CN103936133B - 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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- CN103936133B CN103936133B CN201410202217.0A CN201410202217A CN103936133B CN 103936133 B CN103936133 B CN 103936133B CN 201410202217 A CN201410202217 A CN 201410202217A CN 103936133 B CN103936133 B CN 103936133B
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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 utilizing organic acid synergistic oxidation trivalent arsenic and reduction of hexavalent chromium.
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.
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.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.
At present, the not relevant report of method utilizing As (III) in organic acid associated treatment water body, reduction Cr (VI).
Summary of the invention
The present invention relates to a kind of small molecular organic acid with specified chemical functional group utilizing occurring in nature common is reaction reagent, at normal temperatures and pressures, the reduction of oxidation to trivalent arsenic As (III) in water body and sexavalent chrome Cr (VI) can be realized 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 utilizing organic acid synergistic oxidation trivalent arsenic and reduction of hexavalent chromium, the treating method comprises: at normal temperatures and pressures, small molecular organic acid is added by the pending water body containing trivalent arsenic As (III), sexavalent chrome Cr (VI), adjust ph, can cause the conversion to carbonic acid gas of the oxidation of arsenic in water body, the reduction of chromium and organic acid.
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.
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 these small molecular organic acids existed in water body and realize having hypertoxicity material trivalent arsenic and chromic associated treatment, final three kinds of objectionable impuritiess are all converted into the less or completely harmless product of toxicity, realize the automatically cleaning of water body, without the need to adding any chemical reducing agent or oxygenant in addition, therefore this technical scheme be arsenic, the improvement of the chromium pollution water thinking that provides a kind of cheapness, clean, achieve many things at one stroke.
Compared with prior art, the invention has the beneficial effects as follows:
(1) small molecular organic acid common in water body is utilized, such as, 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 to be converted into the final removal that toxicity pentavalent arsenic that is less, that more easily remove is conducive to arsenic, hypertoxicity material sexavalent chrome is converted into nontoxic trivalent chromium simultaneously.
(2) organic acid in water body can also be converted into carbonic acid gas by the inventive method being oxidized arsenious while simultaneously, realizes the automatically cleaning of water body, this technology environmental protection, without harm, has the possibility used on a large scale.
(3) just can react when only having three kinds of materials to coexist in the inventive method, any two kinds of materials coexist and all can not react.
(4) without the need to the input of outside resources in the reaction process of the inventive method, without the interpolation of chemical substance, non-secondary pollution, without the generation of precipitation, mud.The reactant utilized 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) for 5:1:3, the oxidation efficiency of As (III) and the reduction efficiency of Cr (VI);
When Fig. 5 embodiment 4 selects citric acid/As (III)/Cr (VI) for 3:1:0.5, the oxidation efficiency of As (III) and the reduction efficiency of Cr (VI);
When Fig. 6 embodiment 5 selects oxalic acid/As (III)/Cr (VI) for 10:1:4, the oxidation efficiency of As (III) and the reduction efficiency of Cr (VI).
Embodiment
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described:
Embodiment 1:
The water body mesoxalic acid 2mM of to be 1mM, Cr (VI) concentration by As (III) concentration be 0.6mM, utilizes sulfuric acid that pH value is adjusted to 3, mixing solutions 100mL;
One is the mixing solutions 100mL of 1mM and oxalic acid 2mM for As (III) concentration, utilizes sulfuric acid that pH value is adjusted to 3; One is the mixing solutions 100mL of 0.6mM and oxalic acid 2mM for Cr (VI) concentration, utilizes sulfuric acid that pH value is adjusted to 3; One is the mixing solutions 100mL of 0.6mM for As (III) concentration is 1mM and Cr (VI) concentration, utilizes sulfuric acid that pH value is adjusted to 3.
As depicted in figs. 1 and 2, react when As (III), Cr (VI) and oxalic acid three kinds coexist and just can carry out, and processing efficiency is higher.Other any two kinds of materials do not react when coexisting.
Embodiment 2:
Be 1mM, Cr (VI) concentration by As (III) concentration be citric acid 4mM in the water body of 1.2mM, utilize sulfuric acid that pH value is adjusted to 2, mixing solutions 100mL;
As shown in Figure 3, the citric acid with two carboxyl structure can make As (III) too, synergistic oxidation reduction effect occurs Cr (VI).
Embodiment 3:
The water body mesoxalic acid 5mM of to be 1mM, Cr (VI) concentration by As (III) concentration be 3mM, utilizes 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:
Be 1mM, Cr (VI) concentration by As (III) concentration be citric acid 3mM in the water body of 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:
The water body mesoxalic acid 10mM of to be 1mM, Cr (VI) concentration by As (III) concentration be 4mM, utilizes 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 (4)
1. one kind utilizes the treatment process of 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, small molecular organic acid is added by the pending water body containing trivalent arsenic As (III), sexavalent chrome Cr (VI), adjust ph, can cause the conversion to carbonic acid gas of the oxidation of arsenic in water body, the reduction of chromium and organic acid, the mol ratio of described As (III)/small molecular organic acid/Cr (VI) is 1:2 ~ 10:0.5 ~ 4.
2. the treatment process 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 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 utilizing organic acid synergistic oxidation trivalent arsenic and reduction of hexavalent chromium according to any one of claim 1-3, is characterized in that adopting sulfuric acid that pH value is adjusted to 1-4.
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| 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 |
| CN104876318B (en) * | 2015-05-29 | 2017-06-13 | 华中师范大学 | A kind of method for treating water of manganese dioxide/oxalic acid material reduction removal Cr VI |
| 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 |
| CN110713224B (en) * | 2019-10-10 | 2020-10-23 | 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 |
| CN113274687B (en) * | 2021-04-30 | 2022-04-08 | 华中科技大学 | Co-treatment method of chromium slag and acidic arsenic-containing wastewater |
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