CN112495344A - Copper ion adsorbent and preparation method and adsorption method thereof - Google Patents
Copper ion adsorbent and preparation method and adsorption method thereof Download PDFInfo
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- CN112495344A CN112495344A CN202011138723.XA CN202011138723A CN112495344A CN 112495344 A CN112495344 A CN 112495344A CN 202011138723 A CN202011138723 A CN 202011138723A CN 112495344 A CN112495344 A CN 112495344A
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- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 36
- 229910001431 copper ion Inorganic materials 0.000 title claims abstract description 35
- 239000003463 adsorbent Substances 0.000 title claims abstract description 33
- 238000001179 sorption measurement Methods 0.000 title abstract description 66
- 238000002360 preparation method Methods 0.000 title abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 47
- 239000000843 powder Substances 0.000 claims abstract description 34
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims abstract description 32
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229940068041 phytic acid Drugs 0.000 claims abstract description 21
- 235000002949 phytic acid Nutrition 0.000 claims abstract description 21
- 239000000467 phytic acid Substances 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 239000011259 mixed solution Substances 0.000 claims description 26
- 239000007787 solid Substances 0.000 claims description 24
- 239000012498 ultrapure water Substances 0.000 claims description 20
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- -1 polytetrafluoroethylene Polymers 0.000 claims description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 8
- 239000003085 diluting agent Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- 125000000524 functional group Chemical group 0.000 abstract description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 4
- 150000001768 cations Chemical class 0.000 abstract description 4
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 4
- 150000002500 ions Chemical class 0.000 abstract description 4
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 4
- 239000011574 phosphorus Substances 0.000 abstract description 4
- 238000003911 water pollution Methods 0.000 abstract description 2
- 239000010949 copper Substances 0.000 description 35
- 239000006185 dispersion Substances 0.000 description 18
- 239000007788 liquid Substances 0.000 description 14
- 239000000463 material Substances 0.000 description 9
- 239000012286 potassium permanganate Substances 0.000 description 8
- 239000006228 supernatant Substances 0.000 description 8
- 238000010790 dilution Methods 0.000 description 7
- 239000012895 dilution Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000002791 soaking Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000005457 ice water Substances 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000037406 food intake Effects 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
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- 230000010261 cell growth Effects 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
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- 239000006260 foam Substances 0.000 description 1
- 230000011132 hemopoiesis Effects 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
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- 210000000653 nervous system Anatomy 0.000 description 1
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—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
-
- 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
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- 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
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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Abstract
The invention belongs to the technical field of water pollution treatment, and relates to a copper ion adsorbent, and a preparation method and an adsorption method thereof. According to the adsorption method, the phytic acid modified three-dimensional graphene powder is adopted to adsorb copper ions in water, the three-dimensional graphene can obviously improve the stability of an original two-dimensional graphene sheet layer, the specific surface area of the three-dimensional graphene sheet layer is increased, more adsorption sites are provided, the powder form can realize homogeneous adsorption, and the adsorption capacity is maximized. Meanwhile, based on the strong cation chelating ability of the phytic acid molecules and the hydrophilicity of the phosphorus-containing functional groups, the affinity of the phytic acid molecules to copper ions in water can be further improved by modifying the three-dimensional graphene with the phytic acid. The invention provides a simple, convenient, rapid, economic, efficient and practical method for adsorbing copper ions in water, and aims to provide a new idea for treating heavy metal ions in water.
Description
Technical Field
The invention belongs to the technical field of water pollution treatment, and relates to a phytic acid modified three-dimensional graphene powder copper ion adsorbent, and a preparation method and an adsorption method thereof.
Background
With the continuous development of industrialization, a large amount of copper ions (Cu)2+) Along with the discharge of industrial wastewater such as electroplating, leather, printing and dyeing and the like into environmental water, Cu in the water is caused2+The content is greatly increased. Cu in water2+The pollution has the characteristics of biological enrichment, continuous toxicity, nondegradable property and the like, after being ingested by a human body, the pollution has the influence on cell growth, hematopoiesis and enzyme activity, such as hemoglobin denaturation, damages to the respiratory system, the liver system and the nervous system and the like, and death can be caused by excessive ingestion. At the same time, excess Cu2+The copper in the cortex of the plant root system can be accumulated by ingestion, and the nutrient absorption of the root system is inhibited, so that crop diseases are caused; when Cu is in water2+The concentration reaches 0.1 mg.L-1In the process, the biochemical oxygen consumption process of aerobic microorganisms in water is inhibited, and the self-purification function of the water body is further influenced. Therefore, for Cu in the environmental water body2+Effective removal is of great environmental significance.
Adsorption methods are a type of method for removing heavy metal ions in a system by means of the high specific surface area of an adsorption material or the physical/chemical adsorption of specific functional groups. The method overcomes the defects of long time consumption, high cost, possible secondary pollution and the like of the traditional physical, chemical and biological treatment methods such as ion exchange, oxidation reduction, microbial remediation and the like, and depends on wide sources of adsorbing materials, easy preparation, simple and flexible operation and is expected to realize repeated use. Therefore, the adsorption method is considered to be the most economical, simple and effective method for treating the heavy metal pollution of the water body at present.
In recent years, based on the research on traditional adsorbents (such as zeolite, manganese oxide, fly ash and the like), a series of novel adsorbing materials are continuously disclosed to achieve higher-efficiency adsorption performance. Among them, graphene, which is a widely favored nanomaterial, is an indispensable adsorbent due to its characteristics such as a large specific surface area, a rich surface functional group, and a significant boundary effect. However, due to the inherent two-dimensional structure of graphene, aggregation occurs between the sheets due to a strong pi-pi stacking effect, so that the adsorption active sites on the surfaces of the sheets are reduced, and further the adsorption capacity is reduced.
Disclosure of Invention
The invention solves the problem of Cu in water2+The traditional adsorption method has the defects of low adsorption rate, small adsorption capacity, expensive adsorbent and the like, and provides the simple, convenient, quick, economic, efficient and practical water Cu2+An adsorption method.
The technical scheme of the invention is as follows:
the copper ion adsorbent is three-dimensional graphene powder modified based on phytic acid.
A preparation method of a copper ion adsorbent comprises the steps of adding graphene oxide diluent into a phytic acid solution for mixing; transferring the mixture into a polytetrafluoroethylene hydrothermal reaction kettle for hydrothermal reaction, and separating solid particles in the mixed solution to soak in high-purity water after the reaction kettle is cooled to room temperature after the reaction is finished; washing the solid particles with water and then fully oscillating in a shaking table; and drying the solid particles to obtain the phytic acid modified three-dimensional graphene powder.
Furthermore, the reaction temperature in the polytetrafluoroethylene hydrothermal reaction kettle is 130-170 ℃, and the reaction temperature is 1-4 h.
Further, the concentration of the graphene oxide diluent is 0.16-5.4 mg/mL.
Further, the volume ratio of the graphene oxide diluent to the phytic acid solution is 30-50: 0.2-0.8; the concentration of the phytic acid solution is 70%.
Further, after separating solid particles in the reaction kettle by using filter paper, soaking the solid particles in high-purity water for 40-50 hours.
And further, soaking in high-purity water and washing for 3-6 times.
The invention also provides a copper ion adsorption method, which comprises the steps of adding the copper ion adsorbent into a copper ion solution, placing the copper ion solution in a constant temperature oscillator for reaction and filtering.
Further, the reaction conditions of the constant temperature oscillator are 110-130 r/min and 20-30 ℃; the reaction temperature is 2-4 h.
Furthermore, the concentration of the copper ion solution is 20-80 mg/L.
Three-dimensional graphene (PA-Gr) powder modified based on phytic acid for adsorbing Cu in water2+The method comprises the following steps:
(1) firstly, preparing a Graphene Oxide (GO) dispersion liquid;
(2) adding 1-9 mL of GO dispersion (8-15 mg/mL) into 25-50 mL of high-purity water to obtain GO dilution. Taking 30-50 mL of GO diluent, and adding 0.2-0.8 mL of phytic acid solution (70% in H)2O). And transferring the mixed solution into a polytetrafluoroethylene hydrothermal reaction kettle, and carrying out hydrothermal reaction for 1-4 h at the temperature of 130-170 ℃. After the reaction is finished, after the reaction kettle is cooled to room temperature, separating solid particles in the mixed solution by using filter paper, and soaking the mixed solution in high-purity water for 40-50 hours. After 3-6 times of water washing, fully shaking in a shaking table at a slow speed. And separating out the dispersed solid in the water by using filter paper, and fully drying at room temperature to obtain powdery solid, namely PA-Gr powder.
(3) Preparing Cu with the concentration of 20-80 mg/L2+And (3) adding the PA-Gr powder obtained in the step (2) as an adsorbent. The mixed solution is reacted for 2 to 4 hours in a constant temperature oscillator under the conditions of 110 to 130r/min and 20 to 30 ℃.
(4) Filtering the mixed solution by 0.20-0.24 μm filter paper, taking supernatant, and measuring Cu in the supernatant2+And (4) concentration.
Due to the loose porous structure of the three-dimensional graphene, the strong cation chelating capacity of the phytic acid molecules and the hydrophilicity of the phosphorus-containing functional groups of the phytic acid molecules, the prepared PA-Gr powder adsorbent shows the effect of being applied to Cu in water2+Good adsorption capacity.
The invention has the beneficial effects that:
the invention provides a simple, convenient, rapid, economic, efficient and practical method for adsorbing copper ions in water, and the method is used for establishing the method for adsorbing the Cu ions in the water by taking three-dimensional graphene modified by phytic acid as an adsorbent2+The adsorption method is expected to provide a new idea for the treatment of heavy metal ions in water.
According to the technical scheme, the traditional two-dimensional planar graphene is assembled into the three-dimensional structure, so that the stability of a graphene sheet layer can be obviously improved, the specific surface area of the graphene sheet layer can be further increased by the three-dimensional structure, and more adsorption sites can be provided; and the powder form can realize homogeneous adsorption, so that the adsorption capacity is maximized. Meanwhile, based on the strong cation chelating ability of the phytic acid molecules and the hydrophilicity of the phosphorus-containing functional groups, the affinity of the phytic acid molecules to copper ions in water can be further improved by modifying the three-dimensional graphene with the phytic acid.
The surface of the graphene is specifically modified, so that the adsorption performance of the graphene can be further improved. Phytic Acid (PA) is a low-cost natural resource extracted from grains and seeds. The phytic acid is used for modifying the graphene material, and based on the strong cation chelating capacity of phytic acid molecules and the hydrophilicity of phosphorus-containing functional groups of the phytic acid molecules, the Cu in water can be improved by the graphene material2+The affinity of (2) is favorable for the adsorption process. Compared with the existing adsorbent, the copper ion adsorbent provided by the invention has a larger adsorption capacity. The prepared PA-Gr powder adsorbent is obtained by fitting adsorption isotherms to Cu in water2+The maximum adsorption capacity of the graphene oxide reaches 339.27mg/g, which is 9.3 times of that of the activated carbon material (36.6mg/g) and is nearly 3 times of that of the graphene oxide (117.5 mg/g).
Compared with the existing two-dimensional reduced graphene, the copper ion adsorbent provided by the invention can be used for adsorbing Cu in water2+The adsorption capacity of the method is improved, and the original two-dimensional reduced graphene can adsorb Cu in water2+The adsorption capacity of the copper ion adsorbent is 316.586mg/g, and the adsorption capacity of the copper ion adsorbent is improved by 7-10% on the basis of the original two-dimensional reduced graphene.
Compared with the existing massive three-dimensional graphene materials (such as graphene hydrogel, graphene foam and the like) with macroscopic morphology structures, the copper ion adsorbent disclosed by the invention has the advantages that the powdery adsorption material can be dispersed in liquid so as to realize homogeneous adsorption, and the adsorption capacity is maximized.
Drawings
Fig. 1 is a Transmission Electron Microscope (TEM) comparison of two-dimensional graphene (a) and PA-gr (b) having a three-dimensional structure in example 1 of the present invention.
FIG. 2 shows the adsorption of Cu in water by PA-Gr powder in example 42+Langmuir adsorption isotherm of (a).
FIG. 3 shows the adsorption of Cu in water by PA-Gr powder in example 42+Freundlich adsorption isotherm of (1).
Detailed Description
The following describes embodiments of the present invention in detail with reference to the drawings.
Example 1
Preparation of PA-Gr powder
Firstly, preparing GO dispersion liquid, adding 1g of graphite powder into 23mL of concentrated sulfuric acid (98%) under the condition of ice-water bath, slowly adding 3g of potassium permanganate, and simultaneously slowly stirring until the potassium permanganate is completely dissolved. After standing for 24H, highly pure water and 3.5mL of H were added to the mixture in order2O2(30%). The mixed solution is centrifugally washed for several times by using dilute hydrochloric acid (5%) and high-purity water until the pH value is neutral, and the obtained dispersion liquid is the GO dispersion liquid.
4mL of GO dispersion (10mg/mL) is added into 40mL of high-purity water to obtain GO dilution. 42mL of GO dilution was added with 0.4mL of phytic acid solution (70% in H)2O). And transferring the mixed solution to a polytetrafluoroethylene hydrothermal reaction kettle, and carrying out hydrothermal reaction for 3h at 145 ℃. After the reaction is finished, after the reaction kettle is cooled to room temperature, separating solid particles in the mixed solution by using filter paper, and soaking the mixed solution in high-purity water for 45 hours. After 4 times of washing, the mixture was shaken thoroughly in a shaker at a slow speed. And separating out the dispersed solid in the water by using filter paper, and fully drying at room temperature to obtain powdery solid, namely PA-Gr powder.
Fig. 1 is a TEM contrast diagram of two-dimensional graphene (a) and PA-gr (b) having a three-dimensional stereo structure. (A) Obvious folding, wrinkling, curling and the like can be observed in the graph, and the graph belongs to the typical appearance of two-dimensional flat-layer graphene; the PA-Gr shown in the figure (B) has a microscopic three-dimensional structure, and the original two-dimensional lamellar structure disappears. Due to the pi-pi stacking effect between the graphene carbon rings, two-dimensional graphene sheets are easy to agglomerate, the adsorption active sites on the surfaces of the two-dimensional graphene sheets are reduced, and the adsorption capacity is further reduced. The graphene material with the three-dimensional structure resists the coagulation effect caused by the pi-pi stacking effect due to steric hindrance, so that the adsorbent can provide more adsorption sites and is beneficial to improving the adsorption capacity. In addition, tests show that the adsorption capacity of the two-dimensional graphene is reduced by 37% and the adsorption capacity of the PA-Gr is reduced by only 6% when the two-dimensional graphene and the prepared PA-Gr are soaked in water for 168 hours.
Example 2
PA-Gr powder pair for preparing Cu in water sample2+Adsorption of (2):
(1) preparation of PA-Gr powder
Firstly, preparing GO dispersion liquid, namely adding 1g of graphite powder into 23mL of concentrated sulfuric acid (98%) under the condition of ice-water bath, slowly adding 3g of potassium permanganate, and simultaneously slowly stirring until the potassium permanganate is completely dissolved. After standing for 24H, highly pure water and 3.5mL of H were added to the mixture in order2O2(30%). The mixed solution is centrifugally washed for several times by using dilute hydrochloric acid (5%) and high-purity water until the pH value is neutral, and the obtained dispersion liquid is the GO dispersion liquid. 1mL of GO dispersion (8mg/mL) is added into 25mL of high-purity water to obtain GO dilution. 30mL of GO diluted solution is added with 0.2mL of phytic acid solution (70% in H)2O). And transferring the mixed solution into a polytetrafluoroethylene hydrothermal reaction kettle, and carrying out hydrothermal reaction for 1h at 130 ℃. After the reaction is finished, after the reaction kettle is cooled to room temperature, separating solid particles in the mixed solution by using filter paper, and soaking the mixed solution in high-purity water for 40 hours. After 3 times of washing, the mixture was shaken thoroughly in a shaker at a slow speed. And separating out the dispersed solid in the water by using filter paper, and fully drying at room temperature to obtain powdery solid, namely PA-Gr powder.
(2) Preparing Cu with the concentration of 20mg/L2+An aqueous solution to which the prepared PA-Gr powder is added as an adsorbent. The mixed solution reacts for 2 hours in a constant temperature oscillator under the conditions of 110r/min and 20 ℃. The resulting mixture was filtered through a 0.20 μm filter paper, and the supernatant was collected.
(3) Measuring Cu in obtained supernatant by using atomic absorption spectrometer2+The concentration of (c). The PA-Gr powder prepared was determined to be Cu in water under the experimental conditions of steps (1) and (2)2+The removal rate of (A) is up to 71%.
(4) The experimental results were fitted using Langmuir adsorption model and Freundlich adsorption model, R of Langmuir and Freundlich isothermal models2The values are 0.9713 and 0.9566 respectively, and the adsorption process is more consistent with Langmuir adsorption and the likeAnd (4) a temperature model. Calculated, the PA-Gr is used for Cu in water under the condition2+The maximum adsorption amount of (a) was 313.10 mg/g.
Example 3
PA-Gr powder pair for preparing Cu in water sample2+Adsorption of (2):
(1) preparation of PA-Gr powder
Firstly, preparing GO dispersion liquid, namely adding 1g of graphite powder into 23mL of concentrated sulfuric acid (98%) under the condition of ice-water bath, slowly adding 3g of potassium permanganate, and simultaneously slowly stirring until the potassium permanganate is completely dissolved. After standing for 24H, highly pure water and 3.5mL of H were added to the mixture in order2O2(30%). The mixed solution is centrifugally washed for several times by using dilute hydrochloric acid (5%) and high-purity water until the pH value is neutral, and the obtained dispersion liquid is the GO dispersion liquid. And adding 9mL of GO dispersion (15mg/mL) into 50mL of high-purity water to obtain a GO dilution. 50mL of GO diluted solution was added with 0.8mL of phytic acid solution (70% in H)2O). And transferring the mixed solution into a polytetrafluoroethylene hydrothermal reaction kettle, and carrying out hydrothermal reaction for 4h at 170 ℃. After the reaction is finished, after the reaction kettle is cooled to room temperature, separating solid particles in the mixed solution by using filter paper, and soaking the mixed solution in high-purity water for 50 hours. After 5 times of washing, the mixture was shaken thoroughly in a shaker at a slow speed. And separating out the dispersed solid in the water by using filter paper, and fully drying at room temperature to obtain powdery solid, namely PA-Gr powder.
(2) Preparing Cu with the concentration of 70mg/L2+An aqueous solution to which the prepared PA-Gr powder is added as an adsorbent. The mixed solution reacts for 4 hours at the temperature of 30 ℃ at the speed of 130r/min in a constant temperature oscillator. The resulting mixture was filtered through a 0.24 μm filter paper, and the supernatant was collected.
(3) Measuring Cu in obtained supernatant by using atomic absorption spectrometer2+The concentration of (c). The PA-Gr powder prepared was determined to be Cu in water under the experimental conditions of steps (1) and (2)2+The removal rate of (D) is 79%.
(4) The experimental results were fitted using Langmuir adsorption model and Freundlich adsorption model, R of Langmuir and Freundlich isothermal models2The values are 0.9656, and 0.9602, respectively, and the adsorption process more closely follows the Langmuir adsorption isotherm model. Calculated, this isPA-Gr for Cu in water under the condition2+The maximum adsorption amount of (a) was 324.89 mg/g.
Example 4
PA-Gr powder pair for preparing Cu in water sample2+Adsorption of (2):
(1) preparation of PA-Gr powder
Firstly, preparing GO dispersion liquid, namely adding 1g of graphite powder into 23mL of concentrated sulfuric acid (98%) under the condition of ice-water bath, slowly adding 3g of potassium permanganate, and simultaneously slowly stirring until the potassium permanganate is completely dissolved. After standing for 24H, highly pure water and 3.5mL of H were added to the mixture in order2O2(30%). The mixed solution is centrifugally washed for several times by using dilute hydrochloric acid (5%) and high-purity water until the pH value is neutral, and the obtained dispersion liquid is the GO dispersion liquid. Add 3mL GO dispersion (11mg/mL) to 37mL high purity water to obtain GO dilution. 40mL of GO dilution was added with 0.5mL of phytic acid solution (70% in H)2O). And transferring the mixed solution into a polytetrafluoroethylene hydrothermal reaction kettle, and carrying out hydrothermal reaction for 2h at 150 ℃. After the reaction is finished, after the reaction kettle is cooled to room temperature, separating solid particles in the mixed solution by using filter paper, and soaking the mixed solution in high-purity water for 48 hours. After 6 times of washing, the mixture was shaken thoroughly in a shaker at a slow speed. And separating out the dispersed solid in the water by using filter paper, and fully drying at room temperature to obtain powdery solid, namely PA-Gr powder.
(2) Preparing Cu with the concentration of 80mg/L2+An aqueous solution to which the prepared PA-Gr powder is added as an adsorbent. The mixed solution reacts for 3 hours in a constant temperature oscillator under the conditions of 120r/min and 25 ℃. The resulting mixture was filtered through a 0.22 μm filter paper, and the supernatant was collected.
(3) Measuring Cu in obtained supernatant by using atomic absorption spectrometer2+The concentration of (c). The PA-Gr powder prepared was determined to be Cu in water under the experimental conditions of steps (1) and (2)2+The removal rate of the catalyst reaches 84 percent.
(4) The experimental results were fitted using Langmuir adsorption model and Freundlich adsorption model, R of Langmuir and Freundlich isothermal models2The values are 0.9782 and 0.9769, respectively, and the adsorption process is more consistent with the Langmuir adsorption isothermal model. Calculated, the PA-Gr is used for Cu in water under the condition2+The maximum adsorption amount of (a) was 339.27 mg/g.
TABLE 1 adsorption of Cu from PA-Gr powder in example 4 in Water2+Langmuir constant of
TABLE 2 adsorption of Cu from PA-Gr powder in example 4 in Water2+Freundlich constant of
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. The copper ion adsorbent is characterized by being three-dimensional graphene powder modified based on phytic acid.
2. The method for preparing the copper ion adsorbent according to claim 1, wherein the graphene oxide diluent is added to the phytic acid solution and mixed; transferring the mixture into a polytetrafluoroethylene hydrothermal reaction kettle for hydrothermal reaction, and separating solid particles in the mixed solution to soak in high-purity water after the reaction kettle is cooled to room temperature after the reaction is finished; washing the solid particles with water and then fully oscillating in a shaking table; and drying the solid particles to obtain the phytic acid modified three-dimensional graphene powder.
3. The method for preparing the copper ion adsorbent according to claim 2, wherein the reaction temperature in the polytetrafluoroethylene hydrothermal reaction kettle is 130-170 ℃ and the reaction temperature is 1-4 h.
4. The method for preparing the copper ion adsorbent according to claim 2, wherein the concentration of the graphene oxide diluent is 0.16-5.4 mg/mL.
5. The method for preparing the copper ion adsorbent according to claim 2, wherein the volume ratio of the graphene oxide diluent to the phytic acid solution is 30-50: 0.2-0.8; the concentration of the phytic acid solution is 70%.
6. The method for preparing the copper ion adsorbent according to claim 2, wherein the solid particles in the reaction kettle are separated by using filter paper and then soaked in high-purity water for 40-50 h.
7. The method for preparing the copper ion adsorbent according to claim 2, wherein the copper ion adsorbent is soaked in high-purity water and then washed with water for 3 to 6 times.
8. A method for adsorbing copper ions, characterized in that the copper ion adsorbent according to claim 1 is added to a copper ion solution, placed in a constant temperature oscillator for reaction and filtered.
9. The method for adsorbing copper ions according to claim 8, wherein the reaction conditions of the constant temperature oscillator are 110 to 130r/min and 20 to 30 ℃; the reaction temperature is 2-4 h.
10. The method according to claim 8, wherein the concentration of the copper ion solution is 20 to 80 mg/L.
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