CN111495315B - Pb in water body2+Application and preparation method of adsorbing material - Google Patents

Pb in water body2+Application and preparation method of adsorbing material Download PDF

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CN111495315B
CN111495315B CN202010328529.1A CN202010328529A CN111495315B CN 111495315 B CN111495315 B CN 111495315B CN 202010328529 A CN202010328529 A CN 202010328529A CN 111495315 B CN111495315 B CN 111495315B
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biomass
solution
water
mesoporous silica
hydroxyapatite
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CN111495315A (en
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傅晓文
张强
季蕾
李琪
王加宁
李天元
郭书海
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Qilu University of Technology
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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
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
    • 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
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/048—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium containing phosphorus, e.g. phosphates, apatites, hydroxyapatites
    • 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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • 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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28078—Pore diameter
    • B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
    • 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
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • 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
    • C02F2101/20—Heavy metals or heavy metal compounds

Abstract

The invention relates to Pb in water2+The application and preparation method of the adsorption material are characterized in that the adsorption material is prepared by taking agricultural solid waste as a raw material through pyrolysis, template agent reaction and hydroxyapatite modification, and the adsorption material can be used for treating Pb in water2+Has high removing ability. The method not only realizes the resource utilization of the agricultural solid waste, but also achieves the purpose of treating pollution by waste. The invention has rich material source, simple and feasible preparation process and good compatibility with Pb in water2+The method has the advantages of obvious removal effect, no secondary pollution, low preparation and adsorption cost and good application value.

Description

Pb in water body2+Application and preparation method of adsorbing material
Technical Field
The invention relates to Pb in water2+In particular to a hydroxyapatite modified mesoporous silica adsorption material, a preparation method and application thereof in treating Pb in water2+Belonging to the technical field of resource utilization of agricultural solid wastes and preparation of environment-friendly adsorption materials.
Background
With the rapid development of the intensification of agriculture in China, a large amount of agricultural solid waste is generated, and particularly, the agricultural solid waste is used as a byproduct of rice, namely rice husks, of main grain crops. The rice hulls are the largest number of byproducts in the processing of rice, and generally account for about 20% of the mass of rice grains. The main components of the rice hull comprise four substances of cellulose (34-42%), lignin (21-26%), hemicellulose (16-22%) and silicon dioxide (10-21%), and a small amount of crude fat and crude protein. The rice hull is burnt to obtain rice hull ash, and the content of silicon dioxide of the rice hull ash reaches 86.9% -97.3%. Because the rice hulls have hard surfaces and the digestion energy, the metabolism energy and the digestible protein are negative values, the rice hulls are difficult to digest as feed by livestock and poultry and are difficult to decompose by microorganisms. Meanwhile, the rice hulls are rich in silicon and lignin, so that the rice hulls are not easy to absorb water and are not easy to rot when being applied to fields as fertilizers. Therefore, the research on the comprehensive utilization of the rice hull resources is developed, so that the problem of environmental pollution is solved, and natural resources are fully utilized.
With the continuous promotion of the industrialization process, the discharge amount of industrial wastewater in China also increases year by year, and some heavy metal ions enter a water system along with the discharge of the industrial wastewater. After the amount of heavy metal ions in the water body exceeds a certain threshold value, serious threat can be generated to human health. How to eliminate the harm of heavy metals and effectively recycle the heavy metals in the wastewater is also the problem that needs to be solved for the current water body environment protection.
Many studies have been made on methods for treating heavy metal pollution in water. Among them, the adsorption method has many advantages such as low cost, simple operation, and recycling, and is one of the most common effective methods for treating heavy metal water pollution. However, the conventional adsorption materials have the disadvantages of low adsorption capacity, expensive raw materials, complicated preparation method and the like, which results in increased treatment cost and time waste.
Therefore, a suitable process for preparing the novel adsorbing material by utilizing the agricultural solid waste is found, and the adsorbing material prepared by the process is applied to treatment of the heavy metal polluted water body, so that harmless and resource utilization of the agricultural solid waste is realized; thereby achieving the purposes of reducing the environmental pressure and improving the ecological environment.
There are also many patent documents on the preparation of magnetic adsorption materials from agricultural solid wastes, such as: chinese patent document CN104815615A provides a preparation method of a novel rice hull-based modified carbon-silicon composite adsorbent, which takes rice hulls as raw materials to prepare desiliconized activated carbon and rice hull silica gel respectively, but the adsorption capacity of the composite adsorption material to heavy metals is not enough because the rice hulls are not modified. Chinese patent document CN108855006A provides a method for preparing a heavy metal adsorbent, in which mesoporous silica prepared from nitric acid, sodium alkylsulfonate, polyvinyl alcohol and ethyl orthosilicate are used as raw materials, and nanometer hydroxyapatite, calcium silicate and the like are used in combination as an adsorbent for adsorbing heavy metals, but the raw materials and the preparation method of the material are complex, so that the cost of the repairing agent is increased, the risk of secondary pollution is increased, and the hydroxyapatite and the silica are simply physically mixed, so that the adsorption efficiency of heavy metals is insufficient.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides preparation and application of a hydroxyapatite modified mesoporous silica adsorption material.
The invention relates to a method for preparing mesoporous silica material with uniformly distributed pores by carrying out pyrolysis reaction on agricultural wastes and a template agent; the preparation method of the hydroxyapatite modified mesoporous silica adsorption material is disclosed for the first time, hydroxyapatite is generated on the surface and in the pores of the mesoporous silica through modification reaction, and the hydroxyapatite in the pores is in a nano-scale, so that the binding capacity of the hydroxyapatite and the silica is improved; the hydroxyapatite modified mesoporous silica adsorption material has higher adsorption capacity on divalent cations, agricultural solid wastes are recycled, the investment cost is low, and the hydroxyapatite modified mesoporous silica adsorption material has the advantages of high adsorption capacity on Pb in water body2+The removal effect of (2) is remarkable.
The technical scheme of the invention is as follows:
hydroxyapatite modified mesoporous silica adsorption material for adsorbing Pb in water2+The use of (1).
According to the invention, preferably, the hydroxyapatite modified mesoporous silica adsorbing material selectively adsorbs Pb in the water containing various cations2+The use of (1).
Further preferably, the cations contained in the water body remove Pb2+In addition, it also contains Na+、K+Or Ca2+One or more than two.
Further preferably, the cations contained in the water body remove Pb2+In addition, Cd2+And/or Cu2+。
Hydroxyapatite modified mesoporous silica adsorption material for adsorbing Pb in water2+The preparation method of the hydroxyapatite modified mesoporous silica adsorbing material comprises the following steps:
(1) removing impurities from the biomass material: crushing the biomass material, soaking the biomass material in deionized water overnight, filtering, putting the biomass material into dilute hydrochloric acid for boiling, washing the biomass material with the deionized water to be neutral, and drying the cleaned biomass powder at the temperature of 110-;
the step (1) has the functions of removing impurities and moisture in the biomass material and improving the purity and the mesoporous consistency of the silicon dioxide product.
(2) Pyrolysis of biomass materials: placing the biomass powder prepared in the step (1) in a crucible, placing the crucible in a muffle furnace for calcination, wherein the pyrolysis gas environment is air, the pyrolysis temperature is 500-700 ℃, and the pyrolysis time is 2-6h, so as to obtain biomass ash;
the step (2) is used for removing elements such as carbon, oxygen, sulfur and the like in the biomass material through pyrolysis to obtain biomass ash.
(3) Preparation of mesoporous silica: cetyl Trimethyl Ammonium Bromide (CTAB) or polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123) is adopted as a template agent; mixing a template agent, the biomass ash prepared in the step (2) and deionized water, and adjusting the pH of the mixed solution to 6.0-8.0 by using NaOH or HCl; stirring the solution at 80 ℃ for 3-5h at 5-50r/min, transferring the solution into a hydrothermal reaction kettle with a polytetrafluoroethylene lining after the solution is completely mixed, reacting for 5-10h at the temperature of more than 110 ℃, cooling after the reaction is finished, then carrying out solid-liquid separation on the reactant, washing the solid reactant with deionized water, then drying the solid reactant, placing the dried solid reactant in a muffle furnace for calcination at the temperature of 500 ℃ for 700 ℃ for 3-7h, and removing a template agent to finally obtain mesoporous silica;
the purpose of washing the solid reactant with deionized water in the step (3) is to remove excess template agent which is not bound to the biomass ash.
The step (3) aims to obtain the mesoporous silica with narrow pore distribution and better pore distribution orderliness by utilizing the proper mixing proportion and reaction conditions of the template agent, the biomass ash and the deionized water.
(4) The hydroxyapatite modified mesoporous silica comprises the following steps:
uniformly mixing mesoporous silica, concentrated phosphoric acid with the mass concentration of 85% and deionized water to prepare a suspension solution serving as a solution A; the mixing sequence of the components is as follows: uniformly mixing concentrated phosphoric acid with the mass concentration of 85% with deionized water, and then adding mesoporous silica;
uniformly mixing calcium hydroxide and deionized water to prepare a suspension solution as a solution B;
mixing the solution A and the solution B to ensure that the initial mesoporous silica is reacted in the mixed solution: h3PO4：Ca(OH)2In a molar ratio of (1-10): 6: 10, the molar concentration of the phosphoric acid is 0.075-0.3 mol/L; after the solutions are mixed, continuously stirring and adjusting the pH value of the mixed solution to 8.0-10.0, and finishing the reaction when the pH value is constant; and then carrying out solid-liquid separation on the mixed solution, washing the solid reactant with ethanol, and then drying to obtain the hydroxyapatite modified mesoporous silica.
And the purpose of ethanol washing in the step III is to remove moisture and impurities.
The step (4) is used for preparing the hydroxyapatite modified mesoporous silica adsorption material, and the hydroxyapatite generated through the reaction can enter the mesopores of the silica, so that the stability and the adsorption capacity of the modified adsorption material are improved.
Preferably, according to the invention, the biomass material in step (1) is agricultural waste rich in elemental silicon.
Further preferably, the biomass materials in the step (1) are rice hulls, rice straws and corn straws.
According to the invention, preferably, after the biomass material is pulverized in step (1), the biomass powder with the particle size of 10-80 meshes is selected.
According to the invention, the diluted hydrochloric acid in the step (1) has a molar concentration of 0.5-5 moL/L.
Preferably, according to the invention, the boiling time of the dilute hydrochloric acid in step (1) is 4 h.
Preferably, according to the invention, the pyrolysis temperature in step (2) is 600 ℃.
According to the invention, the pyrolysis time in step (2) is preferably 4 h.
Preferably, when cetyltrimethylammonium bromide (CTAB) is used as the template in the step (3), the template: biomass ash: the molar ratio of the deionized water is 0.6: 2: 130. 0.8:2:130 or 1.0: 2: 130.
Preferably, when the polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123) is used as a template in the step (3), the ratio of the template to the total weight of the block copolymer: biomass ash: the molar ratio of the deionized water is 0.017: 1: 136.
the mole number of the biomass ash is SiO2And (4) calculating the mole number of the catalyst.
According to the invention, the calcination temperature of the reactants in the muffle furnace in the step (3) is preferably 600 ℃.
According to the invention, the calcination time of the reactants in the muffle furnace in the step (3) is preferably 5 h.
According to the present invention, preferably, the reaction of the initial mesoporous silica in the mixed solution of step (iii): h3PO4：Ca(OH)2In a molar ratio of 1: 6: 10, phosphoric acid in the mixed solutionThe molar concentration of (A) is 0.15 mol/L.
Preferably, in the third step, the pH of the mixed solution of the solution a and the solution B is adjusted to 10.0 by using 0.1M NaOH solution.
According to the invention, the preferable hydroxyapatite modified mesoporous silica adsorbing material is used for removing Pb in water2+In particular to the removal of Pb in water2+The method comprises the following specific steps:
taking hydroxyapatite modified mesoporous silica adsorbing material, adding Pb-containing material2+Adding the water into the water body, uniformly mixing and adsorbing the water body with the mass concentration of 0.5-1.5g/L, and removing the adsorbing material after the adsorption is finished.
More preferably, the removal effect is better by adjusting the pH value of the water body to be 6-7.
More preferably, the temperature of the water body is adjusted to 25 ℃.
Hydroxyapatite modified biomass adsorbent for adsorbing Pb in water2+The use of (1).
According to the invention, the hydroxyapatite modified biomass adsorbent selectively adsorbs Pb in the water containing various cations2+The use of (1).
Further preferably, the cations contained in the water body remove Pb2+In addition, it also contains Na+、K+Or Ca2+One or more than two.
Further preferably, the cations contained in the water body remove Pb2+In addition, Cd2+And/or Cu2+。
Hydroxyapatite modified biomass adsorbent for adsorbing Pb in water2+The application of the hydroxyapatite-modified biomass adsorbent comprises the following steps:
1) removing impurities from the biomass material: crushing the biomass material, soaking the biomass material in deionized water overnight, filtering, putting the biomass material into dilute hydrochloric acid for boiling, washing the biomass material with the deionized water to be neutral, and drying the cleaned biomass powder at the temperature of 110-;
the step 1) has the functions of removing impurities and moisture in the biomass material and improving the consistency of the gaps of the biomass powder.
2) The hydroxyapatite modified biomass adsorbent comprises the following steps:
a, uniformly mixing biomass powder, concentrated phosphoric acid with the mass concentration of 85% and deionized water to prepare a suspension solution serving as a solution A; the mixing sequence of the components is as follows: uniformly mixing concentrated phosphoric acid with the mass concentration of 85% with deionized water, and then adding mesoporous silica;
b, uniformly mixing calcium hydroxide and deionized water to prepare a suspension solution as a solution B;
c mixing the solution A and the solution B, so that the initial biomass powder is reacted in the mixed solution: h3PO4：Ca(OH)2In a molar ratio of (1-10): 6: 10, the molar concentration of the phosphoric acid is 0.075-0.3 mol/L; after the solutions are mixed, continuously stirring and adjusting the pH value of the mixed solution to 8.0-10.0, and finishing the reaction when the pH value is constant; and then carrying out solid-liquid separation on the mixed solution, washing the solid reactant with ethanol, and then drying to obtain the hydroxyapatite modified biomass adsorbent.
The mole number of the biomass powder is determined by the SiO content2And (4) calculating the mole number of the catalyst.
The purpose of the ethanol washing in the step c is to remove moisture and impurities.
The step 2) is used for preparing the hydroxyapatite modified biomass adsorbent, and the hydroxyapatite generated through the reaction can enter the gaps of the biomass material, so that the stability and the adsorption capacity of the modified biomass material are improved.
Preferably, according to the invention, the biomass material in step 1) is agricultural waste rich in elemental silicon.
Further preferably, the biomass material in the step 1) is rice husk.
According to a preferred embodiment of the invention, after the biomass material has been comminuted in step 1), a biomass powder of between 10 and 80 mesh is selected.
Preferably, according to the invention, the boiling time of the dilute hydrochloric acid in step 1) is 4 h.
Preferably, according to the present invention, the step c mixesReacting initial biomass powder in a liquid mixture: h3PO4：Ca(OH)2In a molar ratio of 1: 6: 10, the molar concentration of the phosphoric acid in the mixed solution is 0.15 mol/L.
According to the invention, the pH of the mixed solution of the solution A and the solution B is preferably adjusted to 10.0 in the step c by using 0.1M NaOH solution.
According to the invention, the hydroxyapatite modified biomass adsorbent is preferably used for removing Pb in water2+In particular to the removal of Pb in water2+The method comprises the following specific steps:
taking hydroxyapatite modified biomass adsorbent, adding the adsorbent containing Pb2+Adding the water into the water body, uniformly mixing and adsorbing the water body with the mass concentration of 0.5-1.5g/L, and removing the adsorbing material after the adsorption is finished.
More preferably, the removal effect is better by adjusting the pH value of the water body to be 6-7.
More preferably, the temperature of the water body is adjusted to 25 ℃.
The invention has the advantages of
1. The method comprises the steps of carrying out pyrolysis reaction on agricultural wastes and a template agent to obtain a mesoporous silica material with uniformly distributed pores; the preparation method of the hydroxyapatite modified mesoporous silica adsorption material is disclosed for the first time, hydroxyapatite is generated on the surface and in the pores of the mesoporous silica through modification reaction, and the hydroxyapatite in the pores is in a nano-scale, so that the binding capacity of the hydroxyapatite and the silica is improved; the mesoporous silica adsorption material modified by hydroxyapatite has higher adsorption capacity on divalent cations,
2. the hydroxyapatite modified mesoporous silica adsorbing material takes agricultural solid waste as a raw material, so that the cost is saved, the problem of environmental pollution caused by random accumulation and incineration of the agricultural solid waste can be effectively reduced, and the resource utilization of the agricultural solid waste is realized.
3. According to the hydroxyapatite-modified mesoporous silica adsorption material, hydroxyapatite can be generated in the mesopores of silica in the form of nanoparticles, so that the binding capacity of the hydroxyapatite and the silica and the heavy gold of the hydroxyapatite and the silica are improvedThe adsorption property of the metal is to Pb in water2+The adsorption capacity of the adsorbent is high and can reach 254.9 mg/g.
4. The hydroxyapatite modified mesoporous silica adsorbing material has the advantages of relatively simple preparation process, short production period, easy popularization and industrial production, no secondary pollution of raw materials and production process, and good environmental compatibility.
5. The adsorbent related to the invention adsorbs Pb in water2+In time, is not influenced by Na+、K+And Ca2+The effects of cations common in these bodies of water; and in Cd2+And/or Cu2+With Pb2+When coexisting in water, the adsorbent related to the invention can adsorb Pb2+Adsorption is preferred.
Drawings
Fig. 1 is a Scanning Electron Microscope (SEM) image of a hydroxyapatite-modified mesoporous silica adsorbent prepared in example 1;
FIG. 2 is a scanning electron microscope image of an unmodified mesoporous silica adsorbent prepared in comparative example 1;
FIG. 3 is a scanning electron microscope image of the hydroxyapatite-modified mesoporous silica material prepared in comparative example 2;
FIG. 4 is a graph showing the effect of various cations in water on adsorption of Pb (II) by HASD;
FIG. 5 is a graph showing the effect of various cations on adsorption of Cd (II) by HASD.
Detailed Description
The present invention will be described in further detail below, but the scope of the present invention is not limited thereto.
Example 1.
A preparation method of a hydroxyapatite modified mesoporous silica adsorption material comprises the following specific steps:
(1) crushing rice hulls, selecting biomass powder of 10-80 meshes, soaking in deionized water overnight, filtering, putting the biomass material into dilute hydrochloric acid (1.0mol/L) to boil for 4 hours, washing with deionized water to be neutral, and drying the cleaned biomass powder at 120 ℃.
(2) And (2) placing the biomass powder prepared in the step (1) into a crucible, placing the crucible into a muffle furnace, calcining for 4 hours at 600 ℃ in a pyrolysis gas environment, taking out the crucible, and cooling to obtain white powdery solid as biomass ash.
(3) Placing 7.289g of CTAB (cetyl trimethyl ammonium bromide) into a 250mL conical flask, adding 58.5mL of deionized water and 3.0g of biomass ash prepared in the step (2) (namely the molar ratio of reactants is CTAB: biomass ash: water is 0.8:2:130) to obtain a mixed solution, and adjusting the pH of the mixed solution to 8.0 by using NaOH; and magnetically stirring the mixed solution at 80 ℃ for 4 hours at 10r/min, completely mixing the solution, transferring the mixed solution into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, reacting at 140 ℃ for 10 hours, naturally cooling, taking out the reactant, performing solid-liquid separation, washing the solid reactant with deionized water, performing vacuum pump filtration, repeatedly washing for 3 times to remove redundant template agent which is not combined with biomass ash, then drying the washed solid reactant in a 120 ℃ drying oven for 12 hours, and finally calcining the solid reactant in a muffle furnace at 600 ℃ for 5 hours to remove the template agent to obtain the mesoporous silica.
The biomass ash is SiO2Calculated, the molar mass was 60 and the CTAB molar mass was 364.45.
(4) The hydroxyapatite modified mesoporous silica comprises the following steps:
uniformly mixing 0.3 part of mesoporous silica prepared in the step (3), 3.5 parts of concentrated phosphoric acid with the mass concentration of 85% and 100 parts of deionized water according to the following components by weight to prepare a suspension solution serving as a solution A; the mixing sequence of the components is as follows: uniformly mixing concentrated phosphoric acid with the mass concentration of 85% with deionized water, and then adding mesoporous silica;
uniformly mixing 3.77 parts by weight of calcium hydroxide and 100 parts by weight of deionized water to prepare a suspension solution serving as a solution B;
mixing the solution A and the solution B to ensure that the initial mesoporous silica is reacted in the mixed solution: h3PO4：Ca(OH)2In a molar ratio of 1: 6: 10, the molar concentration of the phosphoric acid is 0.15mol/L, after the solution is mixed, the solution is continuously stirred, the pH value of the mixed solution is adjusted to 10.0 by using 0.1M NaOH solution, and the reaction is carried outContinuously detecting the pH value of the reactant in the process, and finishing the reaction when the pH value is constant; and then, carrying out solid-liquid separation on the reaction liquid, washing the solid reactant with ethanol for 3 times, and then drying to obtain hydroxyapatite modified mesoporous silica, wherein the label is HASD.
The hydroxyapatite modified mesoporous silica adsorption material is used for removing Pb in wastewater2+The application comprises the following specific steps:
10mg of hydroxyapatite-modified mesoporous silica was added to 30ml of Pb (NO)3)2Solution (Pb)2+Content 100mg/L, pH 6) in a conical flask, shaking for 12h in a constant temperature shaker at 25 ℃ and a rotation speed of 100 rpm, and separating the adsorbent material from the solution by precipitation.
Example 2.
As described in example 1, except that: the rice straw is used as a raw material, and the prepared hydroxyapatite modified mesoporous silica is marked as HASD-1.
Example 3.
As described in example 1, except that: corn stalks are used as raw materials, and the prepared hydroxyapatite modified mesoporous silica is marked as HASD-2.
Example 4:
as described in example 1, except that: when the mesoporous silica is prepared in the step (3), the molar ratio of the template (CTAB), the biomass ash and the deionized water is 1.0: 2:130, and marking the prepared hydroxyapatite modified mesoporous silica as HASD-3.
Example 5:
as described in example 1, except that: when the mesoporous silica is prepared in the step (3), HCl (0.1mol/L) is adopted to adjust the pH value to 6.0, the reaction system is acidic, and the prepared hydroxyapatite modified mesoporous silica is marked as HASD-4.
Example 6:
as described in example 1, except that: when the mesoporous silica is prepared in the step (3), the template agent is polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123), and the molar ratio of the template agent to the biomass ash to the deionized water is 0.017: 1: 136, and marking the prepared hydroxyapatite modified mesoporous silica as HASD-5.
Example 7:
as described in example 1, except that: when the hydroxyapatite is used for modifying the mesoporous silica in the step (4), the adding weight of the mesoporous silica in the step (i) is 3 parts, so that the initial mesoporous silica is reacted in the mixed solution in the step (iii): h3PO4： Ca(OH)2In a molar ratio of 10: 6: 10, the molar concentration of the phosphoric acid is 0.15mol/L, and the final hydroxyapatite modified mesoporous silica is marked as HASD-6.
Example 8:
as described in example 1, except that: when the hydroxyapatite is used for modifying the mesoporous silica in the step (4), 200 parts of deionized water is used in the step (i), and 50 parts of deionized water is used in the step (ii), so that the initial mesoporous silica is reacted in the mixed solution in the step (iii): h3PO4：Ca(OH)2In a molar ratio of 1: 6: 10, the final hydroxyapatite modified mesoporous silica with the molar concentration of phosphoric acid of 0.12mol/L is marked as HASD-7.
Example 9:
as described in example 1, except that: when the hydroxyapatite is used for modifying the mesoporous silica in the step (4), 50 parts of deionized water is used in the step (i) and 50 parts of deionized water is used in the step (ii), so that the initial mesoporous silica is reacted in the mixed solution in the step (iii): h3PO4：Ca(OH)2In a molar ratio of 1: 6: 10, the final hydroxyapatite modified mesoporous silica with the molar concentration of phosphoric acid of 0.3mol/L is marked as HASD-8.
Example 10:
as described in example 1, except that: pb adsorbed by HASD2+The pH of the solution was 2.
Example 11:
as described in example 1, except that: adsorption of Pb in solution with HASD2+When the temperature is 20 ℃.
Example 12:
a preparation method of a hydroxyapatite modified biomass adsorbent comprises the following steps:
1) crushing rice hulls, selecting biomass powder of 10-80 meshes, soaking in deionized water overnight, filtering, putting the biomass material into dilute hydrochloric acid (1.0mol/L) to boil for 4 hours, washing with deionized water to be neutral, and drying the cleaned biomass powder at 120 ℃.
The step 1) has the functions of removing impurities and moisture in the biomass material and improving the consistency of the gaps of the biomass powder.
2) The hydroxyapatite modified biomass material comprises the following steps:
a, uniformly mixing 1.83 parts by weight of biomass powder prepared in the step 1), 3.5 parts by weight of concentrated phosphoric acid with the mass concentration of 85% and 100 parts by weight of deionized water to prepare a suspension solution serving as a solution A; the mixing sequence of the components is as follows: uniformly mixing concentrated phosphoric acid with the mass concentration of 85% with deionized water, and then adding mesoporous silica;
uniformly mixing 3.77 parts by weight of calcium hydroxide and 100 parts by weight of deionized water to prepare a suspension solution serving as a solution B;
mixing the solution A and the solution B to enable the mixed solution to react with the initial biomass powder: h3PO4：Ca(OH)2In a molar ratio of 1: 6: 10, the molar concentration of phosphoric acid is 0.15mol/L, after the solutions are mixed, continuously stirring, adjusting the pH value of the mixed solution to 10.0 by using 0.1M NaOH solution, continuously detecting the pH value of a reactant in the reaction process, and finishing the reaction when the pH value is constant; and then, carrying out solid-liquid separation on the reaction liquid, washing the solid reactant with ethanol for 3 times, and then drying to obtain the hydroxyapatite modified biomass adsorbent, which is marked as HABC.
The mole number of the biomass powder is determined by the SiO content2The weight percent of silica in the hulls was 16.4% calculated as moles.
The hydroxyapatite modified biomass adsorbent is used for removing Pb in wastewater2+The application comprises the following specific steps:
10.00mg of hydroxyapatite-modified biomass adsorbent was added to 30.0ml of Pb (NO)3)2Solution (Pb)2+Content (wt.)100mg/L, pH 6) in a conical flask, shaking for 12h at 25 ℃ in a constant temperature shaker at 100 rpm, and separating the adsorbent material from the solution by precipitation.
Comparative example 1:
as described in example 1, except that: the hydroxyapatite modification of step (4) was not performed, i.e. unmodified mesoporous silica, labeled SD.
Comparative example 2
As described in example 1, except that: when the hydroxyapatite is used for modifying the mesoporous silica in the step (4), the weight part of the mesoporous silica in the step (i) is 0.15, and the mass concentration of the concentrated phosphoric acid with the concentration of 85% is 1.75, so that the initial mesoporous silica is reacted in the mixed solution in the step (iii): h3PO4：Ca(OH)2In a molar ratio of 0.5: 3: 10, the molar concentration of phosphoric acid is 0.075mol/L, and the final hydroxyapatite modified mesoporous silica is marked as HASD-I
Comparative example 3
As described in example 1, except that: when the hydroxyapatite is used for modifying the mesoporous silica in the step (4), the weight part of the mesoporous silica in the step (i) is 0.6, and the mass concentration of the concentrated phosphoric acid with the concentration of 85% is 7, so that the initial mesoporous silica is reacted in the mixed solution in the step (iii): h3PO4：Ca(OH)2In a molar ratio of 1: 6: and 5, the molar concentration of the phosphoric acid is 0.3mol/L, and the final hydroxyapatite modified mesoporous silica is marked as HASD-II.
Comparative example 4
As described in example 12, except that: step 2) is not carried out, and the biomass powder obtained in step 1) is directly used as an adsorbent and is marked as BS.
Examples of effects
Adsorbents prepared in examples 1 to 9, example 12 and comparative examples 1 to 4 were used for Pb2+The adsorption capacity is shown in Table 1, and the same adsorbent can be used for Pb under different application conditions2+The adsorption amounts are shown in table 2; determination of Pb in solution by flame atomic absorption Spectrophotometer2+The concentration, and thus the amount of adsorption was calculated.
TABLE 1
Reference numerals Adsorbent and process for producing the same Pb2+Adsorption amount, mg/g Initial solution Pb2+，mg/L Pb of adsorbed solution2+，mg/L
Example 1 HASD 254.9 100 15.05
Example 2 HASD-1 225.6 100 24.80
Example 3 HASD-2 220.8 100 26.40
Example 4 HASD-3 159.0 100 47.00
Example 5 HASD-4 150.6 100 49.80
Example 6 HASD-5 178.1 100 40.65
Example 7 HASD-6 137.9 100 54.05
Example 8 HASD-7 190.7 100 36.45
Example 9 HASD-8 199.9 100 33.35
Example 12 HABC 153.9 100 48.70
Comparative example 1 SD 109.5 100 63.50
Comparative example 2 HASD-I 115.9 100 61.37
Comparative example 3 HASD-II 98.12 100 67.30
Comparative example 4 BS 89.93 100 70.03
TABLE 2
Reference numerals pH Temperature of Pb2+Adsorption amount, mg/g Initial solution Pb2+，mg/L Pb of adsorbed solution2+，mg/L
Example 1 6 25 254.9 100 15.05
Example 10 2 25 48.45 100 83.85
Example 11 6 20 224.0 100 25.35
As is clear from the data results in Table 1, the method for preparing hydroxyapatite-modified mesoporous silica according to the present invention is directed to Pb2+The adsorption quantity of the mesoporous silica has great influence, and the modification of the mesoporous silica into hydroxyapatite modified mesoporous silica has great influence on Pb2+The adsorption effect of the mesoporous silica is obviously improved, and the unmodified mesoporous silica has good effect on Pb2+The adsorption capacity of the mesoporous silica is 109.5mg/g, and the hydroxyapatite modified mesoporous silica is obtained by modification to Pb2+The adsorption capacity reaches 254.9 mg/g.
The preparation method of the hydroxyapatite modified biomass adsorbent related to the invention is used for adsorbing Pb2+The adsorption amount of the raw material is obviously improved, and the unmodified biomass powder has a good effect on Pb2+The adsorption amount of the hydroxyapatite modified biomass adsorbent is 89.93mg/g, and the hydroxyapatite modified biomass adsorbent obtained by modifying the biomass powder can adsorb Pb2+The adsorption amount of (A) was 153.9 mg/g.
As can be seen from the data results in table 2, when the hydroxyapatite-modified mesoporous silica adsorbent according to the present invention is applied, the hydroxyapatite-modified mesoporous silica adsorbent is able to adsorb Pb at a pH of 6.0 and a temperature of 25 ℃2+The adsorption effect is more remarkable.
The technical scheme of the invention can realize the realization of the preparation of Pb in aqueous solution by hydroxyapatite modified mesoporous silica or modified biomass material2+The adsorption efficiency is not greatly influenced by different raw materials of the hydroxyapatite modified mesoporous silica, but the yield of the mesoporous silica is influenced due to different silicon contents in the raw materials, and the weight percentages of the silica in the rice husks, the rice straws and the corn straws used in the above embodiment are respectively 16.4%, 6.3% and 1.5%. In the preparation process of the hydroxyapatite modified mesoporous silica, the types and the dosages of different template agents and the dosage of related substance components in the hydroxyapatite modification are compared, and finally Pb is added2+The adsorption amount of (A) has a certain influence. Through the comparison example, under the condition that the same raw material (such as rice husk) is used, the prepared mesoporous silica has a more uniform porous structure than the biochar, hydroxyapatite particles closer to a nanometer grade can be formed in a pore channel when hydroxyapatite is adopted for modification, and the prepared adsorbing material has higher efficient adsorption capacity on heavy metal ions.
FIGS. 4 and 5 show Na+、K+、Ca2+、Pb2+、Cd2+And Cu2+Competition of these 6 ions on the adsorbent involved in the present inventionAdsorption relationship (wherein QPbAnd QCdRespectively for the adsorbent HASD to Pb2+And Cd2+Adsorption capacity of (C)0To add a concentration of competing ions), the following metal ions are all nitrates. FIG. 4 shows that the amount of Pb in the solution is 100mg/L2+In competitive adsorption for background solution, Na is added with univalent cation+And K+And other divalent cations Ca2+、Cd2+And Cu2+The increase in concentration has little effect on the adsorption of Pb ions. FIG. 5 shows that Cd at 100mg/L2+In competitive adsorption for background solutions, part of the metal ions (Na)+、K+、Ca2+) Will not affect the adsorbent pair Cd2+Adsorption of (3); but with Cu2+When the concentration of (2) is increased to 60mg/L, the HASD is used for Cd2+Until the Cu adsorption capacity begins to be affected2+When the concentration reaches 100mg/L, HASD pairs Cd2+The adsorption capacity of (A) is reduced by 11.8%; when 40mg/L of Pb is present in the solution2+Then, HASD pairs Cd2+Is significantly affected by Pb2+The ion concentration is increased until the concentration is increased to 100mg/L, and the HASD is used for Cd2+The adsorption capacity of the ions continues to decrease. The above examples show that the modified hydroxyapatite benefits from divalent cations (except for Ca)2+Other than) selective adsorption capacity, Na+、K+And Ca2+For the invention to the adsorbent pair Pb2+And Cd2+There is no competitive relationship with adsorption of (A); when it is Pb2+、Cd2+And Cu2+When these 3 ions coexist, the invention relates to the adsorbent to Pb2+Preferred is adsorption.
The adsorbents according to the present invention are Na-free+、K+And Ca2+The characteristics of the influence of common cations in the water body can be applied to the restoration of Pb in the saline wastewater2+And Cd2+Is used in the preparation of the medicament. The adsorbent according to the present invention is capable of preferentially adsorbing Pb2+Can be applied to selectively adsorb Pb in water2+。
The technical means disclosed by the technical scheme of the invention also comprises the technical scheme consisting of any combination of the technical characteristics. It will be apparent to those skilled in the art that various modifications and variations can be made without departing from the principles of the invention, and these modifications and variations are considered to be within the scope of the invention.

Claims (26)

1. Hydroxyapatite modified mesoporous silica adsorption material for adsorbing Pb in water2+The use of (1);
the preparation method of the hydroxyapatite modified mesoporous silica adsorption material comprises the following steps:
(1) removing impurities from the biomass material: crushing the biomass material, soaking the biomass material in deionized water overnight, filtering, putting the biomass material into dilute hydrochloric acid for boiling, washing the biomass material with the deionized water to be neutral, and drying the cleaned biomass powder at the temperature of 110-;
(2) pyrolysis of biomass materials: placing the biomass powder prepared in the step (1) in a crucible, placing the crucible in a muffle furnace for calcination, wherein the pyrolysis gas environment is air, the pyrolysis temperature is 500-700 ℃, and the pyrolysis time is 2-6h, so as to obtain biomass ash;
(3) preparation of mesoporous silica: cetyl Trimethyl Ammonium Bromide (CTAB) or polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123) is adopted as a template agent; mixing a template agent, the biomass ash prepared in the step (2) and deionized water, and adjusting the pH of the mixed solution to 6.0-8.0 by using NaOH or HCl; stirring the solution at 80 ℃ for 3-5h at 5-50r/min, transferring the solution into a hydrothermal reaction kettle with a polytetrafluoroethylene lining after the solution is completely mixed, reacting for 5-10h at the temperature of more than 110 ℃, cooling after the reaction is finished, then carrying out solid-liquid separation on the reactant, washing the solid reactant with deionized water, then drying the solid reactant, placing the dried solid reactant in a muffle furnace for calcination at the temperature of 500 ℃ for 700 ℃ for 3-7h, and removing a template agent to finally obtain mesoporous silica;
(4) the hydroxyapatite modified mesoporous silica comprises the following steps:
uniformly mixing mesoporous silica, concentrated phosphoric acid with the mass concentration of 85% and deionized water to prepare a suspension solution serving as a solution A; the mixing sequence of the components is as follows: uniformly mixing concentrated phosphoric acid with the mass concentration of 85% with deionized water, and then adding mesoporous silica;
uniformly mixing calcium hydroxide and deionized water to prepare a suspension solution as a solution B;
mixing the solution A and the solution B to ensure that the initial mesoporous silica is reacted in the mixed solution: h3PO4：Ca(OH)2In a molar ratio of (1-10): 6: 10, the molar concentration of the phosphoric acid is 0.075-0.3 mol/L; after the solutions are mixed, continuously stirring and adjusting the pH value of the mixed solution to 8.0-10.0, and finishing the reaction when the pH value is constant; and then carrying out solid-liquid separation on the mixed solution, washing the solid reactant with ethanol, and then drying to obtain the hydroxyapatite modified mesoporous silica.
2. The application of claim 1, wherein the hydroxyapatite modified mesoporous silica adsorbent material selectively adsorbs Pb in a water body containing multiple cations2+The use of (1).
3. The use according to claim 2, wherein the cations contained in the body of water are Pb-free2+In addition, it also contains Na+、K+Or Ca2+One or more than two.
4. The use according to claim 2, wherein the cations contained in the body of water are Pb-free2+In addition, Cd2+And/or Cu2+。
5. The use of claim 1, wherein the biomass material of step (1) is a silicon-rich agricultural waste.
6. The use of claim 5, wherein the biomass material of step (1) is rice hulls, rice straw, and corn stover.
7. The use of claim 5, wherein in step (1) after the biomass material has been comminuted, a biomass powder of between 10 and 80 mesh size is selected.
8. The use according to claim 5, wherein the diluted hydrochloric acid in the step (1) has a molar concentration of 0.5 to 5 moL/L;
boiling diluted hydrochloric acid for 4 hours in the step (1);
the pyrolysis temperature in the step (2) is 600 ℃;
the pyrolysis time in the step (2) is 4 h.
9. The use of claim 5, wherein when cetyltrimethylammonium bromide (CTAB) is used as the template in step (3), the ratio of the template: biomass ash: the molar ratio of the deionized water is 0.6: 2: 130. 0.8:2:130 or 1.0: 2: 130.
10. The use of claim 9, wherein when the polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123) of step (3) is used as a templating agent, the ratio of templating agent: biomass ash: the molar ratio of the deionized water is 0.017: 1: 136;
the calcination temperature of the reactants in the muffle furnace in the step (3) is 600 ℃;
and (3) the calcination time of the reactants in the muffle furnace is 5 h.
11. The use of claim 9, wherein step (c) reacts the initial mesoporous silica in the mixed solution: h3PO4：Ca(OH)2In a molar ratio of 1: 6: 10, the molar concentration of the phosphoric acid in the mixed solution is 0.15 mol/L.
12. The use of claim 11, wherein the pH of the mixture of solution A and solution B is adjusted to 10.0 with 0.1M NaOH solution.
13. Use according to any one of claims 1 to 12, characterised in thatIn particular to the removal of Pb from water bodies2+The method comprises the following specific steps:
taking hydroxyapatite modified mesoporous silica adsorbing material, adding Pb-containing material2+Adding the water into the water body, uniformly mixing and adsorbing the water body with the mass concentration of 0.5-1.5g/L, and removing the adsorbing material after the adsorption is finished.
14. The use of claim 13, wherein the pH of the body of water is adjusted to 6-7; the temperature of the water body is adjusted to be 25 ℃.
15. Hydroxyapatite modified biomass adsorbent for adsorbing Pb in water2+The use of (1);
in particular to a preparation method of the hydroxyapatite modified biomass adsorbent, which comprises the following steps:
1) removing impurities from the biomass material: crushing the biomass material, soaking the biomass material in deionized water overnight, filtering, putting the biomass material into dilute hydrochloric acid for boiling, washing the biomass material with the deionized water to be neutral, and drying the cleaned biomass powder at the temperature of 110-;
2) the hydroxyapatite modified biomass adsorbent comprises the following steps:
a, uniformly mixing biomass powder, concentrated phosphoric acid with the mass concentration of 85% and deionized water to prepare a suspension solution serving as a solution A; the mixing sequence of the components is as follows: uniformly mixing concentrated phosphoric acid with the mass concentration of 85% with deionized water, and then adding mesoporous silica;
b, uniformly mixing calcium hydroxide and deionized water to prepare a suspension solution as a solution B;
c mixing the solution A and the solution B, so that the initial biomass powder is reacted in the mixed solution: h3PO4：Ca(OH)2In a molar ratio of (1-10): 6: 10, the molar concentration of the phosphoric acid is 0.075-0.3 mol/L; after the solutions are mixed, continuously stirring and adjusting the pH value of the mixed solution to 8.0-10.0, and finishing the reaction when the pH value is constant; and then carrying out solid-liquid separation on the mixed solution, washing the solid reactant with ethanol, and then drying to obtain the hydroxyapatite modified biomass adsorbent.
16. The use of claim 15, wherein the hydroxyapatite-modified biomass adsorbent selectively adsorbs Pb in a body of water containing a plurality of cations2+The use of (1).
17. The use of claim 16, wherein the cations contained in the body of water are Pb-depleted2+In addition, it also contains Na+、K+Or Ca2+One or more than two.
18. The use of claim 16, wherein the cations contained in the body of water are Pb-depleted2+In addition, Cd2+And/or Cu2+。
19. The use of claim 15, wherein the biomass material in step 1) is agricultural waste rich in elemental silicon.
20. The use of claim 19 wherein the biomass material of step 1) is rice hulls.
21. The use of claim 19, wherein after the biomass material is pulverized in step 1), the biomass powder is selected to be between 10 and 80 mesh.
22. The use according to claim 19, wherein the dilute hydrochloric acid in step 1) is boiled for 4 hours.
23. The use of claim 19, wherein step c reacts the initial biomass powder in the mixed liquor: h3PO4：Ca(OH)2In a molar ratio of 1: 6: 10, the molar concentration of the phosphoric acid in the mixed solution is 0.15 mol/L.
24. The use of claim 19, wherein in step c, the pH of the mixture of solution a and solution B is adjusted to 10.0 with 0.1M NaOH solution.
25. Use according to any one of claims 15 to 24, in particular for removing Pb from a body of water2+The method comprises the following specific steps:
taking hydroxyapatite modified biomass adsorbent, adding the adsorbent containing Pb2+Adding the water into the water body, uniformly mixing and adsorbing the water body with the mass concentration of 0.5-1.5g/L, and removing the adsorbing material after the adsorption is finished.
26. The use of claim 25, wherein the pH of the body of water is adjusted to 6-7; the temperature of the water body is adjusted to be 25 ℃.
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4423645B2 (en) * 2006-04-28 2010-03-03 小野田化学工業株式会社 Hydroxyapatite silica composite porous material adsorbent and method for producing the same
CN102464810A (en) * 2010-11-12 2012-05-23 国家纳米技术与工程研究院 Hydroxyapatite-chitosan (HA-CTS) composite material for treating waste water and preparation method thereof
CN103861567A (en) * 2014-03-21 2014-06-18 桂林理工大学 Preparation method of hydroxyapatite/bagasse active carbon
CN104001471A (en) * 2014-06-13 2014-08-27 淮海工学院 Preparation method of silicon dioxide immobilized hydroxyapatite material
CN104667874A (en) * 2015-02-21 2015-06-03 桂林理工大学 Preparation method of hydroxyapatite modified compound heavy metal adsorbent with eucalyptus structure
CN106044734A (en) * 2016-06-23 2016-10-26 宝钢发展有限公司 Method for preparing nano-hydroxyapatite
CN109731542A (en) * 2019-03-13 2019-05-10 淮海工学院 A kind of hydroxyapatite and the preparation method and application thereof with absorption heavy metal lead ion

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4423645B2 (en) * 2006-04-28 2010-03-03 小野田化学工業株式会社 Hydroxyapatite silica composite porous material adsorbent and method for producing the same
CN102464810A (en) * 2010-11-12 2012-05-23 国家纳米技术与工程研究院 Hydroxyapatite-chitosan (HA-CTS) composite material for treating waste water and preparation method thereof
CN103861567A (en) * 2014-03-21 2014-06-18 桂林理工大学 Preparation method of hydroxyapatite/bagasse active carbon
CN104001471A (en) * 2014-06-13 2014-08-27 淮海工学院 Preparation method of silicon dioxide immobilized hydroxyapatite material
CN104667874A (en) * 2015-02-21 2015-06-03 桂林理工大学 Preparation method of hydroxyapatite modified compound heavy metal adsorbent with eucalyptus structure
CN106044734A (en) * 2016-06-23 2016-10-26 宝钢发展有限公司 Method for preparing nano-hydroxyapatite
CN109731542A (en) * 2019-03-13 2019-05-10 淮海工学院 A kind of hydroxyapatite and the preparation method and application thereof with absorption heavy metal lead ion

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
"Efficiency and lead uptake mechanism of a phosphonate functionalized mesoporous silica through P/Pb association ratio";José A et al.;《Materials Chemistry and Physics》;20190820;第239卷;第2页左栏第2段 *
"用稻壳灰为硅源合成有序介孔二氧化硅材料的研究";侯贵华等;《材料科学与工程学报》;20060820;第24卷(第4期);第528-529页第2.1-2.2部分、第528页左栏第1段 *
"石英砂负载羟基磷灰石对铅镉吸附性能";覃海富等;《科学技术与工程》;20180718;第18卷(第20期);摘要、第2页左栏第2段 *

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