CN103936136B - Ultraviolet excitation oxalic acid is utilized to be oxidized arsenious treatment process in water body - Google Patents
Ultraviolet excitation oxalic acid is utilized to be oxidized arsenious treatment process in water body Download PDFInfo
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- CN103936136B CN103936136B CN201410203116.5A CN201410203116A CN103936136B CN 103936136 B CN103936136 B CN 103936136B CN 201410203116 A CN201410203116 A CN 201410203116A CN 103936136 B CN103936136 B CN 103936136B
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Abstract
The present invention relates to sewage treatment area, ultraviolet excitation oxalic acid is utilized to be oxidized arsenious treatment process in water body in particular to one, pending is added oxalic acid containing in the water body of trivalent arsenic As (III), adjust ph, under ultraviolet excitation, As in water body (III) is oxidized to As (V), water body mesoxalic acid is converted into carbonic acid gas simultaneously.Present invention utilizes the oxalic acid existed in water body, under the exciting of UV-light, realization is to having the arsenious oxide treatment of hypertoxicity material, and final trivalent arsenic is converted into less, the easier pentavalent arsenic being removed by physical technique, fix of toxicity.Oxalic acid simultaneously in water body is converted into titanium dioxide, realizes the organic removal of water body, realizes the automatically cleaning of water body, this technology environmental protection, without harm, can use on a large scale.
Description
Technical field
The present invention relates to sewage treatment area, particularly one utilizes ultraviolet excitation oxalic acid to be oxidized arsenious treatment process in water body.
Background technology
Arsenic (As) is a kind of element of extensively distribution in the earth's crust, and is acknowledged as a kind of poisonous carcinogenic substance.The compound of As has trivalent and pentavalent two kinds of forms, and toxicity and the mobility of As (III) are larger.Research shows, with AsO
3 3-as (III) ratio existed is with AsO
4 3-the toxicity of the As (V) existed will exceed 60 times.Arsenide is while the production fields such as mining, smelting, glass manufacture, agricultural chemicals and wood preservative are used widely, cause a considerable amount of arsenic compound entered environment, and be present in water body, soil, plant, animal, marine organisms and human body with different shape by chemical process and bio-transformation effect, and form circulation between each arsenide.
According to the research of the World Health Organization, as long as there is a small amount of As in tap water, be just enough to the healthy occurrence injury to human body.Long-term drinking, containing the water of As, may cause a series of health problems such as Skin pigmentation, skin keratin, skin carcinoma, bladder cancer, hypertension, cardiovascular and cerebrovascular disease, DPN, diabetes.That pollutes the significant damage of HUMAN HEALTH and As in view of As is on the rise, and 1993, WHO took the lead in the desired value of As in tap water to be down to 10 μm/L by 50 μm/L.Subsequently, respective tap water As standard is also decided to be 10 μ g/L by Japan, European Union, the U.S. respectively." drinking water sanitary standard " (GB5749-2006) that China uses at present requires that the peak concentration of As in tap water must lower than 10 μ g/L.Therefore be very urgent for the process containing High Concentration of Arsenic trade effluent.
At present, coagulation is widely used except aluminium, iron-based flocculation agent in As method, the adsorption arsenic-adsorbing that the method mainly utilizes coagulating agent powerful, then by filter or with filter membrane except the arsenic in anhydrating.Experimental result shows, molysite to the removal efficiency of arsenic apparently higher than aluminium salt.Molysite is most economical, the most effective precipitation agent.But As (III) toxicity is comparatively large and be difficult to be flocculated realization and remove completely.And the toxicity of As (V) is relatively little, and easily adsorbed, be able to efficient removal.Therefore need to carry out preoxidation to As (III) before applying flocculation technique arsenic removal, namely AS (III) initial oxidation is become As (V), and then remove.Conventional oxygenant mainly contains chlorinated lime, hydrogen peroxide, chlorine, ozone and Manganse Dioxide etc.But the method needs to add a large amount of flocculation agents, produce a large amount of arsenic-containing waste residues and also can cause secondary pollution, therefore make the application of the method be restricted.
At present, be photocatalysis technology what carry out extensively research, utilize ultraviolet excitation photocatalyst (as titanium dioxide) to produce active substance hydroxyl radical free radical, realize arsenious oxidation with this.But the shortcomings such as catalyzer Costco Wholesale is high, difficult recovery, easily generation mud significantly limit its industrial application.Meanwhile, the relevant report utilizing ultraviolet excitation oxalic acid to be oxidized arsenious treatment process in water body is not first had.
Summary of the invention
The present invention is directed to the existing defect about trivalent arsenic treatment technology, develop a kind of green, efficient trivalent arsenic treatment process, realize the oxidation to trivalent arsenic As (III) in water body, be conducive to the final removal of arsenic in water body on the one hand, water body mesoxalic acid is converted into carbonic acid gas simultaneously, realizes the clean of water body.
Technical scheme of the present invention is:
One utilizes ultraviolet excitation oxalic acid to be oxidized arsenious treatment process in water body, the treating method comprises: pending is added oxalic acid containing in the water body of trivalent arsenic As (III), adjust ph, under ultraviolet excitation, As in water body (III) is oxidized to As (V), water body mesoxalic acid is converted into carbonic acid gas simultaneously.
Preferably, the mol ratio of oxalic acid/As (III) is not less than 1.
Preferably, the mol ratio 1 ~ 10:1 of oxalic acid/As (III)
Preferably, sulfuric acid or salt acid for adjusting pH value is adopted to be adjusted to 2-6.
Preferably, the intensity of described UV-light is 175-400W, and selects light application time to be generally 30-120min according to processing requirements.
Containing a large amount of organic acids in nature water body, these organic acids mainly come from intermediate product or the final product of vegetation body fluid and organic-biological degraded, and namely such as oxalic acid be common are machine acid in a kind of water body, and its concentration can reach 20mM.But these organism are by direct or indirect mode, affect water body physics, chemistry and biological property.These organism be present in water body can consume the dissolved oxygen in water body in generation biodegradation process, when the oxygen consumed in Oxidative Degradation Process can not supplement in time, oxygen in water will be caused to reduce rapidly, these organism will carry out anaerobic digestion simultaneously, produce organic acid, alcohol, aldehyde material and other reductibility product, make water hypoxia, blackening is smelly, water quality deterioration, cause fish and hydrobiont anoxia asphyxia or be poisoned to death, cause the eutrophication of water body, the utilizability of water body is reduced greatly.
And present invention utilizes the oxalic acid existed in water body, under the exciting of UV-light, realization is to having the arsenious oxide treatment of hypertoxicity material, and final trivalent arsenic is converted into less, the easier pentavalent arsenic being removed by physical technique, fix of toxicity.Oxalic acid simultaneously in water body is converted into carbonic acid gas, realizes the organic removal of water body.Therefore this technical scheme is that the oxidation of arsenic in water body provides a kind of efficient, clean roadmap.
Oxidation mechanisms: under the action of uv light, structure changes oxalic acid, generates triplet state organism, deposits and can produce hydroxyl radical free radical, single line oxygen, superoxide radical isoreactivity material in case, and then can be oxidized trivalent arsenic at molecular oxygen.
Compared with prior art, the invention has the beneficial effects as follows:
(1) utilize small molecular organic acid oxalic acid common in water body to be reactant, hypertoxicity trivalent arsenic in water body can be realized to be converted into the pentavalent arsenic that toxicity is less, more easily remove under ultraviolet source excites, cost is low, efficiently, and environmental protection.
(2) organic acid in water body can also be converted into carbonic acid gas by treatment process of the present invention being oxidized arsenious while simultaneously, realizes the automatically cleaning of water body, this technology environmental protection, without harm, can use on a large scale.
Accompanying drawing explanation
Fig. 1 is the oxidation efficiency of the embodiment of the present invention 1 As (III) under ultraviolet excitation
Fig. 2 is the oxidation efficiency of the embodiment of the present invention 2 As (III) under ultraviolet excitation
Fig. 3 is the oxidation efficiency of the embodiment of the present invention 3 As (III) under ultraviolet excitation
Fig. 4 is the oxidation efficiency of the embodiment of the present invention 4 As (III) under ultraviolet excitation
Fig. 5 is the oxidation efficiency of the embodiment of the present invention 5 As (III) under ultraviolet excitation.
Embodiment
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described:
Embodiment 1:
The mixing solutions 500mL that As (III) concentration is 0.1mM, concentration of oxalic acid is 0.5mM, and with sulfuric acid, pH value is adjusted to 4, inject Shanghai respectively than bright company BL-GHX-I type photo catalysis reactor, during work, ultraviolet ray intensity is 400W, and the treatment time is 50min.
As shown in Figure 1, the pentavalent arsenic content in treating processes in waste water solution constantly increases, and when not adding oxalic acid, trivalent arsenic can only occur to be oxidized slowly, and its major cause is the effect of dissolved oxygen.
Embodiment 2:
As (III) concentration is 0.1mM, concentration of oxalic acid is 0.3mM mixing, and with sulfuric acid, pH value is adjusted to 2, ultraviolet ray intensity is 400W, and the treatment time is 40min.
As shown in Figure 2, find: oxalic acid amount is larger, and the less arsenious oxidation effectiveness of pH is better
Embodiment 3:
As (III) concentration is 0.1mM, concentration of oxalic acid is 1mM mixing, and with sulfuric acid, pH value is adjusted to 6, ultraviolet ray intensity is 400W, and the treatment time is 100min.
As shown in Figure 3, find: oxalic acid amount increases, but when pH is larger, arsenious rate of oxidation is slack-off.
Embodiment 4:
As (III) concentration is 0.1mM, concentration of oxalic acid is 0.1mM mixing, and with sulfuric acid, pH value is adjusted to 4, ultraviolet ray intensity is 400W, and the treatment time is 60min.
As shown in Figure 4, find: when As (III)/oxalic acid is 1:1, trivalent arsenic still can be oxidized completely.
Embodiment 5:
As (III) concentration is 0.1mM, concentration of oxalic acid is 0.1mM mixing, and with sulfuric acid, pH value is adjusted to 4, ultraviolet ray intensity is 175W, and the treatment time is 120min.
As shown in Figure 5, find: when As (III)/oxalic acid is 1:1, when ultraviolet ray intensity is 175W, trivalent arsenic can be able to complete oxidation in 120min.
Claims (5)
1. utilize ultraviolet excitation oxalic acid to be oxidized an arsenious treatment process in water body, it is characterized in that, the treating method comprises: pending is only added oxalic acid containing in the water body of trivalent arsenic As (III), no longer adds other photocatalyst; As in water body (III), to 2-6, is oxidized to As (V) by adjust ph under ultraviolet excitation, and water body mesoxalic acid is converted into carbonic acid gas simultaneously.
2. the ultraviolet excitation oxalic acid that utilizes according to claim 1 is oxidized arsenious treatment process in water body, it is characterized in that the mol ratio of oxalic acid/As (III) is not less than 1.
3. the ultraviolet excitation oxalic acid that utilizes according to claim 2 is oxidized arsenious treatment process in water body, it is characterized in that the mol ratio 1 ~ 10:1 of oxalic acid/As (III).
4. the ultraviolet excitation oxalic acid that utilizes according to claim 1 is oxidized arsenious treatment process in water body, it is characterized in that adopting sulfuric acid or salt acid for adjusting pH value to regulate.
5. the ultraviolet excitation oxalic acid that utilizes according to any one of claim 1-4 is oxidized arsenious treatment process in water body, it is characterized in that the intensity of described UV-light is 175-400W, and selects light application time to be 30-120min according to processing requirements.
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| JPH1157752A (en) * | 1997-08-19 | 1999-03-02 | Japan Organo Co Ltd | Controlling method and device of toc component removal |
| CN1623921A (en) * | 2003-12-04 | 2005-06-08 | 陈小华 | Process for removing arsenic in water using oxydol as oxidative agent |
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| CN101508479A (en) * | 2009-02-13 | 2009-08-19 | 中南大学 | Oxidation method for trivalent arsenic in solution |
| CN102992445A (en) * | 2011-09-16 | 2013-03-27 | 苏州科技学院 | Method for treating organic pollutants through steel slag-oxalic acid photo Fenton |
| CN103304000A (en) * | 2013-06-26 | 2013-09-18 | 武汉大学 | Method for removing trivalent arsenic in water through oxidization |
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2014
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1157752A (en) * | 1997-08-19 | 1999-03-02 | Japan Organo Co Ltd | Controlling method and device of toc component removal |
| CN1623921A (en) * | 2003-12-04 | 2005-06-08 | 陈小华 | Process for removing arsenic in water using oxydol as oxidative agent |
| CN101219829A (en) * | 2008-01-18 | 2008-07-16 | 哈尔滨工业大学 | Method for removing As(III) in water |
| CN101508479A (en) * | 2009-02-13 | 2009-08-19 | 中南大学 | Oxidation method for trivalent arsenic in solution |
| CN102992445A (en) * | 2011-09-16 | 2013-03-27 | 苏州科技学院 | Method for treating organic pollutants through steel slag-oxalic acid photo Fenton |
| CN103304000A (en) * | 2013-06-26 | 2013-09-18 | 武汉大学 | Method for removing trivalent arsenic in water through oxidization |
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