CN115286790B - Iodine capturing material and preparation method and application thereof - Google Patents
Iodine capturing material and preparation method and application thereof Download PDFInfo
- Publication number
- CN115286790B CN115286790B CN202210814331.3A CN202210814331A CN115286790B CN 115286790 B CN115286790 B CN 115286790B CN 202210814331 A CN202210814331 A CN 202210814331A CN 115286790 B CN115286790 B CN 115286790B
- Authority
- CN
- China
- Prior art keywords
- iodine
- phytic acid
- aniline
- capturing
- persulfate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/026—Wholly aromatic polyamines
- C08G73/0266—Polyanilines or derivatives thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
-
- 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
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/20—Halogens or halogen compounds
- B01D2257/202—Single element halogens
-
- 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
- C02F2101/006—Radioactive compounds
-
- 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
- C02F2101/12—Halogens or halogen-containing compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention belongs to the technical field of environmental pollution control, and provides an iodine capture material, a preparation method and application thereof, wherein an aniline phytic acid aqueous solution and an oxidant are mixed for polymerization reaction, and a product is washed and dried to obtain the iodine capture material; the aniline monomer content is 0.001-1 mol; the molar ratio of the oxidant to the aniline is 0.01:1-4:1; the concentration of phytic acid is 0.01-1M; the polymerization temperature is 25-80 ℃ and the reaction time is 0.5-24 h; and (5) washing with deionized water. The polyaniline is doped in situ by the phytic acid, so that the obtained polymer has strong chemical affinity to molecular iodine, and has good capturing effect to iodine simple substances in iodine-containing wastewater and gaseous iodine, and the wide application range of the material is shown. The iodine capturing material prepared by the method has high iodine removing efficiency, wide application range and simple using steps; meanwhile, the preparation method has the advantages of simple and easy operation process, low process cost and wide application range, and can realize industrial production.
Description
Technical Field
The invention belongs to the technical field of environmental pollution control, and particularly relates to an iodine capture material, a preparation method and application thereof.
Background
Radioiodine (I) 129 ) Worldwide attention is paid to the long half-life, high fluidity and adverse damage to the environment and human health. Such hazardous materials, which are mainly derived from spent fuel reprocessing and accident nuclear leakage, are easily diffused worldwide if not effectively controlled. In addition, many chemical enterprises and pharmaceutical enterprises face the difficult problem of treating iodine-containing wastewater and waste gas. Therefore, the exploration of effective iodine capture materials has important theoretical significance and practical value.
Although some trapping techniques, including silver-exchanged zeolites, organic amine impregnated activated carbon, silver-loaded aluminosilicate aerogels, and metal organic framework materials, have good results in trapping radioiodine, silver-based trapping materials are costly and metal organic framework materials are unstable in humid conditions, which limits their use to some extent.
Recently, porous organic polymers such as porous aromatic frameworks, porous organic frameworks, porous hydrogen phenazine frameworks, conjugated microporous polymers, covalent organic frameworks, covalent triazine frameworks, and super-crosslinked polymers have been widely used for iodine capture, however, these porous organic polymers require complicated and expensive precursors, cumbersome preparation steps, and use of highly toxic organic solvents in the preparation process. Therefore, the method for exploring and preparing the iodine capture material with environmental friendliness and excellent effect has important scientific significance and application value.
Disclosure of Invention
Aiming at the technical problems, the invention provides the iodine capturing material, the preparation method and the application thereof, and the iodine capturing material prepared by the method has high iodine removing efficiency, wide application range and simple using steps; meanwhile, the preparation method has the advantages of simple and easy operation process, low process cost and wide application range, and can realize industrial production.
In order to achieve the above purpose, the invention adopts the following technical scheme: the preparation method of the iodine capturing material comprises the steps of mixing an aniline phytic acid aqueous solution with a phytic acid aqueous solution of an oxidant, carrying out polymerization reaction, washing a product, and drying to obtain the iodine capturing material; the content of the aniline monomer is 0.001-1 mol; the molar ratio of the oxidant to the aniline is 0.01:1-4:1, and the polymerization reaction is carried out for less than or equal to 24 and h.
The aniline and the oxidant are respectively dissolved in a phytic acid aqueous solution before being mixed; the concentration of the phytic acid aqueous solution is 0.01-1M; the oxidant is any one of persulfate or peroxide; the persulfate is any one of ammonium persulfate, sodium persulfate, potassium persulfate, manganese persulfate, potassium persulfate or potassium peroxymonosulfonate; the peroxide is hydrogen peroxide or peracetic acid.
The content of the aniline monomer is 0.001-0.02 mol; the molar ratio of the oxidant to the aniline is 1:1-2:1.
Preferably, the aniline monomer content is 0.004 mol; the molar ratio of the oxidant to the aniline is 1:1.
Preferably, the persulfate is ammonium persulfate; the concentration of the aqueous phytic acid solution was 0.1. 0.1M. The temperature of the polymerization reaction was 25 ℃. The polymerization was carried out for a period of 6 h and the polymer was washed with deionized water.
The iodine capturing material prepared by the method.
The application of the iodine capture material in removing iodine and gaseous iodine in wastewater comprises the following specific steps: the wastewater is iodine-containing wastewater, the initial pH value is 3-9, the concentration of molecular iodine in the iodine-containing wastewater is 100-500 mg/L, an iodine capturing material is added in the treatment process, the usage amount of the iodine capturing material is 0.01-5 g/L, the wastewater treatment temperature is 15-45 ℃, and the treatment time is 0.1-24 h.
Further, the initial pH value of the wastewater is 3-7, the concentration of molecular iodine in the iodine-containing wastewater is 200-500mg/L, the usage amount of iodine capturing materials is 0.1-0.5 g/L, the temperature of wastewater treatment is 15-25 ℃, and the treatment time is 0.5-2 h.
The iodine capture material prepared by the method has extremely high removal effect on iodine-containing wastewater, and the removal rate of the iodine capture material in 1 h under the condition of initial pH=7 reaches more than 95 percent.
In the present invention, phytic acid is used as a dopant for the polyaniline trapping material. This is because the pH of the system must be acidic in polyaniline synthesis, and although hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid can be used to prepare polyaniline theoretically, these inorganic acids form polyaniline with a relatively compact structure and poor hydrophilicity. Phytic acid is a high molecular organic acid, and the aqueous solution of the phytic acid can not only provide a lower pH value, but also can be used as a cross-linking agent to link aniline molecules to form polymer hydrogel. In addition, the benzene ring, amine and imine functional groups exist in the polymer to form a large number of conjugated pi electrons and hydrogen bonds, and strong chemical affinity is formed between the conjugated pi electrons and the iodine simple substance, so that the polymer has strong iodine capturing capability, and has good capturing capability on simple substance iodine in iodine-containing aqueous solution and gas-phase iodine vapor. The method has certain innovation and application potential by utilizing the strong chemical affinity between the organic functional group and iodine and applying the method to the treatment of iodine-containing wastewater and waste gas.
Compared with the prior art, the invention has the beneficial effects that: the iodine capturing material is used for replacing silver-exchanged zeolite, silver-loaded aerogel and porous organic polymer, so that the cost of wastewater treatment is reduced, and the secondary pollution to the environment is reduced; the preparation method is simple and is easy for industrial production; the method can be used for treating iodine-containing organic wastewater and iodine-containing waste gas, and has a wide application range; the reaction system can react at room temperature, the device is simple, the cost is low, the environment is friendly, and the method has an industrialized application prospect.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments of the present invention will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a Scanning Electron Microscope (SEM) chart (a-b) and an element distribution spectrum of the iodine capturing material prepared in example 1;
FIG. 2 is an X-ray photoelectron spectrum of the iodine capturing material prepared in example 1;
FIG. 3 is an X-ray photoelectron spectrum of a sample of the iodine capture material prepared in example 1 after iodine capture and washing with different substances;
FIG. 4 is a Raman spectrum of the iodine capturing material prepared in example 1 before and after capturing iodine;
FIG. 5 is a graph showing the effect of iodine capture materials prepared from different aniline contents on the removal of iodine-containing wastewater;
FIG. 6 is a graph showing the removal effect of iodine capture materials prepared from an oxidant and aniline at different molar ratios on iodine-containing wastewater;
FIG. 7 is a graph showing the effect of iodine capture materials prepared during doping of different acids on removal of iodine-containing wastewater;
FIG. 8 is a graph showing the effect of iodine capture materials prepared at different acid concentrations on removal of iodine-containing wastewater;
FIG. 9 is a graph showing the effect of iodine capture material prepared at different polymerization temperatures on removal of iodine-containing wastewater;
FIG. 10 is a graph showing the effect of iodine capture material prepared at different polymerization times on the removal of iodine-containing wastewater;
FIG. 11 is a graph showing the effect of iodine capture material prepared in different post-treatment modes on removal of iodine-containing wastewater;
FIG. 12 is a graph showing the effect of the iodine scavenger material prepared in example 1 on removal of iodine-containing wastewater at different pH values;
FIG. 13 is a graph showing the effect of the iodine capturing material prepared in example 1 on removal of iodine-containing wastewater of different concentrations;
FIG. 14 is a graph showing the effect of iodine-containing wastewater removal by the iodine-capturing material prepared in example 1 at different amounts of addition;
FIG. 15 is a graph showing the effect of the iodine capturing material prepared in example 1 on removal of iodine-containing wastewater at different temperatures;
FIG. 16 is a graph showing the effect of the iodine scavenger material prepared in example 1 on the removal of iodine-containing wastewater in the presence of different anions;
fig. 17 is a graph showing the effect of the iodine capturing material prepared in example 1 on capturing gaseous iodine.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments; all other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs, the disclosure of which is incorporated herein by reference as is commonly understood by reference.
Those skilled in the art will recognize that equivalents of the specific embodiments described, as well as those known by routine experimentation, are intended to be encompassed within the present application.
The experimental methods in the following examples are conventional methods unless otherwise specified. The instruments used in the following examples are laboratory conventional instruments unless otherwise specified; the experimental materials used in the examples described below, unless otherwise specified, were purchased from conventional biochemical reagent stores.
1. Preparation of iodine capture material: according to the data set forth in Table 1, 0.364 mL aniline (0.004 mol) was dissolved in 180 mL of a 0.1M phytic acid solution, and 0.912 g oxidizer ammonium persulfate (0.004 mol) was dissolved in 20 mL of a 0.1M phytic acid solution. The two were mixed and stirred on a magnetic stirrer at room temperature for 6 hours to initiate the polymerization. After the reaction is completed, the product is collected, washed by deionized water, filtered and dried to obtain the iodine capturing material.
TABLE 1 preparation test parameters of iodine Capture Material
2. Characterization of iodine capture material:
(1) Surface morphology of iodine capturing material: example 1 a Scanning Electron Microscope (SEM) photograph of an iodine capturing material obtained during the preparation process is shown in fig. 1, and it can be seen that the freshly prepared iodine capturing material has a shape of a nanorod, a length of 100-160 a nm a diameter of 40-50 a nm a. Further, as can be seen from the element energy spectrum surface distribution image of the material surface, C, N and P elements are uniformly distributed on the polymer surface. As the aniline monomer contains N element and the phytic acid molecule contains P element in the preparation process, the energy spectrum surface distribution of the element shows that the phytic acid doped polyaniline iodine capturing material is successfully prepared.
(2) Chemical composition of iodine capture material: the chemical composition of the iodine capturing material prepared in example 1 was identified by X-ray photoelectron spectroscopy (XPS). The results are shown in FIG. 2, and the XPS survey spectrum shows that the samples except C1s And O1sOutside the peak of (2), obvious N1 was also detectedsAnd P2pPeaks, which are consistent with the elemental energy spectrum surface distribution results, indicateThe phytic acid is successfully doped into the polyaniline skeleton. Further, the distribution ratio of N and P elements on the surface of the material is analyzed, and the atomic ratio C of the N element to the P element is found to be 100:16:12.
(3) Mechanism of iodine-containing wastewater treatment: due to molecular iodine (I) 2 ) And iodide ion (I) − ) Co-exist in the aqueous phase, so that iodine in the iodine-containing wastewater may be trapped as polyiodide ions (I 3 − And I 5 − ) In the form of a gel. Characterization of the iodine-captured material by X-ray photoelectron spectroscopy (XPS), as shown in FIG. 3, revealed that significant I3 was found on the spectrumdStructural double bands, respectively representing I3d 3/2 And I3d 5/2 . The high resolution spectra of these two bands were further analyzed and found to be split into two bimodal peaks, with a bimodal peak at 630.2 eV and 618.8 eV with elemental iodine (I 2 ) Completely coincident, while the other bimodal is at a higher binding energy position (619.9 eV) than would be the case at a lower binding energy position I 3 − And I 5 − Is not consistent, indicating that the trapped iodine is not present as I 3 − And I 5 − In the form of, but mainly as I 2 Exists in a form and is due to I 2 Strong chemical affinity with iodine capture material, part I 2 I3 of (2)dThe binding energy position moves in a higher direction. The Raman spectrum of the material after iodine capture supports this determination, and the Raman spectrum is shown in FIG. 4, except 1345 cm on the Raman spectrum −1 D peak at and 1590 cm −1 At the G peak, at 107 cm −1 Sum 164 cm −1 No part is observed to belong to I 3 − And I 5 − Is a characteristic peak of (2). These results indicate that the iodine capture material captures iodine in aqueous solution mainly as I 2 Form of the invention.
In conventional polyaniline synthesis, the pH of the system must be acidic, so hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid can be used to prepare polyaniline in theory. However, polyaniline formed by the inorganic acids has a compact structure, a small specific surface area and poor hydrophilicity, and is unfavorable for capturing iodine in water. Phytic acid is a high molecular organic acid, and the aqueous solution of the phytic acid can not only provide a lower pH value, but also can be used as a cross-linking agent to link aniline molecules to form polymer hydrogel. Moreover, the benzene ring, amine and imine functional groups exist in the polymer to form a large number of conjugated pi electrons and hydrogen bonds, and strong chemical affinity is formed between the conjugated pi electrons and the iodine simple substance, so that the polymer has strong iodine capturing capability.
Thus, when the sample after iodine capture was washed with ethanol, the amount of iodine dissolved in the ethanol was less than the capture amount, and a distinct I3 d peak was still detected by XPS (fig. 4). Further washing with deionized water after ammonia water washing, a distinct I3 d peak is still detected on the iodine capture material by XPS, which indicates that elemental iodine is very tightly bound to the iodine capture material, and the strong affinity prevents the iodine from desorbing again after being captured, which is very advantageous for high concentration radioactive iodine removal, since the iodine captured material can be buried deep in the ground as a whole in the form of waste.
3. Performance test of iodine capturing material in iodine-containing wastewater: catalytic degradation experiments were performed in 150 mL iodometric flasks, with typical reaction systems containing 0.3 g/L of iodine capture material prepared, initial iodine concentrations of 100-500 mg/L selected from the experiments, solution volumes of 100 ml, ph=3-9. The reaction solution was sealed and placed in a constant temperature shaker, and the reaction was shaken at 160 rpm at 25 ℃. After a certain time interval, the supernatant was removed and filtered through a 0.22 μm membrane to remove the iodine capturing material, and the iodine element (I) in the filtrate was measured simultaneously with an ultraviolet-visible spectrophotometer 2 ) And iodide ion (I) − ) Concentration.
Iodine-containing wastewater treatment example 1: influence of monomer concentration: the iodine scavenger material was prepared by selecting the iodine scavenger material prepared in example 1 and the iodine scavenger materials prepared in comparative examples 1 to 6 for treatment of iodine-containing wastewater, and since the iodine scavenger material was prepared by oxidative polymerization of aniline monomer, the influence of the monomer on the preparation of the iodine scavenger material was examined first. The results are shown in FIG. 5: with increasing aniline content, the obtained iodine capture material had a capture efficiency at ph=7 for an initial iodine concentration of 500mg/L and was relatively close, with no obvious rule, but the iodine capture effect of the obtained material began to decrease when the aniline monomer content exceeded 0.01 mol. This is because, at a given concentration of the oxidizing agent, the concentration of the monomer is insufficient, and all the monomers are polymerized, so that the concentration of the monomer has a limited influence on the iodine capturing effect of the obtained iodine capturing material. However, excessive monomer may cause incomplete polymerization, and incomplete polymer network structure, which may not only affect the yield of iodine capturing material, but also cause a decrease in iodine capturing effect.
Iodine-containing wastewater treatment example 2: effect of oxidant concentration: the iodine capturing material was selected from the iodine capturing material prepared in example 1 and the materials prepared in comparative examples 7 to 14 for treatment of iodine-containing wastewater, and polymerization of each monomer was accompanied by transfer of two electrons and two protons during aniline polymerization. This type of polymerization requires a large amount of oxidizing agent. When each monomer is combined with another monomer and reacts, the oxidizing agent is consumed, and therefore the molar concentration of the oxidizing agent should be close to that of the monomer. As shown in FIG. 6, the experimental results show that the molar ratio of the oxidant to the aniline is 1.0:1-2.0:1, and higher removal efficiency is achieved. However, too high an amount of the oxidizing agent does not increase the yield of polyaniline, and only a part of polyaniline is converted from the reduced state to the oxidized state, so that the amount of the oxidizing agent is preferably 1.0.
Iodine-containing wastewater treatment example 3: influence of the doping acid species: the polymerization of aniline needs to be carried out in the presence of protonic acid, and the protonic acid plays a role in providing protons for the reaction, maintaining the pH value required by the reaction and entering the polyaniline as a doping agent to make the polyaniline conductive, so that inorganic and organic acid mediums are examined respectively. As can be seen from FIG. 7, when common mineral acids such as hydrochloric acid (HCl), nitric acid (HNO) are used respectively 3 ) Sulfuric acid (H) 2 SO 4 ) Phosphoric acid (H) 3 PO 4 ) And organic acids, which have similar iodine removal effects, and which exhibit higher iodine capture efficiency. This is because although these acids can be used to provide acidity, they can be used to provide bothThe phytic acid can also be used as a cross-linking agent to connect aniline molecules to form polymer hydrogel, so that the hydrophilicity of the polymer is increased, the contact opportunity of active sites and iodine molecules in aqueous solution is increased, and the iodine capturing capability of the polymer is enhanced.
Iodine-containing wastewater treatment example 4: influence of acid solution concentration: as can be seen from fig. 8, the capture removal rate of iodine from the prepared polymer increases and then decreases as the concentration of phytic acid increases from 0 to 0.5. 0.5M. Particularly, when the concentration of phytic acid is less than 0.02 and M, the concentration of phytic acid is too low to provide sufficient acidity for the solution, and the formed polymer is incomplete, so that the iodine capturing effect is poor. Whereas at phytic acid concentrations of 0.02 to 0.1M, the formed polymer suddenly jumps the capture of iodine, confirming that a sufficient amount of phytic acid is necessary. When the concentration of phytic acid is as high as 0.5 and M, the capturing effect of the polymer on iodine is remarkably reduced, because the active site of the polymer is mainly on benzene rings and amino functional groups formed by aniline polymerization, and excessive phytic acid cannot increase the active site and even does not participate in polymerization reaction, but rather prevents aniline monomers from contacting each other, inhibits the formation of the polymer and weakens the iodine capturing capability of the polymer, so that the concentration of phytic acid is preferably 0.1M.
Iodine-containing wastewater treatment example 5: influence of polymerization temperature: polymerization is a chemical reaction in which monomer molecules are interconnected in solution to form a polymer, and thus the degree of polymerization and the nature of the polymer are closely related to the polymerization temperature. When the polymerization temperature was increased from room temperature (25 ℃) to 60℃and even 80℃the efficiency of iodine capture by the resulting polymer was only increased by about 10%, and the results at 60℃and 80℃were comparable (FIG. 9), which indicated that aniline molecules were readily polymerized and that a higher polymerization temperature was not required. Further, from the aspect of energy saving, room temperature is selected as the preparation temperature of the phytic acid doped polymer.
Iodine-containing wastewater treatment example 6: influence of polymerization time: the aniline molecules polymerize from a liquid state to a solid state and form a hydrogel polymer by phytic acid doping, which requires a certain polymerization reaction time. The reaction initiation time was preset to 2 h in consideration of the completion of the polymerization reaction and even the complete formation of the polymer, cooling, aging. Further extension of the reaction time, the efficiency of iodine capture by the resulting polymer increased, and after a polymerization reaction time exceeding 6 h, the capture of iodine by the resulting polymer was no longer significantly increased (fig. 10), indicating that excessively long polymerization times did not result in significant structural improvement to the already formed polymer.
Iodine-containing wastewater treatment example 7: effect of post-treatment: when the polymerization reaction is completed, the polymer formed is generally washed in a variety of ways, mainly to remove unreacted monomers and other reactants. When the washed matter is changed from water to ammonia water and hydrochloric acid solution, the capturing efficiency of the obtained polymer to iodine is slightly reduced (fig. 11), because the acid or alkali solution changes the microstructure of the polymer, so that the polymer is doped or undoped, and the doping effect of the phytic acid on the polymer is affected, and the reaction is more suitable to use water washing.
Iodine-containing wastewater treatment example 8: influence of the pH of the solution: the iodine capturing material is prepared by selecting the iodine capturing material prepared in the example 1 to treat iodine-containing wastewater, and when the iodine is captured under the condition that the initial pH value of the iodine-containing wastewater is 3-9, the iodine capturing material prepared in the example 1 has good capturing effect at all pH values. The results are shown in fig. 12, which shows that: as the pH increases, the removal rate of iodine in the solution gradually decreases. This is because iodine molecules (I) 2 ) With iodide ions (I) − ) The mutual conversion coexists, and when the alkalinity is enhanced, iodine molecules in the solution are easy to convert into iodine ions, which indicates that the alkaline solution is unfavorable for capturing iodine, so that the capturing experiment is preferably carried out at the pH of 3-7.
Iodine-containing wastewater treatment example 9: effect of initial iodine concentration: the wastewater was treated with the iodine capturing material prepared in example 1 with an initial iodine concentration of 100mg/L to 500mg/L, and the experimental results are shown in FIG. 13, and the results show that: the iodine capture material prepared in example 1 achieved 89% iodine removal in 60 minutes as the iodine concentration increased from 100mg/L to 500mg/L, with an increase in iodine capture capacity. Particularly, when the concentration is between 200 and 500 and mg/L, the removal rate can reach more than 90 percent. This shows that iodine capture can be performed at very fast rates at various concentrations, which is very advantageous for high concentration iodine-containing wastewater treatment.
Iodine-containing wastewater treatment example 10: influence of the amount of polymer added: as the amount of polymer added was increased from 0.1g/L to 1.0g/L, the efficiency of the polymer to capture iodine was also increased (fig. 14), since the total active sites available to react with iodine in solution increased with increasing amount of polymer added. However, since the amount of iodine trapped per unit mass of the polymer decreases as the amount of the polymer to be added increases, the amount of the polymer to be added is preferably 0.3 g/L.
Iodine-containing wastewater treatment example 11: influence of solution temperature: when the temperature of the iodine solution was increased from 15 ℃ to 45 ℃, the efficiency of the polymer for capturing iodine did not increase significantly, even a decrease occurred at 45 ℃ (fig. 15). This is because iodine has low solubility in water and low melting point, and iodine is easily separated out from the solution and volatilized as the reaction temperature increases, so increasing the temperature is not favorable for capturing iodine in the solution.
Iodine-containing wastewater treatment example 12: effect of coexisting anions: since many anions and cations exist in the actual wastewater, particularly iodine simple substance is easily converted into iodine ions, it is of great importance to examine the influence of coexisting anions. When 1.0 mmol F is added into the wastewater − 、Cl − 、Br − 、I − 、IO 3 − 、CO 3 2− 、SO 4 2− And PO (PO) 4 3− The effect of anions on the capture capacity of the iodine capture material prepared in example 1 at ph=7 was different, and the experimental results are shown in fig. 16. The results show that: in the halide X − (F, cl, br, I) Capture Capacity in the Presence of F − ~ Cl − < Br − ~I − Is reduced in order. In the presence of polyoxoanions, the capturing capacity influence sequence is IO 3 − < CO 3 2− ，SO 4 2− < PO 4 3− 。
13. Performance test of iodine capture material in iodine-containing vapor: since a part of iodine is usually present in a gaseous form after leakage of radioactive iodine, an experiment for capturing gaseous iodine was performed. The amount of iodine captured was measured gravimetrically at 80 c and at ambient pressure at different time intervals. The results of the comparison with the conventional commercially available activated carbon under the same conditions are shown in FIG. 17. As can be seen from the figure, the iodine capturing material prepared in example 1 has a good capturing effect on vapor iodine within 5 hours, and both the capturing rate and the capturing amount are superior to those of the commercial activated carbon (activated carbon for super capacitor, manufactured by Nanjing Xianfeng nano materials science and technology Co., ltd., product No. 100566, SSA: 1800 m) 2 /g, pore size: 2.0-2.2. 2.2 nm), indicating that the iodine capture material prepared in example 1 is a very promising gaseous iodine capture material. The performance test research shows that the iodine capture material has good capture effect on iodine and gaseous iodine in aqueous solution, and the technology of the invention has wider application range.
Example 2: the oxidant is sodium persulfate and the remainder of the process is as described in example 1.
Example 3: the oxidant was potassium hydrogen persulfate and the remainder of the procedure was as described in example 1.
Example 4: the oxidant is hydrogen peroxide and the remainder of the process is as described in example 1.
Example 5: the oxidant is peracetic acid and the remainder of the process is as described in example 1.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (9)
1. A preparation method of an iodine capture material is characterized by comprising the following steps: mixing an aniline phytic acid aqueous solution and a phytic acid aqueous solution of an oxidant, performing polymerization reaction, washing a product, and drying to obtain an iodine capturing material; the content of the aniline monomer is 0.001-1 mol; the molar ratio of the oxidant to the aniline is 0.01:1-4:1; the concentration of phytic acid in the phytic acid aqueous solution is 0.01-1M; the polymerization temperature is 25-80 ℃; the polymerization reaction is carried out for a time of 0.5 to 24 h; the washing mode is deionized water washing;
the aniline and the oxidant are respectively dissolved in a phytic acid aqueous solution before being mixed; the oxidant is any one of persulfate or peroxide; the persulfate is any one of ammonium persulfate, sodium persulfate, potassium persulfate, manganese persulfate, potassium persulfate or potassium peroxymonosulfonate; the peroxide is hydrogen peroxide or peracetic acid.
2. The method for preparing an iodine capturing material according to claim 1, wherein: the aniline monomer content is 0.004 mol; the molar ratio of the oxidant to the aniline is 1:1; the concentration of phytic acid in the phytic acid aqueous solution is 0.1M.
3. The method for preparing an iodine capturing material according to claim 1, wherein: the persulfate is ammonium persulfate.
4. The method for preparing an iodine capturing material according to claim 1, wherein: the temperature of the polymerization reaction is 25 ℃; the polymerization was carried out for a period of time of 6 h.
5. An iodine capturing material prepared by the method of any one of claims 1 to 4.
6. Use of the iodine scavenger material of claim 5 for removing iodine from wastewater, characterized in that: the specific method comprises the following steps: the wastewater is iodine-containing wastewater, the initial pH value is 3-9, the concentration of molecular iodine in the iodine-containing wastewater is 100-500 mg/L, an iodine capturing material is added in the treatment process, the using amount of the iodine capturing material is 0.01-5 g/L, and the wastewater treatment time is 0.1-24 h; and (5) washing the iodine capture material after the treatment is finished.
7. The use of an iodine scavenger material according to claim 6 for removing iodine from waste water, wherein: the initial pH value of the wastewater is 3-7, the concentration of molecular iodine in the iodine-containing wastewater is 200-500mg/L, the usage amount of iodine capturing materials is 0.1-0.5 g/L, the temperature of wastewater treatment is 15-25 ℃, and the treatment time is 0.5-2 h.
8. The use of an iodine scavenger material according to claim 6 for removing iodine from waste water, wherein: the amount of iodine scavenger material used was 0.3 g/L.
9. Use of the iodine scavenger material of claim 7 for removing iodine from an iodine-containing waste gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210814331.3A CN115286790B (en) | 2022-07-12 | 2022-07-12 | Iodine capturing material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210814331.3A CN115286790B (en) | 2022-07-12 | 2022-07-12 | Iodine capturing material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115286790A CN115286790A (en) | 2022-11-04 |
| CN115286790B true CN115286790B (en) | 2023-05-23 |
Family
ID=83822557
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210814331.3A Active CN115286790B (en) | 2022-07-12 | 2022-07-12 | Iodine capturing material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115286790B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006308739A (en) * | 2005-04-27 | 2006-11-09 | Seiko Epson Corp | Liquid electrostatic developer and method for manufacturing same |
| CN102076665A (en) * | 2008-06-27 | 2011-05-25 | 诺瓦提斯公司 | Organic compounds |
| CN103100314A (en) * | 2013-01-28 | 2013-05-15 | 大连理工大学 | Method for preparing polyaniline modified neutral conductive filter membrane |
| CN103539939A (en) * | 2013-09-23 | 2014-01-29 | 哈尔滨工业大学（威海） | Preparation method for polyaniline |
| CN106824100A (en) * | 2017-03-14 | 2017-06-13 | 山西师范大学 | A kind of zinc MOF poromerics of efficient capture iodine and preparation method and application |
-
2022
- 2022-07-12 CN CN202210814331.3A patent/CN115286790B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006308739A (en) * | 2005-04-27 | 2006-11-09 | Seiko Epson Corp | Liquid electrostatic developer and method for manufacturing same |
| CN102076665A (en) * | 2008-06-27 | 2011-05-25 | 诺瓦提斯公司 | Organic compounds |
| CN103100314A (en) * | 2013-01-28 | 2013-05-15 | 大连理工大学 | Method for preparing polyaniline modified neutral conductive filter membrane |
| CN103539939A (en) * | 2013-09-23 | 2014-01-29 | 哈尔滨工业大学（威海） | Preparation method for polyaniline |
| CN106824100A (en) * | 2017-03-14 | 2017-06-13 | 山西师范大学 | A kind of zinc MOF poromerics of efficient capture iodine and preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| 不同加工工艺制取菜籽油理化性质的研究;韦东林;魏冰;孟橘;胡小华;李林风;;粮食与食品工业(06);全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115286790A (en) | 2022-11-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Kim et al. | Phytic acid doped polyaniline nanofibers for enhanced aqueous copper (II) adsorption capability | |
| Li et al. | Redox Sorption and Recovery of Silver Ions as Silver Nanocrystals on Poly (aniline‐co‐5‐sulfo‐2‐anisidine) Nanosorbents | |
| JP5380535B2 (en) | Organic porous polymer material and synthesis method thereof | |
| Belalia et al. | Preparation of hybrid material based of PANI with SiO 2 and its adsorption of phenol from aqueous solution | |
| Liu et al. | Integration of MIL-101-NH2 into cellulosic foams for efficient Cr (VI) reduction under visible light | |
| Haspulat Taymaz et al. | Photocatalytic activity of polyaniline and neutral polyaniline for degradation of methylene blue and malachite green dyes under UV Light | |
| Zheng et al. | Construction of hydrophobic interface on natural biomaterials for higher efficient and reversible radioactive iodine adsorption in water | |
| Mirzaei et al. | Facile synthesis of polyaniline@ UiO-66 Nanohybrids for efficient and rapid adsorption of methyl orange from aqueous media | |
| CN113042011B (en) | Application of fluorine-containing conjugated microporous polymer | |
| CN110624514A (en) | Method for improving adsorption capacity of humic acid on metal ions | |
| Ali et al. | Efficient Enrichment of Eu 3+, Tb 3+, La 3+ and Sm 3+ on a Double Core Shell Nano Composite Based Silica | |
| Morsi et al. | Polyaniline nanotubes: mercury and competative heavy metals uptake | |
| Karim et al. | Termination of Structural Deformation and Proton–Electron Conductive Inflection of Graphene Oxide in Six Years | |
| Manhooei et al. | Cellulose nanocrystal modified with 3‐chloro propyl trimethoxysilane: a new bio‐adsorbent for nitrate removal from water | |
| CN112321744B (en) | Sodium alginate-phthalocyanine-like photosensitizer, photocatalytic composite material and preparation method and application thereof | |
| CN115286790B (en) | Iodine capturing material and preparation method and application thereof | |
| CN100400568C (en) | Prepn of poly-alpha-amino anthraquinone | |
| Xu et al. | Construction of dual-carbon-confined metal sulfide nanocrystals via bio-mimetic reactors enabling superior Fenton-like catalysis | |
| Zhou et al. | Preparation of Fe3O4@ SiO2@ MnO2 microspheres as an adsorbent for Th (IV) removal from aqueous solution | |
| Bai et al. | Synthesis of microporous aromatic framework with scholl-coupling reaction for efficient uranium (VI) capture | |
| Wang et al. | Visualized adsorption and enhanced photocatalytic removal of Cr6+ by carbon dots-incorporated fluorescent nanocellulose aerogels | |
| CN115715980B (en) | Mn3O4CNTs Fenton-like catalyst and preparation method and application thereof | |
| Yantasee et al. | Electrophilic aromatic substitutions of amine and sulfonate onto fine-grained activated carbon for aqueous-phase metal ion removal | |
| Ye et al. | Photo-Fenton catalytic anti-fouling membranes for efficient elimination of radionuclides and organic contaminants | |
| CN112174964B (en) | Cationic non-porous macrocyclic organic compound and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |