CN102266719B - Industrial tail gas recycling system - Google Patents
Industrial tail gas recycling system Download PDFInfo
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- CN102266719B CN102266719B CN201110156266.1A CN201110156266A CN102266719B CN 102266719 B CN102266719 B CN 102266719B CN 201110156266 A CN201110156266 A CN 201110156266A CN 102266719 B CN102266719 B CN 102266719B
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- synthesis gas
- separator
- tail gas
- fermentation strain
- industrial tail
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- 238000004064 recycling Methods 0.000 title abstract 5
- 238000000855 fermentation Methods 0.000 claims abstract description 138
- 230000004151 fermentation Effects 0.000 claims abstract description 138
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 86
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 86
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 72
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 71
- 230000012010 growth Effects 0.000 claims abstract description 43
- 241000195493 Cryptophyta Species 0.000 claims description 119
- 238000012258 culturing Methods 0.000 claims description 42
- 239000007788 liquid Substances 0.000 claims description 26
- 235000015097 nutrients Nutrition 0.000 claims description 26
- 238000006392 deoxygenation reaction Methods 0.000 claims description 21
- 238000010521 absorption reaction Methods 0.000 claims description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 18
- 239000002283 diesel fuel Substances 0.000 claims description 16
- FRXSZNDVFUDTIR-UHFFFAOYSA-N 6-methoxy-1,2,3,4-tetrahydroquinoline Chemical compound N1CCCC2=CC(OC)=CC=C21 FRXSZNDVFUDTIR-UHFFFAOYSA-N 0.000 claims description 11
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 7
- 239000012528 membrane Substances 0.000 claims description 5
- 230000000306 recurrent effect Effects 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 229940043237 diethanolamine Drugs 0.000 claims description 2
- 239000006227 byproduct Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000007789 gas Substances 0.000 description 120
- 241000196324 Embryophyta Species 0.000 description 20
- 239000006228 supernatant Substances 0.000 description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 229910000831 Steel Inorganic materials 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 150000001720 carbohydrates Chemical class 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- 230000001580 bacterial effect Effects 0.000 description 5
- 235000014633 carbohydrates Nutrition 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 241001656809 Clostridium autoethanogenum Species 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
- 239000000284 extract Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 244000005700 microbiome Species 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 238000012262 fermentative production Methods 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 239000002207 metabolite Substances 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- 241001611022 Clostridium carboxidivorans Species 0.000 description 2
- 241000186566 Clostridium ljungdahlii Species 0.000 description 2
- 241000193459 Moorella thermoacetica Species 0.000 description 2
- 239000003225 biodiesel Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 230000002906 microbiologic effect Effects 0.000 description 2
- 230000008520 organization Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 241000195649 Chlorella <Chlorellales> Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000008935 nutritious Nutrition 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 238000000108 ultra-filtration Methods 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
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
-
- 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
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
-
- 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
- Y02E50/10—Biofuels, e.g. bio-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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/59—Biological synthesis; Biological purification
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Landscapes
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Apparatus Associated With Microorganisms And Enzymes (AREA)
Abstract
The invention discloses an industrial tail gas recycling system. In the industrial tail gas recycling system, a microalgae oil production device is organically coupled with a synthesis gas fermentation strain growth tank and a synthesis gas fermentation strain fermentation tank. By the industrial tail gas recycling system, CO2 and CO in the tail gas can be recycled effectively, so that two types of clean energy, namely ethanol and diesel, and a few of acetic acid by-products can be obtained. Thus, components of the industrial tail gas can be treated fully through a biologic mode, energy is recycled; therefore, pollution of industrial tail gas emission to the environment can be relieved; and the industrial tail gas energy recycling system has significant use value.
Description
Technical field:
The invention belongs to exhaust-gas treatment and development of clean energy field, relate generally to the system of the recovery energy of industrial tail gas.
Background technology:
Industrial plant every year not only wastes energy but also also brings huge pressure to environment to a large amount of hydrocarbon of airborne release.Wherein with ammonia synthesizing industry, petroleum refining industry, steel plant, the problem of the intensive industry emission of carbon of wood pulp papermaking industry homenergic oxygen compound is particularly outstanding.The hydrocarbon of these industry dischargings causes heavy burden to environment.
Little algae is that a class can be utilized CO fast
2, and producing the biology of grease simultaneously, it is widely used in the production biodiesel.Except the lipid component of little algae own, it also has rich saccharide can supply to utilize, thereby little algae is a kind of energy CO that extremely is fit to
2Biology.
The synthesis gas fermentation strain is that a class can be utilized CO, CO simultaneously under the strictly anaerobic environment
2/ H
2With carbohydrate fermentation producing and ethanol microorganism, yet at normal temperatures and pressures, its utilization ratio to gaseous carbon source is relatively low.This quasi-microorganism comprises Clostridium thermoaceticum, Clostridium autoethanogenum, Peptostreptoccus productus, Eubacteriam limosum, Butyribacterium methylotrophicum, Clostridium ljungdahlii and Clostridium carboxidivorans etc.The growth of synthesis gas fermentation strain needs different culture environment with alcohol fermentation.The main metabolites of this quasi-microorganism bacterial strain in the environment of favourable growth is an acids, and the primary product of bacterial strain is an alcohols under disadvantageous growth conditions.
Such chemistry of micro-organisms metering-type is as follows:
6CO+3H
2O→CH
3CH
2OH+4CO
2 ΔH＝-217.9kJ/mol
2CO
2+6H
2→CH
3CH
2OH+3H
2O ΔH＝-97.3kJ/mol
4CO+2H
2O→CH
3COOH+2CO
2 ΔH＝-154.9kJ/mol
2CO
2+4H
2→CH
3COOH+2H
2O ΔH＝-75.3kJ/mol
As from the foregoing, though the synthesis gas fermentation strain has the unique ability of utilizing CO in the tail gas, its efficient is lower, and under the condition that lacks reducing power, portion C O will be arranged
2Produce.And the cultivation of introducing little algae can improve these deficiencies, and the existence one of little algae is can more efficient use CO
2The 2nd, little algae contain the growth that sugar moieties can be used for promoting the synthesis gas fermentation strain.Therefore, the effective hydrocarbon in processing plant's tail gas of synthesis gas fermentation strain and little algae coupling.
The plant tail gas intermittent entry is another difficult problem of tail gas microbiological treatment, and vent gas treatment need be by the specific device combination to adapt to interrupted tail gas environment.
Summary of the invention:
The purpose of this invention is to provide a kind of pollution that can alleviate industrial tail gas discharging to environment, utilize hydrocarbon in the tail gas to obtain the industrial tail gas energy system of ethanol and diesel oil two class clean energy resourcies and small amount of acetic acid byproduct fully.
Industrial tail gas energy of the present invention system comprises CO
2Absorption plant, CO
2Absorption plant respectively with N
2Separator, CO
2Separator is connected with the first deoxygenation post, and the first deoxygenation post also links to each other CO with synthesis gas fermentation strain growth jar with synthesis gas fermentation strain fermentation tank respectively
2Separator and micro algae culturing device, little algae and micro algae culturing liquid separator, little algae separator, little algae is extracted the diesel oil reactor and is connected successively with the diesel oil output channel, also be connected with the micro algae culturing liquid Returning pipe between micro algae culturing device and little algae and the micro algae culturing liquid separator, the little algae separator and the second deoxygenation post, synthesis gas fermentation strain growth jar, the separated from acetic acid device, synthesis gas fermentation strain fermentation tank, the ethanol separator is connected successively with the ethanol output channel, also be connected with synthesis gas fermentation strain nutrient solution Returning pipe between separated from acetic acid device and the synthesis gas fermentation strain growth jar, also be connected with thalline between synthesis gas fermentation strain fermentation tank and the ethanol separator, the nutrient solution Returning pipe, the acetate output port of separated from acetic acid device respectively with the acetate output channel with link to each other with micro algae culturing device through the acetate recurrent canal, synthesis gas fermentation strain fermentation tank also passes through CO+CO
2Returning pipe and CO
2Absorption plant links to each other.
Described N
2Separator is with N in the industrial tail gas
2From tail gas, separate, can pass through technologies such as molecular sieve, low-temperature fractionation and separate N
2, this belongs to the common practise of this area.
Described CO
2CO is housed in the absorption plant
2Lyosoption, lyosoption can be MEA, diethanol amine, triethanolamine and Selexol
TM
Described CO
2Separator is with CO
2Absorb saturated solvent and make CO by means such as heating
2And CO
2Lyosoption separates.
Described micro algae culturing device is preferably closed photo bioreactor, as fermentation pot type Photoreactor, and the tubular type Photoreactor, board-like Photoreactor, further preferred described closed photo bioreactor has can receive extraneous CO
2Opening.Its nutrient solution can derive from steel mill's waste water or configuration voluntarily.By receiving extraneous CO
2Opening utilize airborne CO
2Component is controlled little algae and is cultured to optimum temperature and intensity of illumination, and the sun or artificial light sources all can be the illumination source.After algae liquid length is dense, just can isolate little algae and nutrient solution by little algae and micro algae culturing liquid separator, little algae makes little algae-residue separate with little algae supernatant through little algae separator again, and little algae-residue is used for the preparation of biodiesel, and the little algae supernatant that contains sugar is used for the growth of synthesis gas fermentation strain.
Described little algae separator is preferably centrifuge, utilizes centrifuge that the supernatant of little algae-residue and little algae is separated.
Described little algae and micro algae culturing liquid separator, separated from acetic acid device and ethanol separator are preferably can realize that little algae separates with micro algae culturing liquid, separated from acetic acid is separated with ethanol filter, micro-filtration, ultrafiltration apparatus separate equipment with centrifugal etc., and those skilled in the art can go to select and implement according to the common practise of this area.
The described first deoxygenation post and the second deoxygenation post are preferably by the high temperature copper catalyst and remove oxygen or pass through metal oxide containing precious metals and H such as other palladiums and platinum
2Oxygen is removed in reaction.
Described synthesis gas fermentation strain growth jar is preferably the conventional fermentation tank of suitable strain growths such as upflow bioreactor, CSTR, trickle bed anaerobic reactor and bubble type anaerobic reactor.
Described synthesis gas fermentation strain fermentation tank is preferably the reactor that suitable microorganisms such as upflow bioreactor, CSTR, trickle bed anaerobic reactor, bubble type anaerobic reactor and membrane reactor utilize CO.
Described synthesis gas fermentation strain growth jar and synthesis gas fermentation strain fermentation tank are in order to cultivate the synthesis gas fermentation strain, described synthesis gas fermentation strain comprises Clostridium thermoaceticum, Clostridium autoethanogenum, Peptostreptoccus productus, Eubacteriam limosum, Butyribacterium methylotrophicum, Clostridium ljungdahlii and Clostridium carboxidivorans etc.
The operation method of industrial tail gas energy of the present invention system is:
Industrial tail gas is through N
2Separator separates N
2After, enter and contain CO
2The CO of lyosoption
2Absorption plant, CO
2Be absorbed, remaining gas is mainly the gas that contains CO, and this gas feeds synthesis gas fermentation strain growth jar and synthesis gas fermentation strain fermentation tank respectively after the first deoxygenation post is removed oxygen, use for growth of synthesis gas fermentation strain and fermentation; CO
2Absorb saturated solvent and flow into CO
2Separator is carried out gas-water separation, makes CO
2Separate isolated CO
2Feed micro algae culturing device, utilized by little algae, little algae and micro algae culturing liquid make little algae separate with nutrient solution through little algae and micro algae culturing liquid separator, nutrient solution flows into micro algae culturing device through the micro algae culturing liquid Returning pipe, little algae makes little algae-residue separate with little algae supernatant through little algae separator again, little algae-residue extracts the diesel oil reactor through little algae and extracts diesel oil, enter in the diesel oil output channel, little algae supernatant is after the second deoxygenation post is removed oxygen, enter in the synthesis gas fermentation strain growth jar, synthesis gas fermentation strain in the synthesis gas fermentation strain growth jar is under this favourable growing environment, its metabolite is mainly acids, the bacterium liquid of synthesis gas fermentation strain growth jar is isolated thalline through the separated from acetic acid device, thalline enters in the synthesis gas fermentation strain fermentation tank and carries out fermentative production of ethanol, supernatant obtains nutrient solution after isolating acetate, nutrient solution turns back in the synthesis gas fermentation strain growth jar through synthesis gas fermentation strain nutrient solution Returning pipe, zymotic fluid after the fermentation is realized the separation of ethanol through the ethanol separator, ethanol enters in the ethanol output channel, isolate thalline behind the ethanol and nutrient solution through thalline, the nutrient solution Returning pipe turns back in the synthesis gas fermentation strain fermentation tank, the acetate that separates through the separated from acetic acid device can feed in the acetate output channel, or be back in the micro algae culturing device CO that generates in the synthesis gas fermentation strain fermentation tank through the acetate recurrent canal
2Can pass through CO+CO with a small amount of unemployed CO
2Recurrent canal reenters CO
2Again utilized in the absorption plant.
The gas supply amount that the present invention is particularly useful in the industrial tail gas is unstable and discontinuous, the present invention is by the coupling micro algae culturing device, it is discontinuous to solve in the prior art industrial tail gas, the gas supply amount is unstable and cause the difficult problem of tail gas microbiological treatment, and obtain metastable carbon source environment, concrete grammar is as follows:
At CO
2Under the low situation of concentration, the carbon source of little algae is from air;
Under the lower condition of CO concentration, in synthesis gas fermentation strain growth jar, feed the little algae supernatant that contains carbohydrate, cultivate microorganism acquisition bacterial strain and be used to the CO that ferments;
Under the low excessively condition of CO component, in synthesis gas fermentation strain growth jar and synthesis gas fermentation strain fermentation tank, all feed the little algae supernatant fermentation producing and ethanol that contains carbohydrate.
CO
2Concentration is crossed under the low situation, under the higher situation of CO concentration, all can feed gaseous carbon source CO in synthesis gas fermentation strain growth jar and the synthesis gas fermentation strain fermentation tank.The acetate input micro algae culturing device that separates can be used for little algae heterotrophism produce oil simultaneously.
By regulating and control little algae CO
2Coupling process fixing and bacterial strain CO fermentation can be kept the relatively stable of biological respinse environment, effectively solves the difficult problem of plant tail gas intermittent entry.
The present invention is by the optimum organization of various piece, organically with little algae oil production plant and synthesis gas fermentation strain growth fermentation and coupling, the effectively CO in the energy tail gas
2And CO, obtained the energy and a spot of acetic acid by-product that ethanol and diesel oil two classes clean.This shows that the present invention has handled each component of industrial tail gas fully by biological mode, and has realized energy, therefore have very important use value.
Description of drawings:
Fig. 1 is the schematic diagram of industrial tail gas energy of the present invention system;
Wherein 1, CO
2Absorption plant; 2, CO
2Separator; 3, micro algae culturing device; 4, little algae and micro algae culturing liquid separator; 5, little algae separator; 6, little algae is extracted the diesel oil reactor; 7, the first deoxygenation post; 8, synthesis gas fermentation strain growth jar; 9, separated from acetic acid device; 10, synthesis gas fermentation strain fermentation tank; 11, ethanol separator; 12, the second deoxygenation post; 13, N
2Separator.
The specific embodiment:
Below be to further specify to of the present invention, rather than limitation of the present invention.
Embodiment 1:
The industrial tail gas energy system of present embodiment comprises CO
2Absorption plant 1, CO
2Absorption plant 1 respectively with N
2Separator 13, CO
2Separator 2 is connected with the first deoxygenation post 7, and the first deoxygenation post 7 also links to each other CO with synthesis gas fermentation strain growth jars 8 with synthesis gas fermentation strain fermentation tank 10 respectively
2Separator 2 and micro algae culturing device 3, little algae and micro algae culturing liquid separator 4, little algae separator 5, little algae is extracted diesel oil reactor 6 and is connected successively with the diesel oil output channel, also be connected with the micro algae culturing liquid Returning pipe between micro algae culturing device 3 and little algae and the micro algae culturing liquid separator 4, the little algae separator 5 and the second deoxygenation post 12, synthesis gas fermentation strain growth jar 8, separated from acetic acid device 9, synthesis gas fermentation strain fermentation tank 10, ethanol separator 11 is connected successively with the ethanol output channel, also be connected with synthesis gas fermentation strain nutrient solution Returning pipe between separated from acetic acid device 9 and the synthesis gas fermentation strain growth jar 8, also be connected with thalline between synthesis gas fermentation strain fermentation tank 10 and the ethanol separator 11, the nutrient solution Returning pipe, the acetate output port of separated from acetic acid device 9 respectively with the acetate output channel with link to each other with micro algae culturing device 3 through the acetate recurrent canal, synthesis gas fermentation strain fermentation tank 10 also passes through CO+CO
2Returning pipe and CO
2Absorption plant 1 links to each other.
Described CO
2In the absorption plant 1 Selexol is housed
TMAs lyosoption, described CO
2Separator 2 is by heating CO
2Saturated Selexol
TMMake CO
2With Selexol
TMSeparate Selexol
TMAgain return CO
2In the absorption plant 1.
Described micro algae culturing device 3 has and can accept extraneous CO for fermentation pot type Photoreactor
2Opening.
Described little algae and micro algae culturing liquid separator 4 are to adopt membrane separation process to separate little algae and nutrient solution.
Described little algae separator 5 is a centrifuge, by centrifugal little algae-residue is separated with little algae supernatant.
The described first deoxygenation post 7 and the second deoxygenation post 12 are goes back the native copper post.
Described synthesis gas fermentation strain growth jar 8 is a CSTR.
Described separated from acetic acid device 9 also is to adopt membrane separation process separating acetic acid, nutrient solution and thalline.
Described synthesis gas fermentation strain fermentation tank 10 is a upflow bioreactor.
Described ethanol separator 11 also is to adopt membrane separation process to separate separating alcohol and thalline, nutrient solution.
Described N
2Separator 13 is to adopt molecular sieve to isolate N
2
In order better to understand present embodiment, the running of the industrial tail gas energy system of present embodiment is as follows:
The industrial tail gas of present embodiment is steel mill's tail gas, the CO fermentation strain bacterial strain of synthesis gas fermentation strain growth jars 8 and synthesis gas fermentation strain fermentation tank 10 (promptly) is Clostridium autoethanogenum, and little algae is stable on heating chlorella (Chorella sorokiniana).
Steel mill's tail gas is through N
2The molecular sieve of separator 13 is isolated N
2, residual gas is by the definite CO wherein of measurement mechanism
2With the composition of CO, feed again and contain CO
2Lyosoption Selexol
TMCO
2Absorption plant 1, Selexol
TMAbsorb CO
2, remaining gas is mainly the gas that contains CO, and this gas feeds synthesis gas fermentation strain growth jar 8 and synthesis gas fermentation strain fermentation tank 10 respectively after the first deoxygenation post 7 is removed oxygen, use for growth of synthesis gas fermentation strain and fermentation; Selexol
TMAbsorb saturated back and flow into CO
2Separator 2 by heating, makes CO
2With Selexol
TMSeparate Selexol
TMAgain be back to CO
2Absorption plant 1, isolated CO
2Feed micro algae culturing device 3, little algae fixation of C O
2, in fermentation pot type Photoreactor 3, carrying out, the nutrient solution of little algae can derive from steel mill's waste water or preparation voluntarily.Contain deliquescent nitrogen, phosphorus, sulphur, trace element, vitamins and other nutritious components through Separation of Solid and Liquid corn flour hydrolyzate and steel mill's waste water, can be directly as the culture medium of the little algae of hear resistance, the little algae of hear resistance is inserted the light reaction jar, utilize to come from gas circuit or airborne CO
2Component, control fermentation pot type Photoreactor temperature is 20 ℃, and intensity of illumination is 1000-2000Lux, can use artificial light sources when cloudy day or night, and the little algae of hear resistance utilizes photofixation CO respectively in Photoreactor
2After algae liquid length is dense, feeding little algae and micro algae culturing liquid separator 4 makes little algae separate with nutrient solution, nutrient solution flows into micro algae culturing device 3 through the micro algae culturing liquid Returning pipe, and little algae is again through little algae separator 5, and promptly centrifuge makes little algae-residue separate with the little algae supernatant that contains sugar, little algae-residue extracts diesel oil reactor 6 through little algae and extracts diesel oil, enter in the diesel oil output channel, the little algae supernatant that contains sugar enters in the synthesis gas fermentation strain growth jar 8 after the second deoxygenation post 12 is removed oxygen.Synthesis gas fermentation strain Clostridium autoethanogenum in the synthesis gas fermentation strain growth jar 8 is under this favourable growing environment, its metabolite is mainly acids, the bacterium liquid of synthesis gas fermentation strain growth jar 8 is fed in the separated from acetic acid device 9, the synthesis gas fermentation strain carries out fermentative production of ethanol in the input synthesis gas fermentation strain fermentation tank 10 after film separates, and supernatant obtains nutrient solution after reclaiming acetate, nutrient solution turns back in the synthesis gas fermentation strain growth jar 8 through synthesis gas fermentation strain nutrient solution Returning pipe, continue to carry out alcohol fermentation at synthesis gas fermentation strain fermentation tank 10, the film of zymotic fluid after the fermentation in ethanol separator 11 isolated ethanol, ethanol enters in the ethanol output channel, isolate thalline behind the ethanol and nutrient solution through thalline, the nutrient solution Returning pipe turns back in the synthesis gas fermentation strain fermentation tank 10, the acetate that separates through separated from acetic acid device 9 can feed in the acetate output channel, or be back in the micro algae culturing device 3 through the acetate recurrent canal, the CO2 that generates in the synthesis gas fermentation strain fermentation tank and a small amount of unemployed CO can pass through CO+CO
2Recurrent canal refluxes and enters CO
2In the absorption plant 1.
The reduction potential and the pH value of synthesis gas fermentation strain growth jars 8 and synthesis gas fermentation strain fermentation tank 10, monitoring also are adjusted in the most in real time just when 4.7 ,-200mv; 6.0 ,-200mv.
Unstable and the discontinuous device of industrial tail gas gas supply amount is regulated, according to tail gas CO and CO
2Form and regulate:
At CO
2Concentration is lower: Photoreactor is uncovered, and little algae carbon source is from atmosphere;
Lower in CO concentration: the little algae supernatant that contains carbohydrate feeds in the synthesis gas fermentation strain growth jar 8, and only synthesis gas fermentation strain fermentation tank is handled CO;
Low excessively in the CO component: as in synthesis gas fermentation strain growth jar 8 and synthesis gas fermentation strain fermentation tank 10, all to feed the little algae supernatant fermentative production of ethanol that contains sugar;
CO
2Concentration is crossed low and CO concentration is higher, and synthesis gas fermentation strain growth jars 8 and synthesis gas fermentation strain fermentation tank 10 are all from gaseous carbon source CO.
Optimum organization by each several part of the present invention improves biological comprehensive utilization ratio to tail gas, by gas and little algae carbohydrate control strain growth and fermentation level.
Utilize the industrial tail gas energy system of present embodiment,, can effectively utilize hydrocarbon component harmful in the industrial tail gas, obtained the energy of ethanol and diesel oil two classes cleaning simultaneously, also obtained a spot of acetic acid by-product simultaneously according to the said process operation.
What more than exemplify only is specific embodiment of this patent.Other distortion of this patent all belong to the protection domain of this patent.
Claims (9)
1. an industrial tail gas energy system is characterized in that, comprises CO
2Absorption plant (1), CO
2Absorption plant (1) respectively with N
2Separator (13), CO
2Separator (2) is connected with the first deoxygenation post (7), and the first deoxygenation post (7) also links to each other CO with synthesis gas fermentation strain growth jar (8) with synthesis gas fermentation strain fermentation tank (10) respectively
2Separator (2) and micro algae culturing device (3), little algae and micro algae culturing liquid separator (4), little algae separator (5), little algae is extracted diesel oil reactor (6) and is connected successively with the diesel oil output channel, also be connected with the micro algae culturing liquid Returning pipe between micro algae culturing device (3) and little algae and the micro algae culturing liquid separator (4), the little algae separator (5) and the second deoxygenation post (12), synthesis gas fermentation strain growth jar (8), separated from acetic acid device (9), synthesis gas fermentation strain fermentation tank (10), ethanol separator (11) is connected successively with the ethanol output channel, also be connected with synthesis gas fermentation strain nutrient solution Returning pipe between separated from acetic acid device (9) and the synthesis gas fermentation strain growth jar (8), also be connected with thalline between synthesis gas fermentation strain fermentation tank (10) and the ethanol separator (11), the nutrient solution Returning pipe, the acetate output port of separated from acetic acid device (9) respectively with the acetate output channel with link to each other with micro algae culturing device (3) through the acetate recurrent canal, synthesis gas fermentation strain fermentation tank (10) also passes through CO+CO
2Returning pipe and CO
2Absorption plant (1) links to each other.
2. industrial tail gas energy according to claim 1 system is characterized in that described CO
2Absorption plant (1) is for containing MEA, diethanol amine, triethanolamine or Selexol
TMCO as lyosoption
2Absorption plant.
3. industrial tail gas energy according to claim 1 system is characterized in that described micro algae culturing device (3) is a closed photo bioreactor, and this closed photo bioreactor has can receive extraneous CO
2Opening.
4. industrial tail gas energy according to claim 3 system is characterized in that, described closed photo bioreactor is fermentation pot type Photoreactor, tubular type Photoreactor or board-like Photoreactor.
5. industrial tail gas energy according to claim 1 system is characterized in that described little algae separator (5) is a centrifuge.
6. industrial tail gas energy according to claim 1 system, it is characterized in that described little algae and micro algae culturing liquid separator (4), separated from acetic acid device (9) and ethanol separator (11) are for can realize filter or the centrifugal separation equipment that little algae separates with micro algae culturing liquid, separated from acetic acid is separated with ethanol.
7. industrial tail gas energy according to claim 1 system is characterized in that the described first deoxygenation post (7) and the second deoxygenation post (12) are goes back the native copper post.
8. industrial tail gas energy according to claim 1 system is characterized in that, described synthesis gas fermentation strain growth jar (8) is upflow bioreactor, CSTR, trickle bed anaerobic reactor or bubble type anaerobic reactor.
9. industrial tail gas energy according to claim 1 system, it is characterized in that described synthesis gas fermentation strain fermentation tank (10) is upflow bioreactor, CSTR, trickle bed anaerobic reactor, bubble type anaerobic reactor or membrane reactor.
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| US10603632B2 (en) * | 2017-06-12 | 2020-03-31 | David C. ALDOUS | Methods and apparatus for recycling tail gas in syngas fermentation to ethanol |
| CN111644187B (en) * | 2020-05-06 | 2021-10-15 | 北京化工大学 | Catalytic system for producing medium-chain fatty acid or/and alcohol, preparation method and application |
| CN111807366B (en) * | 2020-07-24 | 2023-06-20 | 中国科学院上海应用物理研究所 | Device and method for preparing synthesis gas by assistance of high-temperature electrochemical device |
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|---|---|---|---|---|
| CN101368193A (en) * | 2008-10-14 | 2009-02-18 | 蔡志武 | Process for preparing fine algae cultivation coupling biological diesel oil refining |
| US20100064573A1 (en) * | 2008-09-15 | 2010-03-18 | Mario Araya Brenes | Method for producing a liquid biofuel or at least one of its primary components |
| CN101768540A (en) * | 2010-02-12 | 2010-07-07 | 中国科学院广州能源研究所 | Reaction device for producing organic acid and alcohol through synthesis gas fermentation |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20100064573A1 (en) * | 2008-09-15 | 2010-03-18 | Mario Araya Brenes | Method for producing a liquid biofuel or at least one of its primary components |
| CN101368193A (en) * | 2008-10-14 | 2009-02-18 | 蔡志武 | Process for preparing fine algae cultivation coupling biological diesel oil refining |
| CN101768540A (en) * | 2010-02-12 | 2010-07-07 | 中国科学院广州能源研究所 | Reaction device for producing organic acid and alcohol through synthesis gas fermentation |
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| JP特开平7-246086A 1995.09.26 |
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