CN107377608A - It is a kind of efficiently to remove Cr in acid soil6+Microbial fuel cell unit and method - Google Patents
It is a kind of efficiently to remove Cr in acid soil6+Microbial fuel cell unit and method Download PDFInfo
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- CN107377608A CN107377608A CN201710584197.1A CN201710584197A CN107377608A CN 107377608 A CN107377608 A CN 107377608A CN 201710584197 A CN201710584197 A CN 201710584197A CN 107377608 A CN107377608 A CN 107377608A
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- anode
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- porous carbon
- acid
- fuel cell
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/06—Reclamation of contaminated soil thermally
- B09C1/065—Reclamation of contaminated soil thermally by pyrolysis
Abstract
Cr in acid soil is efficiently removed the invention discloses a kind of6+Microbial fuel cell unit and method, be mainly used in soil pollution and repair field, including porous carbon doping biomembrane anode and carbon felt negative electrode, the anode and negative electrode are spaced-apart to be embedded in Cr6+Connected in the acid soil of pollution and by wire, external load resistance, PEM is laid between anode and cathode or without PEM.The present apparatus is when in use, porous carbon doping biomembrane anode and carbon felt negative electrode are embedded in contaminated soil respectively, substrate in microorganism local use soil is as fuel, caused electronics is gathered in anode, heavy metal Cr VI near anode is reduced, so as to promote the degraded and conversion of acid soil heavy metal hexavalent chromium pollutant.Porous carbon doping biological membrane electrode technical method and MFCs are combined and acid soil are repaired by the present invention, have the advantages that low cost, efficiency high, equipment investment be small, production capacity, have wide market prospects and application value.
Description
Technical field
The invention belongs to heavy metal pollution of soil recovery technique field, and in particular to a kind of Cr VI (Cr6+) pollution acid
The prosthetic device and method of property soil.
Background technology
Acid soil refers to the soil general name that pH value is less than 7.Acid soil harm is a lot, most importantly has a strong impact on soil
Bioactivity and soil texture, are unfavorable for plant growth.In addition, compared in nonacid soil, acid soil heavy metal from
The relative stability difference of son and the bioactivity of heavy metal ion are high.The heavy metal for causing acid soil to pollute mainly includes
Cr, Mn, Cu, As, Cd, Hg, Pb etc., these heavy metals are not easily decomposed, and toxicity is big after people is edible, or even can be with other compound knots
Symphysis is into the bigger secondary pollution of toxicity, wherein especially the most prominent and universal with the toxicity of heavy metal chromium (Cr) and pollution.
After acid soil is by pollution of chromium, soil can be caused seriously to degenerate inactivation, not even a blade of grass grows by severe patient, loses ecological work(
Energy.Therefore the acid soil by pollution of chromium must be repaired.
The atomic number of chromium is 24, molecular weight 51.996, and valence state specifically be present is mostly+2 ,+3 ,+6.The unstable easy oxygen of+divalent
Change ,+trivalent strong acid salt is readily soluble, and+6 valencys are more with chromate (CrO4 2-), bichromate (Cr2O7 2-) based on.Wherein most paid close attention to by everybody
Be Cr VI (Cr6+)。
Cr VI (Cr6+) there is strong toxicity and stronger mutagenesis, carcinogenesis, have to environment persistently dangerous.
Cr VI (Cr6+) soluble in water, permeability is strong, not degradable, and metastatic is strong, easy enriching plant, and it is easy to be inhaled by human body
Receive, human body can be invaded by digestion, respiratory tract, skin and mucous membrane, contact for a long time or suction can cause greatly to health
Threaten.Therefore strengthen to Cr6+Specific aim repair it is particularly important.
At present, it is mostly that tradition is repaired for pollution of chromium restorative procedure in soil.Traditional restorative procedure is mainly physics, changed
Method, mainly there are pyrolysis absorption method, chemical leaching, chemistry redox and electro reclamation etc..But due to Cr VI (Cr6+)
Soluble in water, permeability is strong, and separating difficulty is big, and processing cost is high, and high efficiency, low energy are extremely difficult to using traditional restorative procedure
Consumption, the repairing effect of low input, and easily cause and pollute again, destroy soil ecology.But specifically for acid soil sexavalence
The restorative procedure and prosthetic device of pollution of chromium are extremely rare, and some researchers make efforts for this.
Chinese patent literature CN201610627504 discloses one kind《A kind of synchronous electrode for removing nitrate and Cr VI
Biofilm reactor》, the reactor is provided with bio-carrier between cathode and anode material ring plate, promotes pollutant and microorganism
Contact, by impressed current, realize system autotrophy-heterotrophism collaboration denitrification, and hydrogen caused by current electroanalysis water is reduction
Cr VI provides electronics, can reach synchronous high-efficiency and removes combined pollution nitrate and Cr VI.Of the invention it can need by a variety of
Material, process is complicated, and processing equipment is complicated, and operating cost is high, and consumes energy, unsuitable popularization and application.
CN201420221484 discloses one kind《A kind of MFC devices of the hexavalent chromium polluted soil of in-situ immobilization heavy metal》,
Anode unit and cathode sets are embedded in contaminated soil by the device respectively, and the organic matter in anode unit local use soil is as combustion
Material, caused electronics reach cathode sets by anode and wire, and the heavy metal Cr VI adsorbed in cathode sets is reduced, with
So as to promote the degraded of heavy metal-polluted soil hexavalent chromium pollutant and conversion, realize that the original position of Cr VI heavy-metal contaminated soil is repaiied
It is multiple.But the device electrode used therein is unmodified, and electric charge transfer internal resistance is relatively large, and electron transport rate is smaller, and treatment effect is not
It is good.
The present invention prepares biological membrane electrode using porous carbon doping techniques, by building MFCs systems to acid soil sexavalence
Chromium carries out reproducibility reparation, simple in construction, and preparation, operating cost are low, do not consume energy not only, can also produce a small amount of electric energy.Moreover, should
Device is due to being applied in the environment of acid anaerobism, Cr6+Efficiency high is reduced under acid anaerobic environment, strengthens dress
The disposal ability put.
The content of the invention
Present invention aims at provide one kind to repair sexavalence using porous carbon doping biological membrane electrode structure MFC system high efficiencies
The method and device of the acid soil of pollution of chromium.
The technical solution adopted in the present invention is：It is a kind of efficiently to remove Cr in acid soil6+Microbiological fuel cell dress
Put and method, be mainly used in soil pollution and repair field, including porous carbon doping biomembrane anode and carbon felt negative electrode, the anode
With negative electrode is spaced-apart is embedded in Cr6+Connected in the acid soil of pollution and by wire, external load resistance, anode and cathode it
Between lay PEM.
The improvement of technical solution of the present invention is further used as, the anode uses porous carbon doping biomembrane anode.
The improvement of technical solution of the present invention is further used as, biomembrane anode is prepared using porous carbon doping techniques.
Specific method is as follows：
(1) preparation of porous carbon：In high-purity N2Under atmosphere, 10 DEG C/min of the rate of heat addition is warming up to 400 DEG C of holding 0.5h, will
30% corncob sample is carbonized.The sample after carbonization is placed in 5wt%HCl, 3wt%HF successively afterwards and distinguishes 6h, washing
To neutrality, dried at 80 DEG C to moisture content and be less than 5%.Using KOH as activator, 10 DEG C/min of the rate of heat addition under N2 atmosphere, if
Put and be warming up to 800 DEG C, retention time 2h, KOH activators ratio 5:1.Sample after activation is soaked into 24h in 5wt%HCl, washing
To neutrality, dried at 80 DEG C to moisture content and be less than 5%, obtain porous carbon sample.(specific surface area 3192.01m2/ g, specific capacitance
For 198.61F/g)
(2) culture of bacteria suspension：Weigh 1.23g CH3COONa, 0.75g NH4Cl, 0.15g NaCl, 0.15g
MgCl2·6H2O, 0.0225g CaCl2, 19.5g Na2HPO4·12H2O, 2.22g KH2PO4, add in 1.5L deionized waters,
It is uniformly mixed, obtains nutrient solution.Nitrogen 50min is continually fed into nutrient solution and removes dissolved oxygen.And it is added dropwise into nutrient solution
Appropriate 35%Hcl, regulation PH are 5, and phosphate buffer is added dropwise and ensures that PH is stable.By the porous carbon anode by running steadily in the long term
Grind, be inoculated in above-mentioned nutrient solution, the sealing culture 24h in 35 DEG C of constant-temperature tables that rotating speed is 100r/min.
(3) preparation of porous carbon doping biomembrane anode：The preparation of porous carbon doping biomembrane anode is mixed using porous carbon
Acrobatics art.The porous carbon suspension that 30mL concentration is 50mg/L is well mixed with 270mL bacteria suspensions, is finally configured to porous carbon
Content 1.5mg porous carbon-microorganism mixed liquor.Two layers of aperture is existed for the stainless steel filter screen interfolded of 1 μm of 1 μ m
Together as filter layer, by porous carbon-microorganism mixed liquor vacuum filter to stainless steel filter screen top layer, porous carbon is prepared into
Adulterate biological membrane electrode.
The improvement of technical solution of the present invention is further used as, the negative electrode uses carbon felt electrode, and carbon felt electrode possesses extremely
Flourishing pore structure, surface functional group species is more, and surface Gibbs energy is small, and clean-up effect is good.
The improvement of technical solution of the present invention is further used as, PEM is laid between anode and cathode or without proton exchange
Film.
MFC building modes：
MFC is using symmetrical structure structure battery the two poles of the earth.Using porous carbon doping biological membrane electrode obtained above as anode
Buried depth adds the above-mentioned nutrient solutions of 20ml in container bottom, the supplement above-mentioned nutrient solutions of 1.0mL per 24h.Cathode material is common carbon
Felt, water and soil interface is placed in, negative and positive the two poles of the earth are connected by outer meeting resistance using crocodile clip wire, form closed-loop path.Anode exists
About 5cm above container bottom, negative electrode are embedded in surface water level (3 cm below the water surface).The Ω connections of load resistance 1000
Between the anode and cathode, the distance between two electrodes about 8cm.The dischargeable capacity 2.5L of MFC systems, anode set size
15cm × 15cm, negative electrode set size 10cm × 10cm.
The MFCs methods degraded Cr VI speed that the present invention uses is fast, efficiency high, does not consume energy not only, can also conversely produce a small amount of
Electric energy, and any chemical agent need not be added during pollution control, secondary pollution will not be produced, is a kind of environment-friendly
Recovery technique.The preparation of nutrient solution can ensure the relatively low oxidation-reduction potential of anode, reduce in environment other electron acceptors to electricity
The shunting action of son, is advantageous to the raising of capacity efficiency.Cr6+Efficiency high is reduced under acid anaerobic environment, phosphoric acid is added and delays
Fliud flushing keeps the relatively low PH of solution and pretreatment to carry out rushing N2Remove O2All be advantageous to Cr6+Reduction.Present invention processing sexavalence
Chromium, has that cost is low, efficiency high, equipment investment are small, and operation is simple, the advantages that production capacity, has wide market prospects and application
Value, it is worth large-scale promotion, application.
Brief description of the drawings
Fig. 1 is structural representation of the embodiment of the present invention；
Fig. 2 is porous carbon doping biology anode schematic diagram；
Fig. 3 is using the actual effect figure of invention degraded Cr VI under sour environment；
Fig. 4 is using the actual effect figure of invention degraded Cr VI under neutral environment.
Embodiment
Embodiment
Simulate different Cr6+The acid soil environment of concentration, the device designed using the present invention are handled (the He of reference picture 1
Fig. 2), Cr is observed6+Removal efficiency.Take 20kg red soil (acid soil, pH value 5), by mortar grinder and lead to after natural air drying
Cross 2mm sieve, obtain diameter be less than or equal to 2mm uniform soil, added respectively in every 4kg soil samples 500mg, 750mg,
1000mg, 1250mg, 1500mg potassium bichromate, and 3L water is added, Cr VI is fully distributed in soil sample, form Cr6+Concentration
100mg/kg, 150mg/kg, 200mg/kg, 250mg/kg and 300mg/kg pollution soil sample, are respectively designated as system 1,2,3,4
With 5.And contrast test is set, take 4kg naturally native (PH=7), using the above method, obtain Cr6+Concentration 100mg/kg, 150mg/
Kg, 200mg/kg, 250mg/kg and 300mg/kg pollution soil sample, method of testing is as above.Using apparatus of the present invention to simulation acid
Property soil is handled, and passes through the Cr of leaching of the atomic absorption spectrophotometer to contaminated soil6+Carry out concentration determination.Table 1 is
1,2,3,4,5 Cr after apparatus of the present invention are handled of system under acid, neutral environment6+Change in concentration table.
Table 1
It is used efficiently to remove Cr in acid soil from Fig. 3 and Fig. 4 results6+Microbiological fuel cell reparation
Method is to Cr6+Treatment effect is splendid, to Cr in acid soil6+Content (100mg/kg, 150mg/kg, 200mg/kg, 250mg/
Kg and 300mg/kg) and neutral soil Cr6+Content (100mg/kg, 150mg/kg, 200mg/kg, 250mg/kg and 300mg/kg)
Soil obtain good repairing effect, Cr6+It is reduced under acid anaerobic environment more efficient.
Claims (5)
1. a kind of efficiently remove Cr in acid soil6+Microbial fuel cell unit and method, it is characterised in that：Including porous
Carbon doping biomembrane anode and carbon felt negative electrode, the anode and negative electrode are spaced-apart to be embedded in Cr6+In contaminated soil and pass through
Wire is connected, external load resistance, and PEM is laid between anode and cathode.
2. according to claim 1 efficiently remove Cr in acid soil6+Microbial fuel cell unit and method, it is special
Sign is：The anode uses porous carbon doping biomembrane anode.
3. according to claim 2 efficiently remove Cr in acid soil6+Microbial fuel cell unit and method, it is special
Sign is：Biomembrane anode is prepared using porous carbon doping techniques.
4. according to claim 1 efficiently remove Cr in acid soil6+Microbial fuel cell unit and method, it is special
Sign is：The negative electrode uses carbon felt electrode, and carbon felt electrode possesses extremely flourishing pore structure, and surface functional group species is more,
Surface Gibbs energy is small, and clean-up effect is good.
5. the MFC devices of the hexavalent chromium polluted soil of in-situ immobilization heavy metal according to claim 1, it is characterised in that：It is cloudy
PEM is laid between anode or without PEM.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108555018A (en) * | 2017-12-26 | 2018-09-21 | 同济大学 | A method of improving phytoremediation contaminated soil efficiency using active carbon fiber felt |
| CN108704933A (en) * | 2018-04-26 | 2018-10-26 | 中国石油大学(北京) | A kind of device and method of the hexavalent chromium polluted soil of in-situ immobilization |
| CN111146483A (en) * | 2019-11-22 | 2020-05-12 | 西安理工大学 | Three-chamber soil microbial fuel cell and method for removing heavy metals |
| CN113877959A (en) * | 2021-10-11 | 2022-01-04 | 中国计量大学 | Method for repairing polycyclic aromatic hydrocarbon polluted soil by using plant microbial fuel cell technology |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102249424A (en) * | 2011-04-02 | 2011-11-23 | 大连民族学院 | Proton exchange membrane-free microbiological fuel cell sewage treatment system and application method thereof |
| CN203862665U (en) * | 2014-04-30 | 2014-10-08 | 东莞市环境科学研究所 | MFC device for in-situ remediation of heavy-metal hexavalent chromium contaminated soil |
| CN104386826A (en) * | 2014-09-19 | 2015-03-04 | 浙江大学 | Microbial fuel cell based method for treatment and detection of chromium-containing electroplating wastewater |
| CN104624628A (en) * | 2014-12-09 | 2015-05-20 | 东南大学 | System and method for removing heavy metals by using microbial fuel cell established in soil |
| CN105280940A (en) * | 2015-09-16 | 2016-01-27 | 太原理工大学 | Method for coking wastewater degradation and synchronous power generation by taking coking active bacterium as biocatalyst |
-
2017
- 2017-07-18 CN CN201710584197.1A patent/CN107377608A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102249424A (en) * | 2011-04-02 | 2011-11-23 | 大连民族学院 | Proton exchange membrane-free microbiological fuel cell sewage treatment system and application method thereof |
| CN203862665U (en) * | 2014-04-30 | 2014-10-08 | 东莞市环境科学研究所 | MFC device for in-situ remediation of heavy-metal hexavalent chromium contaminated soil |
| CN104386826A (en) * | 2014-09-19 | 2015-03-04 | 浙江大学 | Microbial fuel cell based method for treatment and detection of chromium-containing electroplating wastewater |
| CN104624628A (en) * | 2014-12-09 | 2015-05-20 | 东南大学 | System and method for removing heavy metals by using microbial fuel cell established in soil |
| CN105280940A (en) * | 2015-09-16 | 2016-01-27 | 太原理工大学 | Method for coking wastewater degradation and synchronous power generation by taking coking active bacterium as biocatalyst |
Non-Patent Citations (1)
| Title |
|---|
| 王鑫: "铬污染土壤的修复技术研究综述", 《环境工程》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108555018A (en) * | 2017-12-26 | 2018-09-21 | 同济大学 | A method of improving phytoremediation contaminated soil efficiency using active carbon fiber felt |
| CN108704933A (en) * | 2018-04-26 | 2018-10-26 | 中国石油大学(北京) | A kind of device and method of the hexavalent chromium polluted soil of in-situ immobilization |
| CN108704933B (en) * | 2018-04-26 | 2020-09-11 | 中国石油大学(北京) | Device and method for in-situ remediation of hexavalent chromium contaminated soil |
| CN111146483A (en) * | 2019-11-22 | 2020-05-12 | 西安理工大学 | Three-chamber soil microbial fuel cell and method for removing heavy metals |
| CN113877959A (en) * | 2021-10-11 | 2022-01-04 | 中国计量大学 | Method for repairing polycyclic aromatic hydrocarbon polluted soil by using plant microbial fuel cell technology |
| CN113877959B (en) * | 2021-10-11 | 2023-09-15 | 中国计量大学 | Method for repairing soil polluted by polycyclic aromatic hydrocarbon by using plant microbial fuel cell technology |
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Application publication date: 20171124 |