CN110433765B - Preparation method and application of EDTA (ethylene diamine tetraacetic acid) intercalated ferro-manganese layered double hydroxides - Google Patents
Preparation method and application of EDTA (ethylene diamine tetraacetic acid) intercalated ferro-manganese layered double hydroxides Download PDFInfo
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- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 title claims abstract description 34
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 229910000616 Ferromanganese Inorganic materials 0.000 title claims abstract description 29
- 150000004679 hydroxides Chemical class 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 229960001484 edetic acid Drugs 0.000 title description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000009830 intercalation Methods 0.000 claims abstract description 15
- 230000002687 intercalation Effects 0.000 claims abstract description 15
- 239000011259 mixed solution Substances 0.000 claims abstract description 15
- 238000007789 sealing Methods 0.000 claims abstract description 14
- 239000003513 alkali Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 8
- 239000012266 salt solution Substances 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 230000032683 aging Effects 0.000 claims abstract description 4
- 239000007864 aqueous solution Substances 0.000 claims abstract description 4
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 238000000967 suction filtration Methods 0.000 claims abstract description 4
- 239000000725 suspension Substances 0.000 claims abstract description 4
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 4
- 239000012498 ultrapure water Substances 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- 230000002431 foraging effect Effects 0.000 claims abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 26
- 238000001179 sorption measurement Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000003760 magnetic stirring Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 150000002696 manganese Chemical class 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 2
- 150000002505 iron Chemical class 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 238000009777 vacuum freeze-drying Methods 0.000 claims description 2
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims 1
- 229910052785 arsenic Inorganic materials 0.000 abstract description 11
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 abstract description 11
- 239000002351 wastewater Substances 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 239000003814 drug Substances 0.000 abstract 1
- 230000005518 electrochemistry Effects 0.000 abstract 1
- 239000000706 filtrate Substances 0.000 abstract 1
- 229910000000 metal hydroxide Inorganic materials 0.000 abstract 1
- 150000004692 metal hydroxides Chemical class 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 12
- 239000000243 solution Substances 0.000 description 9
- 239000003344 environmental pollutant Substances 0.000 description 6
- 231100000719 pollutant Toxicity 0.000 description 6
- 239000006228 supernatant Substances 0.000 description 6
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- 241000282414 Homo sapiens Species 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000009616 inductively coupled plasma Methods 0.000 description 3
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical class [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- LXAHHHIGZXPRKQ-UHFFFAOYSA-N 5-fluoro-2-methylpyridine Chemical compound CC1=CC=C(F)C=N1 LXAHHHIGZXPRKQ-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 208000024172 Cardiovascular disease Diseases 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
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- 150000004696 coordination complex Chemical class 0.000 description 1
- 230000001079 digestive effect Effects 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229910001412 inorganic anion Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000000926 neurological effect Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000011197 physicochemical method Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 231100000444 skin lesion Toxicity 0.000 description 1
- 206010040882 skin lesion Diseases 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
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- 239000003440 toxic substance Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000003911 water pollution Methods 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0222—Compounds of Mn, Re
-
- 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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
- B01J20/0229—Compounds of Fe
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/103—Arsenic 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
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention discloses a preparation method and application of EDTA intercalation ferro-manganese layered double hydroxides. Preparing a ferro-manganese mixed salt solution and an alkali mixed solution. Adding 100 mL of ultrapure water into a three-neck flask, sealing, magnetically stirring under a nitrogen atmosphere, dripping an alkali mixed solution into the three-neck flask to enable the pH value of an aqueous solution to be 10-12, then simultaneously dripping a ferro-manganese mixed salt solution and the alkali mixed solution into the three-neck flask, maintaining the nitrogen atmosphere in the three-neck flask during the dripping, keeping the pH value of a mixed solution to be 10-12, after the dripping is finished, continuously sealing and stirring the obtained suspension for 10 min, then placing the suspension into a water bath kettle for aging at 60 ℃ for 2-12 h, cooling to room temperature after the aging is finished, carrying out suction filtration and washing for 3-5 times, and drying the filtrate for 24h to obtain the EDTA intercalation ferro-manganese layered double metal hydroxide. Is applied to the treatment of arsenic-containing wastewater. The Fe/Mn-EDTA-LDH obtained by the method has a good layered structure, can be used for adsorbing and treating arsenic-containing wastewater, and has potential application values in the aspects of catalysis, medicine and electrochemistry.
Description
Technical Field
The invention belongs to the technical field of water environment treatment, and particularly relates to a preparation method and application of EDTA intercalation ferro-manganese layered double hydroxides.
Background
While the economy develops rapidly, the negative influence of economic benefits on the environment is increasingly prominent, and the heavy metals pollute the environment and have greater and greater influence on human beings. Among them, heavy metals cause the most serious and difficult control of water pollution. The technology for treating heavy metal wastewater can be summarized into three types: chemical, biological and physicochemical methods. They mainly include various methods such as precipitation, bioflocculation, ion exchange, adsorption, etc. Many of them are expensive and have certain limitations (e.g. secondary pollutants, short service life, high process conditions, etc.). The adsorption method is attracting attention due to its advantages of low cost, convenient operation, high efficiency, simple equipment, easy regeneration of materials, etc.
Arsenic is a toxic and carcinogenic substance that can cause skin lesions, neurological, digestive and cardiovascular disorders. Arsenic has two valence states of trivalent and pentavalent in the environment, the toxicity of trivalent arsenic is about 60 times that of pentavalent arsenic, and the treatment of trivalent arsenic is a global scientific problem. Statistical data show that about 11 million tons of arsenic enters the water environment through various ways every year in the world, and causes pollution to surface water and underground water, thereby seriously threatening human health. Therefore, the problem of arsenic contamination is urgently solved.
Layered Double Hydroxides (LDHs), i.e., hydrotalcite compounds, have been developed for over 100 years to date and are widely used in various fields due to their unique structural characteristics. The adsorption and intercalation performances are two current research hotspots of LDHs. On the one hand, the LDHs have larger specific surface area (20-250 m)2/g) and developed pore structure, indicating that it can act as a getterAn additive; when the LDHs is used as an adsorbent, the LDHs has the effects of electrostatic adsorption, surface complexation, physical adsorption, chemical adsorption and the like, so that the LDHs can be widely applied to removal of various pollutants, and reports of using the LDHs as the adsorbent in aspects of printing and dyeing, papermaking, electroplating and the like are provided. On the other hand, LDHs is the only layered material capable of carrying out intercalation reaction, and by utilizing the characteristic, a specific object can be inserted between layers of the LDHs to assemble the layered material to obtain the required functional layered nano-material, so that target pollutants can be selectively removed. Currently, the research reports that the ferro manganese layered double hydroxides mostly use inorganic anions such as carbonate, nitrate and chloride ions as interlayer anions, and the interlayer anions mainly fix pollutants between laminated plates through ion exchange so as to remove the pollutants. EDTA (ethylene diamine tetraacetic acid) as a metal complex can form stable chelate with heavy metal ions in the solution, and EDTA is introduced between LDHs layers, so that not only can the structural characteristics of LDHs be exerted, but also the chelation of EDTA can be exerted, and the removal effect of LDHs on pollutants is greatly improved.
Disclosure of Invention
The invention aims to provide a preparation method and application of EDTA intercalated ferro-manganese layered double hydroxides. The EDTA intercalation ferro-manganese layered double hydroxide Fe/Mn-EDTA-LDH is directly synthesized in one step by a low saturation coprecipitation method, the phase, the structure, the composition, the morphological characteristics and the like of the EDTA intercalation ferro-manganese layered double hydroxide are characterized, and the EDTA intercalation ferro-manganese layered double hydroxide is applied to an adsorption test of simulated wastewater containing As (III) and As (V), so that the As (III) and As (V) in the water are efficiently removed.
The preparation method of the EDTA intercalation ferro-manganese layered double hydroxide comprises the following specific steps:
(1) mixing iron salt and manganese salt with the molar ratio of iron to manganese of 1:2, dissolving the mixture in 50 mL of deoxidized water, sealing, and dissolving the mixture by magnetic stirring to obtain a mixed iron-manganese salt solution.
(2) Mixing sodium hydroxide and disodium ethylenediamine tetraacetate, dissolving in 100 mL of deoxidized water, sealing, and dissolving by magnetic stirring to obtain an alkali mixed solution.
(3) Adding 100 mL of ultrapure water into a three-neck flask, sealing, magnetically stirring under a nitrogen atmosphere, dripping the alkali mixed solution prepared in the step (2) into the three-neck flask to ensure that the pH value of the aqueous solution is 10-12, then dropwise adding the ferro-manganese mixed salt solution prepared in the step (1) and the alkali mixed solution prepared in the step (2) into a three-neck flask simultaneously, maintaining the nitrogen atmosphere in the three-neck flask during the process, keeping the pH value of the mixed solution at 10-12, continuously sealing and stirring the obtained suspension for 10 min after the dripping is finished, then placing the mixture in a water bath kettle for aging at 60 ℃ for 2-12 h, cooling to room temperature after the aging is finished, carrying out suction filtration and washing for 3-5 times, placing the filtered substance in a 60 ℃ drying oven or a-40 ℃ vacuum freeze-drying machine for drying for 24h, thus obtaining the EDTA intercalation ferro-manganese layered double hydroxides, then sieving with a 100-mesh sieve, sealing and storing for later use.
The iron and manganese salts are preferably chloride salts.
The EDTA intercalated ferro-manganese layered double hydroxide prepared by the invention is applied to the adsorption separation of As (III) and As (V) in water.
The invention has the advantages that: the EDTA intercalated ferro-manganese layered double hydroxide prepared by the invention has a good layered structure of typical hydrotalcite, and has a high removal effect on As (III) and As (V) in water under a neutral condition. The method has simple process and short preparation period, and has important significance for removing arsenic which is seriously harmful to human bodies.
Drawings
FIG. 1 is an XRD spectrum of an EDTA intercalated ferrimanganic layered double hydroxide Fe/Mn-EDTA-LDH prepared by the embodiment of the invention.
FIG. 2 is an FTIR spectrum of EDTA intercalated ferrimanganic layered double hydroxide Fe/Mn-EDTA-LDH prepared by the embodiment of the invention.
FIG. 3 is an SEM image of an EDTA intercalated ferro-manganese layered double hydroxide Fe/Mn-EDTA-LDH prepared by the embodiment of the invention.
FIG. 4 is a graph showing the effect of pH on the adsorption of As (III) and As (V) by EDTA intercalated ferrimanganic layered double hydroxide Fe/Mn-EDTA-LDH.
FIG. 5 is a graph showing the effect of time on the adsorption of As (III) and As (V) by the EDTA intercalated ferrimanganic layered double hydroxide Fe/Mn-EDTA-LDH.
FIG. 6 is a graph showing the effect of concentration on the adsorption of As (III) and As (V) by EDTA intercalated ferrimanganic layered double hydroxide Fe/Mn-EDTA-LDH.
Detailed Description
Example (b):
preparing an EDTA intercalation ferro-manganese layered double hydroxide Fe/Mn-EDTA-LDH:
(1) 4.505 g of FeCl were weighed3·6H2O(s) and 6.583 g MnCl2·4H2And O (S) is added into 50 mL of deoxidized water at the same time, sealed and dissolved by magnetic stirring to obtain a ferro-manganese mixed salt solution (Sol S).
(2) A mixed solution of NaOH 9.6 g and EDTA disodium 4.653 g was dissolved in 100 mL of deoxygenated water, sealed, and dissolved by magnetic stirring to obtain a mixed base solution (Sol B).
(3) After adding 100 mL of ultrapure water to the three-necked flask, sealing, introducing nitrogen gas under magnetic stirring for 10 min, slowly dropping (Sol B) into the three-necked flask to adjust the pH of the solution to 12, and then slowly dropping (Sol S) and (Sol B) into the flask simultaneously while continuing to introduce nitrogen gas while keeping the pH at 12.
(4) After the dropwise addition, the mixed solution was stirred in a sealed manner for 10 min and then aged in a 60 ℃ water bath for 2 h.
(5) Cooling to room temperature after aging, and performing suction filtration and washing for 3 times.
(6) Drying the obtained product in a vacuum freeze dryer at the temperature of-40 ℃ for 24h to obtain EDTA intercalation ferro-manganese layered double hydroxide Fe/Mn-EDTA-LDH, sieving with a 100-mesh sieve, and sealing and storing for later use.
The EDTA intercalated ferromanganese layered double hydroxide Fe/Mn-EDTA-LDH prepared in this example was used to conduct the following adsorption removal tests for As (III) and As (V).
Effect of pH on the adsorption of As (III) and As (V) by Fe/Mn-EDTA-LDH
Respectively taking 25 mL of As (III) and As (V) solutions with the concentration of 50 mg/L and the pH value of 2-12 into a 100 mL plastic centrifuge tube, wherein the dosage of Fe/Mn-EDTA-LDH is 1.2 g/L. Reacting for 24h on a shaking table with the rotation speed of 180 rpm at 25 +/-0.1 ℃, taking a supernatant, filtering the supernatant by a filter membrane, and measuring the concentrations of As (III) and As (V) in the residual solution by an inductively coupled plasma spectrometer (ICP-OES), wherein the result is shown in figure 4. As can be seen from the figure, in the pH value range of 2-10, the adsorption performance of the Fe/Mn-EDTA-LDH prepared by the embodiment on arsenic is hardly influenced by pH, and the Fe/Mn-EDTA-LDH has higher adsorption quantity and good removal effect on As (III) and As (V).
Effect of time on the adsorption of As (III) and As (V) by Fe/Mn-EDTA-LDH
25 mL of 50 mg/L As (III) and As (V) solutions were added to a 100 mL plastic centrifuge tube to adjust the pH to 7 and the amount of Fe/Mn-EDTA-LDH added to the tube to 0.5 g/L. Reacting on a shaking table with the temperature of 25 +/-0.1 ℃ and the rotating speed of 180 rpm for 5 min-24 h, taking a supernatant, filtering the supernatant by a membrane, and measuring the concentrations of the residual As (III) and As (V) in the solution by an inductively coupled plasma spectrometer (ICP-OES), wherein the result is shown in figure 5. As can be seen from the figure, the Fe/Mn-EDTA-LDH prepared by the embodiment has good removal effect on As (III) and As (V), the adsorption amount is gradually increased along with the increase of time, and the adsorption on As (III) and As (V) is basically stable after 300 min and 700 min respectively.
Effect of concentration on the adsorption of As (III) and As (V) by Fe/Mn-EDTA-LDH
Respectively taking 25 mL of As (III) and As (V) solutions with the concentration of 5-50 mg/L and the pH value of 7 into a 100 mL plastic centrifuge tube, wherein the adding amount of Fe/Mn-EDTA-LDH is 0.5 g/L. Reacting on a shaking table with the rotation speed of 180 rpm at 25 +/-0.1 ℃ for 24 hours, taking a supernatant, filtering the supernatant by a filter membrane, and measuring the residual As (III) and As (V) concentrations of the solution by an inductively coupled plasma spectrometer (ICP-OES), wherein the result is shown in figure 6. As can be seen from the figure, the Fe/Mn-EDTA-LDH prepared by the embodiment has good removal effect on low-concentration As (III) and As (V), and the removal rate of 50 mg/L of As (III) and As (V) is more than 50%.
Claims (3)
1. A preparation method of EDTA intercalation ferro-manganese layered double hydroxides for adsorbing and separating As (III) and As (V) in water is characterized by comprising the following specific steps:
(1) mixing iron salt and manganese salt with the molar ratio of iron to manganese of 1:2, dissolving the mixture in 50 mL of deoxidized water, sealing, and dissolving the mixture by magnetic stirring to obtain a mixed iron-manganese salt solution;
(2) mixing sodium hydroxide and disodium ethylene diamine tetraacetate, dissolving in 100 mL of deoxidized water, sealing, and dissolving by magnetic stirring to obtain an alkali mixed solution;
(3) adding 100 mL of ultrapure water into a three-neck flask, sealing, magnetically stirring under a nitrogen atmosphere, dripping the alkali mixed solution prepared in the step (2) into the three-neck flask to ensure that the pH value of the aqueous solution is 10-12, then dropwise adding the ferro-manganese mixed salt solution prepared in the step (1) and the alkali mixed solution prepared in the step (2) into a three-neck flask simultaneously, maintaining the nitrogen atmosphere in the three-neck flask during the process, keeping the pH value of the mixed solution at 10-12, continuously sealing and stirring the obtained suspension for 10 min after the dripping is finished, then placing the mixture in a water bath kettle for aging at 60 ℃ for 2-12 h, cooling to room temperature after the aging is finished, carrying out suction filtration and washing for 3-5 times, placing the filtered substance in a 60 ℃ drying oven or a-40 ℃ vacuum freeze-drying machine for drying for 24h, thus obtaining the EDTA intercalation ferro-manganese layered double hydroxides, then sieving with a 100-mesh sieve, sealing and storing for later use.
2. The preparation method of the EDTA intercalation ferro-manganese layered double hydroxide according to claim 1, characterized in that in step (3), the pH of the aqueous solution is firstly adjusted to 10-12 under nitrogen atmosphere, and the nitrogen atmosphere in the container is always maintained during the dropwise addition of the ferro-manganese mixed salt solution and the alkali mixed solution.
3. Use of the EDTA intercalated ferromanganese layered double hydroxide prepared by the preparation method according to claim 1 or 2, wherein the EDTA intercalated ferromanganese layered double hydroxide is used for adsorption separation of as (iii) and as (v) in water.
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| CN201910761528.3A CN110433765B (en) | 2019-08-18 | 2019-08-18 | Preparation method and application of EDTA (ethylene diamine tetraacetic acid) intercalated ferro-manganese layered double hydroxides |
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