CN106179242A - A kind of preparation method and applications of biscuit cross-linked chitosan adsorbent - Google Patents
A kind of preparation method and applications of biscuit cross-linked chitosan adsorbent Download PDFInfo
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- CN106179242A CN106179242A CN201610584695.1A CN201610584695A CN106179242A CN 106179242 A CN106179242 A CN 106179242A CN 201610584695 A CN201610584695 A CN 201610584695A CN 106179242 A CN106179242 A CN 106179242A
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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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28042—Shaped bodies; Monolithic structures
- B01J20/28045—Honeycomb or cellular structures; Solid foams or sponges
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- 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
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
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- 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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Water Treatment By Sorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention belongs to environment functional material field, relate to a kind of method preparing biscuit cross-linked chitosan adsorbent and application thereof.This adsorbent, is that this adsorbent has spongy with transiting state metal ion and the chitosan crosslinked composite being composited；Described transiting state metal ion is metal salt solution, and metal ion content in the composite is 10 ~ 30%, percentage by weight.The adsorbent prepared is applied to the absorption of anionic dye in waste water, and adsorbent input amount is little, reaches time of equilibrium adsorption short, and adsorption capacity is high；Easily separated and can regenerate and reuse.Biscuit cross-linked chitosan adsorbent prepared by the present invention, Antacid effectiveness is good, and adsorption capacity is big, can be directly separated；Remove waste water from dyestuff process simple, environmental friendliness, with low cost, in field of waste water treatment, there is excellent application prospect.
Description
Technical field
The invention belongs to environment functional material technical field, specifically, be that a kind of biscuit cross-linked chitosan is inhaled
The preparation method and applications of attached dose.
Background technology
Along with the development of the industries such as weaving, leather, a large amount of waste water from dyestuff are discharged in water body environment.Due to work
Industry kind of dyes is many, complicated component；Further, synthetic dyestuffs have antibiont degraded, resist photodegradative characteristic to be difficult to from water
In body remove, thus interference and broken ring water body in biological growthing environment, cause serious water pollution.Therefore, waste water from dyestuff
Improvement and reclaiming sustainable development and the environmental conservation of enterprise are had great importance.
At present, the dye waste water treatment method that industry is conventional mainly has physics, chemistry and biological treatment.Wherein at physics
Absorption method in logos is waste water from dyestuff processing method the most direct, maximally effective, is widely used in each big business.The most frequently used suction
Attached dose is activated carbon, but it is difficult to there is solid-liquid separation in actual application, it is impossible to realizes the shortcoming such as recovery of dyestuff, needs research and development one badly
Plant efficient adsorbent it is substituted.In recent years, both at home and abroad new adsorbent and preparation method thereof has been carried out substantial amounts of
Research, most of adsorbents concentrate on the postgraduate of micron, nano material, and this type of adsorbent has that specific surface area is big, absorption
The advantage that capacity is high；But, there is also that granule is little, it is difficult to separate, cannot realize drawbacks such as reusing, in actual commercial Application
In be extremely limited.Chitosan obtain paying much attention in water treatment field as a kind of natural macromolecular material adsorbent and
Widely studied.Containing substantial amounts of amino and hydroxyl functional groups on chitosan molecule chain, to heavy metal in waste water and dye molecule
There is good elimination effect.Therefore this patent utilizes chitosan to study further as novel absorption material, designs one
Kind of biscuit base cross-linked chitosan adsorbent so that it is have that adsorption time is short, adsorption capacity is big, easily separated, repeatable make
Characteristic so that it is be widely used in the process of industrial dye waste water.
Summary of the invention
It is an object of the invention to be to solve existing adsorbent exists that adsorption capacity is little, it is difficult to separate, can not reuse,
The drawback that dyestuff recycles cannot be realized, it is provided that the preparation method of a kind of biscuit cross-linked chitosan adsorbent, and will
This adsorbent is applied to remove anionic dye in waste water.
The purpose of the present invention can be achieved through the following technical solutions.
A kind of biscuit cross-linked chitosan adsorbent, is to be composited with chitosan crosslinked with transiting state metal ion
Composite, this adsorbent has spongy；Described transiting state metal ion is metal salt solution, and metal ion is at composite wood
Content in material is 10 ~ 30%, percentage by weight.
Present invention also offers the preparation method of a kind of biscuit cross-linked chitosan adsorbent, comprise the steps:
1) Chitosan powder is directly dissolved in metal salt solution；Wherein chitosan is 1:2 ~ 1 with the mol ratio of tenor:
4；
2) adding the NaOH solution of 1 ~ 2 mole, the pH value regulating above-mentioned solution is the most neutral, adds the cross-linking agent of 1 ~ 3%, stirs 2
After ~ 4h, stored refrigerated；
3) by 2) solution sprays in liquid nitrogen in aerocolloidal mode by atomizing type by the solution that obtains, it is thus achieved that white solid；
Again this white solid is redissolved in ethanol-water solution, agitated, washing after, it is thus achieved that colloid solution；
4) with mould by colloid solution molding, after drying, it is thus achieved that biscuit cross-linked chitosan adsorbent.
Further, described metal salt solution is the saline solution of titanium, zirconium；The preparation method of described titanium salt solution is by titanium
Acid four butyl esters are dissolved in concentrated hydrochloric acid, remove upper strata Organic substance and obtain；The preparation method of described zirconium salt solution is by oxychlorination
Zirconium is directly dissolved in water and prepares.
Further, described cross-linking agent is glutaraldehyde, formaldehyde, Biformyl or epoxychloropropane, and addition is the 1 of total solution
~ 3%, percentage by weight.
Further, described white solid redissolves in alcohol-water mixed solution, and concentration of alcohol is 40% ~ 60%, weight hundred
Proportion by subtraction.
Further, described drying mode is lyophilization.Other drying mode, is not affecting sorbent shapes, fragility
Under conditions of be used as, the most within the scope of the present invention.
Further, it is that triangle, tetragon, polygon or circle etc. are variously-shaped in preparation process mold shape.
Present invention also offers a kind of biscuit cross-linked chitosan adsorbing material to give up at process dyestuff as adsorbent
Application in water, removes anionic dye in waste water, in particular for adsorbing orange II dyestuff.
The removal of anionic dye, its anionic dye in biscuit cross-linked chitosan Adsorbent For Removal of Heavy of the present invention
Select orange II dyestuff: weigh the adsorbent prepared, record its quality, join in the orange II of variable concentrations,
Regulation pH value, vibrate under room temperature or stir, after question response terminates, utilize ultraviolet spectrophotometer measure solution adsorb before and after dense
Degree, calculates the adsorbent adsorption capacity to orange II according to concentration difference.Test result shows, the adsorbent of the present invention is to orange II
Checkout time is short, adsorbance big, directly take out and can realize separating；Further, the adsorbent low concentration of orange II is adsorbed
NaOH can realize the recovery of dyestuff and the recycling of adsorbent.
Compared with prior art, the positive effect of the present invention is:
(1) the biscuit cross-linked chitosan adsorbent of the present invention, cheaper starting materials, is easy to get, sorbent material controlled shape.
(2) the biscuit cross-linked chitosan adsorbent of the present invention, has good stability, energy in acid condition
High-efficient cleaning removes anionic dye molecule.According to experimental data, the adsorbance of orange II dyestuff is up to 1143 mg/g.
(3) dye molecule can be desorbed from adsorbent by the alkali liquor of low concentration, thus realizes the recovery of dyestuff, adsorbent
Reuse.
(4) adsorbent is after adsorpting dye molecule, has good stability, and can directly remove from waste water, it is achieved separate.
(5) the biscuit cross-linked chitosan adsorbent that prepared by the present invention, preparation method is simple, environmental friendliness, cost
Cheap, its adsorbent capacity is big, easily separated, can realize dyestuff recovery and adsorbent is reused, have good application
Prospect.
Accompanying drawing explanation
Fig. 1 is the shape appearance figure of biscuit titanium crosslink chitosan absorbent.
Fig. 2 is the spongy Titanium cross-linked chitosan adsorbent Adsorption Effect figure to orange II under different solutions pH value.
Fig. 3 is the shape appearance figure that biscuit titanium crosslink chitosan adsorbs orange II.
Fig. 4 be biscuit titanium crosslink chitosan absorbent reuse figure.
Detailed description of the invention:
Being embodied as of the preparation method and applications of the present invention presented below a kind of biscuit cross-linked chitosan adsorbent
Example.
Embodiment 1
Weigh 4.34g butyl titanate solution, add concentrated hydrochloric acid 6mL so that it is fully dissolve；After removing upper organic layer, add water
To 100mL.Weigh 2g Chitosan powder, be slowly added in the hydrochloric acid solution of titanium, stir 1h, Chitosan powder is fully dissolved
And make uniform solution.Neutral with 1M NaOH solution regulation pH value, the glutaraldehyde of addition 5mL 5%, as cross-linking agent, continues to stir
Mixing 2h, at 4 DEG C, stored refrigerated is overnight.Mixed liquor is loaded aerosol apparatus, sprays into acquisition white solid in liquid nitrogen, utilize the second of 50%
Solid is redissolved by alcohol-water mixtures, with stirring 0.5h, obtains colloidal solution after washing 3 ~ 4 times with water.With square mold glue
Freezen protective after the sizing of shape solution, then its lyophilization is obtained biscuit titanium crosslink chitosan absorbent (see figure 1).From
Fig. 1 it can be seen that obtain Titanium cross-linked chitosan become spongy, outward appearance is milky, its quality be 0.0211g ~
0.0236g。
Embodiment 2-11
By the application of biscuit titanium crosslink chitosan absorbent and the absorption research of anionic dye in water, select anion dye
Material is orange II.The pH(pH=2 of regulation different solutions, 3,4,5,6,7,8,9,10,11), the initial concentration of fixing orange II is
100mg/L, carries out adsorption reaction 2h under room temperature, its adsorption curve refers to Fig. 2.As shown in Figure 2, this adsorbent is in acid condition
Orange II is had good adsorption capacity, and optimal pH is 2；And under neutral or basic conditions, orange II is contaminated by adsorbent
Material almost without adsorption effect, this phenomenon be the recovery of dyestuff and adsorbent reuse the condition of creating.
Embodiment 12 ~ 19
In the solution that pH is 2, change initial concentration, from 30mg/L ~ 300mg/L, investigate adsorbent the denseest in difference
Impact on dye adsorption capacity under degree, refers to table 1.
Table 1: adsorbent adsorption capacity to orange II dyestuff under different initial concentrations
As can be drawn from Table 1, under different initial concentrations, adsorbent to the adsorbent solution of orange II along with the increase of initial concentration
And ever-increasing, maximum adsorption capacity is up to 1143mg/g；And under the initial concentration chosen, clear to dyestuff of adsorbent
Except rate is both greater than 80%；When initial concentration is less than 100mg/L, adsorption time 2h, clearance rate is up to more than 97%.Above-mentioned tables of data
Face, biscuit titanium crosslink chitosan absorbent II orange to anion dyestuff has good adsorption effect, and can realize
From waste water, quickly remove dye molecule.Adsorbent after wherein being adsorbed by 100mg/L is taken pictures, and refers to Fig. 3.Can from Fig. 3
To find out, square adsorbent color reddens, and illustrates that orange II adsorbs on its surface；And the shape of square adsorbent does not has
There is the biggest change, it can be seen that, this adsorbent directly can take out from waste water and realize separating.
Embodiment 20 ~ 22
As can be known from Fig. 2, adsorbent is almost 0 to the adsorption capacity of orange II in the basic conditions.Therefore, low concentration is utilized
This is desorbed by NaOH solution, and the orange II of circulation absorption, and its effect curve refers to Fig. 4.As can be drawn from Figure 4, pass through
Three times adsorption-desorption-sorption cycle uses, and adsorbent is also maintained at the level of more than 95%, explanation to the adsorption efficiency of orange II
This adsorbent has good reusability.
Above-mentioned embodiment is the present invention preferably embodiment, but embodiments of the present invention are not real by above-mentioned enforcement
The restriction of example, the change made under other any spirit without departing from the present invention and principle, modify, substitute, combine, letter
Change, all should be the substitute mode of equivalence, within being included in protection scope of the present invention.
Claims (11)
1. a biscuit cross-linked chitosan adsorbent, it is characterised in that be to hand over chitosan with transiting state metal ion
The composite that connection is composited, this adsorbent has spongy；Described transiting state metal ion is metal salt solution, metal from
Son content in the composite is 10 ~ 30%, percentage by weight.
2. the preparation method of a biscuit cross-linked chitosan adsorbent, it is characterised in that comprise the steps:
Chitosan powder is directly dissolved in metal salt solution；Wherein chitosan is 1:2 ~ 1:4 with the mol ratio of tenor；
Add the NaOH solution of 1 ~ 2 mole, regulate the pH value of above-mentioned solution to neutral, add the cross-linking agent of 1 ~ 3%, stirring 2 ~
After 4h, stored refrigerated；
By 2) solution sprays in liquid nitrogen in aerocolloidal mode by atomizing type by the solution that obtains, it is thus achieved that white solid；Again
This white solid is redissolved in ethanol-water solution, agitated, washing after, it is thus achieved that colloid solution；
With mould by colloid solution molding, after drying, it is thus achieved that biscuit cross-linked chitosan adsorbent.
The preparation method of a kind of biscuit cross-linked chitosan adsorbent the most according to claim 2, it is characterised in that
Described metal salt solution is the saline solution of titanium, zirconium.
The preparation method of a kind of biscuit cross-linked chitosan adsorbent the most according to claim 3, it is characterised in that
One of preparation method of described titanium salt solution is to be dissolved in concentrated hydrochloric acid by butyl titanate, removes upper strata Organic substance and obtains.
The preparation method of a kind of biscuit cross-linked chitosan adsorbent the most according to claim 3, it is characterised in that
One of preparation method of described zirconium salt solution is to be directly dissolved in zirconium oxychloride in water to prepare.
The preparation method of a kind of biscuit cross-linked chitosan adsorbent the most according to claim 2, it is characterised in that
Described cross-linking agent is glutaraldehyde, formaldehyde, Biformyl or epoxychloropropane, and addition is the 1 ~ 3% of total solution, percentage by weight.
The preparation method of a kind of biscuit cross-linked chitosan adsorbent the most according to claim 2, it is characterised in that
Described white solid redissolves in alcohol-water mixed solution, and concentration of alcohol is 40% ~ 60%, percentage by weight.
The preparation method of a kind of biscuit cross-linked chitosan adsorbent the most according to claim 2, it is characterised in that
Described drying mode is lyophilization.
The preparation method of a kind of biscuit cross-linked chitosan adsorbent the most according to claim 2, wherein feature exists
In, its preparation process mold shape is that triangle, tetragon, polygon or circle etc. are variously-shaped.
10. a biscuit cross-linked chitosan adsorbing material is as adsorbent application in processing waste water from dyestuff.
The application of 11. biscuit cross-linked chitosan adsorbing materials according to claim 10, is used for adsorbing in waste water
Anionic dye.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108516611A (en) * | 2018-05-30 | 2018-09-11 | 东莞市环境监测中心站（东江水系东莞环境保护监测站） | The preparation method and application of chitosan nano fiber ligand exchanger |
| CN108976468A (en) * | 2018-06-22 | 2018-12-11 | 南京林业大学 | A kind of hydrophobically modified method of sodium alginate sponge and products thereof and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070116955A1 (en) * | 2005-11-18 | 2007-05-24 | National Cheng Kung University | Magnetic nanoparticles and method for producing the same |
| CN102583637A (en) * | 2012-01-17 | 2012-07-18 | 同济大学 | Method for efficiently removing high-concentration dye wastewater by combination of adsorption and photocatalysis |
| CN102974230A (en) * | 2012-12-04 | 2013-03-20 | 天津大学 | Chitosan/titanium dioxide ultrathin hybrid film, and preparation method and application thereof |
-
2016
- 2016-07-25 CN CN201610584695.1A patent/CN106179242B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070116955A1 (en) * | 2005-11-18 | 2007-05-24 | National Cheng Kung University | Magnetic nanoparticles and method for producing the same |
| CN102583637A (en) * | 2012-01-17 | 2012-07-18 | 同济大学 | Method for efficiently removing high-concentration dye wastewater by combination of adsorption and photocatalysis |
| CN102974230A (en) * | 2012-12-04 | 2013-03-20 | 天津大学 | Chitosan/titanium dioxide ultrathin hybrid film, and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| KATSUTOSHI INOUE等: "Adsorptive separation of some metal ions by complexing agent types of chemically modified chitosan", 《ANALYTICA CHIMICA ACTA》 * |
| 张立彦等: "制备条件对壳聚糖/胶原蛋白海绵敷料性能的影响", 《化工进展》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108516611A (en) * | 2018-05-30 | 2018-09-11 | 东莞市环境监测中心站（东江水系东莞环境保护监测站） | The preparation method and application of chitosan nano fiber ligand exchanger |
| CN108976468A (en) * | 2018-06-22 | 2018-12-11 | 南京林业大学 | A kind of hydrophobically modified method of sodium alginate sponge and products thereof and application |
| CN108976468B (en) * | 2018-06-22 | 2020-11-27 | 南京林业大学 | Hydrophobic modification method of sodium alginate sponge, product and application thereof |
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