CN106853362B - A kind of chitosan/aluminium hydroxide compound adsorbent preparation method for adsorbing fluorine - Google Patents
A kind of chitosan/aluminium hydroxide compound adsorbent preparation method for adsorbing fluorine Download PDFInfo
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- CN106853362B CN106853362B CN201710017631.8A CN201710017631A CN106853362B CN 106853362 B CN106853362 B CN 106853362B CN 201710017631 A CN201710017631 A CN 201710017631A CN 106853362 B CN106853362 B CN 106853362B
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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
- B01J20/02—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
- B01J20/08—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 comprising aluminium oxide or hydroxide; comprising bauxite
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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
- B01J20/28016—Particle form
- B01J20/28019—Spherical, ellipsoidal or cylindrical
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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
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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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
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing compounds
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Abstract
The present invention is directed to existing environmental problem, provides a kind of chitosan/aluminium hydroxide compound adsorbent preparation method for adsorbing fluorine.It first uses aluminum saline solution to dissolve chitosan for solvent, then sodium hydroxide solution is added dropwise in dissolution acquired solution, in-situ preparation chitosan/aluminium hydroxide compound adds glutaraldehyde solution crosslinking, chitosan/aluminium hydroxide adsorbent can be obtained.Preparation method of the present invention is economic and environment-friendly, and can realize compound on chitosan and aluminium hydroxide molecular level, is conducive to be prepared the adsorbent for having high adsorption effect to fluorine.
Description
Technical field
The invention belongs to field of environmental technology, and in particular to a kind of chitosan/aluminium hydroxide compound adsorbent for adsorbing fluorine
Preparation method.
Background technique
Absorption method is one of the technology of water fluoridation of current most study, and absorption method is to utilize high-specific surface area, Yi Zaisheng
Adsorbent material, by the way that the fluorine ion dissolved in water is adsorbed to reducing fluorine content the effects of physics, chemistry.Adsorbent absorption
The ability of fluorine depends on sorbent used type and performance.The specific surface area of adsorbent is bigger, and adsorption site is more, adsorption energy
Power is stronger.
According to the difference of raw material, the adsorbent for removing fluorine in fluorinated water can be divided into: modified zeolite class adsorbent, aluminium salt absorption
Agent, molysite adsorbent, terres rares adsorbent, biological adsorption agent and other class adsorbents.The cost of absorption method is low, and fluorine removal is imitated
Fruit is good, is always the important method of fluoride wastewater treatment.But traditional adsorbent does not enable the adsorption capacity of fluorine ion in water
People is satisfied.Therefore, research and develop that a kind of new, the de-fluoridation adsorbent with higher cost benefit is particularly significant.
Chitosan and aluminium salt are all the common adsorbents for adsorbing fluorine, and in the research of forefathers, single chitosan-based and shell is poly-
Sugar/aluminium salt compound adsorbent has report.Wen Yuezhong is reported in its patent (CN102671633 B) is dissolved in chlorine for chitosan
Change in aluminum water solution, add ferric chloride solution, obtain chitosan/aluminium chloride/iron chloride composite solution, be added precipitating reagent without
Water-ethanol is added in glutaraldehyde water solution and is crosslinked after obtaining solid precipitating, obtains chitosan aluminum-iron composite adsorbent, have studied
Its adsorption effect to fluorine ion in water.But this chitosan aluminum-iron composite adsorbent after adsorbing fluorine the problem is that be easy
Chloride ion is introduced in water.
In order to prepare chitosan/aluminium hydroxide compound adsorbent that a kind of pair of fluorine has high adsorption, invention
A kind of preparation method of chitosan/aluminium hydroxide compound adsorbent.Chitosan is dissolved using aluminum saline solution first, is prepared
Chitosan/aluminum salt solution, then chitosan/aluminum saline solution is added in sodium hydroxide solution, so that aluminium salt is converted into situ
Aluminium hydroxide obtains chitosan/aluminium hydroxide bead, this is distinct with the patent CN102671633 B of Wen Yuezhong, is
Chitosan/aluminium chloride/iron chloride composite solution is obtained after physics is miscible, and the present invention is to obtain shell by chemical reaction to gather
Sugar/aluminium hydroxide bead, and removing chloride is removed after may filter that, it then adds glutaraldehyde or epichlorohydrin solution crosslinking is prepared into
To chitosan/aluminium hydroxide compound adsorbent, the spherical compound adsorbent large specific surface area of formation, adsorption effect is more preferable.
Summary of the invention
The present invention is directed to existing environmental problem, provides a kind of chitosan/aluminium hydroxide compound adsorbent for adsorbing fluorine
Preparation method.The present invention directlys adopt aluminum saline solution dissolution chitosan, and generates aluminum hydroxide precipitation in situ, and it is poly- to obtain shell
Sugar/aluminium hydroxide composite pellets, present invention process route is simple, and the composite adsorption for having high adsorption effect to fluorine can be prepared
Agent.
The purpose of the present invention is what is realized by following technical measures, wherein the raw material score is unless otherwise specified, it is
Weight fraction.
It is a kind of adsorb fluorine chitosan/aluminium hydroxide compound adsorbent preparation method, be first use aluminum saline solution for
Solvent dissolves chitosan aluminium salt composite solution, then will be added drop-wise in sodium hydroxide solution in dissolution acquired solution, in-situ preparation shell
Chitosan/aluminium hydroxide composite pellets are then added in glutaraldehyde or epichlorohydrin solution and hand over by glycan/aluminium hydroxide composite pellets
Connection, can be obtained chitosan/aluminium hydroxide adsorbent.
Specific step is as follows:
(1) it is dissolved in deionized water using aluminium salt and is made into 1 ~ 3 wt% aqueous solution, add chitosan into aluminum saline solution
In, and 1 ~ 2 h of heating stirring in 60 ~ 90 DEG C of water-baths, obtain 1 ~ 5 wt% chitosan aqueous solution；
(2) chitosan aqueous solution being prepared in (1) is added dropwise to 4 ~ 10 wt% sodium hydrate aqueous solutions simultaneously with strong
Strong stirring action obtains chitosan/aluminium hydroxide bead, and is rinsed with deionized water and remove chloride ion；
(3) chitosan being prepared in (2)/aluminium hydroxide bead is added to 5 ~ 10 wt% glutaraldehydes or epichlorohydrin water
In solution, the volume mass ratio of glutaraldehyde or epichlorohydrin solution and chitosan is 1mL:1g, full cross-linked anti-at 30 ~ 60 DEG C
1 ~ 2 h is answered, and chitosan/aluminium hydroxide that gained is crosslinked is rinsed with deionized water, to remove unreacted glutaraldehyde or table
Chloropharin solution；
(4) above-mentioned gained chitosan/aluminium hydroxide is crosslinked bead drying for standby in freeze drier, can obtained to fluorine
Chitosan with high adsorption/aluminium hydroxide compound adsorbent.
Wherein the mass ratio of chitosan and sodium hydroxide is 1:2 ~ 1:5.
Wherein the volume mass ratio of glutaraldehyde or epichlorohydrin solution and chitosan is 1mL:1g.
Wherein aluminium salt is aluminium chloride or aluminum nitrate.
The present invention has the advantage that
(1) the use of aluminum saline solution is chitosan solvent, avoids the use of the conventional solvent acetic acid of chitosan, dissolving
It can preferably protect chitosan non-degradable in the process, obtain chitosan aluminium salt composite solution.
(2) after dissolution obtains chitosan aluminium salt composite solution, sodium hydroxide is added drop-wise in chitosan aluminium salt composite solution
In solution, so that the aluminium salt in solution is converted into aluminium hydroxide, chitosan/aluminium hydroxide composite pellets are obtained.
(3) in the present invention, aluminum salt solution both provides solute effect to chitosan, also can be used as the forerunner of aluminium hydroxide
Body uses.The preparation method of adsorbent is economic and environment-friendly, and can realize it is compound on chitosan and aluminium hydroxide molecular level, favorably
In the adsorbent for having high adsorption effect to fluorine is prepared.
Specific embodiment
Further to disclose rather than the present invention is limited, the present invention is described in further detail below in conjunction with example.
Embodiment 1
1.0 g chitosans are taken, 0.5 g Aluminium chloride hexahydrate is dissolved in 48.5 g deionized waters, heats under 90 DEG C of water-baths
2 h are stirred, so that chitosan is completely dissolved, chitosan/aluminum chloride aqueous solution is prepared, 15 ml are added dropwise in the solution
10 wt% sodium hydrate aqueous solution, chitosan/aluminum hydroxide precipitation can be continuously generated in solution, by chitosan/hydroxide
Aluminum precipitation deionized water repeated flushing, then gained floccule is added to 15 ml 10 wt% glutaraldehyde solution in 40 DEG C
2 h of lower crosslinking, and products therefrom is dried into 24 h in freeze drier, chitosan/aluminium hydroxide compound adsorbent can be obtained.
Embodiment 2
1.0 g chitosans are taken, 1.0 g, six nitric hydrate aluminium is dissolved in 48 g deionized waters, heats and stir under 90 DEG C of water-baths
2 h are mixed, so that chitosan is completely dissolved, chitosan/aluminum chloride aqueous solution is prepared, is added dropwise 15 ml's in the solution
The sodium hydrate aqueous solution of 10 wt% can be continuously generated chitosan/aluminum hydroxide precipitation in solution, by chitosan/aluminium hydroxide
Precipitating deionized water repeated flushing, then gained floccule is added to 15 ml 10 wt% glutaraldehyde solution at 40 DEG C
2 h are crosslinked, and products therefrom is dried into 24 h in freeze drier, chitosan/aluminium hydroxide compound adsorbent can be obtained.
Embodiment 3
1.5 g chitosans are taken, 1.5 g Aluminium chloride hexahydrates are dissolved in 47 g deionized waters, heat and stir under 90 DEG C of water-baths
2 h are mixed, so that chitosan is completely dissolved, chitosan/aluminum chloride aqueous solution is prepared, is added dropwise 25 ml's in the solution
The sodium hydrate aqueous solution of 10 wt% can be continuously generated chitosan/aluminum hydroxide precipitation in solution, by chitosan/aluminium hydroxide
Precipitating deionized water repeated flushing, then gained floccule is added to 25 ml 10 wt% glutaraldehyde solution at 60 DEG C
2 h are crosslinked, and products therefrom is dried into 24 h in freeze drier, chitosan/aluminium hydroxide compound adsorbent can be obtained.
Embodiment 4
2.5 g chitosans are taken, 2.0 g Aluminium chloride hexahydrates are dissolved in 45.5 g deionized waters, heat under 90 DEG C of water-baths
2 h are stirred, so that chitosan is completely dissolved, chitosan/aluminum chloride aqueous solution is prepared, 35 ml are added dropwise in the solution
10 wt% sodium hydrate aqueous solution, chitosan/aluminum hydroxide precipitation can be continuously generated in solution, by chitosan/hydroxide
Aluminum precipitation deionized water repeated flushing, then gained floccule is added to 40 ml 10 wt% glutaraldehyde solution in 60 DEG C
2 h of lower crosslinking, and products therefrom is dried into 24 h in freeze drier, chitosan/aluminium hydroxide compound adsorbent can be obtained.
Embodiment 5
2.5 g chitosans are taken, 2.5 g Aluminium chloride hexahydrates are dissolved in 45 g deionized waters, heat and stir under 90 DEG C of water-baths
2 h are mixed, so that chitosan is completely dissolved, chitosan/aluminum chloride aqueous solution is prepared, is added dropwise 35 ml's in the solution
The sodium hydrate aqueous solution of 10 wt% can be continuously generated chitosan/aluminum hydroxide precipitation in solution, by chitosan/aluminium hydroxide
Precipitating deionized water repeated flushing, then gained floccule is added to 40 ml 10 wt% glutaraldehyde solution at 60 DEG C
2 h are crosslinked, and products therefrom is dried into 24 h in freeze drier, chitosan/aluminium hydroxide compound adsorbent can be obtained.
The test that chitosan in embodiment 1-5/aluminium hydroxide compound adsorbent is carried out to following adsorption experiment, as a result arranges
In table 1:
Chitosan/aluminium hydroxide the compound adsorbent respectively prepared in 0.1 g embodiment 1-5 is added separately to 500 ml's
Fluorinion concentration is to be then placed in water-bath constant temperature oscillator in the aqueous solution of 10 mg/L, vibrate 24 at 150 rpm respectively
Then h with the concentration of M519 type fluorine ionometer measurement fluorine ion and calculates adsorbance according to the following formula.
Fluorine ion adsorbance qe (mg/g)= (Ci−Ce)V/m×1000 mg F−/g
Wherein, CiIt (mg/L) is F in waste water−Initial concentration；Ce(mg/L) be adsorption equilibrium when F−Initial concentration；V
(L) be fluoride waste volume；M (g) is sorbent used quality.
1 chitosan of table/iron hydroxide compound adsorbent performance indicator
As can be seen from Table 1, the chitosan/aluminium hydroxide compound adsorbent prepared in example 1-5 is adsorbed to have fluorine ion
There is preferable adsorption effect, and is improved with the increase of chlorination aluminium content in compound adsorbent.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, is all covered by the present invention.
Claims (4)
1. a kind of chitosan/aluminium hydroxide compound adsorbent preparation method for adsorbing fluorine, it is characterised in that: water-soluble using aluminium salt
Liquid directly dissolves chitosan, and chitosan/aluminum saline solution is prepared, and adds sodium hydroxide solution and generates chitosan/hydrogen-oxygen
Change aluminum precipitation bead, and the precipitated pellets are added in glutaraldehyde or epichlorohydrin solution and are crosslinked；Specific step is as follows:
Step 1: it is dissolved in deionized water using aluminium salt and is made into 1 ~ 3 wt% aqueous solution, added chitosan into aluminum saline solution,
And 1 ~ 2 h of heating stirring in 60 ~ 90 DEG C of water-baths, obtain 1 ~ 5 wt% chitosan aqueous solution；
Step 2: the chitosan aqueous solution being prepared in step 1 being added dropwise in 4 ~ 10 wt% sodium hydrate aqueous solutions, and companion
With strong stirring action, chitosan/aluminium hydroxide bead is obtained；
Step 3: the chitosan being prepared in step 2/aluminium hydroxide bead is added to 5 ~ 10 wt% glutaraldehydes or epichlorohydrin water
In solution, 1 ~ 2 h of full cross-linked reaction at 30 ~ 60 DEG C, and chitosan/aluminium hydroxide that gained is crosslinked is rushed with deionized water
It washes, to remove unreacted glutaraldehyde or epichlorohydrin solution；
Step 4: step 3 gained chitosan/aluminium hydroxide being crosslinked bead drying for standby in freeze drier, it is poly- to obtain shell
Sugar/aluminium hydroxide compound adsorbent.
2. a kind of chitosan/aluminium hydroxide compound adsorbent preparation method for adsorbing fluorine according to claim 1,
Be characterized in that: the mass ratio of chitosan and sodium hydroxide is 1:2 ~ 1:5.
3. a kind of chitosan/aluminium hydroxide compound adsorbent preparation method for adsorbing fluorine according to claim 1,
Be characterized in that: wherein the volume mass ratio of glutaraldehyde or epichlorohydrin solution and chitosan is 1mL:1g.
4. a kind of chitosan/aluminium hydroxide compound adsorbent preparation method for adsorbing fluorine according to claim 1,
Be characterized in that: wherein aluminium salt is aluminium chloride or aluminum nitrate.
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| CN107376859A (en) * | 2017-08-14 | 2017-11-24 | 东华理工大学 | A kind of glutaraldehyde cross-linking chitosan/nickel hydroxide microballoon compound adsorbent preparation method |
| CN109821510A (en) * | 2019-02-28 | 2019-05-31 | 长沙埃比林环保科技有限公司 | A kind of preparation method of chitosan composite adsorbing material |
| CN111013549B (en) * | 2019-12-26 | 2022-05-03 | 西南石油大学 | Preparation method and application of modified chitosan fluoride ion adsorbent |
| CN111282556B (en) * | 2020-03-27 | 2023-03-28 | 神华神东煤炭集团有限责任公司 | Defluorination composite fiber membrane, preparation method and application thereof |
| CN113952920A (en) * | 2020-07-21 | 2022-01-21 | 天津大学 | Preparation method and application of millimeter-grade aluminum-lanthanum composite hydroxide gel ball adsorbent |
| CN114437152B (en) * | 2021-12-31 | 2024-03-26 | 蚌埠市华东生物科技有限公司 | Decoloring and impurity removing method for stevioside aqueous extract |
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