CN106622113A - Preparation and application of attapulgite stabilizing delta-MnO2 - Google Patents

Preparation and application of attapulgite stabilizing delta-MnO2 Download PDF

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Publication number
CN106622113A
CN106622113A CN201710036703.3A CN201710036703A CN106622113A CN 106622113 A CN106622113 A CN 106622113A CN 201710036703 A CN201710036703 A CN 201710036703A CN 106622113 A CN106622113 A CN 106622113A
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China
Prior art keywords
attapulgite
mno
water body
pollutant
delta
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CN201710036703.3A
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Chinese (zh)
Inventor
江卢华
刘云国
曾光明
刘少博
尹志红
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Hunan University
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Hunan University
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Publication of CN106622113A publication Critical patent/CN106622113A/en
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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
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/12—Naturally occurring clays or bleaching earth
    • 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
    • C02F2101/30—Organic compounds
    • C02F2101/34—Organic compounds containing oxygen

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Dispersion Chemistry (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Steroid Compounds (AREA)

Abstract

The invention relates to preparation and application of an attapulgite stabilizing delta-MnO2 material for removing 17 beta-estradiol in a water body. Attapulgite is used as a carrier, a site can be provided for delta-MnO2 for attachement, and the stability and the dispersibility of nano delta-MnO2 particles can be increased, so that the adsorption performace of the nano delta-MnO2 on a pollutant of the 17 beta-estradiol in the water body can be enhanced. The preparation comprises the following specific steps: firstly preparing a mixture of the attapulgite and Mn<2+>, and then dropwise adding a mixed solution of potassium permanganate and sodium hydroxide in the mixture of the attapulgite and the Mn<2+> for carrying out sufficient reaction. The attapulgite stabilizing delta-MnO2 material prepared through a method provided by the invention has a higher ability for removing the 17 beta-estradiol in the water body; the adsorption rate of the attapulgite stabilizing delta-MnO2 material is quick, and the 17 beta-estradiol in the water body can be quickly treated; the attapulgite stabilizing delta-MnO2 material is low in cost and simple in preparation, and is an efficient and cheap adsorption material which can be used for removing the 17 beta-estradiol in the water body.

Description

Attapulgite stabilisation δ-MnO2Preparation and application
Technical field
The invention belongs to environment functional material and water process new technical field, and in particular to a kind of 17 β in water body-female of removing The attapulgite stabilisation δ-MnO of glycol2Preparation method and applications.
Background technology
Environment incretion interferent refer to due to produce naturally or the production of the mankind and life activity and around being discharged into The chemical substance of human body and normal hormonal function and hormonal system in animal body in environment, is affected, is to enjoy pass 21 century The new micropollutants of one class of note.Known environment incretion interferent species is a lot, and natural and synthetic estrogen is considered as Milter in rivers and creeks is caused to feminize most important first kinds of pollution matter, wherein 17 beta estradiols particularly endanger.Conventional scientists master Have studied 17 beta estradiols presence situation in different environments, sewage treatment plant, artificial swamp, soil, river, subsoil water With aqueous surface sediments, sea water and marine sediment etc., it was demonstrated that all there are 17 different degrees of beta estradiols in these environment dirty Dye.Environment is feminized and is increasingly becoming a big Health challenges of facing mankind.So, the minimizing technology for seeking 17 beta estradiols is compeled In the eyebrows and eyelashes.
17 general beta estradiol sewage water treatment methods have absorption, oxidative degradation, photocatalysis, membrane separation technique and biological drop Solution etc..The unique chemical composition of manganese dioxide and physicochemical properties so as to good absorption property.Synthesized with chemical method Manganese dioxide have various crystal formations, the crystallization degree of various form manganese dioxide, specific surface area and surface charge have differences, Their absorption property is also different.The crystal property of wherein δ types manganese dioxide is poor, and specific surface area is big, and surface adsorption site is more, changes Learn activity big, be a kind of effective adsorbing material.However, nm delta-MnO2Easily occur to reunite, suppress its absorbability.Attapulgite The granule of stone is tiny, a kind of stabilizer of surface area wonderful works, can prevent nm delta-MnO2Agglomerate grain, receives so as to strengthen Rice δ-MnO2Absorption property to 17 beta estradiol pollutant in water body.
The content of the invention
The technical problem to be solved is：For the water body of current 17 beta estradiol pollution, exploitation is a kind of efficiently The attapulgite stabilisation δ-MnO that can be used for 17 beta estradiol pollutant of adsorption treatment2。
A kind of attapulgite stabilisation δ-MnO proposed by the present invention2Preparation method, be using attapulgite to nm delta- MnO2Granule carries out stabilizing treatment, to improve nm delta-MnO2The stability and dispersibility of granule, so as to strengthen nm delta-MnO2 Absorption property to pollutant in water body.And by obtained attapulgite stabilisation δ-MnO2Materials application is 17 in water body is removed Beta estradiol pollutant.Comprise the following steps that：
In the MnSO of 20mL4(0.2g) 1g attapulgites are added in solution, and in N2Purification under, stirring 1h form concavo-convex Rod stone-Mn2+Mixture.Then, then by the mixed liquor of 20mL potassium permanganate (1g) and sodium hydroxide (0.6g) it is added dropwise to concavo-convex Rod stone-Mn2+Mixture in, stirred with 200 revs/min of rotating speed in course of reaction.After continuing stirring reaction 3h, attapulgite is produced Stone/δ-MnO2Complex, places it in growth 24h in room temperature (25 ± 1 DEG C).
In above-mentioned preparation method, need to be passed through nitrogen in solution, to remove the dissolved oxygen in solution.
In above-mentioned preparation method, the mass ratio of the concave and convex rod stone powder and manganese sulfate is 5:1.
In above-mentioned preparation method, the mass ratio of the manganese sulfate, potassium permanganate and sodium hydroxide is 1:5:3.
In above-mentioned preparation method, in course of reaction, agitator is stirred with 200 revs/min of speed.
In above-mentioned preparation method, in reaction after completion of dropwise addition, stirring reaction 3h should be continued.
In above-mentioned preparation method, after reaction, suspension need to be grown up under room temperature (25 ± 1 DEG C) 24h.
The attapulgite stabilisation δ-MnO prepared using the inventive method2Remove 17 beta estradiols pollution in water body Thing.
Compared with prior art, it is an advantage of the current invention that：
1. the attapulgite stabilisation δ-MnO of the present invention2The preparation method simple possible of material, speed of production fast period It is short, it is not necessary to complicated chemical industry equipment, industrialized production can be realized.
2. product is nontoxic, environmentally friendly, and the cost of raw material is low.
3. the attapulgite stabilisation δ-MnO of the present invention2It is high to the removal efficiency of 17 beta estradiol pollutant.
Description of the drawings
Fig. 1 is the attapulgite stabilisation δ-MnO of the embodiment of the present invention 12Scanning electron microscope schematic diagram；
Fig. 2 is the attapulgite stabilisation δ-MnO of the embodiment of the present invention 1217 β-female two are processed under different initial concentrations Alcohol；
Fig. 3 is the attapulgite stabilisation δ-MnO of the embodiment of the present invention 1217 beta estradiols are processed under different time；
Specific embodiment
The present invention is described in further details below with reference to Figure of description and specific embodiment.
Embodiment 1：
A kind of attapulgite stabilisation δ-MnO of the present invention2Concrete preparation method it is as follows：
In the MnSO of 20mL4(0.2g) 1g attapulgites are added in solution, and in N2Purification under, stirring 1h form concavo-convex Rod stone-Mn2+Mixture.Then, then by the mixed liquor of 20mL potassium permanganate (1g) and sodium hydroxide (0.6g) it is added dropwise to concavo-convex Rod stone-Mn2+Mixture in, stirred with 200 revs/min of rotating speed in course of reaction.After continuing stirring reaction 3h, attapulgite is produced Stone/δ-MnO2Complex, places it in growth 24h in room temperature (25 ± 1 DEG C).
The attapulgite stabilisation δ-MnO for preparing2Material is more stable in suspension, and agglomeration does not occur. Observe under scanning electron microscope, as shown in Figure 1, it can be seen that δ-MnO2It is evenly distributed in the surface of attapulgite.
Embodiment 2：
The attapulgite stabilisation δ-MnO of the present invention217 beta estradiols in material process water body, comprise the following steps：
1～8mg/L17 beta estradiol solution 50mL are taken respectively in conical flask, and the 0.01g materials are added in each conical flask After material, it is placed in water-bath constant temperature oscillator, reacts under the conditions of 25 DEG C.After 24h, each conical flask takes 10mL solution respectively and carries out Centrifugation, by 0.45 μm of membrane filtration after centrifugation, takes filtrate in centrifuge tube.It is reacted using fluorescence scene photometer detection Solution concentration.As a result as shown in Fig. 2 under the conditions of different 17 beta estradiol initial concentrations, the material is to 17 β in water body-female two Alcohol is with compared with high absorption capacity.Under conditions of initial concentration is 1mg/L, the material has the adsorbance of 8.83mg/g, and with first Beginning concentration increases and increases, and under conditions of 8mg/L, the adsorbance of the adsorbent reaches 59.93mg/g.
Embodiment 3：
The attapulgite stabilisation δ-MnO of the present invention2In material process water body, 17 beta estradiol of salt, comprises the following steps：
In the 17 beta estradiol solution of the 6mg/L that the 0.01g materials are added to 50mL, water-bath constant temperature oscillator is placed in In, react under the conditions of 25 DEG C.10mL solution is taken respectively in different points interval time to be centrifuged, and passes through 0.45 μm after centrifugation Membrane filtration, takes filtrate in centrifuge tube.Reacted solution concentration is detected using spectrofluorophotometer.Under different time Adsorbance result as shown in Figure 3, attapulgite stabilisation δ-MnO2Material to the adsorbance of 17 beta estradiols in water body with The increase of time is continuously increased.Between 10min to 120min, adsorbance quickly increases, and starts to reach after 180min Saturation.This explanation attapulgite stabilisation δ-MnO2Material can quick adsorption process water body in 17 beta estradiols.
Embodiment 4：
The attapulgite stabilisation δ-MnO of the present invention2In material process water body, 17 beta estradiol of salt, comprises the following steps：
The 17 beta estradiol solution of the 6mg/L of 7 parts of 50mL of configuration, adjust pH with the NaOH and HCl of 1mol/L and are respectively 4.2,5.4,6.1,7.3,8.2,9.1 and 10.2.Add above-mentioned material 10mg.It is placed in water-bath constant temperature oscillator, in 25 DEG C of bars React under part.10mL solution is taken respectively in different points interval time to be centrifuged, and by 0.45 μm of membrane filtration after centrifugation, is taken Filtrate is in centrifuge tube.Reacted solution concentration is detected using spectrofluorophotometer.Adsorbance result under different pH is such as Shown in table 1.
Table 1：Adsorbance data under different pH value
As shown in Table 1, condition of different pH exists on absorption and affects.It is unfavorable for adsorbent to 17 beta estradiols when pH is higher Remove, as pH is raised, adsorbance is gradually reduced.
The above is only the preferred embodiment of the present invention, protection scope of the present invention is not limited merely to above-described embodiment, Various process programs without substantial differences are in protection scope of the present invention with present inventive concept.

Claims (7)

1. in a kind of Adsorption water body 17 beta estradiol pollutant attapulgite stabilisation δ-MnO2, it is characterised in that it is concavo-convex Rod masonry is carrier, can provide site and give δ-MnO2Attachment, can improve nm delta-MnO2The stability and dispersibility of granule, So as to strengthen nm delta-MnO2Absorption property to 17 beta estradiol pollutant in water body.
2. in a kind of a kind of Adsorption water body as claimed in claim 1 17 beta estradiol pollutant attapulgite stabilisation δ-MnO2Preparation method, comprise the following steps：
In the MnSO of 20mL4(0.2g) 1g attapulgites are added in solution, and in N2Purification under, stirring 1h formed attapulgite- Mn2+Mixture.Then, then by the mixed liquor of 20mL potassium permanganate (1g) and sodium hydroxide (0.6g) be added dropwise to attapulgite- Mn2+Mixture in, stirred with 200 revs/min of rotating speed in course of reaction.After continuing stirring reaction 3h, generation attapulgite/δ- MnO2Complex, places it in growth 24h in room temperature (25 ± 1 DEG C).
3. in a kind of Adsorption water body as claimed in claim 2 17 beta estradiol pollutant attapulgite stabilisation δ- MnO2Preparation method, it is characterised in that the order of preparation is first to configure attapulgite and Mn2+Mixture, then again by height The storing solution of potassium manganate and sodium hydroxide is added dropwise to attapulgite and Mn2+Reacted in mixture.
4. in a kind of Adsorption water body as claimed in claim 2 17 beta estradiol pollutant attapulgite stabilisation δ- MnO2Preparation method, it is characterised in that the mass ratio of concave and convex rod stone powder and manganese sulfate be 5:1, manganese sulfate, potassium permanganate and The mass ratio of sodium hydroxide is 1:5:3.
5. in a kind of Adsorption water body as claimed in claim 2 17 beta estradiol pollutant attapulgite stabilisation δ- MnO2Preparation method, it is characterised in that in course of reaction agitator with 200 revs/min of speed vigorous agitation, in reaction drip Plus after terminating, stirring reaction 3h should be continued.
6. in a kind of Adsorption water body as claimed in claim 2 17 beta estradiol pollutant attapulgite stabilisation δ- MnO2Purposes, it is characterised in that with the material be used for Adsorption water body in 17 beta estradiol pollutant.
7. purposes according to claim 6, it is characterised in that attapulgite stabilisation δ that the inventive method is prepared- MnO217 beta estradiol pollutant in water body have higher removal ability.17 beta estradiol pollutant Adsorption speed Hurry up, can comparatively fast process 17 beta estradiol pollutant in water body.
CN201710036703.3A 2017-01-18 2017-01-18 Preparation and application of attapulgite stabilizing delta-MnO2 Pending CN106622113A (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101306864A (en) * 2008-06-25 2008-11-19 浙江工业大学 Degradation process for environment estrogenic pollutant in water body
CN103157488A (en) * 2011-12-08 2013-06-19 江苏东大热能机械制造有限公司 Medium-low-temperature denitrification catalyst taking attapulgite as support for flue gas and preparation method for same
CN103394703A (en) * 2013-08-05 2013-11-20 中国科学技术大学 Coal gangue load-type zero-valent iron nanocomposite and preparation method thereof
CN103418338A (en) * 2013-09-03 2013-12-04 四川大学 Concave soil adsorption material carrying manganite and method for removing S2- in tannery wastewater
CN104607180A (en) * 2015-01-21 2015-05-13 常州大学 Mixed-crystal MnO2/rod-like clay low-temperature denitration catalyst and preparation method thereof
CN106311130A (en) * 2016-09-13 2017-01-11 哈尔滨工程大学 Modified attapulgite material and its preparation and application methods

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101306864A (en) * 2008-06-25 2008-11-19 浙江工业大学 Degradation process for environment estrogenic pollutant in water body
CN103157488A (en) * 2011-12-08 2013-06-19 江苏东大热能机械制造有限公司 Medium-low-temperature denitrification catalyst taking attapulgite as support for flue gas and preparation method for same
CN103394703A (en) * 2013-08-05 2013-11-20 中国科学技术大学 Coal gangue load-type zero-valent iron nanocomposite and preparation method thereof
CN103418338A (en) * 2013-09-03 2013-12-04 四川大学 Concave soil adsorption material carrying manganite and method for removing S2- in tannery wastewater
CN104607180A (en) * 2015-01-21 2015-05-13 常州大学 Mixed-crystal MnO2/rod-like clay low-temperature denitration catalyst and preparation method thereof
CN106311130A (en) * 2016-09-13 2017-01-11 哈尔滨工程大学 Modified attapulgite material and its preparation and application methods

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
崔振水: ""新生态MnO2/凹凸棒土复合催化剂对苯酚臭氧化反应的催化作用"", 《河北化工》 *

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