CN109894095A - A kind of sodium alginate-chitosan composite gel microsphere absorption arsenic removal material and preparation method thereof containing iron and manganese oxides - Google Patents
A kind of sodium alginate-chitosan composite gel microsphere absorption arsenic removal material and preparation method thereof containing iron and manganese oxides Download PDFInfo
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- CN109894095A CN109894095A CN201910241276.1A CN201910241276A CN109894095A CN 109894095 A CN109894095 A CN 109894095A CN 201910241276 A CN201910241276 A CN 201910241276A CN 109894095 A CN109894095 A CN 109894095A
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- sodium alginate
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- manganese oxides
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Abstract
The present invention relates to a kind of sodium alginate-chitosan composite gel microsphere absorption arsenic removal material and preparation method thereof containing iron and manganese oxides, it uses for reference biology and medical field prepares the thinking of sodium alginate-chitosan plural gel, by sodium alginate, the chitosan initiator that dilute hydrochloric acid that mass fraction is 2% is added after deionized water dissolving as electrostatic interaction, mud waste material mixed dissolution is backwashed with the deferrization and demanganization by being ground up, sieved, ultrasonic disperse instills CaCl with peristaltic pump2In solution, the sodium alginate-chitosan composite gel microsphere containing iron and manganese oxides of partial size about 2mm is prepared.By the composite gel microsphere compression strength with higher and stability being crosslinked and electrostatic interaction is formed, convenient for saving, arsenic removal rate is up to 70% or more.The present invention solves that existing arsenic removal material machine compression strength is low, the defect of stability difference, while powdered form ferrimanganic mud that will be discarded recycles, and particulate form (composite gel microsphere) adsorbent is made, convenient for separating after absorption arsenic removal with water body.
Description
Technical field
The invention belongs to water treatment fields, and in particular to a kind of sodium alginate-chitosan containing iron and manganese oxides is compound solidifying
Glue microballoon absorption arsenic removal material and preparation method thereof.
Background technique
Arsenic is considered as that drinking water Poisoning is maximum, one of carcinogenic natural pollutant.With mankind's activity and industry hair
Exhibition, water body arsenic pollution have become the environmental problem of global concern, and long-term water energy of the intake containing arsenic leads to the generation of various diseases,
It is serious also to cause death.Therefore, the World Health Organization (WHO), USA and EU Environmental Protection Agency provide Arsenic in Drinking Water
10 μ g/L of limiting concentration value, also by the concentration mark of arsenic in China's latest edition " standards for drinking water quality " (GB 5749-2006)
Standard is reduced to 10 μ g/L by 50 μ g/L.
Currently, there is the common methods of arsenic removal in water process: absorption method, membrane separation process, ion-exchange, microbial method etc.,
Wherein absorption method is widely used because of having the advantages that efficient, economical, easy to operate.In numerous adsorbent materials, iron
AS (III) in water body can be oxidized to AS (V) by manganese base adsorbent, and had good effect of removing arsenic and be concerned and grind
Study carefully.However, the iron and manganese oxides of powdered form are after absorption, it is difficult to be separated from the water recycling, deal with improperly, can generate new
Environmental problem.To solve separation problem, many novel absorption materials are made of in recent years, such as ferrimanganic mud-sodium alginate gel
Microballoon, ferrimanganic mud-chitosan gel rubber microballoon etc., though solving the separation problem after absorption, all there is certain defects.Such as iron
Manganese mud-sodium alginate gel microsphere compression strength is insufficient, easily swells after water suction, and there are resistance to for chitosan gel rubber microballoon for ferrimanganic mud-
The defects of acid poor, mass density is small, stability is poor.
Based on the above issues, novel absorption arsenic removal material is urgently excavated.
Summary of the invention
The present invention is to use for reference biology and medical field preparation for shortcoming present in current absorption arsenic removal material
It is micro- to provide a kind of sodium alginate-chitosan plural gel containing iron and manganese oxides for the thinking of sodium alginate-chitosan plural gel
Ball absorption arsenic removal material and its methods for making and using same, to efficiently remove the arsenic in water.
In order to solve the above-mentioned technical problem, The technical solution adopted by the invention is as follows:
A kind of sodium alginate-chitosan composite gel microsphere absorption arsenic removal material containing iron and manganese oxides, it is characterized in that:
The composite gel microsphere adsorbent material be by sodium alginate, chitosan 2-2.5 ratio than 1 in mass ratio be dissolved in from
In sub- water, and electrostatic interaction occurs for the dilute hydrochloric acid acidification for being 2% by mass fraction, and by being ground up, sieved except iron removes
Manganese backwashes mud waste material and is mixed into uniform solution by 1.5-2 mass ratio than 1, and through peristaltic pump nozzle diameter
The pipe of 0.5-1mm is added dropwise to CaCl2In solution, mixed liquor will be cross-linked to form with certain compression strength and compared with stiff stability
Composite gel microsphere, partial size 1.8-2.5mm.
A kind of preparation method of the sodium alginate-chitosan composite gel microsphere absorption arsenic removal material containing iron and manganese oxides,
Include the following steps:
(1) backwashing wastewater in deferrization and demanganization filter tank of the iron and manganese oxides from collection settles a few days, separates top
Water, takes out the ferrimanganic mud of bottom, natural air drying, sieve with 100 mesh sieve after being grinded with a mortar be placed in it is spare at dry；
(2) (sodium alginate, chitosan mass ratio are 2-2.5 ratios to the sodium alginate and Chitosan powder for weighing certain mass
1), with deionized water dissolving, and it is 2% dilute hydrochloric acid that mass fraction, which is added, and magnetic agitation 30-45min is mixed at 40~60 DEG C
Uniformly, it stands at room temperature and treated iron and manganese oxides are added after degassing 30-45min continue magnetic agitation 1-2h, and through super
Sound dispersion disperses the large-size particles that partial size is more than 0.1mm, spare；
(3) CaCl that mass fraction is 2-5% is prepared2Solution, it is spare；
(4) it is connected on wriggling pump hose, is adjusted to suitable pump speed (60- using nozzle diameter 0.5-1mm pipe
150rpm), sodium alginate-chitosan-ferrimanganic mud mixture is instilled into CaCl2In solution, diameter 1.8-2.5mm is formed it into,
Uniform composite gel microsphere；
(5) being formed by plural gel ball microballoon need to be in CaCl2Strengthen 12-24h in solution, sufficiently uses deionization after reaction
Water flushing three times spare；
(6) the plural gel ball use in a short time prepared in aforementioned manners can will save in deionized water, long-term preservation
Gel ball can be taken out, be freeze-dried after drying 12-24h at 50-60 DEG C in an oven after 10-12h and be sealed.
Compared with prior art, the beneficial effects of the present invention are:
1, the thinking that biology and medical field prepare sodium alginate-chitosan gel is used to prepare Fe-Mn oxidation by the present invention
On object adsorbent, the sodium alginate-chitosan composite gel microsphere containing iron and manganese oxides of acquisition is mutual by crosslinking and electrostatic
Effect has compression strength high, and stability is strong, is convenient for the features such as saving；
2, the sodium alginate-chitosan composite gel microsphere of the present invention containing iron and manganese oxides has good absorption
Performance, can not only arsenic-adsorbing, moreover it is possible to and the big AS of toxicity (III) is oxidized to AS (V), has effects that oxidation and adsorption dual, it is right
AS (III) and AS (V) has good removal effect；
3, the present invention prepares the backwash mud that raw material is deferrization and demanganization filter tank, and preparation process reaction condition is mild, to waste
It recycles and provides environmentally protective new approaches；
4, it the present invention can obtain particulate form microsphere adsorbing agent, is separated after being easy to absorb arsenic removal with water body.
5, the sodium alginate-chitosan composite gel microsphere of the present invention containing iron and manganese oxides can use dilute hydroxide
It is continued to use after sodium solution regeneration.
Detailed description of the invention
Fig. 1 is that embodiment 1 obtains the sodium alginate-chitosan composite gel microsphere adsorbent material containing iron and manganese oxides
Fig. 2 is that embodiment 2 obtains the sodium alginate-chitosan composite gel microsphere adsorbent material containing iron and manganese oxides
Specific embodiment
Now by taking laboratory simulation experiment as an example, non-limiting examples are described below:
Embodiment 1
The deferrization and demanganization water factory biofilter operated normally is selected, the backwashing wastewater in filter tank, quiet heavy a few days, separation are collected
Supernatant, takes out the ferrimanganic mud of bottom, natural air drying, sieves with 100 mesh sieve that be placed in natural air drying at dry spare after being grinded with a mortar.
It weighs 7g sodium alginate and 3g Chitosan powder is put into beaker, with 150ml deionized water dissolving, the magnetic at 45 DEG C
After power stirs 5min, the dilute hydrochloric acid that 1ml mass fraction is 2% is added and continues to stir evenly.After standing degassing 30min at room temperature
5g treated ferrimanganic mud is added and continues magnetic agitation to being uniformly mixed, it is spare.
Prepare the CaCl that 100ml mass fraction is 2.5%2Solution installs pipe on wriggling pump hose in conical flask
The pipe that mouth diameter is 1mm, is added drop-wise to configured mass fraction for sodium alginate-chitosan ferrimanganic mud mixed liquor with peristaltic pump
For 2.5% CaCl2In solution, adjustment pump speed is 120rpm, makes the microballoon that gel particle is about 2mm at the partial size of rule.It will
Sodium alginate-chitosan composite gel microsphere obtained containing iron and manganese oxides is in CaCl2Strengthening 12h in solution can reach
To certain intensity.It is washed with deionized 3 times, obtains the sodium alginate-chitosan composite gel microsphere containing iron and manganese oxides
Adsorbent material (as shown in Figure 1).
The 1g arsenic removal material, and detection architecture are added in AS (V) solution that 100ml initial concentration is 10mg/L, ph=7
The concentration of middle AS (V) changes with time, calculating AS (V) removal rate, and after 12h, which can to the removal rate of AS in solution (V)
Reach 81.62%.
Embodiment 2
The deferrization and demanganization water factory biofilter operated normally is selected, the backwashing wastewater in filter tank, quiet heavy a few days, separation are collected
Supernatant, takes out the ferrimanganic mud of bottom, natural air drying, sieves with 100 mesh sieve that be placed in natural air drying at dry spare after being grinded with a mortar.
It weighs 10g sodium alginate and 5g Chitosan powder is put into beaker, with 200ml deionized water dissolving, at 45 DEG C
After magnetic agitation 5min, the dilute hydrochloric acid that 1ml mass fraction is 2% is added and continues to stir evenly.Degassing 30min is stood at room temperature
5g treated ferrimanganic mud is added after not having bubble to emerge and continues magnetic agitation to being uniformly mixed, it is spare.
Prepare the CaCl that 100ml mass fraction is 5%2It is straight to install nozzle in conical flask on wriggling pump hose for solution
Diameter is the pipe of 1mm, and sodium alginate-chitosan ferrimanganic mud mixed liquor, which is added drop-wise to configured mass fraction, with peristaltic pump is
5% CaCl2In solution, adjustment pump speed is 100rpm, makes the microballoon that gel particle is about 2mm at the partial size of rule.It will be made
The sodium alginate-chitosan composite gel microsphere containing iron and manganese oxides in CaCl2One can be reached by strengthening 12h in solution
Fixed intensity.It is washed with deionized 3 times, by freeze-drying after taking-up, places into baking oven and dried for 24 hours at 50 DEG C, obtained
To dry and sodium alginate-chitosan composite gel microsphere particle (as shown in Figure 2) of the rough surface containing iron and manganese oxides.
The 0.1g arsenic removal material is added in AS (V) solution that 100ml initial concentration is 20mg/L, ph=7, and detects body
The concentration of AS (V) changes with time in system, calculating AS (V) removal rate, after 12h, removal rate of the material to AS in solution (V)
It can reach 73.47%.
Claims (4)
1. a kind of preparation method of the sodium alginate-chitosan composite gel microsphere absorption arsenic removal material containing iron and manganese oxides,
It is characterized in that:
Iron and manganese oxides used are from deferrization and demanganization filter back washing ferrimanganic mud, and after natural air drying, grinding is sieved with 100 mesh sieve；
By sodium alginate, ratio dissolution of the chitosan in mass ratio 2-2.5 than 1 in deionized water, and passes through mass fraction and is
Electrostatic interaction occurs for 2% dilute hydrochloric acid acidification, and through the deferrization and demanganization filter back washing ferrimanganic mud that being ground up, sieved by
1.5-2 mass ratio than 1 is mixed into uniform solution, and is dripped through peristaltic pump with the pipe that nozzle diameter is 0.5-1mm
Enter to CaCl2In solution, in CaCl2Strengthen 12-24h in solution and obtains plural gel ball.
2. according to the method described in claim 1, it is characterized by:
The magnetic agitation 30- at 40~60 DEG C is added after the dilute hydrochloric acid that mass fraction is 2% in sodium alginate-chitosan mixture
45min makes it uniformly, then stands at room temperature and treated iron and manganese oxides are added after degassing 30-45min continue magnetic agitation
1-2h, through ultrasonic disperse by partial size be more than 0.1mm large-size particles dispersion, it is spare.
3. according to the method described in claim 1, it is characterized by:
The hydrochloric acid content of addition is the CaCl that every 100ml mass fraction is 2-5%2The dilute hydrochloric acid that mass fraction is 2% is added in solution
1ml；It is that control speed be 60-150rpm by the sodium alginate-containing iron and manganese oxides to 0.5-1mm by peristaltic pump and nozzle diameter
Chitosan compound instills CaCl2The gel micro-ball that diameter is 1.8-2.5mm is made in solution.
4. according to the method described in claim 1, it is characterized in that
The plural gel ball uses in a short time saves plural gel ball in deionized water, and long-term preservation takes gel ball
Out and it is freeze-dried 10-12h, is sealed after 50-60 DEG C of drying 12-24h in an oven.
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| CN112007619A (en) * | 2020-08-28 | 2020-12-01 | 玉林师范学院 | Chitosan calcium carbonate composite adsorbent for adsorption and preparation method thereof |
| CN112169776A (en) * | 2019-07-05 | 2021-01-05 | 天津工业大学 | Preparation method of adsorbing material for efficient recovery of sodium alginate in printing wastewater and textile washing |
| CN112221477A (en) * | 2020-09-28 | 2021-01-15 | 湖北富邦科技股份有限公司 | Polyacrylamide modified Fe-Mn-S/sodium alginate composite microsphere and preparation method thereof |
| CN112246225A (en) * | 2020-09-28 | 2021-01-22 | 湖北富邦科技股份有限公司 | Method for continuously producing sodium alginate microspheres capable of efficiently removing heavy metals |
| CN113976074A (en) * | 2021-11-23 | 2022-01-28 | 沈阳建筑大学 | Iron-manganese mud composite gel ball adsorption antimony removal material and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112007619B (en) * | 2020-08-28 | 2023-03-31 | 玉林师范学院 | Chitosan calcium carbonate composite adsorbent for adsorption and preparation method thereof |
| CN112221477A (en) * | 2020-09-28 | 2021-01-15 | 湖北富邦科技股份有限公司 | Polyacrylamide modified Fe-Mn-S/sodium alginate composite microsphere and preparation method thereof |
| CN112246225A (en) * | 2020-09-28 | 2021-01-22 | 湖北富邦科技股份有限公司 | Method for continuously producing sodium alginate microspheres capable of efficiently removing heavy metals |
| CN113976074A (en) * | 2021-11-23 | 2022-01-28 | 沈阳建筑大学 | Iron-manganese mud composite gel ball adsorption antimony removal material and preparation method thereof |
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