CN105623761B - A kind of method of coke-stove gas biosynthesis natural gas - Google Patents
A kind of method of coke-stove gas biosynthesis natural gas Download PDFInfo
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- CN105623761B CN105623761B CN201510870806.0A CN201510870806A CN105623761B CN 105623761 B CN105623761 B CN 105623761B CN 201510870806 A CN201510870806 A CN 201510870806A CN 105623761 B CN105623761 B CN 105623761B
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 279
- 239000007789 gas Substances 0.000 title claims abstract description 97
- 239000003345 natural gas Substances 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 31
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 20
- 238000000855 fermentation Methods 0.000 claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 claims abstract description 20
- 239000010802 sludge Substances 0.000 claims abstract description 20
- 241000894006 Bacteria Species 0.000 claims abstract description 17
- 239000002002 slurry Substances 0.000 claims abstract description 17
- 229920001817 Agar Polymers 0.000 claims abstract description 16
- 239000008272 agar Substances 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 239000010815 organic waste Substances 0.000 claims abstract description 15
- 238000000926 separation method Methods 0.000 claims abstract description 15
- 230000002269 spontaneous effect Effects 0.000 claims abstract description 14
- 239000002054 inoculum Substances 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 238000006392 deoxygenation reaction Methods 0.000 claims abstract description 6
- 239000001963 growth medium Substances 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 37
- 229910052757 nitrogen Inorganic materials 0.000 claims description 20
- 241001478240 Coccus Species 0.000 claims description 17
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 14
- 239000010865 sewage Substances 0.000 claims description 14
- 230000004060 metabolic process Effects 0.000 claims description 13
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 9
- 239000005416 organic matter Substances 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 241000205265 Methanospirillum Species 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 7
- 239000012528 membrane Substances 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
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 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
- 241000193454 Clostridium beijerinckii Species 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
- 229910000019 calcium carbonate Inorganic materials 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
- 229910000359 iron(II) sulfate Inorganic materials 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
- 239000011780 sodium chloride Substances 0.000 claims description 5
- 230000004103 aerobic respiration Effects 0.000 claims description 4
- 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 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 241000192023 Sarcina Species 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 230000005587 bubbling Effects 0.000 claims description 2
- 239000013049 sediment Substances 0.000 claims description 2
- 239000002699 waste material Substances 0.000 claims description 2
- 241001137871 Thermoanaerobacterium saccharolyticum Species 0.000 claims 1
- 239000002154 agricultural waste Substances 0.000 claims 1
- 241000193403 Clostridium Species 0.000 description 7
- 241000202974 Methanobacterium Species 0.000 description 6
- 238000004939 coking Methods 0.000 description 6
- 239000003245 coal Substances 0.000 description 5
- 239000000571 coke Substances 0.000 description 5
- 241000193401 Clostridium acetobutylicum Species 0.000 description 4
- 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
- 239000004615 ingredient Substances 0.000 description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 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
- 239000006227 byproduct Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 241000193171 Clostridium butyricum Species 0.000 description 2
- 241000193469 Clostridium pasteurianum Species 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 241001302042 Methanothermobacter thermautotrophicus Species 0.000 description 2
- 241000193446 Thermoanaerobacterium thermosaccharolyticum Species 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000004151 fermentation Effects 0.000 description 2
- 239000008246 gaseous mixture Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000001360 synchronised effect Effects 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- GDSOZVZXVXTJMI-SNAWJCMRSA-N (e)-1-methylbut-1-ene-1,2,4-tricarboxylic acid Chemical compound OC(=O)C(/C)=C(C(O)=O)\CCC(O)=O GDSOZVZXVXTJMI-SNAWJCMRSA-N 0.000 description 1
- 241000193830 Bacillus <bacterium> Species 0.000 description 1
- 241000306283 Clostridium acidisoli Species 0.000 description 1
- 241000306276 Clostridium akagii Species 0.000 description 1
- 241000193161 Clostridium formicaceticum Species 0.000 description 1
- 241000605008 Spirillum Species 0.000 description 1
- 241001137870 Thermoanaerobacterium Species 0.000 description 1
- 241000229117 [Clostridium] hungatei Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052564 epsomite Inorganic materials 0.000 description 1
- PGOXZLRCNXIVSN-UHFFFAOYSA-N formic acid methane Chemical compound C.C(=O)O.C(=O)O PGOXZLRCNXIVSN-UHFFFAOYSA-N 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 238000011081 inoculation Methods 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 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
- 239000000047 product Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000000241 respiratory effect Effects 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
Abstract
The present invention relates to a kind of methods of coke-stove gas biosynthesis natural gas, comprising the following steps: (1) organic waste, coke-stove gas, aerobic activated sludge is passed through closed deoxidation bioreactor and carries out micro- aerobe reaction deoxidation；(2) coke-stove gas after nitrogen-free agar, deoxidation, spontaneous anaerobic nitrogen-fixation bacterium are passed through closed denitrification organisms reactor and carry out anaerobic organism reaction denitrogenation；(3) organic waste for completing micro- aerobe deoxygenation from closed deoxidation bioreactor, production biogas inoculum are passed through closed production marsh gas reactor and carry out producing methane through anaerobic fermentation；(4) residues for completing producing methane through anaerobic fermentation are separated by solid-liquid separation, filtered biogas slurry nutriment rich in, the culture medium as subsequent anaerobic fermentation methane phase；(5) coke-stove gas, biogas, filtering biogas slurry, the methanogen after deoxidation/denitrogenation are passed through closed methane-producing reactor and carry out anaerobic fermentation methane phase.
Description
Technical field
The invention belongs to artificial synthesized natural gas technical fields, and in particular to a kind of coke-stove gas biosynthesis natural gas side
Method.
Background technique
China is maximum coke production, consumption and exported country, while the coke-oven coal of more than 700 billion cubic meters of association in the world
Gas (tail gas).Wherein half is combustion-supporting for melting down for these coke-stove gas, the other half needs special device recycling.Due to China
Coking industry only focuses on coke production and ignores byproduct recycling, and coking production principal by product coke-stove gas (tail gas) is a large amount of straight
Connect burning release --- it is commonly called as " point day lamp ".Economic loss resulting from reaches tens billion of members, causes the very big wave of scarce resource
Take；Great pollution is also resulted in environment simultaneously.According to measuring and calculating, calculates according to China year coke total output, burn up in vain every year
More than 300 billion cubic meters of coke-stove gas are equivalent to national " more than 2 times of West-east Gas design year displacement.
Coke-stove gas is the by-product in coal destructive distillation process of coking, and main component composition is shown in Table 1:
1 coke-stove gas main component of table composition
| Ingredient | H2 | CH4 | CO | CO2 | N2 | O2 |
| It forms (vol.%) | 50~60 | 20~30 | 5~9 | 2~5 | 3~6 | 0.3~0.8 |
With the increase of China's energy demand total amount and the adjustment of energy consumption structure, the demand to natural gas is increasingly
Greatly.Annual China's natural gas yield is 1210 billion cubic meters within 2013, and Natural Gas Consumption Using is 1676 billion cubic meters, and supply and demand lacks
Mouthful up to 466 billion cubic meters.As Natural Gas Demand continues to increase, the technology of various synthesis of artificial natural gases is emerged in large numbers one after another, such as coal
Natural, bio-natural gas of system etc., but consider from economy, applicability etc., synthesizing natural gas from coke oven gas has stronger city
Field competitiveness.
As it can be seen from table 1 coke-stove gas produces natural gas, there are two types of schemes: one is divide the methane in coke-stove gas
It is come out from purification, second is that by the N in coke-stove gas2、O2It removes and H2、CO、CO2It is changed into methane.Currently, coke-stove gas system
Natural gas is taken largely to use the first scheme, for example, by using UF membrane and cryogenic rectification (granted patent
ZL200810239548.6), liquefying and rectifying (granted patent ZL200810135211.0,102654348 A of publication CN),
Pressure-variable adsorption (ZL201110024062.2).This scheme can only recycle the methane gas in coke-stove gas, can not be by H2、CO、
CO2It is changed into methane, the yield of coke-stove gas preparing natural gas is lower.
Granted patent (ZL200910018047.X) and publication (103131490 A of CN) disclose a kind of coke-oven coal
The technique of gas methanation synthetic natural gas is reacted by two sections of chemical catalysis, by CO, CO2Generation is reacted with the vapor being passed through
CH4, then pass through pressure-variable adsorption or UF membrane etc. for CH4And H2Separation, to obtain natural gas.This method can be by CO, CO2Turn
Become CH4, but can not be by H2It is changed into methane, and the N in coke-stove gas can not be removed2And O2。
Publication (102311822 A of CN) discloses a kind of synthesizing natural gas from coke oven gas method, by taking back
The methanator and temperature transmitter of stream are reacted with the catalysis that compressor interlocks, by CO, CO2And H2It is changed into CH4.Equally,
This method can not remove the N in coke-stove gas2And O2.And from the point of view of coke-stove gas composition and chemical equation, due to lacking C
More H, can not be by H2It is completely reformed into CH4, in product gas at least also containing 10% or more H2。
Publication (103087793 A of CN) disclose it is a kind of using anaerobe realize oven gas prepare natural gas
Technique, pass through supplemented with exogenous CO2Using anaerobic methane production microorganism by CO, CO2And H2It is changed into CH4.But this method passes through change
Press absorption or cryogenic separation by N2And O2It is separated, and requires supplementation with CO2, cause operation energy consumption and production cost higher.
Publication (103113010 A of CN), which discloses, a kind of synchronous realizes coke-oven gas methanation and biogas in-situ purification
Method, utilize biogas fermentation generate CO2The few deficiency of the more C of H is made up, realizes the H in coke-stove gas2Full methanation.So
And this method does not disclose N2And O2Removal methods, limit high level, the safe utilization of synthetic natural gas.
Summary of the invention
It is an object of the invention to overcome deficiency in the prior art, a kind of coke-stove gas biosynthesis natural gas is provided
Method realizes the high level safe utilization of coke-stove gas.
The method of coke-stove gas biosynthesis natural gas in the present invention, comprising the following steps:
(1) micro- aerobe reaction deoxidation: organic waste, coke-stove gas, aerobic activated sludge are passed through closed de-
Oxygen bioreactor, controls 20~35 DEG C of temperature, pH value 6.5~8.5 in closed bioreactor, and aerobic activated sludge utilizes
Oxygen in organic matter and coke-stove gas in organic waste carries out aerobic respiration metabolism, consumes the oxygen in coke-stove gas,
It and is subsequent H2Methanation provide CO2, the deoxygenation step is actually still to one kind of organic waste producing methane through anaerobic fermentation
Pretreatment；
Organic matter+O2→CO2+H2O
(2) anaerobic organism reacts denitrogenation: the coke-stove gas after nitrogen-free agar, deoxidation, spontaneous anaerobic nitrogen-fixation bacterium are passed through
Closed denitrification organisms reactor controls 25~68 DEG C of temperature, pH value 6.5~8.5, spontaneous anaerobism in closed bioreactor
Nitrogen-fixing bacteria carry out spontaneous anaerobic nitrogen-fixation metabolism using the non-nitrogen nutriment in nitrogen-free agar and the nitrogen in coke-stove gas, disappear
The nitrogen in coke-stove gas is consumed, the spontaneous anaerobic nitrogen-fixation bacterium in part is simultaneously by H2And CO2Synthesize CH4；
Non-nitrogen nutriment+N2→ cell protein+NH4 +
4H2+CO2→CH4+2H2O
(3) producing methane through anaerobic fermentation: micro- aerobe deoxygenation will be completed from closed deoxidation bioreactor
Organic waste, produce biogas inoculum and be passed through closed production marsh gas reactor, control temperature in closed production marsh gas reactor
25~55 DEG C, pH value 6.8~8.0 produce biogas inoculum and generate biogas using organic waste, a large amount of CO are contained in biogas2, it is
Subsequent H2Methanation provide CO2；
Organic matter → CH4+CO2
(4) residues are separated by solid-liquid separation, filter: the residues that will complete producing methane through anaerobic fermentation carry out solid-liquid point
From, and the biogas slurry after separation is filtered, filtered biogas slurry nutriment rich in, it is produced as subsequent anaerobic fermentation
The culture medium of methane；
(5) anaerobic fermentation methane phase: coke-stove gas, biogas, filtering biogas slurry, the methanogen after deoxidation/denitrogenation are passed through
Closed methane-producing reactor controls 25~60 DEG C of temperature, pH value 6.8~8.0, methanogen in closed methane-producing reactor
Utilize H2、CO2CH is synthesized with CO4；
4H2+CO2→CH4+2H2O
3H2+CO→CH4+H2
The organic waste includes but is not limited to sanitary sewage, industrial organic waste water, house refuse, agriculture waste
Object；
The aerobic activated sludge derives from sewage treatment plant；
The nitrogen-free agar formula is 5~20g containing glucose, KH in every liter of water2PO40.2~3g, MgSO47H2O
0.2~0.5g, NaCl 0.2~1g, FeSO4 0.05~0.1g, CaCl2·2H2O 0.2~0.5g, NaMoO40.01~
0.03g, CaCO33~5g, 0.2~0.4g of L-AA；
The spontaneous anaerobic nitrogen-fixation bacterium bag includes two class of clostridium and hydrogen auxotype methane backeria, and clostridium is clostridium acetobutylicum
(Clostridium acetobutylicum), Clostridium beijerinckii (Clostridium beijerinckii), clostridium butyricum
(Clostridium butyricum), clostridium klebsi (Clostridium kluyverii), clostridium pasteurianum
(Clostridium pasteurianum), Heng Shi clostridium (Clostridium hungatei), Clostridium
formicoaceticum、Clostridium akagii、Clostridium acidisoli、
Thermoanaerobacterium thermosaccharolyticum, hydrogen auxotype methane backeria are folded for Pasteur's methane eight
(Methanosarcina barkeri coccus), Bai Shi methagen (Methanobacterium bryantii), Heng Shi methane
Spirillum (Methanospirillum hungatei), extra large natural pond methane thermal coccus (Methanococcus maripaludis), heat
Autotrophy methane thermal coccus (Methanococcus thermolithotrophicus)；Using when add a kind of their bacterium or more
Kind bacterium combination；
The production biogas inoculum is from methane-generating pit, sewage treatment plant's anaerobic sludge pond, sediment of pond etc.；
The methanogen includes hydrogen auxotype methane backeria and carbon monoxide auxotype methane backeria, hydrogen auxotype methane bacterium bag
It includes but is not limited to Pasteur's methane eight and fold (Methanosarcina barkeri coccus), Bai Shi methagen
(Methanobacterium bryantii), Heng Shi methanospirillum (Methanospirillum hungatei), extra large natural pond methane
Hot-bulb bacterium (Methanococcus maripaludis), hot autotrophy methane thermal coccus (Methanococcus
Thermolithotrophicus), carbon monoxide auxotype methane backeria includes but is not limited to formic acid methagen
(Methanobacterium formieieum), thermophilic tree methagen (Methanobacterium arboriphilicus),
Pasteur's sarcina methanica (Methanosarcina barkeri), Methanobacterium ruminantum,
Methanothermobacter thermoautotrophicus；Using when at least while add in hydrogen auxotype methane backeria
A kind of one of and carbon monoxide auxotype methane backeria；
The closed deoxidation bioreactor, closed denitrification organisms reactor, closed methane-producing reactor class
Type includes stirring reactor, bubbling column reactor, microvesicle reactor, membrane reactor, according to O in fuel gas2、N2、H2、CO
The height of content can be arranged in series multistage closed deoxidation bioreactor, closed denitrification organisms reactor, closed production first
Each component content of gas reaches requirement after alkane reactor guarantee processing；
Closed deoxidation bioreactor, closed denitrification organisms reactor and the closed methane-producing reactor is set
Gas self circular loop is set, gas-liquid contact time in reactor is extended, improves gas conversions；
The closed production marsh gas reactor type includes but is not limited to that stirring reactor (CSTR), up flow type are detested
Oxygen Sludge Bed (UASB), anaerobic filter (AF).
Compared with existing coke-stove gas methane separation method of purification preparing natural gas, innovation of the invention is that it is possible to
By the H in coke-stove gas2、CO、CO2It is changed into CH4, gas yield is higher；With existing synchronous realization coke-oven gas methanation and
The biological method of biogas in-situ purification is compared, and the innovation of the method for the present invention is that it is possible to the N in coke-stove gas2And O2It is de-
It removes, realizes high level, the safe utilization of synthetic natural gas.
Detailed description of the invention
Fig. 1 is the process flow diagram of the method for the present invention
Specific embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Embodiment 1:
The coke-stove gas and neighbouring sanitary sewage of certain small-sized coking plant are collected, coke-stove gas yield is 1000m3/ d, gas
Body forms H250%, CH430%, CO 9%, CO25%, N23%, O20.3%, by sanitary sewage, coke-stove gas, sewage
The aerobic activated sludge for the treatment of plant is passed through closed deoxidation membrane bioreactor, 20 DEG C of reactor temperature of control, pH value 6.5 into
It acts charitably oxygen respiratory metabolism, the aerobic chemoheterotrophic bacteria in aerobic activated sludge passes through reaction equation (organic matter+O2→CO2+H2O) disappear
Consume O2, while generating CO2；Nitrogen-free agar is prepared, is formulated as 5g containing glucose, KH in every liter of water2PO40.2g, MgSO4
7H2O 0.2g, NaCl 0.2g, FeSO4 0.05g, CaCl2·2H2O 0.2g, NaMoO40.01g, CaCO3 3g, L- are anti-bad
Hematic acid 0.2g, by coke-stove gas, the clostridium acetobutylicum (Clostridium after nitrogen-free agar, deoxidation
Acetobutylicum it) is passed through closed denitrogenation microvesicle bioreactor, 25 DEG C of reactor temperature of control, pH value 6.5 carry out
Anaerobic nitrogen-fixation metabolism, clostridium acetobutylicum are carried out using the non-nitrogen nutriment in nitrogen-free agar and the nitrogen in coke-stove gas
Spontaneous anaerobic nitrogen-fixation metabolism, according to reaction equation (non-nitrogen nutriment+N2→ cell protein+NH4 +) consume in coke-stove gas
Nitrogen；The sanitary sewage for completing deoxygenation is taken out from closed deoxidation reactor, fetches the production biogas inoculation from methane-generating pit
Object, it is 30m that sanitary sewage and biogas inoculum, which are passed through volume,3Closed anaerobic filter (AF) produce marsh gas reactor, control
25 DEG C of reactor temperature, pH value 6.8 carry out producing methane through anaerobic fermentation, and pool capacity factor of created gase is 0.4m3/(m3D), biogas output
For 12m3/ d, ingredient CH460% and CO240%, a large amount of CO contained in biogas2For subsequent H2Methanation provide carbon source；It will
The residues for completing producing methane through anaerobic fermentation are separated by solid-liquid separation, and are filtered to the biogas slurry after separation, filtered
Biogas slurry nutriment rich in, the culture medium as subsequent anaerobic fermentation methane phase；By the coke-oven coal after deoxidation/denitrogenation
Gas, biogas, filtering biogas slurry, Bai Shi methagen (Methanobacterium bryantii), formic acid methagen
(Methanobacterium formieieum) is passed through closed methane phase microvesicle reactor, 25 DEG C of reactor temperature of control,
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；It finally obtains yield and methane concentration is respectively 480m3The conjunction of/d and 95%
At natural gas.
Embodiment 2
The coke-stove gas and neighbouring alcohol waste water of certain medium-sized coking plant are collected, coke-stove gas yield is 10000m3/ d, gas
Body forms H255%, CH420%, CO 9%, CO25%, N25%, O20.8%, by alcohol waste water, coke-stove gas, sewage
The aerobic activated sludge for the treatment of plant is passed through closed deoxidation and is bubbled bioreactor, controls 28 DEG C of reactor temperature, pH value 7.5
Aerobic respiration metabolism is carried out, the aerobic chemoheterotrophic bacteria in aerobic activated sludge passes through reaction equation (organic matter+O2→CO2+H2O)
Consume O2, while generating CO2；Nitrogen-free agar is prepared, is formulated as 13g containing glucose, KH in every liter of water2PO41.5g
MgSO4·7H2O 0.35g, NaCl 0.6g, FeSO4 0.07g, CaCl2·2H2O 0.35g, NaMoO40.02g, CaCO3
4g, L-AA 0.3g, by coke-stove gas, the Clostridium beijerinckii (Clostridium after nitrogen-free agar, deoxidation
Beijerinckii), it is anti-to be passed through closed denitrogenation microvesicle biology for Heng Shi methanospirillum (Methanospirillum hungatei)
Device is answered, 45 DEG C of reactor temperature of control, pH value 7.5 carry out anaerobic nitrogen-fixation metabolism, and Clostridium beijerinckii and Heng Shi methanospirillum utilize
Non-nitrogen nutriment in nitrogen-free agar and the nitrogen in coke-stove gas carry out spontaneous anaerobic nitrogen-fixation metabolism, according to reaction equation
(non-nitrogen nutriment+N2→ cell protein+NH4 +) nitrogen in consumption coke-stove gas, Heng Shi methanospirillum simultaneously can be by
According to reaction equation (4H2+CO2→CH4+2H2O) by part H2And CO2Synthesize CH4；It is taken out from closed deoxidation reactor and completes to take off
The alcohol waste water of oxygen reaction fetches the anaerobic sludge from sewage treatment plant as biogas inoculum is produced, by alcohol waste water and biogas
It is 160m that inoculum, which is passed through volume,3Closed up-flow anaerobic sludge blanket (UASB) produce marsh gas reactor, control reactor in
Temperature 45 C, pH value 7.4 carry out producing methane through anaerobic fermentation, and pool capacity factor of created gase is 2.5m3/(m3D), biogas output 396m3/
D, ingredient CH470% and CO230%, a large amount of CO contained in biogas2For subsequent H2Methanation provide carbon source；Completion is detested
The residues that aerobe fermentation produces biogas are separated by solid-liquid separation, and are filtered to the biogas slurry after separation, and filtered biogas slurry contains
There is nutriment abundant, the culture medium as subsequent anaerobic fermentation methane phase；By after deoxidation/denitrogenation coke-stove gas, biogas,
Filter biogas slurry, Pasteur's methane eight folds (Methanosarcina barkeri coccus), Bai Shi methagen
(Methanobacterium bryantii), Heng Shi methanospirillum (Methanospirillum hungatei), formic acid methane
Bacillus (Methanobacterium formieieum), thermophilic tree methagen (Methanobacterium
Arboriphilicus it) is passed through the closed methane phase membrane reactor of two-stage, 38 DEG C of reactor temperature of control, pH value 7.5 carry out
H in anaerobic fermentation methane phase, coke-stove gas and biogas gaseous mixture2、CO2With CO according to reaction equation (4H2+CO2→CH4+2H2O、
3H2+CO→CH4+H2) synthesis CH4；It finally obtains yield and methane concentration is respectively 4704m3The synthetic natural gas of/d and 93%.
Embodiment 3
The coke-stove gas and neighbouring domestic organic garbage of certain large-scale coking plant are collected, coke-stove gas yield is 50000m3/
D, gas composition H260%, CH425%, CO 7%, CO24%, N26%, O20.5%, by domestic organic garbage, coke-oven coal
Gas, sewage treatment plant aerobic activated sludge be passed through closed deoxidation stirring type bioreactor, control reactor temperature 35
DEG C, pH value 8.5 carry out aerobic respiration metabolism, the aerobic chemoheterotrophic bacteria in aerobic activated sludge passes through reaction equation (organic matter+O2
→CO2+H2O O) is consumed2, while generating CO2；Nitrogen-free agar is prepared, is formulated as 20g containing glucose, KH in every liter of water2PO4
3g, MgSO47H2O 0.5g, NaCl 1g, FeSO4 0.1g, CaCl2·2H2O 0.5g, NaMoO40.03g, CaCO35g,
L-AA 0.4g, by coke-stove gas, the Thermoanaerobacterium after nitrogen-free agar, deoxidation
Thermosaccharolyticum, extra large natural pond methane thermal coccus (Methanococcus maripaludis), hot autotrophy methane thermal
Coccus (Methanococcus thermolithotrophicus) is passed through the closed denitrogenation membrane bioreactor of two-stage, and control is anti-
68 DEG C of temperature in device, pH value 8.5 is answered to carry out anaerobic nitrogen-fixation metabolism, Thermoanaerobacterium
Thermosaccharolyticum, extra large natural pond methane thermal coccus, hot autotrophy methane thermal coccus are sought using the non-nitrogen in nitrogen-free agar
The nitrogen supported in substance and coke-stove gas carries out spontaneous anaerobic nitrogen-fixation metabolism, according to reaction equation (non-nitrogen nutriment+N2→ cell
Protein+NH4 +) consumption coke-stove gas in nitrogen, extra large natural pond methane thermal coccus, hot autotrophy methane thermal coccus simultaneously can be according to anti-
Answer formula (4H2+CO2→CH4+2H2O) by part H2And CO2Synthesize CH4；It is anti-that completion deoxidation is taken out from closed deoxidation reactor
The domestic organic garbage answered fetches the anaerobic sludge from methane-generating pit as biogas inoculum is produced, by domestic organic garbage and biogas
It is 3900m that inoculum, which is passed through volume,3Closed stirring produce marsh gas reactor (CSTR), control 55 DEG C of reactor temperature, pH
Value 8.0 carries out producing methane through anaerobic fermentation, and pool capacity factor of created gase is 1.5m3/(m3D), biogas output 5830m3/ d, ingredient CH4
55% and CO245%, a large amount of CO contained in biogas2For subsequent H2Methanation provide carbon source；It will complete anaerobic fermentation and produce natural pond
The residues of gas are separated by solid-liquid separation, and are filtered to the biogas slurry after separation, filtered biogas slurry battalion rich in
Support substance, the culture medium as subsequent anaerobic fermentation methane phase；By after deoxidation/denitrogenation coke-stove gas, biogas, filtering biogas slurry,
Extra large natural pond methane thermal coccus (Methanococcus maripaludis), hot autotrophy methane thermal coccus (Methanococcus
Thermolithotrophicus), Methanothermobacter thermoautotrophicus is passed through closed methane phase
Microvesicle reactor, 60 DEG C of reactor temperature of control, pH value 8.0 carry out anaerobic fermentation methane phase, and coke-stove gas is mixed with biogas
H in gas2、CO2With CO according to reaction equation (4H2+CO2→CH4+2H2O、3H2+CO→CH4+H2) synthesis CH4；Finally obtain yield
It is respectively 25617m with methane concentration3The synthetic natural gas of/d and 94%.
The above enumerated are only specific embodiments of the present invention for finally, it should also be noted that.Obviously, the present invention is unlimited
In above embodiments, acceptable there are many deformations.Those skilled in the art can directly lead from present disclosure
Out or all deformations for associating, it is considered as protection scope of the present invention.
Claims (10)
1. a kind of method of coke-stove gas biosynthesis natural gas, which is characterized in that method includes the following steps:
(1) it is raw that organic waste, coke-stove gas, aerobic activated sludge micro- aerobe reaction deoxidation: are passed through closed deoxidation
Object reactor, controls 20~35 DEG C of temperature, pH value 6.5~8.5 in closed deoxidation bioreactor, and aerobic activated sludge utilizes
Oxygen in organic matter and coke-stove gas in organic waste carries out aerobic respiration metabolism, consumes the oxygen in coke-stove gas,
It and is subsequent H2Methanation provide CO2, the deoxygenation step is actually still to one kind of organic waste producing methane through anaerobic fermentation
Pretreatment；
Organic matter+O2→CO2+H2O
(2) anaerobic organism reacts denitrogenation: the coke-stove gas after nitrogen-free agar, deoxidation, spontaneous anaerobic nitrogen-fixation bacterium being passed through closed
Formula denitrification organisms reactor controls 25~68 DEG C of closed denitrification organisms reactor temperature, pH value 6.5~8.5, spontaneous anaerobism
Nitrogen-fixing bacteria carry out spontaneous anaerobic nitrogen-fixation metabolism using the non-nitrogen nutriment in nitrogen-free agar and the nitrogen in coke-stove gas, disappear
The nitrogen in coke-stove gas is consumed, the spontaneous anaerobic nitrogen-fixation bacterium in part is simultaneously by H2And CO2Synthesize CH4；
Non-nitrogen nutriment+N2→ cell protein+NH4 +
4H2+CO2→CH4+2H2O
(3) producing methane through anaerobic fermentation: having for micro- aerobe deoxygenation will be completed from closed deoxidation bioreactor
Machine waste produces biogas inoculum and is passed through closed production marsh gas reactor, control temperature 25 in closed production marsh gas reactor~
55 DEG C, pH value 6.8~8.0 produce biogas inoculum and generate biogas using organic waste, a large amount of CO are contained in biogas2, it is subsequent H2
Methanation provide CO2；
Organic matter → CH4+CO2
(4) residues are separated by solid-liquid separation, filter: the residues for completing producing methane through anaerobic fermentation are separated by solid-liquid separation,
And the biogas slurry after separation is filtered, filtered biogas slurry nutriment rich in, first is produced as subsequent anaerobic fermentation
The culture medium of alkane；
(5) anaerobic fermentation methane phase: coke-stove gas, biogas, filtering biogas slurry, the methanogen after deoxidation and denitrogenation are passed through closed
Formula methane-producing reactor, controls 25~60 DEG C of temperature, pH value 6.8~8.0 in closed methane-producing reactor, and methanogen utilizes
H2、CO2CH is synthesized with CO4；
4H2+CO2→CH4+2H2O
3H2+CO→CH4+H2。
2. a kind of method of coke-stove gas biosynthesis natural gas according to claim 1, which is characterized in that step (2)
In spontaneous anaerobic nitrogen-fixation bacterium be Clostridium beijerinckii and Heng Shi methanospirillum combination or hot Thermoanaerobactersaccharolyticum and extra large natural pond methane
The combination of hot-bulb bacterium and hot autotrophy methane thermal coccus.
3. a kind of method of coke-stove gas biosynthesis natural gas according to claim 1, which is characterized in that step (5)
In methanogen include hydrogen auxotype methane backeria and carbon monoxide auxotype methane backeria, hydrogen auxotype methane backeria includes but not office
It is limited to folded Pasteur's methane eight, Bai Shi methagen, Heng Shi methanospirillum, extra large natural pond methane thermal coccus or hot autotrophy methane thermal coccus,
Carbon monoxide auxotype methane backeria includes but is not limited to formic acid methagen, thermophilic tree methagen, Pasteur's sarcina methanica；
Using when at least while add one of one of hydrogen auxotype methane backeria and carbon monoxide auxotype methane backeria.
4. a kind of method of coke-stove gas biosynthesis natural gas according to claim 1, which is characterized in that step (2)
In nitrogen-free agar formula be 5~20g containing glucose, KH in every liter of water2PO40.2~3g, MgSO47H2O 0.2~
0.5g, NaCl 0.2~1g, FeSO40.05~0.1g, CaCl2·2H2O 0.2~0.5g, NaMoO40.01~0.03g,
CaCO33~5g, 0.2~0.4g of L-AA.
5. a kind of method of coke-stove gas biosynthesis natural gas according to claim 1, which is characterized in that step (1)
In closed deoxidation bioreactor, the closed denitrification organisms reactor in step (2), the closed production in step (5)
Methane reactor type includes stirring reactor, bubbling column reactor, microvesicle reactor, membrane reactor.
6. a kind of method of coke-stove gas biosynthesis natural gas according to claim 1, which is characterized in that step (1)
In closed deoxidation bioreactor, the closed denitrification organisms reactor in step (2), the closed production in step (5)
The settable level-one of methane reactor is arranged in series multistage.
7. a kind of method of coke-stove gas biosynthesis natural gas according to claim 1, which is characterized in that step (1)
In closed deoxidation bioreactor, the closed denitrification organisms reactor in step (2), the closed production in step (5)
Gas self circular loop is arranged in methane reactor.
8. a kind of method of coke-stove gas biosynthesis natural gas according to claim 1, which is characterized in that step (3)
In closed production marsh gas reactor type include but is not limited to stirring reactor, up-flow anaerobic sludge blanket or anaerobism filter
Device.
9. a kind of method of coke-stove gas biosynthesis natural gas according to claim 1, which is characterized in that step (1)
In organic waste include but is not limited to sanitary sewage, industrial organic waste water, house refuse or agricultural wastes, step
(1) aerobic activated sludge in derives from sewage treatment plant.
10. a kind of method of coke-stove gas biosynthesis natural gas according to claim 1, which is characterized in that step (3)
In production biogas inoculum derive from methane-generating pit, sewage treatment plant's anaerobic sludge pond or sediment of pond.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101870894A (en) * | 2009-04-21 | 2010-10-27 | 张扬 | Method and biological plant for removing carbon dioxide, hydrogen sulfide and ammonia from methane by using microecology principle |
| CN102249406A (en) * | 2011-06-17 | 2011-11-23 | 河南农业大学 | Method and deoxidization reactor for producing nitrogen by utilizing organic wastewater |
| CN102286540A (en) * | 2011-06-17 | 2011-12-21 | 河南农业大学 | Method for performing nitrogen fixation for straw anaerobic fermentation by utilizing organic wastewater |
| CN102351309A (en) * | 2011-06-17 | 2012-02-15 | 河南农业大学 | Azotification method by use of organic wastewater |
| JP2012100547A (en) * | 2010-11-08 | 2012-05-31 | Daicel Corp | Method and apparatus for producing organic matter by feeding gas resource to anaerobic microorganism |
| CN102515439A (en) * | 2011-12-22 | 2012-06-27 | 中国地质大学（北京） | Biological deoxidation denitrification method in oxidative environment groundwater and device thereof |
-
2015
- 2015-11-26 CN CN201510870806.0A patent/CN105623761B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101870894A (en) * | 2009-04-21 | 2010-10-27 | 张扬 | Method and biological plant for removing carbon dioxide, hydrogen sulfide and ammonia from methane by using microecology principle |
| JP2012100547A (en) * | 2010-11-08 | 2012-05-31 | Daicel Corp | Method and apparatus for producing organic matter by feeding gas resource to anaerobic microorganism |
| CN102249406A (en) * | 2011-06-17 | 2011-11-23 | 河南农业大学 | Method and deoxidization reactor for producing nitrogen by utilizing organic wastewater |
| CN102286540A (en) * | 2011-06-17 | 2011-12-21 | 河南农业大学 | Method for performing nitrogen fixation for straw anaerobic fermentation by utilizing organic wastewater |
| CN102351309A (en) * | 2011-06-17 | 2012-02-15 | 河南农业大学 | Azotification method by use of organic wastewater |
| CN102515439A (en) * | 2011-12-22 | 2012-06-27 | 中国地质大学（北京） | Biological deoxidation denitrification method in oxidative environment groundwater and device thereof |
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