CN100548910C - Method and the application thereof of Fe in a kind of reducing solution (III) EDTA - Google Patents

Method and the application thereof of Fe in a kind of reducing solution (III) EDTA Download PDF

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CN100548910C
CN100548910C CNB2007101563687A CN200710156368A CN100548910C CN 100548910 C CN100548910 C CN 100548910C CN B2007101563687 A CNB2007101563687 A CN B2007101563687A CN 200710156368 A CN200710156368 A CN 200710156368A CN 100548910 C CN100548910 C CN 100548910C
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CN101172742A (en
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李伟
糜徐红
张士汉
邵科
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Zhejiang University ZJU
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Abstract

The invention discloses method and the application thereof of Fe in a kind of reducing solution (III) EDTA, the physical electrode that porous carbon material is made carries out iron-reducing bacterium biofilm and domestication, makes the electrode with the iron-reducing bacterium film; To add electron donor and carbon source and basic medium is dissolved in containing in Fe (III) the EDTA solution and makes mixing solutions, to insert in the mixing solutions and energising with the electrode of iron-reducing bacterium film then, the inventive method can be applicable to reduce Fe (III) EDTA in the nitrogen-containing oxide smoke absorption liquid.The inventive method has improved the rate of reduction of Fe (III) EDTA greatly, and simple to operate, stable, floor space is little.

Description

Method and the application thereof of Fe in a kind of reducing solution (III) EDTA
Technical field
The present invention relates to the environmental pollution improvement field, refer to method and the application thereof of Fe in a kind of reducing solution (III) EDTA particularly.
Background technology
Oxynitride (NO x) discharging be the one of the main reasons that causes a series of serious air pollution problems inherent such as acid rain, photo-chemical smog.To the attention of nitrogen oxides pollution and the appearance and the enforcement of relevant laws and regulations, China will be strict day by day to the control of discharged nitrous oxides along with in recent years.NO in the coal-fired flue-gas x, more than 95% NO, NO 2For on a small quantity, therefore, flue-gas denitrification essence is the removal of NO.Because NO is water insoluble substantially, in the wet desulphurization device commonly used, NO can't be removed in the time of desulfurization.If can find a kind of chemical additive, join in the existing process of wet desulphurization, in desulfurization, NO is removed and will be a kind of very economical ideal method.
For this reason, be the NO complexed absorption technology of complexed absorption agent with Fe (II) EDTA (ethylenediamine tetraacetic acid (EDTA) is ferrous), in depth carried out laboratory and pilot scale research (Shi Y, " Environ.Prog. ", 1997,16,301-306 on the U.S., Japan and other places; Li Wei, " China Environmental Science ", 2005,25,306-309).The complexed absorption method utilizes the liquid complexing absorption agent directly to react with NO, increase the solvability of NO in water, thereby make NO be easy to change liquid phase over to from gas phase, this method is specially adapted to handle the coal-fired flue-gas that mainly contains NO, can reach 90% or higher NO decreasing ratio in experimental installation.Ferrous complexed absorption agent can be used as additive and directly adds in the slurries of lime stone-gypsum method flue gas desulfurization, only needs to transform a little on original sweetener, just can realize removing simultaneously SO 2And NO x(Sada E, " Ind.Eng.Chem.Process Des.Dev. ", 1982,21,771-774), save the fixed investment of great number.
But, utilize Fe (II) EDTA to handle NO as the absorption agent complexed absorption xFollowing shortcoming (Sada E, " Ind.Eng.Chem.Res ", 1987,26,1468-1472 are arranged simultaneously; Zang V, " Inorg.Chem. ", 1990,29 (9), 1705-1711): NO and dissolved SO that (1) absorbs 2Reaction becomes N 2O, N 2With some other N-S compound, yet the N-S compound of these by-products is difficult to separate from solution because it is higher water-soluble.(2) owing to generally contain 3%~8% O in the flue gas 2, the Fe in this type of absorption agent (II) is easily by O 2Be oxidized to Fe (III) and lose complex ability, thereby reduce specific absorption NO to NO.At these problems, Chinese scholars has been carried out corresponding research to the regeneration situation of ferrous complexed absorption agent.Na 2S 2O 4, vitamins C, SO 3 2-, HSO 3 -, oxalic dialdehyde etc. reductive agent can be with the absorbent regeneration of oxidation, but the generation of expensive, low regeneration rate or unmanageable by product; People such as Tsai have studied the feasibility that the employing electrochemical method is reduced to Fe (III) EDTA Fe (II) EDTA, the NO decreasing ratio can be stabilized in 70%~80% (Tsai SS in the operational process continuously, " Environ.Prog. ", 1989,8,126-129), be uneconomic but this method is applied to industrial production, because need the electric energy of great number to go the ratio Fe (III) that exists in the reducing solution to have lower reduction potential energy other compositions as dissolved oxygen and so on; Cause single Fe (II) EDTA complexed absorption method in industry, to be applied.
The electrode biomembrane method is the nitrated denitrification treatment technology (Bao Lining of a novel trans that development in recent years is got up, " Anhui Institute Of Architecture Industry journal (natural science edition) ", 2004,12 (5), 1-4), its advantage is mainly reflected in the effect of electrode, both can utilize electrode as biomembranous carrier, can utilize the negative electrode micro-electrolytic water to discharge H again 2CO with anode carbon oxidation generation 2For denitrifying bacteria is put forward hydrogen donor and carbon source.Correlative study show (Ohmura N, " Appl.Environ.Microbial. ", 2002,68,405-407), microorganism is to the reduction of Fe (III), energising and with hydrogen as electron donor, compare with no power, bacterial cell quantity can increase about 10 times.Usefulness electrode biomembrance process such as Tomohide Watanabe are handled the high density nitrate pickling waste waters of copper ions, show that denitrogenation and reduction of metal ion are (the Watanabe T that can carry out simultaneously under the electrode effect, " Wat.Res. ", 2001,35 (17): 4102-4110).M.Kuroda etc. find that also the electrode biomembrane method can utilize organism and additional power source to produce hydrogen as electron donor simultaneously, have strengthened the reducing activity of microorganism, have improved denitrification denitrogenation speed (Kuroda M largely, " Wat.Sci.Tech. ", 1997,35 (8), 161-168).
Summary of the invention
The invention provides method and the application thereof of Fe in the reducing solution that a kind of energy consumption is little, cost is low (III) EDTA.
The method of Fe in a kind of reducing solution (III) EDTA may further comprise the steps:
(1) physical electrode that porous carbon material is made carries out iron-reducing bacterium biofilm and domestication, makes the electrode with the iron-reducing bacterium film.
Wherein porous carbon material is selected graphite, carbon fiber or decolorizing carbon for use.
(2) will add electron donor and carbon source and basic medium and be dissolved in containing in Fe (III) the EDTA solution and make mixing solutions, will insert in the mixing solutions and energising with the electrode of iron-reducing bacterium film then, carry out reduction reaction.
Wherein the electrical current density of electrode is 0.01~1mA/cm 2, 30~60 ℃ of temperature of reaction, mixing solutions pH is 5~8.
Electron donor and the carbon source of adding of the present invention be both for iron-reducing bacterium provides energy, is one of reductive agent of reduction Fe (III) EDTA again, is preferably in glucose, ethanol, the acetate one or more.
Method of the present invention can be applied to reduce Fe (III) EDTA in the nitrogen-containing oxide smoke absorption liquid.
Because contain and contain part oxygen in the nitrogen oxide containing gas, Fe (II) EDTA absorption liquid absorbs in the flue gas process, part Fe in the absorption liquid (II) EDTA is oxidized to Fe (III) EDTA, insert the energising physical electrode of being made by porous carbon material of the iron-reducing bacterium film had in absorption liquid after, the negative electrode micro-electrolytic water discharges H 2, make under the condition of catalyzer H at iron-reducing bacterium 2With add electron donor Fe (III) EDTA be reduced to Fe (II) EDTA, reach the purpose of regeneration absorption liquid.
With glucose is that electron donor is an example, and its biochemical reaction is as follows:
C+2H 2O→CO 2+4H +
2H 2O→H 2+2OH -
Figure C20071015636800051
Figure C20071015636800052
The method of Fe (III) EDTA in a kind of reducing solution provided by the invention, owing to have iron-reducing bacterium to make biological catalyst, and have electric current to produce hydrogen by electrolysis, accelerate the speed of electron transport in the reduction process, thereby improved rate of reduction greatly.
When the inventive method is applied in the nitrogen oxides reduction smoke absorption liquid Fe (III) EDTA, utilize the carrier of electrode on the one hand as microbial film, the hydrogen that can utilize the electrolysis generation on the other hand again is as electron donor, Fe (III) EDTA is reduced to Fe (II) EDTA, has avoided secondary pollution, saved starting material, overcome biological washer and purified problems such as absorbing the obstruction of nitrogen-containing oxide flue gas filler, and present method is simple to operate, and is stable, and floor space is little.
Embodiment
1. iron-reducing bacterium enrichment and domestication
(1) enrichment: get the active sludge in the sanitary sewage disposal factory denitrification pond, leave standstill 24h after, the elimination supernatant liquor takes off layer mud 10mL and is inoculated in the 250mL culturing bottle that contains the 100mL basic culture solution, uses N 2Drive water seal behind the oxygen, place 40 ℃ constant temperature shaking table shaking culture, shaking speed 140r/min is with the NaNO of 1000mg/L 3Carry out enrichment culture as only nitrogen source, through about 14 days, treat NO in the nutrient solution 3 -By mass consumption and observed N 2After the generation, (5000r/min 15min), collects thalline, is mixed with bacterium liquid with the centrifugation of bacterium liquid.
(2) domestication: getting above-mentioned bacterium liquid 10mL, to be inoculated in Fe (III) EDTA concentration be in the 100mL basic culture solution of 2mmol/L, regulate pH value 6.5~7.0, putting into the constant temperature shaking table cultivates, changed a nutrient solution in per 6 days, inoculation 10mL tames in the 100mL fresh medium, is gradient with 2mmol/L, progressively increase the concentration of Fe (III) EDTA in nutrient solution, make it finally reach 20mmol/L, tamed 30 days, make also original bacteria liquid of Fe (III) EDTA.
Basic medium (mg/L): carbon source (glucose) 2500, K 2HPO 43H 2O 1000, KH 2PO 4625, Na 2SO 370, MgSO 4100, CaCl 22, MnSO 40.5, Na 2MoO 40.1, CuSO 45H 2O 0.1.The component of basic medium can be regulated, as long as can satisfy microorganism growth.
2. physical electrode iron-reducing bacterium biofilm
With in advance the domestication Fe (III) EDTA also original bacteria liquid (100mg/L) be seeded in the bio-reactor, this reactor is a cylindrical container, container is built-in with the electrode of being made by graphite, electrode also can be made by other porous carbon material, as: decolorizing carbon or carbon fiber, wherein the anode of electrode is positioned at container center, and 12 cathode electrodes are uniformly distributed in around the anode electrode; Add the mixing solutions of 1L Fe (III) EDTA solution and basic medium simultaneously in reactor, wherein Fe (III) EDTA concentration is 12mmol/L.The feeding current density is 0.01mA/cm 2Electric current is tamed and biofilm, with 0.02mA/cm 2Be gradient, progressively increase current density, make it finally reach 0.6mA/cm 2, if Fe (III) EDTA concentration is lower than 2mmol/L in the reaction solution, stop energising, remove reaction solution, add fresh Fe (III) the EDTA solution that contains, so repeatable operation was tamed 2 months.Utilize environmental scanning electronic microscope technology (ESEM) simultaneously, iron-reducing bacterium growing state on the detecting electrode.Grow when better when iron-reducing bacterium, just realized whole biofilm process.Described reactor places constant temperature water bath, guarantees the homo(io)thermism in the reactor.
3. reduction Fe (III) EDTA
Embodiment 1
With 3mmol FeCl 34H 2O, 3mmol Na 2H 2EDTA Fe (III) the EDTA solution that makes soluble in water, then 30mmol glucose and basic medium concentrated solution are dissolved in above-mentioned solution and make the 1L mixing solutions, the pH value of regulating mixing solutions is 6.5, Fe in the solution (III) EDTA concentration is 3mmol/L, the concentration of basic medium is consistent with the basic medium concentration of enrichment culture, and then mixing solutions is poured in the reactor; In temperature is under 50 ℃ of conditions, will insert in the mixing solutions and energising with the physical electrode of iron-reducing bacterium film, and wherein current density is 0.03mA/cm 2, reduction reaction is after 3 hours, and the Fe in the reactor (III) EDTA is 0.2mmol/L.
Embodiment 2
With 5mmol Fe 2(SO 4) 3, 10mmolNa 2H 2EDTA Fe (III) the EDTA solution that makes soluble in water, then 30mmol ethanol and basic medium concentrated solution are dissolved in above-mentioned solution and make the 1L mixing solutions, the pH value of regulating mixing solutions is 5, Fe in the solution (III) EDTA concentration is 10mmol/L, the concentration of basic medium is consistent with the basic medium concentration of enrichment culture, then mixing solutions is poured in the reactor; In temperature is under 30 ℃ of conditions, will insert mixing solutions and energising with the electrode of iron-reducing bacterium film, and wherein current density is 0.01mA/cm 2, reduction reaction is after 6 hours, and the Fe in the reactor (III) EDTA is 3.4mmol/L.
Embodiment 3
With 10mmol FeCl 34H 2O, 10mmol Na 3HEDTA is soluble in water, then 30mmol sodium acetate and basic medium concentrated solution are dissolved in above-mentioned solution and make the 1L mixing solutions, the pH value of regulating mixing solutions is 6.5, Fe in the solution (III) EDTA concentration is 10mmol/L, the concentration of basic medium is consistent with the basic medium concentration of enrichment culture, then mixing solutions is poured in the reactor; In temperature of reaction is under 60 ℃ of conditions, will insert in the mixing solutions and energising with the electrode of iron-reducing bacterium film, and wherein current density is 0.59mA/cm 2, reducing after 6 hours, the Fe in the reactor (III) EDTA is 2.9mmol/L
Embodiment 4
With 12mmol FeCl 34H 2O, 12mmol Na 4EDTA Fe (III) the EDTA solution that makes soluble in water, then 10mmol glucose and 20mmol ethanol and basic medium concentrated solution are dissolved in and make the 1L mixing solutions in the above-mentioned solution, the pH value of regulating mixing solutions is 8, Fe in the solution (III) EDTA concentration is 12mmol/L, the concentration of basic medium is consistent with the basic medium concentration of enrichment culture, then mixing solutions is poured in the reactor; In temperature of reaction is under 50 ℃ of conditions, will insert in the mixing solutions and energising with the electrode of iron-reducing bacterium film, and wherein current density is 1mA/cm 2, reduction reaction is after 6 hours, and the Fe in the reactor (III) EDTA is 7.8mmol/L.
Embodiment 5
With 10mmol Fe 2(SO 4) 3, 20mmol Na 3HEDTA Fe (III) the EDTA solution that makes soluble in water, then 10mmol glucose, 10mmol ethanol and 10mmol sodium acetate and basic medium concentrated solution are dissolved in and make the 1L mixing solutions in the above-mentioned solution, the pH value of regulator solution is 6.2, Fe in the solution (III) EDTA is 20mmol/L, the concentration of basic medium is consistent with the basic medium concentration of enrichment culture, then mixing solutions is poured in the reactor; In temperature of reaction is under 50 ℃ of conditions, will insert in the mixing solutions and energising with the electrode of iron-reducing bacterium film, and wherein current density is 0.38mA/cm 2, reduction reaction is after 9 hours, and the Fe in the reactor (III) EDTA is 2.4mmol/L
Embodiment 6
With 40mmol FeCl 34H 2O, 40mmol Na 2H 2EDTA Fe (III) the EDTA solution that makes soluble in water, then 30mmol glucose is dissolved in basis cultivation concentrated solution base and makes the 1L mixing solutions in the above-mentioned solution, the pH value of regulating mixing solutions is 6.2, Fe in the solution (III) EDTA is 40mmol/L, the concentration of basic medium is consistent with the basic medium concentration of enrichment culture, then mixing solutions is poured in the reactor; In temperature of reaction is under 50 ℃ of conditions, will insert in the mixing solutions and energising with the electrode of iron-reducing bacterium film, and wherein current density is 0.38mA/cm 2, reduction reaction is after 18 hours, and the Fe in the reactor (III) EDTA is 3.6mmol/L.
Embodiment 7
With 12mmol FeCl 24H 2O, 12mmol Na 2H 2EDTA Fe (III) the EDTA solution that makes soluble in water, with 30mmol glucose and the basic medium concentrated solution smoke absorption liquid that makes soluble in water, Fe in the absorption liquid (II) EDTA is 12mmol/L, the concentration of basic medium is consistent with the basic medium concentration of enrichment culture, then smoke absorption liquid is poured in the reactor; In temperature is under 50 ℃ of conditions, will contain 500ppm nitrogen protoxide, 3% (volume ratio) O 2, all the other are that the simulated flue gas of nitrogen feeds in the reactor, reacts after 2 hours, Fe (III) EDTA in the mensuration absorption liquid is 6.2mmol/L; The pH value of regulating absorption liquid is 6.5 and adds basic medium that will insert in the absorption liquid that has absorbed flue gas and energising with the physical electrode of iron-reducing bacterium film, wherein current density be 0.03mA/cm 2, reducing after 6 hours, the Fe in the reactor (III) EDTA is 0.2mmol/L.

Claims (8)

1. the method for Fe (III) EDTA in the reducing solution may further comprise the steps:
(1) physical electrode that porous carbon material is made carries out iron-reducing bacterium biofilm and domestication, makes the electrode with the iron-reducing bacterium film;
(2) will add electron donor and carbon source and basic medium and be dissolved in containing in Fe (III) the EDTA solution and make mixing solutions, will insert in the mixing solutions and energising with the electrode of iron-reducing bacterium film then, carry out reduction reaction.
2. method according to claim 1 is characterized in that: described iron-reducing bacterium biofilm and domestication may further comprise the steps:
(1) with Fe (III) EDTA also original bacteria liquid, Fe (III) EDTA solution and basic medium mixed solution;
(2) physical electrode that porous carbon material is made is inserted in the solution of step (1) preparation and energising, carries out reduction reaction;
(3) after reaction is finished, replenish Fe (III) EDTA solution in reacted solution, electrode continues energising and carries out reduction reaction, repeated several times.
3. method according to claim 1 is characterized in that: described porous carbon material is graphite, carbon fiber or decolorizing carbon.
4. method according to claim 1 is characterized in that: the electrical current density of electrode is 0.01~1mA/cm in the step (2) 2
5. method according to claim 1 is characterized in that: temperature of reaction is 30~60 ℃ in the step (2).
6. method according to claim 1 is characterized in that: the pH value of mixing solutions is 5~8 in the step (2).
7. method according to claim 1 is characterized in that: described electron donor and the carbon source of adding is in glucose, ethanol, the acetate one or more.
8. the application of method according to claim 1 Fe (III) EDTA in nitrogen oxides reduction smoke absorption liquid.
CNB2007101563687A 2007-10-23 2007-10-23 Method and the application thereof of Fe in a kind of reducing solution (III) EDTA Expired - Fee Related CN100548910C (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101810983B (en) * 2010-03-12 2012-09-05 浙江大学 Method for regenerating nitrogen oxide complexed absorption liquid in smoke denitration
CN102553434A (en) * 2012-03-06 2012-07-11 浙江大学 Device and method for purifying nitrogen oxides in flue gas by utilizing electrode biological membrane
CN114210198A (en) * 2021-11-15 2022-03-22 郑州轻工业大学 Application of biological synergistic electrocatalytic reactor in nitrogen oxide reduction
CN117342688B (en) * 2023-12-04 2024-03-29 中国环境科学研究院 Fenton wastewater treatment system of coupling microbial fuel cell

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
Electrochemical Regeneration of Fe(III) To Support GrowthonAnaerobic Iron Respiration. Naoya Ohmura etc.Applied and Environmental Microbiology,Vol.68 No.1. 2002
Electrochemical Regeneration of Fe(III) To Support GrowthonAnaerobic Iron Respiration. Naoya Ohmura etc.Applied and Environmental Microbiology,Vol.68 No.1. 2002 *
络合吸收脱除NO体系中FeIII(EDTA)的生物还原. 荆国华等.环境科学,第26卷第6期. 2005
络合吸收脱除NO体系中FeIII(EDTA)的生物还原. 荆国华等.环境科学,第26卷第6期. 2005 *

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