干至恒重，采用振动粉碎机粉碎，经60目筛分备用，其平均粒径为0.25mm；
步骤S2：将步骤S1筛分得到的生物质材料在常温下于2M的氢氧化钠溶液中浸渍3h，生物质材料投加比为20g/L，生物质材料经充分碱洗溶胀后过滤，水洗至出水为中性。
步骤S3：将步骤S2溶胀得到的生物质材料在常温下于0.4g/L高锰酸钾溶液中浸渍3h，生物质材料投加比为20g/L，生物质材料经充分酸洗氧化后过滤，水洗至出水为中性。
步骤S4：将步骤S3氧化得到的生物质材料进行乙醇淋洗，然后在100℃下烘干24h，得到预处理生物质材料；
步骤S5：将步骤S4得到的预处理生物质材料加入到浓度为1M的磷酸氢二钠溶液中进行磷酸化加成反应，在60℃下以300rpm的速度混合搅拌，反应24h，其中生物质材料以g为单位的质量与磷酸盐溶液以mL为单位的体积的比值为1:25，待反应结束后过滤，于50℃下烘干12h，得到磷酸化生物质材料；
步骤S6：将步骤S5得到的磷酸化生物质材料缓慢加入到浓度为1.67M的氯化钙溶液中，用氨水调节反应体系pH值维持在10～11，在50℃下以300rpm的速度混合搅拌，反应2h，然后室温下静置陈化24h，其中生物质材料以g为单位的质量与钙离子溶液以mL为单位的体积的比值为1:25；
步骤S7：将步骤S6陈化结束后的生物质材料过滤，水洗至出水为中性，然后乙醇淋洗，在60℃下烘干24h，即得到生物质基羟基磷灰石复合材料，羟基磷灰石固载量为8％。
将上述生物质基羟基磷灰石复合材料应用于氟污染水体处理，水中氟初始浓度为10mg/L，吸附剂投加量为0.5g/L，反应温度25℃，pH＝7条件下，对氟的吸附量为2.5mg/g。
将上述吸附氟离子后的吸附剂使用5wt％氢氧化钠+5wt％氯化钠的碱盐混合溶液进行洗脱 12h，脱附后的吸附剂继续用于下一次的循环吸附，再生后吸附剂投加量为0.5g/L，反应温度25℃，pH＝7条件下，对氟的吸附量为1.7mg/g。
将上述生物质基羟基磷灰石复合材料应用于强竞争离子(含1g/L的硫酸根离子)的氟污染水体进行处理，水中氟初始浓度为10mg/L，吸附剂投加量为0.5g/L，对氟的吸附量为1.0mg/g。
实施例4
本发明的生物质基羟基磷灰石复合材料可通过柱吸附动态试验来考察材料对氟的处理能力。以实施例1～3为例，具体实验步骤如下：
配制模拟含氟污水：F-浓度为5mg/L，HCO 3-/SO 4 2-/Cl-/NO 3-/Ca 2+/Mg 2+/浓度分别为150mg/L、100mg/L、100mg/L、8mg/L、15mg/L、5mg/L，进驻液pH为8.1±0.2，吸附剂湿体积用量为5mL，流速为15-30min/BV，出水氟离子浓度达标要求为F-<1.5mg/L，根据本发明实施例1～3制得的吸附剂对含氟污水的达标处理量分别为72、100、52BV，而在相同条件下预处理生物质材料对氟的达标处理量为8BV。将上述吸附氟离子后的吸附剂使用5wt％氢氧化钠+5wt％氯化钠的碱盐混合溶液进行洗脱，脱附后的吸附剂继续用于下一次的循环吸附，实施例1～3制得的吸附剂再生5次后在相同条件下对氟的处理量分别为40、68、36BV。
另外，对比文献(西安建筑科技大学学报(自然科学版),2002,34(004):325-328)结果，该研究中当水中氟初始浓度为10mg/L，吸附剂投加量为10g/L，反应温度25℃条件下pH＝7时沸石的吸附量仅为0.2～0.4mg/g，活性氧化铝的吸附量仅为0.5～1mg/g，在F-浓度5mg/L，进驻液pH为7.5±0.2的无竞争离子动态柱试验中，沸石对含氟污水的处理量为15～30BV，活性氧化铝对含氟污水的处理量为200～240BV；采用本发明制备的生物质基羟基磷灰石复合材料进行除氟研究时，可以达到较高的除氟效率，特异性吸附剂(羟基磷灰石)与优良载体(生物质材料)的联用可有效提高复合材料的吸附效果和回收再生性能。
以上仅是本发明的优选实施方式，本发明的保护范围并不仅局限于上述实施例，凡属于本发明思路下的技术方案均属于本发明的保护范围。应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理前提下的若干改进和润饰，应视为本发明的保护范围。

Claims (10)

  1. 一种生物质基羟基磷灰石复合材料的制备方法，其特征在于，包括如下步骤：
    步骤S1、取一定量生物质材料，经蒸馏水清洗干净后烘干至恒重，然后粉碎并通过10～60目筛分备用；
    步骤S2、将步骤S1筛分得到的生物质材料进行碱洗溶胀后，水洗至出水为中性；
    步骤S3、将步骤S2碱洗溶胀、水洗后得到的生物质材料经充分酸洗氧化后过滤，水洗至出水为中性；
    步骤S4、将步骤S3酸洗氧化、水洗后得到的生物质材料依次进行乙醇淋洗、烘干，得到预处理生物质材料；
    步骤S5、将步骤S4得到的预处理生物质材料进行磷酸化加成后过滤、烘干，得到磷酸化生物质材料；
    步骤S6、将步骤S5得到的磷酸化生物质材料加入到pH为碱性的钙盐溶液中原位沉淀反应，反应结束后于室温下静置陈化；
    步骤S7、将步骤S6陈化结束后的生物质材料过滤，水洗至出水为中性，然后依次经乙醇淋洗、烘干，得到生物质基羟基磷灰石复合材料。
  2. 根据权利要求1所述的生物质基羟基磷灰石复合材料的制备方法，其特征在于：步骤S1中，所述生物质材料为甘蔗渣、橘子皮、玉米芯、花生壳、稻壳、核桃壳、木屑、竹屑中的一种，筛分后的生物质材料颗粒粒径大小介于0.25～2mm之间。
  3. 根据权利要求1所述的生物质基羟基磷灰石复合材料的制备方法，其特征在于：步骤S2中，碱洗溶胀的方法为，将步骤S1筛分得到的生物质材料用碱溶液于常温下浸泡3～6h，其中，所述碱溶液溶质为氢氧化钠或氢氧化钾,碱溶液的浓度为1～2M，生物质材料在碱溶液中的投加比为20g/L。
  4. 根据权利要求1所述的生物质基羟基磷灰石复合材料的制备方法，其特征在于：步骤S3中，酸洗氧化的方法为，将步骤S2碱洗溶胀、水洗后得到的生物质材料用高锰酸盐溶液于常温下浸泡3～6h，其中，生物质材料与高锰酸盐的混合质量比为100:0.5～2，所述高锰酸盐为高锰酸钾或高锰酸钠中的任一种。
  5. 根据权利要求4所述的生物质基羟基磷灰石复合材料的制备方法，其特征在于：步骤S5中，磷酸化加成反应的方法为，预处理生物质材料加入到浓度为0.3～1M的磷酸盐溶液中，在25～60℃下以200～400rpm的速度混合搅拌，反应12～24h，其中预处理生物质材料按照质量用量与磷酸盐溶液体积比为0.04g/mL，所述磷酸盐溶液为磷酸三钠溶液、磷酸氢二钠溶液、磷 酸氢二铵溶液中的一种。
  6. 根据权利要求5所述的生物质基羟基磷灰石复合材料的制备方法，其特征在于：步骤S6中，将步骤S5得到的磷酸化生物质材料缓慢加入到浓度为0.5～1.67M的钙离子溶液中，用氨水将反应体系pH值维持在10～11，在25～60℃下以200～400rpm的速度混合搅拌，反应1～2h，然后室温下静置陈化12～24h，其中生物质材料按照质量用量与钙离子溶液体积比为0.04g/mL，所述钙离子溶液为氯化钙溶液或硝酸钙溶液中的一种。
  7. 一种生物质基羟基磷灰石复合材料，其特征在于，采用权利要求1～6任一项所述的生物质基羟基磷灰石复合材料的制备方法制备得到。
  8. 权利要求7所述的生物质基羟基磷灰石复合材料用于吸附处理氟污染水体中氟离子的用途。
  9. 根据权利要求8所述的用途，其特征在于：所述氟污染水体包括含强竞争离子的氟污染水体，所述强竞争离子为与氟离子具有强竞争吸附作用的离子。
  10. 根据权利要求8所述的用途，其特征在于：吸附后的生物质基羟基磷灰石复合材料通过碱盐混合液进行脱附再生，其中碱盐混合溶液中的碱为氢氧化钠或氢氧化钾，盐为氯化钠或氯化钾，且碱、盐的质量浓度均为2％～15％。
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