阅读说明：本技术 一种电解氢气鼓泡塔微生物电合成反应器及其使用方法 (A kind of electrolysis hydrogen tympanites bubble column microorganism electro synthesis reactor and its application method ) 是由 郭坤 于 2019-07-25 设计创作，主要内容包括：本发明公开了一种电解氢气鼓泡塔微生物电合成反应器及其使用方法,所述反应器由底部的电解槽、上端的鼓泡塔、以及阴极液外循环系统上的气液接触真空纤维膜组件和pH控制器等组成。置于反应器底部的电解槽为鼓泡塔提供微纳米氢气泡,鼓泡塔内悬浮的微生物将氢气和CO<Sub>2</Sub>转化为相应的有机物。本发明装置既适用于H<Sub>2</Sub>介导的微生物CO<Sub>2</Sub>固定工艺,也适用于H<Sub>2</Sub>驱动的污水微生物脱氮工艺。本发明较传统的基于电极表面生物膜的微生物电合成系统具有电极电流密度高、库伦效率高、反应器启动时间快、生产强度高、系统稳定性高等优点。与传统的基于外源氢气的气体发酵反应器相比,本发明实现了微纳米氢气泡的原位供应,避免了氢的储运和产生微纳米氢气泡的能量消耗。(The invention discloses a kind of electrolysis hydrogen tympanites bubble column microorganism electro synthesis reactor and its application method, the reactor by the electrolytic cell of bottom, the bubble tower of upper end and catholyte external circulating system gas-liquid contact vacuum fiber film component and pH controller etc. form.It is placed in the electrolytic cell of reactor bottom and provides micro-nano bubble hydrogen for bubble tower, the microorganism to suspend in bubble tower is by hydrogen and CO 2 It is converted into corresponding organic matter.Apparatus of the present invention are not only suitable for H 2 The Microbial biomass C O of mediation 2 Technique for fixing is also applied for H 2 The sewage Microbial denitrogenation technique of driving.The more traditional microorganism electro synthesis system based on electrode surface biomembrane of the present invention is high with electrode current density, coulombic efficiency is high, the reactor start-up time is fast, production intensity height, high system stability advantages.Compared with traditional gaseous fermentation reactor based on external source hydrogen, the present invention realizes the supply in situ of micro-nano bubble hydrogen, avoids the storage and transportation of hydrogen and generates the energy consumption of micro-nano bubble hydrogen.)

1. a kind of electrolysis hydrogen tympanites bubble column microorganism electro synthesis reactor, which is characterized in that including electrolytic cell (3), electrolytic cell (3) In be provided with the anode (2) of tubular, the cation-exchange membrane (7) of tubular, cation-exchange membrane (7) are provided on the inside of anode (2) Inside is provided with cathode (5), and anode (2) and cathode (5) are respectively connected to the anode and cathode of DC power supply (1), and cation is handed over It changes on the upside of film (7) and is connected with bubble tower (8), the inside of the cation-exchange membrane (7) and bubble tower (8) forms cathode cavity, Anode cavities are formed between on the inside of the outside and electrolytic cell (3) of the cation-exchange membrane (7) and bubble tower (8), are added in cathode cavity Added with catholyte (9), there are the suspended microspheres or filler of microorganism, anode in catholyte (9) added with suspension microorganism or load Anolyte (4) are added in chamber, the outlet of cathode cavity bottom is connected to bubble tower (8) top by catholyte recycle circuit (17) Inlet, be disposed with water circulating pump (11), gas-liquid contact vacuum fiber film component on catholyte recycle circuit (17) (12) and CO is arranged in pH monitor controller (15), the top of gas-liquid contact vacuum fiber film component (12)₂Air inlet (14), lower part It is provided with cathode exhaust gas outlet (13), the gas outlet at the top of bubble tower (8) is connected to CO by cathode gas recycle circuit (16)₂ Air inlet (14).

2. a kind of electrolysis hydrogen tympanites bubble column microorganism electro synthesis reactor according to claim 1, which is characterized in that described Anode (2) is titanium net cylinder.

3. a kind of electrolysis hydrogen tympanites bubble column microorganism electro synthesis reactor according to claim 1, which is characterized in that described Cathode (5) includes central axis and is uniformly distributed several layers titanium net disk on center shaft.

4. a kind of electrolysis hydrogen tympanites bubble column microorganism electro synthesis reactor according to claim 1, which is characterized in that anode Anodic gas outlet (6) is offered on chamber.

5. a kind of electrolysis hydrogen tympanites bubble column microorganism electro synthesis reactor according to claim 1, which is characterized in that be bubbled Sample tap (10) are provided in the middle part of the outer wall of tower (8).

6. a kind of electrolysis hydrogen tympanites bubble column microorganism electro synthesis reactor according to claim 1, which is characterized in that load There are the suspended microspheres of microorganism or filler is the polymer microsphere or suspension microorganism filler for being embedded with microorganism.

7. a kind of electrolysis hydrogen tympanites bubble column microorganism electro synthesis reactor according to claim 1, which is characterized in that described Anolyte is the H of 0.01mol/L₂SO₄Solution.

8. a kind of electrolysis hydrogen tympanites bubble column microorganism electro synthesis reactor according to claim 1, which is characterized in that described Catholyte is Na₂HPO₄、KH₂PO₄、NH₄Cl、NaCl、MgSO₄·7H₂O、CaCl₂With the mixed solution of peptone, wherein Na₂HPO₄Concentration be 6g/L, KH₂PO₄Concentration be 3g/L, NH₄The concentration of Cl is 0.5g/L, and the concentration of NaCl is 0.5g/L, MgSO₄·7H₂The concentration of O is 0.1g/L, CaCl₂Concentration be 14.6mg/L, the concentration of peptone is 0.5g/L.

9. a kind of application method of electrolysis hydrogen tympanites bubble column microorganism electro synthesis reactor, using one kind described in claim 1 Electrolysis hydrogen tympanites bubble column microorganism electro synthesis reactor, which is characterized in that be separately added into anolyte in anode cavities and cathode cavity (4) and catholyte (9) DC power supply (1), water circulating pump (11) and pH monitor controller (15), are connected, and controls CO₂Air inlet (14) charge flow rate, reactor run 2h or more under aseptic conditions to remove the dissolved oxygen of catholyte (9)；Then to reaction Device inoculation can utilize hydrogen reducing CO₂Anaerobe, microorganism exists with suspended state in the bubble tower (8), Neng Gouli The hydrogen generated with catholyte is by CO₂It is reduced to corresponding organic matter, is detected in reactor operational process micro- in bubble tower (8) Biological concentration, goes out gas velocity and composition, cathode and anode electrode current potential and DC power output voltage at production concentration.

Technical field

The invention belongs to biochemical industries and energy environment technical field, and in particular to a kind of electrolysis hydrogen tympanites bubble column microorganism Electro synthesis reactor and its application method.

Background technique

Since the industrial revolution, the production and living of the mankind consume a large amount of fossil energy, and have discharged into atmosphere more next More CO₂, this seriously destroys the carbon cycle of nature.Therefore, CO₂Emission reduction and resource utilization are that world community man compels One task of the eyebrows and eyelashes.In recent years, in order to substitute fossil energy, the mankind can give birth to the energy (such as wind energy, solar energy, water energy, life Substance energy, geothermal energy, ocean energy etc.) development and utilization in terms of also achieve the achievement advanced by leaps and bounds.However, due to renewable The energy especially wind energy and solar energy have the features such as very strong intermittence, randomness, regionality and unbalanced supply-demand, renewable The practical utilization efficiency of electric energy is also relatively low, causes very big installed capacity waste.Therefore, the storage of Reproduceable electricity is to work as The hot spot studied both at home and abroad down.

Using Reproduceable electricity by CO₂It is reduced into chemicals or fuel, CO both may be implemented₂Resourcable transformation, and can Dump energy is stored, mitigating the dependence to fossil fuel for the mankind and alleviating energy and environment dual-pressure has Highly important realistic meaning.Therefore, one electro-catalysis reduction CO has been started in world wide in recent years₂Research boom, In CO₂Many important achievements have been emerged in terms of electrocatalysis material, reaction mechanism, electrolyte and reactor.However, CO₂Electrochemistry Reduction technique from actual industrialization application it is also far apart, presently, there are main problem be that catalyst activity is high not enough, make It is poor lower with the selectivity of product with stability.

Microorganism electro synthesis (microbial electrosynthesis, MES) is a kind of electrification emerging over 2010 Learn CO₂Reduction technique, it is using microorganism as catalyst by CO₂Electroreduction is organic matter (such as methane, acetic acid, butyric acid) Process.Compared with traditional catalyst, microorganism has that selectivity of product is high, long-time stability high (can self-regeneration), catalysis The advantages of overpotential is low and can produce Long carbon chain organic matter.In in the past few years, people are having found electroactive microorganism, understanding yin It achieves and advances by leaps and bounds in terms of pole-microorganism electron mechanism, optimization cathode electrode material and synthesis high added value organic matter Achievement.But relative to pure electrochemistry CO₂Reduction, the Product formation rate of microorganism electro synthesis is also relatively low, this is mainly Because delivery rate of the electronics from cathode to microorganism is lower (low current density).

Currently, almost all of microorganism electro synthesis reactor is all to rely on the biomembrane of cathode surface as catalyst. Microorganism electro synthesis based on biomembrane has the advantages that electronics utilization efficiency (coulombic efficiency) is high, but the generation of biomembrane is non- Normal time-consuming (several thoughtful some months) and current density room for promotion is extremely limited.The cathode electronics transport mechanism having proposed includes straight Connect the electron transmission of electron transmission and electrolysis hydrogen mediation.Theoretically, the microorganism electro synthesis reactor cathode table mediated based on hydrogen Face biomembrane it is not necessary to, departing from the limitation of biomembrane, one to two orders of magnitude are can be improved in the current density of electrode, As long as the microorganism to suspend in catholyte can timely consume the bubble hydrogen of cathode generation, high coulombic efficiency equally may be implemented Microorganism electro synthesis.However, the microorganism electro synthesis reactor registered at present is difficult to realize high current density and high coulomb Micro- raw electro synthesis of efficiency.Therefore, designing can be to realize the microorganism electricity of high coulombic efficiency in high current density service condition Synthesis reactor is great to the Practical Project application value of microorganism electro synthesis.

Summary of the invention

The purpose of the present invention is to provide a kind of electrolysis hydrogen tympanites bubble column microorganism electro synthesis reactor and its application method, To solve the problems, such as that microorganism electro synthesis high current density and high coulombic efficiency cannot get both, to promote microorganism electro synthesis Practical Project application.

In order to achieve the above objectives, the present invention adopts the following technical scheme:

A kind of electrolysis hydrogen tympanites bubble column microorganism electro synthesis reactor, including electrolytic cell are provided with tubular in electrolytic cell Anode, anode inner side are provided with the cation-exchange membrane of tubular, and cathode, anode and cathode point are provided on the inside of cation-exchange membrane It is not connected to the anode and cathode of DC power supply, bubble tower, the cation-exchange membrane are connected on the upside of cation-exchange membrane Cathode cavity is formed with the inside of bubble tower, forms sun between the cation-exchange membrane and the outside and electrolytic cell inside of bubble tower Pole chamber, is added with catholyte in cathode cavity, in catholyte added with suspension microorganism or load have microorganism suspended microspheres or Filler is added with anolyte in anode cavities, and the outlet of cathode cavity bottom is connected to bubble tower top by catholyte recycle circuit Inlet, water circulating pump, gas-liquid contact vacuum fiber film component and pH monitoring control are disposed on catholyte recycle circuit CO is arranged in the top of device processed, gas-liquid contact vacuum fiber film component₂Air inlet, lower part are provided with cathode exhaust gas outlet, bubble tower The gas outlet at top is connected to CO by cathode gas recycle circuit₂Air inlet.

Further, the anode is titanium net cylinder.

Further, the cathode includes central axis and is uniformly distributed several layers titanium net disk on center shaft.

Further, anodic gas outlet is offered in anode cavities.

Further, sample tap is provided in the middle part of the outer wall of bubble tower.

Further, load has the suspended microspheres of microorganism or filler is polymer microsphere or the suspension for being embedded with microorganism Microbe stuffing.

Further, the anolyte is the H of 0.01mol/L₂SO₄Solution.

Further, the catholyte is Na₂HPO₄、KH₂PO₄、NH₄Cl、NaCl、MgSO₄·7H₂O、CaCl₂And peptone Mixed solution, wherein Na₂HPO₄Concentration be 6g/L, KH₂PO₄Concentration be 3g/L, NH₄The concentration of Cl is 0.5g/L, NaCl Concentration be 0.5g/L, MgSO₄·7H₂The concentration of O is 0.1g/L, CaCl₂Concentration be 14.6mg/L, the concentration of peptone is 0.5g/L。

A kind of application method of electrolysis hydrogen tympanites bubble column microorganism electro synthesis reactor, in anode cavities and cathode cavity respectively Anolyte and catholyte is added, connects DC power supply, water circulating pump and pH monitor controller, and control CO₂The air inlet of air inlet Flow, reactor run 2h or more under aseptic conditions to remove the dissolved oxygen of catholyte；Then it can be utilized to reactor inoculation Hydrogen reducing CO₂Anaerobe, microorganism exists in bubble tower with suspended state, can be generated using catholyte Hydrogen is by CO₂Be reduced to corresponding organic matter, detected in reactor operational process microorganism concn in bubble tower, production concentration, Gas velocity and composition, cathode and anode electrode current potential and DC power output voltage out.

Compared with prior art, the invention has the following beneficial technical effects:

It is the microorganism electro synthesis device based on electrolysis bubble hydrogen and suspension microorganism that the present invention, which is electrolysed bubbling column reactor,. It is placed in the electrolytic cell of reactor bottom and provides micro-nano bubble hydrogen for bubble tower, the microorganism to suspend in bubble tower is produced using electrolysis Raw hydrogen is by the CO of dissolution₂It is reduced to corresponding organic matter.Being electrolysed the bubble generated in situ is micro-nano bubble in solution Residence time it is longer, and electrolyte be in dissolved hydrogen hypersaturated state.It is bubbled tower structure and further ensures microorganism and hydrogen Time of contact.Therefore, dissolved hydrogen supersaturation and longer bubble hydrogen residence time realize reactor in high current density item High coulombic efficiency microorganism electro synthesis under part.

(1) compared with traditional microorganism electro synthesis reactor, electrolysis bubbling column reactor provided by the invention is guaranteeing The electrode current density of reactor and product formation rate is set to improve 10 times or more in the case where high coulombic efficiency.(2) this hair Bright microorganism reactor does not depend on electrode surface biomembrane, can start in 1-3 after reactor inoculation, more traditional based on life The microorganism electro synthesis reactor start-up time of object film shortens 70% or more.(3) microorganism reactor electrode of the invention can be It is run under high current density, electrode area needed for reactor is small, and the constructions cost compared with the reactor based on biomembrane lowers 50% More than.(4) with traditional gaseous fermentation reactor based on external source hydrogen, electrolysis bubbling column reactor hydrogen provided by the invention Microbubble supplies in situ, and avoiding problems energy consumptions needed for the storage and transportation of hydrogen and generation microbubble.

Further, the concentration of microorganism in bubble tower can be improved in the addition of suspension microorganism filler, while can change Ascending path of the transformation electrolytic bubble hydrogen in bubble tower to improve retention time of the bubble hydrogen in tower, and then improves reaction The utilization efficiency of hydrogen in device；It, can be with using being embedded with the polymer microsphere of microorganism as the biocatalyst in bubble tower It improves the biomass in reactor, the starting time for shortening reactor, avoided simultaneously because thallus is lost caused by changing liquid.

Detailed description of the invention

Fig. 1 is electrolysis hydrogen tympanites bubble column microorganism electro synthesis structure of reactor schematic diagram of the invention.

Wherein, 1, DC power supply, 2, anode, 3, electrolytic cell, 4, anolyte, 5, cathode, 6, anodic gas outlet, 7, sun from Proton exchange, 8, bubble tower, 9, catholyte, 10, sample tap, 11, water circulating pump, 12, gas-liquid contact vacuum fiber film component, 13, cathode exhaust gas exports, 14, CO₂Air inlet, 15, pH monitor controller, 16, cathode gas recycle circuit, 17, catholyte follows Loop wire road.

Specific embodiment

Present invention is further described in detail with reference to the accompanying drawing:

Referring to Fig. 1, a kind of electrolysis bubble tower microorganism electro synthesis reactor, including the supply of electrolytic cell 3, bubble tower 8, gas With output system, fluid circulation system, circuit control system etc., each element arrangement of the reactor is as follows: electrolytic cell 3 is placed in The bottom of bubble tower 8 in situ by way of electrolysis can provide bubble hydrogen to bubble tower 8, and the bubble generated is micro-nano Bubble, electrolytic cell 3 is tubular type configuration, from outside to inside successively by titanium net cylinder anode, tubular type cation-exchange membrane and multi-layer discs titanium Net cathode composition.The anode 2 of electrolytic cell 3 is connected with the anode of DC power supply 1 with cathode respectively with cathode 5.Bubble tower 8 is placed in electricity The upper end for solving slot 3, is connected with the cathode 5 of electrolytic cell 3.8 inner cathode liquid 9 of bubble tower is continuously pumped by external circulation line from bottom end To bubble tower top, stirring is sufficiently mixed with realize catholyte.Catholyte outer circulating tube road connects gas-liquid contact vacuum fiber Membrane module 12 and pH monitor controller 15, the former is for dissolving the CO being newly added₂With the unreacted H of recycling₂And CO₂, the latter is used for The pH in bubble tower is monitored and controlled, for converting H₂And CO₂Microorganism be in suspended state rather than be grown in cathode surface Biomembrane.Bubble tower top sets gas vent, the outlet unreacted gas and the CO that newly inputs₂Enter gas-liquid after gas mixing Vacuum fiber film component 12 is contacted, the final tail gas of reactor goes out from the cathode exhaust gas of 12 bottom end of gas-liquid contact vacuum fiber film component Mouth 13 is discharged.

As an improvement of the present invention, suspension microorganism filler, suspension microorganism can be added in the bubble tower The concentration of microorganism object in bubble tower can be improved in the addition of filler, while it is upper in bubble tower to can change electrolysis bubble hydrogen Path is risen, to improve retention time of the bubble hydrogen in tower, and then improves the utilization efficiency of hydrogen in reactor.

It is improved as another kind of the invention, the macromolecule that the microorganism in bubble tower is also possible to be embedded with microorganism is micro- Ball.The polymer microsphere for being embedded with microorganism can be prepared outside reactor.Made using the polymer microsphere for being embedded with microorganism For the biocatalyst in bubble tower, the biomass in reactor can be improved, shorten the starting time of reactor while avoiding Because thallus is lost caused by changing liquid.

Electrolysis hydrogen tympanites bubble column microorganism electro synthesis reactor application method of the invention is as follows: (1) in anode electrolytic cell Anolyte and catholyte are separately added into chamber and cathode cavity；(2) DC power supply, catholyte circulating pump, pH controller, CO are connected₂ Gas controller, reactor run 2h or more under aseptic conditions to remove the dissolved oxygen of catholyte；(3) reactor inoculation can benefit With hydrogen reducing CO₂Anaerobe, microorganism existed with suspended state in being bubbled, can be generated using catholyte Hydrogen is by CO₂It is reduced to corresponding organic matter；(4) reactor catholyte is replaced using batch-type mode, utilizes liquid-level controller It is automatic to add anolyte to compensate the consumption of anode electrolysis water.(5) it is dense that microorganism in bubble tower is detected in reactor operational process Degree, goes out gas velocity and composition, anode and cathode electrode potential and DC power output voltage at production concentration.

Below with reference to embodiment, the present invention will be described in detail:

A kind of electrolysis hydrogen tympanites bubble column microorganism electro synthesis reactor, including DC power supply 1, anode 2, electrolytic cell 3, anode Liquid 4, cathode 5, anodic gas export 6, cation-exchange membrane 7, bubble tower 8, catholyte 9, liquid sampling mouth 10, water circulating pump 11, gas-liquid contact vacuum fiber film component 12, cathode exhaust gas export 13, CO₂Air inlet 14, pH monitor controller 15, cathode gas Body circulation route 16, catholyte recycle circuit 17.

Specifically, 8 internal diameter of bubble tower is 9cm, is highly 60cm, total volume 5.7L；7 diameter of cation-exchange membrane is 9cm is highly 7cm, effective area 190cm²；Anode titanium net cylinder diameter is 9.5cm, is highly 7cm, effective area is 201cm², titanium net；Cathode is made of the platinum plating titanium net disk that 3 diameters are 8cm, total height 7cm, and 3 disks are radially equal Even distribution, cathode effective area are 150cm².Anolyte and cathode formula of liquid are as shown in table 1, the body of anolyte when working condition Product is 1L, and the volume of catholyte is 5L.

1 anolyte of table and cathode formula of liquid