CN113594524B - 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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- 238000000034 method Methods 0.000 title claims abstract description 23
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title description 94
- 239000001569 carbon dioxide Substances 0.000 title description 47
- 229910002092 carbon dioxide Inorganic materials 0.000 title description 47
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- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 6
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 6
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 6
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 6
- 235000013619 trace mineral Nutrition 0.000 claims description 4
- 239000011573 trace mineral Substances 0.000 claims description 4
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- 235000001727 glucose Nutrition 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 abstract description 14
- 230000008901 benefit Effects 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 18
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- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
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Classifications
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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
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- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Biochemistry (AREA)
- Microbiology (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Apparatus Associated With Microorganisms And Enzymes (AREA)
Abstract
The present invention relates to the supply of CO using hollow fiber membranes 2 A microbial electrosynthesis reactor and a method of use thereof;the reactor adopts a mode of combining a stainless steel sheet and a biological carrier with a hollow fiber membrane; the electrode combined by the stainless steel sheet and the biological carrier is utilized to strengthen electron transfer; providing a sufficient carbon source for 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 inside 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 greatest extent is solved; the electrode adopts a method of superposing a stainless steel sheet and a biological carrier, and the current density of the electrode is increased by 10 times on the premise of ensuring high coulomb efficiency. As microbial communities with different functions exist on the biological carrier, the extension of carbon chains is realized, 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 in particular relates to a method for supplying carbon dioxide (CO) by using a hollow fiber membrane 2 ) Is provided.
Background
With the rapid development of global economy, the consumption speed of natural resources by human beings is faster and faster, and the consumption speed of fossil fuels such as coal and petroleum is particularly striking as one of the most important energy sources for survival and development of human beings. The process of these fossil energy consumption is accompanied by a large amount of CO 2 Leading to an increasingly serious greenhouse effect. Due to CO 2 Greenhouse effect by isogas, global ground average temperature has increased by about 0.8 ℃ over the last 100 years, and IPPC related experts speculate that CO by the end of the 21 st century 2 Isothermal cell gases will cause the average earth temperature to rise by 1.1-6.4 ℃. In addition, CO 2 The large amount of emissions of (2) can reduce the relative amount of surface oxygen; the plant diseases and insect pests on the earth are increased; abnormal climate, rising sea level; serious consequences of drought land, increased desertification area and the like. Realization of CO 2 One effective way to control and reduce emissions is to utilize it as a resource. CO 2 The resource transformation of (C) refers to the utilization of physical, chemical and biological technical means to convert CO 2 A method for producing chemical substances and fuel for raw materials. Thus, CO is converted into 2 The resource utilization is the research at home and abroadAnd hot spots.
Microbial electrosynthesis (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 CO 2 The research of synthesizing simple organic matters is vigorous, and the advantage of the method is that an electron acceptor is cheap and easily available; the energy efficiency of electrosynthesis is high, which is about 100 times of 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 membrane. 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 rupture, has the advantages of large specific surface area of the membrane in unit volume, low price, stable flowing state of gas in the inner cavity of the hollow fiber, easy industrial amplification and the like, and various hollow fiber membranes have been developed and put into use at present.
Currently, almost all microbial electrosynthesis reactors rely on biofilms on the cathode surface as catalysts. Biofilm-based microbial electrosynthesis 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 the literature and other data that most microbial electrosynthesis systems are supplied with CO at the cathode 2 The method is that the bubble stone is placed in the catholyte or is directly exploded by an infusion needle, and the problems of the methods are that microorganisms on the surface of the carrier can obtain sufficient carbon sources, microorganisms in the carrier can not obtain sufficient carbon sources, and the activity of the whole microorganism is inhibited; is easy to oversupply CO 2 The gas generates adverse conditions on the biological film, thereby affecting the activity of the biological film and reducing the performance of the microbial electrosynthesis system. The traditional cathode electrode adopts biological carrierThe body or carbon cloth has poor electrochemical performance and difficult electron transfer.
Disclosure of Invention
The present invention aims to provide a method for supplying CO by using hollow fiber membrane 2 The microbial electrosynthesis reactor and the application method thereof adopt a mode of combining a stainless steel sheet with a biological carrier and a hollow fiber membrane to solve the problems of insufficient carbon source and difficult electron transfer in the carrier. The reactor designed by the invention has great significance for improving the performance of the microbial electrosynthesis and realizing engineering application. The electron transfer is enhanced by utilizing an electrode of a combination of a stainless steel sheet and a biological carrier; providing a sufficient carbon source for microorganisms in the biological carrier through the hollow fiber membrane in a bubble-free aeration mode. Thereby, the productivity of the microbial electrosynthesis reactor is improved, and the practical engineering application of the microbial electrosynthesis is promoted.
The invention adopts the following technical scheme:
CO supply by using hollow fiber membrane 2 The microorganism electrosynthesis reactor adopts a mode of combining a stainless steel sheet and a biological carrier and a hollow fiber membrane. The electrode combined by the stainless steel sheet and the biological carrier is utilized to strengthen electron transfer; providing a sufficient carbon source for microorganisms in the biological carrier through the hollow fiber membrane in a bubble-free aeration mode.
The invention utilizes the hollow fiber membrane to supply CO 2 The microbial electrosynthesis reactor comprises a reactor constructed by utilizing organic glass, wherein the 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 upper side surface of the cathode cavity is connected to a liquid inlet on the lower side surface of the cathode cavity through a circulating pump by a cathode circulating route to form catholyte circulation, so that catholyte 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, anode liquid is added in the anode cavity, a liquid outlet on the upper side surface of the anode cavity is connected to a liquid inlet on the lower side surface of the anode cavity through an anode circulation route and a circulation pump to form anode liquid circulation, so that catholyte can flow in the anode cavity in an upward pushing wayA flow of formula (I); the cathode and the anode are respectively connected with the cathode and the anode of the direct current power supply, the cathode is composed of a stainless steel sheet and a carbon felt with a hollow fiber membrane in the middle, and the hollow fiber membrane is connected with CO through a hose 2 A 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 made of stainless steel sheets and biological carriers in a superposition mode, the biological carriers are carbon felts, microorganisms are attached to the carbon felts to form biological films, and the thickness of the biological films is preferably 2-10 mm.
The CO is supplied by using the hollow fiber membrane 2 A hollow fiber membrane is arranged at the center of a cathode carbon felt, and CO is supplied in a bubble-free aeration mode 2 A gas, one end of which is connected with CO through a hose 2 One end of the air bottle is connected with the hose and clamped by the clamp; the clip is opened every fixed time to drain the water in the membrane, so as to prevent the membrane hole from being blocked.
The CO is supplied by using the hollow fiber membrane 2 The sampler is a stainless steel pipe, one section of the stainless steel pipe is sealed, a small hole is formed in the side face of the stainless steel pipe, scales are marked from the position of the small hole to the other end of the stainless steel pipe, and samples with different depths are collected; the small holes are rotated to different directions, samples in different directions can be collected, when the sampling port faces the carbon felt, the solution inside the carbon felt is obtained, and when the sampling port faces away from the carbon felt, the main body solution is obtained, so that samples in different positions are obtained.
CO supply using hollow fiber membranes 2 The method for using the microbial electrosynthesis reactor comprises the steps of respectively adding anode liquid and cathode liquid 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 membrane 2 Is provided; inoculating anaerobic microorganisms, culturing for a period of time, allowing the microorganisms to adhere to the carbon felt to form a biological film, replacing the culture solution, and removing suspended microorganisms to leave only the biological film adhered to the carbon felt. The cathode biomembrane can utilize electrons provided by a direct current power supply and protons provided by an anode to convert CO 2 Reducing the organic matters into organic matters with high added value.
The anode liquid is preferably a mixed solution of glucose, ammonium chloride, sodium dihydrogen phosphate and microelements, 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 microelements is 1ml/L, the pH is 7, and N is utilized 2 The anolyte was purged for 20 minutes to bring the dissolved oxygen therein to less than 0.2mg/L.
The cathode liquid is preferably a mixed solution of ammonium chloride, sodium dihydrogen phosphate and microelements, wherein the concentration of ammonium chloride is 0.382g/L, the concentration of potassium dihydrogen phosphate is 0.043g/L, the volume concentration of microelements is 1ml/L, the pH is 7, and N is utilized 2 The catholyte was purged for 20 minutes to have less than 0.2mg/L dissolved oxygen.
The trace elements in the catholyte and anolyte are preferably composed of MnCl 2 ·4H 2 O concentration is 0.8g/L; coCl 2 ·6H 2 O concentration is 0.6g/L; h 3 BO 3 The concentration is 0.2g/L; cuCl 2 ·2H 2 The O concentration is 1.1g/L; na (Na) 2 MoO 4 ·2H 2 O concentration is 0.1g/L; feSO 4 ·7H 2 The O concentration is 3.2g/L; niCl 2 ·6H 2 O concentration is 0.5g/L; znSO (ZnSO) 4 ·7H 2 The O concentration was 3.2g/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 biomembrane, the invention has the advantages of high electrode current density, high coulomb efficiency, quick start time of the reactor, 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, wherein the stainless steel sheet has good conductive performance and low price, and the carbon felt has higher specific surface area, so that a large number of attachment sites can be provided for microorganisms, and a biological film can obtain high biomass; (2) The advantages of the hollow fiber membrane are utilized to aerate the inside 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 greatest extent is solved; (3) The hollow fiber membrane is utilized to perform 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 out 2 A microorganism of a property; (4) The pH gradient in the carbon felt is controlled by controlling the aeration quantity of the hollow fiber membrane in the carbon felt, so that the carbon felt has a differential steady-state environment in the thickness direction, and the community distribution of microorganisms is uneven. However, the microorganisms are in the present system and macroscopically show a synergistic effect. Due to the synergistic effect of different types of microbial communities, the carbon chain of the product is prolonged, the product is converted into VFAs with higher value, and higher yield is obtained. To control the greenhouse effect, CO 2 The resource utilization and the carbon neutralization provide an effective path.
The invention has the following specific advantages:
(1) The electrode adopts a method of superposing a stainless steel sheet and a biological carrier, and the current density of the electrode is increased by 10 times on the premise of ensuring high coulomb efficiency.
(2) Compared with the traditional method for utilizing CO 2 Compared with the synthesis of acetic acid with low added value, the invention can realize the extension of carbon chains and the synthesis of butyric acid with higher added value due to the existence of microbial communities with different functions on the biological carrier.
Drawings
FIG. 1 is a schematic diagram of the present invention for CO supply using hollow fiber membranes 2 Is a schematic structural diagram of a microorganism electrosynthesis reactor.
Wherein, 1, a direct current power supply, 2, a proton exchange membrane, 3, 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, CO 2 An air inlet line, 13, a cathode exhaust port, 14, a cathode sampling tube, 15, a cathode reference electrode, 16, a cathode water outlet, 17, an anode exhaust port, 18, an anode sampling tube, 19, an anode reference electrode, 20, an anolyte circulation line, 21, an anolyte outlet, 22, anolyte, 23, an anode, 24, an anode stainless steel sheet, 25, an anode carbon felt, 26, an anode water inlet, 27, CO 2 And (3) a gas cylinder.
Detailed Description
The invention is described in further detail below with reference to the attached drawing figures:
referring to FIG. 1, CO is supplied using hollow fiber membranes 2 Comprises a proton exchange membrane 2, a plexiglass reactor 9, a gas supply system, an anolyte and catholyte circulation system 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 overlapped, and a hollow fiber membrane 4 is arranged in the carbon felt, wherein the stainless steel sheet 5 is close to the wall of a reactor 9 and is connected with the negative electrode of an externally-added direct current power supply 1; one end of the hollow fiber membrane 4 is connected with CO 2 The gas cylinder 27 passing through CO 2 The air inlet line 12 is connected, one section 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 overlapped 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 positive electrode of an externally-applied 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 flowing direction of the catholyte 10 and the anolyte 22 in the reactor is from the water inlet hole 3 at the lower side to the water outlet hole 16 at the upper side, and the catholyte circulates through the catholyte circulation line 11 and the water pump 7; the flow direction of the anolyte 22 in the reactor is from the lower water inlet 26 to the upper water outlet 21, and the anolyte 22 is circulated by the anolyte circulation line 20 via the water pump 7.
CO supply using hollow fiber membranes 2 The reactor comprises a cathode and an anode, wherein a cathode chamber and an 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 upper side surface of the cathode cavity is connected to a liquid inlet on the lower side surface of the cathode cavity through a circulating pump by a cathode circulating route to form cathode liquid circulation, and therefore, the cathode liquid can flow in the cathode cavity in an upward pushing way; an anode cavity is formed between the anode and the proton exchange membrane, anode liquid is added in the anode cavity, 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 circulation pump to form anode liquid circulation, so that catholyte can be added in the anode cavityThe anode cavity flows in an upward plug flow mode; the cathode and the anode are respectively connected with the cathode and the anode of the direct current power supply, the biological cathode is composed of a stainless steel sheet and a carrier which is internally clamped with a hollow fiber membrane and can be attached with microorganisms, and the hollow fiber membrane is connected with CO through a pipeline 2 A gas cylinder; the biological anode consists of a stainless steel sheet and a carrier capable of adhering 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 are both made of stainless steel sheets and biological carriers in a superposition mode, and the superposition mode strengthens the path from the electrode to microorganisms; among them, corrosion-resistant stainless steel sheets are preferred, and 3mm carbon felt is preferred as the biological carrier.
The hollow fiber membrane is arranged in the cathode biological carrier, and the bubble-free aeration mode is adopted, namely the pressure of a gas cylinder is under the pressure of first bubbles of membrane wires, so that the mass transfer efficiency is high, and CO 2 Molecules can directly enter the solution, the disturbance to the environment is small, the biological film is not easy to fall off, and one end of the biological film is connected with CO through a pipeline 2 The gas cylinder, the pipeline that one end is connected is in the closed state, and fixed time opens every day, and the aqueous vapor in the membrane is discharged to fixed time, prevents the membrane hole jam.
CO supply using hollow fiber membranes 2 The ratio of the components is about COD: N: P element mass concentration ratio of 100:5:1 and the oxygen in the water is discharged through the sweeping of nitrogen, in order to prevent the toxic effect of the oxygen on anaerobic microorganisms, the specific used substances are glucose, ammonium chloride, sodium dihydrogen phosphate and microelement mixed solution, 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 microelement is 1ml/L, the pH is 7, and the N is utilized 2 The anolyte was purged for 20 minutes to bring the dissolved oxygen therein to less than 0.2mg/L.
CO supply using hollow fiber membranes 2 The ratio of the components of the prepared catholyte is N: the mass concentration ratio of the P element is 5:1 and oxygen in the water is purged by nitrogenIn order to prevent the toxic action of oxygen on anaerobic microorganisms, the substances specifically used are mixed solutions of ammonium chloride, sodium dihydrogen phosphate and microelements, wherein 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 microelements is 1ml/L, the pH is 7, and N is utilized 2 The catholyte was purged for 20 minutes to have less than 0.2mg/L dissolved oxygen.
CO supply using hollow fiber membranes 2 Is prepared from trace elements including MnCl 2 ·4H 2 O concentration is 0.8g/L; coCl 2 ·6H 2 O concentration is 0.6g/L; h 3 BO 3 The concentration is 0.2g/L; cuCl 2 ·2H 2 The O concentration is 1.1g/L; na (Na) 2 MoO 4 ·2H 2 O concentration is 0.1g/L; feSO 4 ·7H 2 The O concentration is 3.2g/L; niCl 2 ·6H 2 O concentration is 0.5g/L; znSO (ZnSO) 4 ·7H 2 The O concentration was 3.2g/L.
CO supply using hollow fiber membranes 2 Adding anode liquid and cathode liquid into anode cavity and cathode cavity, switching on DC power supply and circulating water pump, and controlling CO in hollow fiber membrane 2 Is set at the bubble point pressure of the hollow fiber membrane; then adding a catalyst capable of reducing CO into the reactor 2 Anaerobic sludge is obtained by acclimating secondary sedimentation tank sludge from a Tianjin sewage treatment plant; after 10-20 days of domestication, products (such as acetic acid, propionic acid, butyric acid and the like) which can be stably produced by the cathode are detected; the anode has high degradation rate for COD, which shows that the biological film is domesticated, the catholyte and the anolyte are replaced, suspended microorganisms are removed, and only the biological film attached to the biological carrier is left; the biofilm is capable of converting CO using electrons supplied by the cathode and protons supplied by the anode 2 Reducing into organic matters with high added value, such as acetic acid and butyric acid.
The invention supplies CO by using hollow fiber membrane 2 The specific operation method of the microbial electrosynthesis reactor is as follows: (1) Assembled cathode air supply system, open air supplyA system; (2) Respectively adding catholyte, anolyte and activated sludge into a cathode cavity and an anode cavity of the reactor, and assembling a circulation system of the catholyte and the anolyte; (3) Switching on a direct current power supply, wherein the voltage value is 1V, and switching on an anolyte circulating pump and a catholyte circulating pump; (4) The reactor is periodically sampled and the catholyte and anolyte are replaced in a sequencing batch mode; (5) During the operation of the reactor, the cathode was sampled daily to determine the concentration of inorganic carbon, organic carbon and VFAs in its solution to characterize the performance of the cathode. The anolyte was replaced every 5 days, and 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 fixed time every day, and the water in the membrane wires is discharged at fixed time, and the clamp is used for clamping after the water is drained.
Implementation example 1:
the hollow fiber membrane was placed inside the carbon felt and after the biofilm was used, the reactor was run continuously for 35 days during which period the cathode co-accumulated acetic acid: 549.3mg/L; butyric acid: 615.4mg/L, maximum current density of 11.213 A.m -2 The removal rate of COD is 90+/-2.0%.
Implementation example 2:
the hollow fiber membrane was placed outside the carbon felt, and after using the biofilm, the reactor was run continuously for 35d, co-accumulating acetic acid: 831.2mg/L; butyric acid: 267.3mg/L, maximum current density of 10.94 A.m -2 The removal rate of COD is 83+/-2.0%. Implementation example 3:
placing the hollow fiber membrane in the carbon felt, after using the biological membrane, controlling the pH of the catholyte to 7+/-0.1 by adding a phosphoric acid buffer solution, ensuring the operation under constant pH, and co-accumulating acetic acid in 15 days of continuous operation of the reactor: 1359.8mg/L; butyric acid: 79.02mg/L, maximum current density of 11.777 A.m -2 The removal rate of COD is 90+/-1.0%.
The technical scheme disclosed and proposed by the invention can be realized by a person skilled in the art by appropriately changing the condition route and other links in consideration of the content of the present invention, although the method and the preparation technology of the invention have been described by the preferred embodiment examples, the related person can obviously modify or recombine the method and the technical route described herein to realize the final preparation technology without departing from the content, 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 included within the spirit, scope and content of the invention.
Claims (9)
1. CO supply by using hollow fiber membrane 2 The 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 combined by the stainless steel sheet and the biological carrier is utilized to strengthen electron transfer; providing a sufficient carbon source for microorganisms in the biological carrier through the hollow fiber membrane in a bubble-free aeration mode; the 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 in the cathode cavity, a liquid outlet on the upper side surface of the cathode cavity is connected to a liquid inlet on the lower side surface of the cathode cavity through a circulating pump by a cathode circulating route, and catholyte circulation is formed, so that catholyte can flow in the cathode cavity in an upward pushing flow mode; an anode cavity is formed between the anode and the proton exchange membrane, anode liquid is added in the anode cavity, a liquid outlet on the upper side surface of the anode cavity is connected to a liquid inlet on the lower side surface of the anode cavity through an anode circulation route by a circulation pump to form anode liquid circulation, so that cathode liquid can flow in the anode cavity in an upward pushing flow mode; the cathode and the anode are respectively connected with the cathode and the anode of the direct current power supply, a stainless steel sheet and a carbon felt are overlapped in a cathode chamber, a hollow fiber membrane is arranged in the carbon felt, and the hollow fiber membrane is connected with CO through a hose 2 A gas cylinder; the anode consists of a stainless steel sheet and a carbon felt; the top parts of the cathode and the anode of the reactor are respectively provided with a reference electrode, a sampler and an exhaust port; the biological carrier is carbon felt.
2. Supplying CO with hollow fiber membranes as in claim 1 2 The microbial electrosynthesis reactor is characterized in that a stainless steel sheet and a biological carrier are overlapped on each other.
3. Supplying CO with hollow fiber membranes as in claim 1 2 The 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 film, and the thickness is selected to be 2-10 mm.
4. Supplying CO with hollow fiber membranes as in claim 1 2 A microorganism electrosynthesis reactor of (2) is characterized in that a hollow fiber membrane is arranged at the center of a cathode carbon felt and CO is supplied in a bubble-free aeration mode 2 A gas, one end of which is connected with CO through a hose 2 One end of the air bottle is connected with the hose and clamped by the clamp; the clip is opened every fixed time to drain the water in the membrane, so as to prevent the membrane hole from being blocked.
5. Supplying CO with hollow fiber membranes as in claim 1 2 The microbial electrosynthesis reactor is characterized in that the sampler is a stainless steel pipe, one end of the stainless steel pipe is sealed, a small hole is formed in the side surface of the stainless steel pipe, scales are marked from the position of the small hole until the other end of the stainless steel pipe is reached, and samples with different depths are collected; the small holes are rotated to different directions, samples in different directions can be collected, and when the sampling port faces the carbon felt, a solution in the carbon felt is obtained; when the sampling port is away from the carbon felt, a main body solution is obtained, so that samples at different positions are obtained.
6. A method for supplying CO using hollow fiber membranes as claimed in claim 1 2 The method for using the microbial electrosynthesis reactor is characterized in that anode liquid and cathode liquid 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 controlled 2 Is provided; then inoculating anaerobic microorganisms; initially, microorganisms exist in a suspended state in a reactor, after a period of domestication, the microorganisms adhere to the carbon felt, and a culture solution is replaced to remove the suspended microorganisms, so that only a biological film adhering to the carbon felt is left; thereafter, the reactor was operated steadily and the reactor cathode product concentration was monitored during the reactor operationCurrent variation and inorganic carbon concentration; the anodes were changed every 5 days, and the COD was measured, and the removal rate was calculated to characterize the bioactivity of the anodes.
7. Supplying CO with hollow fiber membranes as in claim 6 2 The 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 is 7, and N is utilized 2 The anolyte was purged for 20 minutes to bring the dissolved oxygen therein to less than 0.2mg/L.
8. Supplying CO with hollow fiber membranes as in claim 6 2 The using method of the microbial electrosynthesis reactor is characterized in that the catholyte is a mixed solution of ammonium chloride, sodium dihydrogen phosphate and microelements, wherein 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 microelements is 1ml/L, the pH is 7, and N is utilized 2 The catholyte was purged for 20 minutes to have less than 0.2mg/L dissolved oxygen.
9. Supplying CO with hollow fiber membranes as in claim 6 2 The using method of the microbial electrosynthesis reactor is characterized in that the microelements in the catholyte and the anolyte comprise MnCl 2 ·4H 2 O concentration is 0.8g/L; coCl 2 ·6H 2 O concentration is 0.6g/L; h 3 BO 3 The concentration is 0.2g/L; cuCl 2 ·2H 2 The O concentration is 1.1g/L; na (Na) 2 MoO 4 ·2H 2 O concentration is 0.1g/L; feSO 4 ·7H 2 The O concentration is 3.2g/L; niCl 2 ·6H 2 O concentration is 0.5g/L; znSO (ZnSO) 4 ·7H 2 The O concentration was 3.2g/L.
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| AU2008201015A1 (en) * | 2002-04-25 | 2008-03-20 | Alteco Medical Ab | Improved separation |
| CN103170251A (en) * | 2011-12-20 | 2013-06-26 | 新奥科技发展有限公司 | Coating liquid used for preparing CO2 separating composite film, and CO2 separating composite film |
| CN103754990A (en) * | 2013-12-19 | 2014-04-30 | 天津工业大学 | Bipolar three-dimension electrode coupling treatment device for treatment of non-biodegradable organic wastewater |
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