CN105441495A - Construction method of microbial electrochemical system for hydrogen phosphide generation reinforcement - Google Patents
Construction method of microbial electrochemical system for hydrogen phosphide generation reinforcement Download PDFInfo
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- CN105441495A CN105441495A CN201510923932.8A CN201510923932A CN105441495A CN 105441495 A CN105441495 A CN 105441495A CN 201510923932 A CN201510923932 A CN 201510923932A CN 105441495 A CN105441495 A CN 105441495A
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- phosphuret
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- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P9/00—Preparation of organic compounds containing a metal or atom other than H, N, C, O, S or halogen
Abstract
The invention belongs to the technical field of microbial electrochemistry and discloses a construction method of a microbial electrochemical system for hydrogen phosphide generation reinforcement. The construction method comprises mixing animal wastes and anaerobic activated sludge, adding the mixture into an anaerobic reactor, carrying out culture through a medium to obtain a phosphine-producing microorganism-rich domesticated activated sludge mixed solution, taking the domesticated activated sludge mixed solution, carrying out centrifugation separation, carrying out washing through a phosphate buffer solution, adding inoculation sludge into a microbial electrolysis cell, carrying out biofilm culturing, applying power for the microbial electrolysis cell, adding the electrolysis product into a medium and carrying out anaerobic cultivation for hydrogen phosphide generation reinforcement. Through construction of the microbial electrolysis cell and domestication of microbes, a hydrogen phosphide yield of phosphate reduction and a hydrogen phosphide production rate are improved. The construction method has a good application prospect.
Description
Technical field
The invention belongs to field of microbial electromechanical technology, be specifically related to a kind of construction process strengthening the microorganism electrochemical system that phosphuret-(t)ed hydrogen produces.
Background technology
Phosphuret-(t)ed hydrogen, as phosphorus carrier important in phosphorus circulation, causes the attention of people just gradually.A large amount of scholar's research finds, phosphorus can be converted into phosphuret-(t)ed hydrogen by microorganism in anaerobic environment.All relevant report is had in the environment such as Sewage Plant anaerobic sludge, feces of livestock and poultry, wetland, rice field.But in the research history in a nearly century, not yet can make the mechanism of production of phosphuret-(t)ed hydrogen and clearly setting forth.The Phosphine content that micro-reduction generates is also all only in trace rank.
Microorganism electrochemical system introduces microorganism on the basis of electro-chemical systems.According to the difference of function, microbiological fuel cell (MFC) and microorganism electrolysis cell (MEC) can be divided into.In microorganism electrolysis cell, microorganism adheres on electrode, growth, under system applies certain voltage or constant potential condition, is formed and has adaptability to electrochemical environment and the microbial film with certain function.Common related application has: the degraded etc. utilizing microorganism electrolysis cell hydrogen producing, strengthening pollutent.
Can carry out strengthening the microorganism reacted with bio-electrochemical process and need to possess the ability that born of the same parents transmit electronics outward.Solvent fermentation bacterium is only had: clostridium sporogenes (Clostridiumsporogenes) in product phosphuret-(t)ed hydrogen bacterial classification known at present, clostridium cochlearium (Clostridiumcochliarium) and acetobutyl bacteria (Clostridiumacetobutyricum), it has stronger electrochemical activity, may be strengthened.
Summary of the invention
Based on above prior art, the object of the present invention is to provide a kind of construction process strengthening the microorganism electrochemical system that phosphuret-(t)ed hydrogen produces.This system is attached to cathode surface growth microorganism under utilizing certain potentials condition is reduced to this reaction of phosphuret-(t)ed hydrogen to strengthen phosphoric acid salt.
The object of the invention is achieved through the following technical solutions:
Strengthen a construction process for the microorganism electrochemical system that phosphuret-(t)ed hydrogen produces, comprise the following steps:
(1) animal excrement are mixed with anaerobic activated sludge, join in anaerobic reactor, then add substratum and cultivate, obtain the active sludge intermixture after being rich in the domestication of producing phosphuret-(t)ed hydrogen microorganism;
(2) get the active sludge intermixture after domestication, through centrifugal and with phosphate buffer solution washing after obtain seed sludge, then seed sludge is joined in microorganism electrolysis cell and carries out biofilm;
(3) apply current potential and add substratum to carry out Anaerobic culturel to microorganism electrolysis cell, the generation of strengthening phosphuret-(t)ed hydrogen.
The preferred pig manure of described animal excrement.
Substratum described in step (1) is take methyl alcohol as carbon source: COD is 600 ~ 1000mg/L; Take dipotassium hydrogen phosphate as phosphorus source, total phosphorous (TP) is 20 ~ 60mg/L; Take ammonium chloride as nitrogenous source, total nitrogen content (TN) is 20 ~ 40mg/L; Microelement nutritious liquid, add-on 1ml/L; Substratum first removes oxygen before use.
The condition of cultivating described in step (1) is: culture cycle is with 4 ~ 7 days for one-period, and anaerobism lucifuge, temperature 30 ~ 40 DEG C, pH6 ~ 7, redox potential (ORP) remains within the scope of 380 ~ 400mv.
Described microorganism electrolysis cell comprises cathode compartment and anolyte compartment, cathode compartment and anolyte compartment's proton exchange membrane are separated, cathode compartment and anolyte compartment arrange cathode electrode and anode electrode respectively, and Ag/AgCl reference electrode is set at cathode compartment, cathode electrode, anode electrode are connected by potentiostat wire with reference electrode.Its structural representation as shown in Figure 1.
Described cathode electrode and anode electrode are through pretreated carbon felt, described pretreated process is: carbon felt first washes away surface impurity with deionized water, then in NaOH and the HCl solution of 1mol/L, 30min is boiled successively, it is neutral for rushing with deionized water subsequently, finally be placed in baking oven, 105 DEG C of oven dry.
Distance between described cathode electrode and anode electrode is 3 ~ 5cm.
Described proton exchange membrane is soaked through deionized water and dilute sulphuric acid before use successively.
Centrifugal described in step (2) refers to centrifugal 10min under the condition of 3000r/min; Described washing refers to washs 3 times with 50mmol/L phosphate buffer solution (pH7.0).
Apply current potential described in step (3) and refer to the cathode potential applying-660mv ~-1410mv.
Substratum described in step (3) is identical with step (1); The condition of cultivating described in step (3) is: 1 ~ 4 day reaction time, culture temperature 30 ~ 40 DEG C, keeps stirring and anaerobic environment.
Construction process tool of the present invention has the following advantages and beneficial effect:
(1) the present invention by carrying out enrichment culture to product phosphuret-(t)ed hydrogen microorganism in advance outside microorganism electrolysis cell, improves success ratio of inoculation, shorten start time;
(2) cathode surface in the microorganism electrochemical system constructed by the present invention grow based on the mixed bacterial of solvent fermentation bacterium, not only there is phosphoric acid salt restoring function, and under suitable potential condition, output and the speed of the phosphuret-(t)ed hydrogen that phosphoric acid salt reduction generates can be improved;
(3) the present invention provides the environment with specific redox potential at cathode compartment by potentiostat, to microorganism, there is certain selective action, can tame out further to have and produce phosphuret-(t)ed hydrogen ability and possess compared with the chemically active microorganism of forceful electric power, and then optimize phosphuret-(t)ed hydrogen reducing property;
(4) convenience of drawing materials of the present invention, equipment is simple, easy to operate, with low cost.
Accompanying drawing explanation
Fig. 1 is the structural representation of microorganism electrolysis cell of the present invention.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
The microorganism electrolysis cell assembling process that following examples use is as follows:
Cut the proton exchange membrane of 6cm × 6cm, put into deionized water and soak 1 day, more stand-by after soaking half a day with dilute sulphuric acid;
Positive and negative electrode all adopts diameter to be 3cm, and thickness is 3mm carbon felt.Carbon felt first washes away surface impurity with deionized water, boils 30min successively in NaOH and the HCl solution of 1mol/L, and it is neutral for rushing with deionized water subsequently, is finally placed in baking oven, 105 DEG C of oven dry.
Room, microorganism electrolysis cell positive and negative pole useful volume is all 38mL, and cathode compartment is provided with Ar inlet, water-in, water outlet and gas acquisition port; Wrapped up by microorganism electrolysis cell masking foil, place proton exchange membrane and positive and negative electrode, interelectrode distance 3cm, the titanium silk that electronics is 1mm by diameter is derived; Insert Ag/AgCl reference electrode at cathode compartment and put into the rotor that can stir.Anode, negative electrode are respectively electrode, working electrode, and connect the corresponding joint of potentiostat respectively to reference electrode.
Embodiment 1
(1) enrichment culture of phosphuret-(t)ed hydrogen microorganism outside microorganism electrolysis cell is produced: in the brown anaerobism bottle of 3L, add 300g pig manure and 300g anaerobic sludge and 1L substratum, substratum take methyl alcohol as carbon source, COD is 800mg/L, take dipotassium hydrogen phosphate as phosphorus source, and TP is 50mg/L; Take ammonium chloride as nitrogenous source be nitrogenous source, TN is 30mg/L.Microelement nutritious liquid, add-on 1ml/L.Logical argon gas 5min deoxygenation before substratum uses, 35 DEG C of Anaerobic culturel in thermostat container, pH6.5, ORP are within the scope of 380 ~ 400mv.In 4 days each cycles, 8 all after dates complete the enrichment of producing phosphuret-(t)ed hydrogen microorganism, obtain the active sludge intermixture after being rich in the domestication of producing phosphuret-(t)ed hydrogen microorganism.
(2) the active sludge intermixture 10mL after domestication is got, through the centrifugal 10min of whizzer 3000r/min, obtain seed sludge after washing 3 times with 50mmol/L phosphate buffer solution (pH7.0), then seed sludge is joined in microorganism electrolysis cell and carry out biofilm.
(3) start microorganism electrolysis cell, set cathode potential as-660mv by potentiostat, use the substratum identical with step (1) to carry out Anaerobic culturel, logical argon gas 5min deoxygenation before substratum uses.Reaction time, 4d, ran about 20 cycles altogether.Suitably add phosphate buffer soln according to the changing conditions of pH or shorten reaction time.Culture temperature about 35 DEG C, pH keeps neutral.By the object regulating magnet rotor rotating speed to reach low rate mixing, the generation of strengthening phosphuret-(t)ed hydrogen, the phosphine gas of generation is discharged by the gas collecting mouth of microorganism electrolysis cell.
Embodiment 2
(1) enrichment culture of phosphuret-(t)ed hydrogen microorganism outside microorganism electrolysis cell is produced: in the brown anaerobism bottle of 3L, add 300g pig manure and 300g anaerobic sludge and 1L substratum, substratum take methyl alcohol as carbon source, COD is 800mg/L, take dipotassium hydrogen phosphate as phosphorus source, and TP is 50mg/L; Take ammonium chloride as nitrogenous source be nitrogenous source, TN is 30mg/L.Microelement nutritious liquid, add-on 1ml/L.Logical argon gas 5min deoxygenation before substratum uses, 35 DEG C of Anaerobic culturel in thermostat container, pH6.5, ORP are within the scope of 380 ~ 400mv.In 4 days each cycles, 8 all after dates complete the enrichment of producing phosphuret-(t)ed hydrogen microorganism, obtain the active sludge intermixture after being rich in the domestication of producing phosphuret-(t)ed hydrogen microorganism.
(2) the active sludge intermixture 10mL after domestication is got, through the centrifugal 10min of whizzer 3000r/min, obtain seed sludge after washing 3 times with 50mmol/L phosphate buffer solution (pH7.0), then seed sludge is joined in microorganism electrolysis cell and carry out biofilm.
(3) start microorganism electrolysis cell, set cathode potential as-760mv by potentiostat, use the substratum identical with step (1) to carry out Anaerobic culturel, logical argon gas 5min deoxygenation before substratum uses.Reaction time, 2d, ran about 20 cycles altogether.Suitably add phosphate buffer soln according to the changing conditions of pH or shorten reaction time.Culture temperature about 35 DEG C, pH keeps neutral.By the object regulating magnet rotor rotating speed to reach low rate mixing, the generation of strengthening phosphuret-(t)ed hydrogen, the phosphine gas of generation is discharged by the gas collecting mouth of microorganism electrolysis cell.
Embodiment 3
(1) enrichment culture of phosphuret-(t)ed hydrogen microorganism outside microorganism electrolysis cell is produced: in the brown anaerobism bottle of 3L, add 300g pig manure and 300g anaerobic sludge and 1L substratum, substratum take methyl alcohol as carbon source, COD is 800mg/L, take dipotassium hydrogen phosphate as phosphorus source, and TP is 50mg/L; Take ammonium chloride as nitrogenous source be nitrogenous source, TN is 30mg/L.Microelement nutritious liquid, add-on 1ml/L.Logical argon gas 5min deoxygenation before substratum uses, 35 DEG C of Anaerobic culturel in thermostat container, pH6.5, ORP are within the scope of 380 ~ 400mv.In 4 days each cycles, 8 all after dates complete the enrichment of producing phosphuret-(t)ed hydrogen microorganism, obtain the active sludge intermixture after being rich in the domestication of producing phosphuret-(t)ed hydrogen microorganism.
(2) the active sludge intermixture 10mL after domestication is got, through the centrifugal 10min of whizzer 3000r/min, obtain seed sludge after washing 3 times with 50mmol/L phosphate buffer solution (pH7.0), then seed sludge is joined in microorganism electrolysis cell and carry out biofilm.
(3) start microorganism electrolysis cell, set cathode potential as-1410mv by potentiostat, use the substratum identical with step (1) to carry out Anaerobic culturel, logical argon gas 5min deoxygenation before substratum uses.Reaction time, 1d, ran about 40 cycles altogether.Suitably add phosphate buffer soln according to the changing conditions of pH or shorten reaction time.Culture temperature about 35 DEG C, pH keeps neutral.By the object regulating magnet rotor rotating speed to reach low rate mixing, the generation of strengthening phosphuret-(t)ed hydrogen, the phosphine gas of generation is discharged by the gas collecting mouth of microorganism electrolysis cell.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. can strengthen a construction process for the microorganism electrochemical system that phosphuret-(t)ed hydrogen produces, it is characterized in that, comprise the following steps:
(1) animal excrement are mixed with anaerobic activated sludge, join in anaerobic reactor, then add substratum and cultivate, obtain the active sludge intermixture after being rich in the domestication of producing phosphuret-(t)ed hydrogen microorganism;
(2) get the active sludge intermixture after domestication, through centrifugal and with phosphate buffer solution washing after obtain seed sludge, then seed sludge is joined in microorganism electrolysis cell and carries out biofilm;
(3) apply current potential and add substratum to carry out Anaerobic culturel to microorganism electrolysis cell, the generation of strengthening phosphuret-(t)ed hydrogen.
2. a kind of construction process strengthening the microorganism electrochemical system that phosphuret-(t)ed hydrogen produces according to claim 1, is characterized in that: described animal excrement refer to pig manure.
3. a kind of construction process strengthening the microorganism electrochemical system that phosphuret-(t)ed hydrogen produces according to claim 1, it is characterized in that: the substratum described in step (1) take methyl alcohol as carbon source, COD is 600 ~ 1000mg/L; Take dipotassium hydrogen phosphate as phosphorus source, total phosphorous is 20 ~ 60mg/L; Take ammonium chloride as nitrogenous source, total nitrogen content is 20 ~ 40mg/L; Microelement nutritious liquid, add-on 1ml/L; Substratum first removes oxygen before use.
4. a kind of construction process strengthening the microorganism electrochemical system that phosphuret-(t)ed hydrogen produces according to claim 1, it is characterized in that: described in step (1) cultivate condition be: culture cycle with 4 ~ 7 days for one-period, anaerobism lucifuge, temperature 30 ~ 40 DEG C, pH6 ~ 7, redox potential remains within the scope of 380 ~ 400mv.
5. a kind of construction process strengthening the microorganism electrochemical system that phosphuret-(t)ed hydrogen produces according to claim 1, it is characterized in that: described microorganism electrolysis cell comprises cathode compartment and anolyte compartment, cathode compartment and anolyte compartment's proton exchange membrane are separated, cathode compartment and anolyte compartment arrange cathode electrode and anode electrode respectively, and Ag/AgCl reference electrode is set at cathode compartment, cathode electrode, anode electrode are connected by potentiostat wire with reference electrode.
6. a kind of construction process strengthening the microorganism electrochemical system that phosphuret-(t)ed hydrogen produces according to claim 5, it is characterized in that: described cathode electrode and anode electrode are through pretreated carbon felt, described pretreated process is: carbon felt first washes away surface impurity with deionized water, then in NaOH and the HCl solution of 1mol/L, 30min is boiled successively, it is neutral for rushing with deionized water subsequently, finally be placed in baking oven, 105 DEG C of oven dry; Described proton exchange membrane is soaked through deionized water and dilute sulphuric acid before use successively.
7. a kind of construction process strengthening the microorganism electrochemical system that phosphuret-(t)ed hydrogen produces according to claim 5 or 6, is characterized in that: the distance between described cathode electrode and anode electrode is 3 ~ 5cm.
8. a kind of construction process of microorganism electrochemical system strengthened phosphuret-(t)ed hydrogen and produce according to claim 1, is characterized in that: centrifugal described in step (2) refers to centrifugal 10min under the condition of 3000r/min; Described washing refers to the washing of 50mmol/L phosphate buffer solution.
9. a kind of construction process strengthening the microorganism electrochemical system that phosphuret-(t)ed hydrogen produces according to claim 1, is characterized in that: apply current potential described in step (3) and refer to the cathode potential applying-660mv ~-1410mv.
10. a kind of construction process strengthening the microorganism electrochemical system that phosphuret-(t)ed hydrogen produces according to claim 1, is characterized in that: the substratum described in step (3) is identical with step (1); The condition of cultivating described in step (3) is: 1 ~ 4 day reaction time, culture temperature 30 ~ 40 DEG C, keeps stirring and anaerobic environment.
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Cited By (4)
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| CN106731542A (en) * | 2016-12-26 | 2017-05-31 | 浙江工商大学 | The apparatus for electrochemical treatment and method of a kind of phosphine gas |
| CN107673463A (en) * | 2017-08-25 | 2018-02-09 | 国家海洋局天津海水淡化与综合利用研究所 | A kind of method of microorganism electro-catalysis efficient degradation parachloronitrobenzene |
| CN109111066A (en) * | 2018-10-11 | 2019-01-01 | 泉州师范学院 | A kind of method of bioelectrochemistry removal pig manure stink |
| CN114250146A (en) * | 2022-01-19 | 2022-03-29 | 中国科技开发院江苏分院 | Device and method for producing acetic acid by reducing carbon dioxide with electrode |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106731542A (en) * | 2016-12-26 | 2017-05-31 | 浙江工商大学 | The apparatus for electrochemical treatment and method of a kind of phosphine gas |
| CN106731542B (en) * | 2016-12-26 | 2024-03-26 | 浙江工商大学 | Electrochemical treatment device and method for phosphine gas |
| CN107673463A (en) * | 2017-08-25 | 2018-02-09 | 国家海洋局天津海水淡化与综合利用研究所 | A kind of method of microorganism electro-catalysis efficient degradation parachloronitrobenzene |
| CN109111066A (en) * | 2018-10-11 | 2019-01-01 | 泉州师范学院 | A kind of method of bioelectrochemistry removal pig manure stink |
| CN109111066B (en) * | 2018-10-11 | 2021-05-04 | 泉州师范学院 | Method for removing pig manure odor through bioelectrochemistry |
| CN114250146A (en) * | 2022-01-19 | 2022-03-29 | 中国科技开发院江苏分院 | Device and method for producing acetic acid by reducing carbon dioxide with electrode |
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