CN109680290B - Coupling type bioelectrochemistry hydrogen production and collection device and system and hydrogen production method - Google Patents

Coupling type bioelectrochemistry hydrogen production and collection device and system and hydrogen production method Download PDF

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CN109680290B
CN109680290B CN201811618595.1A CN201811618595A CN109680290B CN 109680290 B CN109680290 B CN 109680290B CN 201811618595 A CN201811618595 A CN 201811618595A CN 109680290 B CN109680290 B CN 109680290B
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CN109680290A (en
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张志强
张姣
王作斌
夏四清
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Tongji University
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Abstract

The invention provides a coupling type bioelectrochemistry hydrogen production and collection device, a coupling type bioelectrochemistry hydrogen production and collection system and a hydrogen production method, wherein a first hydrophobic breathable film and a second hydrophobic breathable film are respectively arranged at the rear side and the front side of a cathode and respectively collect hydrogen remaining in the cathode side and electrolyte, so that a synergistic effect is achieved, a negative pressure pump realizes double negative pressure gas collection, an air bag is connected with the other end of a third gas collecting pipe through the negative pressure pump and a pipeline and is used for collecting and storing hydrogen, the purpose of quickly collecting the hydrogen generated in the system is achieved, and methanogen in the electrolyte is difficult to contact with the hydrogen; meanwhile, a methanation inhibitor is added into the electrolyte, so that methyl coenzyme M of the methanogen is chemically inactivated, and the methanogen is prevented from consuming hydrogen to generate methane by using the methyl coenzyme M, so that methanation is inhibited; the cathode and the anode are in the same chamber in the system, so that the internal resistance of the system is reduced, the coulomb efficiency is improved, and the aim of high-efficiency and continuous hydrogen production performance of the system is further fulfilled.

Description

Coupling type bioelectrochemistry hydrogen production and collection device and system and hydrogen production method
Technical Field
The invention belongs to the technical field of organic waste/wastewater, and particularly relates to a coupling type bioelectrochemistry hydrogen production and collection device, system and hydrogen production method.
Background
The bioelectrochemistry hydrogen production system can convert the chemical energy in the organic waste/wastewater into hydrogen, realizes the resource utilization of the organic waste/wastewater, and has wide development prospect in the field of organic waste/wastewater treatment. The bioelectrochemistry hydrogen production system is divided into two types of double chambers and a single chamber, and hydrogen is collected by gas diffusion. The anode and the cathode of the double-chamber bioelectrochemistry hydrogen production system are divided into two chambers by the ion exchange membrane, so that the methanogen is difficult to contact with hydrogen, and does not compete with the electrogen in the aspect of substrate utilization, so that the methanation degree is low; however, the anode and the cathode are respectively divided into two chambers, so that the system internal resistance is large, the coulombic efficiency is low, and the hydrogen production performance is poor. The anode and the cathode of the single-chamber bioelectrochemistry hydrogen production system are in the same chamber, so that the system has low internal resistance, high coulombic efficiency and good hydrogen production performance, and becomes a mainstream for development; however, hydrogen is easy to diffuse into the electrolyte, and methanogens produce methane by consuming hydrogen through methyl coenzyme M, so that the methanogens multiply greatly, the methanation phenomenon is serious, and the hydrogen production performance is gradually reduced. At present, the following methods are used for inhibiting the methanation of the bioelectrochemistry hydrogen production system:
1. the physical method comprises the following steps: 1) the introduction of air inhibits methanogenic activity, but this also reduces the activity of the electrogenic bacteria; 2) the applied voltage is increased to be more than 0.7V, the method is effective only in the initial stage, and the reactor still mainly produces methane after running for half a month; 3) the temperature is reduced to 4 ℃, methane bacteria are completely inhibited, but the reaction rate is reduced, and the energy consumption is increased; 4) ultraviolet irradiation, which is only effective for systems that have not undergone methanation, will not work once a stable methanogenic system is established in the system; 5) the configuration of the reactor is changed, a polytetrafluoroethylene membrane is additionally arranged between a cathode and an anode for separation, the cathode is tightly attached to the other side of the membrane, and a negative pressure pump is arranged at the tail end of the reactor, so that although hydrogen is effectively prevented from diffusing to the electrolyte side, the membrane between the anode and the cathode increases the internal resistance of a system, reduces the coulombic efficiency, has poor hydrogen production performance, and simultaneously has the problems of membrane pollution, scaling and the like caused by ion migration.
2. The chemical method comprises the following steps: 1) adding acid to reduce the pH value of the electrolyte and inhibit the activity of methanogens, but the activity of the methanogens can be reduced; 2) coenzyme M analogue is added as a methanation inhibitor, the currently effective coenzyme M analogue has 2-bromoethane sulfonate, an obvious inhibition effect can be observed, the concentration needs to be close to 0.6mM to completely inhibit the generation of methane, meanwhile, the 2-bromoethane sulfonate has certain toxicity, can stimulate eyes, a respiratory system and skin, and basically cannot be degraded in N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid (BES); 3) the halogenated aliphatic hydrocarbon, wherein chloroform in methyl chloride has a structure similar to methyl and a carbon-hydrogen bond with strong activity, can inhibit biological effects of functional enzymes such as methyl coenzyme M and the like, but has toxicity and irritation, and is a suspicious carcinogen.
Disclosure of Invention
Aiming at the defects of methanation, large internal resistance, gradual performance reduction and the like of a bioelectrochemistry hydrogen production system in the prior art, the invention mainly aims to provide a coupling type bioelectrochemistry hydrogen production and collection device.
The second purpose of the invention is to provide a coupled bioelectrochemical hydrogen production and collection system for realizing the device.
The third purpose of the invention is to provide a hydrogen production method using the system.
In order to achieve the above purpose, the solution of the invention is as follows:
a coupled bioelectrochemistry hydrogen production and collection device comprises an electrolysis chamber 1, an anode 2, a cathode 3, a first hydrophobic breathable film 4, a first gas collecting pipe 9, a second hydrophobic breathable film 6, a second gas collecting pipe 10, a third gas collecting pipe 11, a tee joint 8, a negative pressure pump 12 and an air bag 13.
Therein, an electrolysis chamber 1 for containing an electrolyte. Adding a methanation inhibitor into the electrolyte.
Anode 2 for supplying electrons and H+。
And a cathode 3 for generating hydrogen, wherein the rear side of the cathode 3 is tightly attached to the first hydrophobic breathable film 4.
And one end of the first gas collecting pipe 9 penetrates through the side wall of the first gas collecting chamber 5 and is arranged at the rear side of the cathode 3, and is used for collecting hydrogen at the side of the cathode 3.
One end of the second gas collecting pipe 10 penetrates through the side wall of the electrolysis chamber 1 and is arranged on the front side of the cathode 3, the tail end of the second gas collecting pipe is provided with a second hydrophobic breathable film 6, the second hydrophobic breathable film 6 is arranged in the electrolyte, and the second gas collecting pipe 10 is used for collecting residual hydrogen in the electrolyte.
And the tee joint 8 is used for connecting the other end of the first gas collecting pipe 9, the other end of the second gas collecting pipe 10 and one end of the third gas collecting pipe 11.
And the negative pressure pump 12 is connected with the tee joint 8 through the other end of the third gas collecting pipe 11 and is used for applying negative pressure to the inside of the first gas collecting pipe 9 and the inside of the second gas collecting pipe 10 through the third gas collecting pipe 11 and the tee joint 8 respectively.
And an air bag 13 connected to the other end of the third gas collecting pipe 11 through a negative pressure pump 12 and a pipeline, for collecting and storing hydrogen.
Preferably, the first hydrophobic breathable film 4 and the second hydrophobic breathable film 6 are each selected from one or more of a polytetrafluoroethylene film, a polyvinylidene fluoride film, and a polyethylene film.
Preferably, the methanation inhibitor is 3-nitroester-1-propanol at a concentration of 5.0X 10-6-5.0×10-3mol/L。
Preferably, the electrolyte is selected from a mixed solution containing a low-molecular organic acid.
Preferably, the mixed solution containing the low molecular organic acid is selected from one or more of organic waste anaerobic fermentation broth, organic wastewater anaerobic fermentation broth, and low molecular organic acid mixed solution with carbon chain number within twelve.
Preferably, the anode 2 is selected from one or more of a carbon brush, a carbon felt, a graphite felt, and a carbon cloth.
Preferably, the cathode 3 is selected from more than one of stainless steel felt, graphene electrode, carbon nanotube electrode, palladium modified electrode and platinum modified electrode.
Preferably, the negative pressure pump 12 is selected from one or more of a vacuum pump and a suction pump.
The coupled bioelectrochemistry hydrogen production and collection system for realizing the coupled bioelectrochemistry hydrogen production and collection device further comprises an external power supply 14, a resistor 15 and a collector 16.
The external power supply 14 is a voltage-stabilizing external power supply, and is used for adjusting the voltage of the system; the external power supply 14 is connected with the anode 2 and the cathode 3 through leads 17 respectively.
The collector 16 is a digital collector for displaying the current of the system; the digital collector is connected with two ends of the resistor 15 through a wire 17.
Preferably, the voltage of the external power supply 14 is 0.3-1.8V.
A method for realizing hydrogen production according to the coupled bioelectrochemistry hydrogen production and collection system comprises the following steps:
(1) culturing anode electrogenesis bacteria in microbial fuel cell mode
Mixing a culture medium and an inoculum according to the volume ratio of 1:1, removing dissolved oxygen, and then adding the mixture into a microbial fuel cell; connecting a resistor in a closed circuit system, operating in a static batch mode, directly adding a culture medium into the microbial fuel cell without using an inoculum after the voltage at two ends of the resistor exceeds 0.1V, repeating at least three cycles until the microbial fuel cell stably outputs the maximum voltage, and considering that the anode electrogenesis bacteria are enriched;
(2) hydrogen production in microbial cell mode
After the anode biomembrane is acclimated, starting the microbial electrolysis cell, replacing the cathode of the microbial fuel cell with the cathode of the microbial electrolysis cell, switching into a microbial electrolysis cell mode under an external voltage of 0.3-1.8V, connecting the anode (2) with the anode of an external power supply (14) through a lead, connecting the cathode (3) with the cathode of the external power supply (14) through a lead, and releasing electrons and H in the process of degrading organic matters by the anode (2)+And carbon dioxide, the electrons reaching the cathode (3) via an external circuit and being coupled to H at the cathode (3)+Generating hydrogen in a combined manner, simultaneously adding a methanation inhibitor into the electrolyte of the electrolytic cell and stirring the electrolyte, and operating in a static batch mode; when the current in the microbial electrolysis cell is lower than 0.1mA, replacing the fresh electrolyte, recording as an operation cycle, and repeating a plurality of cycles until the microbial electrolysis cell starts to produce hydrogen.
Preferably, the methanation inhibitor is 3-nitroester-1-propanol at a concentration of 5.0X 10-6-5.0×10-3mol/L。
Preferably, the culture medium consists of sodium acetate, phosphate buffer, vitamins and trace elements.
Preferably, the inoculum is selected from one or more of excess sludge and anaerobic sludge.
Preferably, the stirring manner is selected from more than one of turbine stirring, impeller stirring, paddle stirring, anchor stirring, propeller stirring and magnetic stirring.
Due to the adoption of the scheme, the invention has the beneficial effects that:
first, in the system of the invention, the first hydrophobic breathable film and the second hydrophobic breathable film are respectively arranged at the rear side and the front side of the cathode and respectively collect the hydrogen remaining in the cathode side and the electrolyte, thereby playing a synergistic role, i.e. the negative pressure pump collects the hydrogen on the cathode side through the first gas collecting pipe and collects the hydrogen remaining in the electrolyte through the second gas collecting pipe, so that the negative pressure pump realizes double negative pressure gas collection, thereby achieving the purpose of rapidly collecting the hydrogen generated in the system, leading methanogen in the electrolyte to be difficult to contact with the hydrogen, avoiding the methanogen to consume the hydrogen by utilizing methyl coenzyme M to generate methane, and further inhibiting methanation.
Secondly, the invention adds 5.0 multiplied by 10 in the hydrogen production method of bioelectrochemistry-6-5.0×10-3The 3-NOP methanation inhibitor enables methyl coenzyme M of the methanogen to be chemically inactivated, hydrogen consumption of the methanogen through the methyl coenzyme M is avoided, metabolic pathways of the methanogen are cut off, and the purpose of inhibiting methanation is further achieved, so that the hydrogen production performance of the system is remarkably enhanced, and the bioelectrochemistry hydrogen production system has higher application and popularization values.
Thirdly, the cathode and the anode are in the same chamber in the system, so that the internal resistance of the system is reduced, the coulombic efficiency is improved, and the aim of high-efficiency and continuous hydrogen production performance of the system is further fulfilled.
Drawings
FIG. 1 is a schematic structural diagram of coupled bioelectrochemical hydrogen production and collection systems according to example 1 of the present invention and a comparative example.
Fig. 2 is a schematic structural diagram of the coupled bioelectrochemical hydrogen production and collection system according to embodiment 2 of the present invention.
FIG. 3 is a schematic diagram of the hydrogen production effect of each embodiment and comparative example in the coupled bioelectrochemical hydrogen production and collection system of the present invention.
Detailed Description
The invention provides a coupling type bioelectrochemistry hydrogen production and collection device, a coupling type bioelectrochemistry hydrogen production and collection system and a hydrogen production method.
< coupled bioelectrochemical hydrogen production and collection apparatus >
A coupled bioelectrochemistry hydrogen production and collection device is shown in figure 1 and comprises an electrolysis chamber 1, an anode 2, a cathode 3, a first hydrophobic breathable film 4, a first gas collecting pipe 9, a second hydrophobic breathable film 6, a second gas collecting pipe 10, a third gas collecting pipe 11, a tee joint 8, a negative pressure pump 12 and an air bag 13.
Wherein the electrolytic chamber 1 is used for accommodating electrolyte, and the methanation inhibitor added in the electrolyte is 3-nitroester-1-propanol (3-NOP), the concentration of which is 5.0 multiplied by 10-6-5.0×10-3The mol/L can not only ensure the effective inhibition to methanogen, but also not reduce the activity of electrogenesis bacteria, and achieve the purpose of improving the coulombic efficiency, thereby ensuring the efficient and continuous hydrogen production performance of the system.
Therefore, the introduction of the methanation inhibitor 3-NOP into the electrolyte can cause the chemical inactivation of the methyl coenzyme M of the methanogen, avoid the methanogen from consuming hydrogen to generate methane through the methyl coenzyme M, cut off the metabolic pathway of the methanogen, and achieve the aim of inhibiting methanation, thereby enhancing the hydrogen production performance of the system. The 3-NOP mainly blocks the normal metabolism of methanogens by targeting the active site of methyl coenzyme M reductase, and has no toxic effect on organisms. However, 3-NOP is currently used for research on inhibition of methane emission in rumen of ruminant animals, and 3-NOP can effectively reduce about 30% of methane emission in rumen of dairy cow without generating toxic action on dairy cow.
The electrolyte is selected from a mixed solution containing low molecular organic acid which can be utilized by the anode electrogenic bacteria more quickly, thereby meaning that free electrons and H are generated more quickly+The electrochemical performance of the device is improved, and the generation of hydrogen is accelerated; the electrolyte comprises but is not limited to organic waste anaerobic fermentation liquor, low molecular organic acid mixed liquor with carbon chain number within twelve, and the like, is easy to be utilized by electrogenesis bacteria in the anode biomembrane, and is further beneficial to continuously and stably supplying free electrons and H to the anode 2+。
The anode 2 is used for supplying electrons and H+(ii) a The anode 2 includes but is not limited to carbon brush, carbon felt, graphite felt and carbon cloth, the anode 2 is an electrode with easy attachment of microorganism and large specific surface area, which is beneficial to anode persistence and stabilityFree electrons and H are supplied to ground+Not only improves the electrochemical performance of the device, but also accelerates the generation of hydrogen.
The cathode 3 is used for generating hydrogen, the rear side of the cathode 3 is tightly attached to the first hydrophobic breathable film 4, the length of the first hydrophobic breathable film 4 is larger than that of the cathode 3, the first hydrophobic breathable film 4 is divided into a main part and a secondary part, the length of the main part of the first hydrophobic breathable film 4 is the same as that of the cathode 3, the secondary part of the first hydrophobic breathable film 4 is a part formed by the two end sides of the cathode 3 and the side wall of the electrolysis chamber 1, the main part of the first hydrophobic breathable film 4 collects the hydrogen on the cathode 3 side, the secondary part of the first hydrophobic breathable film 4 not only collects the hydrogen on the cathode 3 side but also collects the hydrogen remained in the electrolyte, and the main part of the first hydrophobic breathable film 4 and the secondary part of the first hydrophobic breathable film 4 play a synergistic effect and jointly collect the hydrogen near the; the first gas collecting pipe 9 is used for collecting hydrogen on the cathode 3 side, penetrates through the side wall of the first gas collecting chamber 5 and is arranged on the rear side of the cathode 3, so that the first hydrophobic gas-permeable membrane 4 on the rear side of the cathode 3 and the adjacent electrolysis chamber 1 form the first gas collecting chamber 5 for the first gas collecting pipe 9 to collect the hydrogen, and the hydrogen can be collected quickly; the cathode 3 is an electrode with low hydrogen evolution potential and alkali corrosion resistance, including but not limited to a stainless steel felt, a graphene electrode, a carbon nanotube electrode, a palladium modified electrode or a platinum modified electrode, and the like, and is beneficial to free electrons and H+Hydrogen gas is formed in combination at the cathode 3, thereby improving the hydrogen generation performance of the device.
The second gas collecting pipe 10 penetrates through the side wall of the electrolysis chamber 1 and is arranged on the front side of the cathode 3, the funnel structure is inverted at the lower end of the second gas collecting pipe 10, a second hydrophobic gas-permeable membrane 6 is arranged at the end face of the funnel structure, the second hydrophobic gas-permeable membrane 6 is arranged in the electrolyte, a second gas collecting chamber 7 for the second gas collecting pipe 10 to collect hydrogen is formed between the second hydrophobic gas-permeable membrane 6 and the inverted funnel structure, and therefore the second gas collecting pipe 10 collects residual hydrogen in the electrolyte.
The tee joint 8 is used for connecting the other end of the first gas collecting pipe 9, the other end of the second gas collecting pipe 10 and one end of the third gas collecting pipe 11.
The negative pressure pump 12 is connected with the tee joint 8 through the other end of the third gas collecting pipe 11 and is used for applying negative pressure to the first gas collecting pipe 9 and the second gas collecting pipe 10 through the third gas collecting pipe 11 and the tee joint 8 respectively; the negative pressure pump 12 comprises, but is not limited to, a vacuum pump, a suction pump and the like, hydrogen generated by the cathode 3 electrode is collected through negative pressure lower than atmospheric pressure, so that methanogens in the electrolyte are difficult to contact with the hydrogen, the methanogens are prevented from consuming the hydrogen to generate methane by using methyl coenzyme M, the purpose of suppressing methanation is achieved, and therefore the efficient and continuous hydrogen production performance of the system is guaranteed.
As can be seen from the above, the first hydrophobic gas-permeable membrane 4 and the second hydrophobic gas-permeable membrane 6 are respectively disposed at the rear side and the front side of the cathode 3 to respectively collect hydrogen remaining at the cathode 3 side and in the electrolyte, and simultaneously play a role in synergy, that is, the negative pressure pump 12 mainly collects hydrogen at the cathode 3 side through the first gas collecting pipe 9, and also collects hydrogen remaining in the electrolyte through the second gas collecting pipe 10, so that the negative pressure pump 12 realizes double negative pressure gas collection to achieve the purpose of rapidly collecting hydrogen generated in the device, so that methanogen in the electrolyte is difficult to contact with hydrogen, and methanogen is prevented from consuming hydrogen to generate methane by using methyl coenzyme M, thereby inhibiting methanation; in addition, the anode 2 and the cathode 3 are in the same chamber, so that the internal resistance of the system is reduced, the coulombic efficiency is improved, and the aim of efficiently and continuously generating hydrogen by the system is further fulfilled.
The air bag 13 is connected with the other end of the third gas collecting pipe 11 through a pipeline and a negative pressure pump 12, and is used for collecting and storing hydrogen.
Specifically, the working process of the coupling type bioelectrochemistry hydrogen production and collection device is as follows: adding methanation inhibitor 3-NOP into the electrolyte in the coupling type bioelectrochemistry hydrogen production and collection device, and releasing electrons and H in the process of degrading organic matters by using the anode biomembrane+The electrons reach the cathode 3 through an external circuit and are at the cathode 3 and H+Combining to produce hydrogen; the negative pressure pump 12 collects hydrogen generated by the cathode 3 from the first gas collecting cavity 5 at the first gas collecting pipe 9 through the tee joint 8, and simultaneously intensively collects residual hydrogen in the electrolyte from the second gas collecting cavity 7 at the second gas collecting pipe 10, so that methanogens in the electrolyte are difficult to contact with the hydrogen, and the methanogens are prevented from consuming the hydrogen to generate methane by using methyl coenzyme M, and methanation is inhibited.
Coupled bioelectrochemical hydrogen production and collection system
A coupled bioelectrochemistry hydrogen production and collection system comprises the construction of the coupled bioelectrochemistry hydrogen production and collection system and the operation of the coupled bioelectrochemistry hydrogen production and collection system.
Wherein, the construction of the coupling type bioelectrochemistry hydrogen production and collection system comprises: the device comprises an electrolysis chamber 1, an anode 2, a cathode 3, a first hydrophobic breathable film 4, a first gas collecting chamber 5, a second hydrophobic breathable film 6, a second gas collecting chamber 7, a tee joint 8, a first gas collecting pipe 9, a second gas collecting pipe 10, a third gas collecting pipe 11, a negative pressure pump 12, a gas bag 13, an external power supply 14, a resistor 15, a collector 16 and a lead 17.
Wherein, the external power supply 14 is a voltage-stabilizing external power supply and is used for adjusting the voltage of the system; the external power supply 14 is respectively connected with the anode 2 and the cathode 3 through leads 17; the voltage of the external power supply 14 is 0.3-1.8V.
The collector 16 is a digital collector and is used for displaying the current of the system; the digital collector is connected with two ends of the resistor 15 through a wire 17.
The whole system is fixed by bolts, rubber plugs or rubber rings are used for sealing all the positions, and the joints are coated with epoxy resin to ensure the sealing performance of the whole system.
The operation of the coupled bioelectrochemical hydrogen production and collection system comprises the following steps: filling electrolyte into the electrolysis chamber 1, adding a methanation inhibitor 3-NOP into the electrolyte, controlling the voltage of the system to be 0.3-1.8V by a voltage-stabilizing external power supply, simultaneously starting a negative pressure pump 12, and respectively collecting hydrogen into an air bag 13 from a first gas collecting chamber 5 at a first gas collecting pipe 9 and a second gas collecting chamber 7 at a second gas collecting pipe 10 through a tee joint 8, namely, the generated hydrogen is quickly separated from a cathode 3 through a first hydrophobic breathable film 4 and a second hydrophobic breathable film 6 under the negative pressure applied by the negative pressure pump and is collected into the air bag 13; if the system is operated in a sequential batch mode, when the data acquisition unit displays that the current of the system is lower than 0.1mA, recording as an operation period, and replacing fresh electrolyte; if the continuous flow mode is used, the flow rate of the electrolyte is adjusted to enable the current of the system to be not lower than 0.1 mA.
< method for producing Hydrogen >
The invention firstly runs in a Microbial Fuel Cell (MFC) mode, carries out electrogenesis bacteria enrichment on an anode electrode, the top end of the MFC is provided with an opening, one side of a cathode carrying catalyst is directly contacted with electrolyte, and the other side of the cathode carrying catalyst is directly exposed in the air; and secondly, after the operation is switched into a Microbial Electrolysis Cell (MEC) mode, the top end of the MEC is sealed, one side of a cathode electrode is directly contacted with the electrolyte, and the other side of the cathode electrode is tightly attached to a hydrophobic breathable film and is connected with a negative pressure pump through a gas collecting pipe and then is connected with an air bag through the gas collecting pipe.
Specifically, the method for producing hydrogen by using the coupled bioelectrochemistry hydrogen production and collection system comprises the following steps:
(1) culturing anode electrogenesis bacteria in microbial fuel cell mode
Mixing a culture medium and an inoculum according to a volume ratio of 1:1, introducing high-purity nitrogen to blow off for 10min to remove dissolved oxygen in water, and then adding the mixture into a microbial fuel cell; connecting a resistor in a closed circuit system, operating in a static batch mode, directly adding a culture medium into the microbial fuel cell without using an inoculum after the voltage at two ends of the resistor exceeds 0.1V, repeating at least three cycles until the microbial fuel cell stably outputs the maximum voltage, and considering that the anode electrogenesis bacteria are enriched;
(2) hydrogen production in microbial cell mode
The microbial electrolysis cell is started after the anode biomembrane is acclimated, the cathode of the microbial fuel cell is replaced by the cathode of the microbial electrolysis cell, the microbial fuel cell (MEC) mode is switched into under the external voltage of 0.3-1.8V, the anode 2 is connected with the anode of an external power supply 14 through a lead, the cathode 3 is connected with the cathode of the external power supply 14 through a lead, the anode 2 releases electrons and H in the process of degrading organic matters+And carbon dioxide, the electrons reaching the cathode 3 through an external circuit and being coupled with H at the cathode 3+Generating hydrogen in a combined manner, simultaneously adding a methanation inhibitor into the electrolyte of the electrolytic cell and stirring the electrolyte, and operating in a static batch mode; when the current in the microbial electrolysis cell is lower than 0.1mA, replacing the fresh electrolyte and recordingRepeating a plurality of cycles for one operation cycle until the microbial electrolysis cell starts to produce hydrogen, and simultaneously starting the negative pressure pump to quickly collect the hydrogen generated by the cathode 3 into the air bag 13.
Wherein the methanation inhibitor is 3-nitro ester-1-propanol with concentration of 5.0 × 10-6-5.0×10-3mol/L。
The culture medium consists of sodium acetate, phosphate buffer solution, vitamins and trace elements.
The inoculum is selected from more than one of excess sludge or anaerobic sludge.
The stirring mode of the electrolyte comprises but is not limited to turbine stirring, impeller stirring, paddle stirring, anchor stirring, propulsion stirring or magnetic stirring and the like, so that the effects of concentration polarization are reduced, and H is accelerated+From the anode 2 electrode to the cathode 3 electrode. Through the stirring of the electrolyte, on one hand, the homogeneity of the electrolyte is ensured to the maximum extent, and the difference between the concentration near the anode and the concentration of the electrolyte in the electrolysis chamber 1 is reduced, so that the concentration polarization can be reduced; on the other hand in favor of H+Migration in the electrolyte, thereby promoting hydrogen gas generation at the cathode; in addition, the internal circulation can also make full use of the low molecular organic acid in the electrolyte.
The present invention will be further described with reference to the following examples.
Example 1:
the structure of the coupled bioelectrochemistry hydrogen production and collection system of the embodiment is shown in fig. 1, and includes an electrolysis chamber 1, an anode 2, a cathode 3, a first hydrophobic breathable film 4, a first gas collection chamber 5, a second hydrophobic breathable film 6, a second gas collection chamber 7, a tee joint 8, a first gas collection pipe 9, a second gas collection pipe 10, a third gas collection pipe 11, a negative pressure pump 12, an air bag 13, an external power supply 14, a resistor 15, a collector 16 and a lead 17, wherein the electrolysis chamber 1 is a cuboid made of organic glass material, a cylindrical cavity (with a cavity volume of 39ml and an effective liquid volume of 30ml) with a height of 5.5cm and a diameter of 3cm is arranged inside the electrolysis chamber 1, the anode 2 adopts a conductive carbon brush with a diameter of 3cm × 3cm, the carbon fiber and the lead with a diameter of 1mm are prepared by a spiral test tube brush, the cathode is a stainless steel felt, the anode 2 and the cathode 3 are both connected with an external circuit by leads with a diameter, the negative pressure pump 12 is a BT-100L flow type Lange negative pressure pump.
The hydrogen production method of the embodiment specifically comprises the following steps:
(1) culturing electrogenic anode bacteria in Microbial Fuel Cell (MFC) mode
Mixing a culture medium (consisting of sodium acetate, phosphate buffer solution, vitamins and trace elements) and an inoculum (excess sludge, sludge taken from a secondary sedimentation tank of a sewage treatment plant) according to the volume ratio of 1:1, introducing high-purity nitrogen gas to blow off for 10min so as to remove dissolved oxygen in water, and then adding the mixture into a microbial fuel cell; connecting a 1000 omega resistor into a closed circuit system, operating in a static batch mode, directly adding a culture medium into the microbial fuel cell without using an inoculum after the voltage at two ends of the resistor exceeds 0.1V, repeating at least three cycles until the microbial fuel cell stably outputs the maximum voltage, and considering that the anode electrogenesis bacteria are enriched;
(2) hydrogen production in microbial cell mode
Replacing the cathode of the microbial fuel cell with the cathode of a microbial electrolytic cell, taking sludge anaerobic fermentation liquor as an anode substrate, switching into a microbial electrolytic cell mode under the condition of 0.8V of external voltage (the anode of a carbon brush is connected with the anode of an external power supply through a lead, and the cathode electrode of a stainless steel felt is connected with the cathode of the external power supply through a lead), and operating in a static batch mode; when the current in the microbial electrolysis cell is lower than 0.1mA, replacing fresh electrolyte, recording as an operation period, operating for 24h per period, starting successfully until the microbial electrolysis cell is stable, and starting to produce hydrogen.
The operation process of the coupled bioelectrochemistry hydrogen production system of the embodiment is as follows: the method comprises the steps of taking sludge anaerobic fermentation liquor as an anode substrate, applying voltage (0.8V) to two sides of a microbial electrolytic cell, simultaneously starting a negative pressure pump, applying negative pressure of 0.01MPa, adding a methanation inhibitor 3-NOP into electrolyte of the electrolytic cell, stirring the electrolyte and carrying out hydrogen production reaction, wherein the hydrogen production rate (hydrogen production/total gas production) of the system is shown as a curve a in figure 3.
Example 2:
the coupled bioelectrochemistry hydrogen production and collection system of the embodiment is simplified based on the common single-chamber MEC, and the structure of the coupled bioelectrochemistry hydrogen production and collection system is shown in fig. 2, and the coupled bioelectrochemistry hydrogen production and collection system comprises an electrolysis chamber 1, an anode 2, a cathode 3, a gas collection port 4, a hydrophobic breathable film 5, a first lead 6, an external power supply 7, a second lead 8, a resistor 9, a third lead 10, a collector 11, a gas collection pipe 12, a negative pressure pump 13, a pipeline 14 and an air bag 15, wherein the electrolysis chamber 1 is a cuboid made of organic glass material, a cylindrical cavity (the cavity volume is about 39ml, the effective liquid volume is 30ml) with the height of 5.5cm and the diameter of 3cm is arranged inside the electrolysis chamber, the anode 2 adopts a conductive carbon brush with the height of 3cm × 3cm, the carbon fiber and the lead with the diameter of 1mm are prepared according to a spiral test tube brush sample, the rear side of the cathode, the cathode is stainless steel felt, the anode 2 and the cathode 3 are both connected with an external circuit by adopting leads with the diameter of 0.5mm, the negative pressure pump 13 is connected with a gas collecting port 4 arranged at the upper end of the microbial electrolysis cell through the other end of the gas collecting pipe 12 and is used for applying negative pressure in the gas collecting pipe 12, and the negative pressure pump 13 is a BT-100L flow type Lange negative pressure pump; the negative pressure pump 13 comprises, but is not limited to, a vacuum pump, a suction pump and the like, hydrogen generated by the cathode 3 electrode is collected through negative pressure lower than atmospheric pressure, so that methanogens in the electrolyte are difficult to contact with the hydrogen, the methanogens are prevented from consuming the hydrogen to generate methane by using methyl coenzyme M, the purpose of suppressing methanation is achieved, and therefore the efficient and continuous hydrogen production performance of the system is guaranteed.
Wherein, the air bag 15 is connected with the other end of the gas collecting pipe 12 through a pipeline and a negative pressure pump 13 and is used for collecting and storing hydrogen.
The external power supply 7 is a voltage-stabilizing external power supply and is used for adjusting the voltage of the system; the external power supply 7 is respectively connected with the anode 2 and the cathode 3 through a first lead 6, a second lead 8 and a third lead 10; the voltage of the external power supply 7 is 0.3-1.8V.
The collector 11 is a digital collector and is used for displaying the current of the system; the digital collector is connected with two ends of a resistor 9 through a second lead 8 and a third lead 10.
The whole system is fixed by bolts, rubber plugs or rubber rings are used for sealing all the positions, and the joints are coated with epoxy resin to ensure the sealing performance of the whole system.
The hydrogen production method in this example is the same as in example 1.
The operation process of the coupled bioelectrochemistry hydrogen production system of the embodiment is as follows: the sludge anaerobic fermentation broth is used as an anode substrate, when voltage (0.8V) is applied to two sides of a microbial electrolytic cell, a negative pressure pump is started simultaneously, negative pressure is applied to the microbial electrolytic cell to be 0.01MPa, a methanation inhibitor 3-NOP is added into the electrolyte of the electrolytic cell to stir the electrolyte and carry out hydrogen production reaction, and the hydrogen production rate (hydrogen production/total gas production) of the system is shown as a curve b in figure 3.
Comparative example 1:
the structure of the coupled bioelectrochemistry hydrogen production and collection system of the comparative example is shown in fig. 1, and comprises an electrolysis chamber 1, an anode 2, a cathode 3, a first hydrophobic breathable film 4, a first gas collection chamber 5, a second hydrophobic breathable film 6, a second gas collection chamber 7, a tee joint 8, a first gas collecting pipe 9, a second gas collecting pipe 10, a third gas collecting pipe 11, a negative pressure pump 12, an air bag 13, an external power supply 14, a resistor 15, a collector 16 and a lead 17, wherein the electrolysis chamber 1 is a cuboid made of organic glass material, a cylindrical cavity (the cavity volume is 39ml, the effective liquid volume is 30ml) with the height of 5.5cm and the diameter of 3cm is arranged in the electrolysis chamber, the anode 2 adopts a conductive carbon brush with the diameter of 3cm multiplied by 3cm, the carbon fiber and the lead with the diameter of 1mm are prepared according to a spiral test tube brush sample, the cathode is a stainless steel felt, the anode 2 and the cathode 3 are both connected with an external circuit by adopting a lead, the negative pressure pump 12 is a BT-100L flow type Lange negative pressure pump.
The hydrogen production method of this comparative example was the same as in example 1.
The operation process of the coupled bioelectrochemistry hydrogen production system of the comparative example is as follows: when sludge anaerobic fermentation liquor is used as an anode substrate, and voltage (0.8V) is applied to two sides of a microbial electrolytic cell, only the negative pressure pump 12 is started and negative pressure of 0.01MPa is applied, and a methanation inhibitor 3-NOP is not added into the electrolyte of the electrolytic cell, the operation is carried out for twenty cycles, and the hydrogen production rate (hydrogen production/total gas production) of the system is shown as a curve c in figure 3.
Comparative example 2:
the structure of the coupled bioelectrochemistry hydrogen production and collection system of the comparative example is shown in fig. 1, and comprises an electrolysis chamber 1, an anode 2, a cathode 3, a first hydrophobic breathable film 4, a first gas collection chamber 5, a second hydrophobic breathable film 6, a second gas collection chamber 7, a tee joint 8, a first gas collecting pipe 9, a second gas collecting pipe 10, a third gas collecting pipe 11, a negative pressure pump 12, an air bag 13, an external power supply 14, a resistor 15, a collector 16 and a lead 17, wherein the electrolysis chamber 1 is a cuboid made of organic glass material, a cylindrical cavity (the cavity volume is about 39ml and the effective liquid volume is 30ml) with the height of 5.5cm and the diameter of 3cm is arranged in the electrolysis chamber, the anode 2 adopts a conductive carbon brush with the diameter of 3cm multiplied by 3cm, the carbon fiber and the lead with the diameter of 1mm are prepared according to a spiral test tube brush sample, the cathode is a stainless steel felt, the anode 2 and the cathode 3 are both connected with an external circuit by adopting a lead, the negative pressure pump 12 is a BT-100L flow type Lange negative pressure pump.
The hydrogen production method of this comparative example was the same as in example 1.
The operation process of the coupled bioelectrochemistry hydrogen production system of the comparative example is as follows: when sludge anaerobic fermentation liquor is used as an anode substrate and voltage (0.8V) is applied to two sides of a microbial electrolytic cell, a negative pressure pump 12 is not started at the same time, only a methanation inhibitor 3-NOP is added into the electrolyte of the electrolytic cell to stir the electrolyte and carry out hydrogen production reaction, and the hydrogen production rate (hydrogen production/total gas production) of the system is shown as a curve d in figure 3.
In conclusion, the hydrogen production rate of the coupled bioelectrochemistry hydrogen production and collection system in the comparative example 1 is kept at a higher level in the initial stage of operation under the condition of negative pressure, which indicates that the methanogenesis reaction in the electrolyte is inhibited, and the system takes the hydrogen production as the main reaction; after the system runs for a certain period, the hydrogen production rate of the system is in a descending trend, which shows that the methane bacteria in the system starts to grow and reproduce again after adapting to the negative pressure low hydrogen condition, so that the hydrogen production rate of the system is reduced; compared with the coupled bioelectrochemistry hydrogen production and collection system in the comparative example 2, when the negative pressure pump is not started and only the methanation inhibitor 3-NOP is added, the hydrogen production rate of the system can be always maintained at a higher level, which shows that the internal methane production reaction is inhibited and only less hydrogen consumption exists; when the system in the embodiment 1 is started, the negative pressure pump is started to apply negative pressure and methanation inhibitor is added into the electrolyte, so that the hydrogen production rate of the system is always kept at a higher level and is higher than the hydrogen production rates of the systems in the comparative examples 1 and 2, and the method in the embodiment has good methanation inhibition consumption compared with the method of applying negative pressure by a simple post-positioned negative pressure pump or adding 3-NOP by a simple methanation inhibitor, and can keep the efficient and continuous hydrogen production performance of the system. Embodiment 2 simplifies the bioelectrochemistry hydrogen production and collection system of embodiment 1, and can collect most of hydrogen generated by the cathode, effectively delay methanation, and maintain good continuous hydrogen production capability; however, the effect was slightly inferior to that of example 1 because the collection of hydrogen gas generated at both ends of the cathode and hydrogen gas remaining in the electrolyte was limited.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. It will be readily apparent to those skilled in the art that various modifications to these embodiments and the generic principles defined herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments. Those skilled in the art should appreciate that many modifications and variations are possible in light of the above teaching without departing from the scope of the invention.

Claims (8)

1. A coupled bioelectrochemical hydrogen production and collection device comprising an electrolysis chamber (1), a first gas collection chamber (5), an anode (2) and a cathode (3), wherein: an electrolysis chamber (1) for containing an electrolyte;
an anode (2) for supplying electrons and H+；
A cathode (3) for generating hydrogen;
the method is characterized in that: it still includes: the device comprises a first hydrophobic breathable film (4), a first gas collecting pipe (9), a second hydrophobic breathable film (6), a second gas collecting pipe (10), a third gas collecting pipe (11), a tee joint (8), a negative pressure pump (12) and an air bag (13);
the rear side of the cathode (3), namely the side close to the first gas collecting chamber (5), is tightly attached to the first hydrophobic breathable film (4);
the first gas collecting chamber (5) is positioned at the rear side of the cathode (3);
the first gas collecting pipe (9) penetrates through the first gas collecting chamber (5) at one end and is used for collecting hydrogen on the side of the cathode (3);
one end of the second gas collecting pipe (10) penetrates through the side wall of the electrolysis chamber (1) and is arranged on the front side of the cathode (3), the tail end of the second gas collecting pipe is provided with the second hydrophobic breathable film (6), the second hydrophobic breathable film (6) is arranged in the electrolyte, and the second gas collecting pipe (10) is used for collecting residual hydrogen in the electrolyte;
the tee joint (8) is used for connecting the other end of the first gas collecting pipe (9), the other end of the second gas collecting pipe (10) and one end of the third gas collecting pipe (11);
the negative pressure pump (12) is connected with the tee joint (8) through the other end of the third gas collecting pipe (11) and is used for applying negative pressure to the first gas collecting pipe (9) and the second gas collecting pipe (10) through the third gas collecting pipe (11) and the tee joint (8) respectively;
the air bag (13) is connected with the other end of the third gas collecting pipe (11) through a negative pressure pump (12) and a pipeline and is used for collecting and storing hydrogen;
adding methanation inhibitor, specifically 3-NOP, into the electrolyte at a concentration of 5.0 × 10-6-5.0×10-3mol/L；
A methanation inhibitor is added into the electrolyte in the coupling type bioelectrochemistry hydrogen production and collection device, the anode biomembrane releases electrons and H + in the process of degrading organic matters, the electrons reach the cathode (3) through an external circuit, and the electrons are combined with the H + at the cathode (3) to produce hydrogen; the negative pressure pump (12) collects hydrogen generated by the cathode (3) from the first gas collecting cavity (5) at the first gas collecting pipe (9) through the tee joint (8), and simultaneously, the hydrogen remained in the electrolyte is intensively collected from the second gas collecting cavity (7) at the second gas collecting pipe (10), so that methanogens in the electrolyte are difficult to contact with the hydrogen, methane is prevented from being generated by the methanogens by consuming the hydrogen through methyl coenzyme M, and methanation is inhibited.
2. The coupled bioelectrochemical hydrogen production and collection device according to claim 1, wherein: the first hydrophobic breathable film (4) and the second hydrophobic breathable film (6) are respectively selected from more than one of polytetrafluoroethylene film, polyvinylidene fluoride film and polyethylene film.
3. The coupled bioelectrochemical hydrogen production and collection device according to claim 1, wherein: the electrolyte is selected from a mixed solution containing low-molecular organic acid;
the mixed liquid containing the low molecular organic acid is selected from more than one of organic waste anaerobic fermentation liquid, organic waste anaerobic fermentation liquid and low molecular organic acid mixed liquid with carbon chain number within twelve.
4. The coupled bioelectrochemical hydrogen production and collection device according to claim 1, wherein: the anode (2) is selected from more than one of a carbon brush, a carbon felt, a graphite felt and a carbon cloth;
the cathode (3) is selected from more than one of stainless steel felt, a graphene electrode, a carbon nanotube electrode, a palladium modified electrode and a platinum modified electrode.
5. The coupled bioelectrochemical hydrogen production and collection device according to claim 1, wherein: the negative pressure pump (12) is selected from one or more of a vacuum pump and a suction pump.
6. A coupled bioelectrochemical hydrogen production and collection method using the coupled bioelectrochemical hydrogen production and collection device according to any one of claims 1 to 5, characterized in that: the device also comprises an external power supply (14), a resistor (15) and a collector (16);
the external power supply (14) is a voltage-stabilizing external power supply and is used for adjusting voltage; the external power supply (14) is respectively connected with the anode (2) and the cathode (3) through leads (17);
the collector (16) is a digital collector and is used for displaying current; the digital collector is connected with two ends of the resistor (15) through a wire (17).
7. The method of claim 6, wherein: the voltage of the external power supply (14) is 0.3-1.8V.
8. The method of claim 7, wherein: the method comprises the following specific steps:
(1) culturing anode electrogenesis bacteria in microbial fuel cell mode
Mixing a culture medium and an inoculum according to the volume ratio of 1:1, removing dissolved oxygen, and then adding the mixture into a microbial fuel cell; connecting a resistor in a closed circuit system, operating in a static batch mode, directly adding the culture medium into the microbial fuel cell without using an inoculum after the voltage at two ends of the resistor exceeds 0.1V, repeating at least three cycles until the microbial fuel cell stably outputs the maximum voltage, and considering that the anode electrogenesis bacteria are enriched;
(2) hydrogen production in microbial cell mode
After the anode biomembrane is acclimated, starting the microbial electrolysis cell, replacing the cathode of the microbial fuel cell with the cathode of the microbial electrolysis cell, switching into a microbial electrolysis cell mode under an external voltage of 0.3-1.8V, connecting the anode (2) with the anode of an external power supply (14) through a lead, connecting the cathode (3) with the cathode of the external power supply (14) through a lead, and releasing electrons and H in the process of degrading organic matters by the anode (2)+And carbon dioxide, the electrons reaching the cathode (3) via an external circuit and being coupled to H at the cathode (3)+Generating hydrogen in a combined manner, simultaneously adding a methanation inhibitor into the electrolyte of the electrolytic cell and stirring the electrolyte, and operating in a static batch mode; when the current in the microbial electrolysis cell is lower than 0.1mA, replacing the fresh electrolyte, recording as an operation cycle, and repeating a plurality of cycles until the microbial electrolysis cell starts to produce hydrogen.
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