CN103936133A - Treatment method for jointly performing oxidation of trivalent arsenic and reduction of hexavalent chromium by using organic acid - Google Patents
Treatment method for jointly performing oxidation of trivalent arsenic and reduction of hexavalent chromium by using organic acid Download PDFInfo
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- CN103936133A CN103936133A CN201410202217.0A CN201410202217A CN103936133A CN 103936133 A CN103936133 A CN 103936133A CN 201410202217 A CN201410202217 A CN 201410202217A CN 103936133 A CN103936133 A CN 103936133A
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Abstract
The invention relates to the field of sewage treatment, and particularly relates to a treatment method for jointly performing oxidation of trivalent arsenic and reduction of hexavalent chromium by using an organic acid. The method comprises the following steps: adding micromolecular organic acid with a double-carboxyl structure to a to-be-treated water body containing trivalent arsenic As(III) and hexavalent chromium Cr(VI), and adjusting the pH value, so as to trigger oxidation of arsenic, reduction of chromium and transformation into carbon dioxide from organic acid in the water body. Synergistic treatment of toxic substances, namely the trivalent arsenic and the hexavalent chromium is achieved by using these micromolecular organic acids existing in the water body, finally the three harmful substances are transformed into the products which are smaller in toxicity, or completely harmless, self-cleaning of the water body is achieved, in addition, no chemical reducer or oxidant is added, the treatment method is free of input of an external energy source, free of adding of chemical substances, free of secondary pollution, free of sediments or sludge, environmental friendly, and free of harm.
Description
Technical field
The present invention relates to sewage treatment area, particularly a kind for the treatment of process of utilizing organic acid synergistic oxidation trivalent arsenic and reduction of hexavalent chromium.
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 As pollutes the significant damage of HUMAN HEALTH and As, 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.The < < drinking water sanitary standard > > (GB5749-2006) that China is used at present requires the peak concentration of As in tap water must be lower than 10 μ g/L.Therefore for the processing that contains High Concentration of Arsenic trade effluent, be very urgent.
At present, coagulation removes aluminium, iron-based flocculation agent in As method and is widely used, and the method is mainly the adsorption arsenic-adsorbing that utilizes coagulating agent powerful, then by filtering or removing the arsenic in anhydrating with filter membrane.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 the application of the method is restricted.
Therefore for the existing defect about trivalent arsenic treatment technology, be badly in need of developing a kind of green, efficient trivalent arsenic treatment technology.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 there is biodegradation process, when 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.
At present, the not relevant report that utilizes the method for As (III) in organic acid associated treatment water body, reduction Cr (VI).
Summary of the invention
The present invention relates to that a kind of to utilize the common small molecular organic acid with specific chemical functional group of occurring in nature be reaction reagent, at normal temperatures and pressures, can realize the reduction to the oxidation of trivalent arsenic As (III) in water body and sexavalent chrome Cr (VI) simultaneously, water body small molecular organic acid is converted into carbonic acid gas simultaneously, realizes the automatically cleaning of water body.
Technical scheme of the present invention is:
A kind for the treatment of process of utilizing organic acid synergistic oxidation trivalent arsenic and reduction of hexavalent chromium, the treating method comprises: at normal temperatures and pressures, to in the pending water body that contains trivalent arsenic As (III), sexavalent chrome Cr (VI), add small molecular organic acid, regulate pH value, can cause the oxidation of arsenic in water body, the reduction of chromium and organic acid to the conversion of carbonic acid gas.
Preferably, described small molecular organic acid has two carboxyl structure,
Preferably, the described small molecular organic acid with two carboxyl structure is oxalic acid, citric acid etc.
Preferably, the mol ratio of As (III)/small molecular organic acid/Cr (VI) is 1:2～10:0.5～4.
Preferably, adopt sulfuric acid that pH value is adjusted to 1-4.
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 there is biodegradation process, when 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 these small molecular organic acids that exist in water body to realize having hypertoxicity material trivalent arsenic and chromic associated treatment, final three kinds of objectionable impuritiess are all converted into the less or complete harmless product of toxicity, realize the automatically cleaning of water body, without adding in addition any chemical reducing agent or oxygenant, so this technical scheme improvement that is arsenic, chromium pollution water thinking of a kind of cheapness being provided, having cleaned, achieve many things at one stroke.
Compared with prior art, the invention has the beneficial effects as follows:
(1) utilize small molecular organic acid common in water body, for example, oxalic acid, citric acids etc. are reactant, cause As (III) and the reduction of Cr (VI) synergistic oxidation, can realize hypertoxicity trivalent arsenic in water body is converted into the final removal that toxicity is less, pentavalent arsenic that more easily remove is conducive to arsenic, hypertoxicity material sexavalent chrome is converted into nontoxic trivalent chromium simultaneously.
(2) the inventive method 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, has the possibility of using on a large scale.
(3) while only having three kinds of materials to coexist in the inventive method, just can react, any two kinds of materials coexist and can not react.
(4) in the reaction process of the inventive method without the input of outside resources, without the interpolation of chemical substance, non-secondary pollution, without the generation of precipitation, mud.The reactant utilizing is for common are machine acid in occurring in nature water body and soil.
Accompanying drawing explanation
When Fig. 1 selects oxalic acid to be organic acid under differential responses condition the oxidation efficiency of As (III);
The reduction efficiency of Cr (VI) under differential responses condition when Fig. 2 selects oxalic acid to be organic acid;
The oxidation efficiency of As (III) and the reduction efficiency of Cr (VI) when Fig. 3 embodiment 2 selects citric acid to be organic acid;
When Fig. 4 embodiment 3 selects oxalic acid/As (III)/Cr (VI) to be 5:1:3, the reduction efficiency of the oxidation efficiency of As (III) and Cr (VI);
When Fig. 5 embodiment 4 selects citric acid/As (III)/Cr (VI) to be 3:1:0.5, the reduction efficiency of the oxidation efficiency of As (III) and Cr (VI);
When Fig. 6 embodiment 5 selects oxalic acid/As (III)/Cr (VI) to be 10:1:4, the reduction efficiency of the oxidation efficiency of As (III) and Cr (VI).
Embodiment
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described:
Embodiment 1:
By As (III) concentration, be the water body mesoxalic acid 2mM that 1mM, Cr (VI) concentration is 0.6mM, utilize sulfuric acid that pH value is adjusted to 3, mixing solutions 100mL;
For As (III) concentration is a mixing solutions 100mL of 1mM and oxalic acid 2mM, utilize sulfuric acid that pH value is adjusted to 3; For Cr (VI) concentration is a mixing solutions 100mL of 0.6mM and oxalic acid 2mM, utilize sulfuric acid that pH value is adjusted to 3; For As (III) concentration is the mixing solutions 100mL that 1mM and Cr (VI) concentration are 0.6mM, utilize sulfuric acid that pH value is adjusted to 3.
As depicted in figs. 1 and 2, when three kinds of As (III), Cr (VI) and oxalic acid coexist, reaction just can be carried out, and processing efficiency is higher.Other any two kinds of materials do not react while coexisting.
Embodiment 2:
By As (III) concentration, be citric acid 4mM in 1mM, Cr (VI) the concentration water body that is 1.2mM, utilize sulfuric acid that pH value is adjusted to 2, mixing solutions 100mL;
As shown in Figure 3, the citric acid that has two carboxyl structure can make As (III), Cr (VI) that synergistic oxidation reduction effect occurs too.
Embodiment 3:
By As (III) concentration, be the water body mesoxalic acid 5mM that 1mM, Cr (VI) concentration is 3mM, utilize sulfuric acid that pH value is adjusted to 2.
As shown in Figure 4, the amount of oxalic acid is larger, and pH value is less, is more conducive to the redox of arsenic and chromium.
Embodiment 4:
By As (III) concentration, be citric acid 3mM in 1mM, Cr (VI) the concentration water body that is 0.5mM, utilize sulfuric acid that pH value is adjusted to 4.
As shown in Figure 5, the redox efficiency of the larger arsenic chromium of pH diminishes.
Embodiment 5:
By As (III) concentration, be the water body mesoxalic acid 10mM that 1mM, Cr (VI) concentration is 4mM, utilize sulfuric acid that pH value is adjusted to 2.
As shown in Figure 6, the increase of oxalic acid amount, is conducive to the redox of arsenic chromium.
Claims (5)
1. a treatment process of utilizing organic acid synergistic oxidation trivalent arsenic and reduction of hexavalent chromium, it is characterized in that, the treating method comprises: at normal temperatures and pressures, to in the pending water body that contains trivalent arsenic As (III), sexavalent chrome Cr (VI), add small molecular organic acid, regulate pH value, can cause the oxidation of arsenic in water body, the reduction of chromium and organic acid to the conversion of carbonic acid gas.
2. the treatment process of utilizing organic acid synergistic oxidation trivalent arsenic and reduction of hexavalent chromium according to claim 1, is characterized in that described small molecular organic acid has two carboxyl structure.
3. the treatment process of utilizing organic acid synergistic oxidation trivalent arsenic and reduction of hexavalent chromium according to claim 2, is characterized in that the described small molecular organic acid with two carboxyl structure is oxalic acid or citric acid etc.
4. the treatment process of utilizing organic acid synergistic oxidation trivalent arsenic and reduction of hexavalent chromium according to claim 1, the mol ratio that it is characterized in that As (III)/small molecular organic acid/Cr (VI) is 1:2～10:0.5～4.
5. according to the treatment process of utilizing organic acid synergistic oxidation trivalent arsenic and reduction of hexavalent chromium described in claim 1-4 any one, it is characterized in that adopting sulfuric acid that pH value is adjusted to 1-4.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104310569A (en) * | 2014-11-10 | 2015-01-28 | 中国石油大学(华东) | Method for water treatment oxidation by using Cr (VI)/SO32 |
| CN104876318A (en) * | 2015-05-29 | 2015-09-02 | 华中师范大学 | Water treatment method for reducing and removing hexavalent chromium with manganese dioxide/oxalic acid substances |
| CN104876374A (en) * | 2015-06-05 | 2015-09-02 | 中国科学院生态环境研究中心 | Electrochemical water treatment method for simultaneously reducing chromium and arsenic oxide |
| CN110713224A (en) * | 2019-10-10 | 2020-01-21 | 华中农业大学 | Shi mineral for removing pollution of trivalent arsenic and hexavalent chromium |
| CN111289639A (en) * | 2020-02-05 | 2020-06-16 | 广西大学 | Method for determining hexavalent chromium in solid waste leachate |
| CN113274687A (en) * | 2021-04-30 | 2021-08-20 | 华中科技大学 | Co-treatment method of chromium slag and acidic arsenic-containing wastewater |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103449629A (en) * | 2013-09-02 | 2013-12-18 | 苏州富奇诺水治理设备有限公司 | Treatment method for wastewater containing chromium and arsenic |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103449629A (en) * | 2013-09-02 | 2013-12-18 | 苏州富奇诺水治理设备有限公司 | Treatment method for wastewater containing chromium and arsenic |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104310569A (en) * | 2014-11-10 | 2015-01-28 | 中国石油大学(华东) | Method for water treatment oxidation by using Cr (VI)/SO32 |
| CN104310569B (en) * | 2014-11-10 | 2016-04-20 | 中国石油大学(华东) | Utilize Cr (VI)/SO 32-the method of water treatment oxidation |
| CN104876318A (en) * | 2015-05-29 | 2015-09-02 | 华中师范大学 | Water treatment method for reducing and removing hexavalent chromium with manganese dioxide/oxalic acid substances |
| CN104876374A (en) * | 2015-06-05 | 2015-09-02 | 中国科学院生态环境研究中心 | Electrochemical water treatment method for simultaneously reducing chromium and arsenic oxide |
| CN104876374B (en) * | 2015-06-05 | 2016-09-21 | 中国科学院生态环境研究中心 | A kind of reduction chromium and the electrochemical water treating method of arsenic oxide arsenoxide simultaneously |
| CN110713224A (en) * | 2019-10-10 | 2020-01-21 | 华中农业大学 | Shi mineral for removing pollution of trivalent arsenic and hexavalent chromium |
| CN111289639A (en) * | 2020-02-05 | 2020-06-16 | 广西大学 | Method for determining hexavalent chromium in solid waste leachate |
| CN113274687A (en) * | 2021-04-30 | 2021-08-20 | 华中科技大学 | Co-treatment method of chromium slag and acidic arsenic-containing wastewater |
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