CN108580529A - A kind of restorative procedure of heavy-metal contaminated soil - Google Patents
A kind of restorative procedure of heavy-metal contaminated soil Download PDFInfo
- Publication number
- CN108580529A CN108580529A CN201810322372.4A CN201810322372A CN108580529A CN 108580529 A CN108580529 A CN 108580529A CN 201810322372 A CN201810322372 A CN 201810322372A CN 108580529 A CN108580529 A CN 108580529A
- Authority
- CN
- China
- Prior art keywords
- soil
- heavy
- heavy metal
- contaminated soil
- porous
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C2101/00—In situ
-
- 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
- C09K2109/00—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE pH regulation
Abstract
The present invention provides a kind of restorative procedure of new heavy-metal contaminated soil, the technical concept of this method is：Using red mud to the adsorbing of heavy metal, the heavy metal in soil is fixed cured characteristic；Meanwhile the plant that collaboration has earth surface planting to absorb heavy metal further enhances removal effect to heavy metal, and the removing to heavy metal is realized after plant is removed, it, can be by the separation of heavy metal and charcoal by by after plant carbonated, elution；In addition, since red mud can discharge excessive OH ions into soil, the Phos in soil can be caused to occur hardened and soil alkalinity is caused to improve, also it is compounded with phosphate solubilizing bacteria and EM bacterium solutions, the reduction of the content of the free state phosphorus in soil is avoided by the effect of phosphate solubilizing bacteria, while avoiding the quick raising of soil alkalinity.
Description
Technical field
The present invention relates to a kind of restorative procedures of heavy-metal contaminated soil, belong to technical field of soil remediation.
Background technology
Heavy metal pollution of soil（heavy metal pollution of the soil）Refer to due to mankind's activity, soil
The content of trace harmful elements in the soil in earth is more than background value, and too high levels caused by excess deposition are referred to as soil
Earth heavy metal pollution.Signified heavy metal is primarily referred to as the significant mercury of bio-toxicity, cadmium, lead, chromium and eka-gold in terms of environmental pollution
Belong to the elements such as arsenic, and the elements such as zinc, copper, nickel for having certain toxicity.When these heavy metal contaminants since mankind's activity enters
Soil and to soil --- botanical system endangers, and will result in heavy metal pollution of soil, and once soil is by heavy metal pollution
It is difficult to restore, these elements can enter human body by food chain, and threat is brought to human health.Heavy metal-polluted soil is dirty
It contaminates there are many kinds of sources, wherein process of industrialization accelerates people's releasing in the industrial activities and rural activity such as mining, metallurgy
Soil is put and entered, the pollution of heavy metal-polluted soil is caused.
In the prior art, the method for having had some to repair heavy-metal contaminated soil includes mainly：Microorganism is repaiied
Multiple method, chemical restoration, physical restoration, phytoremediation etc..Such as：CN106180735A discloses a kind of Modified Micron zero
The preparation method of valence iron and its application process in heavy metal pollution of soil reparation, including clean ferriferous raw material, prepare micron
Iron, extra-fine grinding, modifying processing step use water, xanthans, sulfide, stabilizer, zeolite, blast-furnace cinder in modification procedure
The modifying agent of composition.However, directly using the renovation agent of this inorganic material and without the removal effect of higher heavy metal.
CN106190158A discloses a kind of soil-repairing agent and its production method for administering metallic pollution.The soil-repairing agent,
It is made of each raw material of following weight percent：Active molasses yeast wastewater chelates medicinal powder 35-65%, silica 5-20%,
Calcium oxide 5-15%, magnesia 1-10%, ammonium persulfate 0.3-10%, humic acid and its derivative 5-28%, microcapsule microbial agent 0.1-
15%, macromolecule water-retaining agent 0.1-5%, heavy metal deactivator 0.1-5%, auxiliary agent 1-5%, inorganic fertilizer material 1-45%.However it uses
After this complex repairation agent processing, heavy metal still resides in soil, it is difficult to be separated, affect removal effect.
Invention content
The purpose of the present invention is：Provide a kind of restorative procedure of new heavy-metal contaminated soil, the technology structure of this method
Think of is：Using red mud to the adsorbing of heavy metal, the heavy metal in soil is fixed cured characteristic；Meanwhile collaboration has ground
The plant that table plantation absorbs heavy metal further enhances the removal effect to heavy metal, is realized to heavy metal after plant is removed
Removing, by by it is plant carbonated, elution after, can be by the separation of heavy metal and charcoal；In addition, since red mud can be released into soil
More-OH ions are let off, the Phos in soil can be caused to occur hardened and soil alkalinity is caused to improve, are also compounded with phosphorus decomposing
Bacterium and EM bacterium solutions, the reduction of the content of the free state phosphorus in soil is avoided by the effect of phosphate solubilizing bacteria, while avoiding soil alkali
The quick raising of degree.
Technical solution is：
The first aspect of the invention provides：
A kind of restorative procedure of heavy-metal contaminated soil, includes the following steps：
1st step, by red mud, zeolite, bonding agent, water, pore creating material according to weight ratio 1：0.4~0.6：0.3~0.4：0.1~
0.15：0.05~0.15 is uniformly mixed, then graininess is made by comminutor, then successively after drying, roasting, obtains porous
Inorganic adsorbing material；
Phosphate solubilizing bacteria is inoculated on plating medium and cultivates by the 2nd step, then by after culture phosphate solubilizing bacteria and EM bacterium solutions be inoculated in
Fermentation process is carried out on fermentation medium, obtains composite bacteria liquid, then composite bacteria liquid is mixed with bacterium solution carrier, obtains load strain
Carrier；
3rd step is added porous, inorganic sorbing material in heavy-metal contaminated soil and loads the carrier of strain；
4th step, then planted in the soil of the 3rd step and absorb the plant of heavy metal, and apply nitrogen, phosphorus and potassium fertilizer；When absorption heavy metal
Plant absorption heavy metal after, aerial part is removed, and burning disposal.
The heavy-metal contaminated soil refers to lead, lead or cadmium heavy metal ion contaminated soil.
Further, refer to cation-modified natural zeolite.
Further, the bonding agent is the mixing of one or more of polyvinyl alcohol, glycerine or polyethylene glycol.
Further, the pore creating material is starch.
Further, the drying course is 10~15h of drying under the conditions of 105~115 DEG C.
Further, the roasting is 1~3h of roasting under the conditions of 200~240 DEG C.
Further, the composition of plating medium is：Peptone 5g, glucose 5g, yeast powder 5g, dipotassium hydrogen phosphate 4g,
Beef extract 10g, distilled water 1000ml.
Further, the composition of fermentation medium is：10.6 g/L of starch, 13.5 g/L of soy meal, 6.7 g/L of fish meal,
2.72 g/L of dipotassium hydrogen phosphate, 0.312 g/L of sodium dihydrogen phosphate, 0.2 g/L of calcium carbonate, 0.169 g/L of manganese sulfate, sodium nitrate
0.74 g/L of 0.34 g/L and magnesium sulfate.
Further, the weight ratio of composite bacteria liquid and bacterium solution carrier is 1：3~5.
Further, bacterium solution carrier is degradable macromolecule porous resin.
Further, degradable macromolecule porous resin is polymethacrylate resin.
Further, the preparation method of the polymethacrylate resin is：By weight, acrylic acid 120~
10wt% sodium hydroxide solutions are added dropwise in 130 parts until pH is 6.0~6.5, as acrylic acid solution；20~24 parts of wood is taken again
Sugar alcohol and 30~35 parts of acrylamide are uniformly mixed, then 12~15 parts of 15wt% glutaraldehyde water solutions and 3~6 parts of cause is added dropwise
Agent toluene in hole reacts 20~30min at 65~75 DEG C, after having reacted, then acrylic acid solution is added, while adding 1~5
Crosslinking agent N-N ' the methylene-bisacrylamides of part are warming up to after 70~75 DEG C of 45~60min of progress polymerisation, cooling,
And solid is filtered out, solid passes through successively after the washing of ethyl alcohol and deionized water, and vacuum drying obtains porous adsorption resin.
Further, the plant for absorbing heavy metal be gold leaf Chang it is thin (Acorus gramineus 'Ogon')。
Further, the addition of the carrier of porous, inorganic sorbing material and load strain in the soil is soil weight respectively
The 2~4 and 3~5% of amount.
Further, the applied amount of nitrogen, phosphorus and potassium fertilizer is：Based on N, nitrogenous fertilizer is 200~300kg/hm3；By P2O5Meter, phosphate fertilizer are
30~60 kg/hm3；By K2O is counted, and potash fertilizer is 100~120 kg/hm3。
The second aspect of the invention provides：
A kind of renovation agent for heavy-metal contaminated soil, this renovation agent are by above-mentioned porous, inorganic sorbing material and load
The carrier of strain collectively forms.
The third aspect of the invention provides：
The above-mentioned purposes for the renovation agent of heavy-metal contaminated soil in soil remediation.
Advantageous effect
The restorative procedure of heavy-metal contaminated soil provided by the invention will be native to the adsorbing of heavy metal, cured characteristic using red mud
Heavy metal in earth is fixed；Meanwhile the plant that collaboration has earth surface planting to absorb heavy metal further enhances to heavy metal
Removal effect, removing to heavy metal is realized after plant is removed, can be by heavy metal by by after plant carbonated, elution
With the separation of charcoal；In addition, since red mud can discharge excessive-OH ions into soil, the Phos in soil can be caused to occur
It is hardened and soil alkalinity is caused to improve, it is also compounded with phosphate solubilizing bacteria and EM bacterium solutions, is avoided in soil by the effect of phosphate solubilizing bacteria
The reduction of the content of free state phosphorus, while avoiding the quick raising of soil alkalinity.
Specific implementation mode
Technical problem to be solved by the present invention lies in carry out microorganism to the soil of heavy metal pollution, plant combined repair
It is multiple.In the technical solution of use, first, inorganic porous inorganic adsorbing material is prepared using red mud, due to red in this filler
Mud is the residue generated in aluminum oxide production process, the oxide containing abundant iron, aluminium and calcium, by discharging OH ion pairs soil
Heavy metal plays continual and steady solidification in earth, but the suction-operated of red mud in the soil is weaker, therefore, by red mud and day
Right zeolite prepares porous inorganic material under the action of bonding agent and pore creating material, on the one hand can utilize the release of red mud
On the other hand the characteristic of OH cationic cure heavy metal ion is utilized porous inorganic material and also improves to heavy metal ion
Absorption, improves removal effect.It is also added into zeolitic material in inorganic material, after it is modified by acid, can roast
Increasing specific surface area during burning promotes absorption of the red mud to heavy metal；Simultaneously because the heavy metal ion of red mud release
Can lead to the phosphatic precipitation in soil, so that the phosphorus content in soil is declined, plant availability it is poor, in above-mentioned restorative procedure
In be also added into the precipitation that phosphate solubilizing bacteria avoids phosphorus, the phosphate solubilizing bacteria in the present invention can be selected from penicillium oxalicum（Penicillium oxalicum）, koji mould（Aspergillus japonicus）, bacillus subtilis（Bacillus subtilis）、
Ke Huoerde Salmonellas（Burkholderia sp.）, citrobacter freundii（Citrobacter freundii）, agglomerating intestines bar
Bacterium（Enterobacter agglomerans）, agrobacterium（Agrobacterium sp .）, bacillus amyloliquefaciens
（Bacillus amyloliquefaciens）, acid-producing Klebsiella bacterium（Klebsiella oxytoca）, enterobacter cloacae
(Enterobacter cloacae), cellulase-producing bacillus licheniformis（Bacillus licheniformis）Or oxalic acid
Mould（Penicillium oxalicum）One or more of mixing.Such as bacillus subtilis can be selected from
（Bacillus subtilis）HL-1（CGMCC No.5175）, cellulase-producing bacillus licheniformis
（Bacilluslicheniformis）BL-1（CCTCCNo.M2012457）, bacillus subtilis (Bacillussubtilis)
XF-8（CCTCCNO：M2010182）, bulkholderia cepasea（Burkholderia sp.）21-III（CGMCC No.
7873）, the general bacterium CA of this formula（Pantoea stewartii）（Bi Yinli, Guo Jingting, Liu Rong banyan phosphate solubilizing microorganisms are discarded to coal measures
The refined trabeculectomy environmental project journals of object flyash, 2008（9）：1235-1238）Deng.Meanwhile it being additionally added in processing method
EM bacterium solutions are jointly processed by, and EM bacterium solutions are peaceful happy environment friendly biological technologies of regarding for oneself（Nanjing）Co., Ltd purchases, and contains light
Close bacterium, lactic acid bacteria, more than the 80 kinds of effective active microorganism such as saccharomycete ,/milliliter of viable count >=100,000,000, pH >=3.8, color is
Yellowish-brown, translucent liquid, smell are denseer alcohol tart flavour or tart flavour.Since EM bacterium solutions are acid at obtained product in fermentation process
Property, the problem of red mud release excesses of basic ion can be eliminated and lead to alkalization of soils, the table of phosphorus deposit in soil can be made
The acid-base status in face promotes the decomposition of phosphate solubilizing bacteria, improves the efficiency to dissolving phosphorus；Simultaneously as in EM bacterium solutions rich in actinomyces,
The products such as the amino acid generated after the beneficial microbes such as saccharomycete, photosynthetic bacteria and microbial metabolism, can be mutual with phosphate solubilizing bacteria
Collaboration, makes the nitrogen phosphorus in soil reach balance, keeps the growth result of removing heavy metals plant more preferable.In the restorative procedure of the present invention,
When phosphate solubilizing bacteria and EM bacterium solutions are carried on porous resin carrier, a ring more suitable for growth can be provided to microorganism
Border makes it constantly release acid product and amino acid, improves the synergy with red mud, the polymerization of hydrophilic modifying may be used
Object, since microorganism in the preferable hydrophilic effect in the surface of adsorbent, can be advantageously promoted in the fermentation on surface, phosphorus decomposing
Effect.In the present invention, also the heavy metal in soil is removed by planting the plant of absorption heavy metal on ground, works as plant
In content of beary metal reach a certain amount of after, aerial part can be removed, after burning, elute the weight that will can wherein be enriched with
Metal washes out, and realizes the separation with charcoal, the final effect for realizing removal heavy metal in soil.Meanwhile EM bacterium and phosphate solubilizing bacteria being born
It is loaded on porous resin carrier, a preferable growing environment can be provided for microorganism, can more improve it for soil remediation
In effect, since saliferous, heavy metal amount are higher in soil, in one embodiment, also increase on porous resin
Xylitol, make it is porous carry ionic and non-ionic hydrophilic group, to reduce salt effect and common-ion effect, improve resistance to
Salt.
In following embodiment, contain in the heavy-metal contaminated soil of required reparation：Soil pH value is 5.4, full phosphorus
0.76g.kg-1, rapid available phosphorus 4.70mg.kg-1, organic matter 17.4%, Pb2+Content be 320mg/kg and Cd2+Content be 57mg/
kg。
Embodiment 1
1st step, by red mud, cation-modified natural zeolite, bonding agent glycerine, water, pore creating material starch according to weight ratio 1：
0.4：0.3：0.1：0.05 is uniformly mixed, then is made graininess by comminutor, then drying 10h under the conditions of passing through 105 DEG C successively,
After roasting 1h under the conditions of 200~240 DEG C, porous, inorganic sorbing material is obtained；Cation-modified natural zeolite preparation method is
After natural zeolite is ground, the calcination activation 1h at 300 DEG C, then zeolite is mixed with 10wt% dilute sulfuric acids, it is warming up to 65 DEG C of guarantors
0.5h is held, zeolite is filtered out and is cleaned with deionized water, then is dried in vacuo；Zeolite, poly dimethyl allyl after drying
Ammonium chloride, polyquaternium M550（Dimethyl diallyl ammonium chloride-acrylamide copolymer）According to weight ratio 1：3.5：1.8 mixed
It closes uniform and after stirring 1h, filters out solid at 45 DEG C, after vacuum drying, obtain cation-modified zeolite；
Phosphate solubilizing bacteria bacillus subtilis HL-1 is inoculated on plating medium and cultivates by the 2nd step, and condition of culture is at 25 DEG C
36h, then by after culture phosphate solubilizing bacteria and EM bacterium solutions be inoculated on fermentation medium and carry out fermentation process, fermentation condition is at 32 DEG C
72h obtains composite bacteria liquid, then composite bacteria liquid is mixed with bacterium solution carrier, obtains the carrier of load strain, composite bacteria liquid and bacterium solution
The weight ratio of carrier is 1：4；The composition of plating medium is：Peptone 5g, glucose 5g, yeast powder 5g, dipotassium hydrogen phosphate 4g,
Beef extract 10g, distilled water 1000ml；The composition of fermentation medium is：10.6 g/L of starch, 13.5 g/L of soy meal, fish meal 6.7
G/L, 2.72 g/L of dipotassium hydrogen phosphate, 0.312 g/L of sodium dihydrogen phosphate, 0.2 g/L of calcium carbonate, 0.169 g/L of manganese sulfate, nitre
0.74 g/L of 0.34 g/L of sour sodium and magnesium sulfate；
Bacterium solution carrier is prepared via a method which to obtain：By weight, 10wt% sodium hydroxides are added dropwise in 120 parts of acrylic acid
Solution is until pH is 6.0~6.5, as acrylic acid solution；30 parts of acrylamide is taken again, then 12 part of 15% glutaraldehyde water is added dropwise
Solution and 3 parts of pore-foaming agent toluene, react 20min at 65 DEG C, after having reacted, then acrylic acid solution are added, at the same again plus
Crosslinking agent N-N ' the methylene-bisacrylamides for entering 1 part are warming up to after 70 DEG C of progress polymerisation 45min, cooling, and are filtered out
Solid, solid pass through successively after the washing of ethyl alcohol and deionized water, and vacuum drying obtains porous adsorption resin.
3rd step is added porous, inorganic sorbing material in heavy-metal contaminated soil and loads the carrier of strain, porous, inorganic
The addition of the carrier of sorbing material and load strain in the soil is the 2% and 3% of soil weight respectively；
4th step, then plantation gold leaf Chang is thin in the soil of the 3rd step, planting density is 2 plants/m2, and apply nitrogen, phosphorus and potassium fertilizer, nitrogen phosphorus
The applied amount of potash fertilizer is：Based on N, nitrogenous fertilizer 200kg/hm3；By P2O5Meter, phosphate fertilizer are 30 kg/hm3；By K2O is counted, potash fertilizer 100
kg/hm3；After plantation 2 months, aerial part is removed, and burning disposal.
Embodiment 2
1st step, by red mud, cation-modified natural zeolite, bonding agent glycerine, water, pore creating material starch according to weight ratio 1：
0.6： 0.4： 0.15：0.15 is uniformly mixed, then graininess is made by comminutor, then is dried under the conditions of passing through 115 DEG C successively
15h, under the conditions of 240 DEG C after roasting 3h, porous, inorganic sorbing material is obtained；Cation-modified natural zeolite preparation method be by
After natural zeolite grinding, the calcination activation 1h at 300 DEG C, then zeolite is mixed with 10wt% dilute sulfuric acids, it is warming up to 65 DEG C of holdings
0.5h filters out zeolite and is cleaned with deionized water, then is dried in vacuo；Zeolite, poly dimethyl allyl chlorine after drying
Change ammonium, polyquaternium M550（Dimethyl diallyl ammonium chloride-acrylamide copolymer）According to weight ratio 1：3.5：1.8 mixing
After uniformly and stirring 1h at 45 DEG C, solid is filtered out, after vacuum drying, obtains cation-modified zeolite；
Phosphate solubilizing bacteria bacillus subtilis HL-1 is inoculated on plating medium and cultivates by the 2nd step, and condition of culture is at 30 DEG C
36h, then by after culture phosphate solubilizing bacteria and EM bacterium solutions be inoculated on fermentation medium and carry out fermentation process, fermentation condition is at 35 DEG C
72h obtains composite bacteria liquid, then composite bacteria liquid is mixed with bacterium solution carrier, obtains the carrier of load strain, composite bacteria liquid and bacterium solution
The weight ratio of carrier is 1：4；The composition of plating medium is：Peptone 5g, glucose 5g, yeast powder 5g, dipotassium hydrogen phosphate 4g,
Beef extract 10g, distilled water 1000ml；The composition of fermentation medium is：10.6 g/L of starch, 13.5 g/L of soy meal, fish meal 6.7
G/L, 2.72 g/L of dipotassium hydrogen phosphate, 0.312 g/L of sodium dihydrogen phosphate, 0.2 g/L of calcium carbonate, 0.169 g/L of manganese sulfate, nitre
0.74 g/L of 0.34 g/L of sour sodium and magnesium sulfate；
Bacterium solution carrier is prepared via a method which to obtain：By weight, 10wt% sodium hydroxides are added dropwise in 130 parts of acrylic acid
Solution is until pH is 6.0~6.5, as acrylic acid solution；35 parts of acrylamide is taken again, then 15 parts of 15wt% glutaraldehydes are added dropwise
Aqueous solution and 6 parts of pore-foaming agent toluene, react 30min at 75 DEG C, after having reacted, then acrylic acid solution are added, while again
5 parts of crosslinking agent N-N ' methylene-bisacrylamides are added, are warming up to after 75 DEG C of progress polymerisation 60min, it is cooling, and filter
Go out solid, solid passes through successively after the washing of ethyl alcohol and deionized water, and vacuum drying obtains porous adsorption resin.
3rd step is added porous, inorganic sorbing material in heavy-metal contaminated soil and loads the carrier of strain, porous, inorganic
The addition of the carrier of sorbing material and load strain in the soil is the 4% and 5% of soil weight respectively；
4th step, then plantation gold leaf Chang is thin in the soil of the 3rd step, planting density is 4 plants/m2, and apply nitrogen, phosphorus and potassium fertilizer, nitrogen phosphorus
The applied amount of potash fertilizer is：Based on N, nitrogenous fertilizer 300kg/hm3；By P2O5Meter, phosphate fertilizer are 60 kg/hm3；By K2O is counted, potash fertilizer 120
kg/hm3；After plantation 2 months, aerial part is removed, and burning disposal.
Embodiment 3
1st step, by red mud, cation-modified natural zeolite, bonding agent glycerine, water, pore creating material starch according to weight ratio 1：
0.5：0.35：0.12：0.10 is uniformly mixed, then graininess is made by comminutor, then is dried under the conditions of passing through 105 DEG C successively
12h, under the conditions of 220 DEG C after roasting 2h, porous, inorganic sorbing material is obtained；Cation-modified natural zeolite preparation method be by
After natural zeolite grinding, the calcination activation 1h at 300 DEG C, then zeolite is mixed with 10wt% dilute sulfuric acids, it is warming up to 65 DEG C of holdings
0.5h filters out zeolite and is cleaned with deionized water, then is dried in vacuo；Zeolite, poly dimethyl allyl chlorine after drying
Change ammonium, polyquaternium M550（Dimethyl diallyl ammonium chloride-acrylamide copolymer）According to weight ratio 1：3.5：1.8 mixing
After uniformly and stirring 1h at 45 DEG C, solid is filtered out, after vacuum drying, obtains cation-modified zeolite；
Phosphate solubilizing bacteria bacillus subtilis HL-1 is inoculated on plating medium and cultivates by the 2nd step, and condition of culture is at 28 DEG C
36h, then by after culture phosphate solubilizing bacteria and EM bacterium solutions be inoculated on fermentation medium and carry out fermentation process, fermentation condition is at 33 DEG C
72h obtains composite bacteria liquid, then composite bacteria liquid is mixed with bacterium solution carrier, obtains the carrier of load strain, composite bacteria liquid and bacterium solution
The weight ratio of carrier is 1：4；The composition of plating medium is：Peptone 5g, glucose 5g, yeast powder 5g, dipotassium hydrogen phosphate 4g,
Beef extract 10g, distilled water 1000ml；The composition of fermentation medium is：10.6 g/L of starch, 13.5 g/L of soy meal, fish meal 6.7
G/L, 2.72 g/L of dipotassium hydrogen phosphate, 0.312 g/L of sodium dihydrogen phosphate, 0.2 g/L of calcium carbonate, 0.169 g/L of manganese sulfate, nitre
0.74 g/L of 0.34 g/L of sour sodium and magnesium sulfate；
Bacterium solution carrier is prepared via a method which to obtain：By weight, 10wt% sodium hydroxides are added dropwise in 125 parts of acrylic acid
Solution is until pH is 6.0~6.5, as acrylic acid solution；32 parts of acrylamide is taken again, and 13 parts of 15wt% glutaraldehyde water are added dropwise
Solution and 4 parts of pore-foaming agent toluene, react 25min at 70 DEG C, after having reacted, then acrylic acid solution are added, at the same again plus
Crosslinking agent N-N ' the methylene-bisacrylamides for entering 2 parts are warming up to after 72 DEG C of progress polymerisation 55min, cooling, and are filtered out
Solid, solid pass through successively after the washing of ethyl alcohol and deionized water, and vacuum drying obtains porous adsorption resin.
3rd step is added porous, inorganic sorbing material in heavy-metal contaminated soil and loads the carrier of strain, porous, inorganic
The addition of the carrier of sorbing material and load strain in the soil is the 3% and 4% of soil weight respectively；
4th step, then plantation gold leaf Chang is thin in the soil of the 3rd step, planting density is 3 plants/m2, and apply nitrogen, phosphorus and potassium fertilizer, nitrogen phosphorus
The applied amount of potash fertilizer is：Based on N, nitrogenous fertilizer 250kg/hm3；By P2O5Meter, phosphate fertilizer are 50 kg/hm3；By K2O is counted, potash fertilizer 110
kg/hm3；After plantation 2 months, aerial part is removed, and burning disposal.
Embodiment 4
Difference with embodiment 3 is：The hydrophilic modification processing of xylitol is used to porous adsorption resin.
1st step, by red mud, cation-modified natural zeolite, bonding agent glycerine, water, pore creating material starch according to weight ratio
1：0.5：0.35：0.12：0.10 is uniformly mixed, then graininess is made by comminutor, then is dried under the conditions of passing through 105 DEG C successively
12h, under the conditions of 220 DEG C after roasting 2h, porous, inorganic sorbing material is obtained；Cation-modified natural zeolite preparation method be by
After natural zeolite grinding, the calcination activation 1h at 300 DEG C, then zeolite is mixed with 10wt% dilute sulfuric acids, it is warming up to 65 DEG C of holdings
0.5h filters out zeolite and is cleaned with deionized water, then is dried in vacuo；Zeolite, poly dimethyl allyl chlorine after drying
Change ammonium, polyquaternium M550（Dimethyl diallyl ammonium chloride-acrylamide copolymer）According to weight ratio 1：3.5：1.8 mixing
After uniformly and stirring 1h at 45 DEG C, solid is filtered out, after vacuum drying, obtains cation-modified zeolite；
Phosphate solubilizing bacteria bacillus subtilis HL-1 is inoculated on plating medium and cultivates by the 2nd step, and condition of culture is at 28 DEG C
36h, then by after culture phosphate solubilizing bacteria and EM bacterium solutions be inoculated on fermentation medium and carry out fermentation process, fermentation condition is at 33 DEG C
72h obtains composite bacteria liquid, then composite bacteria liquid is mixed with bacterium solution carrier, obtains the carrier of load strain, composite bacteria liquid and bacterium solution
The weight ratio of carrier is 1：4；The composition of plating medium is：Peptone 5g, glucose 5g, yeast powder 5g, dipotassium hydrogen phosphate 4g,
Beef extract 10g, distilled water 1000ml；The composition of fermentation medium is：10.6 g/L of starch, 13.5 g/L of soy meal, fish meal 6.7
G/L, 2.72 g/L of dipotassium hydrogen phosphate, 0.312 g/L of sodium dihydrogen phosphate, 0.2 g/L of calcium carbonate, 0.169 g/L of manganese sulfate, nitre
0.74 g/L of 0.34 g/L of sour sodium and magnesium sulfate；
Bacterium solution carrier is prepared via a method which to obtain：By weight, 10wt% sodium hydroxides are added dropwise in 125 parts of acrylic acid
Solution is until pH is 6.0~6.5, as acrylic acid solution；22 parts of xylitol and 32 parts of acrylamide is taken to be uniformly mixed again,
The pore-foaming agent toluene of 13 parts of 15wt% glutaraldehyde water solutions and 4 parts is added dropwise again, reacts 25min at 70 DEG C, after having reacted, then will
Acrylic acid solution is added, while adding 2 parts of crosslinking agent N-N ' methylene-bisacrylamides, is warming up to 72 DEG C and polymerize instead
It is cooling after answering 55min, and solid is filtered out, solid passes through successively after the washing of ethyl alcohol and deionized water, and vacuum drying obtains
To porous adsorption resin.
3rd step is added porous, inorganic sorbing material in heavy-metal contaminated soil and loads the carrier of strain, porous, inorganic
The addition of the carrier of sorbing material and load strain in the soil is the 3% and 4% of soil weight respectively；
4th step, then plantation gold leaf Chang is thin in the soil of the 3rd step, planting density is 3 plants/m2, and apply nitrogen, phosphorus and potassium fertilizer, nitrogen phosphorus
The applied amount of potash fertilizer is：Based on N, nitrogenous fertilizer 250kg/hm3；By P2O5Meter, phosphate fertilizer are 50 kg/hm3；By K2O is counted, potash fertilizer 110
kg/hm3；After plantation 2 months, aerial part is removed, and burning disposal.
Reference examples 1
With embodiment 4 difference lies in：The processing that natural zeolite is modified without cationic polymer.
1st step, by red mud, natural zeolite, bonding agent glycerine, water, pore creating material starch according to weight ratio 1：0.5：0.35：
0.12：0.10 is uniformly mixed, then graininess is made by comminutor, then dries 12h, 220 DEG C of items under the conditions of passing through 105 DEG C successively
After roasting 2h under part, porous, inorganic sorbing material is obtained；
Phosphate solubilizing bacteria bacillus subtilis HL-1 is inoculated on plating medium and cultivates by the 2nd step, and condition of culture is at 28 DEG C
36h, then by after culture phosphate solubilizing bacteria and EM bacterium solutions be inoculated on fermentation medium and carry out fermentation process, fermentation condition is at 33 DEG C
72h obtains composite bacteria liquid, then composite bacteria liquid is mixed with bacterium solution carrier, obtains the carrier of load strain, composite bacteria liquid and bacterium solution
The weight ratio of carrier is 1：4；The composition of plating medium is：Peptone 5g, glucose 5g, yeast powder 5g, dipotassium hydrogen phosphate 4g,
Beef extract 10g, distilled water 1000ml；The composition of fermentation medium is：10.6 g/L of starch, 13.5 g/L of soy meal, fish meal 6.7
G/L, 2.72 g/L of dipotassium hydrogen phosphate, 0.312 g/L of sodium dihydrogen phosphate, 0.2 g/L of calcium carbonate, 0.169 g/L of manganese sulfate, nitre
0.74 g/L of 0.34 g/L of sour sodium and magnesium sulfate；
Bacterium solution carrier is prepared via a method which to obtain：By weight, 10wt% sodium hydroxides are added dropwise in 125 parts of acrylic acid
Solution is until pH is 6.0~6.5, as acrylic acid solution；22 parts of xylitol and 32 parts of acrylamide is taken to be uniformly mixed again,
The pore-foaming agent toluene of 13 parts of 15wt% glutaraldehyde water solutions and 4 parts is added dropwise again, reacts 25min at 70 DEG C, after having reacted, then will
Acrylic acid solution is added, while adding 2 parts of crosslinking agent N-N ' methylene-bisacrylamides, is warming up to 72 DEG C and polymerize instead
It is cooling after answering 55min, and solid is filtered out, solid passes through successively after the washing of ethyl alcohol and deionized water, and vacuum drying obtains
To porous adsorption resin.
3rd step is added porous, inorganic sorbing material in heavy-metal contaminated soil and loads the carrier of strain, porous, inorganic
The addition of the carrier of sorbing material and load strain in the soil is the 3% and 4% of soil weight respectively；
4th step, then plantation gold leaf Chang is thin in the soil of the 3rd step, planting density is 3 plants/m2, and apply nitrogen, phosphorus and potassium fertilizer, nitrogen phosphorus
The applied amount of potash fertilizer is：Based on N, nitrogenous fertilizer 250kg/hm3；By P2O5Meter, phosphate fertilizer are 50 kg/hm3；By K2O is counted, potash fertilizer 110
kg/hm3；After plantation 2 months, aerial part is removed, and burning disposal.
Reference examples 2
With embodiment 3 difference lies in：EM bacterium solutions are not added during the fermentation.
1st step, by red mud, cation-modified natural zeolite, bonding agent glycerine, water, pore creating material starch according to weight ratio
1：0.5：0.35：0.12：0.10 is uniformly mixed, then graininess is made by comminutor, then is dried under the conditions of passing through 105 DEG C successively
12h, under the conditions of 220 DEG C after roasting 2h, porous, inorganic sorbing material is obtained；Cation-modified natural zeolite preparation method be by
After natural zeolite grinding, the calcination activation 1h at 300 DEG C, then zeolite is mixed with 10wt% dilute sulfuric acids, it is warming up to 65 DEG C of holdings
0.5h filters out zeolite and is cleaned with deionized water, then is dried in vacuo；Zeolite, poly dimethyl allyl chlorine after drying
Change ammonium, polyquaternium M550（Dimethyl diallyl ammonium chloride-acrylamide copolymer）According to weight ratio 1：3.5：1.8 mixing
After uniformly and stirring 1h at 45 DEG C, solid is filtered out, after vacuum drying, obtains cation-modified zeolite；
Phosphate solubilizing bacteria bacillus subtilis HL-1 is inoculated on plating medium and cultivates by the 2nd step, and condition of culture is at 28 DEG C
36h, then the phosphate solubilizing bacteria after culture is inoculated on fermentation medium and carries out fermentation process, fermentation condition is 72h at 33 DEG C, is obtained
Composite bacteria liquid, then composite bacteria liquid is mixed with bacterium solution carrier, obtain the carrier of load strain, the weight of composite bacteria liquid and bacterium solution carrier
It is 1 to measure ratio：4；The composition of plating medium is：Peptone 5g, glucose 5g, yeast powder 5g, dipotassium hydrogen phosphate 4g, beef extract
10g, distilled water 1000ml；The composition of fermentation medium is：10.6 g/L of starch, 13.5 g/L of soy meal, 6.7 g/L of fish meal,
2.72 g/L of dipotassium hydrogen phosphate, 0.312 g/L of sodium dihydrogen phosphate, 0.2 g/L of calcium carbonate, 0.169 g/L of manganese sulfate, sodium nitrate
0.74 g/L of 0.34 g/L and magnesium sulfate；
Bacterium solution carrier is prepared via a method which to obtain：By weight, 10wt% sodium hydroxides are added dropwise in 125 parts of acrylic acid
Solution is until pH is 6.0~6.5, as acrylic acid solution；22 parts of xylitol and 32 parts of acrylamide is taken to be uniformly mixed again,
The pore-foaming agent toluene of 13 parts of 15wt% glutaraldehyde water solutions and 4 parts is added dropwise again, reacts 25min at 70 DEG C, after having reacted, then will
Acrylic acid solution is added, while adding 2 parts of crosslinking agent N-N ' methylene-bisacrylamides, is warming up to 72 DEG C and polymerize instead
It is cooling after answering 55min, and solid is filtered out, solid passes through successively after the washing of ethyl alcohol and deionized water, and vacuum drying obtains
To porous adsorption resin.
3rd step is added porous, inorganic sorbing material in heavy-metal contaminated soil and loads the carrier of strain, porous, inorganic
The addition of the carrier of sorbing material and load strain in the soil is the 3% and 4% of soil weight respectively；
4th step, then plantation gold leaf Chang is thin in the soil of the 3rd step, planting density is 3 plants/m2, and apply nitrogen, phosphorus and potassium fertilizer, nitrogen phosphorus
The applied amount of potash fertilizer is：Based on N, nitrogenous fertilizer 250kg/hm3；By P2O5Meter, phosphate fertilizer are 50 kg/hm3；By K2O is counted, potash fertilizer 110
kg/hm3；After plantation 2 months, aerial part is removed, and burning disposal.
Reference examples 3
With embodiment 3 difference lies in：Phosphate solubilizing bacteria is not added during fermentation.
1st step, by red mud, cation-modified natural zeolite, bonding agent glycerine, water, pore creating material starch according to weight ratio
1：0.5：0.35：0.12：0.10 is uniformly mixed, then graininess is made by comminutor, then is dried under the conditions of passing through 105 DEG C successively
12h, under the conditions of 220 DEG C after roasting 2h, porous, inorganic sorbing material is obtained；Cation-modified natural zeolite preparation method be by
After natural zeolite grinding, the calcination activation 1h at 300 DEG C, then zeolite is mixed with 10wt% dilute sulfuric acids, it is warming up to 65 DEG C of holdings
0.5h filters out zeolite and is cleaned with deionized water, then is dried in vacuo；Zeolite, poly dimethyl allyl chlorine after drying
Change ammonium, polyquaternium M550（Dimethyl diallyl ammonium chloride-acrylamide copolymer）According to weight ratio 1：3.5：1.8 mixing
After uniformly and stirring 1h at 45 DEG C, solid is filtered out, after vacuum drying, obtains cation-modified zeolite；
EM bacterium solutions are inoculated on fermentation medium and carry out fermentation process by the 2nd step, and fermentation condition is 72h at 33 DEG C, is fermented
Bacterium solution, then zymocyte liquid is mixed with bacterium solution carrier, obtain the carrier of load strain, the weight ratio of zymocyte liquid and bacterium solution carrier
It is 1：4；The composition of plating medium is：Peptone 5g, it glucose 5g, yeast powder 5g, dipotassium hydrogen phosphate 4g, beef extract 10g, steams
Distilled water 1000ml；The composition of fermentation medium is：10.6 g/L of starch, 13.5 g/L of soy meal, 6.7 g/L of fish meal, phosphoric acid hydrogen
2.72 g/L of dipotassium, 0.312 g/L of sodium dihydrogen phosphate, 0.2 g/L of calcium carbonate, 0.169 g/L of manganese sulfate, 0.34 g/ of sodium nitrate
0.74 g/L of L and magnesium sulfate；
Bacterium solution carrier is prepared via a method which to obtain：By weight, 10wt% sodium hydroxides are added dropwise in 125 parts of acrylic acid
Solution is until pH is 6.0~6.5, as acrylic acid solution；22 parts of xylitol and 32 parts of acrylamide is taken to be uniformly mixed again,
The pore-foaming agent toluene of 13 parts of 15wt% glutaraldehyde water solutions and 4 parts is added dropwise again, reacts 25min at 70 DEG C, after having reacted, then will
Acrylic acid solution is added, while adding 2 parts of crosslinking agent N-N ' methylene-bisacrylamides, is warming up to 72 DEG C and polymerize instead
It is cooling after answering 55min, and solid is filtered out, solid passes through successively after the washing of ethyl alcohol and deionized water, and vacuum drying obtains
To porous adsorption resin.
3rd step is added porous, inorganic sorbing material in heavy-metal contaminated soil and loads the carrier of strain, porous, inorganic
The addition of the carrier of sorbing material and load strain in the soil is the 3% and 4% of soil weight respectively；
4th step, then plantation gold leaf Chang is thin in the soil of the 3rd step, planting density is 3 plants/m2, and apply nitrogen, phosphorus and potassium fertilizer, nitrogen phosphorus
The applied amount of potash fertilizer is：Based on N, nitrogenous fertilizer 250kg/hm3；By P2O5Meter, phosphate fertilizer are 50 kg/hm3；By K2O is counted, potash fertilizer 110
kg/hm3；After plantation 2 months, aerial part is removed, and burning disposal.
Reference examples 4
With embodiment 3 difference lies in：Red mud is not added in porous, inorganic sorbing material.
1st step, by cation-modified natural zeolite, bonding agent glycerine, water, pore creating material starch according to weight ratio 1.5：
0.35：0.12：0.10 is uniformly mixed, then is made graininess by comminutor, then drying 12h under the conditions of passing through 105 DEG C successively,
After roasting 2h under the conditions of 220 DEG C, porous, inorganic sorbing material is obtained；Cation-modified natural zeolite preparation method is will be natural
After zeolite grinding, the calcination activation 1h at 300 DEG C, then zeolite is mixed with 10wt% dilute sulfuric acids, it is warming up to 65 DEG C of holdings
0.5h filters out zeolite and is cleaned with deionized water, then is dried in vacuo；Zeolite, poly dimethyl allyl chlorine after drying
Change ammonium, polyquaternium M550（Dimethyl diallyl ammonium chloride-acrylamide copolymer）According to weight ratio 1：3.5：1.8 mixing
After uniformly and stirring 1h at 45 DEG C, solid is filtered out, after vacuum drying, obtains cation-modified zeolite；
Phosphate solubilizing bacteria bacillus subtilis HL-1 is inoculated on plating medium and cultivates by the 2nd step, and condition of culture is at 28 DEG C
36h, then by after culture phosphate solubilizing bacteria and EM bacterium solutions be inoculated on fermentation medium and carry out fermentation process, fermentation condition is at 33 DEG C
72h obtains composite bacteria liquid, then composite bacteria liquid is mixed with bacterium solution carrier, obtains the carrier of load strain, composite bacteria liquid and bacterium solution
The weight ratio of carrier is 1：4；The composition of plating medium is：Peptone 5g, glucose 5g, yeast powder 5g, dipotassium hydrogen phosphate 4g,
Beef extract 10g, distilled water 1000ml；The composition of fermentation medium is：10.6 g/L of starch, 13.5 g/L of soy meal, fish meal 6.7
G/L, 2.72 g/L of dipotassium hydrogen phosphate, 0.312 g/L of sodium dihydrogen phosphate, 0.2 g/L of calcium carbonate, 0.169 g/L of manganese sulfate, nitre
0.74 g/L of 0.34 g/L of sour sodium and magnesium sulfate；
Bacterium solution carrier is prepared via a method which to obtain：By weight, 10wt% sodium hydroxides are added dropwise in 125 parts of acrylic acid
Solution is until pH is 6.0~6.5, as acrylic acid solution；22 parts of xylitol and 32 parts of acrylamide is taken to be uniformly mixed again,
The pore-foaming agent toluene of 13 parts of 15wt% glutaraldehyde water solutions and 4 parts is added dropwise again, reacts 25min at 70 DEG C, after having reacted, then will
Acrylic acid solution is added, while adding 2 parts of crosslinking agent N-N ' methylene-bisacrylamides, is warming up to 72 DEG C and polymerize instead
It is cooling after answering 55min, and solid is filtered out, solid passes through successively after the washing of ethyl alcohol and deionized water, and vacuum drying obtains
To porous adsorption resin.
3rd step is added porous, inorganic sorbing material in heavy-metal contaminated soil and loads the carrier of strain, porous, inorganic
The addition of the carrier of sorbing material and load strain in the soil is the 3% and 4% of soil weight respectively；
4th step, then plantation gold leaf Chang is thin in the soil of the 3rd step, planting density is 3 plants/m2, and apply nitrogen, phosphorus and potassium fertilizer, nitrogen phosphorus
The applied amount of potash fertilizer is：Based on N, nitrogenous fertilizer 250kg/hm3；By P2O5Meter, phosphate fertilizer are 50 kg/hm3；By K2O is counted, potash fertilizer 110
kg/hm3；After plantation 2 months, aerial part is removed, and burning disposal.
The phosphorus decomposing of composite bacteria liquid is tested
Prepare culture medium：Glucose 10.0g, (NH4)2SO40.5g, MgSO4·7H2O 0.3g, NaCl 0.3g, KCl 0.3g,
FeSO4 0.03g, MnSO4·H2O 0.03g, yeast powder 0.5g, Phos 10g, distilled water l000ml, pH7.0.Wherein, inorganic
Phosphorus is respectively Ca3(PO4)2、MgHPO4、Zn3(PO4)2、AlPO4、FePO4；Referred to as phosphorous culture medium 1~5.
The composite bacteria liquid being prepared in 10ml Examples 1 to 4 and control is added in above-mentioned phosphorous culture medium respectively
The composite bacteria liquid that EM bacterium solutions are not added in example 2, in 25 DEG C, 200rmin-1Under stirring condition cultivate 7d after, by zymotic fluid from
Heart 10min (4 DEG C, 10000rmin-1)；Using P-Mo blue spectrophotometry, that is, the 100 μ L of supernatant that take above-mentioned centrifugation to obtain
It is added in the volumetric flask of 50mL, after the deionized water of about 25mL is then added, then adds 1-2 drops 2,4- dinitrophenol dinitrophenolate indicator, then
Add the anti-color developing agent of 5mL molybdenum antimony, then add deionized water constant volume, mixing after standing 0.5h, measures OD values.And it calculates in supernatant
Available phosphorus content and phosphorus decomposing rate.Wherein, phosphorus decomposing rate（%）=（Connect bacterium titanium pigment content-control titanium pigment content）/ be added
Phosphatic amount × 100.Phosphorus decomposing rate is as shown in the table：
As can be seen from the table, composite bacteria liquid provided by the invention can show the effect of preferable dissolved metals.Especially
It is for Ca3(PO4)2、MgHPO4And AlPO4With higher Soluble phosphorus efficiency.
Phosphorus content and pH value variation experiment in soil
After 2 months plants of planting, phosphorus content, pH value in measurement soil, soil is the soil of 10cm depths, takes 50g,
It is repeated 3 times calculating average value, the phosphorus content in the thin stems of gold leaf Chang is measured, takes 10 plants and calculate average value, as shown in the table：
As can be seen from the above table, due to adding EM bacterium solutions in the present invention in restorative procedure, it is 7.0 left effectively to make soil
The right side overcomes the influence of alkalization of soils, phosphorus precipitation that red mud release OH is brought.The phosphorus decomposing effect of phosphate solubilizing bacteria is effectively promoted,
It can be seen that by the comparison of reference examples 2 and embodiment 3 and be effectively improved rapid available phosphorus in soil by being added after EM bacterium solutions
Content and plant in P uptake by plants, promote the growth of removing heavy metals plant.Pass through the comparison of embodiment 3 and embodiment 4
As can be seen that xylitol is utilized in since porous resin surface to have been carried out to the hydrophilic modification of xylitol in embodiment 4
Macroporous absorbent resin is set to be improved with ionic and non-ionic hydrophilic group to reduce salt effect and common-ion effect
Salt tolerance enables macroporous absorbent resin to stablize performance effect.
The growth of removing heavy metals plant and the experiment for inhaling heavy metal amount
After plantation 2 months, the content of beary metal in the thin plant heights of gold leaf Chang, cauline leaf is measured, 10 plants is taken and calculates average value, it is as follows
Shown in table：
It as can be seen from the table, can the effectively enriching heavy metal by the way of in soil by plant absorption using this method.
By embodiment 3 and the comparison of reference examples 3 as can be seen that by the way that phosphate solubilizing bacteria is added in repair process, soil can be effectively improved
The content of rapid available phosphorus in earth, promotes the growth of plant, achievees the purpose that more enriching heavy metal.
Content of beary metal in soil measures experiment
After plantation 2 months, the content of the lead and cadmium in soil is measured, calculates removal rate, soil is the soil of 10cm depths, is taken
50g is repeated 3 times calculating average value, as shown in the table：
As can be seen that method using the present invention can effectively eliminate the heavy metal contaminants in soil, to lead and cadmium in table
Removal rate can reach 50%-70%, can be seen that by the comparison of embodiment 3 and reference examples 4 can be with by the addition of red mud
The heavy metal in the suction-operated fixing soil of red mud is effectively utilized, can be seen that additionally by embodiment 3 and reference examples 1
The specific surface area of compounded mix can be improved by carrying out sour modification to zeolite, red mud is improved and the absorption of heavy metal is made
With.
Claims (9)
1. a kind of restorative procedure of heavy-metal contaminated soil, which is characterized in that include the following steps：
1st step, by red mud, zeolite, bonding agent, water, pore creating material according to weight ratio 1：0.4~0.6：0.3~0.4：0.1~
0.15：0.05~0.15 is uniformly mixed, then graininess is made by comminutor, then successively after drying, roasting, obtains porous
Inorganic adsorbing material；
Phosphate solubilizing bacteria is inoculated on plating medium and cultivates by the 2nd step, then by after culture phosphate solubilizing bacteria and EM bacterium solutions be inoculated in
Fermentation process is carried out on fermentation medium, obtains composite bacteria liquid, then composite bacteria liquid is mixed with bacterium solution carrier, obtains load strain
Carrier；
3rd step is added porous, inorganic sorbing material in heavy-metal contaminated soil and loads the carrier of strain；
4th step, then planted in the soil of the 3rd step and absorb the plant of heavy metal, and apply nitrogen, phosphorus and potassium fertilizer；When absorption heavy metal
Plant absorption heavy metal after, aerial part is removed, and burning disposal.
2. the restorative procedure of heavy-metal contaminated soil according to claim 1, which is characterized in that the heavy metal pollution
Soil refers to lead, lead or cadmium heavy metal ion contaminated soil；The zeolite refers to cation-modified natural zeolite；It is described
Bonding agent be one or more of polyvinyl alcohol, glycerine or polyethylene glycol mixing；The pore creating material is starch.
3. the restorative procedure of heavy-metal contaminated soil according to claim 1, which is characterized in that the drying course is
10~15h is dried under the conditions of 105~115 DEG C；The roasting is 1~3h of roasting under the conditions of 200~240 DEG C.
4. the restorative procedure of heavy-metal contaminated soil according to claim 1, which is characterized in that the composition of plating medium
It is：Peptone 5g, glucose 5g, yeast powder 5g, dipotassium hydrogen phosphate 4g, beef extract 10g, distilled water 1000ml；Fermentation medium
Composition be：10.6 g/L of starch, 13.5 g/L of soy meal, 6.7 g/L of fish meal, 2.72 g/L of dipotassium hydrogen phosphate, biphosphate
0.312 g/L of sodium, 0.2 g/L of calcium carbonate, 0.74 g/L of 0.169 g/L of manganese sulfate, 0.34 g/L of sodium nitrate and magnesium sulfate.
5. the restorative procedure of heavy-metal contaminated soil according to claim 1, which is characterized in that composite bacteria liquid is carried with bacterium solution
The weight ratio of body is 1：3~5；Bacterium solution carrier is degradable macromolecule porous resin.
6. the restorative procedure of heavy-metal contaminated soil according to claim 7, which is characterized in that degradable macromolecule is porous
Resin is polymethacrylate resin；The preparation method of the polymethacrylate resin is：By weight, in acrylic acid
10wt% sodium hydroxide solutions are added dropwise in 120~130 parts until pH is 6.0~6.5, as acrylic acid solution；20~24 parts are taken again
Xylitol and 30~35 parts of acrylamide be uniformly mixed, then 12~15 parts of 15wt% glutaraldehyde water solutions and 3~6 parts are added dropwise
Pore-foaming agent toluene, 20~30min is reacted at 65~75 DEG C, after having reacted, then acrylic acid solution is added, is added simultaneously
1~5 part of crosslinking agent N-N ' methylene-bisacrylamides are warming up to after 70~75 DEG C of 45~60min of progress polymerisation, cold
But, and solid is filtered out, solid passes through successively after the washing of ethyl alcohol and deionized water, and vacuum drying obtains porous adsorption resin.
7. the restorative procedure of heavy-metal contaminated soil according to claim 1, which is characterized in that absorb the plant of heavy metal
It is that gold leaf Chang is thin；The addition of the carrier of porous, inorganic sorbing material and load strain in the soil is the 2 of soil weight respectively
~4 and 3~5%.
8. the restorative procedure of heavy-metal contaminated soil according to claim 1, which is characterized in that the applied amount of nitrogen, phosphorus and potassium fertilizer
It is：Based on N, nitrogenous fertilizer is 200~300kg/hm3；By P2O5Meter, phosphate fertilizer are 30~60 kg/hm3；By K2O count, potash fertilizer be 100~
120 kg/hm3。
9. a kind of renovation agent for heavy-metal contaminated soil, which is characterized in that the renovation agent is described in claim 1
Porous, inorganic sorbing material and load strain carrier collectively form.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810322372.4A CN108580529B (en) | 2018-04-11 | 2018-04-11 | Remediation method for heavy metal contaminated soil |
| CN202010386240.5A CN111410966A (en) | 2018-04-11 | 2018-04-11 | Remediation agent for heavy metal contaminated soil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810322372.4A CN108580529B (en) | 2018-04-11 | 2018-04-11 | Remediation method for heavy metal contaminated soil |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010386240.5A Division CN111410966A (en) | 2018-04-11 | 2018-04-11 | Remediation agent for heavy metal contaminated soil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108580529A true CN108580529A (en) | 2018-09-28 |
| CN108580529B CN108580529B (en) | 2020-07-03 |
Family
ID=63621993
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010386240.5A Withdrawn CN111410966A (en) | 2018-04-11 | 2018-04-11 | Remediation agent for heavy metal contaminated soil |
| CN201810322372.4A Active CN108580529B (en) | 2018-04-11 | 2018-04-11 | Remediation method for heavy metal contaminated soil |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010386240.5A Withdrawn CN111410966A (en) | 2018-04-11 | 2018-04-11 | Remediation agent for heavy metal contaminated soil |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN111410966A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109852393A (en) * | 2019-01-07 | 2019-06-07 | 黑龙江大学 | A kind of water-retaining type heavy-metal contaminated soil repairs the preparation method and applications of particle |
| CN110280583A (en) * | 2019-06-17 | 2019-09-27 | 广西师范大学 | A kind of method that enterobacteria-water pepper joint repairs soil polluted by manganese |
| CN110340123A (en) * | 2019-07-15 | 2019-10-18 | 北京淖尔科技有限公司 | A kind of administering method and device of the Compound Heavy Metals soil of Highways ' |
| CN112427453A (en) * | 2020-10-30 | 2021-03-02 | 杨志恒 | Plant-combined microorganism remediation method for arsenic-polluted farmland soil |
| CN112473619A (en) * | 2020-12-08 | 2021-03-12 | 句容康泰膨润土有限公司 | Efficient and environment-friendly organic-inorganic composite bentonite material |
| CN114410509A (en) * | 2021-12-27 | 2022-04-29 | 中南大学 | Bacterium agent and composition of enterobacter aerogenes combined klebsiella aerogenes and application of bacterium agent and composition |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111979159A (en) * | 2020-09-03 | 2020-11-24 | 中南大学 | Phosphate solubilizing bacterium agent and preparation method and application thereof |
| CN112588816B (en) * | 2020-10-27 | 2022-08-30 | 浙江海洋大学 | Remediation method of heavy metal contaminated soil |
| CN115161033A (en) * | 2022-07-22 | 2022-10-11 | 山东金铎农业科技有限公司 | Water storage agent and application thereof in arid and semi-arid soil |
| CN115634659B (en) * | 2022-10-31 | 2023-06-23 | 生态环境部南京环境科学研究所 | Soil restoration agent based on modified nano zero-valent iron and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103159532A (en) * | 2011-12-08 | 2013-06-19 | 东北林业大学 | Porous lignin particle composite fertilizer preparation method |
| CN106281336A (en) * | 2015-05-14 | 2017-01-04 | 北京市农林科学院 | Heavy metal passivation compositions and application thereof |
| CN106431326A (en) * | 2016-09-27 | 2017-02-22 | 甘肃华晨生态治理有限公司 | Production method of multifunctional quincunx red mud light through-hole ceramsite |
| CN107043274A (en) * | 2017-01-17 | 2017-08-15 | 安徽理工大学 | It is a kind of with large dosage, low cost, the preparation method of high-performance porous ceramics |
| CN107686425A (en) * | 2017-07-13 | 2018-02-13 | 赵郁玺 | A kind of gardens are modified fertilizer and preparation method thereof with soil remediation |
| CN107827485A (en) * | 2017-11-13 | 2018-03-23 | 淮阴师范学院 | A kind of bio-bacterial manure, preparation method and its application in soil phosphorus decomposing |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103272836B (en) * | 2013-06-09 | 2015-04-29 | 湖南农业大学 | Red mud composite material and repairing method thereof for soil |
| CN107384407A (en) * | 2017-08-01 | 2017-11-24 | 中国环境科学研究院 | A kind of cadmium pollution paddy soil passivator and its application |
-
2018
- 2018-04-11 CN CN202010386240.5A patent/CN111410966A/en not_active Withdrawn
- 2018-04-11 CN CN201810322372.4A patent/CN108580529B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103159532A (en) * | 2011-12-08 | 2013-06-19 | 东北林业大学 | Porous lignin particle composite fertilizer preparation method |
| CN106281336A (en) * | 2015-05-14 | 2017-01-04 | 北京市农林科学院 | Heavy metal passivation compositions and application thereof |
| CN106431326A (en) * | 2016-09-27 | 2017-02-22 | 甘肃华晨生态治理有限公司 | Production method of multifunctional quincunx red mud light through-hole ceramsite |
| CN107043274A (en) * | 2017-01-17 | 2017-08-15 | 安徽理工大学 | It is a kind of with large dosage, low cost, the preparation method of high-performance porous ceramics |
| CN107686425A (en) * | 2017-07-13 | 2018-02-13 | 赵郁玺 | A kind of gardens are modified fertilizer and preparation method thereof with soil remediation |
| CN107827485A (en) * | 2017-11-13 | 2018-03-23 | 淮阴师范学院 | A kind of bio-bacterial manure, preparation method and its application in soil phosphorus decomposing |
Non-Patent Citations (3)
| Title |
|---|
| 吴月燕等: "3种植物对重金属富集能力的比较", 《科技通报》 * |
| 慕立义等编著: "《植物化学保护研究方法》", 31 October 1994, 中国农业出版社 * |
| 高积强等编著: "《无机非金属材料制备方法》", 30 September 2009, 西安交通大学出版社 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109852393A (en) * | 2019-01-07 | 2019-06-07 | 黑龙江大学 | A kind of water-retaining type heavy-metal contaminated soil repairs the preparation method and applications of particle |
| CN110280583A (en) * | 2019-06-17 | 2019-09-27 | 广西师范大学 | A kind of method that enterobacteria-water pepper joint repairs soil polluted by manganese |
| CN110340123A (en) * | 2019-07-15 | 2019-10-18 | 北京淖尔科技有限公司 | A kind of administering method and device of the Compound Heavy Metals soil of Highways ' |
| CN112427453A (en) * | 2020-10-30 | 2021-03-02 | 杨志恒 | Plant-combined microorganism remediation method for arsenic-polluted farmland soil |
| CN112473619A (en) * | 2020-12-08 | 2021-03-12 | 句容康泰膨润土有限公司 | Efficient and environment-friendly organic-inorganic composite bentonite material |
| CN114410509A (en) * | 2021-12-27 | 2022-04-29 | 中南大学 | Bacterium agent and composition of enterobacter aerogenes combined klebsiella aerogenes and application of bacterium agent and composition |
| CN114410509B (en) * | 2021-12-27 | 2023-05-26 | 中南大学 | Microbial inoculum, composition and application of gas-producing enterobacter combined Klebsiella oxytoca |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111410966A (en) | 2020-07-14 |
| CN108580529B (en) | 2020-07-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108580529A (en) | A kind of restorative procedure of heavy-metal contaminated soil | |
| CN107488620B (en) | Cadmium-polluted rice field soil microbial passivator | |
| CN109867577B (en) | Liquid organic fertilizer for reducing heavy metal pollution of soil and production method thereof | |
| CN111100652A (en) | Heavy metal contaminated soil remediation agent and preparation method and application method thereof | |
| CN106753392A (en) | A kind of passivator and its preparation and application for administering lead cadmium combined pollution soil | |
| CN106734159A (en) | A kind of restorative procedure of heavy-metal contaminated soil | |
| CN102443399A (en) | Efficient composite powdery soil modifier and preparation method thereof | |
| CN111330970B (en) | Method for reducing bioavailability of heavy metal composite contaminated soil in agricultural land | |
| CN112028713A (en) | Passivator for treating soil arsenic pollution and treatment method | |
| CN112125749A (en) | Composite repairing agent for heavy metal contaminated soil and application method thereof | |
| CN113265362A (en) | Composite microbial inoculum for efficiently converting soil heavy metal chromium as well as preparation method and application thereof | |
| CN106367365A (en) | Microorganism powder product for treating heavy metal polluted saline-alkali soil and manufacturing method thereof | |
| Xie et al. | Advances in research on comprehensive utilization of tea waste | |
| CN104070062A (en) | Microbial in-situ remediation method of heavy metal contaminated soil | |
| CN108329083A (en) | A kind of environmental protection heavy metal-polluted soil renovation agent | |
| CN112342030A (en) | Heavy metal contaminated soil remediation agent and preparation method thereof | |
| CN116656552A (en) | Application of pseudo-intermediate brucella in preparation of microbial inoculum for efficiently adsorbing and converting heavy metals | |
| CN110802107A (en) | Plant adsorption combined remediation method for heavy metal cadmium pollution of acid soil | |
| Winter et al. | Cadmium adsorption by non-living biomass of the semi-macroscopic brown alga, Ectocarpus siliculosus, grown in axenic mass culture and localisation of the adsorbed Cd by transmission electron microscopy | |
| CN109180246A (en) | A kind of biological organic fertilizer and preparation method thereof of efficient degradation heavy metal-polluted soil | |
| CN110282759B (en) | Method for purifying chromium in water body by utilizing interaction of bacillus cereus and Leersia hexandra Swartz | |
| CN110586054B (en) | Adsorbent for removing heavy metals and application thereof | |
| CN110076192B (en) | In-situ remediation method for heavy metal contaminated soil | |
| CN106518393A (en) | Major-element liquid fertilizer containing streptomyces ahygroscopicus metabolites and preparation method of major-element liquid fertilizer | |
| CN107164296B (en) | Method for improving activity of phanerochaete chrysosporium under heavy metal cadmium stress |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20190919 Address after: 210046 Science and Technology Research and Development Base of Maigaoqiao Pioneer Park, Qixia District, Nanjing City, Jiangsu Province, 18 Yinchun Road-Q1916 Applicant after: Nanjing Xiao Xiang Engineering Technology Co., Ltd. Address before: 210002 Nanjing 24 dimensional Environmental Protection Engineering Co., Ltd., 24 floor, Fuxin International Building, 359 Hongwu Road, Qinhuai District, Jiangsu Applicant before: Mao Qiang Ping |
|
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20200611 Address after: 226300 first floor, building 6, Shengfa Science Park, No. 299, Xingyuan Road, Nantong high tech Zone, Nantong City, Jiangsu Province Applicant after: JIANGSU AIJIAFURU SOIL REMEDIATION Co.,Ltd. Address before: 210046 Science and Technology Research and Development Base of Maigaoqiao Pioneer Park, Qixia District, Nanjing City, Jiangsu Province, 18 Yinchun Road-Q1916 Applicant before: NANJING XIAOXIANG ENGINEERING TECHNOLOGY Co.,Ltd. |
|
| TA01 | Transfer of patent application right | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |