CN105602838A - Biogas methanation decarbonization system and method - Google Patents
Biogas methanation decarbonization system and method Download PDFInfo
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- CN105602838A CN105602838A CN201610071545.0A CN201610071545A CN105602838A CN 105602838 A CN105602838 A CN 105602838A CN 201610071545 A CN201610071545 A CN 201610071545A CN 105602838 A CN105602838 A CN 105602838A
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- 238000005262 decarbonization Methods 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 title claims abstract description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 141
- 239000007789 gas Substances 0.000 claims abstract description 111
- 239000001257 hydrogen Substances 0.000 claims abstract description 72
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 72
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000007788 liquid Substances 0.000 claims abstract description 67
- 239000012510 hollow fiber Substances 0.000 claims abstract description 24
- 239000013589 supplement Substances 0.000 claims abstract description 17
- 239000012528 membrane Substances 0.000 claims abstract description 15
- 239000000945 filler Substances 0.000 claims abstract description 9
- 241000894006 Bacteria Species 0.000 claims description 38
- 230000004087 circulation Effects 0.000 claims description 30
- 238000000855 fermentation Methods 0.000 claims description 22
- 230000004151 fermentation Effects 0.000 claims description 22
- 238000005261 decarburization Methods 0.000 claims description 19
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 235000015097 nutrients Nutrition 0.000 claims description 14
- 239000007921 spray Substances 0.000 claims description 14
- 239000007791 liquid phase Substances 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 13
- 238000007599 discharging Methods 0.000 claims description 11
- 238000005276 aerator Methods 0.000 claims description 9
- 239000002054 inoculum Substances 0.000 claims description 8
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 7
- 239000012071 phase Substances 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 238000004891 communication Methods 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000012495 reaction gas Substances 0.000 claims 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 89
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 46
- 239000001569 carbon dioxide Substances 0.000 abstract description 43
- 239000000047 product Substances 0.000 abstract description 11
- 230000001580 bacterial effect Effects 0.000 abstract description 3
- 238000003860 storage Methods 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract 3
- 230000035764 nutrition Effects 0.000 abstract 1
- 235000016709 nutrition Nutrition 0.000 abstract 1
- 239000010815 organic waste Substances 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 12
- 239000000835 fiber Substances 0.000 description 10
- 239000003345 natural gas Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 230000005611 electricity Effects 0.000 description 6
- 241001515935 Methanolobus oregonensis Species 0.000 description 5
- 239000012530 fluid Substances 0.000 description 5
- 241000850383 Methanobacterium alcaliphilum Species 0.000 description 4
- 241001515932 Methanolobus taylorii Species 0.000 description 4
- 241001532621 Methanosalsum zhilinae Species 0.000 description 4
- 235000012489 doughnuts Nutrition 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 241001302042 Methanothermobacter thermautotrophicus Species 0.000 description 3
- 241000228125 Methanothermobacter thermoflexus Species 0.000 description 3
- 230000003203 everyday effect Effects 0.000 description 3
- 210000003608 fece Anatomy 0.000 description 3
- 238000007667 floating Methods 0.000 description 3
- 239000003546 flue gas Substances 0.000 description 3
- 239000010794 food waste Substances 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000005431 greenhouse gas Substances 0.000 description 2
- 239000010871 livestock manure Substances 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- KDRIEERWEFJUSB-UHFFFAOYSA-N carbon dioxide;methane Chemical compound C.O=C=O KDRIEERWEFJUSB-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 244000144977 poultry Species 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
- C12M21/00—Bioreactors or fermenters specially adapted for specific uses
- C12M21/04—Bioreactors or fermenters specially adapted for specific uses for producing gas, e.g. biogas
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
- C12M23/00—Constructional details, e.g. recesses, hinges
- C12M23/36—Means for collection or storage of gas; Gas holders
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- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
- C12M23/00—Constructional details, e.g. recesses, hinges
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- C12M29/00—Means for introduction, extraction or recirculation of materials, e.g. pumps
- C12M29/06—Nozzles; Sprayers; Spargers; Diffusers
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- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P5/00—Preparation of hydrocarbons or halogenated hydrocarbons
- C12P5/02—Preparation of hydrocarbons or halogenated hydrocarbons acyclic
- C12P5/023—Methane
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- 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
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
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Abstract
The invention relates to a biogas methanation decarbonization system, belonging to the fields of organic waste treatment and clean energy development. The system comprises a hydrogen storage tank, an adjusting valve, a gas flowmeter, a gas booster pump and in-situ and off-location methanation anaerobic reactors, which are communicated through a gas circuit, wherein the in-situ methanation anaerobic reactor is provided with a feed port, a feed pump, a discharge port, a gas inlet, a gas outlet and a bacterial liquid supplement port; a hollow fiber membrane component and a filler are arranged in the off-location methanation anaerobic reactor; a liquid circulating pipeline enables a liquid to go out from the lower part and come in from the upper part; a gas inlet of the hollow fiber membrane component is communicated with the gas outlet of the in-situ methanation anaerobic reactor; and the off-location methanation anaerobic reactor is provided with a bacterial liquid supplement port, a nutrition liquid supplement port and a mud outlet. The invention also provides a biogas methanation decarbonization method. In the invention, the useless carbon dioxide in biogas is converted into a target product methane, thus the methane yield is increased, high-value utilization of the carbon dioxide in biogas is realized, and the biogas decarbonization cost is reduced.
Description
Technical field
The present invention relates to a kind for the treatment of technology of biogas, be specifically related to a kind of technology of fire damp decarburization, belong to and haveMachine offal treatment and development of clean energy field.
Background technology
Biological flue gas (being commonly called as biogas) industry be biomass energy source domain development better, more ripe, and stepped into commercializationThe regenerative resource industry in stage, is alleviating energy shortage, Optimization of Energy Structure, reduces environmental pollution, reply climate change, slowSeparate rural economy, rural development and rural demography, carry out the process of urbanization and build and the aspect of developing a circular economy, promote a conservation culture has demonstrated it and can not replaceThe effect in generation. Biogas can obtain the bio-natural gas suitable with natural gas quality after purification.
By the end of the year 2012, China's biogas output reached for 160 billion cubic meter/years, and nearly 80,000 of scale biogas engineering is largeType biogas engineering is approximately more than 4000, but with National Energy Board, scientific and technological authorities formulate to the year two thousand twenty realize produce per year 50,000,000,000 verticalThe biological flue gas developing goal of side's rice also has huge gap. According to the preliminary statistics, the stock number that can be used for producing biological flue gas approximatelyAmount to 2.5 hundred million tons of standard coals, can transform equivalent natural gas 2000 billion cubic meters, be equivalent to national Natural Gas Consumption Using in 2014(1930 billion cubic meter). The composition of biogas is mainly methane and carbon dioxide, after carbon dioxide separation is gone out, can obtain with naturalThe duplicate bio-natural gas of gas composition (biological methane), bio-natural gas can utilize existing natural gas transport and utilizationFacility carries out safe high-value-use.
The technique that bio-natural gas is prepared in the biogas decarburization of engineering application at present mainly contains high-pressure washing, Physical Absorption, changeLearn absorption, pressure-variable adsorption, film separation etc., these decarbonization methods need independent separation equipment just can carry out, and these techniquesDue to needs high pressure or hot conditions, decarburization energy consumption is higher. In order to reduce equipment investment and to reduce separating energy consumption, foreign scholar tastesExamination is carried out original position by the method for anaerobic digestion process control and carbon dioxide stripping and is separated decarburization. They utilize methane and dioxyThe dissolubility difference of changing carbon, is transferred to part zymotic fluid in stripping tower and carries out air or nitrogen stripping, by carbon dioxide separationGo out in anaerobic digester system, realize methane-rich.
No matter be the separation decarburization of offing normal, or original position separates decarburization, its general character and essence are all from biogas by carbon dioxideIn isolate and be discharged in atmosphere, these class methods have not only been caused to greenhouse gas emission, and have greatly wasted resource.Therefore, in order to reduce greenhouse gas emission, improve resource utilization, exploitation carbon dioxide methanation biogas decarburization technique is to biogasHigh-value-use seem particularly important.
Summary of the invention
The object of the invention is to overcome deficiency of the prior art, a kind of system and side of fire damp decarburization is providedMethod, be target product methane by carbon dioxide conversion useless in biogas, improves methane production, realizes carbon dioxide in methaneHigh-value-use, and reduce biogas decarburization cost.
For achieving the above object, the present invention is by the following technical solutions:
First, the invention provides a kind of fire damp decarbonization system, this system comprises by gas communication pipeline to be complied withHydrogen container 1, control valve 2A, gas flowmeter 3A, gas boosting pump 4, the original position methanation anaerobic reactor 5 of inferior connection, off normalMethanation anaerobic reactor 6; On original position methanation anaerobic reactor 5, be provided with fermentation materials charging aperture 7, feed pump 8, discharging opening9, air inlet 5A, gas outlet 5C, bacterium liquid supplement a mouthful 5D, the entering of the gas outlet 1A of hydrogen container and original position methanation anaerobic reactor 5Gas port 5A is communicated with, and air inlet 5A place arranges jet aerator 5B; Methanation anaerobic reactor 6 bottoms of offing normal arrange hollow-fibre membraneAssembly 12, top arranges filler 13, arranges simultaneously and under liquid, goes out enterprising liquid circulation line 16, the entering of hollow fiber film assemblyGas port 6A is communicated with the gas outlet 5C of original position methanation anaerobic reactor, bacterium liquid is set on the methanation anaerobic reactor 6 of offing normal and mendsFill mouth 18, supplementary mouthful 19 of nutrient solution and mud discharging mouth 20.
For ease of technological operation, control gas, liquid and material flow, on each pipeline, be provided with valve 21A～21L。
Further, the gas circulation pipeline 11 entering under going out on gas is set on methanation anaerobic reactor 5 in position,Gas circulation pipeline is communicated with the gas outlet 1A of hydrogen container 1 and the air inlet 5A of original position methanation anaerobic reactor, and gas followsOn endless tube road, be provided with the gas outlet 10 of original position methanation anaerobic reactor 5.
For ease of adjusting the angle of striking that adds of hydrogen, the air inlet that a gas circuit is communicated with hydrogen container and hollow fiber film assembly is setMouthful, and control valve 2B and gas flowmeter 3A are set in this gas circuit.
In conjunction with said system, the present invention also provides a kind of fire damp decarbonization method, comprises the following steps:
1) original position methanation biogas decarburization: by biogas fermentation inoculum and fermentation materials successively from charging aperture 7 by chargingPump 8 pumps into original position methanation anaerobic reactor 5, alkaline-resisting basophilic methanogen bacterium liquid is supplemented to a mouthful 5D from bacterium liquid and pump into original position methaneChange anaerobic reactor 5, add sodium carbonate or sodium acid carbonate regulate pH value in original position methanation anaerobic reactor 5 be 7.5～9.0; At methane fermentating microorganism,, under the effect of the alkaline-resisting methanogen of basophilic, the organic matter in fermentation materials is degraded to firstAlkane and carbon dioxide, as shown in Equation 1, methane is transferred in gas phase from liquid phase, a part of carbon dioxide solubility in liquid phase, itsRemaining carbon dioxide is transferred in gas phase; Hydrogen in hydrogen container 1 is passed through to the jet-flow aeration of gas boosting pump 4 from air inlet 5ADevice 5B pumps in the liquid phase in original position methanation anaerobic reactor 5, and the hydrogen in liquid phase and carbon dioxide produce first at hydrogen auxotypeUnder the effect of alkane bacterium, generate methane, as shown in Equation 2, the gas that has neither part nor lot in reaction is transferred in gas phase: (a) without gas circulating tubeIn the situation on road 11: from original position methanation anaerobic reactor, 5 gas outlet, top 5C out enter the methanation anaerobic reactor of offing normal6; (b) in the situation that having gas circulation pipeline 11: after gas outlet 10 circulations on gas circulation pipeline 11, again pass throughGas boosting pump 4, jet aerator 5B pump into gas in the liquid phase in original position methanation anaerobic reactor 5, at hydrogen auxotypeUnder the effect of methanogen, continue to generate methane, so far a part of carbon dioxide conversion is methane;
Organic matter → CO2+CH4(1)
4H2+CO2→CH4+2H2O(2)
2) the methanation biogas decarburization of offing normal: alkaline-resisting basophilic methanogen bacterium liquid and nutrient solution are supplemented to mouthfuls 18 from bacterium liquid respectivelySupplement mouth 19 with nutrient solution and pump into the methanation anaerobic reactor 6 of offing normal, add sodium carbonate or sodium acid carbonate and regulate the methanation of offing normalPH value in anaerobic reactor 6 is 7.5～9.0, controls just submergence hollow fiber film assembly 12 of the interior liquid level of reactor 6; From formerMethanation anaerobic reactor 5 gas outlet, top 5C biogas out in position also contains part unreacted carbon dioxide and hydrogen completelyGas, by biogas, by gas communication pipeline, the air inlet 6A on hollow fiber film assembly 12 passes into the methanation anaerobic reaction of offing normalIn hollow fiber film assembly 12 in device 6, in the biomembrane of gas from hollow-fibre membrane diffused inside to outside, in biomembraneCarbon dioxide and hydrogen are converted into methane by stationary hydrogen auxotype methanogen, a small amount of unreacted residual carbon dioxide completelyEnter into liquid phase with hydrogen from hollow-fibre membrane outside, and further produced methane by the utilization of suspension hydrogen auxotype methanogen;The liquid of offing normal in methanation anaerobic reactor 6 passes through liquid outlet 14 through liquid circulation pump 15 pumping liquid circulation lines 16, thenCirculation enters spray thrower 22 and sprays under drip; Residual carbon dioxide and hydrogen and a large amount of methane one of trace in reactor 6Play floating, when offing normal the filler 13 on methanation anaerobic reactor top, and from liquid circulation line 16 top spray throwersMethane is further produced in the liquid countercurrent contact that 22 spray drips get off under the effect of hydrogen auxotype methanogen, finally obtainsHigh-purity methane discharge from the gas outlet 6B at methanation anaerobic reactor 6 tops of offing normal.
The described hydrogen passing in hollow fiber film assembly 12 can be to come from original position methanation anaerobic reactor 5 topsThe hydrogen of discharging can be also the hydrogen that has also supplemented hydrogen container 1.
In the original position methanation biogas decarburization stage, the interpolation of the alkaline-resisting methanogen liquid of basophilic and the adjusting of pH value, can be at biogasAfter fermentation inoculum and fermentation materials add, implement immediately, also can after methanation anaerobic reactor starts aerogenesis, implement.
In original position methanation anaerobic reactor 5 or the methanation anaerobic reactor 6 of offing normal, hydrogen intake all should be less than etc.In biogas in each reactor 4 of total CO 2 volume times.
The alkaline-resisting methanogen of described basophilic can separate and obtain from occurring in nature, also can purchase from domestic and international DSMZBuy, can use by single culture, also can use by mixed bacteria, preferably mix and use. The alkaline-resisting methanogen of described basophilic is for publicOpen bacterial classification, including, but not limited to Methanobacteriumthermoalcaliphilum (DSM1053),Methanobacteriumalcaliphilum(DSM3387)、Methanohalophiluszhilinae(DSM4017)、Methanohalophilusoregonense(DSM5435)、Methanobacteriumthermoflexum(DSM7628)、Methanolobustaylorii(DSM9005)、Methanobacteriumsubterraneurn(DSM11074), in bracket, be culture presevation number, DSM is German microorganism fungus kind preservation center, the essential characteristic of these bacterium is in table 1.
The essential characteristic of the alkaline-resisting methanogen of table 1 basophilic
Described biogas fermentation inoculum is including, but not limited to biogas engineering zymotic fluid, sewage treatment plant's anaerobic sludge, pondPool bed mud etc.
Described fermentation materials is including, but not limited to stalk, feces of livestock and poultry, changing food waste, organic wastewater waste residue.
Described hydrogen auxotype methanogen is prevalent in biogas fermentation inoculum and the alkaline-resisting methanogen bacterium of basophilic liquid,It is the ubiquitous methanogen of a class. Owing to containing hydrogen auxotype methanogen in the alkaline-resisting methanogen bacterium of basophilic liquid, hydrogen battalionSupport type methanogen in the time offing normal in methanation anaerobic reactor, a part can be attached to hollow-fibre membrane 23 outsides and form biologyFilm 25, is fixing hydrogen auxotype methanogen 26; A part of be suspended in liquid phase with the form of dissociating, be suspension hydrogen battalionSupport type methanogen 27.
Described nutrient solution is the culture medium of the alkaline-resisting methanogen of basophilic, main component be dipotassium hydrogen phosphate, potassium dihydrogen phosphate,Ammonium chloride, sodium chloride, magnesium sulfate, trace element, vitamin etc.
Shown in (3), in the present invention, the supply of carbon dioxide methanation reaction needed hydrogen, hydrogen can derive from windThe electricity hydrolysis of electricity, solar photoelectric, water power obtains, and due to the more difficult storage of electric energy, can realize energy storage by the mode of electricity gas processed,In addition, in electricity consumption ebb, electricity can be converted into gas, when peak of power consumption, cyclostrophic be turned to electricity.
CO2+4H2→CH4+2H2OΔG0'＝-135kJ/mol(3)
Innovative point of the present invention and advantage are:
(1) utilization of biogas decarburization and carbon dioxide being combined, is target product methane carbon dioxide conversion, carriesHigh methane production;
(2) original position methanation and the methanation of offing normal are joined together, improve the transformation efficiency of carbon dioxide;
(3) stirring of original position methanation anaerobic reactor and the introducing of hydrogen are combined, by the jet spray of gasPenetrate the stirring that realizes marsh-gas fermentation tank, without traditional mechanical agitation;
(4) the methanation anaerobic reactor of offing normal adopts the group technology of doughnut membrane biomembrane and trickle bed, strengthens gasLiquid mass transfer, the transformation efficiency of raising carbon dioxide.
Brief description of the drawings
Fig. 1 is the schematic flow sheet of system of the present invention.
Fig. 2 is doughnut membrane biomembrane fundamental diagram of the present invention.
Wherein:
1: hydrogen container; 1A: hydrogen container gas outlet; 2A: control valve A; 2B: control valve B; 3A: gas flowmeter A; 3B: gasFlowmeter B; 4: gas boosting pump; 5: original position methanation anaerobic reactor; 5A: original position methanation anaerobic reactor air inlet; 5B:Jet aerator; 5C: original position methanation anaerobic reactor gas outlet; 5D: original position methanation anaerobic reactor bacterium liquid supplements mouth; 6:The methanation anaerobic reactor of offing normal; 6A: the air inlet of hollow fiber film assembly; 6B: the methanation anaerobic reactor gas outlet of offing normal;7: charging aperture; 8: feed pump; 9: discharging opening; 10: gas circulation pipeline gas outlet; 11: gas circulation pipeline; 12: doughnutMembrane module; 13: filler; 14: liquid circulation line liquid outlet; 15: liquid circulation pump; 16: liquid circulation line; 17: liquid followsEndless tube road inlet; 18: bacterium liquid supplements mouth; 19: nutrient solution supplements mouth; 20: mud discharging mouth; 21A-21L: valve; 22: spray thrower;23: hollow-fibre membrane; 24: membranous wall; 25: biomembrane; 26: fixing hydrogen auxotype methanogen; 27: suspension hydrogen auxotype produces methaneBacterium.
Detailed description of the invention
Below in conjunction with accompanying drawing, embodiments of the invention are elaborated.
Embodiment 1
As shown in Figure 1, fire damp decarbonization system of the present invention comprises the hydrogen container 1, control valve 2A, the gas that connect successivelyFlowmeter body 3A, gas boosting pump 4, original position methanation anaerobic reactor 5, the methanation anaerobic reactor 6 of offing normal; Original position methanationFermentation materials charging aperture 7, feed pump 8, discharging opening 9, gas outlet 10, the supplementary mouthful 5D of bacterium liquid are set on anaerobic reactor 5, establish simultaneouslyPut the gas circulation pipeline 11 entering under going out on gas, gas circulation pipeline and hydrogen container 1 and original position methanation anaerobic reactor 5Air inlet 5A is communicated with, and air inlet place arranges jet aerator 5B; Methanation anaerobic reactor 6 bottoms of offing normal arrange hollow-fibre membraneAssembly 12, top arranges filler 13, arranges simultaneously and under liquid, goes out enterprising liquid circulation line 16, the entering of hollow fiber film assemblyGas port 6A is communicated with the gas outlet 5C of original position methanation anaerobic reactor 5, and the methanation anaerobic reactor 6 of offing normal arranges bacterium liquid and supplementsMouth 18, nutrient solution supplement mouth 19 and mud discharging mouth 20.
For ease of technological operation, control the turnover of gas, liquid and material, on each pipeline, valve is set.
For ease of adjusting the angle of striking that adds of hydrogen, the air inlet that a gas circuit is communicated with hydrogen container and hollow fiber film assembly is setMouthful, and control valve 2B and gas flowmeter 3A are set in this gas circuit.
Embodiment 2
Carry out biogas fermentation and fire damp decarburization taking pig manure as fermentation materials.
The zymotic fluid of getting certain biogas engineering is pumped into original position methanation from charging aperture 7 by feed pump 8 as inoculum to be detestedIn oxygen reactor 5, add subsequently pig manure to carry out middle temperature (37 DEG C) biogas fermentation, start successfully through 10 days, every day aerogenesis approximately100m3, wherein methane volumetric concentration 60%, carbon dioxide volumetric concentration 40%; Now by alkaline-resisting basophilic product methane blended bacterium(Methanohalophilusoregonense, Methanolobustaylorii and MethanobacteriumThe Mixed Microbes of alcaliphilum) bacterium liquid supplements a mouthful 5D from bacterium liquid and pumps into original position methanation anaerobic reactor, adds sodium acid carbonateRegulating the pH value in original position methanation anaerobic reactor is 7.5, from the jet of original position methanation anaerobic reactor air inlet 5AAerator 5B passes into hydrogen 160m3, hydrogen partial and carbon dioxide reaction generate methane, finally from original position methanation anaerobic reactionDevice top Exhaust Gas 180m3, wherein methane volumetric concentration 44.4%, hydrogen volume concentration 44.4%, carbon dioxide volume is denseDegree 11.2%;
Supplement mouth 19 by supplementary mouthful 18 of bacterium liquid and nutrient solution respectively pumps in advance in the methanation anaerobic reactor 6 of offing normalThe alkaline-resisting product methane blended of basophilic bacterium: Methanohalophilusoregonense, Methanolobustaylorii,Methanobacteriumalcaliphilum bacterium liquid and nutrient solution, then add sodium acid carbonate and regulate the pH value of mixed liquor to be7.5, control just submergence hollow fiber film assembly 12 of liquid level, will discharge from original position methanation anaerobic reactor top gas outlet 5CGas by gas communication pipeline, the air inlet 6A on hollow fiber film assembly 12 passes into the methanation anaerobic reactor of offing normalBuilt-in hollow fiber film assembly, under the biomembranous effect of hollow-fibre membrane, hydrogen and carbon dioxide reaction generate methane, fewAmount unreacted completely residual carbon dioxide and hydrogen enters into liquid phase from hollow-fibre membrane 23 outsides, and is further suspendedHydrogen auxotype methanogen 27 utilization is produced methane, and the residual carbon dioxide of trace and hydrogen float with together with a large amount of methane, warpWhile crossing the filler 13 on the methanation anaerobic reactor top of offing normal, and spray drip from liquid circulation line 16 top spray throwers 22Methane is further produced in the liquid countercurrent contact that carrys out autoreactor 6 of getting off under the effect of hydrogen auxotype methanogen, finallyThe 104m arriving3High concentration methane gas (methane volumetric concentration 95.2%, carbon dioxide 1.0%, hydrogen volume concentration 3.8%)Discharge from the gas outlet 6B at the methanation anaerobic reactor top of offing normal.
The methane production of whole system is from 60m3Bring up to 99m3, improved 65%; Methane concentration is brought up to from 60%95.2％。
Embodiment 3
Carry out biogas fermentation and fire damp decarburization taking sugar production wastewater as fermentation materials.
The zymotic fluid of getting certain biogas engineering is pumped into original position methanation from charging aperture 7 by feed pump 8 as inoculum to be detestedIn oxygen reactor 5, add subsequently sugar production wastewater to carry out middle temperature (37 DEG C) biogas fermentation, start successfully through 5 days, every day aerogenesis approximately1000m3, wherein methane volumetric concentration 50%, carbon dioxide volumetric concentration 50%; Now by alkaline-resisting basophilic product methane blended bacterium:Methanobacteriumalcaliphilum、Methanohalophilusoregonense、MethanolobusThe mixed bacteria liquid of taylorii, Methanobacteriumsubterraneurn and MethanohalophiluszhilinaeSupplement a mouthful 5D from bacterium liquid and pump into original position methanation anaerobic reactor 5, add sodium carbonate and regulate in original position methanation anaerobic reactorPH value be 8.3, pass into hydrogen 900m from the jet aerator 5B of original position methanation anaerobic reactor air inlet 5A3, large portionDivide hydrogen and carbon dioxide reaction to generate methane, the hydrogen and the carbon dioxide that have neither part nor lot on a small quantity reaction are transferred in gas phase, pass throughAfter gas outlet 10 circulations on gas circulation pipeline 11, again incite somebody to action by gas boosting pump 4, air inlet 5A, jet aerator 5BGas in gas phase pumps in the liquid phase in original position methanation anaerobic reactor 5, under the effect of hydrogen auxotype methanogen, continuesThe continuous methane that generates; Finally from original position methanation anaerobic reactor top Exhaust Gas 1100m3, wherein methane volumetric concentration63.6%, hydrogen volume concentration 9.1%, carbon dioxide volumetric concentration 27.3%;
Supplement mouth 19 by supplementary mouthful 18 of bacterium liquid and nutrient solution respectively pumps in advance in the methanation anaerobic reactor 6 of offing normalThe alkaline-resisting product methane blended of basophilic bacterium: Methanobacteriumalcaliphilum, Methanohalophilusoregonense、Methanolobustaylorii、Methanobacteriumsubterraneurn、Bacterium liquid and the nutrient solution of Methanohalophiluszhilinae, then adding sodium acid carbonate, to regulate the pH value of mixed liquor be 8.3,Control liquid level just submergence hollow fiber film assembly 12, by by control valve B and gas flowmeter A from hydrogen container1100m3Hydrogen passes into the gas of discharging from original position methanation anaerobic reactor top gas outlet 5C the methanation of offing normal in the lump to be detestedThe hollow fiber film assembly that oxygen reactor is built-in, under the effect of doughnut membrane biomembrane 25, hydrogen and carbon dioxide reaction are rawBecome methane, a small amount of unreacted completely residual carbon dioxide and hydrogen enters into liquid phase from hollow-fibre membrane 23 outsides, goes forward side by sideThe one step hydrogen auxotype methanogen 27 that suspended utilizes product methane, the residual carbon dioxide of trace and hydrogen and a large amount of methane onePlay floating, when offing normal the filler 13 on methanation anaerobic reactor top, and from liquid circulation line 16 top spray throwersThe liquid countercurrent that carrys out autoreactor 6 that 22 spray drips get off contacts, and under the effect of hydrogen auxotype methanogen, further producesMethane, the 1020m finally obtaining3High concentration methane gas (methane volumetric concentration 97.5%, carbon dioxide 0.5%, hydrogenVolume concentrations 2.0%) discharge from the gas outlet 6B at the methanation anaerobic reactor top of offing normal.
The methane production of whole system is from 500m3Bring up to 995m3, improved 73.3%; Methane concentration is brought up to from 50%97.5％。
Embodiment 4
Carry out biogas fermentation and fire damp decarburization taking changing food waste as fermentation materials.
The zymotic fluid of getting certain biogas engineering is pumped into original position methanation from charging aperture 7 by feed pump 8 as inoculum to be detestedIn oxygen reactor 5, add subsequently changing food waste to carry out high temperature (55 DEG C) biogas fermentation, start successfully through 10 days, every day aerogenesisAbout 2000m3, wherein methane volumetric concentration 65%, carbon dioxide volumetric concentration 35%; Now by alkaline-resisting basophilic product methane blendedBacterium: Methanobacteriumthermoalcaliphilum, Methanobacteriumthermoflexum andThe mixed bacteria liquid of Methanohalophiluszhilinae supplements a mouthful 5D from bacterium liquid and pumps into original position methanation anaerobic reactor 5,The pH value of adding in sodium acid carbonate and sodium carbonate adjusting original position methanation anaerobic reactor is 9.0, anti-from original position methanation anaerobismAnswer the jet aerator 5B at device air inlet 5A place to pass into hydrogen 2500m3, hydrogen partial and carbon dioxide reaction generate methane,Eventually from original position methanation anaerobic reactor top Exhaust Gas 2900m3, wherein methane volumetric concentration 58.6%, hydrogen volume is denseDegree 31.1%, carbon dioxide volumetric concentration 10.3%;
Supplement mouth 19 by supplementary mouthful 18 of bacterium liquid and nutrient solution respectively pumps in advance in the methanation anaerobic reactor 6 of offing normalThe alkaline-resisting product methane blended of basophilic bacterium: Methanobacteriumthermoalcaliphilum, MethanobacteriumThermoflexum, Methanohalophiluszhilinae bacterium liquid and nutrient solution, then add sodium carbonate and regulate mixed liquorPH value is 9.0, controls just submergence hollow fiber film assembly 12 of liquid level, will be from gas outlet, original position methanation anaerobic reactor topBy gas communication pipeline, the air inlet 6A on hollow fiber film assembly 12 passes into the methanation anaerobism of offing normal to the gas that 5C dischargesThe hollow fiber film assembly 12 that reactor is built-in, under the effect of doughnut membrane biomembrane 25, hydrogen and carbon dioxide reaction are rawBecome methane, a small amount of unreacted completely residual carbon dioxide and hydrogen enters into liquid phase from hollow-fibre membrane 23 outsides, goes forward side by sideThe one step hydrogen auxotype methanogen 27 that suspended utilizes product methane, the residual carbon dioxide of trace and hydrogen and a large amount of methane onePlay floating, while passing through the filler 13 on the methanation anaerobic reactor top of offing normal, with the spray from liquid circulation line 16 topsDevice 22 sprays the liquid countercurrent contact that carrys out autoreactor 6 that drip gets off, further under the effect of hydrogen auxotype methanogenProduce methane, the 1975m finally obtaining3High concentration methane gas (methane volumetric concentration 97.4%, carbon dioxide 2.5%, hydrogenVolumetric concentration 0.1%) discharge from the gas outlet at the methanation anaerobic reactor top of offing normal.
The methane production of whole system is from 1300m3Bring up to 1925m3, improved 65%; Methane concentration is brought up to from 60%95.2％。
Claims (5)
1. a fire damp decarbonization system, is characterized in that: this system comprises and connecting successively by gas communication pipelineHydrogen container (1), control valve (2A), gas flowmeter (3A), gas boosting pump (4), original position methanation anaerobic reactor (5), fromPosition methanation anaerobic reactor (6); On original position methanation anaerobic reactor, be provided with fermentation materials charging aperture (7), feed pump(8), discharging opening (9), air inlet (5A), gas outlet (5C), bacterium liquid supplement mouthful (5D), gas outlet (1A) and the original position first of hydrogen containerThe air inlet (5A) of alkanisation anaerobic reactor is communicated with, and air inlet (5A) locates to arrange jet aerator (5B); The methanation anaerobism of offing normalReactor lower part arranges hollow fiber film assembly (12), and top arranges filler (13), arranges simultaneously and under liquid, goes out enterprising liquidCirculation line (16), the air inlet (6A) of hollow fiber film assembly connects with the gas outlet (5C) of original position methanation anaerobic reactorLogical, bacterium liquid is set on the methanation anaerobic reactor of offing normal and supplements mouthful (18), nutrient solution supplementary mouthful (19) and a mud discharging mouth (20).
2. a kind of fire damp decarbonization system as claimed in claim 1, is characterized in that: methanation anaerobic reaction in positionThe gas circulation pipeline (11) entering under going out on gas is set on device, on gas circulation pipeline, is provided with original position methanation anaerobic reactionThe gas outlet (10) of device, the gas outlet (1A) of described gas circulation pipeline and hydrogen container and entering of original position methanation anaerobic reactorGas port (5A) is communicated with.
3. a kind of fire damp decarbonization system as claimed in claim 1 or 2, is characterized in that: hydrogen container and doughnutThe air inlet of membrane module is communicated with by a gas circuit, and in this gas circuit, is provided with control valve (2B) and gas flowmeter (3B).
4. a fire damp decarbonization method, is characterized in that, comprises the following steps:
1) original position methanation biogas decarburization: biogas fermentation inoculum and fermentation materials are successively pumped into original position first from charging aperture (7)Alkanisation anaerobic reactor (5), pumps into original position methanation anaerobism by alkaline-resisting basophilic methanogen bacterium liquid from bacterium liquid supplementary mouthful (5D) anti-Answer device (5), the pH value of adding in sodium carbonate or sodium acid carbonate adjusting original position methanation anaerobic reactor is 7.5～9.0; Again from formerMethanation anaerobic reactor air inlet place, position passes into hydrogen and reacts; In original position methanation anaerobic reactor, have neither part nor lot in reactionGas is transferred to gas phase from liquid phase:
(a) without gas circulation pipeline (11) in the situation that: gas is from gas outlet, original position methanation anaerobic reactor top (5C)Out enter the methanation anaerobic reactor (6) of offing normal;
(b) in the situation that having gas circulation pipeline (11): gas goes out by the gas outlet (10) on gas circulation pipeline (11)After coming, again by gas boosting pump (4), jet aerator (5B), gas is pumped in original position methanation anaerobic reactor (5)Liquid phase in, gas out enters the methanation anaerobism of offing normal from original position methanation anaerobic reactor (5) gas outlet, top (5C) anti-Answer device (6);
2) the methanation biogas decarburization of offing normal: by alkaline-resisting basophilic methanogen bacterium liquid and nutrient solution respectively from bacterium liquid supplement mouthful (18) andNutrient solution supplements mouthful (19) and pumps into the methanation anaerobic reactor (6) of offing normal, and it is 7.5 that interpolation sodium carbonate or sodium acid carbonate regulate pH value～9.0, liquid level is submergence hollow fiber film assembly (12) just; The gas of discharging from original position methanation anaerobic reactor top is logicalThe built-in hollow fiber film assembly of methanation anaerobic reactor that enters to off normal, the liquid in the methanation anaerobic reactor (6) of offing normal is logicalCross liquid circulation line (16) circulation and enter under spray thrower (22) spray drip, the high-purity methane obtaining is detested from the methanation of offing normalDischarge the gas outlet (6B) at oxygen reactor (6) top.
5. a kind of fire damp decarbonization method as claimed in claim 4, is characterized in that, in the methanation biogas decarburization of offing normalIn the stage, also pass into hydrogen from hydrogen container (1) to the built-in hollow fiber film assembly (12) of the methanation anaerobic reactor (6) of offing normal.
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| CN110295073A (en) * | 2019-07-09 | 2019-10-01 | 哈尔滨工业大学 | Methane purification membrane bioreactor and its application method |
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