CN113594524A - Microbial electrosynthesis reactor for supplying carbon dioxide by using hollow fiber membrane and using method thereof - Google Patents
Microbial electrosynthesis reactor for supplying carbon dioxide by using hollow fiber membrane and using method thereof Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/16—Biochemical fuel cells, i.e. cells in which microorganisms function as catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention relates to CO supply by using hollow fiber membranes2The microbial electrosynthesis reactor and the use method thereof; the reactor adopts a mode of combining a stainless steel sheet, a biological carrier and a hollow fiber membrane; the electrode combined by the stainless steel sheet and the biological carrier is utilized to strengthen the electron transfer; and providing sufficient carbon source for the microorganisms in the biological carrier through the hollow fiber membrane in a bubble-free aeration mode. The electrode is formed by combining a stainless steel sheet and a carbon felt, and provides a large number of attachment sites for microorganisms; the advantages of the hollow fiber membrane are utilized to aerate the interior of the carbon felt, so that sufficient carbon sources are provided for microorganisms in the biological membrane, and the problem of limiting the activity of the anaerobic biological membrane to the maximum extent is solved; the electrode of the invention adopts a method of overlapping the stainless steel sheet and the biological carrier, and the current density of the electrode of the reactor is increased by 10 times on the premise of ensuring high coulomb efficiency. Because microbial communities with different functions exist on the biological carrier, the carbon chain is prolonged, and butyric acid with higher added value is synthesized.
Description
Technical Field
The invention belongs to the technical field of biochemical engineering and energy environment, and particularly relates to a method for supplying carbon dioxide (CO) by using a hollow fiber membrane2) The microbial electrosynthesis reactor and the use method thereof.
Background
With the rapid development of global economy, the consumption speed of natural resources by human beings is higher and higher, and fossil fuels such as coal and petroleum are used as the fossil fuelsHuman beings rely on one of the most important energy sources for survival and development, and the consumption rate is particularly remarkable. These fossil energy consumptions are accompanied by large amounts of CO2Resulting in an increasingly severe greenhouse effect. Due to CO2The greenhouse effect caused by the gases has increased by about 0.8 ℃ in the past 100 years, and IPPC-related experts speculated that by the end of the 21 st century, CO2Isothermal chamber gases will cause the average temperature of the earth to rise by 1.1-6.4 ℃. In addition, CO2The relative content of surface oxygen is reduced due to the large discharge of the nitrogen; the number of pests and diseases on the earth is increased; abnormal climate, rising sea level; the serious consequences of drought land, increased desertification area and the like. Realization of CO2One effective method for controlling and reducing emission is to utilize the resource. CO 22The resource conversion refers to the utilization of physical, chemical and biological technical means to convert CO into CO2A process for producing chemicals and fuels from raw materials. Thus, CO is converted2Resource utilization is a hot spot of the current domestic and foreign research.
Microbial Electrosynthesis System (MES) is an electrochemical reduction technology that is receiving increasing attention in the environmental and energy fields. MES is a process of synthesizing energy substances or chemicals by anodic oxidation or cathodic reduction using microorganisms adsorbed on electrodes as catalysts. Compared with the traditional catalyst, the microorganism has the advantages of high product selectivity, high long-term stability (self-regeneration), low catalytic overpotential and capability of producing long carbon chain organic matters. Since 2010 MES was used to fix CO2The research of synthesizing simple organic matters is vigorously developed, and the advantages of the research are that electron acceptors are cheap and easy to obtain; the energy efficiency of electrosynthesis is high and is about 100 times of the photosynthesis of plants; the operation condition is simple and mild; the reaction process is green and pollution-free.
Hollow fiber membranes are an important form of separation membranes. The membrane is in a capillary shape, micropores are positioned on the wall of the tube, the diameter is generally in the range of 0.05-2 mm, the membrane has self-supporting property, can be pressed without cracking, the specific surface area of the membrane in unit volume is large, the price is low, the flowing state of gas in the inner cavity of the hollow fiber is stable, the industrial amplification is easy, and the like.
Currently, almost all microbial electrosynthesis reactors rely on a biofilm on the cathode surface as a catalyst. Microbial electrosynthesis based on biofilms has the advantage of high electron utilization efficiency (coulombic efficiency), but in anaerobic biofilms, carbon source supply is a decisive factor in controlling microbial activity. It is known from literature and other data that most microbial electrosynthesis systems supply CO at the cathode2The mode of (1) is to place the air stone in the catholyte or directly explode air by using an infusion needle, and the modes have the problems that microorganisms on the surface of the carrier can obtain sufficient carbon source, and microorganisms in the carrier can not obtain sufficient carbon source, so that the activity of the whole microorganism is inhibited; easy over-supply of CO2Gas, which creates adverse conditions on the biofilm, and affects the activity of the biofilm, thereby reducing the performance of the microbial electrosynthesis system. The traditional cathode electrode adopts a biological carrier or carbon cloth, and has poor electrochemical performance and difficult electron transfer.
Disclosure of Invention
The invention aims to provide a method for supplying CO by utilizing a hollow fiber membrane2The microbial electrosynthesis reactor and the use method thereof adopt a mode of combining a stainless steel sheet, a biological carrier and a hollow fiber membrane to solve the problems of insufficient carbon source in the carrier and difficult electron transfer. The reactor designed by the invention has great significance for improving the performance of microbial electrosynthesis and realizing engineering application. By using the electrode combined by the stainless steel sheet and the biological carrier, the electron transfer is strengthened; and providing sufficient carbon source for the microorganisms in the biological carrier through the hollow fiber membrane in a bubble-free aeration mode. Thereby improving the productivity of the microbial electrosynthesis reactor and promoting the practical engineering application of microbial electrosynthesis.
The invention adopts the following technical scheme:
CO supply by utilizing hollow fiber membrane2The microbial electrosynthesis reactor adopts a mode of combining a stainless steel sheet, a biological carrier and a hollow fiber membrane. Using a combination of stainless steel sheets and biological carriersAn electrode, which enhances electron transfer; and providing sufficient carbon source for the microorganisms in the biological carrier through the hollow fiber membrane in a bubble-free aeration mode.
CO supply using hollow fiber membranes of the present invention2The reactor is divided into a cathode and an anode, a proton exchange membrane is arranged between the cathode and the anode, a cathode cavity is formed between the cathode and the proton exchange membrane, catholyte is added into the cathode cavity, a liquid outlet on the side surface of the upper part of the cathode cavity is connected to a liquid inlet on the side surface of the lower part of the cathode cavity through a cathode circulation route and a circulation pump to form catholyte circulation, so that catholyte can flow in the cathode cavity in an upward plug flow manner; an anode cavity is formed between the anode and the proton exchange membrane, anolyte is added into the anode cavity, and a liquid outlet on the side surface of the upper part of the anode cavity is connected to a liquid inlet on the side surface of the lower part of the anode cavity through an anode circulation route and a circulating pump to form anolyte circulation, so that catholyte can flow in the anode cavity in an upward plug flow manner; the cathode and the anode are respectively connected with the cathode and the anode of a direct current power supply, the cathode is composed of a stainless steel sheet and a carbon felt with a hollow fiber membrane sandwiched therebetween, and the hollow fiber membrane is connected with CO through a hose2A gas cylinder; the anode consists of a stainless steel sheet and a biological carrier; the top of the cathode and the anode of the reactor are respectively provided with a reference electrode, a sampler and an exhaust port.
The cathode and the anode are both in a mode of superposing a stainless steel sheet and a biological carrier, the biological carrier is a carbon felt, microorganisms are attached to the carbon felt to form a biological film, and the thickness is preferably 2-10 mm.
The CO supply by using the hollow fiber membrane2The reactor has a hollow fiber membrane disposed in the center of a cathode carbon felt, and CO is supplied by bubble-free aeration2Gas, one end of which is connected with CO through a hose2One end of the gas cylinder is connected with a hose and clamped by a clamp; and opening the clamp at fixed intervals to discharge water in the membrane and prevent the membrane pores from being blocked.
The CO supply by using the hollow fiber membrane2The sampler is a stainless steel pipe, one section of which is sealedDrilling a small hole on the side surface, marking scales from the position of the small hole to the other end, and collecting samples at different depths; rotate the aperture to different directions, can gather the sample of equidirectional not, when the sample connection was towards the carbon felt, obtain the inside solution of carbon felt, when the sample connection when the carbon felt dorsad, obtain main part solution to acquire the sample of different positions.
CO supply using hollow fiber membranes2The application method of the microbial electrosynthesis reactor comprises the steps of respectively adding anolyte and catholyte into an anode cavity and a cathode cavity, switching on a direct current power supply and a circulating water pump, and controlling CO in a hollow fiber membrane2The intake air flow rate of (1); inoculating anaerobic microorganisms, culturing for a period of time to allow the microorganisms to attach to the carbon felt to form a biofilm, replacing the culture solution, removing suspended microorganisms, and only leaving the biofilm attached to the carbon felt. The cathode biological membrane can utilize electrons provided by a direct current power supply and protons provided by an anode to convert CO2Reducing the organic matters into organic matters with high added values.
The anolyte is preferably a mixed solution of glucose, ammonium chloride, sodium dihydrogen phosphate and trace elements, wherein the concentration of glucose is 5g/L, the concentration of ammonium chloride is 0.382g/L, the concentration of potassium dihydrogen phosphate is 0.043g/L, the volume concentration of the trace elements is 1ml/L, the pH is 7, and N is utilized2The anolyte was purged for 20 minutes to bring the dissolved oxygen to less than 0.2 mg/L.
The catholyte is preferably a mixed solution of ammonium chloride, sodium dihydrogen phosphate and trace elements, wherein the concentration of ammonium chloride is 0.382g/L, the concentration of potassium dihydrogen phosphate is 0.043g/L, the volume concentration of trace elements is 1ml/L, the pH is 7, and N is used2The catholyte was purged for 20 minutes to bring the dissolved oxygen to less than 0.2 mg/L.
The configured trace elements in the catholyte and anolyte preferably comprise MnCl2·4H2The concentration of O is 0.8 g/L; CoCl2·6H2The concentration of O is 0.6 g/L; h3BO3The concentration is 0.2 g/L; CuCl2·2H2The concentration of O is 1.1 g/L; na (Na)2MoO4·2H2The concentration of O is 0.1 g/L; FeSO4·7H2The concentration of O is 3.2 g/L; NiCl2·6H2The concentration of O is 0.5 g/L; ZnSO4·7H2The O concentration was 3.2 g/L.
Compared with the prior art, the invention has the following beneficial technical effects:
compared with the traditional microbial electrosynthesis system based on the electrode surface biofilm, the invention has the advantages of high electrode current density, high coulombic efficiency, quick reactor starting time, high production intensity, high system stability and the like. The invention is characterized in that: (1) the electrode is formed by combining a stainless steel sheet and a carbon felt, the reason is that the stainless steel sheet has good electric conductivity and low price, and the carbon felt has higher specific surface area and can provide a large number of attachment sites for microorganisms, so that the biological membrane can obtain high biomass; (2) the advantages of the hollow fiber membrane are utilized to aerate the interior of the carbon felt, so that sufficient carbon sources are provided for microorganisms in the biological membrane, and the problem of limiting the activity of the anaerobic biological membrane to the maximum extent is solved; (3) the hollow fiber membrane is utilized for bubble-free aeration, the resistance of gas-liquid mass transfer is small, the disturbance to the surrounding environment is small, microorganisms can be attached to the surface of the hollow fiber membrane, and CO with strong reduction is screened out2A performance microorganism; (4) the pH gradient in the carbon felt is controlled by controlling the aeration quantity of the hollow fiber membrane to the inside of the carbon felt, so that the inside of the carbon felt is in a stable environment with difference along the thickness direction, and the community distribution of microorganisms is not uniform. However, the microorganisms are in the system and show synergy macroscopically. Due to the synergistic effect of different microbial communities, the carbon chain of the product is prolonged, the product is converted to VFAs with higher value, and higher yield is obtained. For controlling greenhouse effect, CO is realized2Resource utilization and carbon neutralization provide an effective way.
The invention has the following specific advantages:
(1) the electrode of the invention adopts a method of overlapping the stainless steel sheet and the biological carrier, and the current density of the electrode of the reactor is increased by 10 times on the premise of ensuring high coulomb efficiency.
(2) With conventional utilization of CO2Compared with the synthesis of acetic acid with low added value, the invention can realize the extension of carbon chains and the synthesis of attached substances due to the existence of microbial communities with different functions on the biological carrierHigher butyric acid was added.
Drawings
FIG. 1 is a schematic representation of CO supply using hollow fiber membranes according to the present invention2The schematic structure of the microbial electrosynthesis reactor of (1).
The device comprises a direct current power supply 1, a proton exchange membrane 2, a cathode water inlet 4, a hollow fiber membrane 5, a cathode carbon felt 6, a cathode stainless steel sheet 7, a water pump 8, a cathode 9, a reactor 10, catholyte 11, a catholyte circulation line 12, CO2Gas inlet line, 13, cathode exhaust port, 14, cathode sampling tube, 15, cathode reference electrode, 16, cathode water outlet, 17, anode exhaust port, 18, anode sampling tube, 19, anode reference electrode, 20, anolyte circulation line, 21, anolyte outlet, 22, anolyte, 23, anode, 24, anode stainless steel sheet, 25, anode carbon felt, 26, anode water inlet, 27, CO2A gas cylinder.
Detailed Description
The invention is described in further detail below with reference to the accompanying drawings:
referring to FIG. 1, CO supply using hollow fiber membranes2The microbial electrosynthesis reactor comprises a proton exchange membrane 2, an organic glass reactor 9, a gas supply system, a circulating system of anolyte and catholyte and the like, wherein the reactor elements are arranged as follows: in the cathode chamber, a stainless steel sheet 6 and a carbon felt 5 are superposed, and a hollow fiber membrane 4 is arranged in the carbon felt, wherein the stainless steel sheet 5 is close to the wall of the reactor 9 and is connected with the cathode of an external direct current power supply 1; one end of the hollow fiber membrane 4 and CO2The gas cylinder 27 is filled with CO2The air inlet line 12 is connected, one section of the air inlet line is connected with a hose, and the hose extends out of the cathode chamber and is clamped by a clamp; in the anode chamber, a stainless steel sheet 24 is superposed with a carbon felt 25, wherein the stainless steel sheet 24 is close to the wall of the reactor 9 and is connected with the anode of an external direct current power supply 1, the anode chamber and the cathode chamber are separated by a proton exchange membrane 2, and a sampling tube 14, a reference electrode 15 and an exhaust hole 17 are arranged above the cathode chamber; an exhaust hole 17, a sampling hole 18 and a reference electrode 19 are arranged above the anode chamber; the flow direction of the catholyte 10 and the anolyte 22 in the reactor is from the inlet opening 3 at the lower side to the outlet opening at the upper side16, the catholyte circulates through the catholyte circulation line 11 through the water pump 7; the flow direction of the anolyte 22 in the reactor is from a lower water inlet 26 to an upper water outlet 21, and the anolyte 22 is circulated by the anolyte circulation line 20 through the water pump 7.
CO supply using hollow fiber membranes2The reactor comprises a cathode and an anode, the cathode chamber and the anode chamber are separated by a proton exchange membrane, a cathode cavity is formed between the cathode and the proton exchange membrane, cathode liquid is added into the cathode cavity, a liquid outlet on the side surface of the upper part of the cathode cavity is connected to a liquid inlet on the side surface of the lower part of the cathode cavity through a cathode circulation route and a circulation pump to form cathode liquid circulation, so that the cathode liquid can flow in the cathode cavity in an upward plug flow manner; an anode cavity is formed between the anode and the proton exchange membrane, anolyte is added into the anode cavity, and a liquid outlet on the side surface of the upper part of the anode cavity is connected to a liquid inlet on the side surface of the lower part of the anode cavity through an anode circulation route and a circulating pump to form anolyte circulation, so that catholyte can flow in the anode cavity in an upward plug flow manner; the cathode and the anode are respectively connected with the cathode and the anode of a direct current power supply, the biological cathode is composed of a stainless steel sheet and a carrier which is clamped with a hollow fiber membrane and can be attached with microorganisms, and the hollow fiber membrane is connected with CO through a pipeline2A gas cylinder; the biological anode consists of a stainless steel sheet and a carrier capable of attaching microorganisms; the top of the cathode and the anode of the reactor are respectively provided with a reference electrode, a sampler and an exhaust port.
The cathode and the anode adopt a mode of overlapping a stainless steel sheet and a biological carrier, and the overlapping mode strengthens the path of electrons from the electrode to microorganisms; the corrosion-resistant stainless steel sheet is preferred, and the biological carrier is preferably a 3mm carbon felt.
The hollow fiber membrane is arranged in the cathode biological carrier in a bubble-free aeration mode, namely the pressure of a gas cylinder is under the pressure of the first bubble of the membrane wire, the mass transfer efficiency is high, and CO is generated2The molecule can directly enter into the solution, has small disturbance to the environment, is not easy to make the biological membrane fall off, and one end of the molecule is connected with CO through a pipeline2Gas cylinder, one end of the pipeline is in a closed state, every timeThe membrane is opened at a fixed time, and the moisture in the membrane is discharged at the fixed time to prevent the membrane pores from being blocked.
CO supply using hollow fiber membranes2The microbial electrosynthesis reactor is provided with anolyte, the mass concentration ratio of COD to N to P elements is about 100:5:1, oxygen in water is discharged through nitrogen purging, in order to prevent the toxic action of the oxygen on anaerobic microorganisms, the specific substances used are mixed solution of glucose, ammonium chloride, sodium dihydrogen phosphate and trace elements, wherein the concentration of the glucose is 5g/L, the concentration of the ammonium chloride is 0.382g/L, the concentration of the potassium dihydrogen phosphate is 0.043g/L, the volume concentration of the trace elements is 1ml/L, the pH is 7, and N is utilized2The anolyte was purged for 20 minutes to bring the dissolved oxygen to less than 0.2 mg/L.
CO supply using hollow fiber membranes2The microbial electrosynthesis reactor is prepared by catholyte, and the mixture ratio of the components is N: mass concentration ratio of P element 5:1, discharging oxygen in water by purging nitrogen, wherein in order to prevent the toxic action of oxygen on anaerobic microorganisms, a mixed solution of ammonium chloride, sodium dihydrogen phosphate and trace elements is specifically used, wherein the concentration of ammonium chloride is 0.382g/L, the concentration of potassium dihydrogen phosphate is 0.043g/L, the volume concentration of trace elements is 1ml/L, the pH value is 7, and N is used2The catholyte was purged for 20 minutes to bring the dissolved oxygen to less than 0.2 mg/L.
CO supply using hollow fiber membranes2The microbial electrosynthesis reactor, the configured microelements in the catholyte and anolyte, including MnCl2·4H2The concentration of O is 0.8 g/L; CoCl2·6H2The concentration of O is 0.6 g/L; h3BO3The concentration is 0.2 g/L; CuCl2·2H2The concentration of O is 1.1 g/L; na (Na)2MoO4·2H2The concentration of O is 0.1 g/L; FeSO4·7H2The concentration of O is 3.2 g/L; NiCl2·6H2The concentration of O is 0.5 g/L; ZnSO4·7H2The O concentration was 3.2 g/L.
CO supply using hollow fiber membranes2The method for acclimating biological membrane of microbial electrosynthesis reactor comprises the steps of placing the biological membrane in an anode cavity and placing the biological membrane in a cathode cavityRespectively adding anolyte and catholyte, connecting DC power supply and circulating water pump, and controlling CO in the hollow fiber membrane2The gas cylinder pressure of (a) is made to be under the bubble point pressure of the hollow fiber membrane; then adding CO which can be reduced into the reactor2The anaerobic activated sludge is derived from sludge in a secondary sedimentation tank of a Tianjin sewage treatment plant, and is domesticated to obtain anaerobic sludge; after acclimation for 10-20 days, detecting products (such as acetic acid, propionic acid, butyric acid and the like) which can be stably produced by the cathode; the anode has high degradation rate to COD, which indicates that the biological membrane is domesticated, the catholyte and the anolyte are replaced, suspended microorganisms are removed, and only the biological membrane attached to the biological carrier is left; the biofilm is capable of converting CO using electrons provided by the cathode and protons provided by the anode2Reducing into high value-added organic matters such as acetic acid and butyric acid.
CO supply with hollow fiber membranes of the invention2The specific operation method of the microbial electrosynthesis reactor is as follows: (1) assembling a cathode gas supply system, and opening the gas supply system; (2) adding catholyte, anolyte and activated sludge into a cathode cavity and an anode cavity of the reactor respectively, and assembling circulating systems of the catholyte and the anolyte; (3) switching on a direct current power supply, wherein the voltage value is 1V, and opening an anolyte circulating pump and a catholyte circulating pump; (4) sampling the reactor periodically and replacing the catholyte and the anolyte by adopting a sequencing batch mode; (5) during reactor operation, the cathode was sampled daily to determine the concentrations of inorganic carbon, organic carbon and VFAs in the solution to characterize the performance of the cathode. The anolyte was replaced every 5 days, its COD was measured, and its removal rate was calculated to monitor the microbial status of the anode. (6) The end of the hollow fiber membrane with the clamp is opened at a fixed time every day, and the time is counted, the water inside the membrane wire is drained, and the clamp is used for clamping when the water is drained completely.
Example 1 was carried out:
the hollow fiber membrane was placed inside the carbon felt and after the biofilm was applied, the reactor was operated continuously for 35 days during which time the cathode co-accumulated acetic acid: 549.3 mg/L; butyric acid: 615.4mg/L, maximum current density 11.213A m-2The removal rate of COD was 90. + -. 2.0%.
Example 2 was carried out:
placing the hollow fiber membrane outside the carbon felt, and after the biological membrane is used, continuously operating the reactor for 35d to accumulate acetic acid: 831.2 mg/L; butyric acid: 267.3mg/L, maximum current density of 10.94A · m-2The removal rate of COD was 83. + -. 2.0%. Example 3 of implementation:
the inside of carbon felt is arranged in to the hollow fiber membrane, after using good biomembrane, controls the pH of catholyte to be 7 +/-0.1 through adding phosphoric acid buffer solution, guarantees to move under invariable pH, accumulates acetic acid altogether in reactor continuous operation 15 d: 1359.8 mg/L; butyric acid: 79.02mg/L, maximum current density 11.777A m-2The removal rate of COD was 90. + -. 1.0%.
While the methods and techniques of the present invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and/or modifications of the methods and techniques described herein may be made without departing from the spirit and scope of the invention. It is expressly intended that all such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and content of the invention.
Claims (10)
1. CO supply by utilizing hollow fiber membrane2The microbial electrosynthesis reactor is characterized in that a mode of combining a stainless steel sheet, a biological carrier and a hollow fiber membrane is adopted, and an electrode combining the stainless steel sheet and the biological carrier is utilized to strengthen electron transfer; and providing sufficient carbon source for the microorganisms in the biological carrier through the hollow fiber membrane in a bubble-free aeration mode.
2. CO supply using hollow fiber membranes according to claim 12The microbial electrosynthesis reactor is characterized by comprising a cathode and an anode, a proton exchange membrane is arranged between the cathode and the anode, a cathode cavity is formed between the cathode and the proton exchange membrane, and catholyte is added into the cathode cavityA liquid outlet on the side surface of the upper part of the cathode cavity is connected to a liquid inlet on the side surface of the lower part of the cathode cavity through a cathode circulation route and a circulation pump to form cathode liquid circulation, so that the cathode liquid can flow in the cathode cavity in an upward plug flow mode; an anode cavity is formed between the anode and the proton exchange membrane, anolyte is added into the anode cavity, and a liquid outlet on the side surface of the upper part of the anode cavity is connected to a liquid inlet on the side surface of the lower part of the anode cavity through an anode circulation route and a circulating pump to form anolyte circulation, so that catholyte can flow in the anode cavity in an upward plug flow manner; the cathode and the anode are respectively connected with the cathode and the anode of a direct current power supply, the cathode is composed of a stainless steel sheet and a carbon felt of a hollow fiber membrane, and the hollow fiber membrane is connected with CO through a hose2A gas cylinder; the anode is composed of a stainless steel sheet and a carbon felt; the top of the cathode and the anode of the reactor are respectively provided with a reference electrode, a sampler and an exhaust port.
3. CO supply using hollow fiber membranes according to claim 22The microbial electrosynthesis reactor is characterized in that a cathode and an anode are overlapped by adopting a stainless steel sheet and a biological carrier.
4. CO supply using hollow fiber membranes according to claim 22The microbial electrosynthesis reactor is characterized in that a carbon felt is selected as a biological carrier, microorganisms are attached to the carbon felt to form a biological membrane, and the thickness is selected to be 2-10 mm.
5. CO supply using hollow fiber membranes according to claim 22The reactor is characterized in that a hollow fiber membrane is arranged in the center of a cathode carbon felt, and CO is supplied in a bubble-free aeration mode2Gas, one end of which is connected with CO through a hose2One end of the gas cylinder is connected with a hose and clamped by a clamp; and opening the clamp at fixed intervals to discharge water in the membrane and prevent the membrane pores from being blocked.
6. CO supply using hollow fiber membranes according to claim 22The microbial electrosynthesis reaction ofThe sampler is characterized in that the sampler is a stainless steel pipe, one end of the sampler is sealed, a small hole is formed in the side surface of the sampler, scales are marked from the position of the small hole to the other end of the sampler, and samples at different depths are collected; rotating the small holes to different directions to collect samples in different directions, and obtaining the solution in the carbon felt when the sampling port faces the carbon felt; the bulk solution was obtained when the sampling port was facing away from the carbon felt, thereby obtaining samples at different locations.
7. CO supply using hollow fiber membranes2The application method of the microbial electrosynthesis reactor is characterized in that anolyte and catholyte are respectively added into an anode cavity and a cathode cavity, a direct current power supply and a circulating water pump are connected, and CO in the hollow fiber membrane is controlled2The intake air flow rate of (1); then inoculating anaerobic microorganisms; initially, the microorganisms are present in suspension in the reactor, after a period of acclimation, the microorganisms are attached to the carbon felt, the culture broth is changed to remove the suspended microorganisms, leaving only the biofilm attached to the carbon felt. After that, the reactor is stably operated, and the concentration of the cathode product, the current change condition and the inorganic carbon concentration of the reactor are monitored during the operation of the reactor; the anode is changed every 5 days, the COD is measured, and the removal rate is calculated to represent the biological activity of the anode.
8. CO supply using hollow fiber membranes according to claim 72The using method of the microbial electrosynthesis reactor is characterized in that the anolyte is a mixed solution of glucose, ammonium chloride, sodium dihydrogen phosphate and trace elements, wherein the concentration of the glucose is 5g/L, the concentration of the ammonium chloride is 0.382g/L, the concentration of the potassium dihydrogen phosphate is 0.043g/L, the volume concentration of the trace elements is 1ml/L, the pH value is 7, and N is utilized2The anolyte was purged for 20 minutes to bring the dissolved oxygen to less than 0.2 mg/L.
9. CO supply using hollow fiber membranes according to claim 72The method for using the microbial electrosynthesis reactor is characterized in that catholyte is a mixed solution of ammonium chloride, sodium dihydrogen phosphate and trace elements, whereinThe concentration of ammonium chloride is 0.382g/L, the concentration of potassium dihydrogen phosphate is 0.043g/L, the volume concentration of trace elements is 1ml/L, the pH value is 7, and N is utilized2The catholyte was purged for 20 minutes to bring the dissolved oxygen to less than 0.2 mg/L.
10. CO supply using hollow fiber membranes according to claim 72The method for using the microbial electrosynthesis reactor is characterized in that configured trace elements in catholyte and anolyte comprise MnCl2·4H2The concentration of O is 0.8 g/L;
CoCl2·6H2the concentration of O is 0.6 g/L; h3BO3The concentration is 0.2 g/L; CuCl2·2H2The concentration of O is 1.1 g/L; na (Na)2MoO4·2H2The concentration of O is 0.1 g/L; FeSO4·7H2The concentration of O is 3.2 g/L; NiCl2·6H2The concentration of O is 0.5 g/L; ZnSO4·7H2The O concentration was 3.2 g/L.
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| US20070269886A1 (en) * | 2006-05-16 | 2007-11-22 | Becton, Dickinson And Company | Extracellular matrix coated surface for culturing cells |
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