CN110283596A - A kind of passivator and restorative procedure for in-situ immobilization soil heavy metal cadmium - Google Patents
A kind of passivator and restorative procedure for in-situ immobilization soil heavy metal cadmium Download PDFInfo
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- CN110283596A CN110283596A CN201910401493.2A CN201910401493A CN110283596A CN 110283596 A CN110283596 A CN 110283596A CN 201910401493 A CN201910401493 A CN 201910401493A CN 110283596 A CN110283596 A CN 110283596A
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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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/40—Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C2101/00—In situ
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2101/00—Agricultural use
Abstract
The invention discloses a kind of passivator and restorative procedure for for in-situ immobilization soil heavy metal cadmium, raw material composition is charcoal, processing bacteria residue, modified meerschaum.The passivator raw material sources are sufficient, and process flow meets enterprise's production requirement, it is ensured that a large amount of preparations of the passivator.Simultaneously, to inhibiting, farmland soil heavy metals cadmium is active, reduces agricultural product edible part heavy metal cadmium content has remarkable result to the passivator, can large-scale application in mild or moderate Cd-polluted farmland in-situ passivation reparation, have broad application prospects to the fields such as mild or moderate Cd-polluted farmland production safety ability are promoted.
Description
Technical field
The present invention relates to agricultural environment pollution prevention and control and repair field, and in particular to one kind is for an in-situ immobilization soil huge sum of money
Belong to the passivator and restorative procedure of cadmium.
Background technique
" the national Soil Pollution Investigation bulletin " announced according to 2014 points out that China mainland pollution of soil object is total
Exceeding standard rate is up to 16.1%, and arable soil point exceeding standard rate is up to 19.4%, and pollutant type is mainly heavy metal.Crop can
It absorbs the heavy metal in soil and is transported to edible part, then built up in human body by food chain, when accumulation amount is more than peace
After full threshold value, harm will be generated to human health.It can be seen that heavy metal pollution of soil has become the life of restricting current agricultural safety
The big resistance produced.
The researcher that the sternness of Heavy Metal Pollution In Cultivated Land also promotes soil environment field carries out soil weight
In the research of metallic pollution reparation, more Heavy Metal Pollution In Cultivated Land recovery technique currently has been developed, such as soil replacement method, again
The high enriching plant extraction method of metal, in-situ passivation recovery technique etc..It is directed to this kind of special land type in arable land, which carry
The key player of grain-production, actual requirement to area huge mild or moderate heavy metal pollution arable land take it is economical, can be simultaneous simultaneously
Gu Xiufu and the heavy metal of grain-production repair mode, therefore in-situ passivation technology is to be best suitable for mild or moderate heavy metal pollution arable land
Reparation mode.
Currently associated researcher has carried out correlative study to a variety of potential heavy metal deactivator raw material, and takes
Obtained biggish breakthrough, it has been found that a variety of raw material have passivation effect, these passivator former materials to heavy metal
Material reduces heavy metal-polluted soil often through modes such as precipitating/co-precipitation, chemisorption, ion exchange, organic complex, redox
Available state activity, to reduce absorption of the crops to heavy metal.However currently also to the research of heavy metal-polluted soil passivating material
There are following obstructions: first is that current research focuses mostly in the passivation effect of original material itself, though develop part
Modified material simultaneously demonstrates its counterweight metal passivation effect higher than original material, however applied preparation process still stays in reality
The small-scale exploitation for testing room, is not suitable for the factorial production.The second is single passivation mode has the passivation effect of heavy metal ion
Limit, and current research focuses mostly in single passivating material, to the heavy metal of the composite passivated material development of multiple functions complementation
Passivation effect research is still less.The third is current research focuses mostly in potting, simulation test, field experiment effect is still relatively lacked
It is weary, however field heavy metal soil remediation be only heavy metal deactivator research and development original intention in addition field trial should be used as examining it is blunt
Change the most important index of effect.
Therefore, there are preparation process complexity, production processes to pollute ring for existing heavy metals in farmland pollution remediation technology at present
Border is not suitable for the factorial production, the problems such as counterweight metallic ion passivation effect is limited.
Summary of the invention
It is an object of the invention to: in view of the above-mentioned problems of the prior art, the present invention from passivator raw material screening,
It gradually visits the part such as modified passivating material fabricating technology formulation, passivator raw material ratio, passivator field test effect
Rope passivator composition, optimum proportioning and passivation effect, provide a kind of passivator for in-situ immobilization soil heavy metal cadmium, and
The restorative procedure of the passivator is provided simultaneously.
The technical solution adopted by the invention is as follows:
A kind of passivator for in-situ immobilization soil heavy metal cadmium, is mixed by the raw material of following parts by weight:
1-5 parts of charcoal, bacteria residue 1-6 parts and 1-10 parts of modified meerschaum of processing.
Further, it is preferable to be mixed by the raw material of following parts by weight:
1-4 parts of charcoal, bacteria residue 1-6 parts and 1-7 parts of modified meerschaum of processing.
Further, it is preferable to be mixed by the raw material of following parts by weight:
1-3 parts of charcoal, bacteria residue 2-4 parts and 2-6 parts of of modified meerschaum of processing
Further, it is preferable to be mixed by the raw material of following parts by weight:
2 parts of charcoal, 3 parts of bacteria residue of processing and 4 parts of modified meerschaum.
Further, charcoal is made by the following method: dry stalk is cut up with a hay cutter into segment, at 200-500 DEG C into
Row anaerobism is carbonized 4-12 hours, crushes after being cooled to room temperature, after 4-60 mesh, charcoal head product is obtained, at the beginning of charcoal
Add water in product, filtered after being sufficiently stirred, collection filtrate is spare, collects residue and simultaneously dries, obtains charcoal；Preferably, biological
Charcoal is made by the following method: by dry stalk hand hay cutter at segment, carrying out anaerobism at 400 DEG C and is carbonized 8 hours, be cooled to room temperature
After crush, after 18 meshes, obtain charcoal head product, in charcoal head product plus water, filtered after being sufficiently stirred, collect filter
Liquid is spare, collects residue and dries, obtains charcoal.
Further, the mass ratio of charcoal head product and water is 1-3:8-12；Preferably, charcoal head product and water
Mass ratio is 1:10.
Charcoal has preferable passivation effect to soil heavy metal cadmium.And the passivation effect of charcoal is prepared by charcoal
Technique is affected, and the difference for being primarily due to carburizing temperature and carbonization time will cause the difference of charcoal material composition and structure
It is different, and then influence charcoal passivation effect.The present invention has found through overtesting, is carbonized 8 hours this techniques using 400 DEG C of anaerobism,
Straw biological charcoal can be made best to the adsorption effect of heavy metal cadmium.
Further, modified meerschaum is made by the following method: gained filtrate in charcoal preparation process is heated to
60 DEG C, Al (NO is then added3)3-Fe(NO3)3Mixed liquor, heating are cooled down and are placed 1-3 days after 1-3 hours, be prepared into pillared
Liquid；Sepiolite is crushed, pillared liquid is added, is mixed, is crushed after 30-60 DEG C of drying, modified meerschaum is made；Preferably, modified
Sepiolite is made by the following method: the filtrate described in 60 DEG C of heated at constant temperature is slowly added to Al (NO in filtrate3)3-Fe
(NO3)3Mixed liquor, heating were cooled down and are placed 2 days after 2 hours, were prepared into pillared liquid；Sepiolite is crushed, pillared liquid is added, is mixed
It is even, it is crushed after 50 DEG C of drying, modified meerschaum is made.
Further, Al (NO3)3-Fe(NO3)3Mixed liquor is according to Al (NO3)3With Fe (NO3)3Molar ratio be 3-6:1-2
Mixed preparing；Preferably, Al (NO3)3-Fe(NO3)3Mixed liquor is according to Al (NO3)3With Fe (NO3)3Molar ratio be 4:1 mixing match
System.
Further, filtrate and Al (NO3)3-Fe(NO3)3The volume ratio of mixed liquor is 2-6:1-3；Preferably, filtrate with
Al(NO3)3-Fe(NO3)3The volume ratio of mixed liquor is 2:1.
Further, the volume ratio of sepiolite powder and pillared liquid is 2-6:1-3；Preferably, sepiolite powder with it is pillared
The volume ratio of liquid is 2:1.
Sepiolite has preferable passivation effect to soil heavy metal cadmium.And the passivation effect of sepiolite is by its surface texture
It influences, its passivation effect to heavy metal cadmium suitably can be obviously improved to sepiolite modification, have a small amount of prior art early period
It is middle that sepiolite is modified using Fe base or Mn base, so that sepiolite surface texture becomes smaller, sepiolite surface area is increased, is mentioned
Rise its adsorption ability.However the study on the modification to sepiolite focuses mostly in laboratory small scale experiments, technique is uncomfortable
For industrial production；And prior art can more or less generate some of the contaminants.The present invention it has been investigated that, joined using Fe-Al
Modified meerschaum is closed, the ability orientation of sepiolite adsorption heavy metal cadmium can be made to maximum, while technique of the invention is very
Suitable for mass production, and any pollutant effulent will not be generated.
During modified meerschaum be added charcoal filtrate effect be to prepare pillared liquid and providing alkaline environment, it is pillared
Liquid needs are prepared under alkaline environment, and alkaline environment provided by charcoal filtrate is just met for pillared liquid preparation and requires.Biology
After charcoal preparation, generally requires and used again after being rinsed with water, and exactly waste, pH value are higher for filtrate, direct emission is to environment
There is certain negative effect, therefore discharge of wastewater is controlled using biology prospecting liquid.Certainly, if being provided with using other modes
Alkaline environment is also feasible, and from the point of view of the circulation of substance inside, present invention preferably employs charcoal filtrates.
Further, the processing method of bacteria residue is handled are as follows: bacteria residue progress physics is loose, then ferment 30-60 days, then at
It is sterilized 1.5-4 hours at 100-140 DEG C；Preferably, the processing method of bacteria residue is handled are as follows: bacteria residue progress physics is loose, then
Fermentation 45 days, is sterilized 2 hours at 120 DEG C.
Bacteria residue is the compost after culturing edible fungus, and such as the compost after cultivation needle mushroom, oyster mushroom, mushroom, bacteria residue is because of richness
Containing organic carbon, surface organo-functional group is more, has certain adsorption capacity to heavy metal ion.Furthermore in the present invention, remove
Outside bacteria residue, other materials is powder or fine particle shape substance, directly enters field post-passivation effect vulnerable to larger impact.Therefore originally
Bacteria residue also carries the integrated support object as composite passivated material other than the function of direct adsorbing heavy metal cadmium in invention
Matter, stablizes charcoal and modified meerschaum adsorbs and fixes ability to heavy metal cadmium in the soil.
The farmland of cadmium slight pollution is turned in the application of the above-mentioned passivator for in-situ immobilization soil heavy metal cadmium
Topsoil uniformly applies passivator, and dosage is 85-110kg/ mus, rotary tillage 2-3 times, planting plants after balance 10 days；For
Cadmium intermediate pollution farmland, turns over topsoil, uniformly applies passivator, and dosage is 120-140kg/ mus, and rotary tillage 2-3 times is put down
Planting plants after weighing apparatus 15 days.
Further, the restorative procedure of the above-mentioned passivator for in-situ immobilization soil heavy metal cadmium, comprising the following steps:
Heavy metals in farmland cadmium content is measured, delimit agriculture according to " farming land standard of soil environment quality " (GB15618-2018)
The land used soil pollution class of pollution specifies heavy metal-polluted soil cadmium content between soil pollution risk screening value and soil pollution control
Farming land between value is to repair object；
With farming land heavy metal cadmium content for i value, when soil pollution risk screening value < i < 2 times soil pollution risk screening
It is heavy metal cadmium slight pollution farming land when value.Reclamation activities to such farming land is after turning over topsoil, uniformly to apply
Passivator is spread, dosage is 85-110kg/ mus, rotary tillage 2-3 times, planting plants after balance 10 days；
It is agricultural for heavy metal cadmium intermediate pollution when 2 times of soil pollution risk screening value < i < soil pollution risk control values
Ground.Reclamation activities to such farming land is after turning over topsoil, uniformly to apply passivator, dosage 120-140kg/
Mu, rotary tillage 2-3 times, planting plants after balancing 15 days.
In conclusion by adopting the above-described technical solution, the beneficial effects of the present invention are:
1, in the present invention, the straw biological charcoal effect that charcoal is carbonized with 400 DEG C is best, carries out to passivating material sepiolite
Fe-Al is combined modified, so that the structure of sepiolite is modified, it is to the fixed function of heavy metal ion more significant, and therefore,
It is that raw material prepares passivator that the present invention, which selects the straw biological charcoal, bacteria residue, the combined modified sepiolite of Fe-Al of 400 DEG C of carbonizations, is had
Good passivation effect；
2, all production processes of the present invention will not generate harmful substance, while will not generate outlet object, production process pair
It is environmental-friendly；
It 3, is in threadiness using passivator made from the technology of the present invention, neither powder, nor cake mass, therefore pole
The earth facilitates uniformly applying for field；
4, the passivator of application the invention patent preparation will not impact crop yield, on the contrary, can also be certain
Crop yield is promoted in degree；
Although 5, passivator effect of the present invention decreases as the time moves back, its range of decrease is little, and is applying
Ideal effect can be still kept after several years, therefore passivator provided by the invention is to slight and moderate cadmium pollution paddy field
With long-term repairing effect.
Detailed description of the invention
In order to illustrate the technical solution of the embodiments of the present invention more clearly, below will be to needed in the embodiment attached
Figure is briefly described, it should be understood that the following drawings illustrates only certain embodiments of the present invention, therefore is not construed as pair
The restriction of range for those of ordinary skill in the art without creative efforts, can also be according to this
A little attached drawings obtain other relevant attached drawings.
Fig. 1 is the adsorption effect of various passivating materials and its modified material to cadmium in solution；
Fig. 2 is that each passivator matches the lower slight and moderate Cd-polluted farmland brown rice cadmium content of material application；
Fig. 3 is influence of the passivator of the present invention to field rice yield；
Fig. 4 is influence of the passivator of the present invention to field rice brown rice cadmium content；
Fig. 5 is influence of the passivator of the present invention to crop field yield of pakchoi；
Fig. 6 is influence of the passivator of the present invention to crop field pakchoi edible part cadmium content.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that described herein, specific examples are only used to explain the present invention, not
For limiting the present invention, i.e., described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is logical
The component for the embodiment of the present invention being often described and illustrated herein in the accompanying drawings can be arranged and be designed with a variety of different configurations.
Therefore, the detailed description of the embodiment of the present invention provided in the accompanying drawings is not intended to limit below claimed
The scope of the present invention, but be merely representative of selected embodiment of the invention.Based on the embodiment of the present invention, those skilled in the art
Member's every other embodiment obtained without making creative work, shall fall within the protection scope of the present invention.
It should be noted that the relational terms of term " first " and " second " or the like be used merely to an entity or
Operation is distinguished with another entity or operation, and without necessarily requiring or implying between these entities or operation, there are any
This actual relationship or sequence.Moreover, the terms "include", "comprise" or its any other variant be intended to it is non-exclusive
Property include so that include a series of elements process, method, article or equipment not only include those elements, but also
Further include other elements that are not explicitly listed, or further include for this process, method, article or equipment it is intrinsic
Element.In the absence of more restrictions, the element limited by sentence "including a ...", it is not excluded that including described
There is also other identical elements in the process, method, article or equipment of element.
Feature and performance of the invention are described in further detail with reference to embodiments.
Embodiment 1
Present pre-ferred embodiments provide a kind of passivator for in-situ immobilization soil heavy metal cadmium.
Passivator for in-situ immobilization soil heavy metal cadmium is mixed by the raw material of following parts by weight:
1 part of charcoal, processing bacteria residue 3 and 5 parts of modified meerschaum.
Charcoal is made by the following method: by dry stalk hand hay cutter at segment, it is small that anaerobism carbonization 8 is carried out at 400 DEG C
When, it is crushed after being cooled to room temperature, after 18 meshes, obtains charcoal head product, water is added in charcoal head product, is sufficiently stirred
After filter, collect filtrate it is spare, collect residue simultaneously dry, obtain charcoal.
Modified meerschaum is made by the following method: in 60 DEG C of heated at constant temperature filtrates, being slowly added to volume in filtrate is
Al (the NO of filtrate volume half3)3-Fe(NO3)3Mixed liquor, Al (NO3)3With Fe (NO3)3Molar ratio is 4:1, is heated 2 hours
It cools down and places 2 days afterwards, be prepared into pillared liquid；Sepiolite is crushed, the pillared liquid that volume is sepiolite volume half is added, mixes
It is even, it is crushed after 50 DEG C of drying, modified meerschaum is made.
Handle the processing method of bacteria residue are as follows: needle mushroom dreg progress physics is loose, it then ferments 45 days, then at 120 DEG C
Lower sterilization 2 hours.
Embodiment 2
Present pre-ferred embodiments provide a kind of passivator for in-situ immobilization soil heavy metal cadmium.
Passivator for in-situ immobilization soil heavy metal cadmium is mixed by the raw material of following parts by weight:
2 parts of charcoal, processing bacteria residue 3 and 4 parts of modified meerschaum.
Charcoal is made by the following method: by dry stalk hand hay cutter at segment, it is small that anaerobism carbonization 8 is carried out at 400 DEG C
When, it is crushed after being cooled to room temperature, after 18 meshes, obtains charcoal head product, water is added in charcoal head product, is sufficiently stirred
After filter, collect filtrate it is spare, collect residue simultaneously dry, obtain charcoal.
Modified meerschaum is made by the following method: in 60 DEG C of heated at constant temperature filtrates, being slowly added to volume in filtrate is
Al (the NO of filtrate volume half3)3-Fe(NO3)3Mixed liquor, Al (NO3)3With Fe (NO3)3Molar ratio is 4:1, is heated 2 hours
It cools down and places 2 days afterwards, be prepared into pillared liquid；Sepiolite is crushed, the pillared liquid that volume is sepiolite volume half is added, mixes
It is even, it is crushed after 50 DEG C of drying, modified meerschaum is made.
Handle the processing method of bacteria residue are as follows: needle mushroom dreg progress physics is loose, it then ferments 45 days, then at 120 DEG C
Lower sterilization 2 hours.
Embodiment 3
Present pre-ferred embodiments provide a kind of passivator for in-situ immobilization soil heavy metal cadmium.
Passivator for in-situ immobilization soil heavy metal cadmium is mixed by the raw material of following parts by weight:
3 parts of charcoal, processing bacteria residue 3 and 3 parts of modified meerschaum.
Charcoal is made by the following method: by dry stalk hand hay cutter at segment, it is small that anaerobism carbonization 8 is carried out at 400 DEG C
When, it is crushed after being cooled to room temperature, after 18 meshes, obtains charcoal head product, water is added in charcoal head product, is sufficiently stirred
After filter, collect filtrate it is spare, collect residue simultaneously dry, obtain charcoal.
Modified meerschaum is made by the following method: in 60 DEG C of heated at constant temperature filtrates, being slowly added to volume in filtrate is
Al (the NO of filtrate volume half3)3-Fe(NO3)3Mixed liquor, Al (NO3)3With Fe (NO3)3Molar ratio is 4:1, is heated 2 hours
It cools down and places 2 days afterwards, be prepared into pillared liquid；Sepiolite is crushed, the pillared liquid that volume is sepiolite volume half is added, mixes
It is even, it is crushed after 50 DEG C of drying, modified meerschaum is made.
Handle the processing method of bacteria residue are as follows: needle mushroom dreg progress physics is loose, it then ferments 45 days, then at 120 DEG C
Lower sterilization 2 hours.
Embodiment 4
Present pre-ferred embodiments provide a kind of passivator for in-situ immobilization soil heavy metal cadmium.
Passivator for in-situ immobilization soil heavy metal cadmium is mixed by the raw material of following parts by weight:
4 parts of charcoal, processing bacteria residue 3 and 2 parts of modified meerschaum.
Charcoal is made by the following method: by dry stalk hand hay cutter at segment, it is small that anaerobism carbonization 8 is carried out at 400 DEG C
When, it is crushed after being cooled to room temperature, after 18 meshes, obtains charcoal head product, water is added in charcoal head product, is sufficiently stirred
After filter, collect filtrate it is spare, collect residue simultaneously dry, obtain charcoal.
Modified meerschaum is made by the following method: in 60 DEG C of heated at constant temperature filtrates, being slowly added to volume in filtrate is
Al (the NO of filtrate volume half3)3-Fe(NO3)3Mixed liquor, Al (NO3)3With Fe (NO3)3Molar ratio is 4:1, is heated 2 hours
It cools down and places 2 days afterwards, be prepared into pillared liquid；Sepiolite is crushed, the pillared liquid that volume is sepiolite volume half is added, mixes
It is even, it is crushed after 50 DEG C of drying, modified meerschaum is made.
Handle the processing method of bacteria residue are as follows: needle mushroom dreg progress physics is loose, it then ferments 45 days, then at 120 DEG C
Lower sterilization 2 hours.
Embodiment 5
Present pre-ferred embodiments provide a kind of passivator for in-situ immobilization soil heavy metal cadmium.
Passivator for in-situ immobilization soil heavy metal cadmium is mixed by the raw material of following parts by weight:
5 parts of charcoal, processing bacteria residue 3 and 1 part of modified meerschaum.
Charcoal is made by the following method: by dry stalk hand hay cutter at segment, it is small that anaerobism carbonization 8 is carried out at 400 DEG C
When, it is crushed after being cooled to room temperature, after 18 meshes, obtains charcoal head product, water is added in charcoal head product, is sufficiently stirred
After filter, collect filtrate it is spare, collect residue simultaneously dry, obtain charcoal.
Modified meerschaum is made by the following method: in 60 DEG C of heated at constant temperature filtrates, being slowly added to volume in filtrate is
Al (the NO of filtrate volume half3)3-Fe(NO3)3Mixed liquor, Al (NO3)3With Fe (NO3)3Molar ratio is 4:1, is heated 2 hours
It cools down and places 2 days afterwards, be prepared into pillared liquid；Sepiolite is crushed, the pillared liquid that volume is sepiolite volume half is added, mixes
It is even, it is crushed after 50 DEG C of drying, modified meerschaum is made.
Handle the processing method of bacteria residue are as follows: needle mushroom dreg progress physics is loose, it then ferments 45 days, then at 120 DEG C
Lower sterilization 2 hours.
Experimental example 1
Carry out heavy metal adsorption experiment with modified material to collecting, specifies each material to heavy metal adsorption effect, filter out
3 kinds of best materials of adsorption effect are as the candidate materials for preparing passivator.Concrete operations are as follows:
1, stalk, building materials sawdust, the sepiolite in the passivating material collected are modified, wherein stalk, building materials wood
Anaerobism carbonization 8h, sepiolite use Fe (NO to bits respectively at 200 DEG C, 300 DEG C, 400 DEG C, 500 DEG C respectively3)3、Al(NO3)3、Fe
(NO3)3With Al (NO3)3Modified meerschaum is made in mixed solution.
2, modified meerschaum is prepared by following methods: 60 DEG C of heated at constant temperature charcoal filtrates, is slowly added to and filtrate volume
Fe (the NO of the 0.4mol/L of half3)3Solution, cooling place 2 days is prepared into Fe (NO after heating 2 hours3)3Pillared liquid；60 DEG C of perseverances
Warm heating biological charcoal filtrate is slowly added to the Al (NO with the 0.4mol/L of filtrate volume half3)3Solution, it is cold after heating 2 hours
But it places 2 days and is prepared into Al (NO3)3Pillared liquid；Configure the Al (NO that molar ratio is 4:13)3-Fe(NO3)3Mixed liquor, wherein Al
(NO3)3Concentration is 0.4mol/L, Fe (NO3)3Concentration is 0.1mol/L, 60 DEG C of heated at constant temperature charcoal filtrates, be slowly added to
Al (the NO of filtrate volume half3)3-Fe(NO3)3Mixed liquor, cooling place 2 days is prepared into pillared liquid after heating 2 hours；It will be extra large
Afrodite crushes, and in sepiolite powder: pillared liquid is that the ratio of 2:1 mixes well by volume, is crushed after low temperature drying.
3, the CdCl of 1mmol/L is packed into each 150ml triangular flask2Solution 50ml adds 0.250g passivation agent material
Or modified passivation agent material shakes for 24 hours, from each triangular flask after preservative film sealing in 25 DEG C, 180r/min constant temperature oscillation box
Middle absorption 10ml liquid 12000r/min is centrifuged 20min, and Aspirate supernatant crosses 0.2 μm of filter membrane, measures Cd content, is repeated 3 times.Examination
It tests and does blank control, adsorption effect is calculated with (Cd content after CK processing Cd content-processing)/CK processing Cd content * 100%.
As a result as shown in Figure 1, it is seen that charcoal, sepiolite, bacteria residue to the adsorption effect of heavy metal cadmium most
Good, the straw biological charcoal effect that wherein charcoal is carbonized with 400 DEG C is best, and modified meerschaum is with the combined modified sepiolite of Fe-Al
Effect is best.Therefore, the quasi- straw biological charcoal for choosing 400 DEG C of carbonizations of the present invention, bacteria residue, the combined modified sepiolite of Fe-Al are original
Material prepares passivator.
Experimental example 2
It sets different charcoal and modified meerschaum to match, carries out native basin potting simulated experiment, analysis different ratio is blunt
Passivation effect of the agent to heavy metal-polluted soil Cd.Concrete operations are as follows:
1, passivator made from Example 1-5 is respectively labeled as T2-T6, then presses charcoal: processing bacteria residue: modified sea
Afrodite is that 0:3:6,6:3:0 configure passivator, is respectively labeled as T1 and T7.
2, the arable soil by Cd slight pollution and intermediate pollution air-dries, and mixes respectively after rejecting stone, respectively selection portion
Divide soil test basic physical and chemical and Cd content, wherein slight pollution soil pH value is 6.32, and full Cd content is 0.714mg/
Kg, intermediate pollution soil pH value are 6.08, and full Cd content is 1.793mg/kg.
3, soil 8kg is packed into 20L barrels, by N 0.3gkg-1、P2O5 0.09g·kg-1And K2O 0.12g·kg-1
Soil applies base fertilizer, then adds the composite passivant 80g of various ratios, transplanting rice after waterflooding balances 10 days, and 2 plants of every basin repeats 3
It is secondary.Brown rice cadmium content is measured when culture to the maturity period.Its result is as shown in Figure 2.
It is seen that brown rice in light, moderate Cd polluted agricultural land can be greatly reduced in the composite passivant of various proportions
Cd content, wherein being very with T3 processing (charcoal: bacteria residue: modified meerschaum ratio is 2:3:4).Therefore charcoal: bacterium is selected
Slag: the composite passivant that modified meerschaum ratio is 2:3:4 is optimum combination.
Experimental example 3
1, the optimum combination composite passivant to configure in embodiment 3, light to Cd respectively, intermediate pollution paddy field, which is carried out, repairs
Test.Wherein Cd slight pollution soil pH value is 6.32, and full Cd content is 0.714mg/kg；Cd intermediate pollution soil pH value is
6.08, full Cd content is 1.793mg/kg.
2, the reclamation activities in Cd slight pollution paddy field is after turning over topsoil, uniformly to apply mixing passivator, dosage
It is 100kg/ mus, rotary tillage 3 times, waterflooding plants rice after balancing 10 days.The reclamation activities in Cd intermediate pollution paddy field is to turn over farming
After layer soil, mixing passivator is uniformly applied, dosage is 130kg/ mus, and rotary tillage 3 times, waterflooding plants rice after balancing 15 days.Together
When every kind of pollution type paddy field be respectively provided with blank control.
3, fertilization mode and field management are constant in cultivation, apply the continuous water for investigating each processing for 3 years after passivator
Rice yield, brown rice Cd content.Its result difference is as shown in Figure 3, Figure 4.
It is seen that the application of passivator not will cause the rice underproduction in low, moderate Cd polluted agricultural land.On the contrary
Ground, in test in 3 years, rice yield has slight increase after applying passivator, therefore passivator provided by the invention can increase
Rice yield.In addition, Brown Rice Cd content can be greatly reduced in the application of passivator in low, moderate Cd polluted agricultural land, and
The range of decrease is above 55%.Although passivator effect decreases as the time moves back, its range of decrease is little, and in application the
Ideal effect can be still kept within 3 years, therefore passivator provided by the invention has low, moderate Cd pollution paddy field
Long-term repairing effect.
Experimental example 4
1, the optimum combination composite passivant to configure in embodiment 3, light to Cd respectively, intermediate pollution vegetable plot, which is carried out, repairs
Test.Wherein Cd slight pollution soil pH value is 6.07, and full Cd content is 0.562mg/kg；Cd intermediate pollution soil pH value is
6.74, full Cd content is 1.242mg/kg.
2, the reclamation activities in Cd slight pollution vegetable plot is after turning over topsoil, uniformly to apply mixing passivator, dosage
It is 100kg/ mus, rotary tillage 3 times, balance planted pakchoi after 10 days.The reclamation activities in Cd intermediate pollution vegetable plot is to turn over arable layer
After soil, mixing passivator is uniformly applied, dosage is 130kg/ mus, and rotary tillage 3 times, balance planted pakchoi after 15 days.It is every simultaneously
Kind pollution type vegetable plot is respectively provided with blank control.
3, fertilization mode and field management are constant in cultivation, continuously plant 3 batches of pakchois after applying passivator, investigate
Yield of pakchoi, the edible part Cd content respectively handled.Its result difference is as shown in Figure 5, Figure 6.
It is seen that the application of passivator significantly increases yield of pakchoi in low, moderate Cd pollution vegetable plot,
Therefore passivator provided by the invention can increase yield of pakchoi.In addition, passivator is applied in low, moderate Cd pollution vegetable plot
Pakchoi edible part Cd content can be greatly reduced with equal, and the range of decrease is above 45%.After although passivator effect is with the time
It moves and decreases, but its range of decrease is little, and can still keep ideal effect, therefore this in third stubble pakchoi
Inventing the passivator provided has long-term repairing effect to low, moderate Cd pollution vegetable plot.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (10)
1. a kind of passivator for in-situ immobilization soil heavy metal cadmium, which is characterized in that mixed by the raw material of following parts by weight
Conjunction is made:
1-5 parts of charcoal, bacteria residue 1-6 parts and 1-10 parts of modified meerschaum of processing.
2. the passivator according to claim 1 for in-situ immobilization soil heavy metal cadmium, which is characterized in that by following heavy
The raw material of amount number is mixed:
2 parts of charcoal, 3 parts of bacteria residue of processing and 4 parts of modified meerschaum.
3. the passivator according to claim 1 for in-situ immobilization soil heavy metal cadmium, which is characterized in that the biology
Charcoal is made by the following method: by dry stalk hand hay cutter at segment, anaerobism carried out at 200-500 DEG C and is carbonized 4-12 hours, it is cold
But to crushing after room temperature, after 4-60 mesh, charcoal head product is obtained, in charcoal head product plus water, after being sufficiently stirred
Filtering, collection filtrate is spare, collects residue and simultaneously dries, obtains charcoal.
4. the passivator according to claim 3 for in-situ immobilization soil heavy metal cadmium, it is characterised in that: the biology
The mass ratio of charcoal head product and water is 1-3:8-12.
5. the passivator according to claim 3 for in-situ immobilization soil heavy metal cadmium, which is characterized in that modified Hai Pao
Stone is made by the following method: gained filtrate in charcoal preparation process being heated to 60 DEG C, Al (NO is then added3)3-Fe
(NO3)3Mixed liquor, heating were cooled down and are placed 1-3 days after 1-3 hours, were prepared into pillared liquid；Sepiolite is crushed, is added pillared
Liquid mixes, and crushes after 30-60 DEG C of drying, modified meerschaum is made.
6. the passivator according to claim 5 for in-situ immobilization soil heavy metal cadmium, it is characterised in that: the Al
(NO3)3-Fe(NO3)3Mixed liquor is according to Al (NO3)3With Fe (NO3)3Molar ratio be 3-6:1-2 mixed preparing.
7. the passivator according to claim 5 for in-situ immobilization soil heavy metal cadmium, it is characterised in that: the filtrate
With Al (NO3)3-Fe(NO3)3The volume ratio of mixed liquor is 2-6:1-3.
8. the passivator according to claim 5 for in-situ immobilization soil heavy metal cadmium, it is characterised in that: the Hai Pao
The volume ratio of stone powder and pillared liquid is 2-6:1-3.
9. the passivator according to claim 1 for in-situ immobilization soil heavy metal cadmium, which is characterized in that the processing
The processing method of bacteria residue are as follows: bacteria residue progress physics is loose, it then ferments 30-60 days, sterilizes 1.5-4 at 100-140 DEG C
Hour.
10. using the passivator of any of claims 1-9 for in-situ immobilization soil heavy metal cadmium to cadmium pollution
The method that soil is repaired, it is characterised in that:
Heavy metal in soil cadmium content is i value, is when soil pollution risk screening value < i < 2 times soil pollution risk screening value
Heavy metal cadmium slight pollution soil, the reclamation activities to such soil are after turning over topsoil, uniformly to apply passivator, are used
Amount is 85-110kg/ mus, rotary tillage 2-3 times, planting plants after balance 10 days；
It is heavy metal cadmium intermediate pollution soil when 2 times of soil pollution risk screening value < i < soil pollution risk control values, to this
The reclamation activities of class soil is uniformly to apply passivator after turning over topsoil, and dosage is 120-140kg/ mus, rotary tillage 2-3
It is secondary, planting plants after balance 15 days.
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