CN103170499A - Method for electrically removing heavy metals and organic pollutants from soil or sludge - Google Patents
Method for electrically removing heavy metals and organic pollutants from soil or sludge Download PDFInfo
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- CN103170499A CN103170499A CN2013100783350A CN201310078335A CN103170499A CN 103170499 A CN103170499 A CN 103170499A CN 2013100783350 A CN2013100783350 A CN 2013100783350A CN 201310078335 A CN201310078335 A CN 201310078335A CN 103170499 A CN103170499 A CN 103170499A
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Abstract
The invention provides a method for electrically removing heavy metals and organic pollutants from soil or sludge. An electric removal device is used in the method and comprises a rotary drum, a gear, an outer closed-loop hinged crawler belt and a closed-loop conveying crawler belt, wherein a conductive material covers the rotary drum, and a reaction material layer is wrapped outside the conductive material; the gear surrounds the rotary drum; the outer closed-loop hinged crawler belt is made of a conductive material and engaged on the gear to realize closed-loop operation; and the closed-loop conveying crawler belt is used for conveying soil or sludge, penetrates through the clearance between the outer closed-loop hinged crawler belt and the rotary drum and is compacted on the rotary drum. By using the device and selecting proper operating industrial parameters, the heavy metals and/or the organic pollutants can be quickly, effectively and simultaneously removed from the polluted soil or the sludge; and the method is easy and convenient to operate and high in removal efficiency, and has a good industrial application prospect.
Description
Technical field
The present invention relates to a kind of method of removing harmful substance from soil or mud, relate to especially a kind of electronic removal method of soil or Heavy Metals in Sludge and organic pollution, belong to soil remediation and sewage sludge harmlessness process field.
Background technology
China has accumulated comparatively serious soil pollution in long-term course of industrialization.For example, in recent years, in Development of China's Urbanization fast, moving back of the closure, suspension, merger and conversion of a large amount of factory and enterprises and city two advances three, and numerous resettlement enterprise has stayed a large amount of carryover contaminations places, wherein enrichment a large amount of harmful heavy metal and Organic Pollutants; And for example due to a large amount of uses and residual for a long time of agricultural chemicals, cause the large tracts of land agricultural land soil to be subject to pollution by pesticides; Oil field prospecting, oil exploitation, oil storage and transportation and gas station's leakage etc. for another example, and caused the soil petroleum hydrocarbon to pollute ... serious soil pollution has all consisted of obvious threat to underground water, agricultural product quality, ecological environment and health.And China is just at the early-stage aspect soil remediation and reparation, and is very urgent to practical soil pollution recovery technique demand.
Up to now, the recovery technique of traditional contaminated soil mainly contains stable/curing technology, advanced oxidation processes, high temperature pyrolytic cracking (HTP), chemical leaching method, phytoremediation, microorganism repairing method, gas phase extraction process etc.
Stable/curing technology is that some chemical substances are joined in contaminated soil, realize the stable of heavy metal and solidify by chemical reaction, although it has reduced the Leaching of heavy metal, can't reduce the pollutant total amount of heavy metal especially in soil, can not tackle the problem at its root.
Advanced oxidation processes is to add oxidant in polluted soil, thereby organic pollution that will be wherein is oxidized to harmless micromolecular compound and inorganic salts, but easily the physicochemical property of soil is caused serious adverse effect.
High temperature pyrolytic cracking (HTP) is heat treatment technics, is by passing into vapours or heat soil with methods such as radio frequency, electrical heating in soil, thereby makes the pollutant in soil resolve into little molecule or innocuous substance.Shortcoming is to consume energy greatlyr, and the physicochemical property of soil is also had adverse effect
The chemical leaching method refers to by means of the solvent that can promote the dissolving of pollutant in soil environment or migration, pollutant be leached out from soil particle, and isolated sewage is processed subsequently, thereby completes the pollutant removal of soil.The method operation is comparatively simple, but only effective to specific soil and pollutant, the scope of application is little, and elution efficiency is low.
Phytoremediation refers to utilize physiological activity absorption or the pollutant in degraded soil of plant or make these pollutants become harmless method, mainly comprise plant extract, plant stability, phytovolatilization, plant degradation, rhizosphere filtering etc., certain plants can also be to the realization of the heavy metal in soil enrichment to a certain degree simultaneously.But the method cost is lower, and is simple to operate, but efficient is too low, consuming time too very long.
The microorganism repairing method is mainly by utilizing nutrition and other chemicals to come activating microorganisms, make their keep the kilter of metabolic activity, can fast decoupled and destroy pollutant.But the method needs constantly to add biologic product in soil, and the mass transfer effect of microorganism in soil is bad, and this method cost is higher, and repairing efficiency is long, and the while can only change the form of heavy metal and the heavy metal of can not degrading.
Soil vapor extraction method (Soil vapour extraction, SVE) be widely used a kind of soil remediation technology in recent decades, this technology is mainly to produce driving force by introduce clean air in contaminated soil, thereby utilize the concentration gradient between solid phase of soil, liquid and gas, the pollutant in soil is converted into the steam form and is removed.SVE is particularly useful for the reparation of high volatile volatile organic polluted soil, as contaminated soils such as gasoline, benzene and tetrachloro-ethylenes, and there is certain limitation for the organic pollutant removal of middle volatility and low volatility: remove that efficient is lower, the cycle grows (being the several years) etc.
Except a large amount of contaminated soils, it is a large amount of mud that produce in urban life, industrial production that another individual important heavy metal and organic matter are originated, especially the municipal sludge that produces in sewage disposal process of sewage treatment plant, enormous amount contains a large amount of heavy metals and moisture.And along with the acceleration of China's Development of China's Urbanization and the raising of sewage centralized treatment rate, China's sewage plant sludge annual production grows with each passing day, according to incompletely statistics, and by the end of the year 2010, the sewage treatment plant of China produces approximately 2,100 ten thousand tons of moisture 80% mud per year, and mud annual production from now on also can accelerated growth.
The innoxious of mud is the cardinal principle of ﹠ Mud, yet the heavy metal that contains in mud is major limitation and the influence factor of recycling sludge and minimizing.
The contamination hazard of heavy metal is serious and lasting, after the mud that contains heavy metal is applied to soil, can increase the content of heavy metal in soil, and the mankind, animal, the plants and soil ecosystem are all existed potential serious harm.Based on this consideration, before mud is applied to agriculture and forestry, must suitably process it, to reduce leachability and the biological effectiveness of heavy metal, weaken the adverse effect of Heavy Metals in Sludge.The curing technology of Heavy Metals in Sludge related generally to cement solidification method, lime solidification method, thermoplastic solidification method, vitrification, from cementation solidifying technology etc., but there is following defective in these methods: (1) has changed the structure of mud largely, make mud sclerosis or increase-volume, limited follow-up recycling; (2) partly solidified method somewhat expensive, complicated operation is difficult to apply.In order to overcome these defectives, people have researched and developed the technology of heavy metal in multiple lignin-sludge, for example:
CN1061012A discloses a kind of method of removing sewage/Heavy Metals in Sludge, is mud is mixed with catalyst oxidant, regenerating oxidant and acid, forms active mud, then separates.
CN1273946A discloses the method for decomposing harmful chemical and heavy metal in mud, to utilize cyclodextrin and natural microbial mixed liquor to process, wherein natural microbial is when decomposing the digestion cyclodextrin, the heavy metal ion that oxidable cyclodextrin adheres to.
WO0109045A discloses the method for coming purifying city mud with hybrid chemical and biological process, mud is mixed with acid leachate, so that the pH value of mud is enough low and be enough to dissolve most of heavy metal, then applies oxidation-reduction potential and separate to realize solid-liquid.
CN1436734A discloses a kind of crystallizing treatment process of heavy metal sewage sludge, mainly uses electrochemical redox and crystallization principle, with heavy metal sewage sludge by moltenly carry, concentrate, the step such as crystallization, realize recovery and the utilization of heavy metal crystalline solid.
CN1544366A discloses a kind of method of lignin-sludge heavy metal, is to adopt sulfide and lime as fixative, realizes the stabilisation of heavy metal, has reduced its leaching rate.
CN1631940A discloses the macromolecular heavy metal chelating agent that is used for heavy metal sewage sludge, uses this chelating agent can make the heavy metal in mud realize stabilisation.
WO2005035149A disclose a kind of from mud the method for separating beavy metal, that the mud that will comprise heavy metal is supplied with in cathodic region to reactive tank, under the existence of reducing atmosphere and strong acid or highly basic atmosphere gas, leaching ability of heavy metal and electrolysis are analysed on cathode surface.
CN101265007A discloses the method that adopts electric repairing technique to remove heavy metals in city sewage sludge, wherein strengthens the electromigration ability of heavy metal as complexing agent with poly-epoxy succinic acid, and the clearance of heavy metal is reached more than 60%.
CN102701551A discloses a kind of industrial sludge treatment method, is to add the non-conductor dispersant to nurse one's health in mud, and then high-temperature baking, pulverize and grind, and carries out heavy metal by wind and static and separate.
CN102408177A discloses a kind of biological complex enzyme for recycling sludge, after this cellulase treatment mud, through dehydration, with fertile soil mixing granulation, mummification after obtain composite soil, this soil can be with heavy metals immobilization.
CN102503059A discloses the method for removing Heavy Metals in Sludge, is to utilize the pretreating process of multigelation to strengthen the electrokinetic process process that catholyte refluxes, thereby improves the removal efficient of heavy metal.
CN102583916A discloses the method for removing Heavy Metals in Sludge, comprises use citric acid and hydrogen peroxide lixiviate heavy metal, heating using microwave, Separation of Solid and Liquid, hydro-oxidation sodium Precipitation heavy metal, and citric acid solution wherein can be recycled.
The people such as Wang Jing (Wang Jing, pay ice-melt, Luo Qishi, Zhang Changbo, Xu Yanying, " the static stabilization research of ferrous salt to heavy metals in city sewage sludge ", " environmental science ", 31 the 4th phases of volume, p.210-214, in April, 2010) disclose in to unite and used ferrous salt and calcium hydroxide, can realize the good stabilisation of Heavy Metals in Sludge, can keep suitable pH value simultaneously.
Studies show that in a large number, simple substance Zero-valent Iron (following sometimes also referred to as Fe) is the very strong reducing agent of a kind of electronation, can react with many heavy metals, is used for the reparation of heavy metal pollution underground water.
Existing many pieces of prior aries disclose the reparation that iron can be used for heavy-metal contaminated soil.
Disclose the method for processing metal Cu contaminated soil with iron wire in CN102039306A, administered thereby can obtain stabilisation, had effective, low cost and other advantages.
WO2004007379A discloses for the original position reparation and has been subjected to the soil of contaminated with halogenated hydrocarbons and/or the carried catalyst of underground water, and it includes Zero-valent Iron.
CN101011703A discloses and has accelerated the method that the organic contaminants in soil deoxidization, degradation transforms, and it has utilized the strong reducing property of Zero-valent Iron simple substance.
CN1899717A discloses the method with electric power and iron PRB Combined Treatment heavy-metal contaminated soil, and iron PRB is installed between electrode and soil, utilize electric power with the heavy metal Migration And Concentration in soil to water body, more again it is removed from water body with iron PRB.
CN1623699A discloses a kind of composite strengthening method that in red soil, copper pollutes of removing, and the place arranges electrolytic cell in two end electrodes, adopts the pH automatic control system to come the acidity of control cathode treatment pond to maintain suitable pH value scope.
In sum, although up to now, people have developed device and/or the method for multiple removal contaminated soil or Heavy Metals in Sludge and organic pollution, but also there are deficiency to a certain degree in these devices and/or method, as complex operation, long processing period, power consumption is large, expense is high, be difficult to promote etc., especially still lacks the heavy metal removed simultaneously wherein and the technological means effective, easy and simple to handle of organic pollution.Therefore, under the real situation that China's contaminated soil area is huge at present, the municipal sludge generation is increasing, how to remove simultaneously wherein plurality of heavy metal and organic pollution, being the important prerequisite that realizes that soil remediation and sewage sludge harmlessness are processed, is also the environment circle great difficult problem for paying close attention to deeply.
Based on above-mentioned; in order to remove simultaneously heavy metal and the organic pollution in contaminated soil or mud; and in the urgent need to a kind of flexibly, treatment facility and/or device and removal method efficiently; this is the key subjects that soil remediation field and sewage sludge harmlessness, resource field faces, and is also the active demand in field of environment protection.
Summary of the invention
Consider the shortcomings and deficiencies of above-mentioned prior art, the present application people is from practical application, through after a large amount of creationary further investigations, develop a kind of method that simple operation, operation are removed efficiently the device of polluted soil and Heavy Metals in Sludge and organic pollution and used this device, novelty design, Collaboration by various structures element and/or parts in this device, and the determining of appropriate process operating parameter, can effective and rapid ground remove simultaneously heavy metal and/or organic pollution in polluted soil or mud.This apparatus and method wide adaptability all has very strong removal ability for most harmful heavy metals and organic pollution, and the integrated performance indexs such as the removal efficient of harmful substance, treatment cycle all are better than all existing known devices and method.
Described method of the present invention is a kind of soil and/or mud to be realized the method that original position or dystopy continous way are removed fast, use by the method, when fast dewatering can be realized, heavy metal and/or the organic beyond thought technique effect that effectively to remove in soil or mud have more been obtained.
The described electronic removal method of soil of the present invention or Heavy Metals in Sludge and organic pollution, described method is used electronic removal device, and this device comprises:
Swing roller is coated with conductive material on it, be coated with the reaction wood bed of material outside conductive material;
Gear, it is arranged to around described swing roller;
Outside closed loop hinge crawler belt, it is made by conductive material, and the closed loop running by being engaged on described gear;
Closed loop is carried crawler belt, and it is used for carrying soil and/or mud, and passes the gap between described outside closed loop hinge crawler belt and described swing roller and be pressed on described swing roller.
Wherein, apply voltage producing uniform electric field between outside closed loop hinge crawler belt and swing roller, thereby heavy metal ion or organic pollution are moved to the swing roller surface, and with the reaction of the reaction wood bed of material and removed.
In the described electronic removal device of soil of the present invention or Heavy Metals in Sludge and organic pollution, the material of described swing roller is special the restriction not, exemplarily can be stainless steel, rigid plastics etc., and it can be any cylinder well known in the prior art.Described swing roller carries crawler belt that identical rotation direction is arranged with described closed loop, and can carry the running of crawler belt and be driven to rotate by described closed loop, and when needing governing speed to require with the removal that adapts to heavy metal and organic pollution, can carry out drive by coupled drive motors.the internal diameter in the cross section of described swing roller (being the circle of nozzle) and external diameter be special the restriction not, for example can carry out suitable selection according to the size of the pending amount of soil and/or mud, for example can select in wide region, exemplarily, its external diameter can be 50-200cm, this scope has comprised any subinterval wherein, exemplarily as 70-180cm, 90-160cm or 110-130cm, and comprised any concrete point value wherein, be exemplarily 50cm, 60cm, 70cm, 80cm, 90cm, 100cm, 110cm, 120cm, 130cm, 140cm, 150cm, 160cm, 170cm, 180cm, 190cm or 200cm, its length can be matched with the width that the described closed loop that transmits soil and/or mud is carried crawler belt, its barrel thickness (being the difference of external diameter and internal diameter) is special the restriction not, is enough to bear running pressure and has the sufficiently long working life as long as it has.
In the described electronic removal device of soil of the present invention or Heavy Metals in Sludge and organic pollution, conductive material on described swing roller is special the restriction not, as long as it can conduct electricity, for example can be conducting metal, as iron, copper etc., and be preferably iron in order to reduce costs meter, for keep in repair and/the rear needs of changing, for example after serious wear, this conductive material can be dismantled when using for a long time, so that this conductive material that more renews; Described conductive material outside coat the function of the described reaction wood bed of material be with the heavy metal or the organic pollution that remove in soil and/or mud.
The described reaction wood bed of material is comprised of reactive metal and active material, wherein can according to the content of the heavy metal in pending soil or mud and organic pollution what and select suitably the ratio of reactive metal and active material, for example the mass ratio of reactive metal and active material can be 1: 0.1-5, for example can 1: 0.1,1: 0.2,1: 0.3,1: 0.4,1: 0.5,1: 1,1: 1.5,1: 2,1: 2.5,1: 3,1: 3.5,1: 4,1: 4.5 or 1: 5, perhaps the amount of reactive metal is the portative maximum of active material.
Can select suitably the thickness of the described reaction wood bed of material according to actual conditions, for example can be 1-50mm, non-limiting ground can exemplify 1mm, 5mm, 10mm, 15mm, 20mm, 25mm, 30mm, 35mm, 40mm, 45mm or 50mm.But should be appreciated that, described reaction material layer thickness is not limited to this, can increase suitably or dwindle according to the amount of pollutant in soil or mud fully, and coordinating the size of voltage gradient and carry out appropriate change.
Described reactive metal is selected from any a group in following (1)-(9): (1) Zero-valent Iron (be iron, sometimes also be expressed as Fe); (2) mixture that is formed by ferriferous oxide and iron; (3) mixture that is formed by iron hydroxide and iron; (4) mixture that is formed by ferriferous oxide, iron hydroxide and iron; (5) the bimetallic mixture that is formed by iron and other metal; (6) the many metal mixtures that formed by iron and other various metals; (7) mixture that is formed by ferriferous oxide, iron and other metal; (8) mixture that is formed by iron hydroxide, iron and other metal; (9) mixture that is formed by ferriferous oxide, iron hydroxide, iron and other metal.
The physical aspect of all these reactive metals in above-mentioned (1)-(9) is powder type, can be nanoscale or micron order for example non-limitingly, and for example its granularity can be 10 orders-500 order, this scope has comprised any subinterval wherein, as 50-450 order, 100-400 order, 150-350 order or 200-300 order, also comprised any concrete point value wherein, as 10 orders, 50 orders, 100 orders, 150 orders, 200 orders, 250 orders, 300 orders, 350 orders, 400 orders, 450 orders or 500 orders.
In the present invention, unless otherwise prescribed, described " ferriferous oxide " both can refer to a kind of ferriferous oxide, can be also the mixture of the many oxide of iron, and described ferriferous oxide for example can be FeO, Fe
2O
3, Fe
3O
4In any one or multiple.
In the present invention, unless otherwise prescribed, described " iron hydroxide " both can refer to a kind of iron hydroxide, can be also the mixture of the multiple hydroxide of iron, and described iron hydroxide can exemplify as Fe (OH)
2Or Fe (OH)
3
In the present invention, described " the bimetallic mixture of iron and other metal " refers to fe and another mixture of planting the elemental metals composition, and described " many metal mixtures that iron and various metals form " refer to the mixture that fe and multiple elemental metals form.For example, described bimetallic mixture can be Ni/Fe, Pb/Fe, Cu/Fe, Ti/Fe, Pt/Fe, Ru/Fe, Ag/Fe, Mg/Fe, Pd/Fe etc., and described many metal mixtures can be the mixture of any two kinds or multiple and Fe in Ni, Pb, Cu, Ti, Pt, Ru, Ag, Mg, Pd etc.Unless otherwise prescribed, in this application from start to finish, "/" expression side by side but not or relation, for example take " Ni/Fe " as example, its implication is Ni and Fe.
Described active material is special the restriction not, as long as it has absorption property (as chemisorbed, physical absorption, ion-exchange absorption etc.), thus thereby can be just heavy metal ion adsorbed, exchange, fixing and removed as reactions such as reduction, catalysis, absorption or co-precipitation with the reactive metal generation.for example described active material can be clay mineral, diatomite, any one in polymeric adsorbent or multiple combination, described clay mineral for example can exemplify various zeolites, vermiculite, active carbon, attapulgite, palygorskite, sepiolite, kaolinite, imvite, atlapulgite, bentonite, bentonite, float stone, illite, allophane, serpentine, pyrophyllite, talcum, saponite, mica, any one in chlorite etc. or multiple combination, its mesolite has comprised all zeolites, as modenite, clinoptilolite, analcime, chabasie, scolecite, heulandite, sodalite, foresite etc.Described polymeric adsorbent can be any resin with absorption property, as any one or the multiple combination in D101 macroporous absorbent resin, D101B macroporous absorbent resin, XDA-1 macroporous absorbent resin, XDA-1B macroporous absorbent resin, H-10 resin, H-20 resin, H-30 resin, H-40 resin, H-50 resin, H-60 resin, CH-90 resin etc.
The granularity of described active material is special the restriction not, as long as be powder, for example granularity can be 10 orders-500 order, this scope has comprised any subinterval wherein, as 50-450 order, 100-400 order, 150-350 order or 200-300 order, also comprised any concrete point value wherein, as 10 orders, 50 orders, 100 orders, 150 orders, 200 orders, 250 orders, 300 orders, 350 orders, 400 orders, 450 orders or 500 orders.
in the described electronic removal device of soil of the present invention or Heavy Metals in Sludge and organic pollution, described gear ring is around described swing roller, select suitably quantity and the size of described gear according to the large I of cylinder external diameter, for example it can be 6-10, but its layout equidistant intervals in the described cylinder outside is arranged, so that engagement described outside closed loop hinge crawler belt thereon can adapt in the excircle radian of described cylinder, and then make the gap that maintains equidistant width between described outside closed loop hinge crawler belt and described cylinder for carrying crawler belt to pass and closely be pressed on described cylinder with the described closed loop of sludge blanket.
In the described electronic removal device of soil of the present invention or Heavy Metals in Sludge and organic pollution, described outside closed loop hinge crawler belt and described gear closely mesh, its maximum can coat the outer circumferential area of whole described swing roller, but preferably coat the 60%-85% of described swing roller outer circumferential area, for example can be 60%, 65%, 70%, 75%, 80% or 85%.Maintain the gap of equidistant width between described outside closed loop hinge crawler belt and described swing roller, this gap can be for carrying crawler belt to pass and closely be pressed on described swing roller with the described closed loop of sludge blanket.Described outside closed loop hinge crawler belt is made by conductive material, as iron, stainless steel, copper etc., but considers based on aspects such as cost and decay resistances, and is preferably stainless steel.
In the described electronic removal device of soil of the present invention or Heavy Metals in Sludge and organic pollution, described closed loop is carried crawler belt porous, permeable and can be with soil or mud load thereon, when it moves to the soil that accommodates soil or mud or sludge conditioning chamber, thick soil or mud move up along with the operation of crawler belt, during most of moisture see through that aperture on crawler belt leaks down and soil or mud after dewatering is retained on crawler belt.this crawler belt continues to move upward, when on the maximum height that arrives its running orbit, driven and the change traffic direction by driving shaft or a driven shaft near described swing roller, enter into subsequently the gap between described outside closed loop hinge crawler belt and described swing roller, and be pressed on described swing roller, described maximum height is the central shaft calculating with described cylinder, can be the arbitrary place higher than described central shaft 0.3-1r, wherein r is the external diameter of described cylinder, for example can be higher than described drum central axis 0.3r, 0.4r, 0.5r, 0.6r, 0.7r, 0.8r, 0.9r or 1r, be preferably the highest arc point place (being the peak place of described cylinder) of described swing roller, namely higher than central shaft 1r place.when this crawler belt enters in the gap, be that it is between described outside closed loop hinge crawler belt and described swing roller, along with continuing around rollers running, moisture in soil or mud is deviate from, simultaneously to described swing roller and the energising of described outside closed loop hinge crawler belt, to apply voltage, for example voltage gradient can be 0.5-10V/cm, can be 0.5V/cm non-limitingly, 1V/cm, 1.5V/cm, 2V/cm, 2.5V/cm, 3V/cm, 3.5V/cm, 4V/cm, 4.5V/cm, 5V/cm, 5.5V/cm, 6V/cm, 6.5V/cm, 7V/cm, 7.5V/cm, 8V/cm, 8.5V/cm, 9V/cm, 9.5V/cm or 10V/cm, making described cylinder is negative electrode and described outside closed loop hinge crawler belt is anode, and formed uniform electric field between cylinder and outside closed loop hinge crawler belt, under the effect of this electric field, being arranged in described closed loop carries soil horizon on track surface or the cationic heavy metal of sludge blanket to move to cathode drum.And for the heavy metal (as trivalent chromium) that is the anion existence in soil or mud, the polarity of interchangeable cylinder and hinge crawler belt, even described cylinder is anode and described outside closed loop hinge crawler belt is negative electrode, so the anion heavy metal still moves to cylinder surface.Because the distance between negative electrode and anode is very little, these heavy metals can arrive described cylinder surface easily, quickly, thereby adsorbed by the active material in the reaction wood bed of material of cylinder surface and removed or transform thereupon reacting with reactive metal (as reduction, catalysis, absorption or co-precipitation etc.), through so processing, greatly reduce the content of beary metal in soil or mud.And when processing by the soil of Organic Pollution or mud, from anode to movable cathode due to the moisture in soil or mud under electrodialytic effect, organic pollution also moves on described swing roller as negative electrode thereupon, and the reactive metal in the outer field reaction wood bed of material of cylinder has very high removal effect to organic pollution, can react as effects such as dehalogenation hydrogenation, catalytic degradation, oxidation, reduction by number of chemical and remove organic matter.This shows, owing to having simultaneously adsorption function and response function in the described reaction wood bed of material, thereby can remove simultaneously heavy metal ion and organic pollution in soil or mud.
When continuing operation forward, when making soil or mud carry crawler belt to rotate gap between described cylinder and described outside closed loop hinge crawler belt with described closed loop, can change its traffic direction by an another driving shaft or driven shaft, for example level run is to an another driving shaft or driven shaft, soil horizon or sludge blanket on it scrapes by removing device such as cleaning shoe in this axle vicinity, and is collected in bucket.Then continuously change its traffic direction by several driven shafts (or one of them be driving shaft, remaining several is driven shafts), make it again enter into the soil that accommodates soil or mud or sludge conditioning chamber, thereby complete an operation cycle.
In this running, for described swing roller, described closed loop carries crawler belt successively to change traffic direction twice, being for the first time in the maximum height place is incorporated into the gap by driving shaft or driven shaft, is changed direction and left described cylinder by driving shaft or driven shaft after passing described gap for the second time.Therefore, two gears at the two ends of the described gear of engagement described outside closed loop hinge crawler belt should be respectively lower than driving shaft or the driven shaft at described maximum height place with make closed loop carry crawler belt to change direction and leave driving shaft or the driven shaft at described cylinder place.
In the described electronic removal device of soil of the present invention or Heavy Metals in Sludge and organic pollution, in order to make load have the described closed loop of Drying soil or mud to carry crawler belt more easily to enter in described gap, preferably with whole mud plate, the soil on crawler belt or mud are arranged before entering, for example can be organized into according to specific needs the regular mud layer of 5mm-20mm thickness, then enter in described gap.
In the described electronic removal device of soil of the present invention or Heavy Metals in Sludge and organic pollution, the material of described whole mud plate and cleaning shoe is special the restriction not, such as can be polyester plastics, polyurethane plastics, stainless steel etc., as long as it can carry out mud regular and scrape, and can carry the width of crawler belt and select suitably its width according to described closed loop, in order to can carry out regular and scrape all soil horizons or sludge blanket.
In the described electronic removal method of soil of the present invention or Heavy Metals in Sludge and organic pollution; also described swing roller part, a plurality of driven shaft and/or driving shaft etc. can be positioned among outer cover; thereby succinct its profile; and avoid the bad weather such as rainy day to produce harmful effect to operations such as whole mud, and the reaction wood bed of material of protection cylinder surface avoid cutting to pieces touch, the fortuitous event such as friction.
Use in the electronic removal method of described device in the present invention, at first polluted soil is joined in soil or sludge conditioning chamber and add entry and make it become Soil slurry, perhaps add in case of necessity acid or other synergist (as metal release agent Na commonly used
2SO
3Deng) in order to strengthen heavy metal or the organic matter desorption from the soil particle; Then closed loop is carried crawler belt upwards operation under the drive of driving shaft and/or driven shaft, thereby with thickness mud or mud load thereon, moisture spills from filter opening, direction through driven shaft changes, closed loop carries crawler belt to enter into gap between closed loop hinge crawler belt and swing roller together with the mud layer on it, thereby and the width of rationally determining this gap carry crawler belt to be pressed on the swing roller surface closed loop.By being applied different electric polarities, closed loop hinge crawler belt and swing roller produce uniform electric field, effect due to uniform electric field, heavy metal ion in mud layer and organic matter are to the swing roller surface migration as negative electrode, and very near the reaction wood bed of material that arrives cylinder surface, through removing heavy metal ion and organic matter with the reaction of active material.Wait removing thoroughly or after reaching standard, closed loop is carried crawler belt to pass the gap and is changed direction through driven shaft/driving shaft, its mud layer that gets on except heavy metal and organic pollution is scraped by cleaning shoe, then change through the direction of a plurality of driven shaft/driving shafts and again enter into soil or sludge conditioning chamber, the next circulation of beginning.
as mentioned above, the invention provides a kind of novelty, can efficiently remove electronic removal device and the removal method of soil or Heavy Metals in Sludge and organic pollution, described apparatus/method has startup rapidly, easy to operate, comprehensive energy consumption is lower, the excellent characteristics such as convenient mobile processing, choice and operation by the appropriate process parameter, can realize simultaneously dehydration in a covering device, the dual operation of removal heavy metal and organic pollution, solved in the prior art dehydration and the heavy metal/organic pollution defective of processing separately separately, simultaneously can be according to negative electrode, the flexible modulation of the voltage between anode and heavy metal/organic pollution is had very high removal efficient, be highly suitable for processing fast and in time of organic material contaminated soil, also be suitable for very much recycling and the rapid integrated improvement of mud.
Description of drawings
The device that uses in order to be illustrated more clearly in described method of the present invention, during the below will describe embodiment, the accompanying drawing of required use is done simple the introduction, but apparent, the accompanying drawing that the following describes is only some embodiment of the inventive method and/or device, for those of ordinary skills, under the prerequisite that need not pay creative work, can also obtain similar modified accompanying drawing according to these accompanying drawings.
Fig. 1 example illustration the present invention remove the formation schematic diagram of the described device of soil or Heavy Metals in Sludge and organic pollution.
Wherein, the corresponding relation of the elements/components of each numeral number and/or code name and device of the present invention is as follows:
1. soil or sludge conditioning chamber 2. closed loops are carried crawler belt 3. driving shafts
4. driven shaft 5. closed loop hinge crawler belt 6. swing rollers
7. gear 8. whole mud plates of cleaning shoe 9.
10. the reaction wood bed of material 11. driven shaft 12. outer covers
The specific embodiment
Following with reference to accompanying drawing; described electric device/method to removal soil of the present invention or Heavy Metals in Sludge and organic pollution describes in detail further and/or sets forth; but should be appreciated that; the exemplary description that this just makes device of the present invention and method of operating thereof; it is intended that to explain/set forth described device of the present invention and implementation method thereof; but not be used for limiting and/or restriction the present invention, more non-protection scope of the present invention is confined to this.
With reference to figure 1, described electric device of the present invention comprises that soil or sludge conditioning chamber close 1, closed loop is carried crawler belt 2, driving shaft 3, driven shaft 4 or 11, closed loop hinge crawler belt 5, swing roller 6, gear 7, cleaning shoe 8, and randomly also comprised whole mud plate 9 and outer cover 12.On the conductive material layer (not shown) of described swing roller 6, be coated with the reaction wood bed of material 10.
As shown in Figure 1, closed loop is carried crawler belt 2 to be driven by driving shaft 3 and a plurality of driven shaft 4 and is realized clockwise operation with closed ring, certainly, also driving shaft 3 can be replaced with driven shaft, simultaneously any one in a plurality of driven shafts 4 replaced with driving shaft, the concrete selection of driving shaft there is no strict restriction, carries crawler belt 2 to realize running as long as it can drive whole closed loop.
With reference to figure 1, the operating principle of device of the present invention and operational process are: polluted soil is joined in soil or sludge conditioning chamber 1 and adds entry make it become Soil slurry, perhaps add in case of necessity acid or other synergist (as metal release agent Na commonly used
2SO
3, surfactant, complexing agent etc.) in order to strengthen heavy metal or the organic matter desorption from the soil particle, described acid can be organic acid or inorganic acid, non-limiting exemplified hydrochloric acid, sulfuric acid, nitric acid, perchloric acid, hypochlorous acid, sulfonic acid, methanesulfonic acid etc., its concentration does not have special restriction, can carry out suitable selection according to the desorption degree of wanting to reach, for example can be 10-70% in mass percent concentration, perhaps directly water-containing sludge is joined in this sludge conditioning chamber 1.Then start the driving device such as the drive motors that are connected with driving shaft, driving closed loop carries crawler belt 2 to turn round in a clockwise direction, thereby extracting is upwards from soil or sludge conditioning chamber 1 with thickness mud or mud, in the process of upwards operation, moisture spills from the filter opening of closed loop conveying crawler belt 2, the water that spills can be collected by other collector (not shown), or directly leads and be back in soil or sludge conditioning chamber 1 with the follow-up soil furnishing mud that added.Carry before crawler belt 2 moves to driven shaft 11 near peak when closed loop, carry the mud layer on crawler belts 2 to arrange by 9 pairs of closed loops of whole mud plate.And when closed loop carries crawler belt 2 to move to the driven shaft 11 of peak, entered by driven shaft 11 change traffic directions and (only marked out a numbering " 7 " by six gears 7, one of low order end owing to not drawing near driven shaft 11) in the closed loop hinge crawler belt 5 and the gap between swing roller 6 that mesh, make closed loop conveying crawler belt 2 be pressed on swing roller 6 by closed loop hinge crawler belt 5 by the gap size between adjusting gear 7 and cylinder 6 (for example realizing by the distance between adjusting gear 7 suitably and cylinder 6 surfaces).Cylinder 6 can be carried the drive of crawler belt 2 and equidirectional rotation by closed loop, or is driven separately by other drive motors (not shown).Due to the conductive material in closed loop hinge crawler belt 5 and swing roller 6 has been applied different electric polarities, be that anode and swing roller 6 are negative electrode and make closed loop hinge crawler belt 5, between has produced uniform electric field, thereby the cation heavy metal in the mud layer of closed loop conveying crawler belt 2 is moved to cathode direction by anode under electric field action.Because the distance between negative electrode and anode is very little, these heavy metals can arrive the surface of swing roller 6 easily, quickly, thereby adsorbed by the reaction wood bed of material 10 of cylinder surface and react with reactive metal and be able to innoxious, through so processing, greatly reduce the content of beary metal in soil or mud.And when processing by the soil of Organic Pollution or mud, from anode to movable cathode due to the moisture in soil or mud under electrodialytic effect, organic pollution also moves on swing roller 6 as negative electrode thereupon, and the reactive metal in the outer field reaction wood bed of material of swing roller 6 has very high removal effect to organic pollution.Carry the continuation operation of crawler belt 2 along with closed loop, it begins to carry out removing of heavy metal and/or organic pollution from first gear, until arrive last gear place's end, the running speed of carrying crawler belt 2 by regulating voltage swing between anode, negative electrode and closed loop can make it just can satisfy on earth heavy metal and/or organic pollutant removal standard during last gear place.After passing from the gap of last gear, closed loop carries crawler belt 2 to change traffic direction thereupon, leave swing roller 6, locate to scrape mud by cleaning shoe 8 below driving shaft 3, carry crawler belt 2 to scrape from closed loop the mud layer of having removed heavy metal and organic pollution, enter in the bucket (not shown) and collect, and carry out subsequent treatment.Scrape except after the closed loop after mud layer carries crawler belt 2 to regulate through the direction of a plurality of driven shafts 4 again, again enter into soil or sludge conditioning chamber 1, so far complete a cycling.
When being anion (as trivalent chromic ion) wait the heavy metal ion of removing, it is that negative electrode and swing roller 6 are anode that the polarity of switching on by change makes closed loop hinge crawler belt 5, so still make the heavy metal into anion move to swing roller 6 directions, thereby realize its removal.
By add continuously polluted soil or water-containing sludge in soil or sludge conditioning chamber 1, can realize the continuous operation of this device.When the reaction wood bed of material 10 serious wear on swing roller 6 or fixing heavy metal reach capacity, can change, thereby keep removing efficiently efficient and good continuity of operation.
The described apparatus and method of the application of the invention can produce following good effect:
(1) energy while removal heavy metal and organic pollution: produced uniform electric field by coated with conductive material on swing roller, drive heavy metal by electrodialysis and electromigratory effect, drive organic matter to electrode by electrodialytic effect, pass through simultaneously coating reaction material layer on conductive material, and creatively realized the quick, efficient of heavy metal ion and organic pollution removed.
(2) have higher removal effect and efficient: the distance between cylinder and inner sealing crawler belt is less, and the distance of pollutant migration is very short, and as easy as rolling off a log arrival electrode surface is removed efficient and greatly improved.
(3) have through engineering approaches operability easily: all parts of package unit is integrated brief, can realize modularization production, and can be assembled into wheeled apparatus to have and load fast and assemble ability, can realize fast overall package at the processing scene, have engineering operability flexibly.Because the enforcement of the method coordinates without any need for civil engineering, so can be used in flexibly the continuous processing at all kinds of soil treatment scene.
The invention will be further described below in conjunction with instantiation, but should be appreciated that, these embodiment only are used for the use exemplify, and be used for absolutely not restriction and intention restriction range of application of the present invention and embodiment, more non-protection scope of the present invention is confined to this.
The preparation of the reaction wood bed of material
The reaction wood bed of material 1: montmorillonite loading nano level Zero-valent Iron active material
With Fe
3+Solution is (as FeCl
3, Fe (NO
3)
3Or Fe
2(SO
4)
3In any one or multiple) the dipping imvite, make all in imvite cation exchange positions all by Fe
3+Institute is saturated, then uses NaHB
4Reducing agent reduces, thus between cheating engaging layer with Fe
3+Be reduced into Zero-valent Iron.Obtained the active material of montmorillonite loading nano level Zero-valent Iron through this processing, this active material has been attached to the skin of the conductive material of swing roller, thickness is 3.5cm, and seals compacting with the permeable packing cloth of one or more layers densification.
The reaction wood bed of material 2: by vermiculite, float stone, Fe
2O
3, the active material that forms of Fe
Granularity is 200 purpose vermiculite and float stones, is 350 purpose Fe with granularity
2O
3Evenly mix with iron powder, the gross mass of vermiculite and float stone equals Fe
2O
3With the gross mass of iron powder, i.e. (vermiculite+float stone)/(Fe
2O
3+ iron powder)=1, and vermiculite and float stone and Fe
2O
3Also be 1: 1 with the mass ratio of iron powder.
After mixing, this active material is attached to the skin of the conductive material of swing roller, thickness is 3cm, and seals compacting with the permeable packing cloth of one or more layers densification.
The reaction wood bed of material 3: the active material that is formed by active carbon, Ni/Cu/Fe, attapulgite, D101 macroporous absorbent resin
Granularity is 400 purpose active carbon powders, attapulgite and D101 macroporous absorbent resin, being 300 many metal mixtures of purpose Ni/Cu/Fe with granularity evenly mixes, wherein the mass ratio of active carbon, attapulgite, D101 macroporous absorbent resin is 1: 1: 1, and their gross mass is 3: 1 with the ratio of the gross mass of these three kinds of metals, and the mass ratio of Ni, Cu, Fe is 1: 1: 3.
After mixing, this active material is attached to the skin of the conductive material of swing roller, thickness is 3cm, and seals compacting with the permeable packing cloth of one or more layers densification.
The reaction wood bed of material 4: by kaolinite, Mg/Fe, Fe (OH)
3The active material that forms
Be 150 purpose kaolinites, Mg, Fe, Fe (OH) with granularity
3Evenly mix, wherein Mg, Fe, Fe (OH)
3Granularity be 100 orders, and kaolinic quality and Mg, Fe, Fe (OH)
3The ratio of gross mass be 1: 1, and Mg, Fe, Fe (OH)
3Mass ratio be 2: 1: 1.
After mixing, this active material is attached to the skin of the conductive material of swing roller, thickness is 4cm, and seals compacting with the permeable packing cloth of one or more layers densification.
The reaction wood bed of material 5: by modenite, CH-90 resin, Ag/Fe, Fe (OH)
3, Fe
3O
4The active material that forms
Be that 500 purpose modenites, granularity are 200 purpose CH-90 resins, Fe (OH) with granularity
3, Fe, Ag, Fe
3O
4Evenly mix, wherein Fe (OH)
3, Fe, Ag, Fe
3O
4Granularity be 150 orders, and the gross mass of modenite and CH-90 resin and Fe (OH)
3, Fe, Ag, Fe
3O
4The ratio of gross mass be 4: 1, and the mass ratio of modenite and CH-90 resin is 1: 1, Fe (OH)
3, Fe, Ag, Fe
3O
4Mass ratio be 2: 2: 2: 1.
After mixing, this active material is attached to the skin of the conductive material of swing roller, thickness is 3.5cm, and seals compacting with the permeable packing cloth of one or more layers densification.
Embodiment 1: the cationic removal of Cr VI in soil
Use described device of the present invention, Cr VI cation contamination soil is processed, in soil, chromic content is 352mg/kg.Wherein, applying voltage for anode closed loop hinge crawler belt with between for the swing roller of negative electrode, voltage gradient is 2.0V/cm.
Use respectively above-mentioned reaction wood bed of material 1-5 to carry out Transformatin, collect the soil after scraping and carry out bone dry, then measure hexavalent chromium content wherein, the results are shown in following table 1.
The content of hexavalent chromium before and after table 1. is processed
This shows, very high to the chromic clearance of heavy metal after processing through apparatus and method of the present invention, effectively realized the efficient removal of heavy metal.
Embodiment 2: the removal of heavy metals in city sewage sludge
Be industrial wastewater in a large number in the municipal sewage that sewage treatment plant processes, the Of Heavy Metal Level In Sludge that the processing industrial wastewater obtains is higher.Get this factory's quality moisture content and be 80% municipal sludge and put into conditioning chamber, adding mass concentration is that to be adjusted to the pH value be 3.0 for 10% watery hydrochloric acid.Use respectively above-mentioned active material 1-5, and the voltage gradient between anode and negative electrode is that 3V/cm processes, concrete outcome sees the following form 2.
Before and after table 2. is processed, (content unit is mgkg in the content of beary metal variation
-1)
This shows, after processing through apparatus and method of the present invention, the clearance of several heavy metal species is higher, can reach the standard of agricultural sludge.
Embodiment 3: the removal of TCE in organic material contaminated soil
Certain chemical plant produces trichloro-ethylene (TCE) product, has caused the place soil pollution, and content is 116.3mg/kg.Get this contaminated soil, adopt device of the present invention that contaminated soil is processed, wherein the reaction wood bed of material is above-mentioned active material 1-5, voltage gradient between anode and negative electrode is 10V/cm, method of operating is that this contaminated soil is mixed with water, making it become moisture by percentage to the quality is 76% Soil slurry, the results are shown in following table 3.
The content of TCE before and after table 3. is processed
This shows, after processing through apparatus and method of the present invention, realized the efficient removal to organic pollution TCE.
Embodiment 4: the removal of pentachlorophenol in organic material contaminated soil
Contain pentachlorophenol in certain site, chemical plant soil, content is 67mg/kg.Adopt device of the present invention that contaminated soil is processed, wherein the reaction wood bed of material is above-mentioned active material 1-5, voltage gradient between anode and negative electrode is 7V/cm, method of operating is that this contaminated soil is mixed with water, making it become moisture by percentage to the quality is 80% Soil slurry, the results are shown in following table 4.
The content of pentachlorophenol before and after table 4. is processed
This shows, after processing through apparatus and method of the present invention, realized the efficient removal to the organic pollution pentachlorophenol.
Embodiment 5: the removal of pesticide contaminated soil DDT
Get certain insecticide factory's site contaminated soil, pollutant is DDT (two (the 4-chlorphenyls)-1,1 of 2,2-, 1-trichloroethanes), and content is 283mg/kg.Adopt device of the present invention that contaminated soil is processed, wherein the reaction wood bed of material is above-mentioned active material 1-5, voltage gradient between anode and negative electrode is 6V/cm, method of operating is that this contaminated soil is mixed with water, making it become moisture by percentage to the quality is 76% Soil slurry, the results are shown in following table 4.
The content of DDT before and after table 5. is processed
This shows, after processing through apparatus and method of the present invention, realized the efficient removal to organic pollution DDT.
In sum, described apparatus and method of the present invention can effectively be applied to the removal reparation of organic pollution in soil or mud and/or heavy metal ion, are a kind of modern designs, remove efficient environment remediation and pollution control apparatus and method high, easy and simple to handle.
Although for for example and the purpose of description, and introduced structure and processing procedure shown in above-mentioned embodiment of the present invention and accompanying drawing.But these are not to be detailed description, scope of the present invention can not be confined to this.For a person skilled in the art, can make numerous modifications and variations to above-mentioned embodiment of the present invention, and these all modifications and/or change all are included in as within claim limited range of the present invention, do not break away from the scope and spirit of the present invention that claim as described limits.
Claims (10)
1. the electronic removal method of a soil or Heavy Metals in Sludge and organic pollution, described method is used electronic removal device, and this device comprises:
Swing roller is coated with conductive material on it, be coated with the reaction wood bed of material outside conductive material;
Gear, it is arranged to around described swing roller;
Outside closed loop hinge crawler belt, it is made by conductive material, and the closed loop running by being engaged on described gear;
Closed loop is carried crawler belt, and it is used for carrying soil or mud, and passes the gap between described outside closed loop hinge crawler belt and described swing roller and be pressed on described swing roller;
Wherein, apply voltage producing uniform electric field between outside closed loop hinge crawler belt and swing roller, thereby heavy metal ion or organic pollution are moved to the swing roller surface, and with the reaction of the reaction wood bed of material and removed.
2. electronic removal method as claimed in claim 1 is characterized in that: described device also is included in described closed loop carry crawler belt to enter described gap before, be used for arranging described closed loop and carry soil on crawler belt or the whole mud plate of mud.
3. electronic removal method as claimed in claim 1 or 2 is characterized in that: described device also comprises after described closed loop carries crawler belt to rotate described gap, is used for scraping soil horizon on it or the cleaning shoe of sludge blanket.
4. electronic removal method as described in claim 1-3 any one, it is characterized in that: the described reaction wood bed of material is comprised of reactive metal and active material.
5. electronic removal method as claimed in claim 4, it is characterized in that: the granularity of described active material and described reactive metal is the 10-500 order.
6. electronic removal method as described in claim 4 or 5, it is characterized in that: the mass ratio of described reactive metal and active material is 1: 0.1-5, or the amount of reactive metal is the portative maximum of active material.
7. electronic removal method as described in claim 4-6 any one, it is characterized in that: described reactive metal is selected from any a group in following (1)-(9): (1) Zero-valent Iron; (2) mixture that is formed by ferriferous oxide and iron; (3) mixture that is formed by iron hydroxide and iron; (4) mixture that is formed by ferriferous oxide, iron hydroxide and iron; (5) the bimetallic mixture that is formed by iron and other metal; (6) the many metal mixtures that formed by iron and other various metals; (7) mixture that is formed by ferriferous oxide, iron and other metal; (8) mixture that is formed by iron hydroxide, iron and other metal; (9) mixture that is formed by ferriferous oxide, iron hydroxide, iron and other metal.
8. electronic removal method as claimed in claim 7, it is characterized in that: described ferriferous oxide is selected from and is FeO, Fe
2O
3, Fe
3O
4In one or more, described iron hydroxide is selected from Fe (OH)
2Or Fe (OH)
3Described bimetallic mixture is selected from Ni/Fe, Pb/Fe, Cu/Fe, Ti/Fe, Pt/Fe, Ru/Fe, Ag/Fe, Mg/Fe or Pd/Fe, and described many metal mixtures are the mixture of any two kinds or multiple and Fe in Ni, Pb, Cu, Ti, Pt, Ru, Ag, Mg, Pd.
9. electronic removal method as described in claim 4-8 any one is characterized in that: described active material is any one or the multiple combination in clay mineral, diatomite, active carbon, polymeric adsorbent.
10. electronic removal method as described in claim 1-9 any one is characterized in that: during to described swing roller and the energising of described outside closed loop hinge crawler belt, voltage gradient between the two is 0.5-10V/cm.
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| CN201310078335.0A CN103170499B (en) | 2013-03-12 | 2013-03-12 | Method for electrically removing heavy metals and organic pollutants from soil or sludge |
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| CN103787568A (en) * | 2014-02-24 | 2014-05-14 | 南京赛佳环保实业有限公司 | Anode for electroosmosis sludge dewatering equipment and manufacturing technology thereof |
| CN104607456A (en) * | 2014-12-19 | 2015-05-13 | 中国环境科学研究院 | A remediation method for soil polluted by chlorobenzenes |
| CN105174672A (en) * | 2015-10-13 | 2015-12-23 | 浙江大学 | Device for removing and recovering heavy metal in sludge through double-layer double-anode electrochemical method |
| CN105532389A (en) * | 2016-01-29 | 2016-05-04 | 德胜（苏州）洋楼有限公司 | Automatic flower watering device |
| CN105583217A (en) * | 2015-12-23 | 2016-05-18 | 江苏盖亚环境工程有限公司 | Conditioner for repairing heavy metal contaminated soil and preparing method for conditioner |
| CN106862252A (en) * | 2017-03-24 | 2017-06-20 | 中国科学院广州能源研究所 | The processing system and method for a kind of heavy metal in soil |
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| CN111718719A (en) * | 2020-06-23 | 2020-09-29 | 中南大学 | Vulcanized nano zero-valent iron-acid activated montmorillonite composite material and preparation method and application thereof |
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