CN101985101A - Hydrophobic chitosan absorbent, and preparation method and application thereof - Google Patents
Hydrophobic chitosan absorbent, and preparation method and application thereof Download PDFInfo
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- CN101985101A CN101985101A CN 201010542992 CN201010542992A CN101985101A CN 101985101 A CN101985101 A CN 101985101A CN 201010542992 CN201010542992 CN 201010542992 CN 201010542992 A CN201010542992 A CN 201010542992A CN 101985101 A CN101985101 A CN 101985101A
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- chitosan absorbent
- hydrophobicity
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- absorbent
- heavy metal
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Abstract
The invention discloses a hydrophobic bead chitosan absorbent and a preparation method thereof. The preparation method comprises the following steps of: dissolving 5 to 20g of chitosan in 100 to 500mL of 3 and 5 volume percent solution of acetic acid; adding 5 to 20mL of cross-linking agent; uniformly stirring at a high speed, adding 10 to 50g of aluminosilicate powder and 5 to 10mL of 100 mass percent ethyl acetate, and continuously stirring to prepare uniform paste; and dropwise adding the paste into 1L of 0.3 to 0.5mol.L<-1> solution of sodium hydroxide which is slowly stirred at the rate of 100 to 200r.min<-1>, reacting for 8 to 24 hours, washing the reaction product to be neutral with distilled water and covering de-ionized water. At normal temperature, heavy metal ions are quickly absorbed by the adsorbent and removed from wastewater, so that the wastewater can be recycled and the adsorption capacity does not attenuate, and the absorbent and the method can be applied to wastewater treatment of industries such as printed circuit boards, electroplating, pigments, metal surface treatment, battery production and the like.
Description
Technical field
The present invention relates to the adsorption technology of heavy metal ion in the industrial wastewater, is a kind of hydrophobicity chitosan absorbent and preparation method thereof and the application in water treatment specifically.
Background technology
Often contain heavy metal ion such as chromium, cadmium, nickel, copper, lead, zinc in the industrial wastewater.In water body, because the refractory organics and the toxic of heavy metal ion have a strong impact on generations such as fishery and agriculturals, and heavy metal ion can also be at human body and biological cylinder accumulation, and can't be degraded by microorganisms, and is detrimental to health directly or indirectly.
Most heavy metal wastewater therebies adopt chemical treatment methods, in comprising and coagulating sedimentation, sulphide precipitation, active carbon adsorption etc.
The neutralization precipitation method is one of method that develops processing heavy metal ion the earliest.It is by adding basic agents such as lime, soda, NaOH, and the pH value of waste water is adjusted to the scope that makes heavy metal ion have minimal solubility, and its form with hydroxide or carbonate is precipitated.When containing both sexes heavy metal ion such as aluminium, zinc in the waste water, the neutralization precipitation method needs strict control pH value, otherwise the precipitate metal hydroxides of generation is dissolved under the situation of high pH once more.
Sulphide precipitation is to add the sulphion precipitating reagent in waste water, and heavy metal is separated with the form of sulfide precipitation.Compare with the neutralization precipitation method, the advantage of this method is: the solubility product of heavy metal sulfide is more much smaller than the solubility product of hydroxide, and reaction pH value is between 7-9, and the waste water after the processing does not generally need to neutralize again.But sulfide precipitation flco in forming process is less, brings difficulty to separation.In addition, the metal sulfide precipitation is met acid can generate hydrogen sulfide gas, produces secondary pollution.
Absorption method is to utilize a sharp method of heavy metal in the porous adsorbing material adsorption treatment waste water, and adsorbent commonly used is an active carbon.Active carbon has good specific surface area, and very strong adsorption capacity is arranged, the clearance height, but owing to cost an arm and a leg, recycling rate of waterused is low, application is restricted.
Shitosan is a kind of natural polymer, be on the earth outside the isolating protein, the nitrogenous natural organic matter of quantity maximum, belong to the polysaccharide in the carbohydrate, it is the product of chitin deacetylase, its molecule contains amino and various active functional group such as hydroxyl, makes it have stronger and ability metallic ion coordination, energy and Cu
2+, Ni
2+, Hg
2+, Pb
2+, Cr
3+Form than stable chelate Deng metal ion.Therefore, shitosan can be used as the heavy metal ion in the sorbent treatment waste water.But drawbacks limit such as shitosan runs off easily, mechanical strength is low, can not regenerate its application.
Summary of the invention
The objective of the invention is to, overcome the defective of prior art, a kind of hydrophobicity chitosan absorbent and preparation method thereof is provided, this hydrophobicity chitosan absorbent can be adsorbed the Cu in the waste water at normal temperatures fast
2+, Ni
2+, Hg
2+, Pb
2+, Cr
3+Etc. heavy metal ion, thereby heavy metal ion is removed from water.
In order to address the above problem, the present invention is compound with chitosan solution and alumino-silicate by crosslinked action, utilize shitosan to be dissolved in acid and be insoluble to the dropping spherical container shaping method principle of alkali, make crosslinked shitosan-alumino-silicate mixture balling-up in sodium hydroxide solution after compound, make the hydrophobicity chitosan absorbent.This adsorbent can adsorb the Cu in the waste water at normal temperatures fast
2+, Ni
2+, Hg
2+, Pb
2+, Cr
3+Etc. heavy metal ion, and, the repeated use of can repeatedly regenerating after this bead adsorbs contents of many kinds of heavy metal ion, and its adsorption capacity does not have obvious decay.
Purpose of the present invention is achieved through the following technical solutions:
A kind of hydrophobicity preparation method of chitosan absorbent comprises the steps:
It is 3%～5% acetum that (1) 5～20g shitosan is dissolved in 100～500mL volumetric concentration, adds 5～20mL crosslinking agent, and high-speed stirred, mixing speed are 700～900rmin
-1
(2) stir that to add 10～50g alumino-silicate powder and 5～10mL mass concentration in above-mentioned solution be 100% ethyl acetate in the back, continue high-speed stirred and make even pastel;
(3) the above-mentioned pastel that makes is dripped at 100～200rmin
-1The concentration of Jiao Baning is 0.3～0.5molL at a slow speed
-1The 1L sodium hydroxide solution in, place sodium hydroxide solution 8～24h after, be washed with distilled water to neutrality, in deionized water, can make the hydrophobicity chitosan absorbent to hydrophobicity chitosan absorbent bubble.
The used crosslinking agent of above-mentioned preparation method is an epoxychloropropane.
The used alumino-silicate of above-mentioned preparation method is an artificial zeolite.
The average grain diameter of the hydrophobicity chitosan absorbent of method for preparing is 2～4mm, and density is 1.02～1.22gcm
-3, moisture content is 65～85%.
The hydrophobicity chitosan absorbent of method for preparing is used for adsorbing fast the heavy metal ion of waste water.
At the concentration and the kind of heavy metal ions in wastewater, can add the hydrophobicity chitosan absorbent of the present invention of appropriate amount separately, also can unite use with other adsorbent.By stirring reaction, heavy metal ion is adsorbed onto on the bead fast, and the concentration of heavy metal ion is lower than discharging standards in the processed waste water.The hydrophobicity shitosan that adsorbs after saturated can carry out desorb with dilute sulfuric acid, and reclaims heavy metal, can not produce secondary pollution.This adsorbent also can be used for recycle-water solution precious metal, and is used to purify the drinking water resource that is subjected to heavy metal pollution.
Hydrophobicity chitosan absorbent of the present invention is used for adsorbing the industrial wastewater heavy metal ion, and normal temperature adsorbs Cu in the waste water down fast
2+, Ni
2+, Hg
2+, Pb
2+, Cr
3+Etc. heavy metal ion,, reach the purpose of removing heavy metal ion in the water by Separation of Solid and Liquid.Raw material sources required for the present invention are extensive, and preparation technology and equipment are simple, and is easy to operate, applicable to the wastewater treatment of industries such as printed substrate, plating, pigment, Treatment of Metal Surface and battery production.
The present invention compared with prior art has following advantage and beneficial effect:
1) hydrophobicity chitosan absorbent wide material sources of the present invention, manufacture craft equipment is simple.
2) hydrophobicity chitosan absorbent of the present invention is not only to Cu in the waste water
2+, Ni
2+, Hg
2+, Pb
2+, Cr
3+Have the good adsorption effect etc. heavy metal ion, and can reclaim heavy metal by the dilute sulfuric acid desorb.
3) the hydrophobicity chitosan absorbent is through after desorb repeatedly and the regeneration, and adsorption capacity is not decay almost.
The specific embodiment
Below in conjunction with embodiment, the present invention is further illustrated:
Embodiment 1
It is 3% acetum that the 5g shitosan is dissolved in 100mL concentration, adds the 5mL epoxychloropropane, according to 700rmin
-1High-speed stirred evenly after, add 10g artificial zeolite powder and 5mL pure ethyl acetate again, continue 700rmin
-1High-speed stirred make even pastel, drip at 100rmin by peristaltic pump
-1The concentration of Jiao Baning is 0.3molL at a slow speed
-1The 1L sodium hydroxide solution in, after the hydrophobicity chitosan absorbent that makes places sodium hydroxide solution 8h, be washed with distilled water to neutrality, again the hydrophobicity chitosan absorbent steeped in deionized water, promptly make the hydrophobicity chitosan absorbent, the normal temperature lower seal is preserved.
Embodiment 2
It is 3% acetum that the 10g shitosan is dissolved in 150mL concentration, adds the 10mL epoxychloropropane, according to 800rmin
-1High-speed stirred evenly after, add 25g artificial zeolite powder and 7mL pure ethyl acetate again, continue 800rmin
-1High-speed stirred make even pastel, drip at 150rmin by peristaltic pump
-1The concentration that stirs at a slow speed be 0.4molL
-1The 1L sodium hydroxide solution in, after the hydrophobicity chitosan absorbent that makes places sodium hydroxide solution 12h, be washed with distilled water to neutrality, again the hydrophobicity chitosan absorbent steeped in deionized water, promptly make the hydrophobicity chitosan absorbent, the normal temperature lower seal is preserved.
Embodiment 3
It is 3% acetum that the 15g shitosan is dissolved in 300mL concentration, adds the 15mL epoxychloropropane, according to 900rmin
-1After high-speed stirred is even, add 35g artificial zeolite powder and 9mL pure ethyl acetate again, continue 900rmin
-1Stirring makes even pastel, drips at 200rmin by peristaltic pump
-1The concentration of Jiao Baning is 0.5mo1L at a slow speed
-1The 1L sodium hydroxide solution in, the hydrophobicity chitosan absorbent that makes is washed with distilled water to neutrality after placing sodium hydroxide solution to place 16h, the hydrophobicity chitosan absorbent is steeped in deionized water again, promptly make the hydrophobicity chitosan absorbent, the normal temperature lower seal is preserved.
Embodiment 4
The 20g shitosan is dissolved in the 500mL acetum, adds the 20mL epoxychloropropane, according to 900rmin
-1High-speed stirred evenly back adds 50g artificial zeolite powder and 10mL pure ethyl acetate, continues 900rmin
-1Stirring makes even pastel, drips at 200rmin by peristaltic pump
-1The concentration of Jiao Baning is 0.5molL at a slow speed
-1The 1L sodium hydroxide solution in, after the hydrophobicity chitosan absorbent that makes places sodium hydroxide solution 24h, be washed with distilled water to neutrality, again the hydrophobicity chitosan absorbent steeped in deionized water, promptly make the hydrophobicity chitosan absorbent, the normal temperature lower seal is preserved.
Table 1
| Technological parameter | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Shitosan/g | ?5 | ?10 | ?15 | ?20 |
| Alumino-silicate/g | ?10 | ?25 | ?35 | ?50 |
| Ethyl acetate/mL | ?5 | ?7 | ?9 | ?10 |
| Crosslinking agent/mL | ?5 | ?10 | ?15 | ?20 |
| Acetum/mL | ?100 | ?150 | ?300 | ?500 |
| Sodium hydroxide solution/L | ?1 | ?1 | ?1 | ?1 |
| Sodium hydroxide solution standing time/h | ?8 | ?12 | ?16 | ?24 |
Select Guangzhou company electroplating wastewater for use, recording copper ion concentration is 51.52mgL
-1, the pH value is 4.5, adds the hydrophobicity chitosan absorbent 10gL of above-mentioned four embodiment respectively
-1, stir speed (S.S.) is 120rmin
-1, static behind the reaction 4h, get supernatant mensuration copper ion concentration and be respectively 0.32mgL
-1, 0.37mgL
-1, 0.41mgL
-1And 0.28mgL
-1, copper ion concentration all reaches discharging standards.The hydrophobicity chitosan absorbent concentration of adsorbing after saturated is 0.05molL
-1The dilute sulfuric acid desorb, resolution factor reaches 97%, can reuse to reach more than 5 times and adsorption capacity is undamped.
Select Guangzhou company electronics waste water for use, recording nickel ion concentration is 31.52mgL
-1, the pH value is 5.7, adds the hydrophobicity chitosan absorbent 5gL of above-mentioned four embodiment respectively
-1, stir speed (S.S.) is 120rmin
-1, reaction is static behind the 5h, gets supernatant and measures its nickel ion concentration and be respectively 0.62mgL
-1, 0.57mgL
-1, 0.48mgL
-1And 0.68mgL
-1, nickel ion concentration all reaches discharging standards.The hydrophobicity chitosan absorbent concentration of adsorbing after saturated is 0.05molL
-1The dilute sulfuric acid desorb, resolution factor reaches more than 90%, can reuse to reach more than 5 times and adsorption capacity is undamped.
Select somewhere, Guangdong mine wastewater for use, record Hg
2+, Pb
2+, Cr
3+Concentration is respectively 2.7mgL
-1, 14.3mgL
-1, 7.3mgL
-1, regulating pH is 7.3, adds the hydrophobicity chitosan absorbent 5gL of above-mentioned four embodiment respectively
-1, stir speed (S.S.) is 120rmin
-1, static behind the reaction 5h, get supernatant and measure its Hg
2+, Pb
2+, Cr
3+Concentration is respectively 0.02mgL
-1, 0.4mgL
-1And 0.78mgL
-10.035mgL
-1, 0.45mgL
-1And 0.36mgL
-10.035mgL
-1, 0.36mgL
-1And 0.33mgL
-10.03mgL
-1, 0.85mgL
-1And 0.79mgL
-1Each ion concentration all reaches discharging standards.Adsorb hydrophobicity chitosan absorbent after saturated with dilute sulfuric acid (concentration 0.05molL
-1) desorb, resolution factor reaches more than 95%, can reuse to reach more than 5 times and adsorption capacity is undamped.
Claims (6)
1. a hydrophobicity preparation method of chitosan absorbent is characterized in that, comprises the steps:
It is 3%～5% acetum that (1) 5～20g shitosan is dissolved in 100～500mL volumetric concentration, adds 5～20mL crosslinking agent, and high-speed stirred, mixing speed are 700～900rmin
-1
(2) stir that to add 10～50g alumino-silicate powder and 5～10mL mass concentration in above-mentioned solution be 100% ethyl acetate in the back, continue above-mentioned high-speed stirred and make even pastel;
(3) the above-mentioned pastel that makes is dripped at 100～200rmin
-1The concentration of Jiao Baning is 0.3～0.5molL at a slow speed
-1The 1L sodium hydroxide solution in, place sodium hydroxide solution 8～24h after, be washed with distilled water to neutrality, hydrophobicity chitosan absorbent bubble in deionized water, is promptly made the hydrophobicity chitosan absorbent.
2. preparation method according to claim 1 is characterized in that, described crosslinking agent is an epoxychloropropane.
3. preparation method according to claim 1 is characterized in that described alumino-silicate is an artificial zeolite.
4. according to the hydrophobicity chitosan absorbent of claim 1 or 2 or 3 described method preparations, it is characterized in that the average grain diameter of described adsorbent is 2～4mm, density is 1.02～1.22gcm
-3, moisture content is 65～85%.
5. the application of the hydrophobicity chitosan absorbent of claim 1 or 2 or 3 described method preparations is characterized in that this adsorbent is used for adsorbing fast the heavy metal ion of waste water.
6. the application of the described adsorbent of claim 5 is characterized in that, described heavy metal ion is Cu
2+, Ni
2+, Hg
2+, Pb
2+And Cr
3+
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|---|---|---|---|
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102500333A (en) * | 2011-10-28 | 2012-06-20 | 上海海洋大学 | Magnetic cationic surfactant modified chitosan / hydroxyapatite / zeolite composite and preparation method and application thereof |
| CN102863045A (en) * | 2012-10-10 | 2013-01-09 | 核工业北京化工冶金研究院 | Method for treating acid uranium-bearing wastewater by utilizing modified chitosan adsorbents |
| CN105032372A (en) * | 2015-09-11 | 2015-11-11 | 江苏振宇环保科技有限公司 | Method for preparing chitosan-bentonite adsorbing material prepared from shrimp shells |
| CN105170101A (en) * | 2015-08-25 | 2015-12-23 | 集美大学 | Boron composite adsorbent, preparation method and applications thereof |
| CN105217765A (en) * | 2015-09-24 | 2016-01-06 | 福州大学 | A kind of composite macromolecular flocculant and preparation method thereof |
| CN105502733A (en) * | 2015-12-02 | 2016-04-20 | 南京大学 | Method for cooperatively removing and selectively recovering heavy metal cations and non-metal anions from wastewater |
| CN115321657A (en) * | 2022-08-31 | 2022-11-11 | 四川农业大学 | Hydrophobic chitosan-polyaluminum chloride Hmcs-PAC composite flocculant and preparation and application thereof |
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| CN1803275A (en) * | 2005-12-06 | 2006-07-19 | 青岛科技大学 | Novel silica gel loaded cross-linked chitosan adsorbent for heavy metal |
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| CN1803275A (en) * | 2005-12-06 | 2006-07-19 | 青岛科技大学 | Novel silica gel loaded cross-linked chitosan adsorbent for heavy metal |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102500333A (en) * | 2011-10-28 | 2012-06-20 | 上海海洋大学 | Magnetic cationic surfactant modified chitosan / hydroxyapatite / zeolite composite and preparation method and application thereof |
| CN102500333B (en) * | 2011-10-28 | 2013-06-26 | 上海海洋大学 | Magnetic cationic surfactant modified chitosan / hydroxyapatite / zeolite composite and preparation method and application thereof |
| CN102863045A (en) * | 2012-10-10 | 2013-01-09 | 核工业北京化工冶金研究院 | Method for treating acid uranium-bearing wastewater by utilizing modified chitosan adsorbents |
| CN105170101A (en) * | 2015-08-25 | 2015-12-23 | 集美大学 | Boron composite adsorbent, preparation method and applications thereof |
| CN105032372A (en) * | 2015-09-11 | 2015-11-11 | 江苏振宇环保科技有限公司 | Method for preparing chitosan-bentonite adsorbing material prepared from shrimp shells |
| CN105217765A (en) * | 2015-09-24 | 2016-01-06 | 福州大学 | A kind of composite macromolecular flocculant and preparation method thereof |
| CN105502733A (en) * | 2015-12-02 | 2016-04-20 | 南京大学 | Method for cooperatively removing and selectively recovering heavy metal cations and non-metal anions from wastewater |
| CN115321657A (en) * | 2022-08-31 | 2022-11-11 | 四川农业大学 | Hydrophobic chitosan-polyaluminum chloride Hmcs-PAC composite flocculant and preparation and application thereof |
| CN115321657B (en) * | 2022-08-31 | 2023-10-03 | 四川农业大学 | Hydrophobic chitosan-polyaluminium chloride Hmcs-PAC composite flocculant and preparation and application thereof |
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| CN101985101B (en) | 2012-10-31 |
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