CN110436728A - A kind of method that new iron-based material collaboration microorganism in situ stabilizes remediating lead-contaminated bed mud - Google Patents
A kind of method that new iron-based material collaboration microorganism in situ stabilizes remediating lead-contaminated bed mud Download PDFInfo
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- CN110436728A CN110436728A CN201910876916.6A CN201910876916A CN110436728A CN 110436728 A CN110436728 A CN 110436728A CN 201910876916 A CN201910876916 A CN 201910876916A CN 110436728 A CN110436728 A CN 110436728A
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- iron
- based material
- bed mud
- lead
- stabilizes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/008—Sludge treatment by fixation or solidification
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/02—Biological treatment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/007—Contaminated open waterways, rivers, lakes or ponds
Abstract
The invention discloses methods and reagent that a kind of new iron-based material collaboration microorganism in situ stabilizes remediating lead-contaminated bed mud.Reagent includes iron-based material and sulfate reducing bacteria bacterium solution, and the iron-based material in an aqueous medium is reacted to obtain with oxalic acid by Iron containing silicate minerals at a temperature of 55~120 DEG C.It adds reagent in lead contamination bed mud, the immobilization efficiency of lead is repaired 97% or more using mode in situ, is not necessarily to extra means, and high-efficient, at low cost, without secondary pollution to the stabilisation of lead.
Description
Technical field
The present invention relates to a kind of lead (II) polluted bed muds to repair reagent, in particular to a kind of iron-based material cooperates with microorganism pair
It is raw to belong to heavy-metal contaminated soil for the reagent of lead (II) polluted bed mud reparation and the reagent and method of lead (II) polluted bed mud reparation
State recovery technique field.
Background technique
With the fast development of domestic economy and society, brought heavy metal pollution problem has caused various circles of society
Strong interest.Lead is distributed more widely in heavy metal pollution, the strong bio-toxicity heavy metal of accumulating capability, lead contamination main source
Using and burn in mining, smelting and processing of metals, IT manufacture, sanitary sewage discharge and doped fuel, at home,
Annual lead discharge amount is about 60,000 tons, and the discharge of lead waste water easily leads to deposition of the lead in bed mud.
Lead in bed mud is contacted with water flow for a long time, and it is unstable for leading to the chemical state of lead, thus often become river,
The main channel of pollution of waterhead.Lead has strong cumulative bad, by the enrichment of food chain, lead in human body can in conjunction with a variety of enzymes from
And the various physiological activities of organism are interfered, the serious nerve for damaging people, digestion, immune and reproductive system, to human health
It threatens, the lead of low dosage just will affect the nervous centralis and skeleton development of people.Therefore, in bed mud lead contamination problem and its
Reparation has become one of the problem of extensive concern.
The repair mode of lead contamination bed mud mainly includes showering and in-situ immobilization.Showering is due to high cost and work
The features such as journey amount is big is only applicable to small area, sudden serious pollution soil, and in-situ immobilization is a kind of economical, efficient, reasonable
And sustainable Treatment process.In-situ remediation method mainly includes peripheral doses, biological prosthetic, chemical remediation etc..
Chemical restoration adsorbs heavy metal, redox, the drop such as precipitating by selecting suitable soil conditioner
The biological effectiveness of low heavy metal becomes contaminated soil remediation in recent years due to the easy to operate and quick characteristic of improvement
Research hotspot, but because the additional of chemical reagent be easier to cause secondary pollution.Therefore, a kind of low in cost, preparation is found
Simple and environmental-friendly chemical reagent or material is the key that chemical restoration.
Microorganism remediation as biological prosthetic one of main method, refer to by microorganism be added pollution environment in, thus
So that heavy metal is transformed into reference state by free state, reaches the method for the remediating lead-contaminated bed mud of fixing/stabilising.Microbial remediation method
Processing cost is low, to surrounding enviroment disturb it is small, do not generate secondary pollution, but suitable microorganism resource is few, and repairing effect is not aobvious enough
It writes.Sulfate reducing bacteria is a kind of strictly anaerobic microorganism that growth metabolism is carried out using sulfate, and the sulfide of generation can be consolidated
Therefore fixed all kinds of heavy metal cations are a kind of microbial inoculums of good heavy metal polluted bed mud fixation in situ reparation.
On the other hand, since bed mud environmental condition is complicated, for example oxygen content is low, flowing transport is big and disturbing factor is more
Deng single restorative procedure tends not to reach good repairing effect, and therefore, it is necessary to combine two or more method
Curing/stabilizing reparation is carried out to lead contamination bed mud, good reparation index can be reached in this way, be also able to achieve the optimization of resource
Configuration.
Summary of the invention
Defect existing for associated restoration technology for existing lead contamination river bottom mud, the first purpose of this invention be
It can be realized the reagent that lead is efficiently repaired in lead contamination bed mud in providing a kind of iron-based material coupling microorganism, the bed mud earth reparation
Reagent cost of material is low, is easily obtained, and is particularly suitable for lead contamination river 97% or more to the coefficient of stabilization of the lead of lead contamination bed mud
The continual and steady reparation of road bed mud.
Second object of the present invention is to be to provide a kind of new iron-based material collaboration microorganism in situ stabilisation reparation
The method of lead contamination bed mud, this method is by using iron-based material collaboration microorganism lead contamination bottom sediment stabilizing agent to lead contamination
The coefficient of stabilization of lead is 97% or more in bed mud.
In order to achieve the above technical purposes, the present invention provides a kind of new iron-based material collaboration microorganism in situ to stabilize
The reagent of remediating lead-contaminated bed mud comprising iron-based material and sulfate reducing bacteria bacterium solution；The iron-based material is by iron content silicic acid
Salt mineral react to obtain at a temperature of 55~120 DEG C in an aqueous medium with oxalic acid.
Preferred scheme, the Iron containing silicate minerals include biotite, iron aluminium garnet, staurolite, fayalite,
At least one of vesuvian, orthoferrosilite, aegirine, hedenbergite, cummingtonite, osannite.These Iron containing silicate minerals
After being reacted with oxalic acid, ferrous oxalate complex compound sediment is generated, is supported on silicate mineral in situ, realizes ferrous oxalate complex compound
Steady load and dispersion.
Preferred scheme, the Iron containing silicate minerals partial size are 45~150 μm.
The liquid-solid ratio of preferred scheme, Iron containing silicate minerals and oxalic acid and water is 2~5mL:1g, Iron containing silicate minerals
It is 1:2~3:1 with oxalic acid mass ratio.
Preferred scheme, reaction time are 0.5~48h.
The ratio of preferred scheme, iron-based material and sulfate reducing bacteria bacterium solution is 20~100g/10~500mL, sulfuric acid
Active strain density is 10 in salt reducing bacteria bacterium solution6~1010A/mL.
The present invention also provides a kind of new iron-based material collaboration microorganism in situ to stabilize remediating lead-contaminated bed mud, the party
Method is added reagent on into lead contamination bed mud, maintenance.
Sulfate reducing bacteria bacterium solution of the invention is direct purchase strain Desulfovibrio (Desulfovibrio
Sp.ATCC 7757) it is obtained by simply expanding culture.The culture medium prescription used is KH2PO40.5g/L,NH4Cl 1g/L,
CaCl2 0.1g/L,MgSO4·7H2O 2.5g/L, sodium lactate 3.5g/L, pH value 6.5.Culture is to logarithmic phase, for use.
Preferred scheme, iron-based material is 20~100g/kg with respect to the additive amount of lead contamination bed mud in reagent, and sulfate is also
Opportunistic pathogen bacterium solution is 10~500mL/kg with respect to the additive amount of lead contamination bed mud.
Preferred scheme, for repair process controlled at 15~35 DEG C, the time is 7~60 days.
Lead content is 50~2000mg/kg in the lead contamination bed mud that the present invention adapts to.
The principle of the iron-based material collaboration remediating lead-contaminated bed mud of microorganism lead contamination bottom sediment stabilizing agent of the invention are as follows:
The present invention is based on the interactions of Iron containing silicate minerals and oxalic acid, using the ferrous components in oxalic acid activation iron-bearing mineral, simultaneously
Solidify oxalate, the iron-based material of silicate mineral load ferrous oxalate active constituent is generated, because of the k of lead oxalatespGreater than grass
Sour ferrous ksp, so lead oxalate precipitating can be generated based on the ion exchange between ferrous and lead ion, and then solidify lead, another party
Face, the oxalate anion in iron-based material can be used as electron donor and utilize for Growth of Sulfate Reducing Bacteria, and further drive
The stabilisation reparation of lead in dynamic lead contamination bed mud, meanwhile, the hydrogen sulfide that sulfate reducing bacteria metabolism generates can vulcanize grass simultaneously
The iron discharged in sour ferrous iron, the ferrous sulfide of formation can further be reacted with the lead in bed mud, and lead is caused to be transformed by free state
Stable residual form.In summary, it is based on synergistic effect system, the continuous coupled joint of chemistry-microbial-chemical can be constructed
Reparation system can promote the stabilisation reparation of the High-efficiency Sustainable in situ of lead contamination bed mud.
Compared with the prior art, technical solution of the present invention advantage is embodied in:
1) lead contamination bottom sediment stabilizing agent of the invention is at low cost, and iron-based material can simply be closed by natural minerals
At sulfate reducing bacteria is directly commercially available.
2) lead contamination bottom sediment stabilizing agent of the invention passes through the collaboration coupling between sulfate reducing bacteria and iron-based material
Left and right is closed, lead contamination bed mud is able to achieve and continues efficiently to repair, the coefficient of stabilization of lead significantly reduces lead 97% or more in bed mud
Migration, improve the bioavailability of bed mud, especially adapt to lead contamination bed mud continual and steady reparation.
3) operation is simple for lead contamination remedying sludge method of the invention, and rehabilitation cost is low, environment friendly and pollution-free, can apply
In large-scale lead contamination bed mud, have a extensive future.
Specific embodiment
Following embodiment is intended to further illustrate the content of present invention, rather than limits the protection model of the claims in the present invention
It encloses.
Embodiment 1
Lead contamination bed mud is derived from Zhuzhou Xiang River section clear water pool bed mud, and sample air-dries sieving (60 mesh), and Basic Characteristics are shown in
Table 1.
1 bed mud fundamental property of table
| pH | 7.8 |
| Organic carbon (g/kg) | 7.88 |
| Organic matter (g/kg) | 13.59 |
| Cation exchange capacity (CEC) CEC (cmol/kg) | 21.6 |
| Total lead (mg/kg) | 733.68 |
The preparation of iron-based material: fayalite and two oxalic acid hydrates being mixed according to 2: 1 ratio, are placed in reactor,
It is 4: 1 addition deionized waters according to liquid-solid ratio, after sealing, is warming up to 90 DEG C of reaction 36h and washs, filter and dry after the reaction was completed
It is dry.
The culture of sulfate reducing bacteria: Desulfovibrio sp.ATCC 7757 is inoculated in anaerobic culture medium
(KH2PO40.5g/L,NH4Cl 1g/L,CaCl2 0.1g/L,MgSO4·7H2O 2.5g/L, sodium lactate 3.5g/L) in, pH value tune
Section is 6.5, spare after growing to logarithmic phase, and the cell density of bacterium solution is 2*108A/mL.
Simulate the reparation of lead contamination bed mud in anaerobic environment.Reparative experiment carries out in the reactor of 5L, in reactor first
The bed mud sample of 1kg and the deionized water of 2L are added afterwards, and is divided into tetra- groups of A, B, C and D.The deionized water that 0.5L is added in A group is made
For blank control, the iron-based material of 50g is added in B group, and the sulfate reducing bacteria bacterium solution of 0.5L is added in C group, and the iron of 50g is added in D group
The bacterium solution of sill and 0.5L.After anti-30d is repaired in simulation, the Lead speciation variation in sample is measured, the results are shown in Table 2.
Metamorphosis before and after 2 lead contamination bed mud immobilized reactant of table
Embodiment 2
Sample is in the same manner as in Example 1.
The preparation of iron-based material: biotite and two oxalic acid hydrates are mixed according to 3: 2 ratio, are placed in reactor, foundation
Liquid-solid ratio is 5: 1 addition deionized waters, after sealing, is warming up to 80 DEG C of reaction 12h and washs, filters and dry after the reaction was completed.
The culture of sulfate reducing bacteria: Desulfovibrio sp.ATCC 7757 is inoculated in anaerobic culture medium
(KH2PO40.5g/L,NH4Cl 1g/L,CaCl2 0.1g/L,MgSO4·7H2O 2.5g/L, sodium lactate 3.5g/L) in, pH value tune
Section is 6.5, spare after growing to logarithmic phase, and the cell density of bacterium solution is 3.2*108A/mL.
Simulate the reparation of lead contamination bed mud in anaerobic environment.Reparative experiment carries out in the reactor of 10L, in reactor first
The bed mud sample of 2kg and the deionized water of 4L are added afterwards, and is divided into tetra- groups of A, B, C and D.The deionized water conduct of A group addition 1L
The iron-based material of 100g is added in blank control, B group, and the sulfate reducing bacteria bacterium solution of 1L is added in C group, and the iron-based of 100g is added in D group
The bacterium solution of material and 1L.After reaction 90d is repaired in simulation, the Lead speciation variation in sample is measured, the results are shown in Table 3.
Embodiment 3
Sample is in the same manner as in Example 1.
The preparation of iron-based material: staurolite and two oxalic acid hydrates are mixed according to 1: 2 ratio, are placed in reactor, foundation
Liquid-solid ratio is 4: 1 addition deionized waters, after sealing, is warming up to 90 DEG C of reactions for 24 hours, after the reaction was completed, washs, filters and dry.
Metamorphosis before and after 3 lead contamination bed mud immobilized reactant of table
The culture of sulfate reducing bacteria: Desulfovibrio sp.ATCC 7757 is inoculated in anaerobic culture medium
(KH2PO40.5g/L,NH4Cl 1g/L,CaCl2 0.1g/L,MgSO4·7H2O 2.5g/L, sodium lactate 3.5g/L) in, pH value tune
Section is 6.5, spare after growing to logarithmic phase, and the cell density of bacterium solution is 3*108A/mL.
Simulate the reparation of lead contamination bed mud in anaerobic environment.Reparative experiment carries out in the reactor of 10L, in reactor first
The bed mud sample of 2kg and the deionized water of 4L are added afterwards, and is divided into tetra- groups of A, B, C and D.The deionized water that 0.5L is added in A group is made
For blank control, the iron-based material of 100g is added in B group, and the sulfate reducing bacteria bacterium solution of 0.5L is added in C group, and D group is added 100g's
The bacterium solution of iron-based material and 0.5L.After reaction 60d is repaired in simulation, the Lead speciation variation in sample is measured, the results are shown in Table 4.
Metamorphosis before and after 4 lead contamination bed mud immobilized reactant of table
| Experimental group | Acid extractable (%) | It can reduction-state (%) | Oxidable state (%) | Residual form (%) |
| Primary sample | 57.83 | 20.42 | 6.32 | 15.43 |
| A | 55.28 | 24.81 | 5.82 | 14.09 |
| B | 23.02 | 26.93 | 9.17 | 40.88 |
| C | 18.71 | 7.62 | 10.34 | 63.33 |
| D | 2.91 | 1.68 | 9.62 | 85.79 |
Claims (9)
1. the reagent that a kind of new iron-based material collaboration microorganism in situ stabilizes remediating lead-contaminated bed mud, it is characterised in that: packet
Include iron-based material and sulfate reducing bacteria bacterium solution；
The iron-based material in an aqueous medium is reacted to obtain with oxalic acid by Iron containing silicate minerals at a temperature of 55~120 DEG C.
2. a kind of new iron-based material collaboration microorganism in situ according to claim 1 stabilizes remediating lead-contaminated bed mud
Reagent, it is characterised in that: the Iron containing silicate minerals include biotite, iron aluminium garnet, staurolite, fayalite, symbol
At least one of mountain stone, orthoferrosilite, aegirine, hedenbergite, cummingtonite, osannite.
3. a kind of new iron-based material collaboration microorganism in situ according to claim 1 stabilizes remediating lead-contaminated bed mud
Reagent, it is characterised in that: the Iron containing silicate minerals partial size is 45~150 μm.
4. a kind of new iron-based material collaboration microorganism in situ according to claim 1 stabilizes remediating lead-contaminated bed mud
Reagent, it is characterised in that: the liquid-solid ratio of Iron containing silicate minerals and oxalic acid and water is 2~5mL:1g, Iron containing silicate minerals and
Oxalic acid mass ratio is 1:2~3:1.
5. a kind of new iron-based material collaboration microorganism in situ according to any one of claims 1 to 4, which stabilizes, repairs lead
The reagent of polluted bed mud, it is characterised in that: the reaction time is 0.5~48h.
6. a kind of new iron-based material collaboration microorganism in situ according to any one of claims 1 to 4, which stabilizes, repairs lead
The reagent of polluted bed mud, it is characterised in that: the ratio of iron-based material and sulfate reducing bacteria bacterium solution be 20~100g/10~
500mL, wherein active strain density is 10 in sulfate reducing bacteria bacterium solution6~1010A/mL.
7. a kind of method that new iron-based material collaboration microorganism in situ stabilizes remediating lead-contaminated bed mud, it is characterised in that: will
Any one of claim 1~6 reagent is added in lead contamination bed mud, is repaired.
8. a kind of new iron-based material collaboration microorganism in situ according to claim 7 stabilizes remediating lead-contaminated bed mud
Method, it is characterised in that: iron-based material is 20~100g/kg, sulfate reduction with respect to the additive amount of lead contamination bed mud in reagent
Bacterium bacterium solution is 10~500mL/kg with respect to the additive amount of lead contamination bed mud.
9. a kind of new iron-based material collaboration microorganism in situ according to claim 7 stabilizes remediating lead-contaminated bed mud
Method, it is characterised in that: in repair process, temperature control is 15~35 DEG C, and the time is 7~60 days.
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