CN105013454A - Preparation method and application of ultrasonic impregnation modified resin - Google Patents
Preparation method and application of ultrasonic impregnation modified resin Download PDFInfo
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- CN105013454A CN105013454A CN201510375666.XA CN201510375666A CN105013454A CN 105013454 A CN105013454 A CN 105013454A CN 201510375666 A CN201510375666 A CN 201510375666A CN 105013454 A CN105013454 A CN 105013454A
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Abstract
The invention discloses a preparation method and application of an ultrasonic impregnation modified resin. The preparation method comprises: adding a certain volume of fresh resin into a sodium chloride solution to conduct soaking pretreatment; subjecting the pretreated resin and a KMnO4 solution to mixing impregnation, and conducting rapid stirring, then performing washing with deionized water and conducting filtration until the filtrate is colorless; adding the obtained impregnated resin rapidly into an FeSO4.7H2O solution by certain volume ratio, and carrying out sealing and ultrasonic impregnation, after full reaction, using a sodium bicarbonate solution and deionized water to perform alternating flushing to neutral pH, and conducting vacuum drying, thus obtaining the ultrasonic impregnated FeOOH modified resin. Compared with unmodified resin, the resin provided by the invention has greatly improved nitrate removal performance, has a removal rate to 10mg/L nitrate water up to 100%, shows very high adsorption efficiency, and can be widely applied in the field of water treatment.
Description
Technical field
The invention belongs to water-treatment technology field, be specifically related to a kind of preparation method and application of ultrasonic immersing modified resin.
Background technology
Along with industrial or agricultural and socioeconomic development, oxidative pollutant increases the weight of gradually to the pollution that water body causes, and these oxidisability owner will comprise nitrate, bromate, perchlorate and volatile organic matter as chloroform etc.In oxidative pollutant, the representational pollutant of most is nitrate, China's groundwater azotate pollution problem started to manifest in the beginning of this century, found in the examining report of Rural Plain Areas of Beijing underground water in 2005: this district's phreatic water nitrate seriously exceedes Drinking Water in China standard (10mg/L); The degree of depth is the poorest at the quality of subground water of 3 ~ 6m, nitrate content average out to 47.53mg/L, and exceeding standard rate and severe overweight rate are all more than 1/2.In addition, the Nitrate content in ground water measurement result of northern China drug in some provinces shows, the nitrate in groundwater mean value of most provinces and cities is close to 12mg/L, and wherein the underground water of about 35% is more than 10mg/L.Nitrate can cause hemoglobin to lose function of carrying oxygen indirectly, thus makes people produce methemoglobinemia.For baby, as long as nitrate content just easily causes baby's methemoglobinemia more than 90mg/L in drinking water, easily bringing out infant produces other complication simultaneously.In view of the harm of nitrate, in recent years, Chinese scholars has carried out large quantity research to nitrate removal technology in water.
Can be used for the technology removing nitrate at present, mainly contain bioanalysis, chemical method, hyperfiltration and absorption method (comprising ion-exchange).Bioanalysis removes nitrate in water body to be needed to add carbon source, thus there is carbon source and adds excessive and secondary pollution problem.Zero-valent Iron is utilized to be nitrogen as reducing agent by the nitrate reduction in water, it is simple to operate, reaction speed is fast, but the proportion of products of Zero-valent Iron reduction nitrate depends primarily on reaction condition, its reduction mechanism changes along with the change of reaction condition, Main By product is ammonia nitrogen in addition, easily brings secondary pollution.Integrated comparative, technique is simple because having for the ion-exchange in absorption method, process rapidly, the advantage such as effect stability, become the treatment technology having development space at present most.Therefore how to obtain more economically, efficiently ion exchange resin become the key removing nitrate in water body.The order of conventional anion exchanger resin adsorption selection ion increases the difficulty removing nitrate, and the method utilizing the load of ultrasonic immersing generation FeOOH to remove nitrate at the modified resin of resin surface have not been reported.
Reaction equation in FeOOH (FeOOH) forming process is as follows:
6H
2O+5Fe
2++MnO
4 -→5FeOOH(s)+7H
++Mn
2+(1)
Summary of the invention
The technical problem to be solved in the present invention overcomes the deficiencies in the prior art, provides a kind of adsorption capacity to stablize, and easy regeneration is reused, applied widely, eco-friendly ultrasonic immersing modified resin.
For achieving the above object, technical scheme of the present invention is:
One of technical scheme:
The preparation method of described ultrasonic immersing modified resin, comprises the following steps:
(1) get the fresh resin of certain volume, join in 5% ~ 20% sodium chloride solution with the volume ratio of 1:5 and soak 2 ~ 6h, then with deionized water rinsing to colourless, naturally dry for subsequent use to constant weight;
(2) taking the pretreatment resin that step (1) obtains, is the KMnO of 2.0g/L ~ 15.0g/L with concentration
4solution is with the volume ratio hybrid infusion of 1:2 ~ 5, and rapid stirring 2h; Then spending deionized water, to be filtered to filtrate colourless;
(3) by the impregnating resin that step (2) obtains, the FeSO of 85.0g/L ~ 176.3g/L is joined fast with the volume ratio of 1:2 ~ 5
47H
2in O solution, and ultrasonic immersing 30min ~ 60min is carried out in sealing, and fully after reaction, the sodium bicarbonate solution with 1% and deionized water replace flushing three times, then gets express developed to pH in neutral by deionized water, and vacuum drying, obtains ultrasonic immersing modified resin.
Fresh resin described in step (1) is preferably D201 large aperture resin anion (R.A.), and sodium chloride concentration is preferably 10%, and soak time is preferably 6h.
Step (2) described volume ratio is preferably 1:2, KMnO
4solution concentration is preferably 2.0g/L.
Step (3) described volume ratio is preferably 1:2, FeSO
47H
2o solution concentration is preferably 85.0g/L, and the ultrasonic immersing time is preferably 30min.
Technical scheme two:
Described modified resin is containing the application in oxidative pollutant water body.
Described oxidative pollutant is chlorate, bromate or nitrate.
Concrete operations are: in water body, add modified resin, and controlling water body pH is 7.0 ~ 7.5, and carries out constant temperature water bath oscillating reactions under the condition of 20 DEG C ~ 30 DEG C, are then separated by modified resin, complete the removal to oxidative pollutant in water body.
In described water body, nitrate concentration is 5.0mg/L ~ 50mg/L; Described constant temperature oscillation reaction condition: thermostat temperature 25 DEG C, frequency of oscillation is, 200rpm, and the reaction time is 0.5h ~ 12h.
Compared with prior art, the invention has the advantages that:
1, modified resin is that the clearance of the nitrate of 10mg/L can reach 100% to initial concentration, and compared to the resin without modification, the removal of modified resin of the present invention to nitrate has excellent effect.
2, the resin prepared of the present invention, easily regeneration reuse, applied widely, and preparation technology is simple, can be widely used in water treatment field.
Accompanying drawing explanation
Fig. 1 is the electron microscope schematic diagram of unmodified resin.
Fig. 2 is the electron microscope schematic diagram of the modified resin that embodiment 1 obtains.
Detailed description of the invention
Below in conjunction with Figure of description and specific embodiment, the invention will be further described.
Embodiment 1:
A preparation method for ultrasonic immersing modified resin, comprises the following steps:
(1) get the fresh resin of certain volume, join in 5% ~ 20% sodium chloride solution with the volume ratio of 1:5 and soak 2 ~ 6h, then with deionized water rinsing to colourless, naturally dry for subsequent use to constant weight;
(2) taking the pretreatment resin that step (1) obtains, is the KMnO of 2.0g/L ~ 15.0g/L with concentration
4solution is with the volume ratio hybrid infusion of 1:2 ~ 5, and rapid stirring 2h; Then spending deionized water, to be filtered to filtrate colourless;
(3) by the impregnating resin that step (2) obtains, the FeSO of 85.0g/L ~ 176.3g/L is joined fast with the volume ratio of 1:2 ~ 5
47H
2in O solution, and ultrasonic immersing 30min ~ 60min is carried out in sealing, and fully after reaction, the sodium bicarbonate solution with 1% and deionized water replace flushing three times, then gets express developed to pH in neutral by deionized water, and vacuum drying, obtains ultrasonic immersing modified resin.
Observe under above-mentioned obtained ultrasonic immersing modified resin is placed in the electron microscope of 100 times, obtain electron microscope picture as shown in Figure 2.Carry out contrast with resin unmodified in Fig. 1 can find out, the modified resin of ultrasonic immersing shown in Fig. 2 presents light green color, shows a certain amount of FeOOH of resin surface load (FeOOH).
Embodiment 2:
Ultrasonic immersing modified resin of the present invention, for the treatment of the nitrate in water body, comprises the following steps:
By ultrasonic immersing modified resin obtained for embodiment 1, being added to 5 groups of 250mL initial concentrations is respectively in the nitrate water body of 5mg/L, 10mg/L, 20mg/L, 40mg/L and 50mg/L, the dosage of ultrasonic immersing modified resin is 0.2g, the initial pH value of water body is 7.0 ± 0.2, constant temperature water bath oscillating reactions is carried out under 25 DEG C of conditions, after this material being separated from water body with filter paper after 12h, measure in water body with ion chromatograph and remain nitrate concentration, calculate the clearance of nitrate, result is as shown in table 1.
Comparative example 1:
Adopt unmodified D201 large aperture resin anion (R.A.).Get the fresh resin of certain volume, the volume ratio of 1:5 joins in 10% sodium chloride solution soaks 6h, then with deionized water rinsing to colourless, naturally dries and save backup.
Getting this resin of 0.2g, to be added to 5 groups of 250mL initial concentrations be in the nitrate water body of 5mg/L, 10mg/L, 20mg/L, 40mg/L and 50mg/L, the initial pH value of water body is 7.0 ± 0.2, constant temperature water bath oscillating reactions is carried out under 25 DEG C of conditions, after this material being separated from water body with filter paper after 12h, measure in water body with ion chromatograph and remain nitrate concentration, calculate the clearance of nitrate, result is as shown in table 1.
Table 1: under different initial concentration condition, modified resin and unmodified resin are to the clearance of nitrate
Comparative example 2 is known with comparative example 1, be under the condition of 5mg/L and 10mg/L at nitrate initial concentration, modified resin can reach 100% to the clearance of nitrate, nitrate can be removed completely (detection of ion chromatograph to nitrate is limited to 0.1mg/L); And unmodified resin only has 79.40% and 77.10% to the clearance of nitrate.When nitrate concentration increases gradually, the clearance of two kinds of resins to nitrate all decreases.When the initial concentration of nitrate increases to 50mg/L, modified resin is approximately 2 times of unmodified resin to the clearance of nitrate.As can be seen here, the resin that ultrasonic immersing is modified is greatly improved than the clearance of unmodified resin to nitrate.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (9)
1. a preparation method for ultrasonic immersing modified resin, is characterized in that, comprises the following steps:
(1) get the fresh resin of certain volume, join in 5% ~ 20% sodium chloride solution with the volume ratio of 1:5 and soak 2 ~ 6h, then with deionized water rinsing to colourless, naturally dry for subsequent use to constant weight;
(2) taking the pretreatment resin that step (1) obtains, is the KMnO of 2.0g/L ~ 15.0g/L with concentration
4solution is with the volume ratio hybrid infusion of 1:2 ~ 5, and rapid stirring 2h; Then spending deionized water, to be filtered to filtrate colourless;
(3) by the impregnating resin that step (2) obtains, the FeSO of 85.0g/L ~ 176.3g/L is joined fast with the volume ratio of 1:2 ~ 5
47H
2in O solution, and ultrasonic immersing 30min ~ 60min is carried out in sealing, and fully after reaction, the sodium bicarbonate solution with 1% and deionized water replace flushing three times, then gets express developed to pH in neutral by deionized water, and vacuum drying, obtains ultrasonic immersing modified resin.
2. the preparation method of ultrasonic immersing modified resin according to claim 1, is characterized in that, step (1) described fresh resin is D201 large aperture resin anion (R.A.).
3. the preparation method of ultrasonic immersing modified resin according to claim 1, is characterized in that, step (1) described sodium chloride concentration is 10%, and soak time is 6h.
4. the preparation method of ultrasonic immersing modified resin according to claim 1, is characterized in that, step (2) described volume ratio is 1:2, KMnO
4solution concentration is 2.0g/L.
5. the preparation method of ultrasonic immersing modified resin according to claim 1, is characterized in that, step (3) described volume ratio is 1:2, FeSO
47H
2o solution concentration is 85.0g/L, and the ultrasonic immersing time is 30min.
6. modified resin according to claim 1 is containing the application in oxidative pollutant water body.
7. application according to claim 6, is characterized in that, described oxidative pollutant is chlorate, bromate or nitrate.
8. application according to claim 6, it is characterized in that, ultrasonic immersing modified resin is added in water body, controlling water body pH is 7.0 ~ 7.5, and constant temperature water bath oscillating reactions is carried out under the condition of 20 DEG C ~ 30 DEG C, then modified resin is separated, completes the removal to oxidative pollutant in water body.
9. application according to claim 8, is characterized in that, in described water body, oxidative pollutant is nitrate, and concentration is 5.0mg/L ~ 50mg/L; Described constant temperature oscillation reaction condition: thermostat temperature 25 DEG C, frequency of oscillation 200rpm, reaction time 0.5h ~ 12h.
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Cited By (8)
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| CN107058765A (en) * | 2017-04-26 | 2017-08-18 | 武汉理工大学 | A kind of V-extracting solvent impregnating resin and its preparation method and application |
| CN107057004A (en) * | 2016-10-19 | 2017-08-18 | 南京大学盐城环保技术与工程研究院 | A kind of high density high adsorption is except nitrate nitrogen resin and preparation method thereof |
| CN107583673A (en) * | 2017-09-19 | 2018-01-16 | 同济大学 | Modified anion resin material and its preparation method and application |
| CN107694612A (en) * | 2017-09-05 | 2018-02-16 | 华南理工大学 | It is a kind of to remove material of bromate and its precursor and its preparation method and application in water removal |
| CN109967134A (en) * | 2019-03-14 | 2019-07-05 | 华南理工大学 | A kind of Nano ferric hydroxide modified anion resin composite materials and the preparation method and application thereof |
| CN111003750A (en) * | 2019-12-16 | 2020-04-14 | 浙江工业大学 | Ultrasonic modified resin and application thereof in removing ammonia nitrogen in wastewater |
| CN115121296A (en) * | 2022-07-05 | 2022-09-30 | 国家电投集团平顶山热电有限公司 | Method for treating heavy organic matter pollution of anion exchange resin |
| CN115818868A (en) * | 2022-11-18 | 2023-03-21 | 科立鑫(珠海)新能源有限公司 | Method for deamination of cobalt carbonate production wastewater |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107057004A (en) * | 2016-10-19 | 2017-08-18 | 南京大学盐城环保技术与工程研究院 | A kind of high density high adsorption is except nitrate nitrogen resin and preparation method thereof |
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| CN107058765B (en) * | 2017-04-26 | 2019-03-19 | 武汉理工大学 | A kind of V-extracting solvent impregnating resin and its preparation method and application |
| CN107058765A (en) * | 2017-04-26 | 2017-08-18 | 武汉理工大学 | A kind of V-extracting solvent impregnating resin and its preparation method and application |
| CN107694612B (en) * | 2017-09-05 | 2020-11-24 | 华南理工大学 | Material for removing bromate and precursor thereof in water, and preparation method and application thereof |
| CN107694612A (en) * | 2017-09-05 | 2018-02-16 | 华南理工大学 | It is a kind of to remove material of bromate and its precursor and its preparation method and application in water removal |
| CN107583673B (en) * | 2017-09-19 | 2020-04-03 | 同济大学 | Modified anion resin material and preparation method and application thereof |
| CN107583673A (en) * | 2017-09-19 | 2018-01-16 | 同济大学 | Modified anion resin material and its preparation method and application |
| CN109967134A (en) * | 2019-03-14 | 2019-07-05 | 华南理工大学 | A kind of Nano ferric hydroxide modified anion resin composite materials and the preparation method and application thereof |
| CN111003750A (en) * | 2019-12-16 | 2020-04-14 | 浙江工业大学 | Ultrasonic modified resin and application thereof in removing ammonia nitrogen in wastewater |
| CN111003750B (en) * | 2019-12-16 | 2022-10-11 | 浙江工业大学 | Ultrasonic modified resin and application thereof in removing ammonia nitrogen in wastewater |
| CN115121296A (en) * | 2022-07-05 | 2022-09-30 | 国家电投集团平顶山热电有限公司 | Method for treating heavy organic matter pollution of anion exchange resin |
| CN115121296B (en) * | 2022-07-05 | 2023-09-05 | 国家电投集团河南电力有限公司平东发电分公司 | Method for treating severe organic matter pollution of anion exchange resin |
| CN115818868A (en) * | 2022-11-18 | 2023-03-21 | 科立鑫(珠海)新能源有限公司 | Method for deamination of cobalt carbonate production wastewater |
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Application publication date: 20151104 |