CN102872825A - Composite adsorption material for removing arsenic ions from natural water and preparation method for adsorption material - Google Patents
Composite adsorption material for removing arsenic ions from natural water and preparation method for adsorption material Download PDFInfo
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- CN102872825A CN102872825A CN2012103417493A CN201210341749A CN102872825A CN 102872825 A CN102872825 A CN 102872825A CN 2012103417493 A CN2012103417493 A CN 2012103417493A CN 201210341749 A CN201210341749 A CN 201210341749A CN 102872825 A CN102872825 A CN 102872825A
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Abstract
The invention discloses a composite adsorption material for removing arsenic ions from natural water and a preparation method for the adsorption material. Modified spent grains and a hydroxyl iron ion solution are used as raw materials. The method comprises the following steps of: adding spent grains subjected to high temperature treatment into a Ca(OH)2 solution for reacting, gelatinizing, aging, washing by using water and absolute ethanol, performing suction filtering, putting into a muffle furnace for firing, cooling, adding distilled water to prepare suspension, adding the hydroxyl iron ion solution, stirring, standing, washing a lower precipitate, drying, and grinding to obtain the adsorption material which has high adsorption property and can be strongly combined with the arsenic ions in the water. The preparation method is innovative, novel and unique, and the prepared material has a good adsorption effect on the arsenic ions in the water.
Description
Technical field
The present invention relates to a kind of composite adsorbing material of removing arsenic ion in the natural water body and preparation method thereof, be specifically related to contain the advanced treating of arsenic ion water body, belong to field of waste water treatment in the environmental protection.
Background technology
Arsenic is a kind of metalloid, because its a lot of characteristics are similar to heavy metal, therefore sometimes it is classified as the row of heavy metal.A large amount of arsenide is present in water, bed mud, soil, plant, marine organisms and the human body with different shape by chemical process and bio-transformation, and forms circulation between each arsenide.Matter arsenic is water insoluble, is absorbed hardly and fully discharge behind the absorption organism, and is generally harmless; But there are many arsenates soluble in water, such as arsenous acid anhydride, arsenic anhydride, sodium arsenite, natrium arsenicum.The water-soluble formation arsenous of arsenous acid anhydride is high, and is larger than the toxicity of arsenic acid.As
3+The strongest to cytotoxicity, the toxicity with arsenic trioxide (being commonly called as arsenic in a natural state, arsenic etc.) is the most violent especially, and its solubility can be up to 30%.As
3+Enter in the human body, except effect has the obvious effect As to mitochondrial respiratory
3+Also can form specific bond with the sulfydryl of zymoprotein (--SH yl) reaction bonded, the catalytic action of inhibitory enzyme, the breathing of block cell and aobvious toxic action, thus the system of affecting the nerves and capillary permeability have spread effect to skin and mucous membrane.Through arsenic and the compound of mucous membrane or skin absorption, major sedimentary is at organs such as hair, nail, bone, liver and kidneys.Can occur feel sick after the poisoning, vomiting, stomachache, four limbs cramp, cause at last stupor, tic, respiratory paralysis and death.If slow poisoning also can cause liver.Renal damage and multiple peripheral neuritis finally can cause lung cancer, cutaneum carcinoma.The arsenic contamination situation of China also allows of no optimist, arsenic content is up to 0.2～2.0mgAs/L in the ground such as the Inner Mongol, the river bend, the Taiwan drinking-water, the serious existing water environment quality standard≤0.05mgAs/L of China (GB3838-2002) that surpasses causes endemic arsenic poisoning.
The pollution of arsenic environment will be difficult to eliminate in environment in case form, particularly to the pollution of water body, and finally can be by food chain or the surface water, underground water enters human body and harm humans is healthy.In the face of the critical conditions of water body arsenic contamination, need research badly, develop arsenic, cadmium treatment technology in the water of high-efficiency and economic, to solve as soon as possible water body arsenic, cadmium pollution to the threat of human survival.
At present, mainly contain ion-exchange, membrane separation process and absorption method etc. about the several common methods of processing industrial arsenic-containing waste water both at home and abroad.Ion-exchange is to exchange and the method for removing the harmful ion in the waste water with the ion on the ion-exchanger and the ion in the waste water, have recycling, treating capacity is large, effluent quality good, the advantage of water re-using, but the defective of maximum was exchanger vulnerable to pollution or oxidation deactivation when ion-exchange was processed waste water, the cost of exchanger resin regeneration is high, be subject to a certain extent the restriction of capacity, one-time investment is larger, and auxiliary device is more, and operating cost is high; Membrane separation process is the technology of selectively carrying out separating substances of utilizing macromolecule or inorganic pellicle to have, have the advantage that separative efficiency is high, power consumption is low is arranged, can reclaim cadmium metal simultaneously, but the difficult design of membrane module, invest also highlyer, affected the application of embrane method; Absorption method is because being a kind of method of removing arsenic ion that is widely used in from the aqueous solution, wherein reaches the purpose of arsenic ion in the removal water between adsorbent and the arsenic ion by electrostatic interaction or adsorbent and arsenic ion chelating.Traditional adsorbent has active carbon, ion exchange resin.Active carbon has that specific area is large, the characteristics of porous, but regeneration cost is higher.Ion exchange resin has the advantage that specific area is large, the porous absorption property is high, but preparation cost is high, complex process.Therefore, need a kind of cost of exploitation low, the sorbing material of wide material sources.
The waste beer grain claims again spent grains, is the Main By product (accounting for more than 80% of accessory substance) in the brewing industry, is take barley as raw material, the residue of soluble-carbohydrate in fermentation extraction seed.According to statistics, every production 1t beer approximately produces the brewex's grains (moisture content 75～80%) of 1/4t, oneself reaches more than 1,000 ten thousand t at present China's brewex's grains annual production, wherein the mass fraction of protein is 23%～27%, it is a kind of good protein resource, and not only contain rich in protein in the wheat grain, also contain abundant crude fibre and fat to wait composition, therefore through making good sorbing material after the processing.
Summary of the invention
The present invention is directed to the high problem of present sorbing material preparation cost, provide a kind of modification spent grains/montmorillonite solution combined sorbing material, this material can be removed the arsenic ion in the water efficiently.
Another object of the present invention is the problem that has solved existing Arsenic in Drinking Water ion remaval method complex process.
For achieving the above object, the technical solution used in the present invention is:
(1) takes by weighing 20g and add through the pretreated spent grains of high temperature that the 100mL mass fraction is housed is 8% Ca (OH)
2In the thin mouth of the 250mL of the solution vial, concussion makes its gelation 13～16h, behind taking-up ageing 1～3d, cleans with deionized water, then cleans with absolute ethyl alcohol, and then suction filtration puts into Muffle furnace calcination 2～4h of 300 ℃, after the taking-up cooling, saves backup;
(2) get an amount of modification spent grains in beaker, adding distil water is mixed with the suspension of 4.5g/L to the pH=11 with the abundant stirring and adjusting solution of agitator, this suspension is slowly poured in the montmorillonite solution of 0.001mol/L, stir with agitator, leave standstill respectively display centrifugal after 2～4 months, abandoning supernatant is gained deposit distilled water flushing several times, and oven dry under 50～60 ℃ of temperature, grinds, and namely gets sorbing material of the present invention.
Described deionized water is by electric dialyzator method, ion-exchanger method, hyperfiltration, the way of distillation and other suitable processing methods, and what make is sealed in the container, and does not contain any additive, water white transparency, water capable of direct drinking.
Described absolute ethyl alcohol is the ethanolic solution of ethanol content 100%, claims again dehydrated alcohol.
Described 0.001mol/L montmorillonite solution is to regulate pH 4～7, with the analytically pure FeCl of 10g
36H
2O is hydrolyzed and gets.
Principle of the present invention is: by useless grain is carried out modification, increase the hydroxyl quantity on surface, can be more and the arsenic ion in the water carry out combination, and then carry out compound with montmorillonite solution, form condensate, strengthen adsorption capacity, simultaneously since the effect of montmorillonite can be deeper and water in arsenic ion carry out complexing, greatly strengthen the absorption property for the arsenic in waste water ion, can be good at processing the arsenic ion in the water.
Application process of the present invention is: with sorbing material 1.5g of the present invention, put in the sewage that 500ml contains arsenic ion 2～4mg/L, regulate pH about 4～7, left standstill 2～4 days after stirring, then filter and take out sorbing material of the present invention and get final product.
The invention has the beneficial effects as follows: the spent grains that the method for the invention makes/montmorillonite composite adsorbing material have simple to operate, cost is low, adsorption capacity is large, the characteristics of wide material sources.Compare with existing sorbing material, described sorbing material is used for the arsenic ion of adsorbed water, can strengthen the combination degree with arsenic ion, increase adsorbance, thus the arsenic ion efficiently in the adsorbed water.
The specific embodiment
Solution combined sorbing material preparation method is as follows for a kind of modification spent grains/montmorillonite:
Take by weighing 20g and add through the pretreated spent grains of high temperature that the 100mL mass fraction is housed is 8% Ca (OH)
2In the thin mouth of the 250mL of the solution vial, concussion makes its gelation 13～16h, behind taking-up ageing 1～3d, cleans with deionized water, then cleans with absolute ethyl alcohol, and then suction filtration puts into Muffle furnace calcination 2～4h of 300 ℃, after the taking-up cooling, saves backup; Get an amount of modification spent grains in beaker, adding distil water is mixed with the suspension of 4.5g/L to the pH=11 with the abundant stirring and adjusting solution of agitator, this suspension is slowly poured in the montmorillonite solution of 0.001mol/L, stir with agitator, leave standstill respectively display centrifugal after 2～4 months, abandoning supernatant is gained deposit distilled water flushing several times, and oven dry under 50～60 ℃ of temperature, grinds, and namely gets sorbing material of the present invention.
Below describe again the present invention in detail with 3 embodiment:
Embodiment 1
Take by weighing 20g and add through the pretreated spent grains of high temperature that the 100mL mass fraction is housed is 8% Ca (OH)
2In the thin mouth of the 250mL of the solution vial, concussion makes its gelation 13h, behind the taking-up ageing 1d, cleans with deionized water, then cleans with absolute ethyl alcohol, and then suction filtration puts into 300 ℃ Muffle furnace calcination 2h, after the taking-up cooling, saves backup; Get an amount of modification spent grains in beaker, adding distil water is mixed with the suspension of 4.5g/L to the pH=11 with the abundant stirring and adjusting solution of agitator, this suspension is slowly poured in the montmorillonite solution of 0.001mol/L, stir with agitator, leave standstill respectively display centrifugal after 2 months, abandoning supernatant is gained deposit distilled water flushing several times, and oven dry under 50 ℃ of temperature, grinds, and namely gets sorbing material of the present invention.
With this sorbing material put into volume be 500mL concentration be 2mg/L contain arsenic from waste water, the pH value was adsorbed 2 days in 4.0 situation, adsorption rate is 96%.
Embodiment 2
Take by weighing 20g and add through the pretreated spent grains of high temperature that the 100mL mass fraction is housed is 8% Ca (OH)
2In the thin mouth of the 250mL of the solution vial, concussion makes its gelation 14h, behind the taking-up ageing 2d, cleans with deionized water, then cleans with absolute ethyl alcohol, and then suction filtration puts into 300 ℃ Muffle furnace calcination 3h, after the taking-up cooling, saves backup; Get an amount of modification spent grains in beaker, adding distil water is mixed with the suspension of 4.5g/L to the pH=11 with the abundant stirring and adjusting solution of agitator, this suspension is slowly poured into the iron carbonyl of 0.001mol/L from solution, stir with agitator, leave standstill respectively display centrifugal after 3 months, abandoning supernatant is gained deposit distilled water flushing several times, and oven dry under 55 ℃ of temperature, grinds, and namely gets sorbing material of the present invention.
It is that 500mL concentration is the waste water that 3mg/L contains arsenic ion that this sorbing material is put into volume, and the pH value was adsorbed 3 days in 5.0 situation, and adsorption rate is 98.2%.
Embodiment 3
Take by weighing 20g and add through the pretreated spent grains of high temperature that the 100mL mass fraction is housed is 8% Ca (OH)
2In the thin mouth of the 250mL of the solution vial, concussion makes its gelation 16h, behind the taking-up ageing 3d, cleans with deionized water, then cleans with absolute ethyl alcohol, and then suction filtration puts into 300 ℃ Muffle furnace calcination 4h, after the taking-up cooling, saves backup; Get an amount of modification spent grains in beaker, adding distil water is mixed with the suspension of 4.5g/L to the pH=11 with the abundant stirring and adjusting solution of agitator, this suspension is slowly poured in the montmorillonite solution of 0.001mol/L, stir with agitator, leave standstill respectively display centrifugal after 4 months, abandoning supernatant is gained deposit distilled water flushing several times, and oven dry under 60 ℃ of temperature, grinds, and namely gets sorbing material of the present invention.
It is that 500mL concentration is the waste water that 4mg/L contains arsenic ion that this sorbing material is put into volume, and the pH value was adsorbed 4 days in 7.0 situation, and adsorption rate is 99.5%.
Claims (6)
1. composite adsorbing material of removing arsenic ion in the natural water body is characterized in that: to be that primary raw material is compound by the useless wheat groove of modification and montmorillonite solution be prepared from this sorbing material.
2. described a kind of preparation method who removes the composite adsorbing material of arsenic ion in the natural water body according to claim 1 is characterized in that the modification wheat groove method of giving up: take by weighing 20g and add through the pretreated spent grains of high temperature that the 100mL mass fraction is housed is 8% Ca (OH)
2In thin mouthful of vial of the 250mL of solution, concussion makes its gelation 13～16h, take out ageing 1～3d after, clean with deionized water, then clean with absolute ethyl alcohol, then suction filtration puts into Muffle furnace calcination 2～4h of 300 ℃, take out cold after, save backup.
3. described a kind of method of removing arsenic ion in the natural water body according to claim 1, the preparation method who it is characterized in that polymerization montmorillonite-useless wheat groove complex: get an amount of modification spent grains in beaker, adding distil water is mixed with the suspension of 4.5g/L to the pH=11 with the abundant stirring and adjusting solution of agitator, this suspension is slowly poured in the montmorillonite solution of 0.001mol/L, stir with agitator, leave standstill respectively display centrifugal after 2～4 months, abandoning supernatant is with gained deposit distilled water flushing several times, and under 50～60 ℃ of temperature, dry, grind, namely get sorbing material of the present invention.
4. a kind of composite adsorbing material of removing arsenic ion in the natural water body described in according to claim 2 and preparation method thereof, it is characterized in that: described deionized water is by electric dialyzator method, ion-exchanger method, hyperfiltration, the way of distillation and other suitable processing methods, what make is sealed in the container, and do not contain any additive, water white transparency, water capable of direct drinking
5. a kind of composite adsorbing material of removing the arsenic in water body ion described in according to claim 2 and preparation method thereof, it is characterized in that: described absolute ethyl alcohol is the ethanolic solution of ethanol content 100%, claims again dehydrated alcohol.
6. a kind of composite adsorbing material of removing arsenic ion in the natural water body described in according to claim 3 and preparation method thereof, it is characterized in that: described 0.001mol/L montmorillonite solution is to regulate pH 4～7, with the analytically pure FeCl of 10g
36H
2O is hydrolyzed and gets.
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Cited By (2)
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| CN106409371A (en) * | 2016-10-13 | 2017-02-15 | 东华理工大学 | Hydroxyapatite-coating PRB filling material and preparing method and underground-water uranium removing application method thereof |
| CN114621599A (en) * | 2022-03-17 | 2022-06-14 | 中南大学 | Nano ferrihydrite-spent grain composite colloidal material and preparation and application thereof |
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| US20050098503A1 (en) * | 2003-09-16 | 2005-05-12 | Ju Young Kim | Lignocellulose-based anion-adsorbing medium (LAM) and process for making and using same for the selective removal of phosphate and arsenic anionic contaminants from aqueous solutions. |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106409371A (en) * | 2016-10-13 | 2017-02-15 | 东华理工大学 | Hydroxyapatite-coating PRB filling material and preparing method and underground-water uranium removing application method thereof |
| CN106409371B (en) * | 2016-10-13 | 2018-06-08 | 东华理工大学 | A kind of Coated With Hydroxyapatite PRB packing materials and preparation method thereof and underground water remove uranium application process |
| CN114621599A (en) * | 2022-03-17 | 2022-06-14 | 中南大学 | Nano ferrihydrite-spent grain composite colloidal material and preparation and application thereof |
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Application publication date: 20130116 |