CN100377800C - Purification method of polluted soil - Google Patents

Purification method of polluted soil Download PDF

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Publication number
CN100377800C
CN100377800C CNB2004100766074A CN200410076607A CN100377800C CN 100377800 C CN100377800 C CN 100377800C CN B2004100766074 A CNB2004100766074 A CN B2004100766074A CN 200410076607 A CN200410076607 A CN 200410076607A CN 100377800 C CN100377800 C CN 100377800C
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China
Prior art keywords
soil
washing
heavy metal
purification
water
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CNB2004100766074A
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Chinese (zh)
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CN1660515A (en
Inventor
森本辰雄
和田信彦
凑秀雄
小泽阳子
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阿斯特古股份有限公司
和田信彦
凑秀雄
小泽阳子
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Priority to JP2004055550A priority Critical patent/JP4235688B2/en
Priority to JP2004055550 priority
Application filed by 阿斯特古股份有限公司, 和田信彦, 凑秀雄, 小泽阳子 filed Critical 阿斯特古股份有限公司
Publication of CN1660515A publication Critical patent/CN1660515A/en
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Publication of CN100377800C publication Critical patent/CN100377800C/en

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B09DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09CRECLAMATION OF CONTAMINATED SOIL
    • B09C1/00Reclamation of contaminated soil
    • B09C1/08Reclamation of contaminated soil chemically
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B09DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09CRECLAMATION OF CONTAMINATED SOIL
    • B09C1/00Reclamation of contaminated soil
    • B09C1/02Extraction using liquids, e.g. washing, leaching, flotation

Abstract

Provided is an engineering method for cleaning contaminated soil by which the problem of the cleaning method such as a washing method can be dissolved, content of contaminants in soil is suppressed below a standard and further elution quantity can be suppressed below a standard. The engineering method for cleaning the contaminated soil comprises a washing process in which contaminated soil with heavy metals is washed and is separated into washing muddy water and washing treated soil and a soil stabilizing process in which elution components of heavy metals from the washing treated soil are fixed. Preferably, the washing muddy water separated in the washing process is then separated into treated water and heavy metal-containing solid in a water treating process.

Description

Pollute the purification method of soil

Technical field

The present invention relates to a kind of purification method of polluting soil, in more detail, relate to will contain in the soil the washing of harmful heavy metal class after, further realize insolublely, and make the purification method of polluting soil stabilizationization, innoxious pollution soil.

Background technology

In the soil pollution countermeasure method of Japan, the heavy metal that cadmium, lead, 6 valency chromium, arsenic, total mercury amount, copper, selenium is such (proportion surpasses the general name of 4 metal species) is defined as the 2nd class special harmful substance jointly with cyanogen, fluorine, boron etc., belongs to the object of restriction.

In this method about heavy metal etc., from by direct picked-up to the risk factor of human body and the picked-up by underground water etc. to the viewpoint of the risk factor of human body, introduce two standards, the former is defined as soil content, the latter is defined as the soil stripping quantity.

The countermeasure of handling soil pollution up to now has: the method for purification etc. 1) sealing method, 2) insoluble and process for fixation, 3).

Intercept water in the sealing method and handle and blocking processing, any one all adopts intercept water wall or blocking-up wall will pollute the method that grave closes, and the soil utilizes extremely difficult again, has near the problem of resident's understanding being difficult to obtain.

Insoluble and process for fixation has chemical insoluble method, adhesive fixation, geochemistry concretion method.The insoluble method of chemistry is a method of utilizing chemical reagent such as frerrous chloride to carry out chemical harmless treatment, has possibility of stripping again, thereby has problems aspect steady in a long-term.The adhesive fixation also has the possibility of stripping again, has problems aspect steady in a long-term.The geochemistry concretion method is the fixing method of special harmful substance in new crystalline mineral, through geochemistry stable after, have excellent long-time stability.Yet, in insoluble and process for fixation, when local nodularization concretion method is above standard on the content that pollutes native concentration, just be not suitable for.

In the purification method up to now, the extracting method of pumping up water, electric decomposition method, heat treated method, washing method.The extracting method of pumping up water is to utilize boring that water is circulated, and extracts the method for removing polluter out; The electricity decomposition method is decomposed for make its electricity by electric current, reclaims the method for metal ion; The heat treated method is to heat to make its volatilization or burning the method that reclaims or disperse in air; Washing method is to carry out the classification washing after pollution soil and the stratum excavation, or carry out high pressure on the spot and wash, remove heavy metal with the particulate deposit, to reduce the method for content and stripping quantity, in above-mentioned arbitrary method, all have the effect that reduces harmful substance, but exist the rate of removing of content of beary metal to be 30-70% to the maximum, have several 10% or the residual problem of above material.

In above-mentioned pollution soil countermeasure, each method all has pluses and minuses, and wherein, to content standard and stripping quantity standard effective method, there are the following problems for washing method as a kind of.

The heavy metal rate of removing by washing method depends primarily on granularmetric composition, and the particulate part rate of after a little while removing reduces.And when increasing the particulate part, though the rate of removing uprises, the discarded object amount that need take out of outside the venue increases, and disposal cost is risen, thereby causes the problem of non-efficient aspect.

Heavy metal and grogs carry out physicochemical combination more securely by absorption, ion-exchange, gluing and chemical combination etc., for this reason, have following problem in the washing method.

(1) clean result depends primarily on the size distribution of object soil, and the reduced rate of content is approximately 30-60%.

(2) be difficult to be applicable to that particulates such as silt particle, clay partly surpass 30% pollution soil.

(3) stripping can take place in Can Yu heavy metal, and exceeds the standard of stripping quantity.

(4) owing to remove silt particle, clay and organic substance, soil characteristic is lost and can't be utilized again.

In addition,, promptly use chemical reagent (acid) and cleaning solution to extract removal out, also can make the stripping quantity increase on the contrary because of the influence of residual chemical reagent (acid) etc. because the proportion of goods damageds rise.

Summary of the invention

Problem of the present invention provides a kind of purification method of polluting soil, and it can solve the existing problem of purification method of washing method and so on, the content of the polluter in the soil is suppressed to below the mark, simultaneously, also is suppressed to stripping quantity below the mark.

Other problem of the present invention describes by following description.

Solve above-mentioned problem by following invention.

(1) pollutes native purification method, it is characterized in that, comprise washing step that washing wash water that heavy metal polluted soil produced is separated with carrying out washing treatment soil and the stripping composition of the heavy metal in the described carrying out washing treatment soil is carried out immobilized soil stabilization step.

(2) according to (1) the described purification method of polluting soil, it is characterized in that, from described washing step, isolate wash water, thereafter,, separate with the solid matter that contains heavy metal handling water by water treatment steps.

(3) according to (1) or (2) the described purification method of polluting soil, it is characterized in that, in described soil stabilization step, in described carrying out washing treatment soil, sneak into cohesive soil, cation-exchanger and calcium compound, carry out the immobilization of the stripping composition of heavy metal and handle.

(4) according to (1) or (2) the described purification method of polluting soil, it is characterized in that, in described soil stabilization step, in described carrying out washing treatment soil, sneak into cohesive soil, cation-exchanger, calcium compound and magnesium compound, carry out the immobilization of the stripping composition of heavy metal and handle.

(5) according to (1) or (2) the described purification method of polluting soil, it is characterized in that, in described soil stabilization step, in described carrying out washing treatment soil, sneak at least a of cohesive soil, cation-exchanger, calcium compound, magnesium compound, divalence or trivalent iron salt and aluminium salt, carry out the immobilization of the stripping composition of heavy metal and handle.

Description of drawings

Fig. 1 represents the flow chart of an embodiment of purification method of the present invention.

Fig. 2 represents to implement the schematic diagram of an embodiment of this concrete grammar that pollutes the native method of purification and device thereof.

Description of reference numerals:

1: washing step

2: water treatment steps

3: the soil stabilization step

10: drum sieve type rotary type rinsing maching

11: the gravitational settling formula is separated and the sand dewatering screen

12: the stabilization processes step

13: setting pot

14: the oxidation reaction groove

15: the coagulation sedimentation groove

16: slurry tank

17: filter press

The specific embodiment

Below, embodiments of the present invention are described.

Among the present invention, the so-called soil that pollutes is meant the soil that contains environmentally harmful material, preferably contain the soil of the 2nd kind of harmful substance in the soil countermeasure method, for example contain: soil such as heavy metal that cadmium, lead, 6 valency chromium, arsenic, total mercury amount, copper, selenium are such and cyanogen, fluorine, boron.

Heavy metal can exist with the form of metal cation, oxide (comprising composite oxides) or low oxide.In the present invention, so-called environmentally harmful material is meant by direct picked-up dangerous and human body is had the material of harm by picked-ups such as underground water to human body.

Below, based on accompanying drawing, an embodiment of purification method of the present invention is described.

Fig. 1 represents the flow chart of an embodiment of purification method of the present invention.

The 1st, washing step is that wash water and carrying out washing treatment soil that the washing heavy metal polluted soil produces are carried out separation steps.

Washing step 1 comprises washing and classification processing.In the process of washing heavy metal polluted soil, preferably wash by washings, in the process that washings disperse, preferably when rotating pollution soil, disperse, pollution soil is contacted fully with washings.Classification in the washing step 1 is preferably carried out classification by particle diameters such as gravel, sand, mud.

The 2nd, handle the water treatment steps of wash water, in water treatment steps 2, add thus in the above-mentioned washing process 1 by the mud of classification, preferably carry out processing such as sedimentation separation, oxidation reaction, coagulation sedimentation.In initial sedimentation separation, separate the soil of upper strata primary water and precipitation.In coagulation sedimentation, separating clarifying is handled the mud of water and sedimentation.The soil of above-mentioned precipitation and the mud of sedimentation, for example: dewater by filter press, form the mud of dewatered cake and curing.

The 3rd, the soil stabilization step of the carrying out washing treatment soil of stablize, immobilization is above-mentioned.In the present invention, contamination with wash soil in washing step reduces the heavy metal in the carrying out washing treatment soil, and the content standard of above-mentioned polluter is satisfied in anticipation.In the present invention, there is ambiguity in the amount standard, that is, even satisfy content standard, in case the stripping in soil of this standard content, having problems such as the situation that does not satisfy the stripping quantity standard, particularly underground water pollution is still remaining serious problems.In the present invention,, solve serious underground water pollution problem, designed the soil stabilization step in order to reach above-mentioned amount standard.

The stabilization method of carrying out washing treatment soil is preferably sneaked into cohesive soil, cation-exchanger and calcium compound in carrying out washing treatment soil, make soil stabilization; As preferred embodiment, can enumerate and in carrying out washing treatment soil, sneak into cohesive soil, cation-exchanger, calcium compound and magnesium compound, make the mode of soil stabilization; In carrying out washing treatment soil, sneak into cohesive soil, cation-exchanger, calcium compound, magnesium compound, divalence or trivalent iron salt and/or aluminium salt, make the mode of soil stabilization.

The cation-exchanger that uses among the present invention is the material with cation exchange material function, and it can exchange absorption with the heavy metal class that exists as cation at short notice in polluting soil, be preferably zeolites.

As zeolite-like materials, can use natural zeolite, any of artificial zeolite, or both use together.

The zeolite-like materials of using among the present invention is that cation exchange capacity is 100meq/100g or above high-cation exchange capacity material, the cation exchange capacity height is high more good more, but for the relation of performance limitations and price etc., on be limited to 220meq/100g or following.If cation exchange capacity is lower than 100meq/100g, owing to increased the volume that adds, thereby be not preferred.More preferably 150meq/100g or more than.Among the present invention, the determination method of cation exchange capacity is Schollenberger method and express method thereof.

In the present invention, zeolite-like materials can be used in Powdered, the particle shape any.Under particle shape and/or pulverous situation, preferred average grain diameter is 5mm or following.In addition, in the present invention, Powdered and emboliform natural and/or artificial zeolite's class suitably can be mixed use.

Zeolite-like materials, the viewpoint of the intensity of additive therefor from keep stabilization method, preferred water carries out saturated.

The calcium compound of Shi Yonging has the function of sorbing material in the present invention, can adsorb the anion in the pollution soil that above-mentioned zeolite-like materials can not adsorb, keep, and have the function of regulating pH value (alkalescence is regulated), can and keep above-mentioned zeolites cation exchange function and adsorption function with reinforcement.As anion, have arsenic-adsorbing (arsenic acid ion, arsenite ion) and other anion anionic functions such as (for example chromate ions).

As above-mentioned calcium compound, can enumerate: Ca (OH) 2(calcium hydroxide), CaO (quick lime), CaCO 3(calcium carbonate), CaCl 2(calcium chloride) etc.Above-mentioned substance can be used separately, also can or use above suitably the mixing 2 kinds.

The magnesium compound that uses among the present invention, have absorb be difficult in zeolite and the clay to be adsorbed maintenance, pollute the miscellaneous function that exists in the soil, form anionic polluter.Therefore, by containing magnesium salts, can prevent that the polluter that pollutes in the soil is insoluble, and further make it innoxious.

As this magnesium compound, can enumerate: Mg (OH) 2(magnesium hydroxide), MgO (magnesia), MgCO 3(magnesium carbonate), MgCl 2(magnesium chloride) etc.Above-mentioned substance can be used separately, also can or use above suitably the mixing 2 kinds.

In addition, in the present invention, can use the compound that contains calcium and magnesium simultaneously.As relevant compound, can enumerate: dolomite etc. for example.

In addition, in the present invention, preferably contain divalence or trivalent iron salt, or aluminium salt.As divalent iron salt, as long as can generate Fe 2+Molysite such as ion, just there is no particular limitation, for example FeCl 2, FeSO 4Deng.If add divalent iron salt, can reduce for example Cr VI, form the low chromium oxide of harmfulness, in the new Ca that forms, Mg hydrous alumino silicates mineral facies, have absorption, fix various cations, anionic effect.As trivalent iron salt, as long as can generate Fe 3+Molysite such as ion, just there is no particular limitation.In addition, aluminium salt is as long as can generate aluminum ions compound, and also just there is no particular limitation.

The cohesive soil that uses among the present invention, preferably because itself and heavy metal class and harmful element have good chemical reactivity, can be with its further absorption, keep, after long-time, (artificial mineral) finally is fixed up with the form of micro constitutent etc. in the new crystalline phase that forms.This be since through long-time, under the state of environment that keeps complying with the nature, can make and pollute the heavy metal class and the harmful element that contain in the soil and exist.

This cohesive soil not only has described characteristic, and is cheap, be easier to obtain also very important, and the clay class that distributes in the face of land is particularly considered its stability (in the face of land, to the stability of ground surface environment), the clay class that preferred weathering generates.

As this cohesive soil, can use the volcano loam (for example Northeast loam) of the product that forms as the slacking of spraying thing by the volcano, the thin sand soil of granite waste etc.

These cohesive soils are along with the more highly crystallineization of the clay mineral of crystalline material that wherein the contained silicic acid and the properties of water-bearing such as iron, aluminium oxide are low and low-crystalline, have the function that heavy metal class in the pollution soil that will be adsorbed by above-mentioned zeolites and calcium compound etc. and harmful element absorb as micro constitutent.

Finally, the most stable silicate mineral mutually in, stabilized on geochemistry as micro constitutent, and can be owing to stripping etc. does not take place water, thus form long-term, stable artificial stratum.

When using cohesive soil, when needs change its character,, clay mineral classes such as bentonite can be sneaked into, on the contrary,, the sand class can be sneaked into if will reduce viscosity for to increase viscosity, to regulate water penetration.

In the present invention, in the stabilization procedures of carrying out washing treatment soil, under the situation of adding cohesive soil, zeolites and calcium compound, above-mentioned carrying out washing treatment soil with respect to 100 weight portions, be added the addition of material, preferred cohesive soil is that 5-30 weight portion, zeolites are that 1-15 weight portion, calcium compound are the scope of 1-10 weight portion.

In addition, if add magnesium compound, with respect to the above-mentioned carrying out washing treatment soil of 100 weight portions, magnesium compound is preferably the scope of 1-5 weight portion.

In addition, when adding divalence or trivalent iron salt and/or aluminium salt, with respect to the above-mentioned carrying out washing treatment soil of 100 weight portions, preferred divalent iron salt etc. is the scope of 0.1-3 weight portion.

Because the stabilizing material that uses among the present invention is mainly natural mineral resource, can not produce new environmental pollution because of artificial materials such as chemical reagent.In addition, reaction of the present invention is that adsorption reaction, ion-exchange reactions, new mineral form mutually substantially, so long as meet the ion of this condition, not being only applicable to pollute only has the harmful heavy metal class in the soil, also may be suitable for for arsenic and other element, so the present invention has significant versatility.

Among the present invention, carrying out washing treatment soil is being carried out in the process of stabilization processes, for example, carrying out washing treatment soil is paved with in specific place, sprinkle in the above as the zeolite-like materials of aforementioned stable agent and calcium compound etc., can adopt the whole bag of tricks that it is mixed, and further mix with clay.The processing soil that stabilization processes is finished is filled into the place that excavates again.

Shown in Fig. 2 is concrete grammar and the device thereof of implementing to pollute native purification method.

At first, with 200m 3Pollute soil and 400m 3Water is put into (" drum sieve " that gas worker Co., Ltd. makes) in the drum sieve type rotary type rinsing maching 10.

Next, be conveyed in separation of gravitational settling formula and the sand dewatering screen 11 (the high sieve aperture grader that gas worker Co., Ltd. makes).In this sand dewatering screen 11, with gravel (5mm or more than), sandstone (75 μ m-5mm) and unnecessary mud (74 μ m or following native 30m as wash water 3With water 360m 3)

With 170m 3Gravel (5mm or more than) is conveyed in the stabilization processes step 12 as carrying out washing treatment soil.In stabilization processes, add 25.5m 3Stabilizing agent, the soil (195.5m that mixes, obtains finishing dealing with 3).

With above-mentioned unnecessary mud (30m 3Soil and 360m 3Water) in setting pot, carry out Separation of Solid and Liquid, send in the acidification reaction groove 14, add the poly-iron that is referred to as " TRP " of ASTEC company manufacturing and handle.Then, in coagulation sedimentation groove 15, add the high polymer coagulant that is referred to as PAC, carry out flocculation treatment.The mud of sedimentation is sent into via slurry tank 16 and is carried out processed in the filter press 17.Coagulation sedimentation is handled water (360m 3) utilize as washings once more.Precipitation in dewatered cake and the above-mentioned setting pot 13 soil sand is carried out waste treatment.

Embodiment

Next shown in is purification method of the present invention.

According to the method shown in Fig. 2, adopt standard law (5 mixing methods) respectively the pH, lead content, lead release, arsenic content, the arsenic stripping quantity that pollute soil, carrying out washing treatment soil, stabilization processes soil, wash water, dewatered cake to be analyzed.

It the results are shown in table 1.

Each sample carries out the sampling of number of times shown in the remarks in about 3 months experimentation, analyze, and lists mean value.

Table 1

Sample ??PH Lead release (mg/L) Lead content (mg/Kg) Arsenic stripping quantity (mg/L) Arsenic content (mg/Kg) Remarks Pollute soil ??8.4 ??0.183 ??223.0 ??0.340 ??176.4 8 mean values in 3 months Carrying out washing treatment soil ??8.4 ??0.05 ??82.9 ??0.022 ??74.1 8 mean values in 3 months Stabilization processes soil ??9.8 ??0.005 ??30.6 ??0.006 ??36.2 24 mean values in 3 months

Lead release standard: 0.01mg/L or following arsenic stripping quantity standard: 0.01mg/L or following

Plumbous amount standard: 150mg/Kg or following arsenic amount standard: 150mg/Kg or following

Claims (5)

1. pollute the purification method of soil, it is characterized in that, comprise washing step that washing wash water that heavy metal polluted soil produced is separated with carrying out washing treatment soil and the stripping composition of the heavy metal in the described carrying out washing treatment soil is carried out immobilized soil stabilization step.
2. the native purification method of pollution according to claim 1 is characterized in that, isolates wash water from described washing step, thereafter, by water treatment steps, separates with the solid matter that contains heavy metal handling water.
3. the native purification method of pollution according to claim 1 and 2, it is characterized in that, in the described soil stabilization step, in described carrying out washing treatment soil, sneak into cohesive soil, cation-exchanger and calcium compound, carry out the immobilization of the stripping composition of heavy metal and handle.
4. claim 1 or the native purification method of 2 described pollutions, it is characterized in that, in described soil stabilization step, in described carrying out washing treatment soil, sneak into cohesive soil, cation-exchanger, calcium compound and magnesium compound, carry out the immobilization of the stripping composition of heavy metal and handle.
5. claim 1 or the native purification method of 2 described pollutions, it is characterized in that, in described soil stabilization step, in described carrying out washing treatment soil, sneak at least a of cohesive soil, cation-exchanger, calcium compound, magnesium compound and divalence or trivalent iron salt and aluminium salt, carry out the immobilization of the stripping composition of heavy metal and handle.
CNB2004100766074A 2004-02-27 2004-07-26 Purification method of polluted soil CN100377800C (en)

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