A kind of microorganism electrochemical denitrogenation method of bio-hydrogen strengthening
Technical field
The present invention relates to the microorganism electrochemical denitrogenation method of a kind of bio-hydrogen strengthening, belong to environmental engineering and derived energy chemical field.
Background technology
In recent years, nitrogen is as global water pollutant, and its removal is subject to increasing attention.Tradition denitrification process can be divided into physics, chemistry and biological three major types.Physical method denitrogenation mainly comprises ion-exchange, reverse osmosis and electrodialysis etc.Chemistry denitrogenation then refers under alkalescence or condition of neutral pH, utilizes molysite or patina by the nitrate transformation ammonification in water.And traditional biological denitrification process principle is divided into three phases, comprise ammonification, nitrification and denitrification.There is the shortcomings such as occupation area of equipment is large, temperature influence is comparatively large, complicated operation, easily generation secondary pollution in tradition denitrification process.And microorganism electrochemical system (BES) is as a kind of novel denitrification process, can be used for processing the nitrogen in polluted-water.BES can improve the activity of the negative electrode of denitrifying bacterium directly on surface, makes nitric nitrogen as electron acceptor(EA) to carry out denitrification process.It has the advantages such as energy consumption is low, easy to operate, integration is good, processing efficiency is high, sludge yield is low, receives increasing concern.
BES denitrification process is due to the restriction of anode current generation speed, and negative electrode denitrification rates is lower, and denitrification process can produce basicity simultaneously, causes catholyte pH to rise; And the hydrogen produced in anaerobic hydrogen production process not only can promote denitrification denitrogenation process as reducing power, along with carbon source hydrolysis, acidization in substrate, the organic acids such as acetic acid, butyric acid, propionic acid, lactic acid can be produced, the basicity that denitrification produces can also be consumed.Therefore, the reducing power of the hydrogen provided in bio-hydrogen process, and under the dual function of pH regulator ability that provides of organic acid, BES nitric efficiency is able to further raising.
Summary of the invention
The invention provides the microorganism electrochemical denitrogenation method of a kind of bio-hydrogen strengthening, for reactor with microorganism electrochemical system (BES), hydrogen microorganism is produced by adding in influent waste water, improve the denitrification rates of biological-cathode denitrifying bacterium, produce acid by the metabolism of hydrogen-producing bacteria simultaneously and consume the basicity that denitrification produces, thus maintain the stable of pH value in BES biological-cathode.
Described microorganism electrochemical system response device comprises anode carbon brush 1, negative electrode carbon brush 2, reference electrode 3, cationic exchange membrane 4, rubber plug 5, external resistance 6, water inlet interface 7, water outlet mouthpiece 8 and fresh feed pump 9.By cationic exchange membrane 4, microorganism electrochemical system response device is divided into room, negative and positive the two poles of the earth, room, each pole volume is 550mL; The anode chamber and the cathode chamber is all that (external diameter is 9cm to synthetic glass reactor customized specially, interior through 7cm, be highly 14cm), carbon brush 1,2 forms by titanium silk and carbon fiber, top, anolyte compartment has water-in and rubber plug 5, and cathode compartment top drilling is for placing reference electrode 3, and bottom side and top has into water interface 7 and water outlet mouthpiece 8, anode and cathode and reference electrode form external circuit by wire, and centre is connected with the resistance of 100 Ω.
Described denitrogenation method comprises the following steps:
(1) starter gear domestication anode: anolyte compartment is the electrogenesis nutritive medium of 550mL and the anaerobic sludge supernatant liquor through the domestication of electrogenesis nutritive medium built with cumulative volume, wherein the volume ratio of electrogenesis nutritive medium and anaerobic sludge supernatant liquor (containing electrogenesis microorganism) is 3:1, when anode potential is stabilized in-0.5V, anode is tamed successfully.
The OD of described anaerobic sludge supernatant liquor
600=0.021-0.025.
The formula (mg/L) of described electrogenesis nutritive medium: KCl0.13, NH
4cl0.31, NaH
2pO
42.7, Na
2hPO
411.55, anhydrous sodium acetate 1.0, micro-1mL/mL, VITAMIN liquid 1mL/mL; Trace element formula (g/L): nitrilotriacetic acid(NTA) 1.5, MgSO
47H
2o3.0, MnSO
4h
2o0.5, NaCl1.0, FeSO
47H
2o0.1, CoCl0.1, CaCl
20.1, ZnSO
47H
2o0.1, CuSO
45H
2o0.01, potassium aluminium alum 0.01, H
3bO
50.01, Na
2moO
40.01; VITAMIN liquid formula (mg/L): vitamin H 2.0, Lin Suanna Vitamin B2 Sodium Phosphate .0, pyridoxine hydrochloride 10.0, vitamins B
15.0, vitamins B
25.0, nicotinic acid 5.0, D-acid calcium 5.0, vitamins B
120.1, para-amino benzoic acid 5.0, Thioctic Acid 5.0.
(2) biological-cathode denitrogenation is started: after anode potential is stable, the denitrification nutritive medium that cumulative volume is 550mL and the anaerobic sludge supernatant liquor (containing denitrifying microorganism) of taming through denitrification nutritive medium is added to negative electrode, wherein the volume ratio of denitrification nutritive medium and anaerobic sludge supernatant liquor is 3:1, when cathode potential is stabilized in-0.24V left and right, is denitrification effect and stablizes.
Described anaerobic sludge supernatant liquor (containing denitrifying microorganism) OD
600=0.010-0.015.
The formula (mg/L) of described denitrification nutritive medium: KNO
31.0, NaCl0.5, NaHCO
32.0, KH
2pO
44.4, K
2hPO
43.4, MgSO
40.2, CaCl
20.015.
(3), after denitrification effect is stablized, in negative electrode water inlet, inoculation accounts for the anaerobic sludge supernatant liquor through 120 DEG C of high-temperature sterilizations (producing hydrogen microorganism is spore state) the conduct product hydrogen microorganism species into water cumulative volume 25%, wherein anaerobic sludge supernatant liquor OD
600=0.013-0.018.
The hydrogen that current strengthening product hydrogen mainly directly utilizes brine electrolysis to generate is to improve the denitrification effect of BES.First the present invention utilizes denitrifying bacterium to realize biological-cathode denitrogenation at negative electrode, and then adds product hydrogen microorganism in the cathode, by bio-hydrogen and the denitrification rates producing acid further negative electrode raising denitrifying bacterium.The microorganism electrochemical denitrification treatment process that the present invention strengthens as a kind of bio-hydrogen, the hydrogen that biological-cathode can utilize Chan Qing Institute of Micro-biology to produce improves denitrification rates, the organic acid that simultaneous hydrogen production microorganism produces can maintain the stable of system pH, further increases rate of reduction and the nitric efficiency of denitrifying bacterium.
Accompanying drawing explanation
Fig. 1 is indication microorganism electrochemical denitrification treatment process apparatus structure schematic diagram of the present invention.
Fig. 2 is the impact of different training method on BES denitrification effect; 1, anode carbon brush; 2, negative electrode carbon brush; 3, reference electrode; 4, cationic exchange membrane; 5, rubber plug; 6, external resistance; 7, water inlet interface; 8, water outlet mouthpiece; 9, fresh feed pump; V1, open circuit voltage; V2, cathode potential; * denitrification rates equation: y=-kx+y
0; K is degradation rate constant, y
0for nitric nitrogen starting point concentration; * A: add simultaneously and produce hydrogen microorganism and denitrification microorganism; B: only add denitrification microorganism; C: abiotic negative electrode.
Embodiment
Embodiment 1 utilizes the mud of Wuxi north of the city sewage work to carry out the microorganism electrochemical denitrogenation of bio-hydrogen strengthening
1,2 be described as follows by reference to the accompanying drawings:
As shown in Figure 1, the present invention is using microorganism electrochemical system as reactor, and this reactor is made up of cathode and anode room, and centre is separated by cationic exchange membrane.Anode is intake by water-in (5), and negative electrode then utilizes peristaltic pump by water-in (7) water inlet, and sampling is then by water outlet (8), and electrogenesis and denitrification microorganism are then attached on carbon brush (1) (2) respectively.
First, inoculating into cumulative volume is in the anode compartment the electrogenesis nutritive medium of 550mL and the anaerobic sludge supernatant liquor through the domestication of electrogenesis nutritive medium, wherein the volume ratio of electrogenesis nutritive medium and anaerobic sludge supernatant liquor (containing electrogenesis microorganism) is 3:1, and anaerobic sludge takes from Wuxi north of the city sewage work.Wherein electrogenesis microorganism supernatant liquor absorbancy under 600nm wavelength, between 0.021-0.025, starts device of the present invention at ambient temperature.After anode potential is stabilized in about-0.5V, continue in cathode compartment, add the denitrification nutritive medium that cumulative volume is 550mL and the anaerobic sludge supernatant liquor (containing denitrifying microorganism) of taming through denitrification nutritive medium, anaerobic sludge takes from Wuxi north of the city sewage work, wherein denitrification supernatant liquor (the anaerobic sludge supernatant liquor containing denitrifying microorganism) under 600nm wavelength absorbancy between 0.010-0.015; When cathode potential maintains about-0.24V, namely after biological-cathode denitrogenation reaches and stablizes, then, in water inlet, add the anaerobic sludge supernatant liquor (mud takes from Wuxi north of the city sewage work) containing product hydrogen microorganism accounted for into water cumulative volume 25%, wherein produce the absorbancy of hydrogen microorganism supernatant liquor under 600nm wavelength between 0.013-0.018.As shown in Figure 2, except adding denitrification microorganism and produce except the experimental group (A) of hydrogen microorganism simultaneously, the abiotic cathode sets (C) of only adding denitrification microorganism group (B) and not adding microorganism is also provided with.Through the operation of 32 days, speed is removed as can be seen from each experimental group nitric nitrogen, the denitrification effect of biological-cathode has obvious lifting relative to abiotic negative electrode, wherein the denitrification rates constant k of experimental group A is 2.729, the denitrification rates constant k of experimental group B is 2.330, but not biological-cathode group is only 1.236.This is because the interpolation of microorganism improves the transfer rate of electronics, and then promotes reduction reaction; Meanwhile, add after producing hydrogen microorganism, denitrification denitrogenation bacterium can utilize hydrogen to carry out reduction reaction, and organic acid can also maintain the stable of system pH, and the nitric efficiency therefore adding the BES producing hydrogen microorganism is significantly improved.
Embodiment 2 utilizes the mud of Condar Feng County, Xuzhou sewage work to carry out the microorganism electrochemical denitrogenation of bio-hydrogen strengthening
In embodiment 2, embodiment is similar to embodiment 1, and the anaerobic sludge unlike electrogenesis microorganism, denitrifying microorganism and product hydrogen microorganism all takes from Condar Feng County, Xuzhou sewage work.Except adding denitrification microorganism and produce except the experimental group of hydrogen microorganism simultaneously, be also provided with the abiotic cathode sets of only adding denitrification microorganism group and not adding microorganism.Through the operation of 32 days, the denitrification effect of biological-cathode had obvious lifting relative to abiotic negative electrode, and result is similar with embodiment 1, does not do additional diagram at this.
In sum, the present invention, by bio-hydrogen enhancement microbiological electrochemistry denitrification treatment process, can produce the promoter action of hydrogen microorganism to denitrification microorganism in realization response device, maintains the stable of system, and then improves nitric efficiency.
Although the present invention with preferred embodiment openly as above; but it is also not used to limit the present invention, any person skilled in the art, without departing from the spirit and scope of the present invention; all can do various changes and modification, what therefore protection scope of the present invention should define with claims is as the criterion.