CN111871389A - Preparation method of lanthanum hydroxide modified aerogel phosphorus removal adsorbent - Google Patents

Preparation method of lanthanum hydroxide modified aerogel phosphorus removal adsorbent Download PDF

Info

Publication number
CN111871389A
CN111871389A CN202010784776.2A CN202010784776A CN111871389A CN 111871389 A CN111871389 A CN 111871389A CN 202010784776 A CN202010784776 A CN 202010784776A CN 111871389 A CN111871389 A CN 111871389A
Authority
CN
China
Prior art keywords
lanthanum hydroxide
phosphorus removal
preparation
adsorbent
modified aerogel
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202010784776.2A
Other languages
Chinese (zh)
Other versions
CN111871389B (en
Inventor
南军
刘博涵
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Harbin Institute of Technology
Original Assignee
Harbin Institute of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Harbin Institute of Technology filed Critical Harbin Institute of Technology
Priority to CN202010784776.2A priority Critical patent/CN111871389B/en
Publication of CN111871389A publication Critical patent/CN111871389A/en
Application granted granted Critical
Publication of CN111871389B publication Critical patent/CN111871389B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • 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
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • 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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—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 form
    • B01J20/28047—Gels
    • 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
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
    • 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
    • C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/46—Materials comprising a mixture of inorganic and organic materials
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
    • 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
    • C02F2101/105—Phosphorus compounds

Abstract

A preparation method of a lanthanum hydroxide modified aerogel phosphorus removal adsorbent relates to a preparation method of a phosphorus removal adsorbent. Aims to solve the problems that the prior dephosphorizing adsorbent has low saturated adsorption quantity, is difficult to recycle after adsorption, has low mechanical property and the like. The preparation method comprises the following steps: mixing the dispersion liquid of the graphene oxide, the aqueous solution of lanthanum hydroxide and the aqueous solution of sodium alginate, violently stirring, dropwise adding the aqueous solution of a cross-linking agent to obtain water condensation beads, standing, performing cross-linking solidification, and finally washing and drying in sequence. The adsorbent disclosed by the invention can be recycled, and has the advantages of low cost, high adsorption speed, high adsorption capacity and good mechanical property. The invention is suitable for preparing the phosphorus removal adsorbent.

Description

Preparation method of lanthanum hydroxide modified aerogel phosphorus removal adsorbent
Technical Field
The invention belongs to the technical field of water pollution treatment, and particularly relates to a preparation method of a phosphorus removal adsorbent.
Background
Phosphorus is an important nutrient that is essential for the growth of organisms and is not renewable. However, excessive phosphate discharge can produce severe eutrophication in water bodies. This may lead to a reduction in dissolved oxygen, the formation of large amounts of algal toxins, which cause abnormal reproduction of algae and other aquatic plants, eventually leading to a breakdown of the ecosystem, posing a great threat to human health. Therefore, the method has important significance in effectively removing and recovering the phosphate in the water body.
Heretofore, various methods for removing phosphorus have been used, including biological methods, chemical precipitation methods, ion exchange methods, membrane treatment methods, adsorption methods, and the like. Among these methods, the adsorption method is considered to be the most effective method because of its simplicity of operation, low cost, no generation of excess sludge, and potential for phosphorus recovery. Over the past several decades, various adsorbents such as biochar, nanofibers, aerogel composites, modified zeolites, modified fly ash, and metal oxide nanomaterials have been developed and used in sewage phosphorous removal. However, since most of the adsorbents have low saturated adsorption amount, low removal efficiency, difficulty in separation process, difficulty in recycling, and the like, the application of these materials is limited.
Therefore, in response to the above problems, it is often selected to immobilize the adsorbent material on certain media to enhance the adsorption capacity. Lanthanum is an environmentally friendly rare earth material. Specificity for phosphate removal was demonstrated due to its strong binding ability to phosphate. Meanwhile, lanthanum can also be loaded on a carrier to carry out dephosphorization in aqueous solution, such as a Phoslock product proposed in Australia.
The biopolymer material has received great attention in the field of wastewater treatment due to its characteristics of low cost, no toxicity, high biocompatibility, environmental friendliness, and the like. In addition, macroporous biocomposites typically have dimensions on the order of millimeters, which can effectively separate spent adsorbent from treated water. Sodium alginate is one of the most common natural polymer materials, and is widely used in sewage purification. It has rich hydroxyl and carboxyl, has strong affinity to high-valence metal ions, and can develop a stable metal-biopolymer composite material through a crosslinking effect. Therefore, lanthanum ions are taken as a core and combined with sodium diatomate, which is beneficial to preparing more stable composite materials. However, most of the metal crosslinked biopolymer composite materials have low mechanical properties, which limits further applications.
Therefore, the development of the recyclable phosphorus removal adsorbent with high mechanical property and good phosphorus removal effect on the phosphorus in the water body is of great significance.
Disclosure of Invention
The invention provides a preparation method of a lanthanum hydroxide modified aerogel phosphorus removal adsorbent, aiming at solving the problems that the existing phosphorus removal adsorbent is low in saturated adsorption quantity, difficult to recycle after adsorption, low in mechanical property and the like.
The preparation method of the lanthanum hydroxide modified aerogel dephosphorization adsorbent comprises the following steps:
firstly, synthesizing lanthanum hydroxide modified water condensation beads:
firstly, dissolving graphene oxide in deionized water and performing ultrasonic dispersion to obtain a graphene oxide dispersion liquid;
dissolving lanthanum hydroxide in deionized water to obtain a lanthanum hydroxide aqueous solution; dissolving sodium alginate in deionized water to obtain sodium alginate aqueous solution;
mixing the dispersion liquid of the graphene oxide, the aqueous solution of lanthanum hydroxide and the aqueous solution of sodium alginate, and violently stirring at room temperature to obtain a mixed solution;
dripping a cross-linking agent aqueous solution into the mixed solution obtained in the step three dropwise under the normal temperature condition to obtain water condensation beads, and standing for 18-24 hours to ensure that the obtained water condensation beads are fully cross-linked and solidified;
and secondly, washing and drying the water condensation beads obtained in the step one in sequence to obtain the lanthanum hydroxide modified aerogel dephosphorization adsorbent.
Compared with the prior art, the invention has the following remarkable advantages:
1. the lanthanum hydroxide modified aerogel phosphorus removal adsorbent prepared by the invention is of a millimeter-scale spherical structure, the interior of the adsorbent is honeycomb-shaped, and lanthanum ions and zirconium ions are combined on a sodium diatomate substrate doped with graphene oxide in an embedding manner. The millimeter-scale spherical structure is beneficial to separation and regeneration, and the reutilization of the adsorbent is realized, so that the use cost is reduced; due to the introduction of the graphene oxide, the pores in the sodium alginate matrix are more uniformly arranged and communicated with each other, so that the diffusion resistance of phosphate ions can be reduced, and the adsorption speed of the phosphate ions is higher.
2. Lanthanum ions in the adsorbent play an important role, hydroxyl in lanthanum hydroxide is subjected to ion exchange with phosphate, lanthanum ions can also form lanthanum phosphate with the phosphate, and zirconium ions in a cross-linking agent are loaded on aerogel and have a relatively strong adsorption effect on the phosphate, so that the lanthanum hydroxide modified aerogel phosphorus removal adsorbent prepared by the invention has relatively high adsorption capacity and specific adsorption capacity on phosphate radicals, the maximum saturated adsorption amount is 307.6mg/g, and the lanthanum hydroxide modified aerogel phosphorus removal adsorbent can be applied to the pH value within the range of 2-10. And the adsorbent can recover more than 85% of original adsorption efficiency by regeneration with 1mol/L NaOH.
3. According to the invention, the sodium diatomate doped with graphene oxide is used for preparing the water condensation beads, so that the mechanical strength of the water condensation beads is improved, the water condensation beads are not easy to break in the vacuum freeze drying process, the structural integrity is maintained, and then the obtained lanthanum hydroxide modified aerogel phosphorus removal adsorbent has good mechanical properties, can stably exist in water, and is suitable for being applied to various practical water bodies.
4. The lanthanum hydroxide modified aerogel prepared by the invention has the characteristics of simple operation, easily obtained raw materials, short preparation period and the like, is beneficial to industrial large-scale production, and is suitable for the environmental protection technical fields of industrial sewage, domestic sewage, surface water treatment and the like.
5. The lanthanum-based raw material is lanthanum hydroxide, and compared with lanthanum chloride, hydroxyl in the lanthanum hydroxide is subjected to ion exchange with phosphate, so that the adsorbent disclosed by the invention has higher adsorption capacity and stronger specific adsorption capacity.
Drawings
FIG. 1 is a surface SEM image (200 μm) of a lanthanum hydroxide-modified aerogel adsorbent of example 1;
FIG. 2 is a cross-sectional SEM image (200 μm) of the lanthanum hydroxide-modified aerogel adsorbent of example 1;
FIG. 3 is a surface SEM image (100 μm) of a lanthanum hydroxide modified aerogel adsorbent of example 1;
FIG. 4 is a cross-sectional SEM image (100 μm) of the lanthanum hydroxide-modified aerogel adsorbent of example 1;
FIG. 5 is a graph showing the addition amount of the lanthanum hydroxide modified aerogel phosphorus removal adsorbent and the phosphate adsorption capacity in example 1;
FIG. 6 is an infrared spectrum of the lanthanum hydroxide modified aerogel of example 1 before and after adsorption; in the figure, a curve 1 is an infrared spectrum curve before adsorption, and a curve 2 is an infrared spectrum curve after adsorption;
FIG. 7 is an X-ray photoelectron spectrum of lanthanum hydroxide modified aerogel adsorbent of example 1 before and after adsorption; in the figure, 1 is an X-ray photoelectron energy spectrum before adsorption, and 2 is an X-ray photoelectron energy spectrum after adsorption;
FIG. 8 is an X-ray photoelectron spectrum of phosphorus before and after adsorption of the lanthanum hydroxide-modified aerogel adsorbent in example 1; in the figure, 1 is an X-ray photoelectron energy spectrum after adsorption, and 2 is an X-ray photoelectron energy spectrum before adsorption;
FIG. 9 is an X-ray photoelectron spectrum of lanthanum before adsorption of the lanthanum hydroxide-modified aerogel adsorbent of example 1;
FIG. 10 is an X-ray photoelectron spectrum of lanthanum element after adsorption of the lanthanum hydroxide-modified aerogel adsorbent in example 1;
FIG. 11 is an adsorption isotherm diagram of the lanthanum hydroxide modified aerogel phosphorus removal adsorbent obtained in example 1; curve 1 in the figure corresponds to 20 ℃, curve 2 in the figure corresponds to 40 ℃ and curve 3 in the figure corresponds to 60 ℃;
FIG. 12 is a graph comparing the adsorption amounts of the lanthanum hydroxide modified aerogel phosphorus removal adsorbent obtained in example 1 at different pH values;
FIG. 13 is a graph comparing the adsorption capacity of the lanthanum hydroxide modified aerogel phosphorus removal adsorbent obtained in example 1 under the interference of different types of anions;
fig. 14 is a diagram showing the desorption regeneration effect of the lanthanum hydroxide modified aerogel phosphorus removal adsorbent obtained in example 1;
fig. 15 is a graph showing the effect of the lanthanum hydroxide modified aerogel phosphorus removal adsorbent obtained in example 1 on removal of COD, total nitrogen and total phosphorus.
Detailed Description
The technical scheme of the invention is not limited to the specific embodiments listed below, and any reasonable combination of the specific embodiments is included.
The first embodiment is as follows: the preparation method of the lanthanum hydroxide modified aerogel phosphorus removal adsorbent comprises the following steps:
firstly, synthesizing lanthanum hydroxide modified water condensation beads:
firstly, dissolving graphene oxide in deionized water and performing ultrasonic dispersion to obtain a graphene oxide dispersion liquid;
dissolving lanthanum hydroxide in deionized water to obtain a lanthanum hydroxide aqueous solution; dissolving sodium alginate in deionized water to obtain sodium alginate aqueous solution;
mixing the dispersion liquid of the graphene oxide, the aqueous solution of lanthanum hydroxide and the aqueous solution of sodium alginate, and violently stirring at room temperature to obtain a mixed solution;
dripping a cross-linking agent aqueous solution into the mixed solution obtained in the step three dropwise under the normal temperature condition to obtain water condensation beads, and standing for 18-24 hours to ensure that the obtained water condensation beads are fully cross-linked and solidified;
and secondly, washing and drying the water condensation beads obtained in the step one in sequence to obtain the lanthanum hydroxide modified aerogel dephosphorization adsorbent.
1. The lanthanum hydroxide modified aerogel phosphorus removal adsorbent prepared by the embodiment is of a millimeter-scale spherical structure, the interior of the adsorbent is honeycomb-shaped, and lanthanum ions and zirconium ions are combined on a sodium diatomate substrate doped with graphene oxide in an embedding manner. The millimeter-scale spherical structure is beneficial to separation and regeneration, and the reutilization of the adsorbent is realized, so that the use cost is reduced; due to the introduction of the graphene oxide, the pores in the sodium alginate matrix are more uniformly arranged and communicated with each other, so that the diffusion resistance of phosphate ions can be reduced, and the adsorption speed of the phosphate ions is higher.
2. Lanthanum ions in the adsorbent of the embodiment play an important role, not only hydroxyl in lanthanum hydroxide is subjected to ion exchange with phosphate, but also lanthanum ions can form lanthanum phosphate with the phosphate, and meanwhile, zirconium ions in the cross-linking agent are loaded on aerogel and have a relatively strong adsorption effect on the phosphate, so that the lanthanum hydroxide modified aerogel phosphorus removal adsorbent prepared by the embodiment has relatively high adsorption capacity and specific adsorption capacity on phosphate, the maximum saturated adsorption amount is 307.6mg/g, and the lanthanum hydroxide modified aerogel phosphorus removal adsorbent can be applied to the range of pH value from 2 to 10. And the adsorbent can recover more than 85% of original adsorption efficiency by regeneration with 1mol/L NaOH.
3. This embodiment utilizes the sodium diatomate preparation water of doping oxidation graphite alkene to congeal the pearl, has improved the mechanical strength of water congeal the pearl, and the water congeals the pearl and is difficult broken in vacuum freeze-drying process, has kept the integrality of structure, and then the lanthanum hydroxide modified aerogel that obtains removes phosphorus adsorbent mechanical properties good, can stably exist in aqueous, is fit for using in all kinds of actual water.
4. The lanthanum hydroxide modified aerogel prepared by the embodiment has the characteristics of simplicity in operation, easiness in obtaining raw materials, short preparation period and the like, is beneficial to industrial large-scale production, and is suitable for the environmental protection technical fields of industrial sewage, domestic sewage, surface water treatment and the like.
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: the ultrasonic dispersion process comprises the following steps: performing ultrasonic treatment for 10-30 min under the ultrasonic power of 100-500W.
The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: the first step is that the mass fraction of graphene oxide in the graphene oxide dispersion liquid is 0.2-0.5%.
The fourth concrete implementation mode: the difference between this embodiment mode and one of the first to third embodiment modes is: step one, the mass fraction of lanthanum hydroxide in the lanthanum hydroxide aqueous solution is 1-10%.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is: step one, the mass fraction of the sodium alginate in the sodium alginate aqueous solution is 2-6%.
The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is: the stirring speed during the violent stirring is 1200-1500 r/min.
The seventh embodiment: the difference between this embodiment and one of the first to sixth embodiments is: the time for vigorous stirring at room temperature is 18-24 hours.
The specific implementation mode is eight: the present embodiment differs from one of the first to seventh embodiments in that: in the first step, the volume ratio of the mixed solution to the cross-linking agent aqueous solution is 1 (3-5).
The specific implementation method nine: the present embodiment differs from the first to eighth embodiments in that: in the step one, the mass fraction of ethanol in the cross-linking agent aqueous solution is 1-3%, and the mass fraction of zirconium oxychloride is 3-5%.
The detailed implementation mode is ten: the present embodiment differs from one of the first to ninth embodiments in that: the washing and drying process in the second step comprises the following steps: firstly, washing the water-coagulated beads with deionized water for 3-5 times, and then, freeze-drying the water-coagulated beads at-50 to-40 ℃ under vacuum for 18-24 hours.
Example 1:
the preparation method of the lanthanum hydroxide modified aerogel phosphorus removal adsorbent provided by the embodiment is carried out according to the following steps:
firstly, synthesizing lanthanum hydroxide modified water condensation beads:
firstly, dissolving 0.5g of graphene oxide in 150ml of deionized water, performing ultrasonic dispersion, and performing ultrasonic treatment for 10min under 100W of ultrasonic power to obtain a graphene oxide dispersion liquid;
dissolving 6g of lanthanum hydroxide in 100mL of deionized water to obtain a lanthanum hydroxide aqueous solution; dissolving 2g of sodium alginate in 50mL of deionized water to obtain a sodium alginate aqueous solution;
mixing the dispersion liquid of the graphene oxide, the aqueous solution of lanthanum hydroxide and the aqueous solution of sodium alginate, and stirring vigorously for 24 hours at room temperature to obtain a mixed solution, wherein the stirring speed is 1200-1500 r/min;
dripping 1000mL of cross-linking agent aqueous solution into the mixed solution obtained in the step III dropwise under the condition of normal temperature to obtain water condensation beads, and standing for 24 hours to ensure that the obtained water condensation beads are fully cross-linked and solidified; the mass fraction of ethanol in the cross-linking agent aqueous solution is 1 percent, and the mass fraction of zirconium oxychloride is 3 percent;
washing and drying the water condensation beads obtained in the step one in sequence to obtain a lanthanum hydroxide modified aerogel dephosphorization adsorbent;
the washing and drying process comprises the following steps: firstly, washing the water-coagulated beads for 5 times by using deionized water, and then, freeze-drying the water-coagulated beads for 24 hours at the temperature of minus 50 ℃ under vacuum;
FIG. 1 is a surface SEM image (200 μm) of a lanthanum hydroxide-modified aerogel adsorbent of example 1; FIG. 2 is a cross-sectional SEM image (200 μm) of the lanthanum hydroxide-modified aerogel adsorbent of example 1; FIG. 3 is a surface SEM image (100 μm) of a lanthanum hydroxide modified aerogel adsorbent of example 1; FIG. 4 is a cross-sectional SEM image (100 μm) of the lanthanum hydroxide-modified aerogel adsorbent of example 1; as can be seen from fig. 1 to 4, the lanthanum hydroxide modified aerogel phosphorus removal adsorbent obtained in example 1 is a spherical structure, and the overall size is millimeter level, so that the lanthanum hydroxide modified aerogel phosphorus removal adsorbent is easy to separate and is favorable for regeneration; the surface of the adsorbent is smooth, and the inside of the adsorbent is of a honeycomb layered structure;
the lanthanum hydroxide modified aerogel-based dephosphorizing adsorbent obtained in example 1 was tested as follows:
1. weighing 5-70 mg of lanthanum hydroxide modified aerogel phosphorus removal adsorbent obtained in example 1, and adding 100ml of KH with initial phosphorus concentration of 150mg/L2PO4In the solution, the solution is shaken for 24 hours under the conditions of constant temperature of 25 ℃ and rotation speed of 150 r/min. Taking the supernatant, filtering the supernatant through a 0.45 mu m microporous filter membrane, and measuring the phosphate concentration in the solution by adopting an ammonium molybdate spectrophotometry.
FIG. 5 is a graph showing the addition amount of the lanthanum hydroxide modified aerogel phosphorus removal adsorbent and the phosphate adsorption capacity in example 1; as can be seen from FIG. 5, the maximum adsorption capacity of 307.6mg/g was achieved when 50mg/L of the adsorbent was added. FIG. 6 is an infrared spectrum of the lanthanum hydroxide modified aerogel of example 1 before and after adsorption; as can be seen from FIG. 6, 522cm after the adsorbent had adsorbed phosphorus-1And 614cm-1The bending vibration peak of phosphate radical appears at 1030cm-1The asymmetric stretching vibration peak of phosphate radical appears, which shows that the aerogel adsorbent has good removal effect on phosphorusAnd (5) effect. FIG. 7 is an X-ray photoelectron spectrum of lanthanum hydroxide modified aerogel adsorbent of example 1 before and after adsorption; FIG. 8 is an X-ray photoelectron spectrum of phosphorus before and after adsorption of the lanthanum hydroxide-modified aerogel adsorbent in example 1; FIG. 9 is an X-ray photoelectron spectrum of lanthanum before adsorption of the lanthanum hydroxide-modified aerogel adsorbent of example 1; FIG. 10 is an X-ray photoelectron spectrum of lanthanum element after adsorption of the lanthanum hydroxide-modified aerogel adsorbent in example 1; as can be seen from FIGS. 7 to 10, La, Zr, O and C elements are present in the adsorbent. After the adsorbent had adsorbed phosphorus, a new binding energy of the P2P peak was observed at 133.12eV, indicating that phosphate had been adsorbed by the aerogel adsorbent. La3d3/2And La3d5/2The core peak of (a) was shifted to a higher value, indicating that electron transfer of La3d occurred and that a La-O-P complex was formed.
2. Weighing 20mg of lanthanum hydroxide modified aerogel phosphorus removal adsorbent obtained in example 1, and respectively adding the lanthanum hydroxide modified aerogel phosphorus removal adsorbent to 100ml of KH with initial phosphorus concentration of 10-100 mg/L2PO4In the solution, the solution is oscillated for 24 hours under the conditions of reaction temperature of 20, 40 and 60 ℃ and rotation speed of 150 r/min. Taking the supernatant, filtering the supernatant through a 0.45 mu m microporous filter membrane, and measuring the phosphate concentration in the solution by adopting an ammonium molybdate spectrophotometry. FIG. 11 is an adsorption isotherm diagram of the lanthanum hydroxide modified aerogel phosphorus removal adsorbent obtained in example 1; as can be seen from fig. 11, the adsorption of phosphate by the adsorbent is an exothermic reaction, and the lower the temperature, the higher the adsorption efficiency.
3. Weighing 20mg of the lanthanum hydroxide modified aerogel phosphorus removal adsorbent obtained in example 1, and respectively adding the lanthanum hydroxide modified aerogel phosphorus removal adsorbent to 100ml of KH with initial pH of 2-12 and initial phosphorus concentration of 50mg/L2PO4In the solution, the solution was shaken for 24 hours at a reaction temperature of 25 ℃ and a rotation speed of 150 r/min. Taking the supernatant, filtering the supernatant through a 0.45 mu m microporous filter membrane, and measuring the phosphate concentration in the solution by adopting an ammonium molybdate spectrophotometry. FIG. 12 is a graph comparing the adsorption amounts of the lanthanum hydroxide modified aerogel phosphorus removal adsorbent obtained in example 1 at different pH values; as can be seen from FIG. 12, the lower the pH, the higher the adsorption efficiency of the lanthanum hydroxide modified aerogel phosphorus removal adsorbent, and the adsorbentCan be applied in a wide pH range (pH 2-10).
4. 20mg of lanthanum hydroxide modified aerogel dephosphorizing adsorbent obtained in example 1 was weighed and added to 100ml of KH with initial phosphorus concentration of 50mg/L2PO4Adding different kinds of anions with the molar ratio of 1:1 to the phosphorus into the solution, and oscillating for 24 hours at the constant temperature of 25 ℃ and the rotating speed of 150 r/min. Taking the supernatant, filtering the supernatant through a 0.45 mu m microporous filter membrane, and measuring the phosphate concentration in the solution by adopting an ammonium molybdate spectrophotometry. Another phosphorus solution without other anions was used as a control. Fig. 13 is a graph comparing the adsorption capacity of the lanthanum hydroxide modified aerogel phosphorus removal adsorbent obtained in example 1 under the interference of different types of anions. As can be seen from fig. 13, the removal of phosphate is hardly affected by four anions, namely chloride, sulfate, nitrate and bicarbonate, which indicates that the lanthanum hydroxide modified aerogel phosphorus removal adsorbent has good specific selectivity and strong interference resistance to phosphate.
5. 0.5g of the lanthanum hydroxide modified aerogel dephosphorizing adsorbent obtained in example 1 was weighed out and added to 1000ml of KH with an initial phosphorus concentration of 50mg/L2PO4In the solution, oscillating for 24 hours under the conditions of constant temperature of 25 ℃ and rotation speed of 150r/min to obtain the saturated adsorbent. And then, washing the obtained saturated adsorbent with deionized water for 3-5 times, adding the saturated adsorbent into a solution containing 1mol/L NaOH, and oscillating for 24 hours at the constant temperature of 25 ℃ and the rotating speed of 150 r/min. Taking the supernatant, filtering the supernatant through a 0.45 mu m microporous filter membrane, and measuring the phosphate concentration in the solution by adopting an ammonium molybdate spectrophotometry. And (4) washing the regenerated adsorbent with deionized water for 3-5 times, and freeze-drying the adsorbent to be used as the adsorbent of the next round for continuous use. This was repeated 5 times. Fig. 14 is a diagram showing the desorption regeneration effect of the lanthanum hydroxide modified aerogel phosphorus removal adsorbent obtained in example 1; as can be seen from FIG. 14, the solution of NaOH of 1mol/L has a better desorption effect on the saturated lanthanum hydroxide modified aerogel dephosphorization adsorbent, and the first desorption rate is higher than 85%. The adsorption capacity of the adsorbent decreases slightly with increasing desorption times. This is due to the formation of partially irreversible products during the adsorption process, occupying the activityThe locus causes. The good desorption capability is beneficial to the regeneration and the utilization of the adsorbent and the recovery of phosphorus resources, thereby further reducing the use cost.
6. Based on the operation of the SBR sequencing batch reactor, each operation period comprises water inlet, reaction, water drainage and idle stages. The circulation mode of the reaction stage is water inlet for 5 minutes, anoxic reaction for 85 minutes, aerobic reaction for 210 minutes, precipitation for 45 minutes and water drainage for 15 minutes. The experimental temperature is controlled to be 20-25 ℃. In the process of oxygen deficiency, the concentration of dissolved oxygen is controlled below 0.5 mg/L. The concentration of dissolved oxygen in the aerobic stage is controlled to be 2-4 mg/L. The mechanical stirring rate of the stirrer was 120 r/min. The sludge concentration is controlled to be 3000-5000 mg/L, and the sludge age is kept between 15-20 days. The sludge is taken from a Harbin Taiping sewage treatment plant and is domesticated and inoculated in an SBR reactor. The average concentration of wastewater inlet water is as follows: COD: 400 mg/L; TN is 20 mg/L; TP 5 mg/L. And adding the lanthanum hydroxide modified aerogel phosphorus removal adsorbent at the last stage of the aerobic reaction for 20-40 minutes. The dosage of the adsorbent is 15 mg/L. And taking another SBR reactor without adding the adsorbent as a control group.
FIG. 15 is a graph showing the effect of the lanthanum hydroxide modified aerogel phosphorus removal adsorbent obtained in example 1 on the removal of COD, total nitrogen and total phosphorus; the figure corresponds to the COD of the control group, ● corresponds to the COD of example 1, a corresponds to the total phosphorus of the control group, a. corresponds to the total phosphorus of example 1, and diamond-solid corresponds to the total nitrogen of the control group, corresponding to the total nitrogen of example 1. As can be seen from fig. 15, the lanthanum hydroxide modified aerogel phosphorus removal adsorbent has an important influence on the phosphorus removal rate in the whole sewage treatment process. The total phosphorus removal rate in the control group was 79.40%, and the effluent phosphorus concentration was reduced to 1.03 mg/L. Compared with the control group, after the adsorbent is added, the total phosphorus removal rate is 96.2%, and the total phosphorus is reduced to about 0.19mg/L and is relatively stable. The result shows that after the lanthanum hydroxide modified aerogel phosphorus removal adsorbent with appropriate concentration is added, the phosphorus removal effect is obvious, and the phosphorus concentration of the effluent is stable and reaches and is superior to the national emission standard A. On the other hand, the average effluent COD concentration of the control group was 14.84mg/L, and the average effluent total nitrogen concentration was 4.35 mg/L. The average COD concentration of the effluent of the experimental group is 14.62mg/L, and the average total nitrogen concentration of the effluent is 4.42 mg/L. There was no statistically significant difference compared to the control group. The results show that the addition of the lanthanum hydroxide modified aerogel phosphorus removal sorbent had little effect on carbon and nitrogen removal.
Example 2:
this example differs from example 1 in that: the amount of graphene oxide was 0.3g and the amount of lanthanum hydroxide was 2 g.
5mg of lanthanum hydroxide modified aerogel phosphorus removal adsorbent obtained in example 2 was weighed, and 100ml of KH with initial phosphorus concentration of 150mg/L was added2PO4In the solution, the solution is shaken for 24 hours under the conditions of constant temperature of 25 ℃ and rotation speed of 150 r/min. Taking the supernatant, filtering the supernatant through a 0.45 mu m microporous filter membrane, and measuring the phosphate concentration in the solution by adopting an ammonium molybdate spectrophotometry. The result shows that the saturated adsorption capacity of the lanthanum hydroxide modified aerogel phosphorus removal adsorbent obtained in example 2 is 175.2mg P/g.
Example 3:
this example differs from example 1 in that: the dosage of the graphene oxide is 0.8g, and the dosage of the lanthanum hydroxide is 10 g.
Weighing 5mg of lanthanum hydroxide modified aerogel phosphorus removal adsorbent obtained in example 3, and adding 100ml of KH with initial phosphorus concentration of 150mg/L2PO4In the solution, the solution is oscillated for 24 hours under the conditions of constant temperature of 25 ℃ and rotation speed of 150 r/min. Taking the supernatant, filtering the supernatant through a 0.45 mu m microporous filter membrane, and measuring the phosphate concentration in the solution by adopting an ammonium molybdate spectrophotometry. The result shows that the saturated adsorption capacity of the lanthanum hydroxide modified aerogel phosphorus removal adsorbent obtained in example 3 is 165.6mg P/g.

Claims (10)

1. A preparation method of a lanthanum hydroxide modified aerogel dephosphorization adsorbent is characterized by comprising the following steps: the method comprises the following steps:
firstly, synthesizing lanthanum hydroxide modified water condensation beads:
firstly, dissolving graphene oxide in deionized water and performing ultrasonic dispersion to obtain a graphene oxide dispersion liquid;
dissolving lanthanum hydroxide in deionized water to obtain a lanthanum hydroxide aqueous solution; dissolving sodium alginate in deionized water to obtain sodium alginate aqueous solution;
mixing the dispersion liquid of the graphene oxide, the aqueous solution of lanthanum hydroxide and the aqueous solution of sodium alginate, and violently stirring at room temperature to obtain a mixed solution;
dripping a cross-linking agent aqueous solution into the mixed solution obtained in the step three dropwise under the normal temperature condition to obtain water condensation beads, and standing for 18-24 hours to ensure that the obtained water condensation beads are fully cross-linked and solidified;
and secondly, washing and drying the water condensation beads obtained in the step one in sequence to obtain the lanthanum hydroxide modified aerogel dephosphorization adsorbent.
2. The preparation method of the lanthanum hydroxide modified aerogel phosphorus removal adsorbent according to claim 1, characterized in that: the ultrasonic dispersion process comprises the following steps: performing ultrasonic treatment for 10-30 min under the ultrasonic power of 100-500W.
3. The preparation method of the lanthanum hydroxide modified aerogel phosphorus removal adsorbent according to claim 1, characterized in that: the first step is that the mass fraction of graphene oxide in the graphene oxide dispersion liquid is 0.2-0.5%.
4. The preparation method of the lanthanum hydroxide modified aerogel phosphorus removal adsorbent according to claim 1, characterized in that: step one, the mass fraction of lanthanum hydroxide in the lanthanum hydroxide aqueous solution is 1-10%.
5. The preparation method of the lanthanum hydroxide modified aerogel phosphorus removal adsorbent according to claim 1, characterized in that: step one, the mass fraction of the sodium alginate in the sodium alginate aqueous solution is 2-6%.
6. The preparation method of the lanthanum hydroxide modified aerogel phosphorus removal adsorbent according to claim 1, characterized in that: the stirring speed during the violent stirring is 1200-1500 r/min.
7. The preparation method of the lanthanum hydroxide modified aerogel phosphorus removal adsorbent according to claim 1, characterized in that: the time for vigorous stirring at room temperature is 18-24 hours.
8. The preparation method of the lanthanum hydroxide modified aerogel phosphorus removal adsorbent according to claim 1, characterized in that: in the first step, the volume ratio of the mixed solution to the cross-linking agent aqueous solution is 1 (3-5).
9. The preparation method of the lanthanum hydroxide modified aerogel phosphorus removal adsorbent according to claim 1, characterized in that: in the step one, the mass fraction of ethanol in the cross-linking agent aqueous solution is 1-3%, and the mass fraction of zirconium oxychloride is 3-5%.
10. The preparation method of the lanthanum hydroxide modified aerogel phosphorus removal adsorbent according to claim 1, characterized in that: the washing and drying process in the second step comprises the following steps: firstly, washing the water-coagulated beads with deionized water for 3-5 times, and then, freeze-drying the water-coagulated beads at-50 to-40 ℃ under vacuum for 18-24 hours.
CN202010784776.2A 2020-08-06 2020-08-06 Preparation method of lanthanum hydroxide modified aerogel dephosphorization adsorbent Active CN111871389B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010784776.2A CN111871389B (en) 2020-08-06 2020-08-06 Preparation method of lanthanum hydroxide modified aerogel dephosphorization adsorbent

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010784776.2A CN111871389B (en) 2020-08-06 2020-08-06 Preparation method of lanthanum hydroxide modified aerogel dephosphorization adsorbent

Publications (2)

Publication Number Publication Date
CN111871389A true CN111871389A (en) 2020-11-03
CN111871389B CN111871389B (en) 2022-06-21

Family

ID=73210778

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010784776.2A Active CN111871389B (en) 2020-08-06 2020-08-06 Preparation method of lanthanum hydroxide modified aerogel dephosphorization adsorbent

Country Status (1)

Country Link
CN (1) CN111871389B (en)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113000016A (en) * 2021-03-15 2021-06-22 中国环境科学研究院 Lanthanum modified volcanic rock material and preparation method and application thereof
CN113274976A (en) * 2021-04-28 2021-08-20 中国矿业大学 Synthetic method of lanthanum-doped graphene oxide nanocomposite fluorine removal agent
CN113491999A (en) * 2021-07-15 2021-10-12 哈尔滨工业大学 Preparation method of lanthanum-modified activated carbon adsorption material
CN113559797A (en) * 2021-08-09 2021-10-29 云南大学 Biochar aerogel material and preparation method and application thereof
CN113750964A (en) * 2021-09-24 2021-12-07 哈尔滨工业大学 Preparation method of lanthanum-loaded graphene aerogel phosphorus adsorbent
CN114558554A (en) * 2022-03-21 2022-05-31 重庆市生态环境科学研究院 Composite material with heterojunction, preparation and application thereof, and method for reducing total phosphorus concentration in water body
CN115121230A (en) * 2022-07-07 2022-09-30 北京师范大学珠海校区 Lanthanum-modified graphene oxide hydrogel and preparation method and application thereof
CN115845824A (en) * 2022-11-23 2023-03-28 中国市政工程东北设计研究总院有限公司 Immobilized composite microsphere dephosphorization adsorption material, and preparation method and application thereof

Citations (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001340756A (en) * 2000-03-27 2001-12-11 Natl Inst Of Advanced Industrial Science & Technology Meti Particles for adsorbing harmful anions and method of producing the same
US6338800B1 (en) * 2000-02-22 2002-01-15 Natural Chemistry, Inc. Methods and compositions using lanthanum for removing phosphates from water
US20050051492A1 (en) * 2003-09-04 2005-03-10 Tranter Troy J. High capacity adsorption media for separating or removing constituents and methods of producing and using the adsorption media
US20060216229A1 (en) * 2003-02-13 2006-09-28 Akzo Nobel N.V. Composition comprising a metal hydroxy salt, its preparation and use as catalyst or sorbent
CN102910625A (en) * 2012-11-14 2013-02-06 北京理工大学 Graphene oxide aerogel, preparation method and application
CN104624174A (en) * 2015-01-28 2015-05-20 哈尔滨工业大学 Preparation method of water body low-concentration phosphorus compound adsorbent
JP2016065029A (en) * 2014-09-15 2016-04-28 富田製薬株式会社 Lanthanum low absorption type oral phosphorus adsorbent
CN105921103A (en) * 2016-05-19 2016-09-07 四川理工学院 Preparation method of La(OH)3 modified kieselguhr and molecular sieve adsorption material for simultaneously fixing nitrogen and phosphorus
CN106693923A (en) * 2016-12-14 2017-05-24 华中科技大学 Gel for recovering phosphorus from water and preparation method and application thereof
CN109529775A (en) * 2019-01-18 2019-03-29 闽南师范大学 A kind of synthetic method and absorption property of graphene oxide-lanthanum hydroxide composite material
CN109529772A (en) * 2019-01-17 2019-03-29 美丽国土（北京）生态环境工程技术研究院有限公司 Phosphorus adsorbent and its preparation method and application
CN109847718A (en) * 2018-12-27 2019-06-07 暨南大学 A kind of hydrous zirconium oxide(HZO)/alginic acid strontium plural gel pearl and its preparation method and application
US20200002193A1 (en) * 2018-06-28 2020-01-02 Board Of Trustees Of The University Of Arkansas Water purification compositions and the method of producing the same
CN111013503A (en) * 2019-12-16 2020-04-17 中国科学院苏州纳米技术与纳米仿生研究所 Liquid metal aerogel, preparation method and application thereof
CN111359591A (en) * 2020-03-26 2020-07-03 山东建筑大学 Superparamagnetic graphene oxide/sodium alginate composite gel material and preparation method thereof
US20200325031A1 (en) * 2017-12-22 2020-10-15 Vito Nv Lanthanide-doped layered double hydroxides and method of producing same
US10938032B1 (en) * 2019-09-27 2021-03-02 The Regents Of The University Of California Composite graphene energy storage methods, devices, and systems
CN113559797A (en) * 2021-08-09 2021-10-29 云南大学 Biochar aerogel material and preparation method and application thereof

Patent Citations (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6338800B1 (en) * 2000-02-22 2002-01-15 Natural Chemistry, Inc. Methods and compositions using lanthanum for removing phosphates from water
JP2001340756A (en) * 2000-03-27 2001-12-11 Natl Inst Of Advanced Industrial Science & Technology Meti Particles for adsorbing harmful anions and method of producing the same
US20060216229A1 (en) * 2003-02-13 2006-09-28 Akzo Nobel N.V. Composition comprising a metal hydroxy salt, its preparation and use as catalyst or sorbent
US20050051492A1 (en) * 2003-09-04 2005-03-10 Tranter Troy J. High capacity adsorption media for separating or removing constituents and methods of producing and using the adsorption media
CN102910625A (en) * 2012-11-14 2013-02-06 北京理工大学 Graphene oxide aerogel, preparation method and application
JP2016065029A (en) * 2014-09-15 2016-04-28 富田製薬株式会社 Lanthanum low absorption type oral phosphorus adsorbent
CN104624174A (en) * 2015-01-28 2015-05-20 哈尔滨工业大学 Preparation method of water body low-concentration phosphorus compound adsorbent
CN105921103A (en) * 2016-05-19 2016-09-07 四川理工学院 Preparation method of La(OH)3 modified kieselguhr and molecular sieve adsorption material for simultaneously fixing nitrogen and phosphorus
CN106693923A (en) * 2016-12-14 2017-05-24 华中科技大学 Gel for recovering phosphorus from water and preparation method and application thereof
US20200325031A1 (en) * 2017-12-22 2020-10-15 Vito Nv Lanthanide-doped layered double hydroxides and method of producing same
US20200002193A1 (en) * 2018-06-28 2020-01-02 Board Of Trustees Of The University Of Arkansas Water purification compositions and the method of producing the same
CN109847718A (en) * 2018-12-27 2019-06-07 暨南大学 A kind of hydrous zirconium oxide(HZO)/alginic acid strontium plural gel pearl and its preparation method and application
CN109529772A (en) * 2019-01-17 2019-03-29 美丽国土（北京）生态环境工程技术研究院有限公司 Phosphorus adsorbent and its preparation method and application
CN109529775A (en) * 2019-01-18 2019-03-29 闽南师范大学 A kind of synthetic method and absorption property of graphene oxide-lanthanum hydroxide composite material
US10938032B1 (en) * 2019-09-27 2021-03-02 The Regents Of The University Of California Composite graphene energy storage methods, devices, and systems
CN111013503A (en) * 2019-12-16 2020-04-17 中国科学院苏州纳米技术与纳米仿生研究所 Liquid metal aerogel, preparation method and application thereof
CN111359591A (en) * 2020-03-26 2020-07-03 山东建筑大学 Superparamagnetic graphene oxide/sodium alginate composite gel material and preparation method thereof
CN113559797A (en) * 2021-08-09 2021-10-29 云南大学 Biochar aerogel material and preparation method and application thereof

Non-Patent Citations (8)

* Cited by examiner, † Cited by third party
Title
ENMIN ZONG等: "Facile preparation and characterization of lanthanum-loaded carboxylated multi-walled carbon nanotubes and their application for the adsorption of phosphate ions", 《JOURNAL OF MATERIALS SCIENCE》 *
JIANWEILIN等: "Immobilization of mobile and bioavailable phosphorus in sediments using lanthanum hydroxide and magnetite/lanthanum hydroxide composite as amendments", 《SCIENCE OF THE TOTAL ENVIRONMENT》 *
KALIMUTHU PANDI等: "A facile synthesis of metal ion-imprinted graphene oxide/alginate hybrid biopolymeric beads for enhanced fluoride sorption", 《RSC ADVANCES》 *
LAKSHMI PRASANNA LINGAMDINNE等: "Facile synthesis of lanthanum hydroxide doped graphene oxide for scavenged of radioactive and heavy elements from water", 《SYNTHETIC METALS》 *
SUJIE SHAN等: "《Highly porous zirconium-crosslinked graphene oxide/alginate aerogel beads for enhanced phosphate removal》", 《CHEMICAL ENGINEERING JOURNAL》 *
YAN DU等: "Enhanced phosphate removal by using La-Zr binary metal oxide nanoparticles confined in millimeter-sized anion exchanger", 《JOURNAL OF COLLOID AND INTERFACE SCIENCE》 *
张宇: "基于镧改性水凝胶制备及强化SBR工艺除磷效能研究", 《中国优秀博硕士学位论文全文数据库(硕士) 工程科技I辑》 *
金烁等: "镧改性材料对水中磷酸盐去除的研究进展", 《净水技术》 *

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113000016A (en) * 2021-03-15 2021-06-22 中国环境科学研究院 Lanthanum modified volcanic rock material and preparation method and application thereof
CN113274976A (en) * 2021-04-28 2021-08-20 中国矿业大学 Synthetic method of lanthanum-doped graphene oxide nanocomposite fluorine removal agent
CN113274976B (en) * 2021-04-28 2022-10-18 中国矿业大学 Synthetic method of lanthanum-doped graphene oxide nanocomposite fluorine removal agent
CN113491999A (en) * 2021-07-15 2021-10-12 哈尔滨工业大学 Preparation method of lanthanum-modified activated carbon adsorption material
CN113559797A (en) * 2021-08-09 2021-10-29 云南大学 Biochar aerogel material and preparation method and application thereof
CN113559797B (en) * 2021-08-09 2022-04-12 云南大学 Biochar aerogel material and preparation method and application thereof
CN113750964A (en) * 2021-09-24 2021-12-07 哈尔滨工业大学 Preparation method of lanthanum-loaded graphene aerogel phosphorus adsorbent
CN114558554A (en) * 2022-03-21 2022-05-31 重庆市生态环境科学研究院 Composite material with heterojunction, preparation and application thereof, and method for reducing total phosphorus concentration in water body
CN115121230A (en) * 2022-07-07 2022-09-30 北京师范大学珠海校区 Lanthanum-modified graphene oxide hydrogel and preparation method and application thereof
CN115121230B (en) * 2022-07-07 2023-11-28 北京师范大学珠海校区 Lanthanum-modified graphene oxide hydrogel and preparation method and application thereof
CN115845824A (en) * 2022-11-23 2023-03-28 中国市政工程东北设计研究总院有限公司 Immobilized composite microsphere dephosphorization adsorption material, and preparation method and application thereof

Also Published As

Publication number Publication date
CN111871389B (en) 2022-06-21

Similar Documents

Publication Publication Date Title
CN111871389B (en) Preparation method of lanthanum hydroxide modified aerogel dephosphorization adsorbent
US20220126267A1 (en) Co-pyrolyzed sludge biochar modified by lanthanum carbonate, preparation method and use thereof
CN101797496B (en) Preparation method of inorganic-organic compound-type adsorbent based on clinoptilolite and application for removing Cr(VI) in industrial waste water
CN114229983A (en) Method for preparing catalytic activated biochar from iron-containing excess sludge and removing antibiotics
CN102211018A (en) Membrane adsorbent for recycling nitrogen and phosphorus resources from waste water as well as preparation method and application thereof
CN114797781B (en) Preparation method of lanthanum-loaded nitrogen-doped porous carbon-phosphorus adsorption material
CN103752286B (en) Composite adsorbing material of a kind of heavy-metal ion removal and its preparation method and application
CN114057279A (en) Method for accelerating iron circulation by using hydrothermal carbon to promote catalytic degradation of organic pollutants
CN113526671A (en) Constructed wetland combined filler and application thereof
CN113979508B (en) Filling material of permeable reactive barrier, preparation method and application
CN110407334B (en) Preparation and application of synchronous denitrification biological filler for adsorbing nitrate ions
CN104001479A (en) Inorganic mineral water treatment agent and preparation method thereof
CN110721654A (en) Magnetic crystal/amorphous lanthanum zirconium iron oxide phosphorus removal adsorbent and synthesis method thereof
CN100415360C (en) Production of sewage dephosphor adsorbent by adsorptive ion rare earth
CN105692583A (en) Method for preparing beta-cyclodextrin-based boron-doped mesoporous carbon material through soft template method
CN110420653A (en) A kind of silver orthophosphate/hydro-thermal charcoal composite photo-catalyst and the preparation method and application thereof
CN110606536B (en) Method for synchronously removing phosphorus and preparing phosphorylated zero-valent iron and application thereof
CN113559839B (en) Preparation method of paper mill coagulation solid waste-based catalyst, product and application thereof
CN113083216B (en) Two-dimensional nickel-based composite metal oxide adsorbent, preparation method and application of adsorbent in removing phosphate radical
CN112844333B (en) Preparation method of organic phosphine doped polyvinyl alcohol chitosan composite sphere
CN100537442C (en) Method for preparing sewage water additive by intermediate product of diatomite purification
CN114700065A (en) Waste resin carbon sphere composite ozone catalyst and preparation method and application thereof
CN110681344B (en) Zirconium series nano hybrid material and application method thereof
CN112094039A (en) Electroplating sewage sludge dewatering curing agent and preparation method thereof
CN109908868B (en) Iron-based porous adsorption material, preparation method thereof and application thereof in wastewater treatment

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant