CN110369473A - Restorative procedure for Coastal beach heavy-metal contaminated soil - Google Patents
Restorative procedure for Coastal beach heavy-metal contaminated soil Download PDFInfo
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- CN110369473A CN110369473A CN201910809186.8A CN201910809186A CN110369473A CN 110369473 A CN110369473 A CN 110369473A CN 201910809186 A CN201910809186 A CN 201910809186A CN 110369473 A CN110369473 A CN 110369473A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/02—Extraction using liquids, e.g. washing, leaching, flotation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
Abstract
The present invention is provided to the restorative procedure of Coastal beach heavy-metal contaminated soil, belong to environmental science, including soil modification is provided, reduces the viscosity of mud-flat soil；Elution, the higher mobility heavy metal of removal activity are provided；Heavy metal stabilizer, fixed and stabilisation heavy metal are provided；It include the multiporous biological matter matrix of acid carbonization and the fixative of multi-layer film structure in above-mentioned heavy metal stabilizer.Restorative procedure provided by the invention can immobilize heavy metal element；By destroying soil capillary continuity, increase soil porosity, to destroy heavy metal transformation path and reduce its migration；Enhance phosphatase activity in soil, improves soil with organic matter, P bioavailability；The heavy metal stabilizer of offer can enhance urase and catalase activity in soil, the preventing poison ability increase soil fertility with plant to hydrogen peroxide, contained fixative can be recycled and be reused, and reduce soil remediation cost, and preparation method can reduce sour dosage and production cost.
Description
Technical field
The invention belongs to environmental sciences, and in particular to the restorative procedure for Coastal beach heavy-metal contaminated soil.
Background technique
Tidal Flat Reclamation and exploitation are one of the main paths of China's Coastal Areas arable land supplement, to China's Coastal Areas agricultural
There is important strategic importance with economic sustainable development.China's beach area is about 2,500,000 hm2, and every year with
5000hm2Left and right extends at Lu Sudu to sea.Since most of beach are formed by reclaiming coastal land, the high saliferous of soil
Amount, underground water high mineralization degree and heavy metal pollution are seriously the key constraints that beach utilizes.Up to now, the beach in China
The utilization rate of exploitation is applied less than 50%.Due to beach saline-alkali belong to sandy silt soil property, soil property is barren, it is difficult to provide plant
Nutrient needed for growth, and largely life, the discharge of trade effluent, so that heavy metal and poisonous and harmful substance in mud-flat soil
Content is high, while the nutriments such as organic matter rich in and N, P.The nutriments such as N, P in soil are easily leached with tail water,
Secondary pollution is generated to surrounding water；Heavy metal is difficult to decompose in the natural environment, into soil after can change edaphon
Sociales, can also be entered in plant by plant absorption, and be constituted a threat to indirectly to human body by food chain, into water
Body can pollute the ecological environment of aquatic organism, enter human body by biological chain amplification, do harm to huamn body.Heavy metal pollution with have
The pollution of machine object is different, and heavy metal itself is difficult to be degraded, and is easy to generate enrichment, therefore soil by plant or animal
The difficulty of governance of heavy metal pollution is larger.The processing of currently used heavy metal pollution of soil, using Agro-ecological Engineering measure,
Special plant and microorganism are bred on the soil by heavy metal pollution, are siphoned away by these special plants and microorganism
Or the heavy metal in degradation soil, thus achieve the purpose that purification soil, but this method processing time length, slow effect, meeting
The soil of processing is allowed to lose utility value in a long time.
Summary of the invention
Heavy metal element can be fixed and be stabilized the purpose of the present invention is to provide a kind of；It can be by destroying soil
Capillary continuity increases soil porosity, to destroy heavy metal transformation path and reduce its migration；Phosphorus in soil can be enhanced
Phytase activity, accelerate soil in organic phosphorus circulation, improve soil with organic matter, P bioavailability be used for Coastal beach heavy metal
The restorative procedure of contaminated soil, the heavy metal stabilizer that this method uses can enhance urase and catalase activity in soil,
The preventing poison ability increase soil fertility with plant to hydrogen peroxide, contained fixative can be recycled and be reused, and reduce soil
Rehabilitation cost, preparation method can reduce sour dosage and production cost.
The technical solution that the present invention is taken to achieve the above object are as follows:
Restorative procedure for Coastal beach heavy-metal contaminated soil, comprising: soil modification is provided, mud-flat soil is reduced
Viscosity；Elution, the higher mobility heavy metal of removal activity are provided；Heavy metal stabilizer, fixed and stabilisation heavy metal are provided；
It include the multiporous biological matter matrix of acid carbonization and the fixative of multi-layer film structure in above-mentioned heavy metal stabilizer.This method by pair
The soil of heavy metal pollution is modified, elutes and stabilizes improved treatment, come reduce heavy metal ions in soil (such as lead, zinc,
Copper, cadmium, arsenic etc.) activity, and the heavy metal element of inactivation is replaced into porous carrier, reduces its migration and biology is living
Property, while absorption of the plant and animal to heavy metal is reduced, complete fixation and stabilisation to heavy metal, beach is repaired with this
Climax band, middle damp band and low tide do not cause secondary pollution, in soil remediation with the heavy metal pollution in soil in repair process
There is wider application in engineering.
In some embodiments, steps are as follows for soil modification: cinder is sieved to and chosen the coal that partial size is less than 5mm
Solid impurity particle is smashed the contaminated soil stirring of area surface layer 0-10cm to be repaired, by cinder: soil=1:1-3 dry weight ratio
Cinder is added into soil, after mixing, sprays moisture by solid-to-liquid ratio 1:1-3 to surface layer, then aging conserves 5-10d, obtains
To modified soil.Cinder is industrial solid wastes, and main component is silicate, iron, calcium etc., and Alkaline minerals ingredient is to heavy metal
There is stronger affinity, acid heavy metal environment can be improved and be conducive to subsequent elution operating, and avoid cinder and throw aside heap
Product phenomenon, reduces the wasting of resources and environmental risk.
In some embodiments, rinsing step is as follows: taking weight ratio is hydrochloric acid, bamboo vinegar and the sulfuric acid of 1:1-2:1-3
It is diluted, is configured to the leacheate that concentration is 0.3-1.0%, is then measured with 2-5 times and modified soil is eluted, repeat 1-
2 times, time interval 10-12h, after separation of solid and liquid, leacheate and soil solids are collected respectively.Acid solution can have heavy metal
There is complexing, small amount of activated heavy metal higher, mobility is strong in soil, while residue such as bamboo vinegar can be eluted,
Soil with organic matter, Available N-P potassium content can be improved, the ecological recovery of soil is conducive to.
In some embodiments, application method of the heavy metal stabilizer in soil remediation is as follows: S1 turns over dry field,
By the soil solids agglomerate fragmentation after elution, 200-300kg/ mus of amount uniform broadcasting heavy metal stabilizer is then pressed；S2 is broadcasted sowing
After complete heavy metal stabilizer, deep ploughing processing is carried out to soil, the topsoil depth for processing of deep ploughing is 10-40cm, and repeats 2-3
Time, it is ensured that it is horizontal and vertical to be uniformly mixed；S3 after deep ploughing, adds water to the water surface higher than soil surface 10-20cm, to soil
Carry out ageing 10-15d；S4 after ageing, drains dry field.Chelating occurs using the heavy metal in stabilizer and soil, sinks
The physics chemical actions such as shallow lake, absorption, the heavy metal element of inactivation is replaced into porous carrier, heavy metal contaminants are effectively reduced
Exchangeable species amount, treatment effeciency it is high and it is steady in a long-term effectively, achieve the effect that repairing and treating.
In some embodiments, the multiporous biological matter matrix of the acid carbonization in heavy metal stabilizer including 25-35wt%
With the fixative of the multi-layer film structure of 40-60wt%.Biomass matrix and fixative can utilize its own active group will a huge sum of money
Belong to enrichment of element, then exchange or be adsorbed in porous carrier, so that heavy metal element is stablized in the carrier by collaboration, keeps away
Exempt from it to assemble in plant or animal body, achievees the purpose that purification soil, and heavy metal stabilizer is small to soil disturbance, after being conducive to
The ecological recovery of continuous soil.
It further include sulphur powder, zeolite powder, carbide slag, lime in heavy metal stabilizer in some specific embodiments
At least one of stone.In stabilizer comprising compatibility good, easily dispersible natural material, stable complexation can be formed with heavy metal
Object, greatly improves the rate of adsorption and adsorption capacity to heavy metal, and the passivation of contaminated soil stabilizes improved effect more preferably.
It in some embodiments, include biomass matrix, sour carbonisation in the multiporous biological matter matrix of acid carbonization
The ammonium material that residual acid and residual acid aminating reaction are formed.Biomass matrix after acid carbonization generates microcellular structure, hole body
Residual acid in product can be such that heavy metal element is enriched with and form reference state and lose activity and aminating reaction shape occurs with ammonia
At ammonium material, ammonium material is adsorbed in carbon matrix, when material is applied to soil, is released slowly and is provided battalion
Element is supported, may advantageously facilitate plant growth.
In some embodiments, biomass matrix includes but is not limited to forest and agriculture waste residue such as sawdust, corn stover
Deng, castoff, cattle waste, agricultural product castoff such as bagasse, cereal residue etc., aquatic products waste such as seaweed,
Sea grass etc., such as sugared process residues of trade waste.
In some embodiments, acid carbonization acid used is sulfuric acid and/or phosphoric acid.If aminating reaction is formed with sulfuric acid
Ammonium material be ammonium sulfate, and the lignin of exposure can form ligninsulfonate in sulfuric acid and biomass, have improvement soil
PH, salinization of soil effect；If the ammonium material that aminating reaction is formed is ammonium dihydrogen phosphate or diammonium hydrogen phosphate with phosphoric acid.
In some specific embodiments, the preparation step of the multiporous biological matter matrix of acid carbonization is as follows: to biomass
The acid that 20-70% weight is added in matrix carries out carbonization 10-30min, and sour mass concentration is 40-80%, after complete reaction,
It is passed through the anhydrous gaseous ammonia of biomass matrix 15-40% weight into system, after reacting 30-60min, recycles raffinate, takes precipitating
It is dry to get.
In some embodiments, tert-butyl hydroquinone and 0.03- containing 0.05-0.1mM in acid carbonization acid used
The alpha naphthol of 0.08mM, the two play synergistic effect in acid carbonization, the combination of lignin and hemicellulose are promoted to solve
It is poly-, it not only improves and forms ligninsulfonate with sulfuric acid after lignin exposes, and can control the sour carbonizing degree to biomass fiber,
Sour dosage and production cost are reduced, on the other hand the two is slowly released from biomass matrix into after soil, can continue to increase
The activity of urase and catalase in strong soil, thus the preventing poison ability increase soil fertility with plant to hydrogen peroxide,
Achieve the purpose that rehabilitating soil.
In some embodiments, the fixative of multi-layer film structure includes that the ethylene-vinyl acetate that partial size is 2-6mm is total
Polymers grain core matches the filled layer that object is formed and the bonding layer formed by poly- hydroxy acid by sugar.Bonding layer enriching heavy metal, passes through
Filled layer is replaced to be immobilized in grain core, is reduced the murder by poisoning of heavy metal on plants, is simultaneously engaged with layer and filled layer
Can natural decomposition in the soil, provide nutrient for plant, increase soil fertility, grain core can be recycled and be reused, and be reduced
Soil remediation cost.
In some embodiments, in the fixative of multi-layer film structure filled layer and bonding layer by way of spraying successively
It is wrapped in a core surface layer；The dosage of above-mentioned filled layer and bonding layer substance is respectively the 5-10% and 8-15% of grain core weight.
In some specific embodiments, poly- hydroxy acid used in bonding layer is the polycondensation of one or more hydroxy acids
Object, it is preferable that hydroxy acid include but is not limited to glycolic, hydracrylic acid, hydroxybutyric acid, hydroxy-iso-butyric acid or they in two
Kind or a variety of compositions.Poly- hydroxy acid is biodegradable polymer, can produce enrichment to heavy metal element,
High affine, stable complex compound sediment is formed with heavy metal ion, reduces its harm to plant.
In some specific embodiments, sugar used in filled layer includes one or more objects comprising glycosidic bond with object
Matter, including but not limited to glucose, starch, pectin, alginic acid or its salt, xanthan gum or two or more of compositions in them.
Preferably, sugar is starch with object.Filled layer can increase the adhesiveness between core and bonding layer, while between bonding layer and grain core
Channel is established, heavy metal element is replaced from fixative surface layer into grain core, the fixation and stabilisation to heavy metal are reached.
The invention has the benefit that
1) restorative procedure provided by the invention is by being modified, eluting and stabilizing improvement to the soil of heavy metal pollution
Processing, to reduce the migration and bioactivity of heavy metal ions in soil, while reducing suction of the plant and animal to heavy metal
It receives, completes the fixation and stabilisation to heavy metal；
2) restorative procedure provided by the invention can improve acid heavy metal environment by soil modification, and cinder is avoided to throw aside heap
Product phenomenon, reduces the wasting of resources and environmental risk, can destroy soil capillary continuity by elution, increase soil porosity,
Its migration is reduced by destroying heavy metal transformation path, moreover it is possible to be enhanced phosphatase activity in soil, be accelerated organic in soil
Phosphorus circulation, to improve soil with organic matter, P bioavailability, is conducive to the ecological recovery of soil；
3) the exchangeable species amount of heavy metal contaminants, treatment effeciency can be effectively reduced in heavy metal stabilizer provided by the invention
It is high and steady in a long-term effective, the rate of adsorption and adsorption capacity to heavy metal are improved, and heavy metal stabilizer is small to soil disturbance,
Conducive to the ecological recovery of subsequent soil, partially stabilized dose of energy provides nutrient for plant, increases soil fertility；
4) the multiporous biological matter matrix of the acid carbonization in heavy metal stabilizer provided by the invention can enhance urase in soil
With the activity of catalase, the preventing poison ability increase soil fertility with plant to hydrogen peroxide, preparation method can be reduced
The fixative of sour dosage and production cost, multi-layer film structure can be recycled and be reused, and reduce soil remediation cost.
The restorative procedure for being used for Coastal beach heavy-metal contaminated soil is provided present invention employs above-mentioned technical proposal, is made up
The deficiencies in the prior art, reasonable design, easy operation.
Detailed description of the invention
Fig. 1 is influence schematic diagram of the different restorative procedures to urease activity in soil；
Fig. 2 is influence schematic diagram of the different restorative procedures to catalase activity in soil；
Fig. 3 is influence schematic diagram of the different restorative procedures to phosphatase activity in soil.
Specific embodiment
Technical solution of the present invention is described in further detail below in conjunction with specific embodiment and attached drawing:
Embodiment 1:
Restorative procedure for Coastal beach heavy-metal contaminated soil, comprising: soil modification is provided, mud-flat soil is reduced
Viscosity；Elution, the higher mobility heavy metal of removal activity are provided；Heavy metal stabilizer, fixed and stabilisation heavy metal are provided；
It include the multiporous biological matter matrix of acid carbonization and the fixative of multi-layer film structure in above-mentioned heavy metal stabilizer.This method by pair
The soil of heavy metal pollution is modified, elutes and stabilizes improved treatment, come reduce heavy metal ions in soil (such as lead, zinc,
Copper, cadmium, arsenic etc.) activity, and the heavy metal element of inactivation is replaced into porous carrier, reduces its migration and biology is living
Property, while absorption of the plant and animal to heavy metal is reduced, complete fixation and stabilisation to heavy metal, beach is repaired with this
Climax band, middle damp band and low tide do not cause secondary pollution, in soil remediation with the heavy metal pollution in soil in repair process
There is wider application in engineering.
Steps are as follows for above-mentioned soil modification: cinder is sieved to and is chosen the coal slag granules that partial size is less than 5mm, it will be to be repaired
The contaminated soil stirring of the surface layer Fu Qu 10cm is smashed, and by cinder: cinder is added into soil for soil=1:2 dry weight ratio,
After mixing, moisture is sprayed by solid-to-liquid ratio 1:2 to surface layer, then aging conserves 10d, obtains modified soil.Cinder is industry
Solid waste, main component are silicate, iron, calcium etc., and Alkaline minerals ingredient has stronger affinity, Ji Nenggai to heavy metal
Good acid heavy metal environment, and subsequent elution can be conducive to and operated, and avoid cinder and throw aside packing phenomenon, reduce the wasting of resources with
Environmental risk.
Above-mentioned rinsing step is as follows: taking weight ratio is that hydrochloric acid, bamboo vinegar and the sulfuric acid of 1:1:2 is diluted, and is configured to dense
The leacheate that degree is 1.0%, then elutes modified soil with 4 times of amounts, is repeated 2 times, time interval 12h, solid-liquid point
From rear, leacheate and soil solids are collected respectively.Acid solution can have complexing to heavy metal, can elute small in soil
Amount of activated heavy metal higher, mobility is strong, while residue such as bamboo vinegar, can improve soil with organic matter, Available N-P
Potassium content is conducive to the ecological recovery of soil.
Application method of the above-mentioned heavy metal stabilizer in soil remediation is as follows, and: S1 turns over dry field, by the solid after elution
Then 300kg/ mus of amount uniform broadcasting heavy metal stabilizer is pressed in aggravation of soil fragmentation；S2, after having broadcasted sowing heavy metal stabilizer,
Deep ploughing processing is carried out to soil, the topsoil depth for processing of deep ploughing is 30cm, and is repeated 3 times, it is ensured that horizontal and vertical mixing is equal
It is even；S3 after deep ploughing, adds water to the water surface higher than soil surface 10cm, carries out ageing 15d to soil；S4, after ageing,
Drain dry field.The physics chemical actions such as chelating, precipitating, absorption occur using the heavy metal in stabilizer and soil, by inactivation
Heavy metal element is replaced into porous carrier, and the exchangeable species amount of heavy metal contaminants is effectively reduced, and treatment effeciency is high and long-term
Stablize effectively, achievees the effect that repairing and treating.
The multiporous biological matter matrix of acid carbonization in above-mentioned heavy metal stabilizer including 35wt% and the multilayer film of 50wt%
The fixative of structure.Heavy metal element can be enriched with by biomass matrix and fixative using its own active group, then be exchanged
Or be adsorbed in porous carrier, so that heavy metal element is stablized in the carrier by collaboration, avoid it in plant or animal body
Interior aggregation achievees the purpose that purification soil, and heavy metal stabilizer is small to soil disturbance, conducive to the ecological recovery of subsequent soil.
It further include the sulphur powder of 5wt% and the lime stone of 10wt% in above-mentioned heavy metal stabilizer.It include phase in stabilizer
Capacitive is good, easily dispersible natural material, can form stable comple with heavy metal, greatly improve the rate of adsorption to heavy metal
And adsorption capacity, the passivation of contaminated soil stabilize improved effect more preferably.
Residual acid and residual acid in the multiporous biological matter matrix of above-mentioned acid carbonization comprising biomass matrix, sour carbonisation
The ammonium material that aminating reaction is formed.Biomass matrix after acid carbonization generates microcellular structure, and the residual acid in pore volume was both
Heavy metal element can be made to be enriched with and form reference state and lose activity, and aminating reaction can occur with ammonia and form ammonium material, ammonium
Substance is adsorbed in carbon matrix, when material is applied to soil, is released slowly and is provided nutrient, be conducive to promote
Into plant growth.
Above-mentioned biomass matrix includes but is not limited to forest and agriculture waste residue such as sawdust, corn stover etc., castoff,
Cattle waste, agricultural product castoff such as bagasse, cereal residue etc., aquatic products waste such as seaweed, sea grass etc., industrial waste
Such as sugared process residues of object.
Above-mentioned acid carbonization acid used is the sulfuric acid and phosphoric acid that weight ratio is 1:1.If with sulfuric acid, the ammonium of aminating reaction formation
Substance is ammonium sulfate, and the lignin of exposure can form ligninsulfonate in sulfuric acid and biomass, has improvement soil pH, salt
Alkalinization；If the ammonium material that aminating reaction is formed is ammonium dihydrogen phosphate or diammonium hydrogen phosphate with phosphoric acid.
The preparation step of the multiporous biological matter matrix of above-mentioned acid carbonization is as follows: 30% weight is added into biomass matrix
Acid carries out carbon 15min, and sour mass concentration is 50%, after complete reaction, 20% weight of biomass matrix is passed through into system
Anhydrous gaseous ammonia react 40min, recycle raffinate, take precipitating dry to get.
The alpha naphthol of the tert-butyl hydroquinone containing 0.07mM and 0.08mM, the two are carbonized in acid in above-mentioned acid carbonization acid used
Shi Fahui synergistic effect, promote the combination of lignin and hemicellulose occur depolymerization, not only improve lignin exposure after with sulphur
Acid forms ligninsulfonate, and can control acid to the carbonizing degree of biomass fiber, reduces sour dosage and production cost, another party
Both faces are slowly released from biomass matrix into after soil, can continue the work of urase and catalase in enhancing soil
Property, so that the preventing poison ability increase soil fertility with plant to hydrogen peroxide, achievees the purpose that rehabilitating soil.
The fixative of above-mentioned multi-layer film structure includes the ethylene-vinyl acetate copolymer grain core that partial size is 5mm, is matched by sugar
The filled layer that object is formed and the bonding layer formed by poly- hydroxy acid.Bonding layer enriching heavy metal, is replaced by filled layer
It is immobilized into grain core, reduces the murder by poisoning of heavy metal on plants, simultaneously engaged with layer and filled layer can be natural in the soil
It decomposes, provides nutrient for plant, increase soil fertility, grain core can be recycled and be reused, and reduce soil remediation cost.
Filled layer and bonding layer are successively wrapped in a core table by way of spraying in the fixative of above-mentioned multi-layer film structure
Layer；The dosage of above-mentioned filled layer and bonding layer substance is respectively the 10% and 10% of grain core weight.
Poly- hydroxy acid used in above-mentioned bonding layer is the condensation polymer of one or more hydroxy acids, it is preferable that hydroxy acid
For hydroxybutyric acid.Poly- hydroxy acid is biodegradable polymer, enrichment can be produced to heavy metal element, with a huge sum of money
Belong to ion and form high affine, stable complex compound sediment, reduces its harm to plant.
Sugar used in above-mentioned filled layer includes one or more substances comprising glycosidic bond with object, it is preferable that sugar is to form sediment with object
Powder.Filled layer can increase the adhesiveness between core and bonding layer, while establish channel between bonding layer and grain core, by heavy metal
Element is replaced from fixative surface layer into grain core, and the fixation and stabilisation to heavy metal are reached.
Embodiment 2:
For the restorative procedure of Coastal beach heavy-metal contaminated soil, the specific steps of which are as follows:
(1) cinder is sieved to and is chosen the coal slag granules that partial size is less than 5mm, by the pollution of area surface layer 10cm to be repaired
Soil stirring is smashed, and by cinder: cinder is added into soil for soil=1:1.5 dry weight ratio, after mixing, to surface layer
Moisture is sprayed by solid-to-liquid ratio 1:1.5, then aging conserves 7d, obtains modified soil；
(2) taking weight ratio is that hydrochloric acid, bamboo vinegar and the sulfuric acid of 1:2:1.5 is diluted, and is configured to the leaching that concentration is 0.5%
Then washing lotion elutes modified soil with 3 times of amounts, is repeated 2 times, time interval 10h, after separation of solid and liquid, collects respectively
Leacheate and soil solids；
(3) acid that 35% weight is added into biomass matrix carries out carbonization 30min, after complete reaction, into system
It is passed through the anhydrous gaseous ammonia reaction 45min of 25% weight of biomass matrix, recycles raffinate, takes precipitating dry to get acid carbonization
Multiporous biological matter matrix, above-mentioned acid carbonization acid used are the sulfuric acid and phosphoric acid that weight ratio is 1:1, and sour mass concentration is 45%,
The alpha naphthol of tert-butyl hydroquinone containing 0.05mM and 0.05mM in above-mentioned acid；
(4) choosing partial size is the ethylene-vinyl acetate copolymer of 5mm as grain core, is grain core weight 8% by weight
Starch spraying is wrapped in a core surface layer and forms filled layer, and the poly- hydracrylic acid that weight is grain core weight 12% is then sprayed package
Bonding layer is formed outside filled layer, and the fixative of multi-layer film structure is made；
The fixative of the multi-layer film structure of the multiporous biological matter matrix, 45wt% that (5) successively take the acid of 35wt% to be carbonized,
The sulphur powder of 10wt%, the zeolite powder of 5wt%, 5wt% carbide slag after mixing, be made heavy metal stabilizer；
(6) dry field is turned over, by the soil solids agglomerate fragmentation after elution, then by a 250kg/ mus of amount uniform broadcasting huge sum of moneys
Belong to stabilizer；After having broadcasted sowing heavy metal stabilizer, deep ploughing processing is carried out to soil, the topsoil depth for processing of deep ploughing is 15cm,
And repeat 2 times, it is ensured that horizontal and vertical to be uniformly mixed；After deep ploughing, the water surface is added water to higher than soil surface 15cm, to soil
Carry out ageing 14d；After ageing, dry field is drained.
Embodiment 3:
The present embodiment the difference is that only with embodiment 2: further include respectively hydrochloric acid in leacheate used in step (2)
The furancarboxylic acid of weight 0.04% and 0.06% ethoxyquinoline, the two synergistic effect can elution when, utilize functional group be embedded in coal
Slag inside configuration, and soil capillary continuity is destroyed using different degrees of hydrophily, increase soil porosity, and then destroy
Heavy metal transformation path reduces its migration, and on the other hand the two can enhance phosphatase activity in soil, accelerates organic in soil
Phosphorus circulation, to improve Phosphorus in Soil validity and soil fertility.
Embodiment 4:
The present embodiment the difference is that only with embodiment 2: be not added with tert-butyl hydrogen in step (3) acid carbonization acid used
Quinone and alpha naphthol.
Embodiment 5:
The present embodiment the difference is that only with embodiment 2: be not added with tert-butyl hydrogen in step (3) acid carbonization acid used
Quinone and alpha naphthol, and the mass concentration of acid carbonization acid used is 55%, sour dosage make a living the 65% of material matrix weight.
Embodiment 6:
The present embodiment the difference is that only with embodiment 2: step (5) concrete measure are as follows: successively take the acid of 80wt%
The multiporous biological matter matrix of carbonization, the sulphur powder of 10wt%, the zeolite powder of 5wt%, 5wt% carbide slag after mixing, system
Obtain heavy metal stabilizer；The fixative of multi-layer film structure is not added in heavy metal stabilizer.
Embodiment 7:
The present embodiment the difference is that only with embodiment 2: step (5) concrete measure are as follows: successively take that 80wt%'s is more
The fixative of film structure, the sulphur powder of 10wt%, the zeolite powder of 5wt%, 5wt% carbide slag after mixing, be made weight
Metallic stabilizer；The multiporous biological matter matrix of acid carbonization is not added in heavy metal stabilizer.
Test example 1:
Heavy metal in soil content detection under different restorative procedures
Test method: it takes the soil after repairing in each embodiment as test specimen at random, is sent out with inductively coupled plasma
Spectrographic determination copper, zinc, lead, chromium are penetrated, with reference to the 5th part of ocean inspection criterion (GB 17378.5-2007), respectively with no flame
Atomic absorption spectroscopy determination cadmium, with Atomic Fluorescence Spectrometry arsenic and mercury.Testing result statistics is shown in Table 1.
1 heavy metal in soil content detection result of table
As seen from the above table, heavy metal in soil content meets " GB15618-1995 standard of soil environment quality " after reparation
II grade standard.The reparation result of embodiment 2-5 is significantly better than embodiment 6 and 7, illustrates heavy metal stabilizer pair in embodiment 2-5
The immobilization effect of heavy metal element is significantly better than heavy metal stabilizer used in embodiment 6 and 7.Embodiment 2 and embodiment 5
It is unobvious to repair result difference, but sour dosage and concentration are all higher than embodiment 2 in embodiment 5, illustrates to prepare sour carbon in embodiment 2
The method of the multiporous biological matter matrix of change can be reduced sour dosage compared with embodiment 5, can significantly reduce production cost in actual production.
Embodiment 2 and embodiment 3,4 compare, and the reparation result of embodiment 3 is optimal, and embodiment 2 is taken second place, and embodiment 4 is worst, illustrates to implement
In example 3 restorative procedure compared with embodiment 2 repairing effect more preferably, the migration of heavy metal can be reduced, reach fixing-stableization a huge sum of money
The effect of category；For embodiment 2 is compared with embodiment 4, illustrate that the heavy metal stabilizer repairing effect in embodiment 2 is better than embodiment 4,
The restorative procedure of embodiment 2 is more worthy of promotion and application.
Test example 2:
Influence of the different restorative procedures to soil porosity
Test method: respectively according to embodiment 2,3 method washing tests soil after, collect elution obtained solid soil, with
The soil not eluted is control group.The soil for randomly choosing identical weight respectively is sampled, and after sample air-dries, utilizes 0.25mm
The sieve of specification is sieved to soil sample, is then packed, is stored under the conditions of 4 DEG C using the poly- second refining bag of sealing, spare；So
Soil porosity is measured using core cutter method afterwards.It counts and interpretation of result is as shown in table 2.
The measurement result of soil porosity under the different restorative procedures of table 2
As seen from the above table, the restorative procedure of embodiment 2 and 3 can increase soil porosity, soil after increase compared with control group
Size hole ratio is moderate, advantageously reduces heavy metals mobilization；For the restorative procedure of embodiment 3 is compared with embodiment 2, embodiment
The porosity increasing degree of soil is bigger after 3 method elution, and porosity is higher, is conducive to destroy soil capillary continuity,
To achieve the purpose that destroy heavy metal transformation path to reduce its migration.
Test example 3:
Influence of the different restorative procedures to Enzyme Activities in Soils
(1) respectively according to embodiment 2,4 method rehabilitating soils after, using the soil that do not repair as control group.Soil modification,
Elution and application heavy metal stabilizer each stage detect urase in soil and catalase activity, and urease activity uses
Sodium phenate colorimetric method, catalase activity use permanganimetric method.Statistics and analysis result are as shown in attached drawing 1,2.
Fig. 1 is influence schematic diagram of the different restorative procedures to urease activity in soil, and Fig. 2 is different restorative procedures to soil
The influence schematic diagram of middle catalase activity.As seen from the figure, embodiment 2,4 and control group be before heavy metal stabilizer application,
Urase and catalase activity difference are unobvious in soil, urase and catalase activity respectively in 0.4-0.8mg/g and
It is fluctuated between 0.4-0.9mg/g, after applying stabilizer, embodiment 4 and control group are still in normal fluctuation range, and embodiment
Urase and catalase activity rise to 1.23mg/g and 1.35mg/g respectively in 2, and increasing degree is larger, significant difference.It says
For restorative procedure is compared with embodiment 4 in bright embodiment 2, the activity of urase and catalase in soil can be enhanced, so as to improve
Soil fertility and preventing poison ability to hydrogen peroxide, achieve the purpose that rehabilitating soil.
(2) respectively according to embodiment 2,3 method rehabilitating soils after, using the soil that do not repair as control group.Soil modification,
Elution and application heavy metal stabilizer each stage detect phosphatase activity in soil, and phosphatase activity uses benzenephosphonic acid two
Sodium colorimetric method.Statistics and analysis result are as shown in Fig. 3.
Fig. 3 is influence schematic diagram of the different restorative procedures to phosphatase activity in soil.As seen from the figure, embodiment 2,3 with
Control group is before elution, and phosphatase activity difference is unobvious in test soil, phosphatase activity wave between 1.2-1.7mg/g
Dynamic, after elution, embodiment 2 and control group are still in normal fluctuation range, and phosphatase activity rises in embodiment 3
2.3mg/g, increasing degree is larger, significant difference, and remains to the high activity that duration keeps phosphatase after applying stabilizer.Explanation
For restorative procedure is compared with embodiment 2 in embodiment 3, phosphatase activity in soil can be enhanced, organic phosphorus in soil follow is accelerated with this
Ring improves Phosphorus in Soil validity and soil fertility.
The prior art of routine techniques dawn known to those skilled in the art in above-described embodiment, therefore herein no longer in detail
It repeats.
The above embodiments are only used to illustrate the present invention, and not limitation of the present invention, the ordinary skill people of this field
Member can also make a variety of changes and modification without departing from the spirit and scope of the present invention.Therefore, all equivalent
Technical solution also belong to scope of the invention, scope of patent protection of the invention should be defined by the claims.
Claims (10)
1. being used for the restorative procedure of Coastal beach heavy-metal contaminated soil, comprising:
Soil modification is provided, the viscosity of mud-flat soil is reduced；
Elution, the higher mobility heavy metal of removal activity are provided；
Heavy metal stabilizer, fixed and stabilisation heavy metal are provided；
It include the multiporous biological matter matrix of acid carbonization and the fixative of multi-layer film structure in the heavy metal stabilizer.
2. the restorative procedure according to claim 1 for Coastal beach heavy-metal contaminated soil, it is characterised in that: described
Steps are as follows for soil modification: cinder being sieved to and chosen the coal slag granules that partial size is less than 5mm, by area surface layer 0- to be repaired
The contaminated soil stirring of 10cm is smashed, by cinder: cinder is added into soil for soil=1:1-3 dry weight ratio, and mixing is equal
After even, moisture is sprayed by solid-to-liquid ratio 1:1-3 to surface layer, then aging conserves 5-10d, obtains modified soil.
3. the restorative procedure according to claim 1 for Coastal beach heavy-metal contaminated soil, it is characterised in that: described
Eluting eluent concentration used is 0.3-1.0%, includes hydrochloric acid, bamboo vinegar that weight ratio is 1:1-2:1-3 in the leacheate
And sulfuric acid.
4. the restorative procedure according to claim 1 for Coastal beach heavy-metal contaminated soil, it is characterised in that: described
The amount of application of heavy metal stabilizer in the soil is 200-300kg/ mus；It is 10- to depth after the heavy metal stabilizer application
The topsoil of 40cm carries out deep ploughing processing, and water is added to carry out ageing 10-15d.
5. the restorative procedure according to claim 1 for Coastal beach heavy-metal contaminated soil, it is characterised in that: described
The multi-layer film structure of the multiporous biological matter matrix and 40-60wt% of acid carbonization in heavy metal stabilizer including 25-35wt%
Fixative.
6. the restorative procedure according to claim 1 for Coastal beach heavy-metal contaminated soil, it is characterised in that: described
It is formed in the multiporous biological matter matrix of acid carbonization comprising biomass matrix, the residual acid of sour carbonisation and residual acid aminating reaction
Ammonium material.
7. the restorative procedure for Coastal beach heavy-metal contaminated soil according to claim 1 or 6, it is characterised in that:
The multiporous biological matter matrix preparation acid used of the acid carbonization is at least one of sulfuric acid and phosphoric acid, and the mass concentration of acid used is
40-80%；The alpha naphthol of tert-butyl hydroquinone containing 0.05-0.1mM and 0.03-0.08mM in the acid carbonization acid used.
8. being used for the restorative procedure of Coastal beach heavy-metal contaminated soil according to claim 1 or 5, it is characterised in that:
It is described acid carbonization multiporous biological matter matrix preparation step it is as follows: into biomass matrix add 20-70% weight acid into
Row carbonization 10-30min is passed through the anhydrous gaseous ammonia of biomass matrix 15-40% weight into system, instead after complete reaction
After answering 30-60min, recycle raffinate, take precipitating dry to get.
9. being used for the restorative procedure of Coastal beach heavy-metal contaminated soil according to claim 1 or 5, it is characterised in that:
The fixative of the multi-layer film structure includes the ethylene-vinyl acetate copolymer grain core that partial size is 2-6mm, is formed by sugar with object
Filled layer and the bonding layer that is formed by poly- hydroxy acid.
10. being used for the restorative procedure of Coastal beach heavy-metal contaminated soil according to claim 1 or 5, it is characterised in that:
Filled layer and bonding layer are successively wrapped in a core surface layer by way of spraying in the fixative of the multi-layer film structure；It is described to fill out
The dosage for filling layer and bonding layer substance is respectively the 5-10% and 8-15% of grain core weight.
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