CN102755877A - Composite adsorbing material for adsorbing arsenic in water and preparation method thereof - Google Patents
Composite adsorbing material for adsorbing arsenic in water and preparation method thereof Download PDFInfo
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- CN102755877A CN102755877A CN2012102714399A CN201210271439A CN102755877A CN 102755877 A CN102755877 A CN 102755877A CN 2012102714399 A CN2012102714399 A CN 2012102714399A CN 201210271439 A CN201210271439 A CN 201210271439A CN 102755877 A CN102755877 A CN 102755877A
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Abstract
The invention discloses a composite adsorbing material for adsorbing arsenic in water and a preparation method thereof, wherein the composite adsorbing material for adsorbing the arsenic in the water is a composite adsorbing material which is obtained by performing intercalation compounding on graphite oxide and nano iron oxide according to a mass ratio of 1:1-2:3; the nano iron oxide is previously subjected to surface modification treatment of sodium dodecyl benzene sulfonate; and the mass ratio of the sodium dodecyl benzene sulfonate to the nano iron oxide is 1-3:5. The preparation method of the composite adsorbing material comprises the following steps of: mixing the graphite oxide and the nano iron oxide according to the mass ratio of 1:1-2:3, grinding, adding water and performing ultrasonic dispersion to form sol; adjusting the pH value to be 3-4 with hydrochloric acid; stirring to react for 5-7 hours at 20-30 DEG C; and filtering and drying to obtain the interpolation compounded adsorbing material. Compared with active carbon and hydroxyl iron oxide, the composite adsorbing material has the advantages of higher adsorption rate, good adsorption effect, arsenic removal rate of 6.5 mg/g under low concentration, no iron ions and no secondary pollution caused to water.
Description
One, technical field
The present invention relates to a kind of sorbing material and preparation method thereof, specifically a kind of composite adsorbing material that is used for adsorbed water arsenic and preparation method thereof.
Two, background technology
Arsenic is in the abundant existence of nature, and the compound of arsenic is a kind of plasm poisonous substance with metalloid characteristic, has biological effect widely, yet arsenic is a kind of chronic carcinogen, and the people is had serious harmfulness.Because often efficient is low for the homogenous material arsenic-adsorbing that tradition adopts, and receive other ion interference bigger when handling, remove the arsenic in anhydrating so there is Many researchers to be devoted to develop composite.Composite utilize two or more material according to a certain percentage mixed together process, usually wide than the suitable scope of single sorbing material, absorption property is good, and receives other ion interference little.And the drinking water arsenic index National standard after handling, so arsenic has wide practical prospect in the composite absorption drinking water.`
Composite adsorbing material of the prior art mainly contains: active carbon and zeolitic material arsenic-adsorbing hydrochlorate reach 60%, are to be carrier with active carbon, activated alumina, macroreticular resin, are activating reagent with molysite etc., and the final arsenic removal of arsenate 0.254mg/L reaches 2.56mg/g.Fe-Ce synthesis of metal oxide arsenic drops to 10ug/L from 60-100ug/L.Though above sorbing material adsorption effect is good, because of containing iron ion, be prone to cause the secondary pollution of water, and from solution separation difficulty.
Three, summary of the invention
The present invention aims to provide a kind of composite adsorbing material that is used for adsorbed water arsenic and preparation method thereof, and technical problem to be solved is to improve sorbing material to the adsorption rate of arsenic and can not cause the secondary pollution at water source.
Technical solution problem of the present invention adopts following technical scheme:
The present invention is used for the composite adsorbing material of adsorbed water arsenic, is the composite adsorbing material that is obtained after compound than intercalation according to the quality of 1:1-2:3 by graphite oxide and nano-sized iron oxide.
Said nano-sized iron oxide is the better effects if after the neopelex surface modification treatment in advance, and wherein the mass ratio of neopelex and nano-sized iron oxide is 1-3:5.
The present invention is used for the preparation method of the composite adsorbing material of adsorbed water arsenic, comprises each unit process of preparation of preparation, PREPARATION OF NANO FERRIC OXIDE and the composite adsorbing material of graphite oxide:
The preparation of said graphite oxide is to adopt the Hummers method to prepare graphite oxide (Zou Yanhong, Li Bo, the Hummers legal system influence technological factor research of degree of oxidation, charcoal element, total the 125th phase 11-14 of 2005 the 04th phases when being equipped with graphite oxide for Fu Ling, Liu Hongbo);
Said PREPARATION OF NANO FERRIC OXIDE is to be that oxidant oxidation green vitriol prepares nano-sized iron oxide (Luo Wenzhong, Mao Minghua, iron oxide yellow prepare the physio-chemical study [J] of process, chemical industry metallurgical, 1990 with sodium chlorate; 11 (1); 27-32);
The preparation of said composite adsorbing material be with graphite oxide and nano-sized iron oxide mix according to the mass ratio of 1:1-2:3 and grind after add the ultrasonic dispersion of water and form colloidal sol; Amount of water is 2-4 a times of graphite oxide quality; With hydrochloric acid adjust pH 3-4; In 20-30 ℃ of stirring reaction 5-7 hour, filter also and obtain the intercalation composite adsorbing material after the drying, baking temperature generally is not higher than 60 ℃.
Said nano-sized iron oxide is to be decentralized medium with the deionized water through the neopelex surface modification treatment in advance, and the mass ratio of neopelex and nano-sized iron oxide is 1-3:5, the temperature 70-90 of surface modification ℃, and reaction time 1-3 hour.
Place the 100mL of pH value 2.8-6.0 to contain As (V) solution the composite adsorbing material 0.2g of the present invention's preparation, left standstill under the room temperature 8 days, adopt the arsenic content in the hydride Atomic Absorption Spectrometry solution.
Compared with present technology, beneficial effect of the present invention is embodied in:
1, composite adsorbing material of the present invention is compared with FeOOH with active carbon and is had higher adsorption rate, advantages of good adsorption effect, and (arsenic content 20ppm) arsenic removal reaches 6.5mg/g under the low concentration, and does not contain iron ion, can not cause the secondary pollution of water.
2, composite adsorbing material of the present invention has better chemical stability.Nano oxidized iron surface has uneven current potential, and the compound that forms with graphite oxide cross-linking agent and arsenic salt has very strong mechanical strength, and chemical stability is fine; Add surface area that composite is huge and stronger absorption affinity, many materials all had certain suction-operated, arsenic ion through be adsorbed, effect such as parcel or complexing deposits to rete; Utilize these characteristics can reach the purpose of removing arsenic in the water body.
3, the raw material of composite adsorbing material of the present invention is easy to get and is cheap.
Four, description of drawings
Fig. 1 be composite adsorbing material of the present invention infrared spectrogram and with compound before contrast, wherein Fig. 1 (a) is a nano-sized iron oxide, Fig. 1 (b) is graphite and graphite oxide, Fig. 1 (c) is a composite adsorbing material of the present invention.Can find out 3700cm by Fig. 1 (c)
-1The absworption peak of left and right sides Qiang Erkuan is-the stretching vibration absworption peak of OH; With compound preceding relatively (Fig. 1 (b)), vibration peak is moved to low frequency, and peak shape broadens; And absorption intensity reduces; Show that association has taken place a large amount of oh group and the transparent ferric oxides in compound rear oxidation graphite flake layer surface, form intermolecular hydrogen bonding, indication has interface contact preferably between the two.3000cm
-1The bimodal of place is the asymmetric stretching vibration absworption peak of aliphatic-CH.1631cm
-1The absworption peak at place is the distinctive C=C stretching vibration of a phenyl ring skeleton absworption peak; Its absorption intensity is low; Reason possibly be that graphite oxide shows that not oxidized aromatic rings zone and transparent ferric oxide form π-pi-conjugated, suppress the stretching vibration of phenyl ring, thereby cause absorption intensity to reduce.1546cm
-1The absworption peak at place is-CH
2In-the group-and the deformation vibration characteristic absorption peak of CH-key, 1117cm
-1The place is because of the C-O stretching vibration absworption peak of epoxy radicals, 600cm
-1Measure two absworption peaks and belong to α-Fe at the place
2O
3γ-Fe
2O
3The stretching vibration absworption peak.Can know, form chemical bond between graphite oxide and the transparent ferric oxide and made a concerted effort to have the good interface compatibility by above analysis, thereby make graphite oxide and transparent ferric oxide fine compound.
Fig. 2 is the XRD spectra of composite adsorbing material of the present invention.As can be seen from Figure 2 compound fine of nano-sized iron oxide and graphite oxide.
Fig. 3 be composite adsorbing material of the present invention thermogravimetric curve and with compound before contrast, wherein Fig. 3 (a) is a nano-sized iron oxide, Fig. 3 (b) is a graphite oxide, Fig. 3 (c) is a composite adsorbing material of the present invention.As can be seen from Figure 3, it is weightless that composite adsorbing material of the present invention begins about 150 ℃, is the removing of Free water in the graphite oxide; Weightlessness about 200 ℃ mainly is that nano-sized iron oxide becomes alpha-ferric oxide; Weightlessness about 500 ℃ mainly is that alpha-ferric oxide becomes more stable gamma-iron oxide; But, temperature compares with pure zirconia graphite or pure nano-sized iron oxide is compared along with raising; Hysteresis quality appears in the thermal weight loss of composite, and 700 ℃ survival rate is higher than graphite oxide or the remaining rate of nano-sized iron oxide.Hence one can see that; The composite stability of graphite oxide and transparent ferric oxide is fine; Nano-sized iron oxide has formed stable dispersion and has had the good interface compatibility in graphite oxide; Graphite oxide causes the hysteresis quality of the loss in weight in the release of the volatile components of high temperature prevention transparent ferric oxide.Simultaneously weight should be both weight with.
Fig. 4 is the transmission electron microscope photo of composite adsorbing material of the present invention.Wherein (a) is the transmission electron microscope picture of graphite oxide, (b) is the transmission electron microscope picture of nano-sized iron oxide, (c) is the transmission electron microscope picture of composite adsorbing material.Can draw composite materials from transmission electron microscope picture and infrared and thermogravimetric analysis figure combines fine.Composite adsorbing material of the present invention has open structure and bigger surface area.
Five, the specific embodiment
Below in conjunction with embodiment the present invention is done further to analyze explanation.
1, the preparation of graphite oxide
The concentrated sulfuric acid that in the beaker of drying, adds 50mL mass concentration 98%; Under condition of ice bath, stir adding 2g graphite powder, 1g sodium nitrate and 3g potassium permanganate, the control temperature is not higher than 10 ℃, reaction 4h; Be warming up to 30-40 ℃ of stirring reaction 30min then; Be warming up to 90-100 ℃ of stirring reaction 30min with continued, during reaction add deionized water reactant liquor is diluted to the hydrogen peroxide solution 10mL that adds mass concentration 30% behind the 1000mL, filter while hot; (hydrochloric acid: watery hydrochloric acid washing leaching cake water) 3 times, spending deionised water does not again have SO to filtrating with volume ratio 1:10
4 2+(BaCl
2Detect), the filter cake after the washing in 50 ℃ of dryings 48 hours, is ground the back sealing and preserves.
2, PREPARATION OF NANO FERRIC OXIDE
The preparation of a, high ferro
In there-necked flask, add 10gFeSO
47H
2The sulfuric acid solution of O, water and 5mL mass concentration 98% adds 10mLH subsequently again
2O
2, stirring and to be warming up to 35 ℃, the color of reactant liquor becomes celadon by green and becomes lark again and become yellowish red color at last, the temperature to 90 that raises then ℃, insulation reaction made excessive H in 2 hours
2O
2Decompose and obtain high iron solution.
The preparation of b, CI
Get the high iron solution 50mL of step a preparation, thin up, being warming up to 40 ℃ of stirring adding NaOH solution adjust pHs is 7, forms yellowish red color colloidal solution, filtering and impurity removing obtains CI solution.
C, PREPARATION OF NANO FERRIC OXIDE
The high iron solution 50mL of step a preparation and the CI solution 30mL of step b preparation are mixed, add water under stirring and mix, be warming up to 85 ℃ then; Add the 1g iron powder; The pH value was transferred to 4.3 back insulation reaction 3 hours, and reactant liquor becomes yellowish-brown, removes supernatant liquor behind the standing demix.
The surface treatment of d, nano-sized iron oxide
In the 5g nano-sized iron oxide, add deionized water, add the 2g neopelex under stirring, 80 ℃ were reacted 2 hours, reacted and finished after obtain the surface-treated nano-sized iron oxide after filtration, washing, drying and the grinding.
3, the preparation of composite adsorbing material
With surface-treated nano-sized iron oxide and graphite oxide mix and grind after add water (quality is than graphite oxide: water=1:3) ultrasonic dispersion form colloidal sol; The quality of nano-sized iron oxide is provided with contrast test according to 0%, 10%, 30%, 55%, 60% and 100% of nano-sized iron oxide and graphite oxide gross mass respectively; Hydrochloric acid adjust pH 3-4; In 25 ℃ of stirring reactions 6 hours, filter and also after 50 ℃ of dryings, obtain the intercalation composite adsorbing material.
4, the adsorptivity of arsenic test
Contain As (V) solution with what the composite adsorbing material 0.2g of the present invention preparation placed 100mLpH value 3.0, left standstill the arsenic content in the employing hydride Atomic Absorption Spectrometry solution under the room temperature 8 days.
The nano oxidized iron content of table 1 is to the influence of arsenic adsorption rate
| ? | Nano-sized iron oxide/% | c(As)/ppm | Adsorption rate/(mg/g) |
| |
0 | 20 | 0 |
| Group 2 | 10 | 20 | 5 |
| Group 3 | 10 | 20 | 5.2 |
| Group 4 | 30 | 20 | 6 |
| Group 5 | 55 | 20 | 6.5 |
| |
55 | 40 | 20 |
| Group 7 | 55 | 52 | 25 |
| Group 8 | 60 | 20 | 6.3 |
| Group 9 | 100 | 20 | 2.56 |
By can finding out in the table 1, along with nano oxidized iron content increases the also corresponding increase of adsorption rate, be best during to nano oxidized iron content 55%, the adsorption rate of composite adsorbing material is higher than homogenous material adsorption rate.
Claims (5)
1. composite adsorbing material that is used for adsorbed water arsenic is characterized in that: be the composite adsorbing material that is obtained after compound than intercalation according to the quality of 1:1-2:3 by graphite oxide and nano-sized iron oxide.
2. the composite adsorbing material that is used for adsorbed water arsenic according to claim 1; It is characterized in that: said nano-sized iron oxide is in advance through the neopelex surface modification treatment, and wherein the mass ratio of neopelex and nano-sized iron oxide is 1-3:5.
3. claim 1 or the 2 described preparation methods that are used for the composite adsorbing material of adsorbed water arsenic comprise it is characterized in that each unit process of preparation of preparation, PREPARATION OF NANO FERRIC OXIDE and the composite adsorbing material of graphite oxide:
The preparation of said composite adsorbing material be with graphite oxide and nano-sized iron oxide mix according to the mass ratio of 1:1-2:3 and grind after add the ultrasonic dispersion of water and form colloidal sol; With hydrochloric acid adjust pH 3-4; In 20-30 ℃ of stirring reaction 5-7 hour, filter also and obtain the intercalation composite adsorbing material after the drying.
4. preparation method according to claim 3 is characterized in that: said nano-sized iron oxide is in advance through the neopelex surface modification treatment, and the temperature 70-90 of surface modification ℃, reaction time 1-3 hour.
5. preparation method according to claim 3 is characterized in that: amount of water is 2-4 a times of graphite oxide quality.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104437389A (en) * | 2014-11-27 | 2015-03-25 | 昆明理工大学 | Preparation method and application of adsorbent for treating lead-containing waste water |
| CN106000365A (en) * | 2016-05-17 | 2016-10-12 | 北京化工大学 | Preparation method and application of iron hydroxide-expanded graphite composite material |
| CN106492753A (en) * | 2016-02-16 | 2017-03-15 | 朱小平 | A kind of preparation method of arsenic adsorbent material |
| WO2017122153A1 (en) * | 2016-01-15 | 2017-07-20 | Metoxs Pte. Ltd. | Compositions for treatment of fluids |
| RU2652704C1 (en) * | 2017-08-02 | 2018-04-28 | Закрытое акционерное общество "Институт новых углеродных материалов и технологий" (ЗАО "ИНУМиТ") | Method of producing sorbent based on thermally expanded graphite and sorbent |
| CN108998040A (en) * | 2018-05-28 | 2018-12-14 | 上海环科环境评估咨询有限公司 | Arsenic in soil and pollution of chromium based on organic clay load nanometer iron-series repair medicament |
| CN111111615A (en) * | 2019-12-27 | 2020-05-08 | 扬州大学 | Preparation method of coralline-like charcoal/hydrated iron oxide composite arsenic removal agent |
| CN114307987A (en) * | 2021-10-14 | 2022-04-12 | 蚌埠市天星树脂有限责任公司 | Preparation method of macroporous adsorption resin for polyphenol purification |
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| CN102500755A (en) * | 2011-11-03 | 2012-06-20 | 苏州大学 | Preparation method for graphene-supported metal nanoparticle compound |
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| CN102500755A (en) * | 2011-11-03 | 2012-06-20 | 苏州大学 | Preparation method for graphene-supported metal nanoparticle compound |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104437389A (en) * | 2014-11-27 | 2015-03-25 | 昆明理工大学 | Preparation method and application of adsorbent for treating lead-containing waste water |
| CN104437389B (en) * | 2014-11-27 | 2017-01-04 | 昆明理工大学 | A kind of preparation method and application processing lead waste water adsorbent |
| WO2017122153A1 (en) * | 2016-01-15 | 2017-07-20 | Metoxs Pte. Ltd. | Compositions for treatment of fluids |
| CN106492753A (en) * | 2016-02-16 | 2017-03-15 | 朱小平 | A kind of preparation method of arsenic adsorbent material |
| CN106000365A (en) * | 2016-05-17 | 2016-10-12 | 北京化工大学 | Preparation method and application of iron hydroxide-expanded graphite composite material |
| RU2652704C1 (en) * | 2017-08-02 | 2018-04-28 | Закрытое акционерное общество "Институт новых углеродных материалов и технологий" (ЗАО "ИНУМиТ") | Method of producing sorbent based on thermally expanded graphite and sorbent |
| CN108998040A (en) * | 2018-05-28 | 2018-12-14 | 上海环科环境评估咨询有限公司 | Arsenic in soil and pollution of chromium based on organic clay load nanometer iron-series repair medicament |
| CN108998040B (en) * | 2018-05-28 | 2020-07-03 | 上海建科环境技术有限公司 | Soil arsenic and chromium pollution remediation agent based on organic clay loaded nano iron system |
| CN111111615A (en) * | 2019-12-27 | 2020-05-08 | 扬州大学 | Preparation method of coralline-like charcoal/hydrated iron oxide composite arsenic removal agent |
| CN114307987A (en) * | 2021-10-14 | 2022-04-12 | 蚌埠市天星树脂有限责任公司 | Preparation method of macroporous adsorption resin for polyphenol purification |
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Application publication date: 20121031 |