CN105623761A - Method for biologically synthesizing natural gas from coke oven gas - Google Patents
Method for biologically synthesizing natural gas from coke oven gas Download PDFInfo
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- CN105623761A CN105623761A CN201510870806.0A CN201510870806A CN105623761A CN 105623761 A CN105623761 A CN 105623761A CN 201510870806 A CN201510870806 A CN 201510870806A CN 105623761 A CN105623761 A CN 105623761A
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 272
- 239000007789 gas Substances 0.000 title claims abstract description 96
- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000003345 natural gas Substances 0.000 title claims abstract description 29
- 239000000571 coke Substances 0.000 title abstract description 11
- 230000002194 synthesizing effect Effects 0.000 title abstract description 4
- 238000000855 fermentation Methods 0.000 claims abstract description 28
- 239000010802 sludge Substances 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 241000894006 Bacteria Species 0.000 claims abstract description 17
- 239000010815 organic waste Substances 0.000 claims abstract description 16
- 239000002054 inoculum Substances 0.000 claims abstract description 13
- 238000000926 separation method Methods 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 11
- 239000001963 growth medium Substances 0.000 claims abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 38
- 229910052757 nitrogen Inorganic materials 0.000 claims description 20
- 241001478240 Coccus Species 0.000 claims description 18
- 230000015572 biosynthetic process Effects 0.000 claims description 18
- 239000000126 substance Substances 0.000 claims description 17
- 229920001817 Agar Polymers 0.000 claims description 15
- 239000008272 agar Substances 0.000 claims description 15
- 235000015097 nutrients Nutrition 0.000 claims description 15
- 239000002002 slurry Substances 0.000 claims description 15
- 239000010865 sewage Substances 0.000 claims description 14
- 230000004060 metabolic process Effects 0.000 claims description 13
- 230000002269 spontaneous effect Effects 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 9
- 239000005416 organic matter Substances 0.000 claims description 9
- 241000193403 Clostridium Species 0.000 claims description 8
- 241000205265 Methanospirillum Species 0.000 claims description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 8
- 238000006392 deoxygenation reaction Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 6
- 241000193401 Clostridium acetobutylicum Species 0.000 claims description 6
- 241000193454 Clostridium beijerinckii Species 0.000 claims description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 5
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 5
- 229910018890 NaMoO4 Inorganic materials 0.000 claims description 5
- 230000004103 aerobic respiration Effects 0.000 claims description 5
- 239000001110 calcium chloride Substances 0.000 claims description 5
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 5
- 239000008103 glucose Substances 0.000 claims description 5
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 5
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 5
- 239000012528 membrane Substances 0.000 claims description 5
- 230000000696 methanogenic effect Effects 0.000 claims description 5
- 102000004169 proteins and genes Human genes 0.000 claims description 5
- 108090000623 proteins and genes Proteins 0.000 claims description 5
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- 235000019253 formic acid Nutrition 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 241000193171 Clostridium butyricum Species 0.000 claims description 3
- 241000193469 Clostridium pasteurianum Species 0.000 claims description 3
- 230000005587 bubbling Effects 0.000 claims description 3
- 241000192023 Sarcina Species 0.000 claims description 2
- 239000002154 agricultural waste Substances 0.000 claims description 2
- 239000013049 sediment Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 230000004151 fermentation Effects 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 9
- 238000004939 coking Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 241000202972 Methanobacterium bryantii Species 0.000 description 4
- 241001529871 Methanococcus maripaludis Species 0.000 description 4
- 241000205275 Methanosarcina barkeri Species 0.000 description 4
- 241000205263 Methanospirillum hungatei Species 0.000 description 4
- 241000203382 Methanothermococcus thermolithotrophicus Species 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 241000193446 Thermoanaerobacterium thermosaccharolyticum Species 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000008246 gaseous mixture Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 241001302042 Methanothermobacter thermautotrophicus Species 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 241000306283 Clostridium acidisoli Species 0.000 description 1
- 241000306276 Clostridium akagii Species 0.000 description 1
- 241000193161 Clostridium formicaceticum Species 0.000 description 1
- 241000229117 [Clostridium] hungatei Species 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- -1 house refuse Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000009469 supplementation Effects 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
Landscapes
- Treatment Of Sludge (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention relates to a method for biologically synthesizing natural gas from coke oven gas. The method comprises the following steps: (1) introducing organic wastes, the coke oven gas and aerobic activated sludge into a sealed deoxidization bio-reactor to perform a microaerobic biological deoxidization reaction; (2) introducing a nitrogen-free culture medium, the deoxidized coke oven gas and free-living anaerobic nitrogen-fixing bacteria into a sealed denitriding bio-reactor to perform an anaerobic biological denitriding reaction; (3)introducing the organic wastes subjected to the microaerobic biological deoxidization reaction from the sealed deoxidization bio-reactor, and a biogas producing inoculum into a sealed biogas producing reactor to perform biogas production by anaerobic fermentation; (4) performing solid-liquid separation on fermentation residues after biogas production by anaerobic fermentation, wherein a filtered biogas liquid contains rich nutriments and serves as a culture medium for subsequent methane production by anaerobic fermentation; and (5) introducing the deoxidized/denitrified coke oven gas, the biogas, the filtered biogas liquid and methane producing bacteria into a sealed methane producing reactor to perform methane production by anaerobic fermentation.
Description
Technical field
The invention belongs to synthetic natural gas technical field, be specifically related to a kind of coke-stove gas biosynthesis natural gas method.
Background technology
China is maximum in the world coke production, consumption and exported country, simultaneously the coke-stove gas (tail gas) of association billion cubic meter more than 700. These coke-stove gas wherein half is used for melting down combustion-supporting, and second half needs special device and reclaims. Only focusing on coke production due to China's coking industry and ignore side-product and reclaim, a large amount of directly burning of coking production principal by product coke-stove gas (tail gas) is diffused and is commonly called as " some sky lamp ". The economic loss thereby resulted in reaches tens billion of unit, causes the significant wastage of scarce resource; Environment is also resulted in great pollution simultaneously. According to measuring and calculating, calculate according to China's year coke total output, the coke-stove gas burnt in vain every year billion cubic meter more than 300, be equivalent to country's " more than 2 times of West-east Gas design year displacement.
Coke-stove gas is the by-product in coal dry distilling process of coking, and its main component forms in Table 1:
Table 1 coke-stove gas main component forms
| Composition | H2 | CH4 | CO | CO2 | N2 | O2 |
| Composition (vol.%) | 50��60 | 20��30 | 5��9 | 2��5 | 3��6 | 0.3��0.8 |
Along with the adjustment of the increase of China's energy demand total amount and energy consumption structure, the demand of natural gas is increasing. Within 2013, annual China's natural gas yield is 1210 billion cubic meters, and Natural Gas Consumption Using is 1676 billion cubic meters, and insufficiency of supply-demand reaches 466 billion cubic meters. Along with Natural Gas Demand continues to increase, the technology of various synthesis of artificial natural gass is emerged in large numbers one after another, as natural in coal system, bio-natural gas etc., but from the viewpoint of economy, the suitability etc., synthesizing natural gas from coke oven gas has the higher market competitiveness.
As it can be seen from table 1 coke-stove gas produces natural gas two schemes: a kind of is purify out by the methane separation in coke-stove gas, and two is by the N in coke-stove gas2��O2Elimination is also H2��CO��CO2It is changed into methane. At present, coke-stove gas is produced natural gas major part and is adopted the first scheme, for instance adopt membrance separation and cryogenic rectification (granted patent ZL200810239548.6), liquefying and rectifying (granted patent ZL200810135211.0, publication CN102654348A), pressure-variable adsorption (ZL201110024062.2). This scheme can only reclaim the methane gas in coke-stove gas, it is impossible to by H2��CO��CO2Being changed into methane, the productivity of coke-stove gas preparing natural gas is relatively low.
Granted patent (ZL200910018047.X) and publication (CN103131490A) disclose the technique of a kind of gas employing methanation of coke oven synthetic natural gas, are reacted by two sections of chemical catalysis, by CO, CO2Generation CH is reacted with the steam passed into4, again through pressure-variable adsorption or membrance separation etc. by CH4And H2Separate, thus obtaining natural gas. The method can by CO, CO2It is changed into CH4, but cannot by H2It is changed into methane, and the N in coke-stove gas cannot be removed2And O2��
Publication (CN102311822A) discloses a kind of synthesizing natural gas from coke oven gas method, and the catalytic reaction of the methanator refluxed by band and temperature transmitter and compressor interlocking, by CO, CO2And H2It is changed into CH4. Equally, the method cannot remove the N in coke-stove gas2And O2. And from coke-stove gas composition and chemical equation, due to the many H of scarce C, it is impossible to by H2It is completely reformed into CH4, at least possibly together with the H of more than 10% in gas product2��
Publication (CN103087793A) discloses and a kind of utilizes anaerobe to realize oven gas to prepare the technique of natural gas, by supplemented with exogenous CO2Utilize anaerobic methane production microorganism by CO, CO2And H2It is changed into CH4. But the method passes through pressure-variable adsorption or cryogenic separation by N2And O2It is easily separated, and requires supplementation with CO2, cause operation energy consumption and production cost higher.
Publication (CN103113010A) discloses a kind of synchronization and realizes coke-oven gas methanation and the method for biogas in-situ purification, utilizes the CO that biogas fermentation produces2Make up the few deficiency of the many C of H, it is achieved the H in coke-stove gas2Full methanation. But, the method does not disclose N2And O2Removal methods, limit the high level of synthetic natural gas, safe utilization.
Summary of the invention
It is an object of the invention to overcome deficiency of the prior art, it is provided that a kind of method of coke-stove gas biosynthesis natural gas, it is achieved the high level safe utilization of coke-stove gas.
The method of coke-stove gas biosynthesis natural gas in the present invention, comprises the following steps:
(1) micro-aerobe reaction deoxidation: organic waste, coke-stove gas, aerobic activated sludge are passed into closed deoxidation bioreactor, control temperature 20��35 DEG C, pH value 6.5��8.5 in closed bioreactor, aerobic activated sludge utilizes the organic matter in organic waste and the oxygen in coke-stove gas to carry out aerobic respiration metabolism, consume the oxygen in coke-stove gas, and be follow-up H2Methanation provide CO2, a kind of pretreatment actually or to organic waste producing methane through anaerobic fermentation of this deoxygenation step;
Organic matter+O2��CO2+H2O
(2) Anaerobe reaction denitrogenation: the coke-stove gas after nitrogen-free agar, deoxidation, spontaneous anaerobic nitrogen-fixation bacterium are passed into closed denitrification organisms reactor, control temperature 25��68 DEG C, pH value 6.5��8.5 in closed bioreactor, spontaneous anaerobic nitrogen-fixation bacterium utilizes the non-nitrogen nutrient substance in nitrogen-free agar and the nitrogen in coke-stove gas to carry out spontaneous anaerobic nitrogen-fixation metabolism, consuming the nitrogen in coke-stove gas, the spontaneous anaerobic nitrogen-fixation bacterium of part is simultaneously by H2And CO2Synthesis CH4;
Non-nitrogen nutrient substance+N2�� cell protein+NH4 +
4H2+CO2��CH4+2H2O
(3) producing methane through anaerobic fermentation: by coming from closed deoxidation bioreactor and complete the organic waste of micro-aerobe deoxygenation, produce biogas inoculum and pass into closed and produce marsh gas reactor, control temperature 25��55 DEG C in closed product marsh gas reactor, pH value 6.8��8.0 produces biogas inoculum and utilizes organic waste to produce biogas, containing a large amount of CO in biogas2, for follow-up H2Methanation provide CO2;
Organic matter �� CH4+CO2
(4) residues solid-liquid separation, filtration: the residues completing producing methane through anaerobic fermentation is carried out solid-liquid separation, and the biogas slurry after separating is filtered, biogas slurry after filtration contains abundant nutrient substance, as the methanogenic culture medium of follow-up anaerobic fermentation;
(5) anaerobic fermentation methane phase: the coke-stove gas after deoxidation/denitrogenation, biogas, filtration biogas slurry, methanogen are passed into closed methane-producing reactor, controlling temperature 25��60 DEG C, pH value 6.8��8.0 in closed methane-producing reactor, methanogen utilizes H2��CO2CH is synthesized with CO4;
4H2+CO2��CH4+2H2O
3H2+CO��CH4+H2
Described organic waste is including, but not limited to sanitary sewage, industrial organic waste water, house refuse, agricultural wastes;
Described aerobic activated sludge derives from sewage treatment plant;
Described nitrogen-free agar formula is containing glucose 5��20g, KH in every liter of water2PO40.2��3g, MgSO4 7H2O0.2��0.5g, NaCl0.2��1g, FeSO40.05��0.1g, CaCl2��2H2O0.2��0.5g, NaMoO40.01��0.03g, CaCO33��5g, L-AA 0.2��0.4g;
Described spontaneous anaerobic nitrogen-fixation bacterium includes clostridium and hydrogen auxotype methane backeria two class, and clostridium is clostridium acetobutylicum (Clostridiumacetobutylicum), Clostridium beijerinckii (Clostridiumbeijerinckii), Clostridium butyricum (Clostridiumbutyricum), kirschner clostridium (Clostridiumkluyverii), clostridium pasteurianum (Clostridiumpasteurianum), Heng Shi clostridium (Clostridiumhungatei), Clostridiumformicoaceticum, Clostridiumakagii, Clostridiumacidisoli, Thermoanaerobacteriumthermosaccharolyticum, hydrogen auxotype methane backeria is Pasteur's methane eight folded (Methanosarcinabarkeri coccus), Bai Shi methagen (Methanobacteriumbryantii), Heng Shi methanospirillum (Methanospirillumhungatei), natural pond methane thermal coccus, sea (Methanococcusmaripaludis), hot autotrophy methane thermal coccus (Methanococcusthermolithotrophicus), their a kind of bacterium or the combination of multiple bacterium is added during application,
Described product biogas inoculum derives from methane-generating pit, sewage treatment plant's anaerobic sludge pond, sediment of pond etc.;
Described methanogen includes hydrogen auxotype methane backeria and carbon monoxide auxotype methane backeria, hydrogen auxotype methane backeria is including, but not limited to Pasteur's methane eight folded (Methanosarcinabarkeri coccus), Bai Shi methagen (Methanobacteriumbryantii), Heng Shi methanospirillum (Methanospirillumhungatei), natural pond methane thermal coccus, sea (Methanococcusmaripaludis), hot autotrophy methane thermal coccus (Methanococcusthermolithotrophicus), carbon monoxide auxotype methane backeria is including, but not limited to formic acid methagen (Methanobacteriumformieieum), addicted to tree methagen (Methanobacteriumarboriphilicus), Pasteur's sarcina methanica (Methanosarcinabarkeri), Methanobacteriumruminantum, Methanothermobacterthermoautotrophicus, the one in a kind of and carbon monoxide auxotype methane backeria in hydrogen auxotype methane backeria is at least while added during application,
Described closed deoxidation bioreactor, closed denitrification organisms reactor, closed methane-producing reactor type include stirring reactor, bubbling column reactor, microvesicle reactor, membrane reactor, according to O in fuel gas2��N2��H2, CO content height can be arranged in series multistage dense enclosed deoxidation bioreactor, closed denitrification organisms reactor, closed methane-producing reactor guarantee process after each component content of gas reach requirement;
Described closed deoxidation bioreactor, closed denitrification organisms reactor and closed methane-producing reactor arrange gas self circular loop, gas-liquid contact time in extension reactor, improve gas conversions;
Described closed produces marsh gas reactor type including, but not limited to stirring reactor (CSTR), up-flow anaerobic sludge blanket (UASB), anaerobic filter (AF).
Compared with existing coke-stove gas methane separation method of purification preparing natural gas, the innovation of the present invention is in that, it is possible to by the H in coke-stove gas2��CO��CO2Being changed into CH4, gas yield is higher; Compared with the biological method that existing synchronization realizes coke-oven gas methanation and biogas in-situ purification, the innovation of the inventive method is in that, it is possible to by the N in coke-stove gas2And O2Elimination, it is achieved the high level of synthetic natural gas, safe utilization.
Accompanying drawing explanation
Fig. 1 is the process flow diagram of the inventive method
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Embodiment 1:
Collecting the coke-stove gas of certain small-sized coking plant and neighbouring sanitary sewage, coke-stove gas yield is 1000m3/ d, gas composition H250%, CH430%, CO9%, CO25%, N23%, O20.3%, by sanitary sewage, coke-stove gas, sewage treatment plant aerobic activated sludge pass into closed deoxidation membrane bioreactor, control reactor temperature 20 DEG C, pH value 6.5 carries out aerobic respiration metabolism, and the aerobic chemoheterotrophic bacteria in aerobic activated sludge passes through reaction equation (organic matter+O2��CO2+ H2O) O is consumed2, it is simultaneously generated CO2; Preparation nitrogen-free agar, formula is containing glucose 5g, KH in every liter of water2PO40.2g, MgSO4 7H2O0.2g, NaCl0.2g, FeSO40.05g, CaCl2��2H2O0.2g, NaMoO40.01g, CaCO33g, L-AA 0.2g, coke-stove gas after nitrogen-free agar, deoxidation, clostridium acetobutylicum (Clostridiumacetobutylicum) are passed into closed denitrogenation microvesicle bioreactor, control reactor temperature 25 DEG C, pH value 6.5 carries out anaerobic nitrogen-fixation metabolism, clostridium acetobutylicum utilizes the non-nitrogen nutrient substance in nitrogen-free agar and the nitrogen in coke-stove gas to carry out spontaneous anaerobic nitrogen-fixation metabolism, according to reaction equation (non-nitrogen nutrient substance+N2�� cell protein+NH4 +) consume the nitrogen in coke-stove gas; Having taken out the sanitary sewage of deoxygenation from closed deoxidation reactor, fetched the product biogas inoculum from methane-generating pit, sanitary sewage and biogas inoculum are passed into volume is 30m3Closed anaerobic filter (AF) produce marsh gas reactor, control reactor temperature 25 DEG C, pH value 6.8 carries out producing methane through anaerobic fermentation, it is 0.4m that pond holds factor of created gase3/(m3D), biogas output is 12m3/ d, composition is CH460% and CO240%, a large amount of CO contained in biogas2For follow-up H2Methanation provide carbon source; The residues completing producing methane through anaerobic fermentation carrying out solid-liquid separation, and the biogas slurry after separating is filtered, the biogas slurry after filtration contains abundant nutrient substance, as the methanogenic culture medium of follow-up anaerobic fermentation; Coke-stove gas after deoxidation/denitrogenation, biogas, filtration biogas slurry, Bai Shi methagen (Methanobacteriumbryantii), formic acid methagen (Methanobacteriumformieieum) are passed into closed methane phase microvesicle reactor, control reactor temperature 25 DEG C, pH value 6.8 carries out anaerobic fermentation methane phase, the H in coke-stove gas and biogas gaseous mixture2��CO2With CO according to reaction equation (4H2+CO2��CH4+2H2O��3H2+CO��CH4+H2) synthesis CH4; Finally obtain yield and methane concentration respectively 480m3The synthetic natural gas of/d and 95%.
Embodiment 2
Collecting the coke-stove gas of certain medium-sized coking plant and neighbouring alcohol waste water, coke-stove gas yield is 10000m3/ d, gas composition H255%, CH420%, CO9%, CO25%, N25%, O20.8%, by alcohol waste water, coke-stove gas, sewage treatment plant aerobic activated sludge pass into closed deoxidation bubbling bioreactor, control reactor temperature 28 DEG C, pH value 7.5 carries out aerobic respiration metabolism, and the aerobic chemoheterotrophic bacteria in aerobic activated sludge passes through reaction equation (organic matter+O2��CO2+H2O) O is consumed2, it is simultaneously generated CO2; Preparation nitrogen-free agar, formula is containing glucose 13g, KH in every liter of water2PO41.5g, MgSO4 7H2O0.35g, NaCl0.6g, FeSO40.07g, CaCl2��2H2O0.35g, NaMoO40.02g, CaCO34g, L-AA 0.3g, coke-stove gas after nitrogen-free agar, deoxidation, Clostridium beijerinckii (Clostridiumbeijerinckii), Heng Shi methanospirillum (Methanospirillumhungatei) are passed into closed denitrogenation microvesicle bioreactor, control reactor temperature 45 DEG C, pH value 7.5 carries out anaerobic nitrogen-fixation metabolism, Clostridium beijerinckii and Heng Shi methanospirillum utilize the non-nitrogen nutrient substance in nitrogen-free agar and the nitrogen in coke-stove gas to carry out spontaneous anaerobic nitrogen-fixation metabolism, according to reaction equation (non-nitrogen nutrient substance+N2�� cell protein+NH4 +) consuming the nitrogen in coke-stove gas, Heng Shi methanospirillum simultaneously can according to reaction equation (4H2+CO2��CH4+2H2O) by part H2And CO2Synthesis CH4; Having taken out the alcohol waste water of deoxygenation from closed deoxidation reactor, fetched from the anaerobic sludge of sewage treatment plant as producing biogas inoculum, alcohol waste water and biogas inoculum are passed into volume is 160m3Closed up-flow anaerobic sludge blanket (UASB) produce marsh gas reactor, control reactor temperature 45 DEG C, pH value 7.4 carries out producing methane through anaerobic fermentation, it is 2.5m that pond holds factor of created gase3/(m3D), biogas output is 396m3/ d, composition is CH470% and CO230%, a large amount of CO contained in biogas2For follow-up H2Methanation provide carbon source, the residues completing producing methane through anaerobic fermentation carrying out solid-liquid separation, and the biogas slurry after separating is filtered, the biogas slurry after filtration contains abundant nutrient substance, as the methanogenic culture medium of follow-up anaerobic fermentation, by the coke-stove gas after deoxidation/denitrogenation, biogas, filter biogas slurry, Pasteur's methane eight folded (Methanosarcinabarkeri coccus), Bai Shi methagen (Methanobacteriumbryantii), Heng Shi methanospirillum (Methanospirillumhungatei), formic acid methagen (Methanobacteriumformieieum), two-stage closed methane phase membrane reactor is passed into addicted to tree methagen (Methanobacteriumarboriphilicus), control reactor temperature 38 DEG C, pH value 7.5 carries out anaerobic fermentation methane phase, coke-stove gas and the H in biogas gaseous mixture2��CO2With CO according to reaction equation (4H2+CO2��CH4+2H2O��3H2+CO��CH4+H2) synthesis CH4; Finally obtain yield and methane concentration respectively 4704m3The synthetic natural gas of/d and 93%.
Embodiment 3
Collecting the coke-stove gas of certain large-scale coking plant and neighbouring domestic organic garbage, coke-stove gas yield is 50000m3/ d, gas composition H260%, CH425%, CO7%, CO24%, N26%, O20.5%, by domestic organic garbage, coke-stove gas, sewage treatment plant aerobic activated sludge pass into closed deoxidation stirring type bioreactor, control reactor temperature 35 DEG C, pH value 8.5 carries out aerobic respiration metabolism, and the aerobic chemoheterotrophic bacteria in aerobic activated sludge passes through reaction equation (organic matter+O2��CO2+H2O) O is consumed2, it is simultaneously generated CO2; Preparation nitrogen-free agar, formula is containing glucose 20g, KH in every liter of water2PO43g, MgSO4 7H2O0.5g, NaCl1g, FeSO40.1g, CaCl2��2H2O0.5g, NaMoO40.03g, CaCO35g, L-AA 0.4g, by nitrogen-free agar, coke-stove gas after deoxidation, Thermoanaerobacteriumthermosaccharolyticum, natural pond methane thermal coccus, sea (Methanococcusmaripaludis), hot autotrophy methane thermal coccus (Methanococcusthermolithotrophicus) passes into two-stage closed denitrogenation membrane bioreactor, control reactor temperature 68 DEG C, pH value 8.5 carries out anaerobic nitrogen-fixation metabolism, Thermoanaerobacteriumthermosaccharolyticum, natural pond, sea methane thermal coccus, hot autotrophy methane thermal coccus utilizes the non-nitrogen nutrient substance in nitrogen-free agar and the nitrogen in coke-stove gas to carry out spontaneous anaerobic nitrogen-fixation metabolism, according to reaction equation (non-nitrogen nutrient substance+N2�� cell protein+NH4 +) consume the nitrogen in coke-stove gas, can according to reaction equation (4H the while of natural pond, sea methane thermal coccus, hot autotrophy methane thermal coccus2+CO2��CH4+2H2O) by part H2And CO2Synthesis CH4; Having taken out the domestic organic garbage of deoxygenation from closed deoxidation reactor, fetched from the anaerobic sludge of methane-generating pit as producing biogas inoculum, domestic organic garbage and biogas inoculum are passed into volume is 3900m3Closed stirring produce marsh gas reactor (CSTR), control reactor temperature 55 DEG C, pH value 8.0 and carry out producing methane through anaerobic fermentation, it is 1.5m that pond holds factor of created gase3/(m3D), biogas output is 5830m3/ d, composition is CH455% and CO245%, a large amount of CO contained in biogas2For follow-up H2Methanation provide carbon source; The residues completing producing methane through anaerobic fermentation carrying out solid-liquid separation, and the biogas slurry after separating is filtered, the biogas slurry after filtration contains abundant nutrient substance, as the methanogenic culture medium of follow-up anaerobic fermentation; Coke-stove gas after deoxidation/denitrogenation, biogas, filtration biogas slurry, natural pond methane thermal coccus, sea (Methanococcusmaripaludis), hot autotrophy methane thermal coccus (Methanococcusthermolithotrophicus), Methanothermobacterthermoautotrophicus are passed into closed methane phase microvesicle reactor, control reactor temperature 60 DEG C, pH value 8.0 carries out anaerobic fermentation methane phase, the H in coke-stove gas and biogas gaseous mixture2��CO2With CO according to reaction equation (4H2+CO2��CH4+2H2O��3H2+CO��CH4+H2) synthesis CH4; Finally obtain yield and methane concentration respectively 25617m3The synthetic natural gas of/d and 94%.
Finally, in addition it is also necessary to it is noted that listed above is only specific embodiments of the invention. It is clear that the invention is not restricted to above example, it is also possible to there are many deformation. All deformation that those of ordinary skill in the art can directly derive from present disclosure or associate, are all considered as protection scope of the present invention.
Claims (10)
1. the method for a coke-stove gas biosynthesis natural gas, it is characterised in that the method comprises the following steps:
(1) micro-aerobe reaction deoxidation: organic waste, coke-stove gas, aerobic activated sludge are passed into closed deoxidation bioreactor, control temperature 20��35 DEG C, pH value 6.5��8.5 in closed bioreactor, aerobic activated sludge utilizes the organic matter in organic waste and the oxygen in coke-stove gas to carry out aerobic respiration metabolism, consume the oxygen in coke-stove gas, and be follow-up H2Methanation provide CO2, a kind of pretreatment actually or to organic waste producing methane through anaerobic fermentation of this deoxygenation step;
Organic matter+O2��CO2+H2O;
(2) Anaerobe reaction denitrogenation: the coke-stove gas after nitrogen-free agar, deoxidation, spontaneous anaerobic nitrogen-fixation bacterium are passed into closed denitrification organisms reactor, control temperature 25��68 DEG C, pH value 6.5��8.5 in closed bioreactor, spontaneous anaerobic nitrogen-fixation bacterium utilizes the non-nitrogen nutrient substance in nitrogen-free agar and the nitrogen in coke-stove gas to carry out spontaneous anaerobic nitrogen-fixation metabolism, consuming the nitrogen in coke-stove gas, the spontaneous anaerobic nitrogen-fixation bacterium of part is simultaneously by H2And CO2Synthesis CH4;
Non-nitrogen nutrient substance+N2�� cell protein+NH4 +
4H2+CO2��CH4+2H2O;
(3) producing methane through anaerobic fermentation: by coming from closed deoxidation bioreactor and complete the organic waste of micro-aerobe deoxygenation, produce biogas inoculum and pass into closed and produce marsh gas reactor, control temperature 25��55 DEG C in closed product marsh gas reactor, pH value 6.8��8.0 produces biogas inoculum and utilizes organic waste to produce biogas, containing a large amount of CO in biogas2, for follow-up H2Methanation provide CO2;
Organic matter �� CH4+CO2;
(4) residues solid-liquid separation, filtration: the residues completing producing methane through anaerobic fermentation is carried out solid-liquid separation, and the biogas slurry after separating is filtered, biogas slurry after filtration contains abundant nutrient substance, as the methanogenic culture medium of follow-up anaerobic fermentation;
(5) anaerobic fermentation methane phase: the coke-stove gas after deoxidation/denitrogenation, biogas, filtration biogas slurry, methanogen are passed into closed methane-producing reactor, controlling temperature 25��60 DEG C, pH value 6.8��8.0 in closed methane-producing reactor, methanogen utilizes H2��CO2CH is synthesized with CO4;
4H2+CO2��CH4+2H2O
3H2+CO��CH4+H2��
2. the method for a kind of coke-stove gas biosynthesis natural gas according to claim 1, it is characterized in that, spontaneous anaerobic nitrogen-fixation bacterium in step (2) includes clostridium and hydrogen auxotype methane backeria two class, clostridium is clostridium acetobutylicum, Clostridium beijerinckii, Clostridium butyricum, kirschner clostridium, clostridium pasteurianum or Heng Shi clostridium, hydrogen auxotype methane backeria is that Pasteur's methane eight is folded, Bai Shi methagen, Heng Shi methanospirillum, sea natural pond methane thermal coccus or hot autotrophy methane thermal coccus; Their a kind of bacterium or the combination of multiple bacterium is added during application.
3. the method for a kind of coke-stove gas biosynthesis natural gas according to claim 1, it is characterized in that, methanogen in step (5) includes hydrogen auxotype methane backeria and carbon monoxide auxotype methane backeria, hydrogen auxotype methane backeria is folded including, but not limited to Pasteur's methane eight, Bai Shi methagen, Heng Shi methanospirillum, sea natural pond methane thermal coccus or hot autotrophy methane thermal coccus, carbon monoxide auxotype methane backeria is including, but not limited to formic acid methagen, addicted to tree methagen, Pasteur's sarcina methanica; The one in a kind of and carbon monoxide auxotype methane backeria in hydrogen auxotype methane backeria is at least while added during application.
4. the method for a kind of coke-stove gas biosynthesis natural gas according to claim 1, it is characterised in that the nitrogen-free agar formula in step (2) is containing glucose 5��20g, KH in every liter of water2PO40.2��3g, MgSO4 7H2O0.2��0.5g, NaCl0.2��1g, FeSO40.05��0.1g, CaCl2��2H2O0.2��0.5g, NaMoO40.01��0.03g, CaCO33��5g, L-AA 0.2��0.4g.
5. the method for a kind of coke-stove gas biosynthesis natural gas according to claim 1, it is characterized in that, the closed methane-producing reactor type in the closed deoxidation bioreactor in step (1), the closed denitrification organisms reactor in step (2), step (5) includes stirring reactor, bubbling column reactor, microvesicle reactor, membrane reactor.
6. the method for a kind of coke-stove gas biosynthesis natural gas according to claim 1, it is characterized in that, the closed methane-producing reactor in the closed deoxidation bioreactor in step (1), the closed denitrification organisms reactor in step (2), step (5) can arrange one-level or be arranged in series multistage.
7. the method for a kind of coke-stove gas biosynthesis natural gas according to claim 1, it is characterized in that, the closed methane-producing reactor in the closed deoxidation bioreactor in step (1), the closed denitrification organisms reactor in step (2), step (5) arranges gas self circular loop.
8. the method for a kind of coke-stove gas biosynthesis natural gas according to claim 1, it is characterized in that, the closed in step (3) produces marsh gas reactor type including, but not limited to stirring reactor, up-flow anaerobic sludge blanket or anaerobic filter.
9. the method for a kind of coke-stove gas biosynthesis natural gas according to claim 1, it is characterized in that, organic waste in step (1) is including, but not limited to sanitary sewage, industrial organic waste water, house refuse or agricultural wastes, and the aerobic activated sludge in step (1) derives from sewage treatment plant.
10. the method for a kind of coke-stove gas biosynthesis natural gas according to claim 1, it is characterised in that the product biogas inoculum in step (3) derives from methane-generating pit, sewage treatment plant's anaerobic sludge pond or sediment of pond.
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