CN114887602B - Cellulose/polydopamine/lanthanum hydroxide composite material for high-efficiency dephosphorization of water body - Google Patents
Cellulose/polydopamine/lanthanum hydroxide composite material for high-efficiency dephosphorization of water body Download PDFInfo
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- 229920001690 polydopamine Polymers 0.000 title claims abstract description 95
- 239000002131 composite material Substances 0.000 title claims abstract description 66
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 229920002678 cellulose Polymers 0.000 title claims abstract description 30
- 239000001913 cellulose Substances 0.000 title claims abstract description 30
- YXEUGTSPQFTXTR-UHFFFAOYSA-K lanthanum(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[La+3] YXEUGTSPQFTXTR-UHFFFAOYSA-K 0.000 title claims abstract description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 90
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229960001149 dopamine hydrochloride Drugs 0.000 claims abstract description 23
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 72
- 238000000034 method Methods 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000005303 weighing Methods 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 10
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000004108 freeze drying Methods 0.000 claims description 5
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 4
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 52
- 239000000463 material Substances 0.000 abstract description 47
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 40
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 40
- 239000011574 phosphorus Substances 0.000 abstract description 40
- 229910052746 lanthanum Inorganic materials 0.000 abstract description 12
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 abstract description 12
- 238000004064 recycling Methods 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract 2
- 239000003463 adsorbent Substances 0.000 abstract 1
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 230000001276 controlling effect Effects 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 238000011156 evaluation Methods 0.000 abstract 1
- 238000011835 investigation Methods 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 229920002749 Bacterial cellulose Polymers 0.000 description 92
- 239000005016 bacterial cellulose Substances 0.000 description 92
- 230000000052 comparative effect Effects 0.000 description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 150000001449 anionic compounds Chemical class 0.000 description 3
- 229960003638 dopamine Drugs 0.000 description 3
- 229910001412 inorganic anion Inorganic materials 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 235000015097 nutrients Nutrition 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 229910002422 La(NO3)3·6H2O Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- -1 lanthanum phosphate compound Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
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
- B01J20/22—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
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a cellulose/polydopamine/lanthanum hydroxide composite material for high-efficiency dephosphorization of water. The raw materials for preparing the composite material comprise: cellulose, dopamine hydrochloride, lanthanum nitrate hexahydrate and sodium hydroxide. The adsorption and dephosphorization performance of the composite material is optimized by regulating and controlling the consumption of raw materials such as dopamine hydrochloride, lanthanum nitrate hexahydrate, sodium hydroxide and the like, and the optimal technological parameters of material preparation are determined. The practical application capability of the material is highlighted through the phosphorus removal performance, stability investigation and environmental impact factor evaluation of the material. In conclusion, the material has simple and convenient preparation process and controllable 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 dephosphorization adsorbent. The invention not only provides a certain theoretical support for the design of the water dephosphorization composite material, but also has stronger practical application potential.
Description
Technical Field
The invention belongs to the technical field of water treatment, and relates to a cellulose/polydopamine/lanthanum hydroxide composite material for high-efficiency dephosphorization of water.
Background
Enrichment of nutrients in the body of water, particularly phosphorus (P) and nitrogen (N), accelerates the process of eutrophication of the body of water, resulting in a sustained deterioration of the global ecological environment. In order to strictly control the enrichment of nutrient substances in water, the government and related departments of China clearly prescribe the discharge standard of phosphorus in the water environment. According to the requirements of Chinese water quality standards, the phosphorus content in the secondary effluent standard of a sewage treatment plant (WWTPs) is not higher than 0.5mg/L, which puts higher requirements on the water dephosphorization technology. At present, the water dephosphorization technology with wider application 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 water dephosphorization field.
According to the report of the prior literature, lanthanum (La) can be coordinated with phosphate radical in water to generate a lanthanum phosphate compound, so that inorganic phosphorus in the water environment is efficiently removed. However, lanthanum hydroxide (La (OH) was directly used 3 ) The adsorption material has low efficiency, and the particles are extremely easy to agglomerate and the like; a large amount of supported lanthanum-based adsorption materials taking inorganic materials as base materials can effectively avoid agglomeration of particles, but the problem of secondary pollution caused by metal species loss cannot be avoided. Research shows that the lanthanum-based adsorption material designed by utilizing the organic polymer has higher adsorption capacity to phosphorus and can effectively improve the stability of the lanthanum-based adsorption material in the adsorption process, but the high cost and the complex process restrict the large-scale popularization and application of the lanthanum-based adsorption material in the field of water body phosphorus removal. In addition, most of organic polymers adopted at the present stage cannot be naturally degraded by the environment, and secondary pollution of the water body environment can be caused. Therefore, the environment-friendly lanthanum-based adsorption material with low cost, simple process and stable performance is expected to break the application bottleneck of the environment-friendly lanthanum-based adsorption material in the field of water dephosphorization.
As a low cost, widely available high molecular biomass material, cellulosic materials have proven to be excellent templates for supported materials. Taking Bacterial Cellulose (BC) as an example, the bacterial cellulose has the characteristics of high chemical purity, rich hydroxyl on the surface, excellent biocompatibility and the like, and has great practical application prospect in the field of research and development of water treatment functional materials. Previous work by applicant has directly deposited lanthanum hydroxide on bacterial cellulose surfaces, which results indicate that adsorption capacity is low and loss of lanthanum species is unavoidable. According to literature reports, polydopamine (PDA) can adsorb metal nano particles through the action of covalent bonds or non-covalent bonds, so that the stability of the Polydopamine (PDA) in the application process is improved. Therefore, introducing dopamine into the bacterial cellulose/lanthanum hydroxide composite material is expected to improve the adsorption capacity and adsorption rate of the dopamine to phosphorus, strengthen 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 high-efficiency dephosphorization of water.
The invention adopts the following technical scheme:
the preparation method of the cellulose/polydopamine/lanthanum hydroxide composite material comprises the following steps of: and polymerizing polydopamine materials on the surface of bacterial cellulose in situ, and then depositing lanthanum hydroxide nano particles on the surface of the polydopamine materials in situ.
The method specifically comprises the following steps:
step 1, preparing dopamine hydrochloride solution, performing ultrasonic dissolution, then weighing cellulose, immersing the cellulose in the solution, and performing ultrasonic dispersion;
step 2, adding tris (hydroxymethyl) aminomethane into the solution in the step 1 to adjust the pH of the solution to 8.5, placing the solution in a constant temperature shaking table for shaking, taking out a sample, washing the sample with ethanol and water for multiple times, and freeze-drying to obtain a cellulose/polydopamine composite material;
step 3, weighing the cellulose/polydopamine composite material and lanthanum nitrate hexahydrate, dispersing the composite material and the lanthanum nitrate hexahydrate in an ethanol-water mixed solution, and carrying out ultrasonic treatment for 30min;
and 4, slowly adding a sodium hydroxide solution into the solution 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 0.005-0.05mol/L.
Further, in the step 1, the concentration of the dopamine hydrochloride is 0.02mol/L.
Further, in the step 3, the dosage of the lanthanum nitrate hexahydrate is 0.002-0.02mol/L.
Further, in the step 3, the dosage of the lanthanum nitrate hexahydrate is 0.003mol/L.
Further, in the step 3, the volume ratio of ethanol to water is 1:1.
Further, in the step 4, the concentration of NaOH is 0.01-0.4mol/L.
Further, in the step 4, the concentration of NaOH is 0.1mol/L.
Compared with the prior art, the invention has the advantages that:
(1) The method is simple and convenient, has low cost and mild 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 complex environment water.
Drawings
FIG. 1 shows BC, BC/PDA/La (OH) 3 Is a photo of the light source; FIG. 1 (a) is an optical photograph of BC and FIG. 1 (b) is BC/PDA/La (OH) prepared according to the above procedure 3 Optical photographs of the composite material.
FIG. 2 is La (OH) 3 ,BC/La(OH) 3 BC/PDA and BC/PDA/La (OH) 3 The adsorption capacity of inorganic phosphorus to water body.
FIG. 3 shows BC/PDA/La (OH) prepared with varying amounts of dopamine hydrochloride 3 The adsorption capacity of inorganic phosphorus to water body.
FIG. 4 shows the different La (NO 3 ) 3 ·6H 2 BC/PDA/La (OH) prepared with O amount 3 The adsorption capacity of inorganic phosphorus to water body.
FIG. 5 shows BC/PDA/La (OH) prepared with varying amounts of NaOH 3 The adsorption capacity of inorganic phosphorus to water body.
FIG. 6 is BC/PDA/La (OH) 3 Lanthanum leakage during five cycles of 1.
FIG. 7 is BC/PDA/La (OH) 3 -1 five cycle performance.
FIG. 8 is BC/PDA/La (OH) 3 -1 absorption of inorganic phosphorus from water bodies in different pH environmentsWith capacity.
FIG. 9 is BC/PDA/La (OH) 3 -1 adsorption capacity for inorganic phosphorus of a body of water in the presence of different inorganic anions.
FIG. 10 is BC/PDA/La (OH) 3 -1 adsorption capacity for inorganic phosphorus of a water body in the presence of a soluble organic matter.
FIG. 11 is BC/PDA/La (OH) 3 -1 the adsorption capacity for inorganic phosphorus in a simulated water body and an actual water body.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings, examples and comparative examples.
The invention provides a cellulose/polydopamine/lanthanum hydroxide composite material, wherein bacterial cellulose is taken as an example of cellulose, and the cellulose/polydopamine/lanthanum hydroxide composite material comprises the following steps:
and 1, weighing dopamine hydrochloride, completely dissolving under ultrasonic conditions, and weighing BC (30 mm multiplied by 30 mm) and immersing in 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 with ethanol and water for multiple times, 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 O was dispersed in 40mL ethanol-water (volume ratio 1:1) mixed solution and sonicated for 30min.
Step 4, then NaOH solution was slowly added to the solution in step 3, and stirred at 25℃and 300rpm for 4 hours. Obtaining BC/PDA/La (OH) 3 A composite material.
In the step 1, the concentration of the dopamine hydrochloride is 0.005-0.05mol/L.
In step 3, the above-mentioned La (NO 3 ) 3 ·6H 2 The dosage of O is 0.002-0.02mol/L.
In the step 3, the concentration of NaOH is 0.01-0.4mol/L.
The BC/PDA composite material is prepared by chemical oxidative polymerization of dopamine and BC. Immersing BC membrane (30 mm×30 mm) in dopamine hydrochloride (0.005, 0.01,0.02,0.03,0.05 mol/L) for dissolvingIn the liquid, ultrasound is carried out for 30min at 25 ℃. And adding tris (hydroxymethyl) aminomethane into the solution to adjust the pH value of the solution to 8.5, placing the solution in a constant temperature shaking table at 30 ℃ and oscillating at 200rpm for 12 hours, and obtaining the BC/PDA composite material through freeze drying (10 Pa, -40 ℃). Subsequently, 0.1g of BC/PDA composite material and a set amount (0.002, 0.003,0.004,0.008,0.02 mol/L) of La (NO 3 ) 3 ·6H 2 O was dispersed in a mixed solution of 20mL ethanol and 20mL water and sonicated for 30min. Then 20mL of NaOH (0.01, 0.05,0.1,0.2,0.5 mol/L) solution was slowly added with stirring at 25℃and 300 rpm. The solution was stirred at 300rpm for 4h. Obtain BC/PDA/La (OH) 3 A composite material. BC and BC/PDA/La (OH) before and after preparation 3 An optical photograph of (2) is shown in figure 1.
BC/PDA/La(OH) 3 Embodiment of dephosphorization performance of composite material
Step 1, 100ml of an inorganic phosphorus solution with a concentration of 50mg/L is prepared.
Step 2, weighing 10mg BC/PDA/La (OH) 3 The composite material was added to an inorganic phosphorus solution and the pH was adjusted to 7.0 using hydrochloric acid and sodium hydroxide.
And step 3, placing the solution in a constant temperature shaking box, and shaking and adsorbing at the temperature of 25 ℃ at the rotating speed of 200 rpm.
Step 4, BC/PDA/La (OH) after the adsorption is completed 3 The composite material is taken out from the solution, desorbed by ultrasonic in methanol solution containing 0.1mol/L NaOH, washed for many times in ethanol and pure water, and freeze-dried for standby.
And (3) optionally adding inorganic anions and soluble organic matters in the step (1).
The pH value of the solution in the step 2 can be 5.0,6.0,7.0,8.0,9.0.
The following examples are provided to illustrate specific data of the present invention
Example 1
Step 1, BC (30 mm. Times.30 mm) is weighed and immersed in 0.02mol/L dopamine hydrochloride solution (0.379 g dissolved in 100mL deionized water), and the solution is dispersed and dissolved by ultrasonic for 30min.
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 with ethanol and water for multiple times, and freeze-drying the sample to obtain the BC/PDA composite material.
Step 3, weighing the BC/PDA composite material and 0.003mol/L (0.15 g) La (NO) 3 ) 3 ·6H 2 O was dispersed in 40mL ethanol-water (volume ratio 1:1) mixed solution and sonicated for 30min.
Step 4, followed by slow addition of NaOH solution (20 mL of 0.1 mol/L) to the solution in step 3, stirring at 25℃and 300rpm for 4h. Obtaining BC/PDA/La (OH) 3 A composite material. Named BC/PDA/La (OH) 3 -1。
Comparative examples of specific data of the present invention are provided below
Comparative example 1
Step 1, step 2 is identical to step 1, step 2 in the embodiment. The resulting material was named BC/PDA.
Comparative example 2
Step 1 is the same as step 1 in example 1.
Step 2, BC (30 mm. Times.30 mm) material and 0.003mol/L (0.15 g) La (NO) 3 ) 3 ·6H 2 O was dispersed in 40mL ethanol-water (volume ratio 1:1) mixed solution and sonicated for 30min.
Step 3, followed by slow addition of NaOH solution (20 mL of 0.1 mol/L) to the solution in step 2, stirring at 25℃and 300rpm for 4h. Obtaining BC/La (OH) 3 A composite material. The material obtained was named BC/La (OH) 3 。
Comparative example 3
Step 1, BC (30 mm. Times.30 mm) is weighed and immersed in a 0.005mol/L dopamine hydrochloride solution (0.095 g dissolved in 100mL deionized water), and the solution is dispersed and dissolved by ultrasonic for 30min.
Step 2, step 3, step 4 is the same as step 2, step 3, step 4 in the embodiment. The material obtained was named BC/PDA/La (OH) 3 -2。
Comparative example 4
Step 1, BC (30 mm. Times.30 mm) was weighed and immersed in a 0.01mol/L dopamine hydrochloride solution (0.189 g dissolved in 100mL deionized water), and dissolved by ultrasonic dispersion for 30min.
Step 2, step 3, step 4 and step 2, step 3, step 4 in the embodiment4 are identical. The material obtained was named BC/PDA/La (OH) 3 -3。
Comparative example 5
Step 1, BC (30 mm. Times.30 mm) is weighed and immersed in a 0.03mol/L dopamine hydrochloride solution (0.568 g dissolved in 100mL deionized water), and the solution is dispersed and dissolved by ultrasonic waves for 30min.
Step 2, step 3, step 4 is the same as step 2, step 3, step 4 in the embodiment. The material obtained was named BC/PDA/La (OH) 3 -4。
Comparative example 6
Step 1, BC (30 mm. Times.30 mm) is weighed and immersed in a 0.05mol/L dopamine hydrochloride solution (0.947 g dissolved in 100mL deionized water), and the solution is dispersed and dissolved by ultrasonic for 30min.
Step 2, step 3, step 4 is the same as step 2, step 3, step 4 in the embodiment. The material obtained was named BC/PDA/La (OH) 3 -5。
Comparative example 7
Step 1, step 2 is the same as step 1, step 2 in example 1
Step 3, weighing the BC/PDA composite material and 0.002mol/L (0.1 g) La (NO) 3 ) 3 ·6H 2 O was dispersed in 40mL ethanol-water (volume ratio 1:1) mixed solution and sonicated for 30min.
Step 4 is the same as step 4 in the example. The material obtained was named BC/PDA/La (OH) 3 -6。
Comparative example 8
Step 1, step 2 is the same as step 1, step 2 in example 1
Step 3, weighing the BC/PDA composite material and 0.004mol/L (0.2 g) La (NO) 3 ) 3 ·6H 2 O was dispersed in 40mL ethanol-water (volume ratio 1:1) mixed solution and sonicated for 30min.
Step 4 is the same as step 4 in the example. The material obtained was named BC/PDA/La (OH) 3 -7。
Comparative example 9
Step 1, step 2 is the same as step 1, step 2 in example 1
Step 3, weighing the BC/PDA composite material and 0.008mol/L (0.4 g) La (NO) 3 ) 3 ·6H 2 O was dispersed in 40mL ethanol-water (volume ratio 1:1) mixed solution and sonicated for 30min.
Step 4 is the same as step 4 in the example. The material obtained was named BC/PDA/La (OH) 3 -8。
Comparative example 10
Step 1, step 2 is the same as step 1, step 2 in example 1
Step 3, weighing the BC/PDA composite material and 0.02mol/L (1.0 g) La (NO) 3 ) 3 ·6H 2 O was dispersed in 40mL ethanol-water (volume ratio 1:1) mixed solution and sonicated for 30min.
Step 4 is the same as step 4 in the example. The material obtained was named BC/PDA/La (OH) 3 -9。
Comparative example 11,
step 1, step 2, step 3 is the same as step 1, step 2, step 3 in example 1
Step 4, followed by slow addition of NaOH solution (20 mL of 0.01 mol/L) to the solution in step 3, stirring at 25℃and 300rpm for 4h. Obtaining BC/PDA/La (OH) 3 A composite material. The material obtained was named BC/PDA/La (OH) 3 -10。
Comparative example 12,
step 1, step 2, step 3 is the same as step 1, step 2, step 3 in example 1
Step 4, followed by slow addition of NaOH solution (20 mL of 0.05 mol/L) to the solution in step 3, stirring at 25℃and 300rpm for 4h. Obtaining BC/PDA/La (OH) 3 A composite material. The material obtained was named BC/PDA/La (OH) 3 -11。
Comparative example 13,
step 1, step 2, step 3 is the same as step 1, step 2, step 3 in example 1
Step 4, followed by slow addition of NaOH solution (20 mL of 0.2 mol/L) to the solution in step 3, stirring at 25℃and 300rpm for 4h. Obtaining BC/PDA/La (OH) 3 A composite material. The material obtained was named BC/PDA/La (OH) 3 -12。
Comparative example 14,
step 1, step 2, step 3 is the same as step 1, step 2, step 3 in example 1
Step 4, followed by slow addition of NaOH solution (20 mL of 0.4 mol/L) to the solution in step 3, stirring at 25℃and 300rpm for 4h. Obtaining BC/PDA/La (OH) 3 A composite material. The material obtained was named BC/PDA/La (OH) 3 -13。
The following provides examples of application of specific data of the present invention
Application example 1,
step 1, 100ml of an inorganic phosphorus solution with a concentration of 50mg/L is prepared.
Step 2, weighing 10mg BC/PDA/La (OH) 3 The composite material was added to an inorganic phosphorus solution and the pH was adjusted to 7.0 using hydrochloric acid and sodium hydroxide.
And 3, placing the solution in a constant temperature shaking box, and shaking and adsorbing at the speed of 200rpm and the temperature of 25 ℃.
Step 4, BC/PDA/La (OH) after the adsorption is completed 3 The composite material is taken out from the solution, desorbed by ultrasonic in methanol solution containing 0.1mol/L NaOH, washed for many times in ethanol and pure water, and freeze-dried for standby.
Application example 2 the process was carried out in a batch manner,
step 1 is the same as step 1 in application example 1.
Step 2, weighing 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, step 4 is the same as step 3, step 4 in application example 1.
Application example 3 in the case of the present invention,
step 1 is the same as step 1 in application example 1.
Step 2, weighing 10mg BC/PDA/La (OH) 3 The composite material was added to an inorganic phosphorus solution and the pH was adjusted to 6.0 using hydrochloric acid and sodium hydroxide.
Step 3, step 4 is the same as step 3, step 4 in application example 1.
Application example 4 the process was carried out in a batch manner,
step 1 is the same as step 1 in application example 1.
Step 2, weighing 10mg BC/PDA/La (OH) 3 Composite materialThe material was added to an inorganic phosphorus solution and the pH was adjusted to 8.0 using hydrochloric acid and sodium hydroxide.
Step 3, step 4 is the same as step 3, step 4 in application example 1.
Application example 5 in the case of the present invention,
step 1 is the same as step 1 in application example 1.
Step 2, weighing 10mg BC/PDA/La (OH) 3 The composite material was added to an inorganic phosphorus solution and the pH was adjusted to 9.0 using hydrochloric acid and sodium hydroxide.
Step 3, step 4 is the same as step 3, step 4 in application example 1.
Application example 6 the process was carried out in accordance with the method of the invention,
step 1, 100ml of an inorganic phosphorus solution having a concentration of 50mg/L was prepared, and 100mg/L of NaCl was added thereto.
Step 2, step 3 and step 4 are the same as step 2, step 3 and step 4 in application example 1.
Application example 7,
step 1, 100ml of an inorganic phosphorus solution having a concentration of 50mg/L was prepared, and 100mg/L of Na was added thereto 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.
Application example 8 the process was carried out in accordance with the present invention,
step 1, 100ml of an inorganic phosphorus solution having a concentration of 50mg/L was prepared, and 100mg/L of Na was added thereto 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.
Application example 9 in the case of the present invention,
step 1, preparing 100ml of inorganic phosphorus solution with the concentration of 50mg/L, and adding 100mg/L of NaNO into the solution 3 。
Step 2, step 3 and step 4 are the same as step 2, step 3 and step 4 in application example 1.
Application example 10,
step 1, 100ml of an inorganic phosphorus solution having a concentration of 50mg/L was prepared, and 100mg/L of HA was added thereto.
Step 2, step 3 and step 4 are the same as step 2, step 3 and step 4 in application example 1.
Application example 11 the process was carried out in accordance with the invention,
step 1, 100ml of an inorganic phosphorus solution having a concentration of 50mg/L was prepared, and 100mg/L of BSA was added thereto.
Step 2, step 3 and step 4 are the same as step 2, step 3 and step 4 in application example 1.
Application example 12 the process was carried out in accordance with the application example 12,
step 1, taking 100ml of Nanjing purple green lake water, filtering with a 0.22 mu m filter membrane for standby, and adding 50mg/L inorganic phosphorus into the solution.
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 in conjunction with FIG. 2, the phosphorus adsorption capacity of comparative sample BC was 0mg/g; the phosphorus adsorption capacity of BC/PDA is 12.6mg/g; BC// La (OH) 3 The phosphorus adsorption capacity of (2) was 91.2mg/g, and BC/PDA/La (OH) 3 The phosphorus adsorption capacity of (C) is improved to 159.8mg/g. The adsorption capacity of the related material designed by the invention is proved to be higher than that of the phosphorus reported in the general literature.
As can be seen from FIG. 3, the amount of dopamine hydrochloride affects BC/PDA/La (OH) 3 Is a phosphorus adsorption capacity of (a). The result shows that the adsorption capacity of the material is increased along with the increase of the consumption of the dopamine hydrochloride, and when the consumption of the dopamine hydrochloride reaches 0.02mol/L, the adsorption capacity of the material reaches 159.8mg/g, and the consumption of the dopamine hydrochloride is continuously increased, so that the adsorption capacity of the material is not obviously increased. As can be seen from FIG. 4, la (NO 3 ) 3 ·6H 2 The amount of O will affect BC/PDA/La (OH) 3 With La (NO) 3 ) 3 ·6H 2 The increase of the O dosage increases the adsorption capacity of the material, and when La (NO 3 ) 3 ·6H 2 When the O consumption reaches 0.003mol/L, the adsorption capacity of the material reaches 159.8mg/g, and La (NO) is continuously increased 3 ) 3 ·6H 2 The amount of O does not increase significantly the adsorption capacity of the material. As can be seen from FIG. 5, the amount of NaOH affects BC/PDA/La (OH) 3 The adsorption capacity of the material shows a trend of increasing and then decreasing with the increase of the using amount of NaOH, and when the using amount of NaOH reaches 0.1mol/L, the adsorption capacity of the material reaches159.8mg/g. Thus, BC/PDA/La (OH) was prepared 3 The optimal condition of (2) is to control the consumption of dopamine hydrochloride to be 0.02mol/L and La (NO) 3 ) 3 ·6H 2 The dosage of O is 0.003mol/L, and the dosage of NaOH is controlled to be 0.1mol/L.
In an application example, as can be seen in connection with FIG. 6, BC/PDA/La (OH) 3 1, the leakage amount of La in the five-time recycling process of the composite material is lower than 5mg/L, and the composite material has excellent stability; as can be seen in FIG. 7, BC/PDA/La (OH) 3 The adsorption capacity of the composite material can be kept to be more than 110mg/g in the five recycling processes. As can be seen in FIG. 8, BC/PDA/La (OH) 3 -1 the composite material is capable of maintaining an adsorption capacity of more than 150mg/g in a wide range of pH environments (5-9); as can be seen in FIG. 10 in conjunction with FIG. 9, BC/PDA/La (OH) 3 And (1) the adsorption dephosphorization process of the composite material is less influenced by inorganic anions and soluble organic matters, so that the excellent environment applicability of the material is shown. As can be seen from FIG. 11, the BC/PDA/La (OH) was prepared 3 The phosphorus adsorption capacity in the actual water body is 143.4mg/g, which indicates BC/PDA/La (OH) 3 Has certain practical application potential.
From the above data, it can be seen that the cellulose/polydopamine/lanthanum hydroxide composite material can remove phosphorus with high efficiency (the phosphorus concentration after treatment is lower than the detection limit). The cellulose/polydopamine/lanthanum hydroxide composite material has low lanthanum leakage (lower 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, bacterial cellulose is taken as an example, a preparation method of a cellulose/polydopamine/lanthanum hydroxide composite material and application of the composite material in the aspect of water dephosphorization are provided, and the result shows that the composite material has good practical application prospect.
Claims (4)
1. A preparation method of a cellulose/polydopamine/lanthanum hydroxide composite material for high-efficiency dephosphorization of water is characterized in that
The method comprises the following steps:
step 1, preparing a dopamine hydrochloride solution, performing ultrasonic dissolution, then weighing cellulose, immersing the cellulose in the solution, and performing ultrasonic dispersion;
step 2, adding tris (hydroxymethyl) aminomethane into the solution in the step 1 to adjust the pH of the solution to 8.5, placing the solution in a constant temperature shaking table for shaking, taking out a sample, washing the sample with ethanol and water for multiple times, and freeze-drying to obtain a cellulose/polydopamine composite material;
step 3, weighing the cellulose/polydopamine composite material and lanthanum nitrate hexahydrate, dispersing the composite material and the lanthanum nitrate hexahydrate in an ethanol-water mixed solution, and carrying out ultrasonic treatment for 30min;
step 4, slowly adding sodium hydroxide solution into the solution in the step 3, and stirring at 25 ℃ and 300rpm for 4h to obtain a cellulose/polydopamine/lanthanum hydroxide composite material;
in the step 1, the concentration of the dopamine hydrochloride is 0.005-0.05 mol/L;
in the step 3, the dosage of the lanthanum nitrate hexahydrate is 0.002-0.02 mol/L;
in the step 3, the volume ratio of ethanol to water is 1:1;
in the step 4, the concentration of NaOH is 0.01-0.4mol/L.
2. The method for preparing a cellulose/polydopamine/lanthanum hydroxide composite material for high-efficiency dephosphorization of water according to claim 1, wherein in the step 1, the concentration of dopamine hydrochloride is 0.02mol/L.
3. The method for preparing a cellulose/polydopamine/lanthanum hydroxide composite material for efficient dephosphorization of water according to claim 1, wherein in the step 3, the amount of lanthanum nitrate hexahydrate is 0.003mol/L.
4. The method for preparing a cellulose/polydopamine/lanthanum hydroxide composite material for efficient dephosphorization of water according to claim 1, wherein in step 4, the concentration of NaOH is 0.1mol/L.
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| 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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