CN103936136A - Treatment method of trivalent arsenic in oxalic acid oxidized water body by ultraviolet excitation - Google Patents
Treatment method of trivalent arsenic in oxalic acid oxidized water body by ultraviolet excitation Download PDFInfo
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- CN103936136A CN103936136A CN201410203116.5A CN201410203116A CN103936136A CN 103936136 A CN103936136 A CN 103936136A CN 201410203116 A CN201410203116 A CN 201410203116A CN 103936136 A CN103936136 A CN 103936136A
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- oxalic acid
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Abstract
The invention relates to the field of sewage treatment and particularly relates to a treatment method of trivalent arsenic in an oxalic acid oxidized water body by ultraviolet excitation. The method comprises the following steps: adding oxalic acid into a to-be-treated water body comprising trivalent arsenic As (III); adjusting the pH value; oxidizing As (III) in the water body into As (V) under ultraviolet excitation; and meanwhile, converting oxalic acid in the water body into carbon dioxide. According to the method provided by the invention, the hypertoxic matter trivalent arsenic is subjected to oxidation treatment under ultraviolet excitation by means of oxalic acid in the water body, and finally the trivalent arsenic is converted into pentavalent arsenic which is less in toxicity and easily removed and immobilized through physical technologies. The oxalic acid in the water body is converted into titanium dioxide to remove organic matters in the water body so as to self-clean the water body. The treatment method is green and environment-friendly and free from damage and can be used on a large scale.
Description
Technical field
The present invention relates to sewage treatment area, particularly one is utilized arsenious treatment process in ultraviolet excitation oxalic acid oxidation water body.
Background technology
Arsenic (As) is a kind of element extensively distributing in the earth's crust, and is acknowledged as a kind of poisonous carcinogenic substance.The compound of As has trivalent and two kinds of forms of pentavalent, and toxicity and the mobility of As (III) are larger.Research shows, with AsO
3 3-as (III) ratio existing is with AsO
4 3-the toxicity of the As (V) existing will exceed 60 times.Arsenide is when 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 environments, 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 health of human body to endanger.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.In view of being on the rise that the significant damage of As to HUMAN HEALTH and As pollute, 1993, WHO took the lead in the desired value of As in tap water to be down to 10 μ m/L by 50 μ m/L.Subsequently, Japan, European Union, the U.S. are also decided to be 10 μ g/L by tap water As standard separately respectively." drinking water sanitary standard " that China is used at present (GB5749-2006) requires the peak concentration of As in tap water must be lower than 10 μ g/L.Therefore be very urgent for the processing that contains High Concentration of Arsenic trade effluent.
At present, coagulation is widely used except aluminium, iron-based flocculation agent in As method, and the method is mainly the adsorption arsenic-adsorbing that 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 large and be difficult to be flocculated realization and remove completely.And the toxicity of As (V) is relatively little, and be easily adsorbed, be able to efficient removal.Therefore before applying flocculation technique arsenic removal, need As (III) to carry out preoxidation, AS (III) initial oxidation is become to As (V), and then remove.Conventional oxygenant mainly contains chlorinated lime, hydrogen peroxide, chlorine, ozone and Manganse Dioxide etc.But the method need 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 broad research, utilize ultraviolet excitation photocatalyst (as titanium dioxide) to produce active substance hydroxyl radical free radical, realize arsenious oxidation with this.Limit greatly its industrial application but catalyzer Costco Wholesale is high, difficulty reclaims, easily produce the shortcomings such as mud.Meanwhile, first there is not the relevant report of utilizing arsenious treatment process in ultraviolet excitation oxalic acid oxidation water body.
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 on the one hand the final removal of arsenic in water body, 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 is utilized arsenious treatment process in ultraviolet excitation oxalic acid oxidation water body, the treating method comprises: will in the pending water body that contains trivalent arsenic As (III), add oxalic acid, regulate pH value, 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, mol ratio 1～10:1 of oxalic acid/As (III)
Preferably, adopt sulfuric acid or salt acid for adjusting pH value to be adjusted to 2-6.
Preferably, described ultraviolet light intensity is 175-400W, and selects light application time to be generally 30-120min according to processing requirements.
In nature water body, contain a large amount of organic acids, these organic acids mainly come from intermediate product or the final product of vegetation body fluid and organic-biological degraded, and for example oxalic acid be in a kind of water body, to common are machine acid, and its concentration can reach 20mM.But these organism can, by direct or indirect mode, affect water body physics, chemistry and biological property.These organism that are present in water body can consume the dissolved oxygen in water body in generation biodegradation process, in the time that the oxygen consuming in Oxidative Degradation Process can not supplement in time, to cause oxygen in water 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 the present invention has utilized the oxalic acid existing in water body, under the exciting of UV-light realization to thering is the arsenious oxide treatment of hypertoxicity material, final trivalent arsenic be converted into toxicity less, more easily by physical technique remove, fixing pentavalent arsenic.Oxalic acid in water body is converted into carbonic acid gas simultaneously, realizes the organic removal of water body.Therefore the oxidation that this technical scheme is arsenic in water body provides a kind of efficient, clean processing thinking.
Oxidation mechanisms: oxalic acid is under the effect of UV-light, and structure changes, generates triplet state organism, can produce hydroxyl radical free radical, single line oxygen, superoxide radical isoreactivity material, and then can be oxidized trivalent arsenic in the situation that molecular oxygen exists.
Compared with prior art, the invention has the beneficial effects as follows:
(1) utilizing small molecular organic acid oxalic acid common in water body is reactant, excites lower can realization that hypertoxicity trivalent arsenic in water body is converted into toxicity pentavalent arsenic less, that more easily remove at ultraviolet source, and cost is low, efficient, environmental protection.
(2) treatment process of the present invention can also be converted into carbonic acid gas by organic acid in water body in the arsenious while of oxidation simultaneously, realizes the automatically cleaning of water body, and this technology environmental protection, without harm, can be used on a large scale.
Brief description of the drawings
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 brief description of the drawings the specific embodiment of the present invention:
Embodiment 1:
As (III) concentration is the mixing solutions 500mL that 0.1mM, concentration of oxalic acid are 0.5mM, and pH value is adjusted to 4 with sulfuric acid, inject respectively the Shanghai BL-GHX-I of Bi Lang company type photo catalysis reactor, when 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 while 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 that 0.1mM, concentration of oxalic acid are that 0.3mM mixes, and pH value is adjusted to 2 with sulfuric acid, and 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 that 0.1mM, concentration of oxalic acid are that 1mM mixes, and pH value is adjusted to 6 with sulfuric acid, and 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 that 0.1mM, concentration of oxalic acid are that 0.1mM mixes, and pH value is adjusted to 4 with sulfuric acid, and ultraviolet ray intensity is 400W, and the treatment time is 60min.
As shown in Figure 4, find: in the time that As (III)/oxalic acid is 1:1, trivalent arsenic still can be oxidized completely.
Embodiment 5:
As (III) concentration is that 0.1mM, concentration of oxalic acid are that 0.1mM mixes, and pH value is adjusted to 4 with sulfuric acid, and ultraviolet ray intensity is 175W, and the treatment time is 120min.
As shown in Figure 5, find: in the time that As (III)/oxalic acid is 1:1, in the time that ultraviolet ray intensity is 175W, trivalent arsenic can be able to complete oxidation in 120min.
Claims (5)
1. one kind is utilized arsenious treatment process in ultraviolet excitation oxalic acid oxidation water body, it is characterized in that, the treating method comprises: will in the pending water body that contains trivalent arsenic As (III), add oxalic acid, regulate pH value, under ultraviolet excitation, As in water body (III) is oxidized to As (V), 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 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 be adjusted to 2-6.
5. according to the arsenious treatment process in ultraviolet excitation oxalic acid oxidation water body of utilizing described in claim 1-4 any one, it is characterized in that described ultraviolet light intensity is 175-400W, and select light application time to be generally 30-120min according to processing requirements.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105129959A (en) * | 2015-07-24 | 2015-12-09 | 南京大学 | Method of photo-oxidizing treatment on trivalent arsenic in water through small-molecular diketone |
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| JPH1157752A (en) * | 1997-08-19 | 1999-03-02 | Japan Organo Co Ltd | Controlling method and device of toc component removal |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105129959A (en) * | 2015-07-24 | 2015-12-09 | 南京大学 | Method of photo-oxidizing treatment on trivalent arsenic in water through small-molecular diketone |
| CN105129959B (en) * | 2015-07-24 | 2017-06-16 | 南京大学 | Using the method for trivalent arsenic in small molecule diketone photooxidation treatment water |
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