CN102503059B - Method for removing heavy metal from sludge and device thereof - Google Patents
Method for removing heavy metal from sludge and device thereof Download PDFInfo
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- CN102503059B CN102503059B CN 201110375456 CN201110375456A CN102503059B CN 102503059 B CN102503059 B CN 102503059B CN 201110375456 CN201110375456 CN 201110375456 CN 201110375456 A CN201110375456 A CN 201110375456A CN 102503059 B CN102503059 B CN 102503059B
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Abstract
The invention relates to a method for removing heavy metal from sludge and a device, belongs to the technical field of environmental protection and particularly relates to the removing method for the heavy metal in the sludge. The method is characterized in that a repeatedly freezing and thawing pretreatment process is utilized to enhance an electric treating process of cathode liquid backflow, thereby obviously improving the efficiency in removing the heavy metal. A constructed treating device is utilized to perform repeated freezing and thawing pretreatment on the initial sludge; and then the sludge is placed into a sludge chamber; direct current voltage is applied to cathode and anode ends; the cathode liquid backflow process is externally adopted so as to neutralize the cathode and anode liquid; and the electrifying time is 144h. The method has the positive effects that the mobility of the heavy metal in the initial sludge is enhanced from the source; the electric removing efficiency of the heavy metal is obviously increased; no external material is added into the system; and the method is an environment-friendly and feasible enhancing method.
Description
Technical field
The invention belongs to environmental protection technical field, particularly heavy metal pretreatment technology and enhancement method thereof in a kind of eco-friendly mud.
Background technology
Municipal sludge is produce when disposing of sewage solid-state, semi-solid state and liquid waste, is the inevitable outcome of sewage work, contains nutrition such as a large amount of organism, nitrogen phosphorus, is a kind of urban pollutant that later use is worth that has.Yet a large amount of harmful heavy metals in the municipal sludge have limited the recycling of mud.Therefore, the problem of heavy metal content needs to be resolved hurrily in reduction or the removal municipal sludge.Electronic reparation (Electrokinetic Remediation) is subjected to extensive concern in recent years as a kind of emerging green high-efficient based technique for in-situ remediation.This technology has that expense is low, reagent dosage is few, installation and simple to operate, energy consumption is low and the remediation efficiency advantages of higher.Its ultimate principle is to insert electrode in solid phase or liquid phase systems, apply volts DS and form electric-force gradient, pollutent carries out orientation and moves, assembles, and collect and handle the purpose that the realization pollution medium subtracts dirt or cleaning through further solution under effects such as electric field, electrochemistry.The height key of mud electrokinetic process efficient depends on following two point: ⑴. the control of pH value in the electrokinetic process; ⑵. the form of heavy metal in the initial mud.In the galvanization, the brine electrolysis reaction taking place near the electrode, produce a large amount of OH-and H+ respectively in cathode and anode, makes near the pH value of electrode rise respectively and descend, the sludge pH value variation that brings thus causes near the heavy metal precipitation of negative electrode, has hindered the removal of heavy metal; The form of heavy metal distributes and has a strong impact on its removal efficient in the initial mud, studies show that, the heavy metal that exists with exchangeable species more easily is removed, and removing efficient can reach more than 90%, and only is 30% with the removal efficient that organically combines the heavy metal that attitude and residual form exist.
In order to improve the electrokinetic process efficient of heavy metal in the mud, many enhancement methods are applied to wherein, mainly comprise: the municipal sludge acidifying, and the heavy metal that accelerates to exist with other forms transforms in solution; Utilize ion-exchange membrane to prevent that current density from reducing.Yet these methods have not only been introduced allogenic material in sludge system, strengthened environmental risk, and rehabilitation cost is increased greatly, have limited its large-scale application.
It is to utilize constant current amount peristaltic pump with the technology of catholyte and anolyte neutralization that catholyte refluxes a kind of, in system, do not add any allogenic material, but catholyte and the continuous anolyte that reduces of pH value that the pH value constantly raises neutralized, form a circulating system, keep the pH value of anode and cathode liquid, with the sludge pH that keeps relative stability, the effective heavy metal precipitation in control cathode zone.Yet the heavy metal that exists with combination attitude and residual form in the initial mud does not occupy the minority, and single use catholyte reflux technique can be good at the pH value of Controlling System, but still can't fundamentally improve the electronic removal efficient of this part heavy metal.
Summary of the invention
The objective of the invention is to seek a kind of method of heavy metal in the mud and its device removed that finally to realize removing heavy metal purpose in the municipal sludge.
The technical scheme that the present invention takes is:
A kind of device of removing heavy metal in the mud, it is poor to comprise a rectangular decontamination, its structure is: the poor two ends of decontamination are respectively the cathode pools of inserting the anode pond of anode electrode and inserting cathode electrode, cloudy, be connected in series direct supply and the data collector of series connection between the anode, it is the mud room of placing mud between anode pond and cathode pool, between anode pond and mud room, be provided with the clamping plate with holes of four layers of separation usefulness of being made by synthetic glass, fill anionite-exchange resin between the clamping plate, the porous surface of two ends clamping plate covers filter paper, has delivery port and the constant current amount peristaltic pump that is joining pipe to join respectively at the poor two ends of decontamination.
A kind of method of utilizing said apparatus to remove heavy metal in the mud, finished by the following steps operation:
1) mud is implemented the multigelation pre-treatment,
2) the pretreated mud of multigelation is put into the mud room of device,
3) in electrode cell, add distilled water as electrolytic solution,
4) extremely apply volts DS in negative and positive, keeping voltage gradient is 0.97v/cm～1.05v/cm;
5) open constant current amount peristaltic pump, implement the electrolytic solution reflux technique by the negative electrode anode,
6) analysis of the mud chamber of experimentizing is taken out in power-on servicing after 6 days, and heavy metal in the mud of contrast treatment front and back
Total amount.
Positively effect of the present invention is:
Compare with other enhancement methods, the pretreatment technology of multigelation makes the microorganism cells generation fragmentation in various degree in the mud, variation has taken place with this part combined heavy metals form in extinction and organic minimizing along with microorganism, has strengthened its transport property.Its reinforcing process with the catholyte backflow is combined, can hold the heavy metal form the mud from the source, control simultaneously system-wide pH value during the course, can fundamentally solve two guardian technique difficult problems in the mud electrokinetic process, significantly improve the removal efficient of heavy metal in the mud, this enhancement method is simple to operate simultaneously, and required expense is low, and not introducing any allogenic material in system, is a kind of environmental friendliness, practicable enhancement method.
Description of drawings
Fig. 1 realizes electrokinetic process device synoptic diagram of the present invention.
Embodiment
Now the invention will be further described by reference to the accompanying drawings
A kind of method of removing heavy metal in the mud, finished by the following steps operation:
1) mud is implemented the multigelation pre-treatment,
2) the pretreated mud of multigelation is put into the mud room of device,
3) in electrode cell, add distilled water as electrolytic solution,
4) extremely apply volts DS in negative and positive, keeping voltage gradient is 0.97v/cm～1.05v/cm;
5) open constant current amount peristaltic pump, implement the electrolytic solution reflux technique by the negative electrode anode,
6) power-on servicing is taken out the mud chamber of experimentizing and is analyzed after 6 days, and the total amount of heavy metal in the mud before and after the contrast treatment.
A kind of device of removing heavy metal in the mud, it is poor to comprise a rectangular decontamination, its structure is: the poor two ends of decontamination are respectively the cathode pools 4 of inserting the anode pond 2 of anode electrode 1 and inserting cathode electrode 3, cloudy, be connected in series direct supply 5 and the data collector 6 of series connection between the anode, it is the mud room 7 of placing mud between anode pond and cathode pool, the clamping plate with holes 8 of the separation usefulness of between anode pond and mud room, being made by synthetic glass, fill anionite-exchange resin 9 between the clamping plate, the porous surface of two ends clamping plate covers filter paper, has delivery port and the constant current amount peristaltic pump 11 that is joining pipe 10 to join respectively at the poor two ends of decontamination.
Described multigelation pre-treatment, concrete steps are as follows:
1) get 800g～1200g mud and place the plastic beaker of 2L, be placed in the refrigerator freezingly, freezing temp is-25 ℃, and freezing time is 6h;
2) to regulate temperature be 50 ℃ to water-bath, mud put into water-bath is warm to be melted;
3) repeating step 1), 2), totally 4 times;
4) mud is stirred the abundant mixing of 15min.
Described electrolytic solution reflux technique by the negative electrode anode, concrete steps are as follows:
1) with supporting hose connection cathode pool and the anode pond of constant current amount peristaltic pump;
2) rotating speed of adjusting peristaltic pump, making its corresponding flow velocity is 1.2ml/min, and the flow direction of liquid is for to flow to the anode pond from cathode pool.
Described cathode and anode is columnar electrode, and negative electrode is Graphite Electrodes, and its purity is 99.9%, density is 1.75～1.80g/cm
3, hardness is 45 °; Anode is the ruthenium-iridium-tantalum electrode.
Embodiment
Embodiment 1:
Remove the example of heavy metal Cr in the municipal sludge
Municipal sludge was taken from Shanghai City Tao Pu sewage work in 2009, be mainly trade effluent and the sanitary sewage dewatered sludge after the secondary biochemical treatment.Mud is black, foul smelling, and essential property and pollution condition are as follows: pH is 6.9; Water ratio is 78.5%; Organic matter is 26.8%; Cr content is all in dry-matter more than the 2012.8mg/kg().The electronic prosthetic device that adopts is self-built device (as Fig. 1), and reactor is made by synthetic glass, and negative electrode adopts common Graphite Electrodes, and anode adopts the ruthenium-iridium-tantalum electrode, and the surface scribbles the ruthenium-iridium-tantalum material, can prevent that electrode is corroded.Direct supply provides stabilized voltage, utilizes electric current and voltage monitoring system log (SYSLOG) electric current and changes in resistance.Externally carry liquid from cathode pool anode pond by the peristaltic pump that can regulate flow, the flow velocity of peristaltic pump is 1.2ml/min.Carry out the multigelation pre-treatment for examination mud before processing, make cytoclasis, the easy migration component of heavy metal increases to some extent in the mud, it is put in the reactor compacting successively.Energising and regulating voltage are at 1v/cm, and the virtual voltage gradient is between 0.98～1.02v/cm.
Use the present invention, behind the electronic 144h mud in the mud room being divided equally from the anode to the negative electrode is that five zones (S1-S5) collected specimens is analyzed.Sample grinds behind natural air drying, and sieve (100 order) measured moisture percentage in sewage sludge, pH value, total metals and form thereof and distributed.By wet method clear up-aas determination mud in the content of Cr.Analytical results shows (table 1), and the removal efficient of Cr has improved 67.5% in the mud, and strengthening effect is remarkable.
The electrokinetic process efficient of Cr in table 1 mud
Embodiment 2:
Remove the example of heavy metal Cu, Zn, Cd, Ni in the municipal sludge
Municipal sludge was taken from Shanghai City Tao Pu sewage work in 2011, this mud contains the dewatered sludge of part trade effluent after the secondary biochemical treatment based on sanitary sewage.Mud is black, foul smelling, and essential property and pollution condition are as follows: pH is 6.8; Water ratio is 85%; Organic matter is 34.4%; Pollutant levels are Cu content 1369.6mg/kg; Zn content 1395.1mg/kg; Cd content 39mg/kg; More than the Ni content 218.2mg/kg(all in dry-matter).Experimental technique is the same, and regulating voltage makes that the voltage in the reactor maintains 1v/cm, and the virtual voltage gradient maintains between 0.97～1.05v/cm.
After using the present invention, it is that five zones (S1-S5) collected specimens is analyzed that the mud in the mud room is divided equally from the anode to the negative electrode.Sample grinds behind natural air drying, and sieve (100 order) measured moisture percentage in sewage sludge, pH value, total metals and form thereof and distributed.By wet method clear up-aas determination mud in the content of Cr.Analytical results shows (table 2), and the removal efficient of Cu, Zn, Cd, Ni has improved 61.7%, 78%, 44%, 39.1% respectively in the mud, and effect is remarkable.
The electrokinetic process efficient of Cu, Zn, Cd, Ni in table 2 mud
Claims (5)
1. device of removing heavy metal in the mud, it is poor to comprise a rectangular decontamination, it is characterized in that: the poor two ends of decontamination are respectively the cathode pools (4) of inserting the anode pond (2) of anode electrode (1) and inserting cathode electrode (3), cloudy, be connected in series direct supply (5) and the data collector (6) of series connection between the anode, it is the mud room (7) of placing mud between anode pond and cathode pool, between anode pond and mud room, be provided with the clamping plate with holes (8) of four layers of separation usefulness of being made by synthetic glass, fill anionite-exchange resin (9) between the clamping plate, the porous surface of two ends clamping plate covers filter paper, has delivery port and the constant current amount peristaltic pump (11) that is joining pipe (10) to join respectively at the poor two ends of decontamination.
2. the device of heavy metal in the removal mud according to claim 1 is characterized in that: described cathode and anode, be columnar electrode, and negative electrode is Graphite Electrodes, its purity is 99.9%, density is 1.75～1.80g/cm
3, hardness is 45 °; Anode is the ruthenium-iridium-tantalum electrode.
3. the described device of a utilization such as claim 1-2 is removed the method for heavy metal in the mud, it is characterized in that:
Finished by the following steps operation:
1) mud is implemented the multigelation pre-treatment,
2) the pretreated mud of multigelation is put into the mud room of device,
3) in electrode cell, add distilled water as electrolytic solution,
4) extremely apply volts DS in negative and positive, keeping voltage gradient is 0.97v/cm～1.05v/cm;
5) open constant current amount peristaltic pump, implement the electrolytic solution reflux technique by the negative electrode anode,
6) power-on servicing is taken out the mud chamber of experimentizing and is analyzed after 6 days, and the total amount of heavy metal in the mud before and after the contrast treatment.
4. the method for heavy metal in the removal mud according to claim 3 is characterized in that: described multigelation pre-treatment, and concrete steps are as follows:
1) get 800g～1200g mud and place the plastic beaker of 2L, be placed in the refrigerator freezingly, freezing temp is-25 ℃, and freezing time is 6h;
2) to regulate temperature be 50 ℃ to water-bath, mud put into water-bath is warm to be melted;
3) repeating step 1), 2), totally 4 times;
4) mud is stirred the abundant mixing of 15min.
5. the method for heavy metal in the removal mud according to claim 3 is characterized in that: described electrolytic solution reflux technique by the negative electrode anode, and concrete steps are as follows:
1) with supporting hose connection cathode pool and the anode pond of constant current amount peristaltic pump;
2) rotating speed of adjusting peristaltic pump, making its corresponding flow velocity is 1.2ml/min, and the flow direction of liquid is for to flow to the anode pond from cathode pool.
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102863131B (en) * | 2012-10-22 | 2013-09-11 | 南京中创水务集团股份有限公司 | Method for removing heavy metals from municipal residual sludge |
| CN105314806A (en) * | 2014-08-04 | 2016-02-10 | 昆山美淼环保科技有限公司 | Pretreatment method for deep dehydration of sludge |
| CN104386892A (en) * | 2014-11-21 | 2015-03-04 | 中国矿业大学 | Device for removing heavy metal in excess sludge by using electrodynamic force technology |
| CN104959368B (en) * | 2015-07-31 | 2017-06-09 | 青岛农业大学 | A kind of electrochemical method for removing heavy metal cadmium in silkworm excrement |
| JP2018035383A (en) * | 2016-08-29 | 2018-03-08 | 株式会社ギャラキシー | Valuable article recovering method |
| CN106477833B (en) * | 2016-11-22 | 2019-10-22 | 浙江科技学院 | The electronic eliminating equipment and method of exceeded heavy metal in biogas residue excrement |
| CN110482809B (en) * | 2019-08-20 | 2021-12-24 | 昆明理工大学 | Method and device for electrochemically enhancing sludge concentration and synchronously removing heavy metals |
| CN111333438A (en) * | 2020-03-09 | 2020-06-26 | 广州市环境保护工程设计院有限公司 | System and method for treating surplus sludge of urban domestic sewage |
| CN113526808A (en) * | 2021-07-19 | 2021-10-22 | 天津大学 | Preparation method of sludge-based biochar and sludge-based biochar |
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| JPS51131479A (en) * | 1975-05-13 | 1976-11-15 | Nippon Kokan Kk <Nkk> | A process of condensing an acidic solution containing heavy metal ions |
| US5190628A (en) * | 1992-02-25 | 1993-03-02 | Bibler Jane P | Method and apparatus for removing ions from soil |
| JP3074108B2 (en) * | 1994-02-01 | 2000-08-07 | 株式会社東芝 | Method and apparatus for decontaminating radioactive metal waste |
| JP2000140819A (en) * | 1998-11-02 | 2000-05-23 | Maeda Corp | Method for cleaning heavy metal-contaminated soil |
| CN2721628Y (en) * | 2004-08-27 | 2005-08-31 | 桂林工学院 | DC. electrolytic sludge reactor |
| CN1695834A (en) * | 2005-06-09 | 2005-11-16 | 上海交通大学 | Method of electrodynamics for restoring soil polluted by heavy metal |
| CN200949084Y (en) * | 2006-08-24 | 2007-09-19 | 浙江大学 | Biological leaching and electric technology integrated reactor |
| CN101265007B (en) * | 2008-04-11 | 2011-07-27 | 同济大学 | Method for removing heavy metal in urban sludge by employing electric repairing technique |
| KR20100009709A (en) * | 2008-07-21 | 2010-01-29 | 한국토양복원기술(주) | Method for electrokinetic soil remediation with surfactant |
| KR101034267B1 (en) * | 2008-07-28 | 2011-05-16 | 한국전기연구원 | The system and method for electrokinetic soil recovery using the ion filter |
| KR100954274B1 (en) * | 2009-08-31 | 2010-04-23 | 고성환 | Electrokinetic removal system of heavy metal |
| CN102070288B (en) * | 2010-12-06 | 2012-05-09 | 河海大学 | Device and method used for restoring sludge polluted by heavy metals |
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