CN114887602A - Cellulose/polydopamine/lanthanum hydroxide composite material for efficiently removing phosphorus from water body - Google Patents

Cellulose/polydopamine/lanthanum hydroxide composite material for efficiently removing phosphorus from water body Download PDF

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CN114887602A
CN114887602A CN202210568382.2A CN202210568382A CN114887602A CN 114887602 A CN114887602 A CN 114887602A CN 202210568382 A CN202210568382 A CN 202210568382A CN 114887602 A CN114887602 A CN 114887602A
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composite material
cellulose
polydopamine
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lanthanum
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CN114887602B (en
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钱杰书
刘飞
潘丙才
张延扬
严欣华
申屠丹笛
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Nanjing University of Science and 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
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • 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
    • B01J20/22—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
    • 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
    • C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • 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
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    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract

The invention discloses a cellulose/polydopamine/lanthanum hydroxide composite material for efficiently removing phosphorus from a water body. The raw materials for preparing the composite material comprise: cellulose, dopamine hydrochloride, lanthanum nitrate hexahydrate and sodium hydroxide. The adsorption and phosphorus removal performance of the composite material is optimized by regulating and controlling the use amounts of the raw materials such as dopamine hydrochloride, lanthanum nitrate hexahydrate and sodium hydroxide, and the optimal technological parameters for material preparation are determined. The practical application capability of the material is highlighted through material dephosphorization performance, stability investigation and environmental influence factor evaluation. In conclusion, the material is simple and convenient in preparation process and controllable in conditions, and is beneficial to solving the problems of low adsorption capacity, poor adsorption selectivity, metal species leakage, poor recycling capability and the like of the lanthanum-based phosphorus removal adsorbent. The invention not only provides a certain theoretical support for the design of the water body dephosphorization composite material, but also has strong practical application potential.

Description

Cellulose/polydopamine/lanthanum hydroxide composite material for efficiently removing phosphorus from water body
Technical Field
The invention belongs to the technical field of water treatment, and relates to a cellulose/polydopamine/lanthanum hydroxide composite material for efficiently removing phosphorus from a water body.
Background
The enrichment of nutrients in water, particularly phosphorus (P) and nitrogen (N), accelerates the eutrophication process of water, resulting in a continuous deterioration of the global ecological environment. In order to strictly control the enrichment of nutrient substances in water, the discharge standard of phosphorus in the water environment is definitely regulated by the government and related departments in China. According to the requirements of Chinese water quality standards, the content of phosphorus in secondary effluent standards of sewage treatment plants (WWTPs) is not higher than 0.5mg/L, which puts higher requirements on water body phosphorus removal technology. At present, the water body dephosphorization technology which is widely applied mainly comprises anaerobic/aerobic biodegradation, electrochemistry, membrane filtration, adsorption and the like. Among these, adsorption is one of the simplest, efficient and economical techniques. The development of the adsorption material is particularly important as the core of the adsorption process, and particularly, the novel adsorption material with excellent performance, good stability and low cost is expected to promote the further development and application of the adsorption technology in the field of water body dephosphorization.
According to the report of the existing literature, lanthanum (La) can be coordinated with phosphate radical in water to generate a lanthanum phosphate compound, so that inorganic phosphorus in a water environment can be efficiently removed. However, lanthanum hydroxide (La (OH) is directly utilized 3 ) The efficiency of the adsorption material is low, and the particles are easy to agglomerate; a large amount of supported lanthanum-based adsorption materials taking inorganic materials as base materials can effectively avoid the agglomeration of particles, but the problem of secondary pollution caused by the loss of metal species cannot be avoided. Research shows that the lanthanum-based adsorption material designed by using the organic polymer has higher phosphorus adsorption capacity and can effectively improve the phosphorus adsorption capacityThe stability of the adsorbent in the adsorption process, but the high cost and the complex process restrict the large-scale popularization and application of the adsorbent in the field of water body dephosphorization. In addition, most of the organic polymers adopted at the present stage cannot be naturally degraded by the environment, and secondary pollution to the water environment can be caused. Therefore, the design and preparation of the environment-friendly lanthanum-based adsorption material with low cost, simple and convenient process and stable performance are expected to break the application bottleneck of the lanthanum-based adsorption material in the field of water body phosphorus removal.
As a low-cost, widely available polymeric biomass material, cellulosic materials have proven to be excellent templates for supported materials. Taking Bacterial Cellulose (BC) as an example, the Bacterial Cellulose (BC) has the characteristics of high chemical purity, rich hydroxyl on the surface, excellent biocompatibility and the like, and has huge practical application prospect in the research and development field of water treatment functional materials. The applicant's earlier work directly deposited lanthanum hydroxide on the surface of bacterial cellulose, and the results showed that the adsorption capacity was low and the loss of lanthanum species could not be avoided. According to the literature report, Polydopamine (PDA) can adsorb metal nanoparticles through the action of covalent bonds or non-covalent bonds, so that the stability of the polydopamine in the application process is improved. Therefore, the introduction of dopamine into the bacterial cellulose/lanthanum hydroxide composite material is expected to improve the phosphorus adsorption capacity and adsorption rate of the bacterial cellulose/lanthanum hydroxide composite material, enhance the stability of the material, and have the potential of large-scale popularization and application.
Disclosure of Invention
The invention aims to provide a cellulose/polydopamine/lanthanum hydroxide composite material for efficiently removing phosphorus in a water body.
The purpose of the invention is realized by adopting the following technical scheme:
a cellulose/polydopamine/lanthanum hydroxide composite material, wherein the cellulose is bacterial cellulose as an example, and the preparation method comprises the following steps: polymerizing the polydopamine material on the surface of the bacterial cellulose in situ, and then depositing the lanthanum hydroxide nanoparticles on the surface of the polydopamine material in situ.
The method specifically comprises the following steps:
step 1, preparing a dopamine hydrochloride solution, carrying out ultrasonic dissolution, weighing cellulose, immersing the cellulose in the solution, and carrying out ultrasonic dispersion;
step 2, adding tris (hydroxymethyl) aminomethane into the solution obtained in the step 1 to adjust the pH of the solution to 8.5, placing the solution in a constant-temperature shaking table for oscillation, taking out a sample, washing the sample with ethanol and water for multiple times, and freeze-drying the sample to obtain a cellulose/polydopamine composite material;
step 3, weighing the cellulose/polydopamine composite material and lanthanum nitrate hexahydrate, dispersing in an ethanol-water mixed solution, and carrying out ultrasonic treatment for 30 min;
and 4, slowly adding a sodium hydroxide solution into the solution obtained in the step 3, and stirring at 25 ℃ and 300rpm for 4 hours to obtain the cellulose/polydopamine/lanthanum hydroxide composite material.
Further, in the step 1, the concentration of the dopamine hydrochloride is 0.005-0.05 mol/L.
Further, in the step 1, the concentration of the dopamine hydrochloride is 0.02 mol/L.
Furthermore, in the step 3, the dosage of the lanthanum nitrate hexahydrate is 0.002-0.02 mol/L.
Further, in the step 3, the dosage of the lanthanum nitrate hexahydrate is 0.003 mol/L.
Further, in step 3, the volume ratio of ethanol to water is 1: 1.
Further, in the step 4, the concentration of NaOH is 0.01-0.4 mol/L.
Further, in the step 4, the concentration of NaOH is 0.1 mol/L.
Compared with the prior art, the invention has the advantages that:
(1) the method is simple and convenient, has low cost and mild required reaction conditions.
(2) The cellulose/polydopamine/lanthanum hydroxide composite material prepared by the invention has higher adsorption capacity and faster adsorption kinetics. Compared with the traditional lanthanum-based adsorption material, the cellulose/polydopamine/lanthanum hydroxide composite material has better stability and can keep higher adsorption capacity in a water body in a complex environment.
Drawings
FIG. 1 shows BC and BC/PDA/La (OH) 3 An optical photograph of (a); FIG. 1(a) is an optical photograph of BC1(b) is BC/PDA/La (OH) prepared according to the above procedure 3 Optical photographs of the composite.
FIG. 2 shows La (OH) 3 ,BC/La(OH) 3 BC/PDA and BC/PDA/La (OH) 3 The adsorption capacity to inorganic phosphorus in water.
FIG. 3 shows BC/PDA/La (OH) prepared with different dopamine hydrochloride amounts 3 The adsorption capacity to inorganic phosphorus in water.
FIG. 4 shows the difference La (NO) 3 ) 3 ·6H 2 BC/PDA/La (OH) prepared with O amount 3 The adsorption capacity to inorganic phosphorus in water.
FIG. 5 shows BC/PDA/La (OH) prepared with different amounts of NaOH 3 The adsorption capacity to inorganic phosphorus in water.
FIG. 6 is BC/PDA/La (OH) 3 -1 lanthanum leakage during five cycles.
FIG. 7 is BC/PDA/La (OH) 3 -1 five cycles of performance.
FIG. 8 is BC/PDA/La (OH) 3 -1 adsorption capacity for inorganic phosphorus in water body in different pH environments.
FIG. 9 is BC/PDA/La (OH) 3 -1 adsorption capacity for inorganic phosphorus in water in the presence of different inorganic anions.
FIG. 10 is BC/PDA/La (OH) 3 -1 adsorption capacity for inorganic phosphorus in water in the presence of dissolved organic matter.
FIG. 11 is BC/PDA/La (OH) 3 -1 inorganic phosphorus adsorption capacity in simulated and actual water bodies.
Detailed Description
The present invention will be described in further detail below with reference to the drawings, examples and comparative examples.
The invention provides a cellulose/polydopamine/lanthanum hydroxide composite material, wherein the cellulose takes bacterial cellulose as an example and comprises the following steps:
step 1, weighing dopamine hydrochloride, completely dissolving the dopamine hydrochloride under an ultrasonic condition, weighing BC (30mm multiplied by 30mm) and immersing the BC into the dopamine hydrochloride solution.
And 2, adding the tris (hydroxymethyl) aminomethane into the solution in the step 1 to adjust the pH of the solution to 8.5, and placing the solution in a constant-temperature shaking table for shaking. And then taking out the sample, washing the sample for multiple times by using ethanol and water, and freeze-drying the sample to obtain the BC/PDA composite material.
Step 3, weighing the BC/PDA composite material and La (NO) 3 ) 3 ·6H 2 Dispersing O in 40mL of ethanol-water (volume ratio is 1:1) mixed solution, and carrying out ultrasonic treatment for 30 min.
Step 4, then add NaOH solution slowly to the solution in step 3, stir at 300rpm for 4h at 25 ℃. Obtaining BC/PDA/La (OH) 3 A composite material.
In the step 1, the concentration of the dopamine hydrochloride is 0.005-0.05 mol/L.
In step 3, La (NO) is mentioned 3 ) 3 ·6H 2 The dosage of O is 0.002-0.02 mol/L.
In the step 3, the concentration of NaOH is 0.01-0.4 mol/L.
The BC/PDA composite material is prepared by chemical oxidative polymerization of dopamine and BC. Immersing BC membrane (30mm × 30mm) in dopamine hydrochloride (0.005,0.01,0.02,0.03,0.05mol/L) solution, and performing ultrasonic treatment at 25 deg.C for 30 min. Subsequently, tris (hydroxymethyl) aminomethane was added to the above solution to adjust the pH of the solution to 8.5, and the solution was shaken at 200rpm in a 30 ℃ constant temperature shaker for 12 hours to obtain a BC/PDA composite by freeze-drying (10Pa, -40 ℃). Subsequently, 0.1g of the BC/PDA composite was weighed out with the stated amount (0.002,0.003,0.004,0.008,0.02mol/L) of La (NO) 3 ) 3 ·6H 2 O is dispersed in a mixed solution of 20mL of ethanol and 20mL of water and subjected to ultrasonic treatment for 30 min. Then 20mL NaOH (0.01,0.05,0.1,0.2,0.5mol/L) solution was slowly added at 25 deg.C with stirring at 300 rpm. The solution was stirred at 300rpm for 4 h. To obtain BC/PDA/La (OH) 3 A composite material. BC and BC/PDA/La (OH) before and after preparation 3 The optical photograph of (a) is shown in FIG. 1.
BC/PDA/La(OH) 3 Phosphorus removal performance embodiment of composite material
Step 1, preparing 100ml of inorganic phosphorus solution with the concentration of 50 mg/L.
Step 2, weigh 10mg BC/PDA/La (OH) 3 The composite material is added into inorganic phosphorus solution, and the pH value is adjusted to 7.0 by using hydrochloric acid and sodium hydroxide.
And 3, placing the solution in a constant-temperature oscillation box, and oscillating and adsorbing at the rotating speed of 200rpm and the temperature of 25 ℃.
Step 4, the BC/PDA/La (OH) after the adsorption is finished 3 The composite material is taken out of the solution, is subjected to ultrasonic desorption in a methanol solution containing 0.1mol/L NaOH, is washed in ethanol and pure water for multiple times, and is frozen and dried for later use.
In the step 1, inorganic anions and soluble organic matters are optionally added or not added.
In the step 2, the pH value of the solution can be selected from 5.0,6.0,7.0,8.0 and 9.0.
The following examples are provided to illustrate specific data of the present invention
Example 1
Step 1, weighing BC (30mm multiplied by 30mm) and immersing in 0.02mol/L dopamine hydrochloride solution (0.379g dissolved in 100mL deionized water), and dissolving by ultrasonic dispersion for 30 min.
And 2, adding the tris (hydroxymethyl) aminomethane into the solution in the step 1 to adjust the pH of the solution to 8.5, and placing the solution in a constant-temperature shaking table for shaking. And then taking out the sample, washing the sample for multiple times by using ethanol and water, and freeze-drying the sample to obtain the BC/PDA composite material.
Step 3, weighing the BC/PDA composite material and 0.003mol/L (0.15g) of La (NO) 3 ) 3 ·6H 2 Dispersing O in 40mL of ethanol-water (volume ratio is 1:1) mixed solution, and carrying out ultrasonic treatment for 30 min.
Step 4, then NaOH solution (20mL of 0.1mol/L) was slowly added to the solution in step 3, and stirred at 300rpm for 4h at 25 ℃. Obtaining BC/PDA/La (OH) 3 A composite material. Named BC/PDA/La (OH) 3 -1。
Comparative examples providing specific data of the invention
Comparative example 1
Step 1 and step 2 are the same as step 1 and step 2 in the examples. The resulting material was named BC/PDA.
Comparative example 2
Step 1 is the same as step 1 in example 1.
Step 2, weigh BC (30 mm. times.30 mm) material and 0.003mol/L (0.15g) La (NO) 3 ) 3 ·6H 2 Dispersing O in 40mL of ethanol-water (volume ratio is 1:1) mixed solution, and carrying out ultrasonic treatment for 30 min.
Step 3, then NaOH solution (20mL of 0.1mol/L) was slowly added to the solution in step 2, and stirred at 300rpm for 4h at 25 ℃. To obtain BC/La (OH) 3 A composite material. The resulting material was named BC/La (OH) 3 。
Comparative example 3
Step 1, weighing BC (30mm multiplied by 30mm) and immersing in 0.005mol/L dopamine hydrochloride solution (0.095g dissolved in 100mL deionized water), and dissolving by ultrasonic dispersion for 30 min.
Step 2, step 3 and step 4 are the same as step 2, step 3 and step 4 in the examples. The resulting material was named BC/PDA/La (OH) 3 -2。
Comparative example 4
Step 1, weighing BC (30mm multiplied by 30mm) and immersing in 0.01mol/L dopamine hydrochloride solution (0.189g dissolved in 100mL deionized water), and dissolving by ultrasonic dispersion for 30 min.
Step 2, step 3 and step 4 are the same as step 2, step 3 and step 4 in the examples. The resulting material was named BC/PDA/La (OH) 3 -3。
Comparative example 5
Step 1, weighing BC (30mm multiplied by 30mm) and immersing in 0.03mol/L dopamine hydrochloride solution (0.568g dissolved in 100mL deionized water), and dissolving by ultrasonic dispersion for 30 min.
Step 2, step 3 and step 4 are the same as step 2, step 3 and step 4 in the examples. The resulting material was named BC/PDA/La (OH) 3 -4。
Comparative example 6
Step 1, weighing BC (30mm multiplied by 30mm) and immersing in 0.05mol/L dopamine hydrochloride solution (0.947g dissolved in 100mL deionized water), and dissolving by ultrasonic dispersion for 30 min.
Step 2, step 3 and step 4 are the same as step 2, step 3 and step 4 in the examples. The resulting material was named BC/PDA/La (OH) 3 -5。
Comparative example 7
Step 1 and step 2 are the same as step 1 and step 2 in example 1
Step 3, weighing BC/PDA to recoverThe material and 0.002mol/L (0.1g) of La (NO) 3 ) 3 ·6H 2 Dispersing O in 40mL of ethanol-water (volume ratio is 1:1) mixed solution, and carrying out ultrasonic treatment for 30 min.
Step 4 is the same as step 4 in the example. The resulting material was named BC/PDA/La (OH) 3 -6。
Comparative example 8
Step 1 and step 2 are the same as step 1 and step 2 in example 1
Step 3, weighing the BC/PDA composite material and 0.004mol/L (0.2g) of La (NO) 3 ) 3 ·6H 2 Dispersing O in 40mL of ethanol-water (volume ratio is 1:1) mixed solution, and carrying out ultrasonic treatment for 30 min.
Step 4 is the same as step 4 in the example. The resulting material was named BC/PDA/La (OH) 3 -7。
Comparative example 9
Step 1 and step 2 are the same as step 1 and step 2 in example 1
Step 3, weighing the BC/PDA composite material and 0.008mol/L (0.4g) of La (NO) 3 ) 3 ·6H 2 Dispersing O in 40mL of ethanol-water (volume ratio is 1:1) mixed solution, and carrying out ultrasonic treatment for 30 min.
Step 4 is the same as step 4 in the example. The resulting material was named BC/PDA/La (OH) 3 -8。
Comparative example 10
Step 1 and step 2 are the same as step 1 and step 2 in example 1
Step 3, weighing the BC/PDA composite material and 0.02mol/L (1.0g) of La (NO) 3 ) 3 ·6H 2 Dispersing O in 40mL of ethanol-water (volume ratio is 1:1) mixed solution, and carrying out ultrasonic treatment for 30 min.
Step 4 is the same as step 4 in the example. The resulting material was named BC/PDA/La (OH) 3 -9。
In a comparative example 11,
step 1, step 2, and step 3 were the same as step 1, step 2, and step 3 in example 1
Step 4, then NaOH solution (20mL of 0.01mol/L) was slowly added to the solution in step 3, and stirred at 300rpm for 4h at 25 ℃. Obtaining BC/PDA/La (OH) 3 Composite material. The resulting material was named BC/PDA/La (OH) 3 -10。
In a comparative example 12,
step 1, step 2, and step 3 were the same as step 1, step 2, and step 3 in example 1
Step 4, NaOH solution (20mL of 0.05mol/L) was then added slowly to the solution in step 3, and stirred at 300rpm for 4h at 25 ℃. Obtaining BC/PDA/La (OH) 3 A composite material. The resulting material was named BC/PDA/La (OH) 3 -11。
In a comparative example 13 which was a comparative example,
step 1, step 2, and step 3 were the same as step 1, step 2, and step 3 in example 1
Step 4, then NaOH solution (20mL of 0.2mol/L) was slowly added to the solution in step 3, and stirred at 300rpm for 4h at 25 ℃. Obtaining BC/PDA/La (OH) 3 A composite material. The resulting material was named BC/PDA/La (OH) 3 -12。
In a comparative example 14,
step 1, step 2, and step 3 were the same as step 1, step 2, and step 3 in example 1
Step 4, then NaOH solution (20mL of 0.4mol/L) was slowly added to the solution in step 3, and stirred at 300rpm for 4h at 25 ℃. Obtaining BC/PDA/La (OH) 3 A composite material. The resulting material was named BC/PDA/La (OH) 3 -13。
The following provides application examples of specific data of the present invention
In the case of the application example 1,
step 1, preparing 100ml of inorganic phosphorus solution with the concentration of 50 mg/L.
Step 2, weigh 10mg BC/PDA/La (OH) 3 The composite material is added into inorganic phosphorus solution, and the pH value is adjusted to 7.0 by using hydrochloric acid and sodium hydroxide.
And 3, placing the solution in a constant-temperature oscillation box, and oscillating and adsorbing at the rotating speed of 200rpm and the temperature of 25 ℃.
Step 4, the BC/PDA/La (OH) after the adsorption is finished 3 The composite material is taken out of the solution, ultrasonic desorption is carried out in methanol solution containing 0.1mol/L NaOH, and then the composite material is washed for a plurality of times in ethanol and pure water and cooledFreeze-drying for later use.
In the case of the application example 2,
step 1 is the same as step 1 in application example 1.
Step 2, weigh 10mg BC/PDA/La (OH) 3 The composite material is added into inorganic phosphorus solution, and the pH value is adjusted to 5.0 by using hydrochloric acid and sodium hydroxide.
Step 3 and step 4 are the same as step 3 and step 4 in application example 1.
In the case of the application example 3,
step 1 is the same as step 1 in application example 1.
Step 2, weigh 10mg BC/PDA/La (OH) 3 The composite material is added into inorganic phosphorus solution, and the pH value is adjusted to 6.0 by using hydrochloric acid and sodium hydroxide.
Step 3 and step 4 are the same as step 3 and step 4 in application example 1.
In the case of the application example 4,
step 1 is the same as step 1 in application example 1.
Step 2, weigh 10mg BC/PDA/La (OH) 3 The composite material is added into inorganic phosphorus solution, and the pH value is adjusted to 8.0 by using hydrochloric acid and sodium hydroxide.
Step 3 and step 4 are the same as step 3 and step 4 in application example 1.
In the case of the application example 5,
step 1 is the same as step 1 in application example 1.
Step 2, weigh 10mg BC/PDA/La (OH) 3 The composite material is added into inorganic phosphorus solution, and the pH value is adjusted to 9.0 by using hydrochloric acid and sodium hydroxide.
Step 3 and step 4 are the same as step 3 and step 4 in application example 1.
In the case of the application example 6,
step 1, preparing 100ml of inorganic phosphorus solution with the concentration of 50mg/L, and adding 100mg/L NaCl into the inorganic phosphorus solution.
Step 2, step 3, and step 4 are the same as step 2, step 3, and step 4 in application example 1.
In the case of application example 7,
step 1, preparing 100ml of inorganic phosphorus solution with the concentration of 50mg/L, and adding 100mg/L Na into the inorganic phosphorus solution 2 CO 3 。
Step 2, step 3, and step 4 are the same as step 2, step 3, and step 4 in application example 1.
In the case of the application example 8,
step 1, preparing 100ml of inorganic phosphorus solution with the concentration of 50mg/L, and adding 100mg/L Na into the inorganic phosphorus solution 2 SO 4 。
Step 2, step 3, and step 4 are the same as step 2, step 3, and step 4 in application example 1.
In the case of the application example 9,
step 1, preparing 100ml of inorganic phosphorus solution with the concentration of 50mg/L, and adding 100mg/L NaNO into the inorganic phosphorus solution 3 。
Step 2, step 3, and step 4 are the same as step 2, step 3, and step 4 in application example 1.
In the case of the application example 10,
step 1, preparing 100ml of inorganic phosphorus solution with the concentration of 50mg/L, and adding 100mg/L HA into the inorganic phosphorus solution.
Step 2, step 3, and step 4 are the same as step 2, step 3, and step 4 in application example 1.
In the case of the application example 11,
step 1, preparing 100ml of inorganic phosphorus solution with the concentration of 50mg/L, and adding 100mg/L BSA.
Step 2, step 3, and step 4 are the same as step 2, step 3, and step 4 in application example 1.
In the case of the application example 12,
step 1, 100ml of Nanjing purple light lake water is taken and filtered by a 0.22 mu m filter membrane for standby, and 50mg/L of inorganic phosphorus is added into the water.
Step 2, step 3, and step 4 are the same as step 2, step 3, and step 4 in application example 1.
As can be seen from FIG. 2, the phosphorus adsorption capacity of comparative example BC was 0 mg/g; the phosphorus adsorption capacity of BC/PDA is 12.6 mg/g; BC// La (OH) 3 Has a phosphorus adsorption capacity of 91.2mg/g, and BC/PDA/La (OH) 3 The phosphorus adsorption capacity of the catalyst was increased to 159.8 mg/g. The adsorption capacity of the related material designed by the invention is proved to be higher than that of phosphorus reported in general documents.
As can be seen from the graph in FIG. 3, the dosage of dopamine hydrochloride affects BC/PDA/La (OH) 3 The phosphorus adsorption capacity of (a). The result shows that the adsorption capacity of the material is increased with the increase of the dosage of the dopamine hydrochloride, when the dosage of the dopamine hydrochloride reaches 0.02mol/L, the adsorption capacity of the material reaches 159.8mg/g, and the adsorption capacity of the material is not obviously increased when the dosage of the dopamine hydrochloride is continuously increased. In FIG. 4, La (NO) can be seen 3 ) 3 ·6H 2 The amount of O will affect BC/PDA/La (OH) 3 Phosphorus adsorption capacity with La (NO) 3 ) 3 ·6H 2 The amount of O is increased, the adsorption capacity of the material is increased when La (NO) 3 ) 3 ·6H 2 When the O dosage reaches 0.003mol/L, the adsorption capacity of the material reaches 159.8mg/g, and La (NO) is continuously added 3 ) 3 ·6H 2 The amount of O, the adsorption capacity of the material did not increase significantly. As shown in FIG. 5, the amount of NaOH affects BC/PDA/La (OH) 3 The phosphorus adsorption capacity of the material shows a trend that the adsorption capacity of the material is increased and then reduced along with the increase of the dosage of NaOH, and when the dosage of the NaOH reaches 0.1mol/L, the adsorption capacity of the material reaches 159.8 mg/g. Thus, it can be seen that BC/PDA/La (OH) was prepared 3 The optimal conditions are that the dosage of the dopamine hydrochloride is controlled to be 0.02mol/L, and La (NO) is controlled 3 ) 3 ·6H 2 The dosage of O is 0.003mol/L, and the dosage of NaOH is controlled to be 0.1 mol/L.
In an application example, as can be seen from FIG. 6, BC/PDA/La (OH) 3 The leakage amount of La of the composite material in five times of recycling is lower than 5mg/L, and the excellent stability of the material is shown; as can be seen from FIG. 7, BC/PDA/La (OH) 3 -1 the composite material can maintain the adsorption capacity of more than 110mg/g in five times of recycling. As can be seen from FIG. 8, BC/PDA/La (OH) 3 -1 the composite material can maintain the adsorption capacity of more than 150mg/g in a wider pH environment (5-9); referring to FIG. 10 in conjunction with FIG. 9, it can be seen that BC/PDA/La (OH) 3 The phosphorus absorption and removal process of the-1 composite material is less influenced by inorganic anions and soluble organic matters, and the excellent environment applicability of the material is shown. The BC/PDA/La (OH) prepared can be known from FIG. 11 3 The phosphorus adsorption capacity in the actual water body is 143.4mg/g, which shows BC/PDA/La (OH) 3 Has certain practical requirementsThe application potential is high.
The data show that the cellulose/polydopamine/lanthanum hydroxide composite material can efficiently remove phosphorus (the phosphorus concentration after treatment is lower than the detection limit). The lanthanum leakage of the cellulose/polydopamine/lanthanum hydroxide composite material is low (less than 5 mg/L). The cellulose/polydopamine/lanthanum hydroxide composite material can still keep more than 110mg/g after five times of recycling. In conclusion, the preparation method of the cellulose/polydopamine/lanthanum hydroxide composite material and the application of the cellulose/polydopamine/lanthanum hydroxide composite material in the aspect of water phosphorus removal are provided by taking bacterial cellulose as an example, and the result shows that the composite material has a good practical application prospect.

Claims (9)

1. A composite material for cellulose/polydopamine/lanthanum hydroxide is characterized in that the preparation method of the material is as follows: preparing a dopamine hydrochloride solution, carrying out ultrasonic dissolution, immersing cellulose into the dopamine hydrochloride solution, then adding trihydroxymethyl aminomethane to adjust the pH value of the solution, and carrying out freeze drying to obtain a cellulose/polydopamine composite material; and then, in-situ depositing lanthanum hydroxide nanoparticles on the surface of the cellulose/polydopamine composite material by utilizing lanthanum nitrate hexahydrate to obtain the cellulose/polydopamine/lanthanum hydroxide composite material.
2. A preparation method for a cellulose/polydopamine/lanthanum hydroxide composite material is characterized by comprising the following steps:
step 1, preparing a dopamine hydrochloride solution, carrying out ultrasonic dissolution, weighing cellulose, immersing the cellulose in the solution, and carrying out ultrasonic dispersion;
step 2, adding tris (hydroxymethyl) aminomethane into the solution obtained in the step 1 to adjust the pH of the solution to 8.5, placing the solution in a constant-temperature shaking table for oscillation, taking out a sample, washing the sample with ethanol and water for multiple times, and freeze-drying the sample to obtain a cellulose/polydopamine composite material;
step 3, weighing the cellulose/polydopamine composite material and lanthanum nitrate hexahydrate, dispersing in an ethanol-water mixed solution, and carrying out ultrasonic treatment for 30 min;
and 4, slowly adding a sodium hydroxide solution into the solution obtained in the step 3, and stirring at 25 ℃ and 300rpm for 4 hours to obtain the cellulose/polydopamine/lanthanum hydroxide composite material.
3. The method for preparing the cellulose/polydopamine/lanthanum hydroxide composite material according to claim 2, wherein in the step 1, the concentration of the dopamine hydrochloride is 0.005-0.05 mol/L.
4. The method for preparing the cellulose/polydopamine/lanthanum hydroxide composite material according to claim 3, wherein in the step 1, the concentration of the dopamine hydrochloride is 0.02 mol/L.
5. The method for preparing the cellulose/polydopamine/lanthanum hydroxide composite material according to claim 2, wherein in the step 3, the dosage of the lanthanum nitrate hexahydrate is 0.002-0.02 mol/L.
6. The method for preparing the cellulose/polydopamine/lanthanum hydroxide composite material according to claim 5, wherein in the step 3, the dosage of the lanthanum nitrate hexahydrate is 0.003 mol/L.
7. The method for preparing the cellulose/polydopamine/lanthanum hydroxide composite material according to claim 2, wherein in the step 3, the volume ratio of ethanol to water is 1: 1.
8. The method for preparing the cellulose/polydopamine/lanthanum hydroxide composite material according to claim 2, wherein in the step 4, the concentration of NaOH is 0.01-0.4 mol/L.
9. The method for preparing the cellulose/polydopamine/lanthanum hydroxide composite material according to claim 7, wherein the concentration of NaOH in step 4 is 0.1 mol/L.
CN202210568382.2A 2022-05-23 2022-05-23 Cellulose/polydopamine/lanthanum hydroxide composite material for high-efficiency dephosphorization of water body Active CN114887602B (en)

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CN116380876A (en) * 2023-05-26 2023-07-04 北京市农林科学院智能装备技术研究中心 Method for detecting content of phosphorus element in water body

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CN107983319A (en) * 2017-11-17 2018-05-04 燕山大学 The preparation of Nano-lanthanum hydroxide composite material and the method for removing trace amounts of phosphorus in waste water
CN110947371A (en) * 2019-12-23 2020-04-03 江南大学 Preparation method of modified cellulose-based phosphorus removal adsorbent
US20210054172A1 (en) * 2019-08-20 2021-02-25 B. J. Zh. F. Panther Medical Equipment Co., Ltd. Polydopamine film and preparation method and application thereof

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CN107983319A (en) * 2017-11-17 2018-05-04 燕山大学 The preparation of Nano-lanthanum hydroxide composite material and the method for removing trace amounts of phosphorus in waste water
US20210054172A1 (en) * 2019-08-20 2021-02-25 B. J. Zh. F. Panther Medical Equipment Co., Ltd. Polydopamine film and preparation method and application thereof
CN110947371A (en) * 2019-12-23 2020-04-03 江南大学 Preparation method of modified cellulose-based phosphorus removal adsorbent

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