CN108085010B - A kind of complex repairation agent and its application for heavy metal pollution of soil - Google Patents
A kind of complex repairation agent and its application for heavy metal pollution of soil Download PDFInfo
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- CN108085010B CN108085010B CN201711340581.3A CN201711340581A CN108085010B CN 108085010 B CN108085010 B CN 108085010B CN 201711340581 A CN201711340581 A CN 201711340581A CN 108085010 B CN108085010 B CN 108085010B
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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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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01B—SOIL WORKING IN AGRICULTURE OR FORESTRY; PARTS, DETAILS, OR ACCESSORIES OF AGRICULTURAL MACHINES OR IMPLEMENTS, IN GENERAL
- A01B79/00—Methods for working soil
- A01B79/02—Methods for working soil combined with other agricultural processing, e.g. fertilising, planting
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
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- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
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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
- B09C1/10—Reclamation of contaminated soil microbiologically, biologically or by using enzymes
- B09C1/105—Reclamation of contaminated soil microbiologically, biologically or by using enzymes using fungi or plants
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Abstract
The complex repairation agent and its preparation method and application that the present invention provides a kind of for heavy metal pollution of soil, belongs to soil improvement and environmental protection technical field.A kind of complex repairation agent for Cadmium Pollution in Soils, includes the following parts by weight: modified 10~40 parts of the farm crop straw organism charcoal of 10~30 parts of sodium bentonite, 5~15 parts of bone meal, 5~25 parts of chitosan, 5~30 parts of oyster shell powder, graphene, 10~30 parts of biological organic fertilizer, 15~45 parts of sodium metasilicate, 1~15 part of nanometer Fe O, 1~8 part of carbon nanotubes and 1~10 part of microbial bacterial agent；The rhodotorula mucilaginosa OP11 colony count contained in every 100mg auxiliary material in the microbial bacterial agent is 2.25 × 108~2.5 × 109CFU；The deposit number of the rhodotorula mucilaginosa OP11 is CGMCC No.13540.Application of the complex repairation agent in restoration of soil polluted by heavy metal.
Description
Technical field
The invention belongs to soil improvements and environmental protection technical field, and in particular to a kind of for heavy metal pollution of soil
Complex repairation agent and its application.
Background technique
In recent years, since the excessive emissions of industrial wastewater, various chemical fertilizer insecticides are widely used, lead to heavy metal pollution
It gets worse.As industry and mining etc. develop, mankind's activity is higher and higher to the involvement level of soil environment, and heavy metal pollution has been in
The gesture being on the rise mainly has Hg, Cd, Pb and As etc. to ecological environment and the maximum heavy metal of Health Impact, wherein cadmium
(Cadmium, Cd) is one of most important heavy metal contaminants, has stronger chemical activity in the soil, with other huge sum of moneys
Symbolic animal of the birth year ratio, is easier to be absorbed by plants, and remains in the edible portion of plant, and be detrimental to health by food chain enrichment.
It in the prior art, mainly include that physics, chemistry, biology and Agro-ecology are repaired for the reparation of heavy-metal contaminated soil
Multiple four major class restorative procedures, every kind of restorative procedure have its advantage and disadvantage.Currently, for various heavy in soil and depositing compound
The reparation of pollution is concentrated mainly on chemical restoration, and the mode of passivation is taken to be repaired.This method is with cost is relatively low, repairs
The features such as multiple quick, easy to operate, has preferable superiority to the reparation of large area heavy metal pollution of soil, can preferably expire
The current China of foot administers heavy metal pollution of soil and ensures an urgent demand of crop production safety.
Passivation using chemical restoration to heavy metal in soil is generally taken and applies chemical inactivators to realize, and changes
Learning passivator includes organic passivator and inorganic passivant.A soil available huge sum of money can be greatly lowered in application inorganic passivant
The content of category, and then effectively inhibit plant in-vivo content, but a large amount of application inorganic passivants can generate the physical property of soil
Certain influence, influences the growth of soil flora, and whole fertility level can also decline.Organic passivation agent have both it is heavy metal-passivated and
Improve two kinds of functions of soil physico-chemical property, but exists and easily decompose, the unabiding disadvantage of passivation.
To seek to can make up for it the passivator of chemical inactivators disadvantage, there are various renovation agents, mainly silicon
Calcium substance, phosphorus containg substances, organic material, clay mineral, metal and metal oxide, charcoal and some new materials, but
Mostly at high cost, the slow and effect that works is of short duration, is unsuitable for being widely applied.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of complex repairation agent for heavy metal pollution of soil and its answering
With making the composite passivant not only has the characteristics that at low cost but also have the characteristics that efficient passivation heavy metal in soil.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides a kind of complex repairation agent for Cadmium Pollution in Soils, comprise the following components in parts by weight: sodium base
The modified agricultural crop straw of 10~30 parts of bentonite, 5~15 parts of bone meal, 5~25 parts of chitosan, 5~30 parts of oyster shell powder, graphene
10~40 parts of charcoal, 10~30 parts of biological organic fertilizer, 15~45 parts of sodium metasilicate, 1~15 part of nanometer Fe O, carbon nanotubes 1~8
Part and 1~10 part of microbial bacterial agent；
The microbial bacterial agent includes auxiliary material and rhodotorula mucilaginosa OP11, the rhodotorula mucilaginosa OP11 contained in every 100mg auxiliary material
Colony count is 2.25 × 108~2.5 × 109CFU；The deposit number of the rhodotorula mucilaginosa OP11 is CGMCC No.13540.
Preferably, the rhodotorula mucilaginosa OP11 clump count contained in every 100mg auxiliary material in the microbial bacterial agent is 5 × 108
~1 × 109CFU。
Preferably, the auxiliary material is bagasse, rice bran or the corn stover of crushing.
Preferably, the preparation method of the modified farm crop straw organism charcoal of the graphene, comprising the following steps:
A, agricultural crop straw powder is mixed with graphene, obtains mixture；The matter of agricultural crop straw powder and graphene
Amount is than being 100:4~6；
B, mixture obtained in the step A is heated at 90~110 DEG C 0.5~2h, then obtained heating is produced
Object is warming up to 500~600 DEG C of 3~5h of charing, obtains graphene modification biological charcoal first product；
C, graphene modification biological charcoal first product obtained in the step B is mixed with the hydrochloric acid solution of 1mol/L, will
To mixed liquor be washed to neutrality, the graphene modification biological charcoal to be deashed；
D, the graphene modification biological charcoal to deash obtained in the step C is dried under the conditions of 80~100 DEG C, is ground
Mill, sieving obtain the modified farm crop straw organism charcoal of graphene.
Preferably, agricultural crop straw powder is dried, is crushed, mistake by successively being washed by crop stalk in the step A
Sieve handles to obtain；The temperature of the drying is 80~100 DEG C；The partial size of the sieving is preferably 10~20 mesh.
Preferably, bone meal, oyster shell powder, chitosan, biological organic fertilizer, carbon nanotubes, nanometer Fe O or sodium bentonite
Partial size is preferably 60~100 mesh.
Preferably, the organic fertilizer includes that mass percentage is higher than 6% or more n-p-k element, quality percentage contains
Amino acid of the amount higher than 5% and mass percentage are higher than 45% organic matter.
The present invention provides application of the complex repairation agent in restoration of soil polluted by heavy metal.
Preferably, every kilogram of heavy-metal contaminated soil applies the agent of 5~60g complex repairation.
Preferably, the heavy metal includes cadmium metal.
The present invention provides a kind of complex repairation agent for Cadmium Pollution in Soils, including following parts by weight of component: sodium base is swollen
The modified agricultural crop straw of 10~30 parts of profit soil, 5~15 parts of bone meal, 5~25 parts of chitosan, 5~30 parts of oyster shell powder, graphene is raw
10~40 parts of object charcoal, 10~30 parts of biological organic fertilizer, 15~45 parts of sodium metasilicate, 1~15 part of nanometer Fe O, carbon nanotubes 1~8
Part, 1~10 part of microbial bacterial agent；The rhodotorula mucilaginosa OP11 colony count contained in every 100mg auxiliary material in the microbial bacterial agent
It is 2.25 × 108~2.5 × 109CFU；The deposit number of the rhodotorula mucilaginosa OP11 is CGMCC No.13540.Wherein silicic acid
There is synergistic effect between sodium, bone meal and oyster shell powder, improves soil pH value jointly, reduce the dissolubility of heavy metal；Nanometer
It is mutually cooperateed between carbon pipe, biological organic fertilizer, graphene modification biological charcoal and chitosan, chelates the heavy metal in soil, by force
Change the suction-operated to heavy metal-polluted soil；Sodium bentonite and nanometer Fe O can then play ion exchange and redox
Effect, allows the heavy metal in soil to exchange the cations such as Na, Mg, K, so that heavy metal be made to be adsorbed；Microorganism with
Other materials mutually cooperates with, and release activation phosphorus element reduces absorption of the crop to heavy metal.In complex repairation agent provided by the invention
Each passivation raw material and microorganism synergistic effect, cooperate, repair to heavy-metal contaminated soil, neither draw simultaneously repairing
Enter secondary pollution, and soil fertility can be improved.It is recorded in conjunction with specification embodiment, compared with blank, after applying complex repairation agent,
Effective cadmium content reduced rate is up to 61.02% in soil, and cadmium content reduced rate is also up to 45.78% in rice, the pH value of soil
Also it can achieve and significantly improve；And applying the product for not adding graphene modification biological charcoal and sodium bentonite, cadmium contains in wheat
Amount and available state just only reduce by 16.87% and 22.30% than blank in maximum applied amount respectively, and pH improves 0.24 unit.
Meanwhile complex repairation agent raw material sources provided by the invention are extensive, formula is simple, and each component is mixed by corresponding proportion
Conjunction applies heavy metal Cd contaminated soil when application, easy to use.Passivation effect is significant, and reaction time is short: existing skill
Composite passivant usually requires effect 15 days or more in art, and complex repairation agent of the present invention is in use, it is only necessary to 5~8
It can act on completion, effectively shorten its service life.Reasonable raw material proportioning, by screening passivating agent composition in type and
Specific proportion, obtains that passivation effect is optimal, matches to cadmium content reducing effect is optimal in effective cadmium content of soil and crop
Side, each ingredient play each other complement each other, synergistic technical effect.Compared with prior art, reparation of the present invention
The complex repairation agent of heavy metal cadmium soil helps to improve soil texture, increases soil mushroom, provides tilth to a soil, effectively
Soil compaction phenomenon is avoided, acidified soil is repaired, increases soil nutrient effect, improves the biomass of crop；And it can be effectively blunt
Change the heavy metal Cd in soil, can significantly reduce the Cd content of soil available Cd content and crop, moreover it is possible to improve soil pH
Value has a extensive future for administering vast heavy metal Cd contaminated soil, thus composite passivant of the present invention have it is very high
Economic benefit and Ecological Society effect.
Biological deposits information
Rhodotorula mucilaginosa, Rhodotorula mucilaginosa, strain number: OP11, the bacterial strain are produced in State Intellectual
The specified depositary institution's preservation of power office, in the entitled China Committee for Culture Collection of Microorganisms's common micro-organisms of depositary institution
The heart, preservation address Yard 1, BeiChen xi Road, Chaoyang District, Beijing City 3, Institute of Microorganism, Academia Sinica, the deposit date is 2017
On January 6, in, deposit number are CGMCC No.13540.
Specific embodiment
The present invention provides a kind of complex repairation agent for Cadmium Pollution in Soils, comprise the following components in parts by weight: sodium base
The modified agricultural crop straw of 10~30 parts of bentonite, 5~15 parts of bone meal, 5~25 parts of chitosan, 5~30 parts of oyster shell powder, graphene
10~40 parts of charcoal, 10~30 parts of biological organic fertilizer, 15~45 parts of sodium metasilicate, 1~15 part of nanometer Fe O, carbon nanotubes 1~8
Part and 1~10 part of microbial bacterial agent；
The rhodotorula mucilaginosa OP11 colony count contained in every 100mg auxiliary material in the microbial bacterial agent is 2.25 × 108~
2.5×109CFU；The deposit number of the rhodotorula mucilaginosa OP11 is CGMCC No.13540.
Complex repairation agent provided by the present invention for Cadmium Pollution in Soils includes sodium bentonite.By weight, sodium base
Bentonite is 10~30 parts, preferably 20 parts.In the present invention, the partial size of sodium bentonite is preferably 60~100 mesh, more preferably
For 70~90 mesh, more preferably 80 mesh.Sodium bentonite is the aqueous clay pit based on montmorillonite, and absorption speed is slow, but is inhaled
Water rate and expansion multiple are big, have stronger adsorptivity and cation exchange property, have preferably to heavy metal Cd, Pb, Hg etc.
Suction-operated.The present invention is not particularly limited the source of the sodium bentonite, and use is well-known to those skilled in the art
Sodium bentonite.In the embodiment of the present invention, the sodium bentonite is purchased from hundred million peak Chemical Industry Science Co., Ltd of Guangzhou.
Component provided by the present invention for the complex repairation agent of Cadmium Pollution in Soils includes bone meal.By weight, bone meal
It is 5~15 parts, preferably 10 parts.The partial size of bone meal is preferably 60~100 mesh, more preferably 70~90 mesh, more preferably 80 mesh.
The bone meal main component is tricalcium phosphate, and the acidity of acid heavy metal contaminated soil can be effectively reduced, improve pH value, enhancing
The absorption property of soil promotes heavy metal-polluted soil bio-available Zn concentration and Manual Suture to reduce, improves the growing environment of crop, mentions
The yield of high crop.The present invention is not particularly limited the source of the bone meal, using bone well-known to those skilled in the art
Powder.In the embodiment of the present invention, the bone meal is purchased from Jinan Xin Senyuan Chemical Co., Ltd..
Component provided by the present invention for the complex repairation agent of Cadmium Pollution in Soils includes chitosan.By weight, shell
Glycan is 5~25 parts, preferably 10~20 parts, more preferably 15 parts.The partial size of chitosan is preferably 60~100 mesh, more preferably
For 70~90 mesh, more preferably 80 mesh.The chitosan is high molecular polymer, hydroxyl, amino, the acyl being dispersed on strand
Amido, carboxyl isoreactivity group can with heavy metal ion occur chelating and suction-operated, but due to soil belong to it is more complicated
System, influence factor is more, and chitosan molecule is not only and heavy metal ion in soil occurs simple chemical action and comes
Change its ionic forms, also have an effect with other compositions in soil or biology, to influence the physics and chemically of soil
Shape.Because chitosan has the characteristic that solution is sticky, is easy to form a film, extremely strong film forming function can delay the release of fertilizer element,
It reduces the loss of nutrient and greatly improves fertilizer efficiency；And the amino (- NH contained in chitosan2), with trace elements iron, copper, zinc,
Molybdenum etc. can generate chelation, increase microelement bio-available Zn concentration in chitosan；Chitosan albumen can also stimulate soil to have
Beneficial microorganism growth generates the enzyme that can kill nematode and worm's ovum, kills off the insect pests indirectly；Chitosan energy sufficiently activating rhizosphere state,
Dissolve nutrients molecule, quickly forms the soil liquid, so that the nutrients such as nitrogen, phosphorus, potassium is obtained plant and substantially effectively absorbs.The present invention
The source of the chitosan is not particularly limited, using chitosan well-known to those skilled in the art.The present invention is real
It applies in example, the chitosan is purchased from Qingdao Bo Zhihui power Biotechnology Co., Ltd.
Component provided by the present invention for the complex repairation agent of Cadmium Pollution in Soils includes oyster shell powder.By weight,
Oyster shell powder is 5~30 parts, preferably 10~20 parts, more preferably 15 parts.The partial size of oyster shell powder is preferably 60~100 mesh,
More preferably 70~90 mesh, more preferably 80 mesh.The oyster shell powder main component is calcium carbonate, it is slightly soluble in water and is in alkali
Property, the phenomenon that soil acidification can be effectively improved, and improve and lack calcareous soil, and harmful heavy metal ions in passivation soil
Effect.The present invention is not particularly limited the source of the oyster shell powder, using oyster well-known to those skilled in the art
Shell powder.In the embodiment of the present invention, the oyster shell powder is purchased from Xi'an Fu Zhengyuan Biotechnology Co., Ltd.
Component provided by the present invention for the complex repairation agent of Cadmium Pollution in Soils includes biological organic fertilizer.By weight
Meter, biological organic fertilizer are 10~30 parts, preferably 15~25 parts, more preferably 20 parts.The partial size of biological organic fertilizer is preferably 60
~100 mesh, more preferably 70~90 mesh, more preferably 80 mesh.The biological organic fertilizer include mass percentage 6%~
The amino acid and mass percentage of 10% n-p-k element, mass percentage in 5%-10% have 45%~60%
Machine matter.Bio-organic fertilizer can balance plant growth, improve yield；Degradation residual, rehabilitating soil reduce agricultural product because of application
It is remained caused by inorganic fertilizer, pesticide；Increase the gas permeability of soil, promotes crumb structure to be formed, excellent loam effect of improving the soil；Increase
Add soil beneficial functions bacterium, acted on by occupy-place, inhibits and prevent the breeding of soil-borne disease microorganism；Has reduction soil-borne disease
The effect of evil, raising crop disease-resistant, anti-continuous cropping.The present invention is not particularly limited the source of the biological organic fertilizer, using this
Biological organic fertilizer known to the technical staff of field.In the embodiment of the present invention, the biological organic fertilizer is extensive purchased from Changsha
Bioisystech Co., Ltd.
Component provided by the present invention for the complex repairation agent of Cadmium Pollution in Soils includes sodium metasilicate.By weight, silicon
Sour sodium is 15~45 parts, preferably 20~40 parts, more preferably 30 parts.The partial size of sodium metasilicate is preferably 60~100 mesh, more preferably
For 70~90 mesh, more preferably 80 mesh.The sodium metasilicate can activate beneficial microbe, improve soil, correct soil aciditiy, improve
Soil alkali promotes organic fertilizer to decompose, and inhibits soil germ, anti-continuous cropping and mitigates heavy metal pollution.The present invention is to the silicic acid
The source of sodium is not particularly limited, using sodium metasilicate well-known to those skilled in the art.It is described in the embodiment of the present invention
Sodium metasilicate is purchased from Xingtai County Rui Xin silicon salt Manufacturing Co., Ltd.
Component provided by the present invention for the complex repairation agent of Cadmium Pollution in Soils includes nanometer Fe O.By weight, it receives
Rice FeO is 1~15 part, preferably 10 parts.The partial size of nanometer Fe O is preferably 60~100 mesh, more preferably 70~90 mesh, more excellent
It is selected as 80 mesh.The nanometer Fe O has many advantages, such as small partial size, large specific surface area, high chemical reactivity, can be with a soil huge sum of money
Belong to and reduction reaction occurs.The present invention is not particularly limited the source of the nanometer Fe O, and use is well known to those skilled in the art
Nanometer Fe O.In the embodiment of the present invention, the nanometer Fe O is purchased from Beijing Sheng Bogaotai optics Science and Technology Ltd..
Component provided by the present invention for the complex repairation agent of Cadmium Pollution in Soils includes carbon nanotubes.By weight,
Carbon nanotubes is 1~8 part, preferably 3~6 parts, more preferably 5 parts.The partial size of carbon nanotubes is preferably 60~100 mesh, more excellent
It is selected as 70~90 mesh, more preferably 80 mesh.The carbon nanotubes is single-wall carbon tube, has the peculiar person's character of carbon materials, still
The characteristics of its is light-weight, and hexagonal structure connection is perfect, minor diameter big major diameter, but makes it be easier to absorption weight than common carbon material
Metal.The present invention is not particularly limited the source of the carbon nanotubes, using nano-sized carbon well-known to those skilled in the art
Pipe.In the embodiment of the present invention, the carbon nanotubes is purchased from Nanjing Xian Feng Nono-material Science & Technology Ltd..
Component provided by the present invention for the complex repairation agent of Cadmium Pollution in Soils includes microbial bacterial agent.By weight
Meter, microbial bacterial agent are 1~10 part, preferably 3~7 parts, more preferably 5 parts.In the microbial bacterial agent in every 100mg auxiliary material
The rhodotorula mucilaginosa OP11 colony count contained is 2.25 × 108~2.5 × 109CFU, every 100mg auxiliary material in the microbial bacterial agent
In the rhodotorula mucilaginosa OP11 clump count that contains be 5 × 108~1 × 109CFU.The deposit number of the rhodotorula mucilaginosa OP11 is
CGMCC No.13540。
In the present invention, the preparation method of the microbial bacterial agent preferably includes following steps:
It is 9 × 10 by bacterial concentration7~1 × 109The rhodotorula mucilaginosa OP11 suspension of a CFU/mL connects according to 2%~3%
In kind amount access auxiliary material, it is mixed, obtains microbial bacterial agent.In the present invention, the auxiliary material is preferably bagasse, rice bran or powder
Broken corn stover.The partial size of the auxiliary material is preferably 60~100 mesh, more preferably 80 mesh.Bacterium solution source: under aseptic condition,
By activated rhodotorula mucilaginosa OP11 strain inoculated into the shaking flask of the malt juice liquid medium containing sterilizing, 28 DEG C,
180rpm, shaken cultivation 18h (OD ≈ 1.0), thalline were collected by centrifugation and with being made 9 × 10 after brine7~1 × 109It is a
The rhodotorula mucilaginosa OP11 suspension of CFU/mL。
Complex repairation agent provided by the invention includes the modified farm crop straw organism charcoal of graphene of 10~40 parts by weight, excellent
It is selected as 20~30 parts.
In the present invention, the preparation method of the modified farm crop straw organism charcoal of the graphene preferably includes following steps:
A, agricultural crop straw powder is mixed with graphene, obtains mixture；The matter of agricultural crop straw powder and graphene
Amount is than being 100:4~6；
B, mixture obtained in the step A is heated at 90~110 DEG C 0.5~2h, then obtained heating is produced
Object is warming up to 500~600 DEG C of 3~5h of charing, obtains graphene modification biological charcoal first product；
C, graphene modification biological charcoal first product obtained in the step B is mixed with the hydrochloric acid solution of 1mol/L, will
To mixed liquor be washed to neutrality, the graphene modification biological charcoal to be deashed；
D, the graphene modification biological charcoal to deash obtained in the step C is dried under the conditions of 80~100 DEG C, is ground
Mill, sieving obtain the modified farm crop straw organism charcoal of graphene.
In the present invention, agricultural crop straw powder is preferably successively washed by crop stalk, is dried, and is crushed, sieving processing
It obtains.The temperature of the drying is preferably 80~100 DEG C, and more preferably 90 DEG C；The grain of agricultural crop straw powder after the sieving
Diameter is preferably 10~20 mesh, more preferably 15 mesh.Agricultural crop straw powder is the minus sieve powder being collected into after being sieved.The present invention
In, the agricultural crop straw preferably includes rape stalk, corn stover or wheat stalk.
It is last to obtain agricultural residues powder, the present invention mixes the agricultural crop straw powder with graphene, is mixed
Material；The mass ratio of agricultural crop straw powder and graphene is 100:4~6, preferably 100:5.The present invention is to the graphene
Source is not particularly limited, using the source of graphene well-known to those skilled in the art.In the embodiment of the present invention, institute
Graphene is stated purchased from tsingtauite sea carbon material Co., Ltd.
After obtained mixture, the mixture is heated 0.5~2h by the present invention at 90~110 DEG C, then by heating
Mixture is warming up to 500~600 DEG C of 3~5h of charing, obtains graphene modification biological charcoal first product.
In the present invention, the temperature of the heating is preferably 100 DEG C.The time of the heating is preferably 1.5h.The charing
Temperature be preferably 550 DEG C.The time of the charing is 4h.Be warming up to carbonization temperature heating rate be preferably 5 DEG C/min~
25 DEG C/min, more preferably 15 DEG C/min.The purpose of charing is that carbon element is fixed up by high temperature pyrolysis, makes biomass
Material becomes biological carbon materials.
After obtained graphene modification biological charcoal first product, the present invention by the graphene modification biological charcoal first product and 0.8~
The hydrochloric acid solution of 1.2mol/L mixes, and obtained mixed liquor is washed to neutrality, the graphene modification biological charcoal to be deashed.
In the present invention, the volume ratio of the hydrochloric acid solution of the quality and 1mol/L of the graphene modification biological charcoal first product is 1
~5 (mg): 1~40 (mL), more preferably 2 (mg): 14 (mL).The present invention is not particularly limited the mode of the washing, adopts
With water-washing method well-known to those skilled in the art.
The obtained graphene modification biological charcoal to deash, the present invention exist the graphene modification biological charcoal to deash
It dries, grinds under the conditions of 80~100 DEG C, sieving obtains the modified farm crop straw organism charcoal of graphene.
In the present invention, the temperature of the drying is preferably 90 DEG C.The aperture of sieving is preferably 80~120 mesh, more preferably
100 mesh.
In the present invention, the preparation method of the complex repairation agent for Cadmium Pollution in Soils preferably includes following steps:
By other raw material combination dryings in addition to microbial bacterial agent, to grind, 60~100 mesh powders are collected in sieving, will
The powder arrived is mixed with microbial bacterial agent, obtains complex repairation agent.
The present invention is not particularly limited using hybrid mode well-known to those skilled in the art i.e. the hybrid mode
It can.The temperature of the drying is preferably 35~45 DEG C, and more preferably 40 DEG C.
The present invention provides application of the complex repairation agent in restoration of soil polluted by heavy metal.
In the present invention, every kilogram of metallic pollution soil preferably applies 5~60g complex repairation agent, more preferable 10~40g, most
Preferably 30g.
In the present invention, the heavy metal preferably includes cadmium metal.
In the present invention, soil moisture is kept to reach the 60%~70% of maxmun field capacity after applying complex repairation agent,
Then it balances 5~8 days, can be sowed or be transplanted.Equilibration time is preferably 7 days.The water capacity is preferably 65%.
In the present invention, the complex repairation agent applies in heavy-metal contaminated soil, and the heavy metal ion in soil passes through
Redox reaction occurs with nanometer Fe O etc.；It is co-precipitated with graphene modification biological charcoal, sodium metasilicate, bone meal, chitosan etc.
Heavy metal, is converted to hydroxide and organic complex not soluble in water by reaction, organic complex reaction and suction-operated；
Ion exchange occurs with sodium bentonite etc., the cations such as Na, Mg, K are exchanged, absorption heavy metal makes the life of heavy metal
Object validity reduces, and reaches passivation purpose；Meanwhile the content of organic matter increases substantially, soil physical chemistry is improved.
Below with reference to embodiment to a kind of complex repairation agent and its system for heavy metal pollution of soil provided by the invention
Preparation Method and application are described in detail, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
A kind of complex repairation agent suitable for Cadmium Pollution in Soils, including chitosan 18kg, sodium bentonite 30kg, bone meal
15kg, oyster shell powder 30kg, biological organic fertilizer 20kg, nanometer Fe O 12kg, carbon nanotubes 8kg, graphene modification biological charcoal
25kg, microbial bacterial agent 10kg, sodium metasilicate 30kg.
It is prepared according to the following steps:
(1) prepared by graphene modification biological charcoal: will dry, crushes under the conditions of 90 DEG C after rape stalk distilled water flushing
Cross after 20 mesh (0.85mm) sieve that obtain powdered substance spare.It weighs 5% graphene and the rape stalk powder got ready is abundant
It mixes, load weighted mixed-powder is placed in Muffle furnace, first carbonize 1h at 100 DEG C, then be warming up to 550 DEG C and continue to carbonize
4h is cooled to room temperature, and weighing obtains graphene modification biological charcoal first product.Then it is deashed with the dilute hydrochloric acid of 1mol/L and uses steaming
Distilled water is rinsed to neutrality.By the charcoal finished product to deash, drying to constant weight in 90 DEG C of baking ovens, is then placed in mortar and grinds,
It sieves with 100 mesh sieve, has stayed spare.
(2) prepared by microbial bacterial agent: collection is come, is dried, is crushed, 10~20 meshes are crossed, it is spare.Adjust above-mentioned mixing
Moisture is to 65%, by bacterial concentration about 9 × 107The rhodotorula mucilaginosa OP11 suspension of a CFU/mL is accessed according to 2.5% inoculum concentration
Bagasse is sufficiently mixed stirring to get microorganism mixing.
(3) stock up: according to composite passivated agent prescription, in parts by weight, weigh chitosan 18kg, sodium bentonite 30kg,
Bone meal 15kg, oyster shell powder 30kg, biological organic fertilizer 20kg, nanometer Fe O 12kg, carbon nanotubes 8kg, graphene modification biological
Charcoal 25kg, microbial bacterial agent 10kg, sodium metasilicate 30kg, it is spare；
(4) it mixes: all dry feedstocks in addition to microbial bacterial agent is ground up, sieved, cross 60 and 100 meshes, take partial size
Greater than 60 mesh and it is less than or equal to 100 target materials, is then stirred well to microbial bacterial agent addition uniformly mixed, is made multiple
Close renovation agent.
Embodiment 2
A kind of complex repairation agent suitable for Cadmium Pollution in Soils, including chitosan 25kg, sodium bentonite 20kg, bone meal
5kg, oyster shell powder 20kg, biological organic fertilizer 30kg, nanometer Fe O 10kg, carbon nanotubes 4kg, graphene modification biological charcoal
40kg, microbial bacterial agent 5kg, sodium metasilicate 45kg.It is prepared according to the following steps:
(1) prepared by graphene modification biological charcoal: will dry, crushes under the conditions of 90 DEG C after rape stalk distilled water flushing
Cross after 20 mesh (0.85mm) sieve that obtain powdered substance spare.It weighs 5% graphene and the rape stalk powder got ready is abundant
It mixes, load weighted mixed-powder is placed in Muffle furnace, first carbonize 1h at 100 DEG C, then be warming up to 550 DEG C and continue to carbonize
4h is cooled to room temperature, and weighing obtains graphene modification biological charcoal first product.Then it is deashed with the dilute hydrochloric acid of 1mol/L and uses steaming
Distilled water is rinsed to neutrality.By the charcoal finished product to deash, drying to constant weight in 90 DEG C of baking ovens, is then placed in mortar and grinds,
It sieves with 100 mesh sieve, has stayed spare.
(2) prepared by microbial bacterial agent: collection is come, is dried, is crushed, 10~20 meshes are crossed, it is spare.Adjust above-mentioned mixing
Moisture is to 75%, by bacterial concentration about 1 × 109The rhodotorula mucilaginosa OP11 suspension of a CFU/mL is accessed according to 2.5% inoculum concentration
Bagasse is sufficiently mixed stirring to get microorganism mixing.
(3) stock up: according to composite passivated agent prescription, in parts by weight, weigh chitosan 25kg, sodium bentonite 20kg,
Bone meal 5kg, oyster shell powder 20kg, biological organic fertilizer 30kg, nanometer Fe O 10kg, carbon nanotubes 4kg, graphene modification biological charcoal
40kg, microbial bacterial agent 5kg, sodium metasilicate 45kg, it is spare；
(4) it mixes: all dry feedstocks in addition to microbial bacterial agent is ground up, sieved, cross 60 and 100 meshes, take partial size
Greater than 60 mesh and it is less than or equal to 100 target materials, is then stirred well to microbial bacterial agent addition uniformly mixed, is made multiple
Close renovation agent.
Embodiment 3
A kind of complex repairation agent suitable for Cadmium Pollution in Soils, including according to composite passivated agent prescription, weigh chitosan
5kg, sodium bentonite 10kg, bone meal 10kg, oyster shell powder 5kg, biological organic fertilizer 10kg, nanometer Fe O 1kg, graphene are modified
Charcoal 10kg, microbial bacterial agent 1kg, carbon nanotubes 1kg, sodium metasilicate 15kg.It is prepared according to the following steps:
(1) prepared by graphene modification biological charcoal: will dry, crushes under the conditions of 90 DEG C after rape stalk distilled water flushing
Cross 20 mesh (0.85mm
It is spare that powdered substance is obtained after sieve.5% graphene is weighed to mix well with the rape stalk powder got ready, it will
Load weighted mixed-powder is placed in Muffle furnace, and 1h is first carbonized at 100 DEG C, then is warming up to 550 DEG C and is continued to carbonize 4h, then is cold
But to room temperature, weighing obtains graphene modification biological charcoal (first product).Then it is deashed with the dilute hydrochloric acid of 1mol/L and is rushed with distilled water
It is washed till neutrality.By the charcoal to deash (finished product), drying to constant weight in 90 DEG C of baking ovens, is then placed in mortar and grinds, mistake
100 meshes have been stayed spare.
(2) prepared by microbial bacterial agent: collection is come, is dried, is crushed, 10~20 meshes are crossed, it is spare.Adjust above-mentioned mixing
Moisture is to 65%~75%, by bacterial concentration about 5 × 108The rhodotorula mucilaginosa OP11 suspension of a CFU/mL, according to 2.5% inoculation
Amount access bagasse, is sufficiently mixed stirring to get microorganism mixing.
(3) it stocks up: according to composite passivated agent prescription, in parts by weight, weighing chitosan 5kg, sodium bentonite 10kg, bone
Powder 10kg, oyster shell powder 5kg, biological organic fertilizer 10kg, nanometer Fe O 1kg, graphene modification biological charcoal 10kg, microbial bacterial agent
1kg, carbon nanotubes 1kg, sodium metasilicate 15kg, it is spare；
(4) it mixes: all dry feedstocks in addition to microbial bacterial agent is ground up, sieved, cross 60 and 100 meshes, take partial size
Less than 60 mesh and it is greater than or equal to 100 target materials, is then stirred well to microbial bacterial agent addition uniformly mixed, is made multiple
Close renovation agent.
Experimental example 4
The Qingdao soil seriously polluted by Cd is picked up from for examination soil, soil, which is air-dried, smashes it through 1cm sieve, in loading
The flowerpot of diameter 18cm, high 20cm, every basin fill soil 6kg.Composite passivant is mixed with the soil, is stirred evenly, soil is kept
Moisture reached the 70% of maxmun field capacity, balance after 7 days, carried out wheat planting.Wheat breed is " Jimai 22 ", every basin 3
Cave, 2, every cave Basic Seedling.Test sets five processing, and (complex repairation agent applied amount is respectively 0 (i.e. CK), 0.05% in embodiment 1
(being denoted as X1), 0.1% (X2), 0.25% (X3), 0.5% (X4), and the complex repairation of graphene modification biological charcoal is not added
The applied amount of agent is respectively 0.05% (being denoted as G1), 0.1% (G2), 0.25% (G3), 0.5% (G4)) 4 repetitions, it is random to arrange
Column.Experimental result is shown in Table 1.
Influence of 1. composite passivant of table to cadmium pollution soil and wheat
As seen from the results in Table 1, the renovation agent of graphene modification biological charcoal is not added with the blank for not applying renovation agent and
It compares, this experiment renovation agent used matched can significantly reduce the Cd content in soil available Cd content and rice, moreover it is possible to
Improve soil pH value.Wherein, compared with blank, for Qingdao soil in the case where applying renovation agent, effective cadmium content reduced rate can
Up to 48.65%, cadmium content reduced rate is also up to 33.33% in wheat, and does not add repairing for graphene modification biological charcoal applying
When multiple agent, cadmium content and available state at most just only reduce by 11.11% and 21.6% than blank respectively in wheat, illustrate energy of the present invention
The validity of soil heavy metal cadmium is enough effectively reduced, reduces absorption, enrichment of the crop to cadmium, moreover it is possible to improve acid soil, improve
Soil fertility.
Experimental example 5
The Qingdao soil seriously polluted by Cd is picked up from for examination soil, soil, which is air-dried, smashes it through 1cm sieve, in loading
The flowerpot of diameter 18cm, high 20cm, every basin fill soil 6kg.Composite passivant is mixed with the soil, is stirred evenly, soil is kept
Moisture reached the 70% of maxmun field capacity, balance after 7 days, carried out wheat planting.Wheat breed is " Jimai 22 ", every basin 3
Cave, 2, every cave Basic Seedling.Test sets five processing, and (complex repairation agent applied amount is respectively 0 (i.e. CK), 0.05% in embodiment 1
(being denoted as X1), 0.1% (X2), 0.25% (X3), 0.5% (X4), and the renovation agent of carbon nanotubes and nanometer Fe O is not added
Applied amount be respectively 0.05% (being denoted as N1), 0.1% (N2), 0.25% (N3), 0.5% (N4)) 4 repetitions, random alignment.
Experimental result is shown in Table 2.
Influence of 2. composite passivant of table to cadmium pollution soil and wheat
As seen from the results in Table 2, the renovation agent of carbon nanotubes and nanometer Fe O is not added with the blank for not applying renovation agent and
It compares, this experiment renovation agent used matched can significantly reduce the Cd content in soil available Cd content and rice, moreover it is possible to
Improve soil pH value.Wherein, compared with blank, effective cadmium content reduced rate is up to 41.51% in long sand soil, and cadmium contains in wheat
It measures reduced rate and is also up to 45.28%, and when the renovation agent of carbon nanotubes and nanometer Fe O is not added in application, cadmium content in wheat
17.72% and 18.87% are only just reduced respectively than blank in maximum applied amount with available state.Illustrate that the present invention can significantly drop
The validity of low heavy metal in soil cadmium reduces absorption, enrichment of the crop to cadmium, moreover it is possible to suitably improvement acid soil.
Experimental example 6
Changsha and the Qingdao soil seriously polluted by Cd are picked up from for examination soil, soil is smashed it through through air-drying
1cm sieve, is packed into the flowerpot of internal diameter 18cm, high 20cm, and every basin fills soil 6kg.Composite passivant is mixed with the soil, is stirred
It is even, it keeps soil moisture to reach the 65% of maxmun field capacity, balance after 8 days, carries out wheat planting.Wheat breed is " Ji
Wheat 22 ", every 3 cave of basin, 2, every cave Basic Seedling.Test sets five processing, and (complex repairation agent applied amount is respectively 0 in embodiment 3
(i.e. CK), 0.05% (X1), 0.1% (X2), 0.25% (X3), 0.5% (X4) 4 repetitions, random alignment, experimental result are shown in Table
3。
Influence of 3. composite passivant of table to cadmium pollution soil and wheat
As seen from the results in Table 3, compared with the blank for not applying renovation agent, the present embodiment renovation agent used matched can be significant
Reduce the Cd content in soil available Cd content and wheat, moreover it is possible to improve soil pH value.Wherein effective cadmium in long sand soil
Content reduced rate is up to 62.26%, and cadmium content reduced rate is also up to 60.76% in wheat, and pH value also increases；Qingdao soil
In effectively cadmium content reduced rate up to 59.46%, cadmium content reduced rate is also up to 51.11% in wheat.Illustrate improvement of the present invention
Heavy metal Cd contaminated soil is widely used, and can significantly reduce the validity of heavy metal in soil cadmium, reduces crop to cadmium
It absorbs, enrichment, moreover it is possible to suitably improvement acid soil.
By comparing product of the present invention with the blank product for not applying renovation agent it can be seen from table 1,2,3, group
Split-phase with but product formula under each group distribution ratio different situations, cadmium content, pH value are all variant in soil or in rice, and this
Has the effect of synergy between formula each component in invention, proportion in embodiment 3 is most suitable；It is comprehensively compared, in acid
Property soil on, for applied amount at 0.5%, effect is best, on neutral soil and alkalescent soil, applied amount at 0.1%, effect
Fruit is best.
Experimental example 7
Certain paddy field in Changsha carries out field trial, and sample is primarily present heavy metal Cd pollution, and setting, which is not applied, appoints
What renovation agent (i.e. CK) and the product of the invention for applying 75.0kg (being denoted as F1), 100.0kg (F2), 150.0kg (F3) per acre,
And do not add graphene modification biological charcoal and sodium bentonite product amount of application be similarly 75.0kg (being denoted as M1),
Four processing are arranged in 100.0kg (M2), 150.0kg (M3), repeat three times, totally 12 cells.Passivator applying mode is that will answer
It closes passivator to mix, stir evenly with field topsoil, soil moisture is kept to reach the 70% of maxmun field capacity, put down
Weighing apparatus carried out Rice Cropping after 7 days.The plot area of rice cultivation is 30.0m2, random district's groups arrangement, the setting of trial zone surrounding
2.5 meters wide of protection row.Fertilization Level and other field management measures, are respectively handled completely the same.It is late rice for examination crop varieties
" five excellent 508 ".Experimental result is shown in Table 4.
Influence of the 4. complex repairation agent of table to cadmium pollution soil and rice
As seen from the results in Table 4, compared with the blank product for not applying renovation agent in the prior art or the present invention, institute of the present invention
The composite passivant for stating remediating heavy metal cadmium pollution paddy soil can effectively be passivated Cd in paddy soil, repair acidified soil and
It provides tilth to a soil, can significantly reduce the Cd content in soil available Cd content and rice, moreover it is possible to improve soil pH value.With
Blank is compared, and applies in soil that effectively cadmium content reduced rate is up to 61.02%, and cadmium content reduced rate is also up in rice
45.78%, pH value also can achieve and significantly improve；And apply the production for not adding graphene modification biological charcoal and sodium bentonite
Product, cadmium content and available state just only reduce by 16.87% and 22.30% than blank in maximum applied amount respectively in wheat, and pH is most
Height improves 0.24 unit.By not applying product of the present invention and the blank product of renovation agent and not adding wherein certain several groups
The renovation agent divided compares, and all there were significant differences for cadmium content, pH value in the soil or in rice, illustrates the formula in the present invention
Has the effect of synergy between each component.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (9)
1. a kind of complex repairation agent for Cadmium Pollution in Soils, which is characterized in that including following parts by weight of component: sodium bentonite
10~30 parts, 5~15 parts of bone meal, 5~25 parts of chitosan, 5~30 parts of oyster shell powder, the modified farm crop straw organism charcoal of graphene
10~40 parts, 10~30 parts of biological organic fertilizer, 15~45 parts of sodium metasilicate, 1~15 part of nanometer Fe O, 1~8 part of carbon nanotubes and micro-
1~10 part of bacteria agent；
The microbial bacterial agent includes auxiliary material and rhodotorula mucilaginosa OP11, the rhodotorula mucilaginosa OP11 bacterium colony contained in every 100mg auxiliary material
Number is 2.25 × 108~2.5 × 109CFU；The deposit number of the rhodotorula mucilaginosa OP11 is CGMCC No.13540；
The preparation method of the modified farm crop straw organism charcoal of the graphene, comprising the following steps:
A, agricultural crop straw powder is mixed with graphene, obtains mixture；The matter of the agricultural crop straw powder and graphene
Amount is than being 100:4~6；
B, mixture obtained in the step A is heated into 0.5~2h, then the Heated Products liter that will be obtained at 90~110 DEG C
Temperature obtains graphene modification biological charcoal first product to 500~600 DEG C of 3~5h of charing；
C, graphene modification biological charcoal first product obtained in the step B is mixed with the hydrochloric acid solution of 0.8~1.2mol/L, it will
Obtained mixed liquor is washed to neutrality, the graphene modification biological charcoal wet feed to be deashed；
D, the graphene modification biological charcoal to deash obtained in the step C is dried under the conditions of 80~100 DEG C, is ground,
Sieving obtains the modified farm crop straw organism charcoal of graphene.
2. complex repairation agent according to claim 1, which is characterized in that in the microbial bacterial agent in every 100mg auxiliary material
The rhodotorula mucilaginosa OP11 clump count contained is 5 × 108~1 × 109CFU。
3. complex repairation agent according to claim 1 or 2, which is characterized in that the auxiliary material is bagasse, rice bran or corn
Stalk.
4. complex repairation agent according to claim 3, which is characterized in that agricultural crop straw powder is by agriculture in the step A
Crop straw is successively washed, and is dried, and is crushed, and sieving handles to obtain；The temperature of the drying is 80~100 DEG C；The sieving
Partial size be preferably 10~20 mesh.
5. complex repairation agent according to claim 1, which is characterized in that the bone meal, oyster shell powder, chitosan, biology
Organic fertilizer, carbon nanotubes, nanometer Fe O or sodium bentonite partial size stand alone as 60~100 mesh.
6. complex repairation agent according to claim 1, which is characterized in that the organic fertilizer includes mass percentage height
In 6% or more n-p-k element, mass percentage higher than 5% amino acid and mass percentage higher than 45% it is organic
Matter.
7. application of the complex repairation agent in restoration of soil polluted by heavy metal described in claim 1~6 any one.
8. application according to claim 7, which is characterized in that every kilogram of heavy-metal contaminated soil applies that 5~60g is compound to be repaired
Multiple agent.
9. application according to claim 7 or 8, which is characterized in that the heavy metal includes cadmium metal.
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