CN102229462A - Method for removing heavy metal Cd from river sediment - Google Patents

Method for removing heavy metal Cd from river sediment Download PDF

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Publication number
CN102229462A
CN102229462A CN2011101387361A CN201110138736A CN102229462A CN 102229462 A CN102229462 A CN 102229462A CN 2011101387361 A CN2011101387361 A CN 2011101387361A CN 201110138736 A CN201110138736 A CN 201110138736A CN 102229462 A CN102229462 A CN 102229462A
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heavy metal
reactor
river bottom
mud
inoculation liquid
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CN102229462B (en
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刘国涛
彭绪亚
李建华
刘斌
袁荣焕
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Chongqing University
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Chongqing University
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/20—Sludge processing

Abstract

Relating to a municipal solid waste disposal technology, the invention provides a method for removing heavy metal Cd from river sediment by microbial leaching, and the method of the invention aims to provide a solution to the problems of severe heavy metal Cd pollution in urban river sediment and utilization restriction of dredged sediment in agriculture and forestry. The method is realized by: adding a proper amount of cultured and acclimated inoculation liquid into a reaction system, and keeping a substrate at a concentration of 30g/L, the inoculation liquid in a volume ratio of 5%, the dissolved oxygen at a concentration of 7.5-9.0mg/L and the temperature in a range of 25-32DEG C, and regularly supplementing the moisture evaporated in a reactor. The method of the invention employs microbial leaching so as to make the removal rate of heavy metal Cd reach 16%-18%.

Description

A kind of method of removing heavy metal Cd in the river bottom mud
Technical field
The present invention relates to a kind of river bottom mud heavy metal treatment process, be specifically related to the technological method that a kind of bioleaching method is removed heavy metal Cd in the dredging bed mud.
 
Background technology
It is a current important environmental problem of the whole world that river bottom mud (settling) pollutes.Pollutent is by atmospheric precipitation, discharge of wastewater, rainwater leaching and wash away and enter water body, deposits in the bed mud at last and enrichment gradually, and bed mud is polluted gradually, compiles ground to what bed mud became pollutent at last.After the outer source of pollution to the river have carried out effective control, when water surrounding changes, be deposited on nitrogen phosphorus nutrition element, heavy metal and hardly degraded organic substance in the bed mud and will discharge again and enter water body, influence the water quality of overlying water, form " secondary pollution ".In addition, bed mud is benthic main life area and food source, pollution substance can directly or indirectly cause the evil effect to bottom-dwelling or the biological intoxicating that produces of overlying water, and by processes such as biomagnification, food chain amplifications, further influences terrestrial life and human health.
Lake dredging bottom-mud has characteristics such as quantity is big, water ratio is high, it is serious to pollute, complicated component, if the dredging bed mud is not taked any engineering measure and simple and easy stacking, can take a large amount of soils on the one hand, can cause secondary pollution because of rainwash again on the other hand.In addition, owing to contain the amino acid and the required various trace elements of plant-growth of abundant N, P, K, trace in the bed mud, what domestic and international numerous scholars generally admitted is to transfer the dredging bed mud to the agricultural utilization.This in the long run dredging bed mud method of disposal tallies with the national condition, and constructs recycling economy, realizes recycling, helps the Sustainable development of city and agricultural, has vast potential for future development.
Engineering at heavy-metal contaminated soil and bed mud improvement mainly comprises chemical leaching, electronic reparation, soil change, curing technology etc. at present.(1) chemical leaching: use can promote heavy metal in soil migration or dissolved extraction agent, makes solid phase of soil bonded heavy metal transfer to liquid phase of soil, the liquid that includes heavy metal is extracted from soil layer again, separates the technology with sewage disposal.Chemical leaching is one of effective means of effectively handling difficult volatile heavy metal contaminated soil, and selecting suitable extraction agent is the key of this technology.But all there are also unresolved or perfect technical problems such as recovery, secondary pollution in which kind of extraction agent.(2) electronic reparation: utilize electrode to make heavy metal ion from soil surface desorb and dissolving, directional migration is enriched in cathode zone, and extracting is removed again.This technology has been carried out large-scale engineering test in the Germany and the U.S. at present, is particularly suitable for the clay and the silt soil of low-permeability, economical rationality.But because the complicacy of soil system component, the practical application phenomenon opposite with experimental result often appears, all can influence the effect of electronic reparation as the shock-absorbing capacity of soil, component, ion composition, pollution metal ionic kind etc., itself is corroded metal electrode easily, also can cause the secondary pollution of soil.(3) electric heating reparation: in soil, feed hot steam or, soil is heated, volatile heavy metal is parsed from soil particle, and collect and handle with methods such as radio frequency heating.The weak point of this technology is that the soil organism and water of constitution are subject to destruction, drives soil moisture and need consume a large amount of energy.(4) curing technology: polluted soil is mixed by a certain percentage with solidifying agent, change the physico-chemical property of soil, absorption or precipitating action by heavy metal reduce its biological effectiveness.After toxic metal in the contaminated soil is fixed, not only can alleviates heavy metal to a certain extent the physiology of soil organisms and plant is poisoned, and can alleviate heavy metal to deep subsoil and underground water migration.This method has certain effect, the in-situ solidifying heavy metal reduces cost greatly, but certain limitation is also arranged: just changed heavy metal and have a form in soil, have little understanding to the soil permanent stability with to Ecosystem System Influence, also lack the research of this respect at present.
Because long-term precipitation, cause containing in the river bottom mud a small amount of heavy metal cadmium (Cd), though cadmium content is less relatively, but after undressed lake dredging bottom-mud enters TERRESTRIAL ECOSYSTEMS, heavy metal cadmium can enter food chain and be accumulated to food chain upper strata biology with ecological circulation, and then final harm humans health, cause illnesss such as itai-itai, rickets easily.So how to solve the problem of removing heavy metal cadmium in the lake dredging bottom-mud, become this area research direction.
?
Summary of the invention
At above-mentioned prior art deficiency, the technical problem to be solved in the present invention is: how to provide a kind of technology simple, with low cost, can effectively remove the method for heavy metal cadmium in the river bottom mud, make lake dredging bottom-mud can be used in the effect that the agricultural utilization reaches turns waste into wealth.
In order to solve the problems of the technologies described above, the applicant has studied the existing method of handling the river bottom mud heavy metal in the prior art, compare with existing routine techniques, the method that adopts microorganism leaching technology to carry out biological restoration has that security is higher, expense is lower and advantage such as effect is better, is a kind of environmentally friendly method.Wherein, microorganism leaching technology is to utilize the catalysed oxidn of the acidophilia thiobacillus of special chemosynthetic autotroph to reduce the pH value of sludge system, make the heavy metal of form hard to tolerate enter liquid phase,, and reach the purpose of removing heavy metal in the mud again by sludge dewatering from the solid phase stripping.The bioleaching technology is applied to the stripping and the recovery of metal in difficult lixiviate ore or the lean ore at first, and begins to be applied to the leaching of heavy metal in the mud with the later stage eighties 20th century.The advantage of bioleaching technology is: (1) thiobacterium is not the pathogenic bacteria of humans and animals; (2) can utilize spent acid that mud is carried out pre-acidifying, the sample municipal sludge digestion method combination of can becoming reconciled can make full use of existing operation facility, and working cost is low; (3) thiobacterium viability adaptability is strong in the mud, and breeding is fast, can start the leaching heavy metal fast; (4) simple to operate, operational process need not special control, equal energy leaching heavy metal in 10～37 ℃ of scopes; (5) bioleaching can remove effectively that heavy metal can play the effect of killing pathogenic bacteria again in the mud.Yet, the bioleaching method is scarcely out of swaddling-clothes to the removal research of heavy metal in the lake dredging bottom-mud, for the research of the removal mechanism of bioleaching, influence factor and bioleaching to problem such as the removal efficient of some heavy metal is lower, also be not well solved at present, still need to do a large amount of research.
So the applicant goes out following technical proposals based on microorganism leaching technological development and solves described technical problem behind big quantity research:
A kind of method of removing heavy metal Cd in the river bottom mud, its characteristics are, have adopted the bioleaching technology, are the inoculation liquid that microorganism leaching bacterium is made bioleaching with the thiobacillus ferrooxidant, inoculation liquid is mixed the back aeration with pending river bottom mud and stir, heavy metal Cd is removed.
Specifically the technical program is: employing one has the reactor of oscillation device and aerating apparatus, and pending river bottom mud is added reactor, adds reaction substrate FeSO 47H 2O, and reaction substrate concentration is controlled at 7.5 * 10 -3G/ml; Adopt iron protoxide thiobacterium inoculation liquid to inoculate, and the volume ratio of iron protoxide thiobacterium inoculation liquid is controlled to be 5% into reactor; Temperature in the controlling reactor is 25～32 ℃, and initial pH value is controlled in 4.0～4.5 scopes; Reactor is carried out aeration and vibration promotion reaction, the aeration extent control is 7.5～9.0mg/L at reactor dissolved oxygen DO, vibration reciprocating frequence 100rpm, the supernatant liquor that will contain heavy metal Cd behind reaction 10～12d separates, thereby the heavy metal Cd content in the remaining river bottom mud is reduced.
Through verification experimental verification, adopt present method that river bottom mud is handled, can be so that the clearance of heavy metal Cd reaches 16%～18%, river bottom mud after treatment, the content of its heavy metal cadmium can reach agricultural and use standard, simultaneously can not destroy fertilizer nutrient content in the bed mud, can be used for agroforestry and use, reach the effect that turns waste into wealth.
Wherein as optimizing, described iron protoxide thiobacterium inoculation liquid adopts following method preparation, draw bacterial classification sample 10ml adding 30ml 9k liquid nutrient medium from the effluent in colliery the mud with cheating, under 30 ℃ condition, begin to cultivate,, draw supernatant liquor 10ml and add 9k liquid nutrient medium 90ml when solution becomes reddish-brown, under similarity condition, cultivate again, so switching is 5 times, and the time that occurs to reddish-brown becomes 1d by original 5d, the iron protoxide thiobacterium inoculation liquid that obtains taming; Wherein said 9K substratum is mixed by A component and B component and forms, and mixing back pH value is 2.5, and the A component comprises (NH 4) 2SO 43.0g, KCl 0.1g, K 2HPO 40.5g, MgSO 47H 2O 0.5g, Ca (NO 3) 20.01g, distilled water 700ml, before mixing the A component in 121 ℃, moist heat sterilization 20min under the 0.1MPa; The B component comprises FeSO 47H 2O 44.2g, distilled water 300ml, 10ml/l H 2SO 41ml, the B component is in 105 ℃ of sterilizations down before mixing.Iron protoxide thiobacterium inoculation liquid preparation method after this optimizes has preparation simply, implements characteristics easily.
In sum, the present invention has the following advantages: 1, present method is handled river bottom mud, can make the clearance of heavy metal Cd reach 16%～18%, and treatment effect is better.2, present method is handled river bottom mud, only needs the ordinary reactor that stirs vibration and aeration performance that has, and is convenient to implement, and while method technology is also comparatively simple, and implementation cost is lower, is easy to promote.3, present method can not produce secondary pollution owing to be to adopt the bioleaching technology that river bottom mud is handled, and can not destroy the nutrient content in the mud yet, and the river bottom mud after the processing can be used for agroforestry and use, and reaches the effect that turns waste into wealth.
 
Description of drawings
The reactive system synoptic diagram of Fig. 1 for adopting in the embodiment of the invention.
 
Embodiment
The present invention is described in further detail below in conjunction with the drawings and specific embodiments.
The present invention at first is the cultivation domestication of thiobacterium and the preparation of bioleaching inoculation liquid, draw bacterial classification sample 10ml adding 30ml 9k liquid nutrient medium from the effluent in colliery the mud with cheating, under 30 ℃ condition, begin to cultivate, when solution becomes reddish-brown, draw supernatant liquor 10ml and add 9k liquid nutrient medium 90ml, under similarity condition, cultivate again, so switching is 5 times, the time that occurs to reddish-brown becomes 1d by original 5d, the iron protoxide thiobacterium inoculation liquid (hereinafter to be referred as inoculation liquid) that obtains taming.
The 9K substratum is mixed by A component and B component and forms, and mixing back pH value is 2.5, and the A component comprises (NH 4) 2SO 43.0g, KCl 0.1g, K 2HPO 40.5g, MgSO 47H 2O 0.5g, Ca (NO 3) 20.01g, distilled water 700ml, before mixing the A component in 121 ℃, moist heat sterilization 20min under the 0.1MPa; The B component comprises FeSO 47H 2O 44.2g, distilled water 300ml, 10ml/l H 2SO 41ml, the B component is in 105 ℃ of sterilizations down before mixing.
Get inoculation bacterium liquid 10ml, add 9k substratum 90ml, with distilled water diluting to 200ml, place the 500ml reactive system, add a certain amount of dredging bed mud simultaneously, dissolved oxygen DO in aeration 5 ml/min(controlling reactor is 7.5～9.0mg/L), under the 100rpm oscillation frequency, and to bed mud concentration, temperature, substrate kind (FeSO 47H 2O, S powder and Na 2S 2O 3) and bioleaching important factor in order optimized parameter value such as initial pH value select, its optimized parameter value is respectively: 30g/L, 25～32 ℃, FeSO 47H 2O, 4.0～4.5.
Finally,,, make that the clearance of heavy metal Cd is higher in the mud, can reach 16%～18% through the bioleaching cycle of 10～12d by controlling these conditions.
Experiment embodiment:
The reactive system synoptic diagram that adopts when Fig. 1 is use.As shown in Figure 1, comprise reactor 1, water bath with thermostatic control vibrator 2, aerator 3 and under meter 4; Wherein reactor 1 is positioned at water bath with thermostatic control vibrator 2, and aerator 3 inserts reactor 1 bottom by tracheae, and under meter 4 is positioned on the tracheae, for increasing the reliable results degree, adopts two complete equipments to carry out parallel test.During experiment, get the inoculation bacterium liquid 10ml of above-mentioned domestication, join 9k substratum 90ml, with distilled water diluting to 200ml, place the reactor 1 (one of them reactor is as parallel test) of two 500ml respectively, in reactor 1, add a certain amount of dredging bed mud simultaneously, making its concentration is 30g/L, reactor 1 is placed in the water bath with thermostatic control vibrator 2, start aerator 3, adjusting under meter 4, to make air demand be that dissolved oxygen DO in the 5 ml/min(reactors is 7.5～9.0mg/L), under the 100rpm oscillation frequency, during experiment with FeSO 47H 2O is a reaction substrate, controls its concentration 7.5 * 10 -3G/ml, the controlling reactor temperature is 25～32 ℃, reacting initial pH value is 4.0～4.5.The moisture that evaporation is consumed in the regular replenishment reactor.Every the time sampling 5ml of 2d, sample on whizzer with the centrifugal 45min of 1600r/min, with supernatant and precipitate and separate, the concentration of heavy metal in pH in the clear liquid and ORP and the solution analytically.Through 10～12d bioleaching week after date, the clearance of heavy metal Cd reaches %～18% in its bed mud, satisfies the bed mud agriculturalization substantially and utilizes standard.

Claims (3)

1. method of removing heavy metal Cd in the river bottom mud, it is characterized in that, adopted the bioleaching technology, is the inoculation liquid that microorganism leaching bacterium is made bioleaching with the thiobacillus ferrooxidant, inoculation liquid is mixed the back aeration with pending river bottom mud and stir, heavy metal Cd is removed.
2. the method for heavy metal Cd is characterized in that in the removal river bottom mud as claimed in claim 1, and employing one has the reactor of oscillation device and aerating apparatus, and pending river bottom mud is added reactor, adds reaction substrate FeSO 47H 2O, and reaction substrate concentration is controlled at 7.5 * 10 -3G/ml; Adopt iron protoxide thiobacterium inoculation liquid to inoculate, and the volume ratio of iron protoxide thiobacterium inoculation liquid is controlled to be 5% into reactor; Temperature in the controlling reactor is 25～32 ℃, and initial pH value is controlled in 4.0～4.5 scopes; Reactor is carried out aeration and vibration promotion reaction, the aeration extent control is 7.5～9.0mg/L at reactor dissolved oxygen DO, the vibration reciprocating frequence is 100rpm, and the supernatant liquor that will contain heavy metal Cd behind reaction 10～12d separates, thereby the heavy metal Cd content in the remaining river bottom mud is reduced.
3. the method for heavy metal Cd in the removal river bottom mud as claimed in claim 2, it is characterized in that, described iron protoxide thiobacterium inoculation liquid adopts following method preparation, draw bacterial classification sample 10ml adding 30ml 9k liquid nutrient medium from the effluent in colliery the mud with cheating, under 30 ℃ condition, begin to cultivate, when solution becomes reddish-brown, draw supernatant liquor 10ml and add 9k liquid nutrient medium 90ml, under similarity condition, cultivate again, so switching is 5 times, the time that occurs to reddish-brown becomes 1d by original 5d, the iron protoxide thiobacterium inoculation liquid that obtains taming; Wherein said 9K substratum is mixed by A component and B component and forms, and mixing back pH value is 2.5, and the A component comprises (NH 4) 2SO 43.0g, KCl 0.1g, K 2HPO 40.5g, MgSO 47H 2O 0.5g, Ca (NO 3) 20.01g, distilled water 700ml, before mixing the A component in 121 ℃, moist heat sterilization 20min under the 0.1MPa; The B component comprises FeSO 47H 2O 44.2g, distilled water 300ml, 10ml/l H 2SO 41ml, the B component is in 105 ℃ of sterilizations down before mixing.
CN2011101387361A 2011-05-26 2011-05-26 Method for removing heavy metal Cd from river sediment Expired - Fee Related CN102229462B (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103937705A (en) * 2014-03-10 2014-07-23 赵晗 Achromobacter insolitus and application of Achromobacter insolitus in heavy metal ion removing
CN107058197A (en) * 2017-06-14 2017-08-18 中南大学 A kind of microorganism formulation of Efficient Conversion Heavy Metals in Contaminated Soils cadmium and preparation method thereof
CN107236678A (en) * 2017-06-14 2017-10-10 湖南省农业生物技术研究中心 A kind of method of composite bacteria agent Efficient Conversion soil weak acid reference state cadmium
CN107418913A (en) * 2017-06-14 2017-12-01 湖南省农业生物技术研究中心 A kind of application of the microorganism formulation of Efficient Conversion Heavy Metals in Contaminated Soils cadmium
CN112845560A (en) * 2021-03-25 2021-05-28 重庆大学 Contaminated soil ex-situ remediation device and process

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CN1375553A (en) * 2002-04-25 2002-10-23 南京农业大学 Ferrous oxide theobacillus and sludge heavy-metal eliminating method therewith
CN1648077A (en) * 2004-04-30 2005-08-03 南京农业大学 Process and its device for biologically removing heavy metal in mud
CN101503269A (en) * 2008-12-30 2009-08-12 南京农业大学 Plug flow type bioleaching process and apparatus for sludge treatment
CN101830616A (en) * 2010-05-11 2010-09-15 沈阳建筑大学 Method for removing heavy metal Cr from sludge by bioleaching

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1375553A (en) * 2002-04-25 2002-10-23 南京农业大学 Ferrous oxide theobacillus and sludge heavy-metal eliminating method therewith
CN1648077A (en) * 2004-04-30 2005-08-03 南京农业大学 Process and its device for biologically removing heavy metal in mud
CN101503269A (en) * 2008-12-30 2009-08-12 南京农业大学 Plug flow type bioleaching process and apparatus for sludge treatment
CN101830616A (en) * 2010-05-11 2010-09-15 沈阳建筑大学 Method for removing heavy metal Cr from sludge by bioleaching

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103937705A (en) * 2014-03-10 2014-07-23 赵晗 Achromobacter insolitus and application of Achromobacter insolitus in heavy metal ion removing
CN107058197A (en) * 2017-06-14 2017-08-18 中南大学 A kind of microorganism formulation of Efficient Conversion Heavy Metals in Contaminated Soils cadmium and preparation method thereof
CN107236678A (en) * 2017-06-14 2017-10-10 湖南省农业生物技术研究中心 A kind of method of composite bacteria agent Efficient Conversion soil weak acid reference state cadmium
CN107418913A (en) * 2017-06-14 2017-12-01 湖南省农业生物技术研究中心 A kind of application of the microorganism formulation of Efficient Conversion Heavy Metals in Contaminated Soils cadmium
CN107236678B (en) * 2017-06-14 2020-12-15 湖南省农业生物技术研究所 Method for converting soil weak acid combined cadmium by using composite microbial inoculum
CN107418913B (en) * 2017-06-14 2020-12-22 湖南省农业生物技术研究中心 Application of microbial agent for converting heavy metal cadmium in polluted soil
CN112845560A (en) * 2021-03-25 2021-05-28 重庆大学 Contaminated soil ex-situ remediation device and process

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