CN110340132A - A kind of method that charcoal base Zero-valent Iron cooperates with reparation chromium-polluted soil with microorganism - Google Patents

A kind of method that charcoal base Zero-valent Iron cooperates with reparation chromium-polluted soil with microorganism Download PDF

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Publication number
CN110340132A
CN110340132A CN201910576699.9A CN201910576699A CN110340132A CN 110340132 A CN110340132 A CN 110340132A CN 201910576699 A CN201910576699 A CN 201910576699A CN 110340132 A CN110340132 A CN 110340132A
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chromium
valent iron
charcoal base
soil
polluted soil
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刘伟
吉世明
吴锦华
黄静玲
李平
方战强
朱斌
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Guangdong Zihua Technology Co Ltd
South China University of Technology SCUT
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Guangdong Zihua Technology Co Ltd
South China University of Technology SCUT
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B09DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09CRECLAMATION OF CONTAMINATED SOIL
    • B09C1/00Reclamation of contaminated soil
    • B09C1/002Reclamation of contaminated soil involving in-situ ground water treatment
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B09DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09CRECLAMATION OF CONTAMINATED SOIL
    • B09C1/00Reclamation of contaminated soil
    • B09C1/08Reclamation of contaminated soil chemically
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B09DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09CRECLAMATION OF CONTAMINATED SOIL
    • B09C1/00Reclamation of contaminated soil
    • B09C1/10Reclamation of contaminated soil microbiologically, biologically or by using enzymes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B09DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09CRECLAMATION OF CONTAMINATED SOIL
    • B09C2101/00In situ

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  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Soil Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Water Supply & Treatment (AREA)
  • Hydrology & Water Resources (AREA)
  • Biomedical Technology (AREA)
  • Biotechnology (AREA)
  • General Health & Medical Sciences (AREA)
  • Microbiology (AREA)
  • Molecular Biology (AREA)
  • Mycology (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

The invention discloses a kind of charcoal base Zero-valent Irons to cooperate with the method for repairing chromium-polluted soil with microorganism, is related to the restorative procedure of soil environment, it is intended to be easy to reunite and be oxidized when solving the problems, such as to repair chromium-polluted soil.The method for repairing chromium-polluted soil includes the preparation of charcoal base Zero-valent Iron: biomass being added to soluble iron salting liquid and is modified, is filtered, the biomass of modification by calcination obtains charcoal base Zero-valent Iron repair materials;Strain domestication: it is filtered out from chromium-polluted soil using organic matter and hydrogen as electron donor, Cr VI, ferric iron, sulfate, nitrate and oxygen carry out the dominant bacteria of metabolic activity as electron acceptor and tamed and spread cultivation;It repairs: charcoal base Zero-valent Iron, dominant bacteria is mixed with chromium-polluted soil to be repaired and repaired at normal temperature.This method can not only increase substantially the rate of reduction of Cr VI, reduce the transfer ability and biological effectiveness of chromium, can also improve soil and increase diversity of soil microorganism.

Description

A kind of method that charcoal base Zero-valent Iron cooperates with reparation chromium-polluted soil with microorganism
Technical field
The present invention relates to the restorative procedures of soil environment, and in particular to a kind of charcoal base Zero-valent Iron is cooperateed with microorganism The method for repairing chromium-polluted soil.
Background technique
Chromium is widely used in the industries such as metallurgy, plating, process hides, printing and dyeing as important one of industrial chemicals.Due to The leakage of production process, the not qualified discharge of waste water and diafiltration of chromium residue etc. cause a large amount of chromium to enter place periphery soil Earth and underground water.In soil environment, the form that is primarily present of chromium is trivalent chromium (Cr (III)) and Cr VI (Cr (VI)).Three Valence chromium easily by Soil colloids and minerals matter by absorption, coordination, complexing, precipitating the effects of be fixed in soil, migration and Biological effectiveness is lower.Cr VI is not easy to be adsorbed by soil mineral and colloid and is free in soil gap due to negatively charged, Water-soluble, migration with higher and bioavailability;It has carcinogenesis to human body, and toxicity is 100 times of Cr (III) More than.Meanwhile the existing forms of chromium in the soil also have a significant impact to its toxicity, it can be by soil according to five step continuous extractions The occurrence patterns of middle chromium are divided into water-soluble state, exchange state, carbonate combine state, ferrimanganic reference state, organically combine state and residual form six Kind form.Since the chromium of rear three kinds of forms is substantially fixed in soil particle or mineral, there is higher stability, mainly The chromium of first three form plays toxic effect.
Currently, the reparation of chromium-polluted soil is mainly in accordance with following two approach.One is chromium is removed from soil, or Its concentration is reduced to soil background hereinafter, such as soil improvement by importing soil from other places, phytoremediation.Another kind is to change the presence of chromium in the soil Valence state and form, such as chemical reduction method, biological reducing method, to reduce it in soil-plant and soil-underground water Migration, bio-toxicity and biological effectiveness.This approach because not destroying soil texture, at low cost and easy to operate, be suitable for compared with The reparation of big heavy metal pollution area soil and be taken seriously and be gradually in industry applied.
Carrying out in-situ immobilization to chromium-polluted soil using Nanoscale Iron or Zero-valent Iron is a new skill developed in recent years Art.Fe with bigger serface, strong adsorption capacity and high reproducibility0It can be by absorption, reduction and precipitation by CrO4 2-Also Originally it is that hypotoxicity, the form of indissoluble are fixed in the soil, reaction equation is as follows:
CrO4 2-+Fe0+4H2O→Cr3++Fe3++8OH-
(1-x)Fe3++(x)Cr3++2H2O→Fe(1-x)Cr(x)OOH(s)+3H+
Fe0Directly it can be made to be reduced into Cr (III) to Cr (VI) electron transmission, Fe can also be used0It is generated in corrosion process Fe2+Or H2Cr (VI) is restored.It subsequently generates hydroxide precipitating and ferrochrome sediment is covered on Fe0Surface is coated on life At iron content active mineral in, further decrease the extractibility and biological effectiveness of chromium.But correlative study shows that ferrochrome precipitates Object is deposited on Fe as a kind of inert mineral of indissoluble0Surface can obstruct Fe0With the electron transmission between Cr (VI), sexavalence is hindered The reduction reaction of chromium is until reaction terminating, eventually leads to and be adsorbed on Fe0The Cr (VI) on surface is re-released into soil environment, is made Pollution amelioration effect is had a greatly reduced quality.In addition, Zero-valent Iron large specific surface area, reactivity are high and have magnetic property, make its pole Easy conglomerate, and its to be oxidized tendentiousness very strong, in preservation, transport and reaction process easily by surrounding medium (such as H2O and O2) oxidation, it contacts it with Cr (VI) also and just inactivates.
Summary of the invention
The present invention is easy to reunite when repairing chromium-polluted soil and is oxidized problem for Zero-valent Iron, provides a kind of charcoal Base Zero-valent Iron cooperates with the method for repairing chromium-polluted soil with microorganism.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of method that charcoal base Zero-valent Iron cooperates with reparation chromium-polluted soil with microorganism comprising following steps:
(1) prepared by charcoal base Zero-valent Iron: biomass being added to soluble iron salting liquid and is modified, is filtered, roasting changes Property biomass, obtain charcoal base Zero-valent Iron repair materials;
(2) strain domestication: filtering out from the soil of pollution of chromium place can be using organic matter and hydrogen as electron donor, sexavalence Chromium, ferric iron, sulfate, nitrate and oxygen as electron acceptor carry out metabolic activity dominant bacteria, to dominant bacteria into Row tames and spreads cultivation;
(3) it repairs: charcoal base Zero-valent Iron made from step (1) and step (2) domestication is cultivated into resulting dominant bacteria It is uniformly mixed with chromium-polluted soil to be repaired, water is added to adjust soil moisture content and is repaired at normal temperature.
Further, soluble ferric iron salt described in step (1) is iron chloride, ferric nitrate or ironic citrate.
Further, the concentration of the soluble ferric iron salt is 0.1~1mol/L.
Further, the partial size of the biomass is 0.5~5mm, the biomass and soluble ferric iron salt liquor capacity ratio For 1:5~1:2, mixing time is 4~12h.
Further, step modified described in step (1) is that solution ph is adjusted with ammonium hydroxide to 5~7, the ammonium hydroxide Concentration is 10%.
Further, drying temperature described in step (1) is 70~80 DEG C, 600~800 DEG C of maturing temperature.
Further, obtained charcoal base zero-valent iron particle partial size is 0.3~4mm, and Zero-valent Iron partial size is 0.1~200 μ M, iron content are 0.5~3.5%.
Further, concentration of glucose is 100 in the bacteria culture fluid to spread cultivation in the step (2) to dominant bacteria ~1000mg/L, and strain is tamed using sexavalence Cr E-test, hexavalent chromium concentration is 5~30mg/L.
Further, charcoal base Zero-valent Iron dosage described in step (3) is 0.1~1g/kg, and the dominant bacteria is thrown Dosage is 20~400mg/kg, soil moisture content 50~60%.
Further, chromium-polluted soil pH value described in step (3) is 5~6.5, and partial size is 100~5000 μm, pollution of chromium Concentration is 50~250mg/kg.
Further, repair time is 3~21d in step (3), and temperature is 20~30 DEG C.
Further, roasting described in step (1) carries out under anoxic condition.
Compared with prior art, the invention has the advantages that and the utility model has the advantages that
1. charcoal base Zero-valent Iron of the invention cooperateed with microorganism repair chromium-polluted soil method, with it is cheap and easy to get, Nontoxic, biodegradable charcoal is that matrix loads Zero-valent Iron, and the dispersibility of Zero-valent Iron not only can be improved, can also obstruct Contact of the Zero-valent Iron with oxygen keeps its reduction characteristic, to enhance the activity of Zero-valent Iron, Zero-valent Iron is overcome to repair skill in situ It is easy to reunite in art, oxidation the problem of.In addition, charcoal can provide for microorganism inhabites surface, it is micro- for being alternatively arranged as growth substrate Biology provides energy, improves microbial activity, enhances its rate for restoring Cr (VI).
2. charcoal base Zero-valent Iron of the invention cooperates with the method for repairing chromium-polluted soil with microorganism, microorganism can be consumed The dissolved oxygen that soil crack penetrates into, prevents Zero-valent Iron from directly contacting and being passivated with oxygen, while microorganism can also utilize Zero-valent Iron Corrode the hydrogen generated as the Cr (VI) in electron donor direct-reduction soil, and is acted on by own metabolism by Zero-valent Iron table The Fe of face passivation layer3+It is reduced into the preferable Fe of dissolubility2+, accelerate the corrosion of Zero-valent Iron and the update in surface-active site.Except this Except, microorganism can also be by secreting extracellular polymeric, the Fe of induction zeroth order iron rot release2+Generate lepidocrocite, magnetic iron ore and The high-activity minerals such as patina further promote absorption, reduction and crystallized ability of the Zero-valent Iron to Cr (VI).Pass through charcoal base zero The synergistic effect of valence iron and microorganism can increase substantially the repairing effect of chromium-polluted soil while reducing rehabilitation cost.
3. charcoal base Zero-valent Iron of the invention cooperates with the method for repairing chromium-polluted soil, charcoal (BC) table with microorganism Therefore a large amount of oxygen-content active functional groups of EDS maps have compared with high-cation exchange capacity, can inorganic nutrients in fixing soil simultaneously The surface inhabited is provided for microorganism, and then improves soil fertility and increases Soil Biodiversity.In addition, charcoal and zeroth order There is also light electrolysis effects between iron, can promote zeroth order iron rot and release H2Speed, and then accelerate it in chromium-polluted soil To the absorbing and reducing process of chromium in repair process, the repairing effect of chromium-polluted soil is improved.
Detailed description of the invention:
Fig. 1 is the X-ray diffractogram (XRD) of charcoal base Zero-valent Iron reaction front and back;
Fig. 2 is the scanning electron microscope (SEM) photograph (SEM) before the reaction of charcoal base Zero-valent Iron;
Fig. 3 is the scanning electron microscope (SEM) photograph (SEM) after the reaction of charcoal base Zero-valent Iron;
Fig. 4 is one of the scanning electron microscope (SEM) photograph (SEM) after charcoal base Zero-valent Iron and microorganism concerted reaction;
Fig. 5 is two of the scanning electron microscope (SEM) photograph (SEM) after charcoal base Zero-valent Iron and microorganism concerted reaction;
Fig. 6 is three of the scanning electron microscope (SEM) photograph (SEM) after charcoal base Zero-valent Iron and microorganism concerted reaction.
Specific embodiment:
Technical solution of the present invention is described in further detail below in conjunction with specific embodiments and drawings, but of the invention Embodiment and protection scope are without being limited thereto.
Embodiment 1
0.6g biomass is added in the ferric chloride solution that 100mL concentration is 0.5mol/L, stirs 8h under the conditions of 60rpm It is allowed to uniformly mixed, the ammonium hydroxide that concentration is 10% is then added, adjust pH value of solution to 5~7, filter out biomass and use deionized water Cleaning for several times, in the lower 600 DEG C of roastings 8h of anoxic condition after 80 DEG C of drying, obtains charcoal base Zero-valent Iron repair materials BC-Fe0 (FeCl3)。
0.6g biomass is added in the iron nitrate solution that 100mL concentration is 0.5mol/L, stirs 8h under the conditions of 60rpm It is allowed to uniformly mixed, the ammonium hydroxide that concentration is 10% is then added, adjust solution and adjust pH value of solution to 5~7, filter out biomass and be used in combination Deionized water is cleaned for several times, in the lower 600 DEG C of roastings 8h of anoxic condition after 80 DEG C of drying, obtains charcoal base Zero-valent Iron repair materials BC-Fe0(Fe(NO3)3)。
0.6g biomass is added in the citric acid solution that 100mL concentration is 0.5mol/L, is stirred under the conditions of 60rpm 8h is allowed to uniformly mixed, and the ammonium hydroxide that concentration is 10% is then added, and adjusts solution and adjusts pH value of solution to 5~7, filters out biomass simultaneously It is cleaned for several times with deionized water, in the lower 600 DEG C of roastings 8h of anoxic condition after 80 DEG C of drying, obtains charcoal base Zero-valent Iron and repair material Expect BC-Fe0(FeC6H5O7)。
From the acquisition of pollution of chromium place by chromium-polluted soil 2kg, water use regulation soil moisture content is 60wt%, adds glucose 1g/kg is simultaneously sufficiently mixed with soil sample, with N in anaerobic culture box2:H2:CO2For 85%:10%:5% gaseous mixture in 30 DEG C of items After cultivating 5d under part, 1g/kg glucose matrix is added, adjusting moisture content is 60wt%, in same reaction condition culture 5d. Three periods take out soil after being cultivated, and 1 soil volume clear water is added, is centrifuged after being sufficiently mixed with soil, and it is excellent to obtain chromium reduction Gesture bacterium solution, is examined that it includes iron-reducing bacteria, denitrifying bacterium and sulfatereducting bacterias etc..The chromium restores advantage bacterium solution can be with grape Sugar and hydrogen are electron donor, and Cr VI, nitrate, sulfate and ferric iron carry out metabolic activity as electron acceptor, to six Valence chromium, nitrate and sulfate reduction ability are respectively up to 125mg/ (g MLSS.d), 1000mg/ (g MLSS.d) and 450mg/ (g MLSS.d).For the ability and quantity for further increasing strain reduction of hexavalent chromium, with glucose and hydrogen in anaerobic culture box Gas is cultivated and is spread cultivation as electron donor, in culture solution be added clear water, 1000mg/L glucose, 75mg/L magnesium sulfate, 45mg/L ammonium chloride and 25mg/L dipotassium hydrogen phosphate, and strain is carried out using Cr (VI) E-test (5~25mg/L) Domestication, microorganism concn, which is made, when reduction rate of the strain to the Cr (VI) that concentration in culture solution is 30mg/L reaches 90% is The bacteria suspension of 2g/L.
The chromium-polluted soil that 10g concentration is 200mg/kg is weighed, is moved in 50mL centrifuge tube, soil original soil pH value is 6.2, Water use regulation soil moisture content is 60%, and the bacterium that concentration is 0.25g/kg charcoal base Zero-valent Iron and concentration is 80mg/kg is added Suspension, seals and the stationary culture 14d at 30 DEG C of room temperature after mixing.The amount of reordering deionized water exists after reaction It is centrifuged 10min under the conditions of 4000rpm, measures supernatant chromium concn.
Each repair materials are listed in table 1 to water-soluble state Cr VI in soil/total chromium removal effect.As known from Table 1, at three kinds In the preparation method of charcoal base Zero-valent Iron, the material of ferric nitrate preparation is best to water-soluble state Cr VI/total chromium removal effect, The material of iron chloride preparation takes second place.
Each repair materials of table 1 compare water-soluble state Cr VI in chromium-polluted soil/total chromium removal effect
Embodiment 2
Charcoal base Zero-valent Iron (BC-Fe0(FeCl3)) same as Example 1 with bacteria suspension preparation method.Weigh 10g concentration It for the chromium-polluted soil of 200mg/kg, moves in 50mL centrifuge tube, soil original soil pH value is 6.2, water use regulation soil moisture content It is 60%, the bacteria suspension that concentration is 0.25g/kg Zero-valent Iron or charcoal base Zero-valent Iron and concentration is 80mg/kg is added, mixing is equal It is sealed after even and the stationary culture 14d at 20 DEG C, 25 DEG C and 30 DEG C of room temperature respectively.The amount of reordering deionized water after reaction It is centrifuged 10min under the conditions of 4000rpm, measures supernatant chromium concn;After being repaired by the measurement of multistep continuous extraction in soil The variation of chromium occurrence patterns.
4 kinds of reaction systems are arranged in repair process: 1. blank systems, including blank or chromium-polluted soil and BC individually handle body System;2. microorganism system (Cell), including independent Cell system and Cell+BC system;3. Zero-valent Iron system (Fe0), including list Only Fe0System and independent BC-Fe0System;4. Zero-valent Iron+microorganism system (Fe0+ Cell), including Fe0+ Cell system and BC- Fe0+ Cell system.It, will be through BC-Fe after experiment0System and BC-Fe0Soil after+Cell system reparation is put into -80 DEG C of ice It is taken out after freezing 2h in case, is put into freeze-dryer dry 48h rapidly.Mixture after drying is taken out, in anaerobism gloves Case (N2:H2=95:5) in magnet isolate reaction after ferrous powder granules, while under identical operating conditions collect reaction before Zero-valent iron particle is simultaneously analyzed it using X-ray diffractometer and scanning electron microscope, and the variation of its surface topography and structure is investigated Situation, experimental result is as shown in figs. 1 to 6.
At 30 DEG C, the pollution situation of chromium and the occurrence patterns of chromium are listed in table 2 and table 3 respectively in the soil of reaction front and back.From table 2 It is found that compared to Fe0, BC-Fe0Because dispersibility and inoxidizability are improved, to be mentioned to the removal ability of soil water-soluble state chromium It is 0.6 times high.In BC-Fe0In+Cell system, Zero-valent Iron reaches the removal ability of soil water-soluble state Cr VI and total chromium respectively To 48mg Cr/g Fe0With 67mg Total Cr/g Fe0, than independent Fe0System has been respectively increased 5.9 and 4.6 times.From Fig. 4, Fig. 5 and Fig. 6 can also be seen that under microorganism synergistic effect, the more highly active Fe mineral of Zero-valent Iron Surface Creation are such as fine Iron ore, troilite and patina, these active minerals obtain the ability of Zero-valent Iron absorption, reduction and fixed Cr (VI) significantly It improves on ground.In addition, as known from Table 3, through BC-Fe0+ Cell system repair after, in soil the occurrence patterns of chromium all from high toxicity, can The easy solvent (water-soluble state, exchangeable species and carbonate combine state) of biological utilisation is changed into the fixation of low toxicity evil, difficult biological utilisation State (ferrimanganic reference state, organic and residual form).It can be seen that Zero-valent Iron collaboration microorganism can significantly promote Zero-valent Iron to dirt Contaminate absorption, reduction and the fixed effect of Cr VI in soil.
The pollution situation of chromium is listed in table 4 and table 5 respectively in soil in each reparation system under the conditions of 25 DEG C and 20 DEG C.From table 4 With table 5 it is found that temperature is from when being increased to 25 DEG C for 20 DEG C, Cell system, Fe0System, Fe0+ Cell system and BC-Fe0+ Cell body System has been respectively increased 33%, 10%, 14% and 19% to the removal ability of total chromium.It can be seen that temperature change is to Cell system It is affected, takes second place on Zero-valent Iron+microorganism system influence, to Fe0System influences minimum.
System is respectively repaired at 2 30 DEG C of table to compare water-soluble state Cr VI in chromium-polluted soil/total chromium removal effect
3 charcoal base Zero-valent Iron of table and charcoal base Zero-valent Iron are cooperateed with microorganism repair after chromium occurrence patterns in soil Variation
System is respectively repaired at 4 25 DEG C of table to compare water-soluble state Cr VI in chromium-polluted soil/total chromium removal effect
System is respectively repaired at 5 20 DEG C of table to compare water-soluble state Cr VI in chromium-polluted soil/total chromium removal effect
Embodiment 3
Charcoal base Zero-valent Iron (BC-Fe0(FeCl3)) same as Example 1 with bacteria suspension preparation method.Weigh 10g concentration It for the chromium-polluted soil of 200mg/kg, moves in 50mL centrifuge tube, soil original soil pH value is 6.2, water use regulation soil moisture content It is 60%, the bacterium that concentration is 0.05,0.125,0.25,0.5 or 1g/kg charcoal base Zero-valent Iron and concentration is 80mg/kg is added Suspension, seals and the stationary culture 14d at 30 DEG C of room temperature respectively after mixing.The amount of reordering deionized water after reaction It is centrifuged 10min under the conditions of 4000rpm, measures supernatant chromium concn.As shown in Table 6, charcoal base Zero-valent Iron dosage from 0.05 when increasing to 1g/kg, reacts after 14d to the removal ability of soil water-soluble state Cr VI from 23mg Cr/g Fe0Rise to 53mg Cr/g Fe0, to the removal ability of total chromium from 34mg Total Cr/g Fe0Rise to 79mg Total Cr/g Fe0, but charcoal When base Zero-valent Iron dosage is more than 0.25g/kg, collaboration system is to water-soluble state Cr VI in chromium-polluted soil/total chromium removal energy Power is not obviously improved, and illustrates that microorganism concn is main rate-limiting factor at this time.6 charcoal base Zero-valent Iron dosage pair of table The removal effect comparison of chromium-polluted soil water-soluble state Cr VI/total chromium
Embodiment 4
Charcoal base Zero-valent Iron (BC-Fe0(FeCl3)) same as Example 1 with bacteria suspension preparation method.Weigh 10g concentration It for the chromium-polluted soil of 200mg/kg, moves in 50mL centrifuge tube, soil original soil pH value is 6.2, water use regulation soil moisture content It is 60%, the bacteria suspension that concentration is 0.25g/kg charcoal base Zero-valent Iron and concentration is 20,40,80 or 160mg/kg is added, mixes It is sealed after closing uniformly and the stationary culture 14d at 30 DEG C of room temperature respectively.The amount of reordering deionized water exists after reaction It is centrifuged 10min under the conditions of 4000rpm, measures supernatant chromium concn.As shown in Table 7, microorganism concn increases to 160mg/kg from 20 When, collaboration system is reacted after 14d to the removal ability of soil water-soluble state Cr VI from 26mg Cr/g Fe0Rise to 54mg Cr/g Fe0, to the removal ability of total chromium from 33mg Total Cr/g Fe0Rise to 76mg Total Cr/g Fe0, but microorganism concn When more than 80mg/kg, collaboration system does not mention water-soluble state Cr VI in chromium-polluted soil/total chromium removal ability significantly It rises, illustrate that Zero-valent Iron dosage at this time is the key constraints that chromium removes.
7 microorganism concn of table compares chromium-polluted soil water-soluble state Cr VI/total chromium removal effect
The foregoing is only a preferred embodiment of the present invention, is not intended to limit the present invention in any form.It is all Those skilled in the art, it should be appreciated that the above embodiments and description only describe the principles of invention, are not taking off Under the premise of the technology of the present invention spirit and scope, the present invention also has an equivalent variations of a little variation, modification and evolution, it is all according to According to the variation, modification and evolution etc. of substantial technological any equivalent variations made to the above embodiment of the invention, should all include Within the scope of the present invention.

Claims (10)

1. a kind of charcoal base Zero-valent Iron cooperates with the method for repairing chromium-polluted soil with microorganism, which is characterized in that including following Step:
(1) prepared by charcoal base Zero-valent Iron: biomass is added into soluble iron salting liquid and is modified, is filtered, modification by calcination Biomass obtains charcoal base Zero-valent Iron repair materials;
(2) strain domestication: filtered out from the soil of pollution of chromium place can using organic matter and hydrogen as electron donor, Cr VI, Ferric iron, sulfate, nitrate and oxygen carry out the dominant bacteria of metabolic activity as electron acceptor, carry out to dominant bacteria tame and docile Change and spreads cultivation;
(3) repair: by charcoal base Zero-valent Iron made from step (1) and step (2) tame and spread cultivation resulting dominant bacteria with Chromium-polluted soil to be repaired is uniformly mixed, and is added water to adjust soil moisture content and is repaired at normal temperature.
2. a kind of charcoal base Zero-valent Iron according to claim 1 cooperates with the method for repairing chromium-polluted soil with microorganism, It is characterized by: soluble iron salinity described in step (1) is 0.1~1mol/L, the soluble ferric iron salt is iron chloride, nitre Sour iron or ironic citrate.
3. a kind of charcoal base Zero-valent Iron according to claim 1 or 2 cooperates with the side for repairing chromium-polluted soil with microorganism Method, it is characterised in that: the partial size of biomass described in step (1) is 0.5~5mm, biomass and soluble ferric iron salt liquor capacity Than for 1:5~1:2.
4. a kind of charcoal base Zero-valent Iron according to claim 1 cooperates with the method for repairing chromium-polluted soil with microorganism, It is characterized by: drying temperature described in step (1) is 70~80 DEG C, 600~800 DEG C of maturing temperature.
5. a kind of charcoal base Zero-valent Iron according to claim 1 cooperates with the method for repairing chromium-polluted soil with microorganism, It is characterized by: the partial size of obtained charcoal base zero-valent iron particle is 0.3~4mm, Zero-valent Iron partial size is 0.1~200 μm, iron Content is 0.5~3.5%.
6. a kind of charcoal base Zero-valent Iron according to claim 1 cooperates with the method for repairing chromium-polluted soil with microorganism, It is characterized by: in the bacteria culture fluid to spread cultivation in the step (2) to dominant bacteria concentration of glucose be 100~ 1000mg/L, and strain is tamed using sexavalence Cr E-test, hexavalent chromium concentration is 5~30mg/L.
7. a kind of charcoal base Zero-valent Iron according to claim 1 cooperates with the method for repairing chromium-polluted soil with microorganism, It is characterized by: charcoal base Zero-valent Iron dosage described in step (3) is 0.1~1g/kg, the dominant bacteria dosage is 20~400mg/kg, soil moisture content 50~60%.
8. a kind of charcoal base Zero-valent Iron according to claim 1 cooperates with the method for repairing chromium-polluted soil with microorganism, It is characterized by: chromium-polluted soil pH value described in step (3) is 5~6.5, partial size is 100~5000 μm, and pollution of chromium concentration is 50~250mg/kg.
9. a kind of charcoal base Zero-valent Iron according to claim 1 cooperates with the method for repairing chromium-polluted soil with microorganism, It is characterized by: in step (3) repair time be 3~21d, temperature be 20~30 DEG C.
10. a kind of charcoal base Zero-valent Iron according to claim 1 cooperates with the method for repairing chromium-polluted soil with microorganism, It is characterized by: roasting described in step (1) carries out under anoxic condition.
CN201910576699.9A 2019-06-28 2019-06-28 A kind of method that charcoal base Zero-valent Iron cooperates with reparation chromium-polluted soil with microorganism Pending CN110340132A (en)

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CN110713250A (en) * 2019-10-30 2020-01-21 生态环境部环境规划院 Preparation method of Fe-Cu bimetallic tourmaline synergistic microorganism Cr (VI) removing filler
CN111777186A (en) * 2020-07-10 2020-10-16 北京伦至环境科技有限公司 Anti-blocking zero-valent iron coupling response type slow-release persulfate two-stage permeable reaction wall device and application
CN112143505A (en) * 2020-08-31 2020-12-29 华南理工大学 Cadmium-polluted soil and underground water repairing agent and method for repairing cadmium-polluted soil and underground water by using same
CN113149230A (en) * 2021-02-26 2021-07-23 中南大学 Treatment method for reducing hexavalent chromium by wood charcoal electron transfer enhanced microorganisms
CN113694882A (en) * 2020-05-22 2021-11-26 中国环境科学研究院 Preparation method of bulk phase loaded zero-valent iron biochar material
CN113695385A (en) * 2020-05-23 2021-11-26 中国环境科学研究院 Microbial remediation method for heavy metals in soil layer of agricultural activity area
CN113711723A (en) * 2020-05-24 2021-11-30 中国环境科学研究院 Microbial remediation method for organic pesticide in soil layer of agricultural activity area
CN114232590A (en) * 2021-12-20 2022-03-25 上海毅同环境技术有限公司 Risk control method for hexavalent chromium polluted land by combining vertical partition wall and modified microbial complexing agent
CN114309029A (en) * 2021-12-06 2022-04-12 华南理工大学 Method for repairing polluted soil by using modified biochar in cooperation with protozoon and application of method
CN114433610A (en) * 2020-10-30 2022-05-06 中国环境科学研究院 Water and soil co-treatment method for composite pollution region
CN114990046A (en) * 2022-05-27 2022-09-02 天津科技大学 Biochar-based three-dimensional composite material and method for repairing high-concentration chromium-polluted soil by biochar-based three-dimensional composite material
CN115072936A (en) * 2022-07-12 2022-09-20 国环电池科技(苏州)有限公司 Method for removing hexavalent chromium and total chromium in water by using activated sludge
CN115340194A (en) * 2022-08-09 2022-11-15 华中科技大学 Method for removing hexavalent chromium by sludge iron-rich biochar and pseudomonas aeruginosa in synergistic manner

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CN110713250A (en) * 2019-10-30 2020-01-21 生态环境部环境规划院 Preparation method of Fe-Cu bimetallic tourmaline synergistic microorganism Cr (VI) removing filler
CN113694882A (en) * 2020-05-22 2021-11-26 中国环境科学研究院 Preparation method of bulk phase loaded zero-valent iron biochar material
CN113694882B (en) * 2020-05-22 2023-03-10 中国环境科学研究院 Preparation method of bulk phase loaded zero-valent iron biochar material
CN113695385A (en) * 2020-05-23 2021-11-26 中国环境科学研究院 Microbial remediation method for heavy metals in soil layer of agricultural activity area
CN113695385B (en) * 2020-05-23 2022-11-01 中国环境科学研究院 Microbial remediation method for heavy metals in soil layer of agricultural activity area
CN113711723A (en) * 2020-05-24 2021-11-30 中国环境科学研究院 Microbial remediation method for organic pesticide in soil layer of agricultural activity area
CN111777186A (en) * 2020-07-10 2020-10-16 北京伦至环境科技有限公司 Anti-blocking zero-valent iron coupling response type slow-release persulfate two-stage permeable reaction wall device and application
CN112143505A (en) * 2020-08-31 2020-12-29 华南理工大学 Cadmium-polluted soil and underground water repairing agent and method for repairing cadmium-polluted soil and underground water by using same
CN114433610A (en) * 2020-10-30 2022-05-06 中国环境科学研究院 Water and soil co-treatment method for composite pollution region
CN113149230B (en) * 2021-02-26 2022-04-19 中南大学 Treatment method for reducing hexavalent chromium by wood charcoal electron transfer enhanced microorganisms
CN113149230A (en) * 2021-02-26 2021-07-23 中南大学 Treatment method for reducing hexavalent chromium by wood charcoal electron transfer enhanced microorganisms
CN114309029A (en) * 2021-12-06 2022-04-12 华南理工大学 Method for repairing polluted soil by using modified biochar in cooperation with protozoon and application of method
CN114232590A (en) * 2021-12-20 2022-03-25 上海毅同环境技术有限公司 Risk control method for hexavalent chromium polluted land by combining vertical partition wall and modified microbial complexing agent
WO2023226271A1 (en) * 2022-05-27 2023-11-30 天津科技大学 Biochar-based three-dimensional composite material and method for remediating high-concentration chromium-contaminated soil
CN114990046A (en) * 2022-05-27 2022-09-02 天津科技大学 Biochar-based three-dimensional composite material and method for repairing high-concentration chromium-polluted soil by biochar-based three-dimensional composite material
CN114990046B (en) * 2022-05-27 2024-04-02 天津科技大学 Biochar-based three-dimensional composite material and method for repairing high-concentration chromium-polluted soil by using same
CN115072936A (en) * 2022-07-12 2022-09-20 国环电池科技(苏州)有限公司 Method for removing hexavalent chromium and total chromium in water by using activated sludge
CN115072936B (en) * 2022-07-12 2024-02-27 华辰环保能源(广州)有限责任公司 Method for removing hexavalent chromium and total chromium in water by using activated sludge
CN115340194A (en) * 2022-08-09 2022-11-15 华中科技大学 Method for removing hexavalent chromium by sludge iron-rich biochar and pseudomonas aeruginosa in synergistic manner
CN115340194B (en) * 2022-08-09 2023-12-26 华中科技大学 Method for cooperatively removing hexavalent chromium by sludge iron-rich biochar and pseudomonas aeruginosa

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