CN101519241A - Method for deoxidizing hexavalent chromium in wastewater by using sludge - Google Patents
Method for deoxidizing hexavalent chromium in wastewater by using sludge Download PDFInfo
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- CN101519241A CN101519241A CN200910048910A CN200910048910A CN101519241A CN 101519241 A CN101519241 A CN 101519241A CN 200910048910 A CN200910048910 A CN 200910048910A CN 200910048910 A CN200910048910 A CN 200910048910A CN 101519241 A CN101519241 A CN 101519241A
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Abstract
The invention discloses a method for deoxidizing hexavalent chromium in wastewater by using sludge, and relates to attenuation technology for heavy metal wastewater. Dehydrated sludge in a wastewater plant is dried at temperature between of 45 and 60 DEG C, pulverized and sifted by a sieve with 0.45 mm; siftage is a biomass reducer; the method adopts 0.1 mol/L hydrochloric acid or sulphuric acid solution to carry out protonated pretreatment on the reducer; and subsequently, the reducer and the wastewater containing hexavalent chromium are mixed and react to deoxidize the hexavalent chromium of the wastewater into trivalent chromium. Aiming at the problems of high cost and secondary pollution of the prior chemical reducer, the method comes up with the adoption of the dehydrated sludge of the wastewater plant as the biomass reducer, utilizes the deoxidizing capacity of organism in the sludge to deoxidize the hexavalent chromium in the wastewater, has the advantages of low cost, wide source, simple equipment and small secondary pollution and has strong practicability and wide application prospect. The method is suitable for the attenuation treatment of the wastewater containing hexavalent chromium with upper-limit concentration of 500 mg/L and treats waste by waste; while treating the wastewater containing the hexavalent chromium, the method also provides a novel path for the recycling of the sludge in the sludge plant and has considerable economic, social and environmental benefits.
Description
Technical field
Chromic method in the mud reducing waste water relates to and a kind of hexavalent chrome reduction in the waste water is become chromic technology, belongs to the attenuation technology of heavy metal in the water-treatment technology field.
Background technology
Chromium and compound thereof are widely used as the basic material of mainstay industries such as plating, mining, smelting, process hides, and along with the sustainable development of every profession and trade, the chromium pollutant that contains of its discharging enters environment, and the ecosystem has been proposed acid test.In water environment system, trivalent chromium and sexavalent chrome are main existence forms, compare with trivalent chromium, and sexavalent chrome is soluble in water, and transport property is big, oxidisability is strong and the toxicity height.Therefore, the detoxifcation of hexavalent chromium wastewater and the focal issue that is treated as environmentalist's care.
In view of the toxicity of chromium and the substantial connection of its valence state, usually way is to adopt various means the sexavalent chrome of high poison to be converted into the trivalent chromium of low toxicity, promptly adopt chromic reduction technique to realize the attenuation of waste water, adopt various separation methods that trivalent chromium is removed from water surrounding then, the wherein chromic committed step that is reduced to this method.
The hexavalent chrome reduction technology comprises physico-chemical process and biological process, and wherein the chemical reduction law technology is comparatively ripe, is widely used.Chemical reduction method is chosen one or more chemical reducing agents usually, as sulfide, sulphite, metallic iron etc., with the hexavalent chromium wastewater reaction, be trivalent chromium with the hexavalent chrome reduction in the waste water, its main drawback is to add the expensive and secondary pollution problem that reduction dosage causes greatly.
On the other hand, continuous expansion along with the human being's production scale, the various organic-biological matter wastes that comprise excess sludge, kitchen castoff, agricultural poultry waste, food waste of aquatic produce in a large number, and its treatment and disposal also becomes the key issue that needs to be resolved hurrily in the Sustainable development.
Therefore, developing a kind of is the hexavalent chromium wastewater control techniques of reductive agent with the biomass waste, and to the pollution reparation of water surrounding, the resource utilization of waste is utilized again, promotes the industry and the harmonious development of environment to have the important strategic meaning.
Summary of the invention
The present invention is directed to the expensive of conventional chemical reductive agent and secondary pollution problem, propose to adopt dewatered sludge of urban sewage plant as biomass reductant, utilize in the mud organic reducing power that sexavalent chrome in the waste water is reduced, realize efficient, cheap, greenly control in the water surrounding hexavalent chromium polluted.
For reaching above purpose, the present invention is by finding that to Sewage Plant dewatered sludge The Characteristic Study dewatered sludge is a kind of biomass waste that typically is rich in large amount of organic, mainly is made up of protein, humic acid, polysaccharide, lipid etc.Simultaneously, mud is again that a kind of surface has the porous medium that enriches group.In view of contacting and adsorptive power of organic reducing power and surface group, we think that dewatered sludge is a kind of very potential biomass reductant.Find through secular experiment, from the dewatered sludge to the biomass reductant, crucially in its treating processes be to obtain huge reaction specific surface area, chromicly in organism and the waste water fully contact guaranteeing, organism provides a large amount of electron donors for chromic reduction.Yet mud itself contains a certain amount of metal ion, mainly comprises Ca
2+, Mg
2+, Fe
3+, Na
+Deng.Some metal ions are replaced to liquid phase by hydrogen ion liquid phase pH are risen in reaction process, have influenced the carrying out of reduction reaction to a great extent.Therefore, the present invention adopts hydrochloric acid or sulfuric acid that mud is carried out protonated pre-treatment, for follow-up reduction reaction provides stable p H environment.The control of pH is very crucial in the reduction reaction process, not only influences the speed of reduction reaction, also has influence on trivalent chromium simultaneously in the distribution of solid, liquid in mutually, should strict control.Concrete technical scheme is:
A. the preparation of biomass reductant is dried dewatered sludge of urban sewage plant to constant weight under 45～60 ℃, grinds the back and crosses the 0.45mm sieve, and screen underflow is a biomass reductant;
B. the protonated pre-treatment of biomass reductant, hydrochloric acid or sulphuric acid soln adding stirred reactor that the reductive agent of A step preparation and volumetric molar concentration are 0.1mol/L, the control stirring velocity is 100～300r/min, the add-on of acid solution adds 10～100L acid solution for the 1kg reductive agent, reacts 2～12h under the room temperature, then, natural subsidence 1～2h, expel liquid is stored, and behind adding appropriate hydrochloric acid or the sulfuric acid, can be used further to protonated pre-treatment of biomass reductant or reduction reaction and transfer pH;
C. reduction reaction, the control reductive agent is 1kg reductive agent: 50～500L with adding the waste water ratio, hexavalent chromium wastewater is added above-mentioned reactor, subsequently that reactor is airtight, hydrochloric acid or sulphuric acid soln with 0.1mol/L are transferred pH to 0.5～1.2, the control stirring velocity is 100～300r/min, react 0.5～12h under the room temperature, sexavalent chrome is reduced into trivalent chromium in the waste water, and trivalent chromium mainly is present in the liquid phase, and trivalent chromium is not adsorbed on the reductive agent surface substantially, the revolving horizontal drum whizzer is adopted in the reaction back, separation factor is 1000～2000 to carry out solid-liquid separation, and supernatant liquor is attenuation waste water, and solid is useless reductive agent;
D. subsequent disposal is disposed, and after containing the chromic waste water of attenuation and adopting conventional chemical precipitator method dechromisation, enters municipal sewage pipe network, and useless reductive agent can be used as household waste and carries out treatment and disposal.
Described mud is the excess sludge that the various biological treatment of sewage or waste water process field is produced, and its organic content is greater than 50%.
Described hexavalent chromium wastewater comprises two big classes: a class is the chromic trade effluent that contains that produces in plating, mining, smelting, process hides, the metal processing industry production process; Another kind of is to be subjected to hexavalent chromium polluted former water, comprises river, lake, underground water, wherein is limited to 500mg/L on the hexavalent chromium concentration.
Biomass reductant of the present invention is compared with chromic method in the existing employing chemical reducing agent reducing waste water, has following advantage and effect:
1. biomass reductant wide material sources of the present invention, preparation process are simple, and reducing power is equivalent to the several times of chemical reducing agent commonly used such as ferrous sulfate, S-WAT, and reduction is comparatively thorough, has suitable advantage aspect industrialization promotion.
2. entire reaction course of the present invention has been avoided a large amount of use chemical agents and the secondary chemical pollution that produces, in the time of efficient reduction of hexavalent chromium, reductive agent after the use only need just can be used as household waste through simple flushing processing and carry out the subsequent disposal disposal, have good Environmental compatibility, and do not increase subsequent treatment cost.
3. the present invention proposes to adopt biomass waste to replace chemical reducing agent from methodology, sexavalent chrome in the waste water is reduced attenuation, has very strong promotion potential in actual applications, used mud can be generalized to other biomass waste in the invention, as kitchen castoff, agricultural poultry waste, food waste of aquatic etc.
Embodiment
The invention will be further elaborated below in conjunction with specific embodiment, and these embodiment only are used to the present invention is described and are not used in and limit the scope of the invention.
Embodiment 1
Dewatered sludge is taken from the Shanghai City municipal wastewater treatment plant, and adopting calcination method (CJ/T 96-1999) to measure its volatility organic content is 63.11%.With mud in 60 ℃ of baking oven inner drying 48h to constant weight, taking-up grinds, and crosses 0.45mm national standard sieve, screen underflow is a biomass reductant.Adopt elemental analyser to measure its constituent content, adopt chloroazotic acid clear up-inductively coupled plasma emission spectrography measures its metal content, the results are shown in Table one.Waste water is from certain metal products source mill, and hexavalent chromium concentration is 100mg/L in the employing AWWA-3500 spectrophotometry waste water.
The 100kg reductive agent is added 15m
3The stirred-tank reactor of capacity, simultaneously, the ratio in 1kg reductive agent adding 50L acid solution adds 5m
3The 0.1mol/L hydrochloric acid soln; The control stirring velocity is 200r/min, reacts 8h under the room temperature.Natural subsidence 1.5h discharges supernatant liquor to spent acid basin and prepares against recycle then; Throw out is protonated reductive agent.Handle the ratio of 100L waste water again in the 1kg reductive agent, with 10m
3Waste water adds this reactor, and reactor is airtight, transfers pH to 1.0 with the 0.1mol/L hydrochloric acid soln, and the control stirring velocity is 200r/min, reacts 5h under the room temperature.Post reaction mixture adopts the revolving horizontal drum whizzer, is under 1500 conditions in separation factor, and centrifugal 15min realizes solid-liquid separation.Liquid phase adopts spectrophotometry AWWA-3500 to measure content of 6-valence Cr ions, and its concentration is lower than the detectability of method, and reduction ratio is 100%, has reached the attenuation requirement, can enter other treatment process and carry out subsequent disposal.Solid phase is useless reductive agent, adopt EPA-3060A method alkali to clear up, chromic content in the AWWA-3500 spectrophotometry solid phase, its hexavalent chromium concentration is lower than the detectability of method, adopt chloroazotic acid clear up-inductively coupled plasma emission spectrography measures total chrome content in the solid phase, its content is 1.24mg/g, mainly exists with the trivalent chromium form, meets by common offal treatment requirement; Therefore, dispose the industry solid waste landfill field of handing over.
Embodiment 2
Dewatered sludge reductive agent and protonated pretreatment process thereof are with embodiment 1.
The waste water of handling is from electronic devices and components manufactory, and hexavalent chromium concentration is 150mg/L in the employing spectrophotometry AWWA-3500 mensuration waste water.
The 25m of reductive agent after filling the protonated pre-treatment of 150kg
3In the stirred-tank reactor of capacity, the ratio in 1kg reductive agent processing 100L waste water adds 15m
3Waste water; Reactor is airtight, transfer pH to 0.8 with the 0.1mol/L hydrochloric acid soln, the control stirring velocity is 200r/min, reacts 3h under the room temperature.Post reaction mixture is under 1500 conditions in separation factor, and centrifugal 15min is separated into the solid-liquid two-phase.Liquid phase adopts spectrophotometry AWWA-3500 to measure content of 6-valence Cr ions, and its concentration is lower than the detectability of method, and reduction ratio is 100%, has reached the attenuation requirement, after further handling dechromisation, can enter municipal sewage pipe network.Solid phase is useless reductive agent, after adopting EPA-3060A method alkali to clear up, spectrophotometry AWWA-3500 measures chromic content in the solid phase, its hexavalent chromium concentration is lower than the detectability of method, adopt chloroazotic acid clear up-inductively coupled plasma emission spectrography measures total chrome content in the solid phase, its content is 1.17mg/g, mainly exists with the trivalent chromium form.Meet by common offal treatment requirement; Dispose the industry of handing over solid waste landfill field.
Table one is the mud essential property
Claims (3)
1. chromic method in the mud reducing waste water is characterized in that:
A. the preparation of biomass reductant
Dewatered sludge of urban sewage plant is dried to constant weight under 45～60 ℃, grind the back and cross the 0.45mm sieve, screen underflow is a biomass reductant;
B. the protonated pre-treatment of biomass reductant
Hydrochloric acid or sulphuric acid soln adding stirred reactor that the reductive agent of A step preparation and volumetric molar concentration are 0.1mol/L, the control stirring velocity is 100～300r/min, the add-on of acid solution adds 10～100L acid solution for the 1kg reductive agent, react 2～12h under the room temperature, then, natural subsidence 1～2h, expel liquid is stored, after adding appropriate hydrochloric acid or sulfuric acid, can be used further to protonated pre-treatment of biomass reductant or reduction reaction and transfer pH;
C. reduction reaction
The control reductive agent is 1kg reductive agent: 50～500L with adding the waste water ratio, hexavalent chromium wastewater is added above-mentioned reactor, subsequently that reactor is airtight, hydrochloric acid or sulphuric acid soln with 0.1mol/L are transferred pH to 0.5～1.2, the control stirring velocity is 100～300r/min, react 0.5～12h under the room temperature, sexavalent chrome is reduced into trivalent chromium in the waste water, and trivalent chromium mainly is present in the liquid phase, trivalent chromium is not adsorbed on the reductive agent surface substantially, and the revolving horizontal drum whizzer is adopted in reaction back, and separation factor is 1000～2000 to carry out solid-liquid separation, supernatant liquor is attenuation waste water, and solid is useless reductive agent;
D. subsequent disposal is disposed
After containing the chromic waste water of attenuation employing conventional chemical precipitator method dechromisation, enter municipal sewage pipe network, useless reductive agent can be used as household waste and carries out treatment and disposal.
2. chromic method in the mud reducing waste water according to claim 1 is characterized in that, described dewatered sludge of urban sewage plant is the excess sludge that the various biological treatment of sewage or waste water process field is produced, and its organic content is greater than 50%.
3. chromic method in the mud reducing waste water according to claim 1, it is characterized in that described hexavalent chromium wastewater comprises two big classes: a class is the chromic trade effluent that contains that produces in plating, mining, smelting, process hides, the metal processing industry production process; Another kind of is to be subjected to hexavalent chromium polluted former water, comprises river, lake, underground water, wherein is limited to 500mg/L on the hexavalent chromium concentration.
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Cited By (8)
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| CN103521513A (en) * | 2013-10-18 | 2014-01-22 | 中国科学院南京土壤研究所 | Leaching method of soil polluted by hexavalent chromium |
| CN104338728A (en) * | 2013-08-06 | 2015-02-11 | 中国科学院过程工程研究所 | Biomass wet detoxification method of hexavalent chromium-contained waste residues |
| CN105771914A (en) * | 2016-03-24 | 2016-07-20 | 陕西科技大学 | Method for preparing polyaniline-modified sludge adsorbent and removing hexavalent chromium in water |
| CN106001059A (en) * | 2016-03-08 | 2016-10-12 | 侯绪华 | Chromium slag pulping, curing and detoxifying method |
| CN107739831A (en) * | 2017-10-19 | 2018-02-27 | 大连理工大学 | A kind of abandoned biomass hydrothermal reduction detoxification chromium slag and the method for reclaiming compound |
| CN109796058A (en) * | 2019-01-03 | 2019-05-24 | 华中科技大学 | A method of Cr VI and organic pollutant combined pollution are administered using charcoal |
| CN110935711A (en) * | 2019-11-13 | 2020-03-31 | 武汉钢铁有限公司 | Method for recycling steel multi-component waste |
| CN113666490A (en) * | 2021-09-27 | 2021-11-19 | 长春工业大学 | Method for degrading chromium in surface water of tailing pond by activated sludge |
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| CN104338728A (en) * | 2013-08-06 | 2015-02-11 | 中国科学院过程工程研究所 | Biomass wet detoxification method of hexavalent chromium-contained waste residues |
| CN104338728B (en) * | 2013-08-06 | 2017-02-22 | 中国科学院过程工程研究所 | Biomass wet detoxification method of hexavalent chromium-contained waste residues |
| CN103521513A (en) * | 2013-10-18 | 2014-01-22 | 中国科学院南京土壤研究所 | Leaching method of soil polluted by hexavalent chromium |
| CN103521513B (en) * | 2013-10-18 | 2015-04-01 | 中国科学院南京土壤研究所 | Leaching method of soil polluted by hexavalent chromium |
| CN106001059A (en) * | 2016-03-08 | 2016-10-12 | 侯绪华 | Chromium slag pulping, curing and detoxifying method |
| CN105771914A (en) * | 2016-03-24 | 2016-07-20 | 陕西科技大学 | Method for preparing polyaniline-modified sludge adsorbent and removing hexavalent chromium in water |
| CN107739831A (en) * | 2017-10-19 | 2018-02-27 | 大连理工大学 | A kind of abandoned biomass hydrothermal reduction detoxification chromium slag and the method for reclaiming compound |
| CN107739831B (en) * | 2017-10-19 | 2019-05-28 | 大连理工大学 | A kind of abandoned biomass hydrothermal reduction detoxification chromium slag and the method for recycling compound |
| CN109796058A (en) * | 2019-01-03 | 2019-05-24 | 华中科技大学 | A method of Cr VI and organic pollutant combined pollution are administered using charcoal |
| CN110935711A (en) * | 2019-11-13 | 2020-03-31 | 武汉钢铁有限公司 | Method for recycling steel multi-component waste |
| CN110935711B (en) * | 2019-11-13 | 2022-01-18 | 武汉钢铁有限公司 | Method for recycling steel multi-component waste |
| CN113666490A (en) * | 2021-09-27 | 2021-11-19 | 长春工业大学 | Method for degrading chromium in surface water of tailing pond by activated sludge |
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