CN102059099A - Biological adsorbent for waste water treatment and preparation method thereof - Google Patents
Biological adsorbent for waste water treatment and preparation method thereof Download PDFInfo
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- CN102059099A CN102059099A CN 201010581335 CN201010581335A CN102059099A CN 102059099 A CN102059099 A CN 102059099A CN 201010581335 CN201010581335 CN 201010581335 CN 201010581335 A CN201010581335 A CN 201010581335A CN 102059099 A CN102059099 A CN 102059099A
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Abstract
The invention discloses a biological adsorbent for waste water treatment and a preparation method thereof. The biological adsorbent is a product prepared by pretreating orange peels and then oxidizing and modifying the pretreated orange peels with a KMnO4 aqueous solution or hydrogen peroxide. In the invention, the KMnO4 aqueous solution or hydrogen peroxide is used for oxidization modification to activate surface adsorption points of the orange peels, and the modified orange peel bio-adsorbent has very high adsorption efficiency and very strong adsorption property for heavy metal ions, and large adsorption capacity; experiments prove that the adsorbent has the adsorption rate high up to 96-100% for Cu<2+>, Cd<2+> and Pb<2+>; raw materials have wide sources, and are cheap and easy to obtain so that the products are low in cost; the used modified orange peel bio-adsorbent can also be regenerated through immersion and washing with acid pickle; and the process for applying the adsorbent in waste water treatment is simple, is convenient to operate, and can realize the recovering of heavy metals and the comprehensive recycling of resources.
Description
Technical field
The present invention relates to a kind of heavy metal ion-containing waste water handles with biological adsorption agent and preparation method thereof.
Background technology
Along with the fast development of China's industry, heavy metal ion-containing waste water produces in a large number and discharges, and heavy metal ion content increases in soil and the water source, and heavy metal pollution is serious day by day.Absorption method is to utilize the absorption of porous solid material to remove a kind of effective ways of heavy metal ion in the water.The tradition adsorbent is an active carbon, and it has very strong adsorption capacity, the clearance height, but the active carbon regeneration efficiency is low, and water quality treatment is difficult to reach the reuse requirement, and price is expensive, and application is restricted.In recent years, a lot of experts and scholars turn to some biological adsorption agents more cheap and easy to get to notice.Agriculture and forestry organic waste material is the byproduct that produces in agricultural and production of forestry and the process, enormous amount, having renewable, plurality of advantages such as the regeneration period short, biodegradable, environmental friendliness, is important biomass resource, mainly contains bark, shell, sawdust, stalk, pomace etc.
The object of the present invention is to provide heavy metal ion biological adsorption agent that a kind of cost is low, adsorption rate is fast, efficient is high and preparation method thereof.
Biological adsorption agent of the present invention is the product of being made by the orange peel oxidation modification.
Preparation method of the present invention may further comprise the steps:
(1) after orange peel was cleaned with distilled water, drying and crushing was crossed 100 mesh sieves, gets the orange peel powder;
(2) preliminary treatment: being immersed in the orange peel powder by the sodium hydrate aqueous solution of 0.05～0.5 mol/L and ethanol is in the mixed solvent formed of 1～5:1 by volume, the ratio of its orange peel powder quality and mixed solvent volume is 1:5～20, behind soaking at room temperature 24 h, filter, its filter residue obtains preliminary treatment orange peel adsorbent after cleaning with distilled water;
(3) oxidation modification: get the KMnO that preliminary treatment orange peel adsorbent places 5～20 mmol/L
4In the hydrogen peroxide of the aqueous solution or 2～10 v%, stir, carrying out oxidation modification handles, preliminary treatment orange peel adsorbent mass is 1:10～60 (preferred 1:12～50) with the ratio that oxidation modification liquid amasss, treatment temperature is 25～60 ℃ (preferred 30～55 ℃), and the time is 0.5～12 h (preferred 2～10 h);
(4) purifying: filter, filter residue washs with distilled water, the dry modification orange peel biological adsorption agent that gets.
Advantage of the present invention: adopt potassium permanganate solution or hydrogen peroxide to carry out oxidation modification, activated orange peel surface adsorption site, this modification orange peel biological adsorption agent has very high adsorption efficiency and very strong absorption property to heavy metal ion; Adsorption capacity is big; Through experiment, this adsorbent is to Cu
2+, Cd
2+And Pb
2+Adsorption rate up to 96-100%; Raw material sources are extensive, and are cheap and easy to get, and product cost is low; Used modification orange peel biological adsorption agent also can be by the regeneration of acid pickle washing by soaking; The technology that is applied to wastewater treatment is simple, easy to operate, can realize the recovery of heavy metal and the comprehensive cyclic utilization of resource.
The specific embodiment
The present invention will be further described below in conjunction with embodiment.
Embodiment 1:
(1) after orange peel was cleaned with distilled water, drying and crushing was crossed 100 mesh sieves, gets the orange peel powder;
(2) get orange peel powder 40 g and be immersed in the mixed solvent of being made up of sodium hydrate aqueous solution and the 100 mL ethanol of 300 mL, 0.05 mol/L, behind soaking at room temperature 24 h, filter, filter residue cleans with distilled water, gets preliminary treatment orange peel adsorbent;
(3) get the KMnO that preliminary treatment orange peel adsorbent 10 g place 500 mL, 5 mmol/L
4In the aqueous solution, stir, carry out oxidation modification and handle, treatment temperature is 50 ℃, and the time is 10 h; After preliminary treatment is finished, filter, filter residue washs with distilled water, the dry modification orange peel biological adsorption agent that gets.This adsorbent is to Cu
2+, Cd
2+And Pb
2+Adsorption rate be respectively 95.2%, 97.2% and 98.3%.
To Cu
2+, Cd
2+And Pb
2+Adsorption rate be to obtain by following method:
Get 0.1 g modification orange peel biological adsorption agent under 25 ℃ of room temperatures, to 20 mL, 50 mg/L Cu
2+Or 50 mg/L Cd
2+Or 100 mg/L Pb
2+The static absorption of solution 3 h, before and after the absorption metal ion mass concentration of each solution by atomic absorption spectroscopy determination, adsorption rate (
AdsorptionConcrete computing formula %) is as follows:
In the formula: C
0-original metal ion concentration, mg/L; C
eConcentration of metal ions after the-adsorption equilibrium, mg/L.
Embodiment 2:
After orange peel was cleaned with distilled water, drying and crushing was crossed 100 mesh sieves, gets the orange peel powder.Get orange peel powder 40 g and be immersed in the mixed solvent of being made up of sodium hydrate aqueous solution and the 200 mL ethanol of 400 mL, 0.25 mol/L, behind soaking at room temperature 24 h, filter, filter residue cleans with distilled water, gets preliminary treatment orange peel adsorbent; Get the KMnO that preliminary treatment orange peel adsorbent 10 g place 300 mL, 10 mmol/L
4In the aqueous solution, stir, carry out oxidation modification and handle, treatment temperature is 40 ℃, and the time is 5 h; After preliminary treatment is finished, filter, filter residue washs with distilled water, the dry modification orange peel biological adsorption agent that gets.This adsorbent is to Cu
2+, Cd
2+And Pb
2+Adsorption rate be respectively 97.4%, 99.2% and 99.7%.
Embodiment 3:
After orange peel was cleaned with distilled water, drying and crushing was crossed 100 mesh sieves, gets the orange peel powder.Get orange peel powder 40 g and be immersed in the mixed solvent of being made up of sodium hydrate aqueous solution and the 100 mL ethanol of 200 mL, 0.5 mol/L, behind soaking at room temperature 24 h, filter, filter residue cleans with distilled water, gets preliminary treatment orange peel adsorbent; Get the KMnO that preliminary treatment orange peel adsorbent 10 g place 150 mL, 20 mmol/L
4In the aqueous solution, stir, carry out oxidation modification and handle, treatment temperature is 30 ℃, and the time is 1 h; After preliminary treatment is finished, filter, filter residue washs with distilled water, the dry modification orange peel biological adsorption agent that gets.This adsorbent is to Cu
2+, Cd
2+And Pb
2+Adsorption rate be respectively 96.8%, 98.7% and 100%.
Embodiment 4:
After orange peel was cleaned with distilled water, drying and crushing was crossed 100 mesh sieves, gets the orange peel powder.Get orange peel powder 50 g and be immersed in the mixed solvent of being made up of sodium hydrate aqueous solution and the 300 mL ethanol of 600 mL, 0.05 mol/L, behind soaking at room temperature 24 h, filter, filter residue cleans with distilled water, gets preliminary treatment orange peel adsorbent; Get the hydrogen peroxide that preliminary treatment orange peel adsorbent 10 g place 400 mL, 3 v%, stir, carry out oxidation modification and handle, treatment temperature is 55 ℃, and the time is 10 h; After preliminary treatment is finished, filter, filter residue washs with distilled water, the dry modification orange peel biological adsorption agent that gets.This adsorbent is to Cu
2+, Cd
2+And Pb
2+Adsorption rate be respectively 95.5%, 97.3% and 98.6%.
Embodiment 5:
After orange peel was cleaned with distilled water, drying and crushing was crossed 100 mesh sieves, gets the orange peel powder.Get orange peel powder 50 g and be immersed in the mixed solvent of being made up of sodium hydrate aqueous solution and the 150 mL ethanol of 350 mL, 0.2 mol/L, behind soaking at room temperature 24 h, filter, filter residue cleans with distilled water, gets preliminary treatment orange peel adsorbent; Get the hydrogen peroxide that preliminary treatment orange peel adsorbent 10 g place 250 mL, 5 v%, stir, carry out oxidation modification and handle, treatment temperature is 35 ℃, and the time is 8 h; After preliminary treatment is finished, filter, filter residue washs with distilled water, the dry modification orange peel biological adsorption agent that gets.This adsorbent is to Cu
2+, Cd
2+And Pb
2+Adsorption rate be respectively 98.6%, 99.5% and 100%.
Embodiment 6:
After orange peel was cleaned with distilled water, drying and crushing was crossed 100 mesh sieves, gets the orange peel powder.Get orange peel powder 50 g and be immersed in the mixed solvent of being made up of sodium hydrate aqueous solution and the 100 mL ethanol of 200 mL, 0.5 mol/L, behind soaking at room temperature 24 h, filter, filter residue cleans with distilled water, gets preliminary treatment orange peel adsorbent; Get the hydrogen peroxide that preliminary treatment orange peel adsorbent 10 g place 120 mL, 8 v%, stir, carry out oxidation modification and handle, treatment temperature is 30 ℃, and the time is 2 h; After preliminary treatment is finished, filter, filter residue washs with distilled water, the dry modification orange peel biological adsorption agent that gets.This adsorbent is to Cu
2+, Cd
2+And Pb
2+Adsorption rate be respectively 97.3%, 98.2% and 99.8%.
Embodiment 7:
Place the acid pickle of pH=1 to carry out desorb the modification orange peel biological adsorption agent that has adsorbed heavy metal ion among the embodiment 5, wash dried adsorbent and be reused for Cu respectively
2+, Cd
2+Or Pb
2+Adsorption experiment, found that, after 10 adsorption-desorptions, KMnO
4The orange peel biological adsorption agent of modification is to Cu
2+, Cd
2+And Pb
2+Adsorption rate reduce to 93.4%, 95.6% and 97.7% respectively, H
2O
2The orange peel biological adsorption agent Cu of modification
2+, Cd
2+And Pb
2+Adsorption rate reduce to 92.3%, 95.2% and 97.4 respectively, adsorption capacity all reduces seldom.
Claims (5)
1. a use in waste water treatment biological adsorption agent is characterized in that, be by orange peel after preliminary treatment again through KMnO
4The product that the aqueous solution or hydrogen peroxide oxidation modification are made.
2. the preparation method of a use in waste water treatment biological adsorption agent is characterized in that, may further comprise the steps:
(1) after orange peel was cleaned with distilled water, drying and crushing was crossed 100 mesh sieves, gets the orange peel powder;
(2) preliminary treatment: being immersed in the orange peel powder by the sodium hydrate aqueous solution of 0.05～0.5 mol/L and ethanol is in the mixed solvent formed of 1～5:1 by volume, the ratio of its orange peel powder quality and mixed solvent volume is 1:5～20, behind soaking at room temperature 24 h, filter, its filter residue obtains preliminary treatment orange peel adsorbent after cleaning with distilled water;
(3) oxidation modification: get the KMnO that preliminary treatment orange peel adsorbent places 5～20 mmol/L
4In the hydrogen peroxide of the aqueous solution or 2～10 v%, stir, carry out oxidation modification and handle, preliminary treatment orange peel adsorbent mass is 1:10～60 with the ratio that oxidation modification liquid amasss, and treatment temperature is 25～60 ℃, and the time is 0.5～12 h;
(4) purifying: filter, filter residue washs with distilled water, the dry modification orange peel biological adsorption agent that gets.
3. the volume ratio of described sodium hydrate aqueous solution and ethanol is 2～3:1, and the ratio of orange peel powder quality and mixed solvent volume is 1:6～16.
4. the preparation method of modification orange peel biological adsorption agent according to claim 2, it is characterized in that when carrying out the oxidation modification processing, preliminary treatment orange peel adsorbent mass is 1:12～50 with the ratio that oxidation modification liquid amasss, treatment temperature is 30～55 ℃, and the time is 2～10 h.
5. the preparation method of modification orange peel biological adsorption agent according to claim 2, when it is characterized in that carrying out oxidation modification and handling with hydrogen peroxide, used hydrogen peroxide is 3～8 v%.
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| CN102728327A (en) * | 2012-07-26 | 2012-10-17 | 中国科学院新疆理化技术研究所 | Preparation method and application of modified orange peel biological adsorbent |
| CN102872818A (en) * | 2012-08-28 | 2013-01-16 | 常州大学 | Composite adsorbing material for removing zinc ions in natural water and preparation method thereof |
| CN103170313A (en) * | 2013-03-29 | 2013-06-26 | 赣县世瑞新材料有限公司 | Heavy metal modified bioadsorbent and preparation method thereof as well as application of heavy metal modified bioadsorbent in tungsten-containing waste water treatment |
| CN103464112A (en) * | 2013-09-14 | 2013-12-25 | 四川农业大学 | Method for preparing biological adsorbent by using wheat husks as raw materials |
| CN103599753A (en) * | 2013-11-05 | 2014-02-26 | 李晶 | Preparation method and application of modified giant reed |
| CN104492386A (en) * | 2014-10-27 | 2015-04-08 | 河南城建学院 | Preparation method for oxalic-acid-modified pummelo pericarp biological adsorbent |
| CN105013451A (en) * | 2015-08-03 | 2015-11-04 | 江西省科学院生物资源研究所 | Method for preparing biomass absorbing agent capable of absorbing heavy metal ions in waste water efficiently |
| CN105289524A (en) * | 2015-11-09 | 2016-02-03 | 湖南有色金属研究院 | Shaddock peel heavy metal adsorbent and preparation method and application thereof |
| CN105879830A (en) * | 2016-06-29 | 2016-08-24 | 广西桂柳化工有限责任公司 | Method for preparing manganese dioxide adsorbent |
| CN106268670A (en) * | 2016-08-30 | 2017-01-04 | 运城学院 | A kind of orange peel prepares the method removing PM2.5 biological adsorption agent |
| CN107282009A (en) * | 2017-06-08 | 2017-10-24 | 安徽省金鸿再生资源科技有限公司 | A kind of lead skim extracts the reuse method for the cinder that process of tin is produced |
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| CN109126734A (en) * | 2018-10-11 | 2019-01-04 | 成都其其小数科技有限公司 | A kind of high efficiency, low cost adsorbent and preparation method for heavy metal containing wastewater treatment |
| CN112108127A (en) * | 2020-10-15 | 2020-12-22 | 桂林理工大学 | Passion fruit peel adsorption material and preparation method and application thereof |
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2010
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| CN102728327B (en) * | 2012-07-26 | 2013-12-25 | 中国科学院新疆理化技术研究所 | Preparation method and application of modified orange peel biological adsorbent |
| CN102728327A (en) * | 2012-07-26 | 2012-10-17 | 中国科学院新疆理化技术研究所 | Preparation method and application of modified orange peel biological adsorbent |
| CN102872818A (en) * | 2012-08-28 | 2013-01-16 | 常州大学 | Composite adsorbing material for removing zinc ions in natural water and preparation method thereof |
| CN103170313A (en) * | 2013-03-29 | 2013-06-26 | 赣县世瑞新材料有限公司 | Heavy metal modified bioadsorbent and preparation method thereof as well as application of heavy metal modified bioadsorbent in tungsten-containing waste water treatment |
| CN103464112A (en) * | 2013-09-14 | 2013-12-25 | 四川农业大学 | Method for preparing biological adsorbent by using wheat husks as raw materials |
| CN103599753A (en) * | 2013-11-05 | 2014-02-26 | 李晶 | Preparation method and application of modified giant reed |
| CN104492386B (en) * | 2014-10-27 | 2017-03-29 | 河南城建学院 | A kind of preparation method of the modified pomelo peel biological adsorption agent of oxalic acid |
| CN104492386A (en) * | 2014-10-27 | 2015-04-08 | 河南城建学院 | Preparation method for oxalic-acid-modified pummelo pericarp biological adsorbent |
| CN105013451B (en) * | 2015-08-03 | 2017-09-22 | 江西省科学院生物资源研究所 | A kind of biomass adsorbent preparation method of efficient absorption heavy metal ions in wastewater |
| CN105013451A (en) * | 2015-08-03 | 2015-11-04 | 江西省科学院生物资源研究所 | Method for preparing biomass absorbing agent capable of absorbing heavy metal ions in waste water efficiently |
| CN105289524A (en) * | 2015-11-09 | 2016-02-03 | 湖南有色金属研究院 | Shaddock peel heavy metal adsorbent and preparation method and application thereof |
| CN105879830A (en) * | 2016-06-29 | 2016-08-24 | 广西桂柳化工有限责任公司 | Method for preparing manganese dioxide adsorbent |
| CN106268670A (en) * | 2016-08-30 | 2017-01-04 | 运城学院 | A kind of orange peel prepares the method removing PM2.5 biological adsorption agent |
| CN107282009A (en) * | 2017-06-08 | 2017-10-24 | 安徽省金鸿再生资源科技有限公司 | A kind of lead skim extracts the reuse method for the cinder that process of tin is produced |
| CN108745307A (en) * | 2018-06-28 | 2018-11-06 | 成都先进金属材料产业技术研究院有限公司 | Modified corn core goes the purposes of vanadium in water removal |
| CN109126734A (en) * | 2018-10-11 | 2019-01-04 | 成都其其小数科技有限公司 | A kind of high efficiency, low cost adsorbent and preparation method for heavy metal containing wastewater treatment |
| CN112108127A (en) * | 2020-10-15 | 2020-12-22 | 桂林理工大学 | Passion fruit peel adsorption material and preparation method and application thereof |
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