CN108641944B - CO (carbon monoxide)2Device and method for bioconversion into methane - Google Patents
CO (carbon monoxide)2Device and method for bioconversion into methane Download PDFInfo
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Abstract
The invention relates to CO2The device and the method for biologically converting the methane comprise a material supply system, a biological conversion system, a product separation and circulation system, a substance composition analysis system and a parameter monitoring and adjusting system. Hydrogen and CO2Introducing into a biotransformation system, converting methanogens under suitable anaerobic conditions, monitoring reaction parameters and material composition in the system, periodically replenishing materials according to the parameters and discharging headspace; and finally, separating and collecting methane by the gas product through a membrane separation device, and recycling the non-methane gas back to the conversion system. Compared with the prior art, the invention effectively realizes CO2The method has the advantages of simple and convenient operation, mild conditions, low cost, wide application range and the like.
Description
Technical Field
The invention belongs to CO2The technical field of emission reduction and resource utilization, in particular to CO2An apparatus and method for bioconversion to methane.
Background
With the rapid growth of the global population and economy, fossil fuel combustion releases CO2Continuously increasing, as the main greenhouse gas in the atmosphere, CO 2The emission reduction problem is concerned. How to effectively reduce CO2And realizing resource conversion has become one of the problems of high international concern today. Using microorganisms to convert CO2Can be converted into natural gas (methane) to effectively reduce CO2And the clean energy can be regenerated, and the method has important economic value and practical value. All in oneMeanwhile, the microbial conversion method is economical and environment-friendly, can avoid the problems of harsh reaction conditions, high energy consumption and the like in chemical conversion, and has feasibility and application prospects. Methanogens are archaea that can anaerobically convert inorganic or organic compounds to methane, wherein hydrogenotrophic methanogens can directly utilize CO2And hydrogen to produce methane (CO)2+4H2→CH4 +2H2O) and the overall reaction can proceed thermodynamically spontaneously.
The prior art uses CO2And introducing hydrogen into the anaerobic liquid culture system, and converting by hydrogenotrophic methanogens to produce methane. According to the invention, (1) polyacrylamide (30-100 ppm) is added into an inorganic salt culture medium, so that the moving resistance of reaction gas in a system is increased, and the retention time of the reaction gas in the system is prolonged; (2) a low-pressure ventilation mode is adopted, and a gas reactant is slowly introduced into the reaction liquid through a micropore device (10-100 mu m), so that the volume of bubbles is greatly reduced; (3) the spiral/disc layout is adopted, the micropores are distributed in the reaction liquid, the density of bubbles in the reaction liquid is increased, and by the measures, the contact area between cells and microorganisms is increased, so that the utilization and conversion rate of the microorganisms to the reaction gas is improved. At the same time, the prior art uses a membrane to separate CO 2The hydrogen is separated and returned to the bioreactor, and is not further separated and utilized, so that the utilization rate of the hydrogen is reduced.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for effectively realizing CO2And CO for ensuring continuous operation of the conversion process by on-line monitoring of reaction parameters and products2An apparatus and method for bioconversion to methane.
The purpose of the invention can be realized by the following technical scheme: CO (carbon monoxide)2The device for biologically converting the methane is characterized by comprising a material supply system, a biological conversion system, a product separation and circulation system, a substance composition analysis system and a parameter monitoring and adjusting system, wherein the biological conversion system is respectively connected with the material supply system, the product separation and circulation system and the substance composition analysis system.
The material supply system comprises a hydrogen supply reaction tank and CO2Storage tank, deaerating plant and inorganic salt culture medium and methanogen liquid storage tank, hydrogen retort, CO2The storage tanks are connected in parallel and then connected to a biological conversion system through a deoxidizing device; the inorganic salt culture medium and the methanogen liquid storage tank are communicated with the biotransformation system. The material supply system also comprises necessary valves and an air pump.
Furthermore, the oxygen removing device comprises a glass tube which is internally provided with a copper wire or copper column, the outer wall of the glass tube is wound with a heating tape, and the temperature of the glass tube is more than 360 ℃ so as to remove CO2In addition, the oxidized copper wire or copper column is reduced by introducing hydrogen. The hydrogen supply reaction tank is internally provided with water reaction hydrogen production including but not limited to zero-valent metal, metal oxide, waste iron slag and the like, and the hydrogen is discharged to a biological conversion system by an air pump through a valve; CO 22The storage tank can use CO2CO trapped in high pressure cylinders or plants2And the waste gas is discharged to the biological conversion system by the air pump through a valve.
The biological conversion system comprises a reaction tank, a ventilating device and a gas-liquid inlet and outlet, wherein the gas-liquid inlet and outlet comprises a gas and liquid injection port and a liquid discharge port, the temperature can be controlled, and magnetic stirring is carried out, wherein the ventilating device is a spiral gas pipe or a multilayer disc made of stainless steel or other inert materials, a plurality of tiny holes are formed in the wall of the gas pipe or the disc, the diameter of each hole is 10-100 mu m, so that tiny bubbles can be obtained, and the contact area between the liquid phase and microorganisms is increased.
The product separation and circulation system comprises a membrane separation device, a desulphurization and dehumidification device, a necessary gas circulation pump and a valve, wherein the membrane separation device comprises at least one separation box body, at least two high-performance membranes are arranged in the separation box body, methane is collected through a secondary membrane separation process, non-methane gas returns to a culture solution through the circulation system and continues to be converted by microorganisms, the utilization rate of hydrogen is greatly improved, the conversion rate is accelerated, and CO is reduced 2Discharging;
the high-performance membrane comprises polyimide hollow fiber membranes, polyetherimide hollow fiber membranes, molecular sieve/carbon composite membranes, silicon rubber membranes and the like with different structures.
The desulfurizing and dehumidifying device is filled with an adsorbent, and the adsorbent comprises activated carbon or silica gel; the desulfurization and dehumidification device receives gas discharged from the biological conversion system, and the gas enters the membrane separation device after being desulfurized and dehumidified.
The substance composition analysis system comprises a gas flow monitoring and controlling device, a gas chromatograph and a liquid chromatography-mass spectrometer; aiming at the gas before being injected into the biotransformation system and before and after entering the membrane separation device, the gas flow monitoring and controlling device is used for monitoring and controlling the flow on line, and then the gas chromatography is used for analyzing the composition and the content of the gas on line; the liquid in the biotransformation system is discharged by a liquid pump, and is subjected to online quantitative analysis of organic matters by LC-MS, and simultaneously, part of the discharged liquid is subjected to analysis of microbial composition and inorganic components.
The parameter monitoring and adjusting system is respectively connected with the material supply system, the biological conversion system, the product separation and circulation system and the substance composition analysis system;
the parameter monitoring and adjusting system comprises a parameter monitoring and counter-control device, a liquid tank, a liquid pump and a valve, wherein the parameter monitoring and counter-control device measures reaction parameters, the reaction parameters comprise but are not limited to temperature, pH and oxidation-reduction potential, when the reaction parameters exceed an allowable change range, the counter-control device is started to adjust, and if the reaction parameters exceed the allowable change range, such as temperature change > +/-3 ℃, a temperature control device is started to adjust; the pH change is +/-1.0, and a controllable liquid pump and a valve are reversely filled with hydrochloric acid/sodium hydroxide solution; the change of the oxidation-reduction potential is more than 20mV, and a reversible control liquid pump and a valve are used for injecting a sodium sulfide solution; according to the analysis result of the material composition, the liquid pump and the valve can be controlled reversely, and the inorganic salt culture medium is replaced for continuous culture.
The components of the device also comprise necessary connecting pipelines, valves and pumps.
CO as described above2Method for using a device for bioconversion to methane, characterized in that it comprises the following steps:
(1) opening of CO2Storage tank switch and oxygen removal device using CO2A flushing and sweeping biotransformation system and a product separation and circulation system are adopted to achieve the aim of removing oxygen;
(2) injecting inorganic salt culture medium and methanogen liquid into a reaction tank in the biotransformation system, opening a hydrogen supply reaction tank and CO2A valve of the storage tank, wherein gas is pumped into the liquid phase in the reaction tank through the ventilation device;
(3) setting culture temperature by a temperature control device of the reaction tank, and carrying out culture reaction;
(4) opening a gas outlet valve of the reaction tank, and discharging the headspace mixed gas by a gas pump;
(5) after passing through the desulfurizing and dehumidifying device, the mixed gas is pumped into a membrane separation device for separation, the final product methane is collected in a storage tank, the non-methane gas is recycled into a reaction tank, and the flow, the composition and the content of the gas are monitored on line in the process;
(6) in the reaction process, a liquid phase outlet valve of the reaction tank is opened, the liquid phase organic matter composition is analyzed quantitatively on line by liquid chromatography-mass spectrometry, and meanwhile, the microorganism and the inorganic matter composition are sampled and analyzed;
(7) And monitoring reaction parameters on line through a parameter monitoring and adjusting system, and carrying out system adjustment.
The methanogen in the step (2) comprises the following steps: methanomicrobiales (Methanomicrobials), Methanobacillales (Methanobacteria), Methanococcales (Methanococcales) or Methanocellales (Methanococcales).
The inoculation amount of the methanogenic bacteria liquid in the step (2) is 10-25%.
And (3) adding polyacrylamide into the inorganic salt culture medium in the step (2) to a concentration of 30-100 ppm.
The culture temperature in the step (3) is 25-60 ℃.
And (5) storing the methane gas harvested in the step (5) by a storage tank or directly transporting the methane gas through a pipeline.
The detection in the step (5) is an online detection mode, the temperature change monitored by the parameter monitoring and adjusting system in the step (7) is +/-3 ℃, and a temperature control device is started for adjustment; the pH change is +/-1.0, and a controllable liquid pump and a valve are reversely filled with hydrochloric acid/sodium hydroxide solution; the change of the oxidation-reduction potential is more than 20mV, and a reversible control liquid pump and a valve are used for injecting a sodium sulfide solution; according to the analysis result of the material composition, the liquid pump and the valve can be controlled reversely, and the inorganic salt culture medium is replaced for continuous culture.
Compared with the prior art, the invention is CO2The biological conversion into methane provides an effective device and a method for realizing CO 2The long-term continuous resource transformation and separation, and the parallel feasibility technical means of on-line monitoring and control. Specifically, the invention further optimizes the ventilation mode and the diameter of the air hole, realizes the supply of gas in the conversion system by adopting the ventilation mode, increases the contact area of the microorganism and the reactant, and obviously improves the reaction rate; meanwhile, aiming at the mixed gas product, the invention further adopts a membrane separation mode and a plurality of membrane separation processes to realize methane and CO2Effectively separating hydrogen and non-methane gas after separation, thereby further improving the utilization rate of hydrogen, stimulating the process of producing methane and realizing CO2Rapid conversion to methane. The reaction parameters such as temperature, pH, oxidation-reduction potential and the like, the gas-liquid phase substance composition and content, and the microorganism composition and relative abundance can be monitored on line. The invention can effectively realize CO2The biological conversion into methane has the advantages of simple and convenient operation, mild condition, low cost, wide application range and the like.
Drawings
FIG. 1 is a schematic structural diagram of the present invention.
In the figure, 1-CO2A storage tank; 2-pressure gauge a, 6-pressure gauge b, 12-pressure gauge c; 3-valve a, 4-valve b, 7-valve c, 13-valve d, 17-valve e, 18-valve f, 20-valve g, 21-valve h, 23-valve i, 27-valve j, 29-valve k, 32-valve l; 5-a hydrogen supply reaction tank; 8-air pump, 14-air circulating pump, 31-liquid pump, 33-pump; 9-a deaerator; 10-a reaction tank; 11-a venting device; 15-a sulphur removal dehumidification plant; 16-membrane filtration unit a, 19-membrane filtration unit b; 22-methane storage tank; 24-gas flow monitoring and control device; 25-gas chromatography (combined TCD, FID), MS); 26-parameter monitoring and counter-control device; 28-regulator storage tank; 30, a storage tank; 34-liquid chromatography and mass spectrometry.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
Example 1:
as shown in FIG. 1, the CO of the present invention2The system device for biologically converting the methane comprises a material supply system, a biological conversion system, a product separation and circulation system, a substance composition analysis system and a parameter monitoring and adjusting system;
wherein the material supply system comprises a hydrogen supply reaction tank 5 and CO2The device comprises a storage tank 1, a pressure gauge a2, a pressure gauge b 6, an oxygen removing device 9, a valve a3, a valve b4, a valve c7 and an air pump 8. Zero-valent iron added into the hydrogen supply reaction tank 5 reacts with water to generate hydrogen, and the hydrogen is discharged to the biological conversion system through a valve c7 by an air pump 8; CO 22CO in the storage tank 12Discharged to the biological conversion system by the air pump 8 through a valve a 3; CO 22Before entering a reaction tank 10 of the biotransformation system, the wastewater is treated by an oxygen removal device 9.
The biological conversion system comprises a reaction tank 10, an air breather 11, a pressure gauge 12 and a gas-liquid inlet and outlet. The inorganic salt culture medium and the bacterial liquid are injected from the storage tank 30 through the liquid inlet of the reaction tank 10, the gas is injected from the bottom gas inlet through the spiral gas pipe (with 100 μm air hole) aeration device 11, the flow rate is 0.01vvm, and the culture temperature and the stirring speed are set.
The product separation and circulation system comprises a membrane separation device (a membrane filtration device a 16 and a membrane filtration device b 19), a sulfur removal and dehumidification device 15, a gas circulation pump 14, a valve d13, a valve e17, a valve f18, a valve g20 and a valve h 21. The gas product is discharged from the gas outlet of the biological conversion reaction tank 10, sequentially passes through a valve d13 and a gas circulating pump 14, enters a sulfur removal and dehumidification device 15 filled with activated carbon and silica gel, is continuously injected into a membrane filtering device a 16 and a membrane filtering device b 19, and is internally provided with a high-performance membrane (polyimide hollow fiber membrane alpha)CO2/CH4Is 30.5 and molecular sieve/carbon composite film alphaH2/CH440.2 at normal temperature and 0.3 Mpa), the separated methane is collected in a methane storage tank 22,non-methane gas (CO)2And hydrogen) is returned to the biological conversion system by the membrane separation device for further biological conversion into methane, wherein a valve f18 is arranged on a pipeline between the membrane filtration device a 16 and the membrane filtration device b 19, a valve h21 is arranged between the membrane filtration device b 19 and the methane storage tank 22, a valve e17 is arranged on a pipeline between a non-methane gas outlet at the top of the membrane filtration device a 16 and the biological conversion system, a valve g20 is arranged on a pipeline between the non-methane gas outlet at the top of the membrane filtration device b 19 and the biological conversion system, and a valve i23 is arranged at the top of the methane storage tank 22.
The substance composition analysis system comprises a gas flow monitoring and control device 24, a gas chromatograph 25, a LC-MS 34, a pump 33 and a valve l 32. The gas flow monitoring and controlling device 24 is used for monitoring and controlling the flow of the gas before the gas is injected into the biological conversion reaction tank 10 and before and after the gas enters the membrane separation device on line, and the gas chromatography 25 is used for analyzing the composition and the content of the gas on line; the liquid in the biotransformation reaction tank 10 can be discharged by the pump 33 through the valve l32, and the liquid chromatography/mass spectrometry 34 can be used for on-line quantitative analysis of organic matters, and simultaneously, part of the liquid can be discharged for analysis of microorganism composition and inorganic components.
The parameter monitoring and regulating system comprises a parameter monitoring and back-control device 26, a regulator storage tank 28, a storage tank 30, a liquid pump 31, a valve j27 and a valve k 29. A parameter monitoring and counter-control device 26 connected with the biotransformation reaction tank (10) for on-line monitoring reaction parameters (such as temperature, pH, oxidation-reduction potential, etc.), if the reaction parameters are beyond the allowable variation range, the parameter monitoring and control device 26 can control the liquid pump 31 and the valve j27 reversely, and the liquid is adjusted (such as pH change > +/-1.0, hydrochloric acid/sodium hydroxide solution is injected; the oxidation-reduction potential change is more than 20 mV, and sodium sulfide solution is injected into the solution), if the temperature change is +/-3 ℃, a temperature control device is started for adjustment; in addition to this, the present invention is, according to the analysis result of the material composition, the replaceable inorganic salt culture medium is continuously cultured, part of liquid in the biological conversion reaction tank 10 is discharged by a pump 33 through a valve l32, the parameter monitoring and counter-control device 26 can counter-control a liquid pump 31 and a valve k29, and fresh inorganic salt culture medium and bacterial liquid are injected from an inorganic salt culture medium/bacterial liquid storage tank 30.
A kind ofCO2A process for the bioconversion to methane comprising the steps of:
(1) opening of CO2The storage tank switch valve a3 and the oxygen removing device 9 are made of CO2A flushing and sweeping biotransformation system, a product separation and circulation system and the like are adopted to achieve the aim of removing oxygen;
(2) the inorganic salt medium (composition, see academic journal International Biodetermination) is injected into the biotransformation reaction tank 10 through the liquid injection port&Biograding published paper, DOI: 10.1016/j.ibiod.2017.12.002) and methanogen liquid (Methanobacterium bryantii, belonging to Methanobacterium of Methanobacterium order, deposit number ACCC 00139), wherein the inoculum size is 15%, polyacrylamide (molecular weight 800 ten thousand) is added into the inorganic salt culture medium, and the concentration is 100 ppm. Opening the hydrogen supply reaction tank and CO2A storage tank valve a3, a valve c7, which pumps gas into the liquid phase of the reaction tank 10 through the aeration device 11;
(3) setting the culture temperature to 37 ℃ by a temperature control device of the reaction tank 10 for culture;
(4) opening a gas outlet valve d13 of the biological conversion reaction tank, and discharging headspace gas by a gas circulating pump 14;
(5) the mixed gas is pumped into membrane separation devices (membrane filtration device a 16 and membrane filtration device b 19) (polyimide hollow fiber membrane α) after passing through a desulfurizing and dehumidifying device 15 CO2/CH4Is 30.5 and molecular sieve/carbon composite film alphaH2/CH440.2, and the pressure at normal temperature is 0.3 Mpa), collecting the final product methane in a methane storage tank 22, recycling the non-methane gas into a biological conversion reaction tank, and monitoring the flow, the composition and the content of the gas on line in the process;
(6) in the reaction process, a liquid phase outlet valve l32 of the biotransformation reaction tank can be opened, the liquid phase organic matter composition is analyzed on line and quantitatively by the liquid chromatography-mass spectrometry 34, and meanwhile, the microorganism and the inorganic matter composition are sampled and analyzed.
(7) The temperature, pH, oxidation-reduction potential and the like of the biotransformation system are monitored on line, if the reaction parameters exceed the allowed variation range, the liquid pump 31, the valve j27 and the valve k29 can be controlled reversely to inject solution for adjustment (such as pH variation > +/-1.0, hydrochloric acid/sodium hydroxide solution is injected, oxidation-reduction potential variation >20mV is injected, sodium sulfide solution is injected), and if the temperature variation > +/-3 ℃, the temperature control device is started for adjustment.
Example 2:
as shown in FIG. 1, the CO of the present invention2The system device for biologically converting the methane comprises a material supply system, a biological conversion system, a product separation and circulation system, a substance composition analysis system and a parameter monitoring and adjusting system;
the material supply system comprises a hydrogen supply reaction tank 5 and CO 2The device comprises a storage tank 1, a pressure gauge a2, a pressure gauge b 6, an oxygen removing device 9, a valve a3, a valve b4, a valve c7 and an air pump 8. Ferrous oxide added into the hydrogen supply reaction tank 5 reacts with water to generate hydrogen, and the hydrogen is discharged to the biological conversion system through a valve c7 by an air pump 8; CO 22CO in the storage tank 12Discharged to the biological conversion system by the air pump 8 through a valve a 3; CO 22Before entering the biological conversion reaction tank 10, the wastewater is treated by an oxygen removal device 9.
The biological conversion system comprises a reaction tank 10, an air breather 11, a pressure gauge 12 and a gas-liquid inlet and outlet. The inorganic salt culture medium and the bacterial liquid are injected from the storage tank 30 through the liquid inlet of the biotransformation reaction tank 10, the gas is injected from the bottom gas inlet through the multi-layer disk-shaped (with 50 μm air hole) aeration device 11, the flow rate is 0.05vvm, and the culture temperature and the stirring rate are set.
The product separation and circulation system comprises a membrane separation device (a membrane filtration device a 16 and a membrane filtration device b 19), a sulfur removal and dehumidification device 15, a gas circulation pump 14, a valve d13, a valve e17, a valve f18, a valve g20 and a valve h 21. The gas product is discharged from the gas outlet of the biotransformation reaction tank 10, passes through a sulfur removal and dehumidification device 15 filled with active carbon and silica gel, and is continuously injected into a membrane separation device by a gas circulation pump 14, and a high-performance membrane (polyetherimide hollow fiber membrane alpha) is arranged in the membrane separation device CO2/CH4Is 35.7 and a silicone rubber film alphaH2/CH445.6 at room temperature and 0.2 MPa), the separated methane is collected in the methane storage tank 22, and non-methane gas (CO)2And hydrogen) is returned from the membrane separation unit to the bioconversion system for further bioconversion to methane.
The substance composition analysis system comprises a gas flow monitoring and control device 24, a gas chromatograph 25, a LC-MS 34, a pump 33 and a valve l 32. The gas flow monitoring and controlling device 24 is used for monitoring and controlling the flow of the gas before the gas is injected into the biological conversion reaction tank 10 and before and after the gas enters the membrane separation device on line, and the gas chromatography 25 is used for analyzing the composition and the content of the gas on line; the liquid in the biological conversion reaction tank 10 can be discharged by the pump 33 through the valve l32, and the liquid chromatography/mass spectrometry 34 is used for on-line quantitative analysis of organic matters, and simultaneously, part of the liquid can be discharged for analysis of microbial composition and inorganic components.
The parameter monitoring and adjusting system comprises a parameter monitoring and counter-control device 26, a regulator storage tank 28, a storage tank 30, a liquid pump 31, a valve j27 and a valve k 29. The parameter monitoring and counter-control device 26 connected to the biotransformation reaction tank 10 monitors the reaction parameters (such as temperature, pH, oxidation-reduction potential, etc.) on line, if the reaction parameters exceed the allowable variation range, the parameter monitoring and counter-control device 26 can counter-control the liquid pump 31 and the valve j27, inject the solution from the regulator storage tank 28 to adjust (such as pH variation > +/-1.0, inject hydrochloric acid/sodium hydroxide solution; oxidation-reduction potential variation >20 mV, inject sodium sulfide solution), such as temperature variation > +/-3 ℃, start the temperature control device to adjust; in addition, according to the analysis result of the material composition, the replaceable inorganic salt medium is continuously cultured, part of the liquid in the biological conversion reaction tank 10 is discharged from the pump 33 through the valve l32, the parameter monitoring and counter-control device 26 can counter-control the liquid pump 31 and the valve k29, and fresh inorganic salt medium and bacteria liquid are injected from the inorganic salt medium/bacteria liquid storage tank 30.
CO (carbon monoxide)2A process for the bioconversion to methane comprising the steps of:
(1) opening of CO2The storage tank switch valve a3 and the oxygen removing device 9 are made of CO2A flushing and sweeping biotransformation system, a product separation and circulation system and the like are adopted to achieve the aim of removing oxygen;
(2) injecting inorganic salt culture medium into the biotransformation reaction tank through a liquid injection port (see academic journal International Biodetermination)&Biograding published paper, DOI: 10.1016/j.ibiod.2017.12.002) methanogen liquid (mainly methanogens are Methanobacteriodes of Methanobacterium order, Me of Methanomicrobiales orderthe strain is cultured and stored in the laboratory, and is shown in a paper published in academic journal, and DOI: 10.1016/j. energy.2018.01.087), the inoculum size was 20%, polyacrylamide (molecular weight 1000 ten thousand) was added to the mineral salts medium at a concentration of 30 ppm. Opening the hydrogen supply reaction tank and CO2A storage tank valve a3 and a valve c7, wherein gas is pumped into the liquid phase of the biological conversion reaction tank 10 through the air breather 11;
(3) setting the culture temperature of 55 ℃ by a temperature control device of the biotransformation reaction tank 10;
(4) opening a gas outlet valve d13 of the biological conversion reaction tank, and discharging headspace gas by a gas circulating pump 14;
(5) The mixed gas is pumped into a membrane separation device (the built-in high-performance membrane is a polyetherimide hollow fiber membrane alpha) after passing through a sulfur removal and dehumidification device 15CO2/CH4Is 35.7 and a silicone rubber film alphaH2/CH445.6, and the normal temperature pressure is 0.2 Mpa), collecting the final product methane in a methane storage tank 22, recycling the non-methane gas into a biological conversion reaction tank, and monitoring the flow, the composition and the content of the gas on line in the process;
(6) in the reaction process, a liquid phase outlet valve l32 of the biotransformation reaction tank can be opened, the liquid phase organic matter composition is quantitatively analyzed on line by the liquid chromatography mass spectrometer 34, and meanwhile, the microorganism and the inorganic matter composition are sampled and analyzed.
(7) The temperature, pH, oxidation-reduction potential and the like of the biotransformation system are monitored on line, if the reaction parameters exceed the allowed variation range, the liquid pump 31, the valve j27 and the valve k29 can be controlled reversely to inject solution for adjustment (such as pH variation > +/-1.0, hydrochloric acid/sodium hydroxide solution is injected, oxidation-reduction potential variation >20mV is injected, sodium sulfide solution is injected), such as temperature variation > +/-3 ℃, and a temperature control system is started for adjustment.
The embodiments described above are intended to facilitate the understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (5)
1. CO (carbon monoxide)2The device for biologically converting the methane is characterized by comprising a material supply system, a biological conversion system, a product separation and circulation system, a substance composition analysis system and a parameter monitoring and adjusting system, wherein the biological conversion system is respectively connected with the material supply system, the product separation and circulation system and the substance composition analysis system;
the material supply system comprises a hydrogen supply reaction tank and CO2Storage tank, deaerating plant and inorganic salt culture medium and methanogen liquid storage tank, hydrogen retort, CO2The storage tanks are connected in parallel and then connected to a biological conversion system through a deoxidizing device; the inorganic salt culture medium and the methanogen liquid storage tank are communicated with the biotransformation system;
the deoxidizing device comprises a glass tube which is internally provided with a copper wire or copper column, wherein the outer wall of the glass tube is wound with a heating tape, and the temperature of the glass tube is more than 360 ℃ so as to remove CO2In addition, the oxidized copper wire or copper column is reduced by a method of introducing hydrogen;
the biological conversion system comprises a reaction tank, a ventilation device and a gas-liquid inlet and outlet, wherein the gas-liquid inlet and outlet comprise a gas and liquid injection port and a liquid discharge port, the ventilation device is a spiral gas pipe made of stainless steel or other inert materials or a multilayer disc, a plurality of tiny holes are formed in the wall of the gas pipe or the disc, and the diameter of each hole is 10-100 mu m; the product separation and circulation system comprises a membrane separation device and a desulfurization and dehumidification device, wherein the membrane separation device comprises at least one separation box body, at least two high-performance membranes are arranged in the separation box body, methane is obtained and collected through a secondary membrane separation process, and non-methane gas can be recycled;
The desulfurizing and dehumidifying device is filled with an adsorbent, and the adsorbent comprises activated carbon or silica gel; the desulfurization and dehumidification device receives gas discharged from the biological conversion system, and the gas enters the membrane separation device after being desulfurized and dehumidified;
the substance composition analysis system comprises a gas flow monitoring and controlling device, a gas chromatograph and a liquid chromatography-mass spectrometer; the gas before being injected into the biotransformation system and before and after entering the membrane separation device is monitored and controlled on line by a gas flow monitoring and controlling device, and then the composition and content of the gas are analyzed on line by a gas chromatograph; liquid in the biotransformation system is discharged by a liquid pump, on-line quantitative analysis of organic matters is carried out by liquid chromatography-mass spectrometry, and meanwhile, part of the discharged liquid is used for analyzing the microbial composition and inorganic components;
the parameter monitoring and adjusting system is respectively connected with the material supply system, the biological conversion system, the product separation and circulation system and the substance composition analysis system;
the parameter monitoring and adjusting system comprises a parameter monitoring and counter-control device, a liquid tank, a liquid pump and a valve, wherein the parameter monitoring and counter-control device is used for measuring reaction parameters, the reaction parameters comprise but are not limited to temperature, pH and oxidation-reduction potential, and when the reaction parameters exceed an allowable variation range, the counter-control device is started to adjust; the temperature change > plus or minus 3 ℃ monitored by the parameter monitoring and adjusting system is adjusted by starting a temperature control device; the pH change is +/-1.0, and a controllable liquid pump and a valve are reversely filled with hydrochloric acid/sodium hydroxide solution; the change of the oxidation-reduction potential is more than 20mV, and a reversible control liquid pump and a valve are used for injecting a sodium sulfide solution; according to the analysis result of the material composition, the liquid pump and the valve can be controlled reversely, and the inorganic salt culture medium is replaced for continuous culture.
2. A CO according to claim 12A method of using a device for bioconversion to methane, comprising the steps of:
(1) opening of CO2Storage tank switch and oxygen removal device using CO2A flushing and sweeping biotransformation system and a product separation and circulation system are adopted to achieve the aim of removing oxygen;
(2) injecting inorganic salt culture medium and methanogen liquid into a reaction tank in the biotransformation system, opening a hydrogen supply reaction tank and CO2Valve of storage tank, liquid in reaction tank via ventilation devicePumping gas into the phase;
(3) setting culture temperature by a temperature control device of the reaction tank, and carrying out culture reaction;
(4) opening a gas outlet valve of the reaction tank, and discharging the headspace mixed gas by a gas pump;
(5) after passing through the desulfurizing and dehumidifying device, the mixed gas is pumped into a membrane separation device for separation, the final product methane is collected in a storage tank, the non-methane gas is recycled into a reaction tank, and the flow, the composition and the content of the gas are monitored on line in the process;
(6) in the reaction process, a liquid phase outlet valve of the reaction tank is opened, the liquid phase organic matter composition is analyzed quantitatively on line by liquid chromatography-mass spectrometry, and meanwhile, the microorganism and the inorganic matter composition are sampled and analyzed;
(7) and monitoring reaction parameters on line through a parameter monitoring and adjusting system, and carrying out system adjustment.
3. CO according to claim 22A method for using a device for bioconversion into methane, wherein the methanogens described in step (2) include but are not limited to: methanobactriales (methanobactriales), methanobactriales (methanobacterales), Methanococcales (Methanococcales) or methanobacterales (methanobacterales);
the inoculation amount of the methanogen liquid in the step (2) is 10-25%;
adding polyacrylamide into the inorganic salt culture medium in the step (2), wherein the concentration of the polyacrylamide is 30-100 ppm;
the culture temperature in the step (3) is 25-60 ℃.
4. CO according to claim 22The method for using the device for biologically converting the methane into the methane is characterized in that the methane gas harvested in the step (5) is stored by a storage tank or directly transported by a pipeline.
5. CO according to claim 22The use method of the device for biologically converting the methane is characterized in that the detection in the step (5) is an online detection mode, and the parameter monitoring and regulation in the step (7)Temperature change monitored by system>Starting a temperature control device for regulation at +/-3 ℃; change in pH>+/-1.0, injecting a hydrochloric acid/sodium hydroxide solution into a reversible control liquid pump and a valve; change in redox potential>The sodium sulfide solution is injected into the solution by a reversible control liquid pump and a valve at 20 mV; according to the analysis result of the material composition, the liquid pump and the valve can be controlled reversely, and the inorganic salt culture medium is replaced for continuous culture.
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| CN110042042B (en) * | 2019-04-23 | 2022-04-08 | 山东科技大学 | Methane-oxidizing bacteria domestication culture device and method for simulating underground environment of coal mine |
| JP7406205B2 (en) * | 2020-03-24 | 2023-12-27 | 横河電機株式会社 | Methane generator |
| CN114602398B (en) * | 2020-12-07 | 2023-04-07 | 武汉大学 | Magnetic rotary disc for friction catalysis of semiconductor powder |
| CN113716688A (en) * | 2021-10-08 | 2021-11-30 | 合肥工业大学 | Anaerobic treatment method for coal chemical industry wastewater |
| CN113862134A (en) * | 2021-10-09 | 2021-12-31 | 沈阳航空航天大学 | Micro-nano bubble circulation hydrogen supply anaerobic fermentation tank |
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