CN101829603B - Preparation method of beta-iron oxide hydroxides loaded resin and application thereof in photocatalysis - Google Patents
Preparation method of beta-iron oxide hydroxides loaded resin and application thereof in photocatalysis Download PDFInfo
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- CN101829603B CN101829603B CN2010101517888A CN201010151788A CN101829603B CN 101829603 B CN101829603 B CN 101829603B CN 2010101517888 A CN2010101517888 A CN 2010101517888A CN 201010151788 A CN201010151788 A CN 201010151788A CN 101829603 B CN101829603 B CN 101829603B
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- oxide hydroxides
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Abstract
The invention discloses a preparation method of beta-iron oxide hydroxides loaded resin and application thereof in photocatalysis, relating to the water body treatment technology. The preparation method comprises the following steps of: adding cation exchanger resin after being processed into a ferric trichloride solution, and dropwise adding sodium hydroxide solution into the solution to enable the beta-iron oxide hydroxides to gradually deposit on the surface of the resin; filtering to obtain resin, washing to neutral, and drying in the air to obtain the beta-iron oxide hydroxides loaded resin used as a catalyst; simultaneously adding the catalyst and hydrogen peroxide into a water body containing endocrine disrupters, turning on an ultraviolet lamp and stirring to eliminate the endocrine disrupters in the environment synchronously and the activity of hormone thereof and purify the water. The invention has no secondary pollution, easy separation of solid catalyst after reaction, no introduction of new impurities, simple process flow and good application prospect in the field of deep treatment of the water body.
Description
Technical field
The present invention relates to the water body treatment technology, relate in particular to beta-iron oxide hydroxides loaded resin Preparation of catalysts method and photocatalytic applications thereof, specifically, relate to a kind of catalyst of handling poisonous incretion interferent in the water body and removing its hormonal activity.
Background technology
Most of incretion interferents are introduced environment by mankind's activity, but natural incretion interferent also extensively is present in the water environment like (estradione, estradiol, ethenyl estradiol).Incretion interferent can be simulated the hormone activity and disturbed aquatile and then human health is produced threat.In surface water, estrogenic concentration level can be from pg/L-ng/L.Estradiol (E2) is well-known natural incretion interferent, and its concentration can reach 6-66ng/L in underground water, and endocrine activity is far above synthetic compound.
The control method of at present relevant incretion interferent also emerges in an endless stream, and its middle-and-high-ranking catalytic process (AOPs) is to eliminate one of very promising technology of incretion interferent.In recent years, bibliographical information senior catalytic process eliminate the work of hormonal activity, like ozonization method, chloridising, UV/H
2O
2/ TiO
2Photocatalytic oxidation etc., but the accessory substance that these methods produce in oxidizing process still has estrogen active, can not remove fully hydrobiological harm, has therefore limited its range of application.
Summary of the invention
The objective of the invention is to the deficiency of prior art and a kind of beta-iron oxide hydroxides loaded resin catalyst is provided and uses this catalyst and remove incretion interferent and hormonal activity thereof in water body; This method for preparing catalyst is simple and be convenient to recycle; This catalyst can constitute heterogeneous light with peroxidating and ultraviolet light and help " Fenton " (Fenton) system under relatively mild condition, this system can effectively be removed the poisonous incretion interferent in the water body and eliminate its hormonal activity.
The objective of the invention is to realize like this:
A kind of preparation method of beta-iron oxide hydroxides loaded resin comprises the steps:
(1) cationic ion-exchange resin is flooded 12h with the 1mol/L hydrochloric acid solution, be washed till neutrality, filter with deionized water; Wherein: the volume ratio of resin and hydrochloric acid solution is 1: 10;
(2) resin of step (1) being handled floods 12h with the 1mol/L sodium hydroxide solution, filters, and is washed till neutrality with deionized water, at room temperature dries naturally, and is for use; Wherein: the volume ratio of resin and sodium hydroxide solution is 1: 10;
(3) it is that the volume ratio of resin and solution is 1: 5 in 10% the liquor ferri trichloridi that the resin of step (2) being handled adds mass fraction;
(4) speed with 10mL/h slowly drips the 1mol/L sodium hydroxide solution in step (3) solution, and resin and NaOH volume ratio are 1: 5, mix liquid simultaneously, and the beta-hydroxy iron oxide deposits to resin surface gradually;
(5) filter out step (4) gained resin, be washed till neutrality with deionized water and alcohol, dry naturally under the normal temperature, promptly obtain beta-iron oxide hydroxides loaded resin, this resin is made catalyst and is used.
Above-mentioned beta-iron oxide hydroxides loaded resin is in Application in Photocatalysis:
Beta-iron oxide hydroxides loaded resin catalyst and hydrogen peroxide be added to simultaneously contain in the incretion interferent water body; Open uviol lamp simultaneously and implement and stir; Promptly constitute light and help heterogeneous " Fenton " (Fenton) system for handling; This system can synchronism eliminates environment incretion interferent and hormonal activity thereof, purifying water body.
The present invention has advantage and good effect:
1. the heterogeneous photocatalysis system of load β type FeOOH resin catalyst and hydrogen peroxide and ultraviolet light formation is easy and simple to handle; This technology has very high removal effect and can eliminate its toxicity incretion interferent in the water body; Do not produce secondary pollution; Solid-phase catalyst is easy to Separation and Recovery and utilizes, and effluent quality is up to standard easily;
2. technological process is simple, the Preparation of catalysts method is easy, cost is low, and good actual application prospect is arranged.
The specific embodiment
The application in the incretion interferent in handling water body is elaborated to this catalyst below in conjunction with instance:
Embodiment
The preparation of beta-iron oxide hydroxides loaded resin
Choose
200 of 10mL Sigma company as the target resin; At first use 100mL 1mol/L hydrochloric acid impregnating resin 12h; Be impregnated into again in the 100mL 1mol/L sodium hydroxide solution for preparing in advance after being washed till neutrality with deionized water; Be washed till neutrality with deionized water behind the 12h; Dry under the room temperature, for use.Preparation 50mL mass fraction is 10% liquor ferri trichloridi and moves in the 250mL Erlenmeyer flask, in bottle, adds the resin of washing with bronsted lowry acids and bases bronsted lowry for use, at ambient temperature; In conical flask, slowly splash into sodium hydroxide solution and the continuous stirring solution of 50mL1mol/L with the speed of 10mL/h, along with the adding of aqueous slkali, the pH value of solution raises; Iron loads on the resin with beta-hydroxy iron oxide form gradually; After reaction finishes, also dry naturally at normal temperatures to neutral, obtain the catalyst that 10mL is loaded with beta-iron oxide hydroxides fat with deionized water and alcohol continuous washing resin; Catalyst is deposited in the polyethylene bottle, and is for use.
Beta-iron oxide hydroxides loaded resin is in Application in Photocatalysis:
Choose estradiol as target poisonous and harmful incretion interferent, the water body that simulation is polluted by incretion interferent.The concentration of estradiol is 272 μ g/L; The reactant liquor volume is 1L; With the catalyst (mass concentration 5g/L) of 5g beta-iron oxide hydroxides loaded resin and 1mL mass concentration is that 30% hydrogen peroxide (molar concentration 9.7mmol/L) is put in the 1L reactant liquor; Open uviol lamp simultaneously and implement and stir, at room temperature react 8h, the clearance of estradiol and hormonal activity thereof reaches 99.6%, 94.5% respectively.
(1) operating condition
Estradiol mass concentration: 272 μ g/L; Catalyst quality concentration: 5g/L; Reactant liquor volume: 1L;
Hydrogen peroxide molal weight concentration: 9.7mmol/L; Intensity of illumination (liquid level center): 0.3mW/cm
2
Agitator mixing speed: 200rpm; Reaction temperature: 20 ℃.
(2) experimental result
Estradiol degrading
| Time (hour) | 0 | 1 | 2 | 4 | 6 | 8 |
| Concentration (μ g/L) | 272 | 166 | 136 | 63.7 | 11.5 | 1.19 |
| Degradation rate (%) | 0 | 38.9 | 50 | 76.6 | 95.8 | 99.6 |
Estrogen active is removed
| Time (hour) | 0 | 1 | 2 | 4 | 6 | 8 |
| Hormonal activity (unit) | 1511 | 1465 | 1025 | 792 | 171 | 45 |
| Hormonal activity clearance (%) | 0 | 3 | 32.1 | 47.6 | 88.7 | 94.5 |
Claims (2)
1. the preparation method of a beta-iron oxide hydroxides loaded resin is characterized in that comprising the steps:
(1) cationic ion-exchange resin is flooded 12h with the 1mol/L hydrochloric acid solution, be washed till neutrality, filter with deionized water; Wherein: the volume ratio of resin and hydrochloric acid solution is 1: 10; Said cationic ion-exchange resin is Sigma company
200 cationic ion-exchange resins;
(2) resin of step (1) being handled floods 12h with the 1mol/L sodium hydroxide solution, filters, and is washed till neutrality with deionized water, at room temperature dries naturally, and is for use; Wherein: the volume ratio of resin and sodium hydroxide solution is 1: 10;
(3) it is that the volume ratio of resin and liquor ferri trichloridi is 1: 5 in 10% the liquor ferri trichloridi that the resin of step (2) being handled adds mass fraction;
(4) speed with 10mL/h slowly drips the 1mol/L sodium hydroxide solution in step (3) solution, and resin and sodium hydroxide solution volume ratio are 1: 5, mix liquid simultaneously, and the beta-hydroxy iron oxide deposits to resin surface gradually;
(5) filter out step (4) gained resin, be washed till neutrality with deionized water and alcohol, dry naturally under the normal temperature, promptly obtain beta-iron oxide hydroxides loaded resin, this resin is made catalyst and is used.
2. the beta-iron oxide hydroxides loaded resin of the said method preparation of claim 1 is in Application in Photocatalysis; It is characterized in that: beta-iron oxide hydroxides loaded resin catalyst and hydrogen peroxide are added to simultaneously contain in the incretion interferent water body; Open uviol lamp simultaneously and implement and stir; But synchronism eliminates environment incretion interferent and hormonal activity thereof, purifying water body.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN2010101517888A CN101829603B (en) | 2010-04-20 | 2010-04-20 | Preparation method of beta-iron oxide hydroxides loaded resin and application thereof in photocatalysis |
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| CN2010101517888A CN101829603B (en) | 2010-04-20 | 2010-04-20 | Preparation method of beta-iron oxide hydroxides loaded resin and application thereof in photocatalysis |
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| CN101829603A CN101829603A (en) | 2010-09-15 |
| CN101829603B true CN101829603B (en) | 2012-03-07 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105921151A (en) * | 2016-04-29 | 2016-09-07 | 华东师范大学 | Preparation method and application of beta-FeOOH-loaded graphene oxide catalyst |
| CN106732374A (en) * | 2017-01-18 | 2017-05-31 | 湖南大学 | The preparation and application of hydro-thermal charcoal/attapulgite/β FeOOH compound adsorbents |
| CN108579682A (en) * | 2018-04-20 | 2018-09-28 | 华南理工大学 | A kind of iron carbonyl modified cation resin composite materials and the preparation method and application thereof |
| CN109461944B (en) * | 2018-10-10 | 2021-06-11 | 暨南大学 | Cubic FeOOH or Fe loaded on nano carbon ribbon4(Fe(CN)6)3Preparation method and application of |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1378879A (en) * | 2001-04-06 | 2002-11-13 | 中国科学院化学研究所 | Solid photocatalyst and its preparing process |
| CN1386581A (en) * | 2001-05-18 | 2002-12-25 | 中国科学院化学研究所 | Bionic visible light solid-phase catalyst and its preparing process |
| CN1470329A (en) * | 2002-07-23 | 2004-01-28 | 中国科学院化学研究所 | Solid phase photocatalyst and its preparing method |
| CN1835803A (en) * | 2003-06-13 | 2006-09-20 | 兰爱克谢斯德国有限责任公司 | Arsenic-adsorbing ion exchanger |
| CN101073785A (en) * | 2006-04-11 | 2007-11-21 | 兰爱克谢丝德国有限责任公司 | Ion exchanger for absorbing oxo-anions |
| CN101186357A (en) * | 2007-12-18 | 2008-05-28 | 南京大学 | Method for deep purifying heavy metal micro-polluted water by resin-base nano hydrated ferric oxide |
-
2010
- 2010-04-20 CN CN2010101517888A patent/CN101829603B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1378879A (en) * | 2001-04-06 | 2002-11-13 | 中国科学院化学研究所 | Solid photocatalyst and its preparing process |
| CN1386581A (en) * | 2001-05-18 | 2002-12-25 | 中国科学院化学研究所 | Bionic visible light solid-phase catalyst and its preparing process |
| CN1470329A (en) * | 2002-07-23 | 2004-01-28 | 中国科学院化学研究所 | Solid phase photocatalyst and its preparing method |
| CN1835803A (en) * | 2003-06-13 | 2006-09-20 | 兰爱克谢斯德国有限责任公司 | Arsenic-adsorbing ion exchanger |
| CN101073785A (en) * | 2006-04-11 | 2007-11-21 | 兰爱克谢丝德国有限责任公司 | Ion exchanger for absorbing oxo-anions |
| CN101186357A (en) * | 2007-12-18 | 2008-05-28 | 南京大学 | Method for deep purifying heavy metal micro-polluted water by resin-base nano hydrated ferric oxide |
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