CN102492506A - Method and device for removing carbon dioxide in methane by organic waste water - Google Patents
Method and device for removing carbon dioxide in methane by organic waste water Download PDFInfo
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- CN102492506A CN102492506A CN201110412436.8A CN201110412436A CN102492506A CN 102492506 A CN102492506 A CN 102492506A CN 201110412436 A CN201110412436 A CN 201110412436A CN 102492506 A CN102492506 A CN 102492506A
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- anaerobic reactor
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- anolyte compartment
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 93
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 76
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 26
- 239000010815 organic waste Substances 0.000 title claims abstract description 24
- 229910002092 carbon dioxide Inorganic materials 0.000 title abstract description 9
- 239000001569 carbon dioxide Substances 0.000 title abstract description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000001257 hydrogen Substances 0.000 claims abstract description 42
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 42
- 235000016709 nutrition Nutrition 0.000 claims abstract description 20
- 241000894006 Bacteria Species 0.000 claims abstract description 18
- 230000004060 metabolic process Effects 0.000 claims abstract description 11
- 238000000855 fermentation Methods 0.000 claims abstract description 4
- 238000010521 absorption reaction Methods 0.000 claims description 17
- 235000011089 carbon dioxide Nutrition 0.000 claims description 16
- 239000002994 raw material Substances 0.000 claims description 9
- 230000008676 import Effects 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- 239000005416 organic matter Substances 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims description 2
- 239000002351 wastewater Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 5
- 239000002250 absorbent Substances 0.000 abstract description 3
- 230000002745 absorbent Effects 0.000 abstract description 3
- 238000005262 decarbonization Methods 0.000 abstract description 3
- 230000000813 microbial effect Effects 0.000 abstract 3
- 239000003463 adsorbent Substances 0.000 abstract 1
- 238000009395 breeding Methods 0.000 abstract 1
- 230000008020 evaporation Effects 0.000 abstract 1
- 238000001704 evaporation Methods 0.000 abstract 1
- 230000035764 nutrition Effects 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 11
- 239000003345 natural gas Substances 0.000 description 10
- 241000573729 bacterium 125 Species 0.000 description 5
- 150000007524 organic acids Chemical class 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
- 239000008186 active pharmaceutical agent Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 235000009508 confectionery Nutrition 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000003546 flue gas Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 235000013379 molasses Nutrition 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000010802 sludge Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 238000009834 vaporization Methods 0.000 description 3
- 230000008016 vaporization Effects 0.000 description 3
- 241000202970 Methanobacterium formicicum Species 0.000 description 2
- 241000203375 Methanococcus voltae Species 0.000 description 2
- 241000205275 Methanosarcina barkeri Species 0.000 description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 2
- 229930006000 Sucrose Natural products 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000005261 decarburization Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 239000002594 sorbent Substances 0.000 description 2
- 239000005720 sucrose Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 241001478240 Coccus Species 0.000 description 1
- 241001494297 Geobacter sulfurreducens Species 0.000 description 1
- 241001148572 Pelobacter propionicus Species 0.000 description 1
- 241000589517 Pseudomonas aeruginosa Species 0.000 description 1
- 241001223867 Shewanella oneidensis Species 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 230000022131 cell cycle Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 210000003608 fece Anatomy 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 244000144977 poultry Species 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000010801 sewage sludge Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)
Abstract
The invention provides a method and a device for removing carbon dioxide in methane by organic waste water. The method includes steps of (1) generating hydrogen in an anode chamber of a microbial electrolytic cell by the organic waste water and generating CO2 and H2 under the metabolism action of anaerobic power-generating bacteria; and (2) producing methane by anaerobic fermentation of hydrogen and carbon dioxide in an anaerobic reactor. The device comprises the microbial electrolytic cell, the anaerobic reactor, a flash evaporation tank and connecting pipes. By means of combination of hydrogen producing process of the microbial electrolytic cell and hydrogen nutrition type methane producing process, CO2 in the methane is converted into CH4, and yield of the CH4 is increased while the CO2 in the methane is removed. Meanwhile, the organic waste water is treated and utilized, and comprehensive utilization of resources is realized. Since self-breeding microbes utilized in the process of decarbonization of methane substitute for expensive physical absorbent, chemical absorbent and adsorbent, running cost for decarbonization of the methane is reduced greatly.
Description
Technical field
The invention belongs to organic waste and handle and the development of clean energy field, be specifically related to method and device thereof that a kind of organic waste water removes carbonic acid gas in the biogas.
Technical background
Along with China's rapid economic development, Energy production can't have been satisfied the quick growth of energy expenditure, and the external interdependency of the energy increases year by year, and imbalance between supply and demand is outstanding, and energy shortage will be a secular process.From the energy structure aspect, make a general survey of human use's energy development history, energy form is progressively developed to gas (Sweet natural gas, future possibly be hydrogen) to liquid (oil) by solid (coal) again.From the Sweet natural gas supply and demand, China's natural gas imbalance between supply and demand since two thousand seven increases day by day, and national gas production in 2010 is 967.6 hundred million m
3, and the natural gas consumption amount is 1,180 hundred million m
3, insufficiency of supply-demand reaches 212.4 hundred million m
3Estimate that 2011,2015, the China's natural gas demand of the year two thousand twenty are respectively 1,300 hundred million, 1,500 hundred million and 3,000 hundred million m
3, China's natural gas imbalance between supply and demand when the time comes will be more outstanding.
Through the biological flue gas (biogas) that anaerobically fermenting forms, its major ingredient is CH
4And CO
2, purification can be used as instead of natural gas after purifying.The main raw material of preparation biological flue gas comprises agricultural crop straw, feces of livestock and poultry, organic waste water waste residue, processing of farm products residuum, domestic organic garbage, sewage sludge etc.At present China's stock number of can be used for producing biological flue gas is amounted to 2.5 hundred million tons of standard coal equivalents approximately, can transform equivalent Sweet natural gas (methane) 1200 billion cubic meters, is equivalent to China's natural gas consumption amount in 2010.
The committed step that biogas prepares instead of natural gas is a CO2 removal, and the method that biogas removes carbonic acid gas mainly contains high-pressure washing method, physical absorption method, chemical absorption method, transformation absorption (PSA) method, membrane separation process at present.High-pressure washing, physical absorption, chemical absorption, main absorption/absorption---the Principles of Chemical Engineering of stripping/desorb of utilizing of transformation absorption (PSA); Wherein physical absorption, chemical absorption, transformation absorption also need expensive absorption agent or sorbent material; Membrane sepn uses the marsh gas purifying engineering of this method less owing to need expensive membrane module and higher WP.What is more important, more than whole carbon dioxide de eliminating methods, only be the transfer that has realized carbonic acid gas, promptly from biogas, shift out, do not realize the trans-utilization of carbonic acid gas.
Summary of the invention
The objective of the invention is to overcome deficiency of the prior art; The method and the device thereof that provide a kind of organic waste water to remove carbonic acid gas in the biogas; Carbonic acid gas in the biogas is converted into the staple (methane) in the biogas; Improve methane production, realize the high-value-use of carbonic acid gas in the biogas, and reduce biogas decarburization cost.
Organic waste water removes the method for carbonic acid gas in the biogas among the present invention, may further comprise the steps:
(1) organic waste water produces hydrogen: cultivate anaerobism electrogenesis bacterium in advance in the anolyte compartment of mikrobe electrolytic cell, organic waste water feeds in the anolyte compartment of mikrobe electrolytic cell, and under anaerobic, the organic matter in the waste water forms CO under the metabolism of anaerobism electrogenesis bacterium
2, proton and electronics, CO
2Discharge from the anolyte compartment; Accomplishing the organic clear water that utilizes discharges from the anolyte compartment; Proton passes the cathode compartment that PEM gets into the mikrobe electrolytic cell; Electronics is delivered on the cathode electrode of cathode compartment through external circuit from anode electrode down the auxiliary of extraneous power supply, and under anaerobic, proton and electronics generate H under the katalysis of cathode electrode
2, H
2Discharge from cathode compartment;
Anolyte compartment:
Cathode compartment: 2H
++ 2e
-→ H
2
(2) hydrogen and carbonic acid gas anaerobic fermentation methane: collect the H that said process obtains
2, and (contain CH with biogas
4And CO
2) mix supercharging after, feeding to cultivate in advance has in the anaerobic reactor of hydrogen nutritional type methanogen H
2And CO
2Under the metabolism of hydrogen nutritional type methanogen, generate CH
4, in addition, collect the clear water of discharging and feed in the anaerobic reactor unemployed a part of gaseous state CO in the biogas from the anolyte compartment
2Under reactor drum inner high voltage condition, further absorbed, accomplish CO by clear water
2Biogas after conversion and the absorption (mainly contains CH
4) discharge from the anaerobic reactor top, accomplish CO
2High pressure clear water after the absorption is discharged from the anaerobic reactor bottom and is fed flash tank, utilizes flash tank to reclaim a small amount of methane that is absorbed by clear water, and the methane of recovery and biogas raw materials mix are re-entered in the anaerobic reactor, and last, clear water is discharged from flash tank.
H
2And CO
2Anaerobic fermentation methane:
High pressure water absorbing carbon dioxide: CO
2(g)+H
2O → CO
2(l)+H
2O.
The present invention also provides the device of realizing aforesaid method.
Apparatus of the present invention mainly comprise mikrobe electrolytic cell, anaerobic reactor, flash tank and connecting pipeline.The mikrobe electrolytic cell is divided into anolyte compartment and cathode compartment through PEM; Anolyte compartment and cathode compartment are the anaerobic environment of sealing; Cultivate the anolyte compartment has anaerobism electrogenesis bacterium, and the anolyte compartment is provided with water-in, water outlet, air outlet, and cathode compartment is provided with the air outlet; Anolyte compartment's water outlet is communicated with anaerobic reactor through pipeline, and the cathode compartment air outlet also is communicated with anaerobic reactor through pipeline.The inner cultivation of anaerobic reactor has hydrogen nutritional type methanogen, its top to be provided with the air outlet and is communicated with air water separator, and the bottom is provided with water outlet and is communicated with flash tank, and other is provided with inlet mouth.Flash tank is provided with water outlet and air outlet, and its air outlet is communicated with the inlet mouth of anaerobic reactor through pipeline.
Further improvement of the present invention is:
The pipeline that anolyte compartment's water outlet is communicated with anaerobic reactor is provided with tank and topping-up pump;
To hydrogen container, hydrogen container is communicated with surge tank again through pipeline connection in the cathode compartment air outlet, and surge tank is provided with the biogas import in addition, and is communicated to the inlet mouth of anaerobic reactor through compressor through pipeline.
For ease of technological operation, between each water-in, water outlet, inlet mouth, air outlet and mikrobe electrolytic cell, anaerobic reactor, surge tank, flash tank, the air water separator valve is set.
Described organic waste water is preferably and contains organic acid, carbohydrate, starch based organic waste water.
Described mikrobe electrolytic cell is the conventional mikrobe electrolytic cell of prior art.Its anode electrode, extraneous power supply are connected through external circuit with cathode electrode successively, and extraneous power supply is the direct supply of voltage >=0.2V, and its positive pole links to each other with the anode of mikrobe electrolytic cell, and negative pole links to each other with the negative electrode of mikrobe electrolytic cell.
Described anaerobic reactor is the various anaerobic reactors of prior art, including, but not limited to complete hybrid anaerobic reactor, filling bubble column type anaerobic reactor, trickle bed anaerobic reactor, cell fixation anaerobic reactor, cell cycle anaerobic reactor.
Described anaerobism electrogenesis bacterium and hydrogen nutritional type methanogen can separate obtaining from occurring in nature for disclosing bacterial classification, also can buy from domestic and international DSMZ, but the single culture use, but also associate strain uses, and preferably mixes and uses.Described anaerobism electrogenesis bacterium anaerobism electrogenesis bacterium is including, but not limited to Geobacter sulfurreducens (ATCC 51573), Shewanella oneidensis (ATCC 700550), Pseudomonas aeruginosa (ATCC BAA-427), Pelobacterpropionicu (DSM 2379), and hydrogen nutritional type methanogen is including, but not limited to Methanosarcina barkeri (ATCC 43240), Methanobacterium formicicum (ATCC 33272), Methanococcus voltae (ATCC BAA-1334).
Innovation part of the present invention is, the mikrobe electrolytic cell is produced hydrogen technology and the combination of hydrogen nutritional type product methane technology, with the CO in the biogas
2Be converted into CH
4, not only remove CO in the biogas
2, but also increased CH
4Output, simultaneously again processing and utilizing organic waste water, realized the comprehensive utilization of resource.Because this biogas decarbonization process use is the mikrobe with self-reproduction ability, rather than expensive physical absorbent, chemical absorber or sorbent material, therefore greatly reduce the running cost of biogas decarburization.
Description of drawings
Fig. 1 is apparatus of the present invention schematic flow sheets
Description of reference numerals:
1, mikrobe electrolytic cell; 11, PEM; 12, anolyte compartment; 121, anolyte compartment's water-in; 122, anolyte compartment's water outlet; 123, air outlet, anolyte compartment; 124, anode electrode; 125, anaerobism electrogenesis bacterium; 13, cathode compartment; 131, cathode compartment air outlet; 132, cathode electrode; 14, extraneous power supply; 2, tank; 3, topping-up pump; 4, anaerobic reactor; 41, hydrogen nutritional type methanogen; 5, flash tank; 6, hydrogen container; 7, surge tank; 8, compressor; 9, air water separator.
Embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is elaborated.
As shown in Figure 1; Apparatus of the present invention comprise mikrobe electrolytic cell 1, tank 2, topping-up pump 3, anaerobic reactor 4, flash tank 5 that is communicated with successively and mikrobe electrolytic cell 1, hydrogen container 6, surge tank 7, compressor 8, anaerobic reactor 4, the air water separator 9 that is communicated with successively; Mikrobe electrolytic cell 1 is divided into anolyte compartment 12 and cathode compartment 13 through PEM 11; Anolyte compartment 12 and cathode compartment 13 are the anaerobic environment of sealing; Cultivate anolyte compartment 12 has anaerobism electrogenesis bacterium 125; Anolyte compartment 12 is provided with water-in 121, water outlet 122, air outlet 123, and cathode compartment 13 is provided with air outlet 131, is respectively arranged with anode electrode 124 and cathode electrode 132 in anolyte compartment 12 and the cathode compartment 13; Anode electrode 124, extraneous power supply 14 and cathode electrode 132 are connected through external circuit successively; Extraneous power supply 14 is the direct supply of voltage >=0.2V, and its positive pole links to each other with the anode of mikrobe electrolytic cell 1, and negative pole links to each other with the negative electrode of mikrobe electrolytic cell 1; Anaerobic reactor 4 tops, top, bottom, bottom are respectively arranged with air outlet, water-in, inlet mouth, water outlet, and anaerobic reactor 4 inner cultivations have hydrogen nutritional type methanogen 41; Flash tank 5 tops, top, bottom are respectively arranged with air outlet, water-in, water outlet; Anolyte compartment's water-in 121, anolyte compartment 12, anolyte compartment's water outlet 122, tank 2, topping-up pump 3, anaerobic reactor water-in, anaerobic reactor 4, anaerobic reactor water outlet, flash tank water-in, flash tank 5, flash tank water outlet are communicated with successively; Cathode compartment air outlet 131, hydrogen container 6, surge tank 7, compressor 8, anaerobic reactor inlet mouth, anaerobic reactor 4, anaerobic reactor air outlet, air water separator 9 are communicated with successively; Surge tank 7 is provided with the biogas import, and flash tank 5 air outlets are communicated with the biogas import.
For ease of technological operation, between each water-in, water outlet, inlet mouth, air outlet and mikrobe electrolytic cell 1, anaerobic reactor 4, surge tank 7, flash tank 5, the air water separator 9 valve is set.
Embodiment 1:
At first, from the anaerobic activated sludge of methane-generating pit, screen enrichment respectively and go out anaerobism electrogenesis mixed bacterium and hydrogen nutritional type and produce the methane blended bacterium, and cultivate in the anolyte compartment 12 that places mikrobe electrolytic cell 1 respectively and the complete hybrid anaerobic reactor 4; To contain sucrose organic waste water from the anolyte compartment water-in 121 feeding anolyte compartments 12, sucrose is degraded under the metabolism of anaerobism electrogenesis bacterium 125 and is formed CO
2, proton and electronics, CO
2123 discharge from the air outlet, anolyte compartment; Proton passes PEM 11 and gets into cathode compartment 13; Electronics is delivered on the cathode electrode 132 through external circuit from anode electrode 124 down the auxiliary of extraneous power supply 14 (volts DS 0.4V); Under the condition that does not have extraneous oxygen to exist, proton, electronics generate H under the katalysis of cathode electrode 132
2, the H of generation
2131 discharge and are stored in hydrogen container 6 from the cathode compartment air outlet; Sugar consumption clear water totally is water outlet 122 discharges and 2 storages of introducing tank from the anolyte compartment, utilize topping-up pump 3 that clear water is pressed into complete hybrid anaerobic reactor 4 from anaerobic reactor 4 water-ins subsequently; With the H in the hydrogen container 6
2(calculate with percent by volume, contain 55.0%CH with the biogas raw material
4, 44.0%CO
2, 1.0% other gas) feed in the surge tank respectively and mix, mixed gas is pressed into anaerobic reactor 4 from the inlet mouth of anaerobic reactor 4 bottoms after through compressor boost, in anaerobic reactor 4, H
2And CO
2Under the metabolism of hydrogen nutritional type methanogen 41, give birth to CH
4,, can absorb the CO in a part of biogas because the water in the reactor drum 4 is high pressure water
2, accomplish CO
2The biogas that transforms and absorb is discharged from air outlet, anaerobic reactor 4 top, (calculates with percent by volume, contains 92.5%CH4,6.0%CO through surveying its gaseous constituent after the gas-water separation
2, 1.5% other gas); Accomplish CO
2Flash tank 5 is discharged and fed to the high pressure clear water that absorbs from anaerobic reactor 4 bottom water outlets; In flash tank 5; Rapid drawdown through the jar internal pressure discharges a small amount of methane of dissolved in the clear water and discharges from air outlet, flash tank 5 top; Reclaim at last and incorporate in the biogas raw material, accomplish the clear water of flash vaporization process and discharge from flash tank 5 bottoms.
Embodiment 2
At first; The screening enrichment goes out anaerobism electrogenesis mixed bacterium from the anaerobic activated sludge of methane-generating pit; Methanosarcina barkeri that utilization buys from American Type Culture Collecti (ATCC) and Methanobacterium formicicum produce the methane blended bacterium as the hydrogen nutritional type, above-mentioned anaerobism electrogenesis mixed bacterium 125 and hydrogen nutritional type are produced in anolyte compartment 12 that methane blended bacterium 41 places mikrobe electrolytic cell 1 respectively and the trickle bed anaerobic reactor 4 cultivate; To contain organic acid organic waste water from the anolyte compartment water-in 121 feeding anolyte compartments 12, organic acid is degraded under the metabolism of anaerobism electrogenesis bacterium 125 and is formed CO
2, proton and electronics, CO
2123 discharge from the air outlet, anolyte compartment; Proton passes PEM 11 and gets into cathode compartment 13; Electronics is delivered on the cathode electrode 132 through external circuit from anode electrode 124 down the auxiliary of extraneous power supply 14 (volts DS 0.6V); Under the condition that does not have extraneous oxygen to exist, proton, electronics generate H under the katalysis of cathode electrode 132
2, the H of generation
2131 discharge and are stored in hydrogen container 6 from the cathode compartment air outlet; The clear water of organic acid approach exhaustion is water outlet 122 discharges and 2 storages of introducing tank from the anolyte compartment, utilize topping-up pump 3 that clear water is pressed into anaerobic reactor 4 from anaerobic reactor 4 water-ins subsequently; With the H in the hydrogen container 6
2(calculate with percent by volume, contain 60.0%CH with the biogas raw material
4, 39.0%CO
2, 1.0% other gas) feed respectively in the surge tank 7 and mix, mixed gas is pressed into anaerobic reactor 4 from the inlet mouth of anaerobic reactor 4 bottoms after through compressor boost, in anaerobic reactor 4, H
2And CO
2Under the metabolism of hydrogen nutritional type methanogen 41, generate CH
4,, can absorb the CO in a part of biogas because the water in the reactor drum is high pressure water
2, accomplish CO
2The biogas that transforms and absorb is discharged from air outlet, anaerobic reactor 4 top, (calculates with percent by volume, contains 95%CH through surveying its gaseous constituent after the gas-water separation
4, 3.0%CO
2, 2.0% other gas); Accomplish CO
2Flash tank 5 is discharged and fed to clear water after the absorption from anaerobic reactor 4 bottom water outlets; In flash tank 5; Rapid drawdown through the jar internal pressure discharges a small amount of methane of dissolved in the clear water and discharges from the flash drum overhead air outlet; Reclaim at last and incorporate in the biogas raw material, accomplish the clear water of flash vaporization process and discharge from flash tank 5 bottoms.
Embodiment 3
At first; The screening enrichment goes out anaerobism electrogenesis mixed bacterium from the anaerobic activated sludge of methane-generating pit; Buy Wo Shi methane coccus (M.voltae) as hydrogen nutritional type methanogen from American Type Culture Collecti (ATCC), above-mentioned anaerobism electrogenesis mixed bacterium and hydrogen nutritional type methanogen are placed respectively in anolyte compartment 12 and the cell fixation anaerobic reactor 4 of mikrobe electrolytic cell 1 and cultivate; The organic waste water that will contain molasses is water-in 121 feeding anolyte compartments 12 from the anolyte compartment, and molasses are degraded under the metabolism of anaerobism electrogenesis bacterium 125 and formed CO
2, proton and electronics, CO
2123 discharge from the air outlet, anolyte compartment; Proton passes PEM 11 and gets into cathode compartment 13; Electronics is delivered on the cathode electrode 132 through external circuit from anode electrode 124 down the auxiliary of extraneous power supply (volts DS 0.8V); Under the condition that does not have extraneous oxygen to exist, proton, electronics generate H under the katalysis of cathode electrode 132
2, the H of generation
2131 discharge and are stored in hydrogen container 6 from the cathode compartment air outlet; The clear water of molasses approach exhaustion is water outlet 122 discharges and 2 storages of introducing tank from the anolyte compartment, utilize topping-up pump 3 that clear water is pressed into anaerobic reactor 4 from anaerobic reactor 4 water-ins subsequently; With the H in the hydrogen container 6
2(calculate with percent by volume, contain 60.0%CH with the biogas raw material
4, 39.0%CO
2, 1.0% other gas) feed respectively in the surge tank 7 and mix, mixed gas is pressed into anaerobic reactor 4 from the inlet mouth of anaerobic reactor 4 bottoms after through compressor 8 superchargings, in anaerobic reactor 4, H
2And CO
2Under the metabolism of hydrogen nutritional type methanogen 41, generate CH
4,, can absorb the CO in a part of biogas because the water in the reactor drum is high pressure water
2, accomplish CO
2The biogas that transforms and absorb is discharged from air outlet, anaerobic reactor 4 top, (calculates with percent by volume, contains 94%CH4,4.2%CO through surveying its gaseous constituent after the gas-water separation
2, 1.8% other gas); Accomplish CO
2Flash tank 5 is discharged and fed to clear water after the absorption from anaerobic reactor 4 bottom water outlets; In flash tank 5; Rapid drawdown through the jar internal pressure discharges a small amount of methane of dissolved in the clear water and discharges from the flash drum overhead air outlet; Reclaim at last and incorporate in the biogas raw material, accomplish the clear water of flash vaporization process and discharge from the flash tank bottom.
At last, it is also to be noted that what more than enumerate only is specific embodiment of the present invention.Obviously, the invention is not restricted to above examples of implementation, many distortion can also be arranged.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention all should be thought protection scope of the present invention.
Claims (4)
1. organic waste water removes the method for carbonic acid gas in the biogas, it is characterized in that may further comprise the steps:
(1) organic waste water produces hydrogen: the anolyte compartment of mikrobe electrolytic cell cultivates anaerobism electrogenesis bacterium in advance, and organic waste water feeds in the anolyte compartment of mikrobe electrolytic cell, and under anaerobic, the organic matter in the waste water generates CO under the metabolism of anaerobism electrogenesis bacterium
2And H
2, CO
2Discharge from the anolyte compartment, accomplish the organic clear water that utilizes and discharge H from the anolyte compartment
2Discharge from cathode compartment;
(2) hydrogen and carbonic acid gas anaerobic fermentation methane: collect the H that step (1) obtains
2, and with biogas mixing supercharging after, feeding to cultivate in advance has in the anaerobic reactor of hydrogen nutritional type methanogen H
2And CO
2Under the metabolism of hydrogen nutritional type methanogen, generate CH
4, in addition, collect the clear water of discharging and feed in the anaerobic reactor unemployed a part of gaseous state CO in the biogas from the anolyte compartment
2Under reactor drum inner high voltage condition, further absorbed, accomplish CO by clear water
2Biogas after conversion and the absorption is discharged from the anaerobic reactor top, accomplishes CO
2High pressure clear water after the absorption is discharged from the anaerobic reactor bottom and is fed flash tank, utilizes flash tank to reclaim a small amount of methane that is absorbed by clear water, and the methane of recovery and biogas raw materials mix are re-entered in the anaerobic reactor, and last, clear water is discharged from flash tank.
2. organic waste water as claimed in claim 1 removes the method for carbonic acid gas in the biogas, it is characterized in that: the clear water that the anolyte compartment discharges in the step (2) feeds in the anaerobic reactor after supercharging again.
3. organic waste water removes the device of carbonic acid gas in the biogas, it is characterized in that comprising mikrobe electrolytic cell, anaerobic reactor, flash tank and connecting pipeline; The mikrobe electrolytic cell is divided into anolyte compartment and cathode compartment through PEM; Anolyte compartment and cathode compartment are the anaerobic environment of sealing; Cultivate the anolyte compartment has anaerobism electrogenesis bacterium, and the anolyte compartment is provided with water-in, water outlet, air outlet, and cathode compartment is provided with the air outlet; Anolyte compartment's water outlet is communicated with anaerobic reactor through pipeline, and the cathode compartment air outlet also is communicated with anaerobic reactor through pipeline; The inner cultivation of anaerobic reactor has hydrogen nutritional type methanogen, its top to be provided with the air outlet and is communicated with air water separator, and the bottom is provided with water outlet and is communicated with flash tank, and other is provided with inlet mouth; Flash tank is provided with water outlet and air outlet in addition, and its air outlet is communicated with the inlet mouth of anaerobic reactor through pipeline.
4. remove the device of carbonic acid gas in the biogas like the said organic waste water of claim 3, it is characterized in that: the pipeline that said anolyte compartment water outlet is communicated with anaerobic reactor is provided with tank and topping-up pump; To hydrogen container, hydrogen container is communicated with surge tank again through pipeline connection in the cathode compartment air outlet, and surge tank is provided with the biogas import in addition, and is communicated to the inlet mouth of anaerobic reactor through compressor through pipeline.
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