CN103113010A - Method for synchronous implementation of methanation of coke oven gas and in-situ purification of marsh gas - Google Patents
Method for synchronous implementation of methanation of coke oven gas and in-situ purification of marsh gas Download PDFInfo
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- CN103113010A CN103113010A CN2013100418338A CN201310041833A CN103113010A CN 103113010 A CN103113010 A CN 103113010A CN 2013100418338 A CN2013100418338 A CN 2013100418338A CN 201310041833 A CN201310041833 A CN 201310041833A CN 103113010 A CN103113010 A CN 103113010A
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- gas
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- oven
- anaerobic reactor
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
Abstract
The invention relates to a method for synchronous implementation of methanation of coke oven gas and in-situ purification of marsh gas. The method comprises the following steps: (a) introducing the coke oven gas and organic wastes into an anaerobic reactor; (b) in the anaerobic reactor, degrading the organic wastes with microbes to generate CH4 and CO2, enabling produced CO2 to combine with H2 in the coke oven gas to generate CH4 under the action of the microbes, and reacting CO and CO2 in the coke oven gas with H2 to generate CH4 to get the marsh gas which mainly contains CH4; and (c) separating and removing impurities in the marsh gas obtained in the step (b) to get natural gas with high content of methane. Compared with the prior art, according to the method disclosed by the invention, a microbial process is adopted for introducing the coke oven gas into the anaerobic reactor, the in-situ purification of the marsh gas is simultaneously implemented during the preparation of the natural gas, a catalyst is not required, high temperature and high pressure are not required, and most of components except methane in the coke oven gas and the marsh gas can be converted to methane, so that the new method is provided for solving the problems of shortage of resources, environmental pollution, unreasonable energy structure and the like in the energy field in China.
Description
Technical field
The present invention relates to the comprehensive utilization of coking industry byproduct and methane purification, especially relate to a kind of method that realizes that synchronously coke-oven gas methanation and biogas original position are purified.
Background technology
Anaerobic digestion process is widely used in the processing of high concentrated organic wastewater (vinasse, percolate etc.), organic waste (mud, cow dung, stalk etc.) due to advantages such as having high loading, less energy-consumption, low operating cost, the generation energy.The main component of the biogas that anaerobic digestion process produces is 50-70% methane (CH
4), 30-50% carbonic acid gas (CO
2) and a small amount of hydrogen sulfide (H
2S), water (H
2O), ammonia nitrogen (NH
3), hydrogen (H
2) and carbon monoxide (CO) etc., be a kind of continuable valuable energy derive.Undressed common biogas, energy density is low, and calorific value generally between 5200-6600 kilocalorie/cubic meter, uses as domestic energy for a long time, also is used at present generating.Yet along with the exhaustion of ore fuel, the demand of biogas utilization constantly increases, and is that the bio-natural gas of methane content more than 90% just paid close attention to widely because it utilizes efficiently with methane purification.Biogas calorific value high (8000-9000 kilocalorie/cubic meter) after purifying, but long distance transportation also can be used as vehicle fuel or inject gas distributing system replacement Sweet natural gas.Biogas is converted into the higher Sweet natural gas of calorific value mainly needs to remove wherein CO
2To improve CH
4Concentration, the biogas after purification also needs further to purify the impurity such as the hydrogen sulfide removed wherein, moisture.Methane purification is mainly realized CO by technology such as pressure-variable adsorption, washing, polyoxyethylene glycol washing or membrane sepn industrial at present
2Removal, above technology all need to be added extra equipment and be realized methane purification outside anaerobic reactor, these techniques are all to adopt physico-chemical process to realize methane purification in addition, need high pressure or add chemical substance just can carry out, thereby running cost are higher.The cost of methane purification is subjected to purification techniques, and the impact of biogas plant's scale etc. is at present at 0.18-0.70 dollar/m
3Between.In purification process, the CH of 2%-10% is arranged approximately
4Can lose, with CO
2Be discharged in air.Due to CH
4Greenhouse effect are CO
220 times, so this part CH
4The loss meeting impacts environment.
Coke(oven)gas refers to be mixed with coking coal with several bituminous coal, and through after high temperature carbonization, a kind of inflammable gas that produces in output coke and tar products is the byproduct of coking industry in pit kiln, but dry coal commercial coke oven gas 300-350m per ton
3Its chief component is: H
255%～60%, CH
423%～27%, CO5-8%, C
2Above unsaturated hydrocarbons 2%～4%, CO
21.5%～3%, O
20.3%～0.8%, H
2S0.01%, N
23%～7%.Utilize the coke(oven)gas synthetic natural gas to open up the efficient new way of utilizing of coke(oven)gas, can not only drive the technical progress of coking and energy industry, can also solve environmental pollution and wasting of resources problem that the coke(oven)gas discharging causes.The method of employing coke-oven gas for production of methane mainly comprises chemical process and physical method, wherein chemical process is to be the conversion of other except methane in coke(oven)gas methane, and physical method is to adopt the methods such as pressure-variable adsorption separation, low temperature separation process, membrane sepn, and methane is purified.Associated patent comprises CN191985A, CN101818087A, and CN101591578A, CN101607859A etc., however these methods all need to be in the situation that high temperature, high pressure and have catalyzer to exist to carry out, in addition to H in coke(oven)gas
2And CO
2Utilization also complete not, and the investment running cost all higher.
Summary of the invention
Purpose of the present invention is exactly to provide a kind of method that realizes that synchronously coke-oven gas methanation and biogas original position are purified for the defective that overcomes above-mentioned prior art existence.
Purpose of the present invention can be achieved through the following technical solutions:
A kind of method that realizes that synchronously coke-oven gas methanation and biogas original position are purified, the method comprises the following steps;
(a) coke(oven)gas and organic waste are passed in anaerobic reactor;
(b) in anaerobic reactor, organic waste is degraded by microorganisms and generates CH
4And CO
2, the CO of generation
2With the H in coke(oven)gas
2In conjunction with generating CH
4, under microbial process, the CO in coke(oven)gas and CO
2With H
2Generate CH
4, obtain with CH
4Be main biogas;
(c) separate the impurity of removing in step (b) gained biogas, obtain having the Sweet natural gas of high methane content.
The flow that passes into the coke(oven)gas of anaerobic reactor in step (a) is determined by the following method:
V
Coke(oven)gas=4 * V
CO2/ (P
H2-3 * P
CO-4 * P
CO2)
Wherein, V
Coke(oven)gasBe the flow of coke(oven)gas, V
CO2CO for the anaerobic reactor generation
2Flow, P
H2, P
CO, P
CO2Be respectively H
2, CO and CO
2Component in coke(oven)gas.
Temperature in step (a) or the described anaerobic reactor of step (b) is 30～40 ℃ or 50～60 ℃.
Step (a) or the described anaerobic reactor of step (b) are CSTR reactor or UASB reactor.
Microorganism mainly utilizes following reaction with CO
2Be converted into CH
4
4H
2+CO
2＝CH
4+2H
2O ΔG
0＝-1307KJ/mol
The described organic waste of step (b) is selected from sewage plant sludge, cow dung or pig manure.
In anaerobic reactor, mixing by mechanical stirring, gas stirring or hollow-fibre membrane aeration between organic waste and coke(oven)gas realizes.
The described pressure-variable adsorption that is separated into of step (c) separates or low temperature separation process, and these two kinds of separation methods are the now ripe technique of using.
The described impurity of step (c) comprises N
2, H
2, CO, H
2O, CO
2And H
2S, the total mass mark of impurity is less than 10%.
The described Sweet natural gas with high methane content of step (c) refers to that the massfraction of methane is the Sweet natural gas more than 98%.
The present invention proposes a kind of method of microorganism that utilizes and synchronously realize the method that coke-oven gas methanation and biogas original position are purified.Coke(oven)gas can directly pass into the anaerobic reactor of processing organic waste, and CO wherein can be converted into CH under the anaerobion effect
4, CO
2Can with H
2(can consume the H of 6-12%
2) generation CH
4, remaining approximately 50% H
2CO with the anaerobic reactor generation
2In conjunction with generating CH
4, this technique has not only realized the biogas original position purification of anaerobic reactor, also can realize the methanation of coke(oven)gas.
Compared with prior art, the present invention has the following advantages and beneficial effect:
(1) adopt microbiological processes that coke(oven)gas is passed into anaerobic reactor and realize the purification of biogas original position when producing Sweet natural gas, there is no precedent both at home and abroad, this technique to high-efficiency economy, need not to add catalyzer, need not High Temperature High Pressure, can be the most conversion except methane in coke(oven)gas and biogas methane, the shortage of resources that faces for solving China's energy field, environmental pollution, energy structure is unreasonable etc., and problem provides novel method.
(2) utilized greenhouse gases CO in technological process of the present invention
2, not only reduced CO
2Discharging, and with CO
2Be converted into the new energy, a kind of CO is provided
2Therefore the new way of recycling helps reduction of greenhouse gas discharge.
Description of drawings
Fig. 1 is process flow sheet of the present invention.
In figure, 1 is coke(oven)gas, and 2 is organic waste, and 3 is anaerobic reactor, and 4 is with CH
4Be main biogas, 5 for having the Sweet natural gas of high methane content.
Embodiment
The present invention is described in detail below in conjunction with the drawings and specific embodiments.
Embodiment 1
Take the anaerobism CSTR reactor of the plant excess sludge of disposing of sewage as example, reactor is 100m
3, biogas output is 1m
3/ L/d, CH in biogas
4Content is 60%, CO
2Content is 40%.Coke(oven)gas consists of H
2Content 65%, CO content 5%, CH
4Content 25%, CO
2Content 3%.The flow that coke(oven)gas passes into anaerobic reactor is 421m
3/ d, this reactor adopts mechanical stirring, and stirring velocity is 400rpm.The air-fuel mixture amount that produces is 200m approximately
3/ d, methane concentration are more than 90%, obtain the Sweet natural gas of 98% above methane content through further purifying.
Embodiment 2
A kind of method that realizes that synchronously coke-oven gas methanation and biogas original position are purified, its technique as shown in Figure 1, the method comprises the following steps:
(a) coke(oven)gas 1 is passed in the anaerobic reactor 3 of processing organic waste 2;
(b) in anaerobic reactor 3, organic waste 2 is degraded by microorganisms and produces CH
4And CO
2, the CO of generation
2Further with coke(oven)gas 1 in H
2In conjunction with generating CH
4, a small amount of CO and CO in coke(oven)gas 1
2Also utilized and H by microorganism
2Generate CH
4, obtain take CH4 as main biogas 4, wherein CH
4Massfraction be 91%;
(c) impurity in separating take CH4 as main biogas 4 by pressure-variable adsorption, acquisition has the Sweet natural gas 5 of high methane content (methane content is more than 98%).
Wherein, the flow that passes into the coke(oven)gas 1 of anaerobic reactor 3 in step (a) is determined by the following method:
V
Coke(oven)gas 1=4 * V
CO2/ (P
H2-3 * P
CO-4 * P
CO2)
In formula, V
Coke(oven)gas 1Be the flow of coke(oven)gas 1, V
CO2CO for anaerobic reactor 3 generations
2Flow, P
H2, P
co, P
CO2Be respectively H
2, CO and CO
2Component in coke(oven)gas 1.
The anaerobic reactor 3 of the present embodiment is the CSTR reactor, and the temperature in anaerobic reactor 3 is 30～40 ℃.Organic waste 2 in the present embodiment is sewage plant sludge.In anaerobic reactor 3, mixing between organic waste 2 and coke(oven)gas 1 realizes by mechanical stirring.Step (c) impurity comprises N
2, H
2, CO, H
2O, CO
2And H
2S, the total mass mark of impurity is 9%.
Embodiment 3
A kind of method that realizes that synchronously coke-oven gas methanation and biogas original position are purified, its technique as shown in Figure 1, the method comprises the following steps:
(a) coke(oven)gas 1 is passed in the anaerobic reactor 3 of processing organic waste 2;
(b) in anaerobic reactor 3, organic waste 2 is degraded by microorganisms and produces CH
4And CO
2, the CO of generation
2Further with coke(oven)gas 1 in H
2In conjunction with generating CH
4, a small amount of CO and CO in coke(oven)gas 1
2Also utilized and H by microorganism
2Generate CH
4, obtain take CH4 as main biogas 4, wherein CH
4Massfraction greater than 90%;
(c) impurity in take CH4 as main biogas 4 by low temperature separation process obtains to have the Sweet natural gas 5 of high methane content (methane content is more than 98%).
Wherein, the flow that passes into the coke(oven)gas 1 of anaerobic reactor 3 in step (a) is determined by the following method:
V
Coke(oven)gas 1=4 * V
CO2/ (P
H2-3 * P
CO-4 * P
CO2)
In formula, V
Coke(oven)gas 1Be the flow of coke(oven)gas 1, V
CO2CO for anaerobic reactor 3 generations
2Flow, P
H2, P
co, P
CO2Be respectively H
2, CO and CO
2Component in coke(oven)gas 1.
The anaerobic reactor 3 of the present embodiment is the UASB reactor, and the temperature in anaerobic reactor 3 is 50～60 ℃.Organic waste 2 in the present embodiment is cow dung.In anaerobic reactor 3, mixing by gas stirring between organic waste 2 and coke(oven)gas 1 realizes.Step (c) impurity comprises N
2, H
2, CO, H
2O, CO
2And H
2S, the total mass mark of impurity is less than 10%.
Embodiment 4
A kind of method that realizes that synchronously coke-oven gas methanation and biogas original position are purified, its technique as shown in Figure 1, the method comprises the following steps:
(a) coke(oven)gas 1 is passed in the anaerobic reactor 3 of processing organic waste 2;
(b) in anaerobic reactor 3, organic waste 2 is degraded by microorganisms and produces CH
4And CO
2, the CO of generation
2Further with coke(oven)gas 1 in H
2In conjunction with generating CH
4, a small amount of CO and CO in coke(oven)gas 1
2Also utilized and H by microorganism
2Generate CH
4, obtain take CH4 as main biogas 4, wherein CH
4Massfraction be 90%;
(c) impurity in take CH4 as main biogas 4 by low temperature separation process obtains to have the Sweet natural gas 5 of high methane content (methane content is more than 98%).
Wherein, the flow that passes into the coke(oven)gas 1 of anaerobic reactor 3 in step (a) is determined by the following method:
V
Coke(oven)gas 1=4 * V
CO2/ (P
H2-3 * P
CO-4 * P
CO2)
In formula, V
Coke(oven)gas 1Be the flow of coke(oven)gas 1, V
CO2CO for anaerobic reactor 3 generations
2Flow, P
H2, P
CO, P
CO2Be respectively H
2, CO and CO
2Component in coke(oven)gas 1.
The anaerobic reactor 3 of the present embodiment is the CSTR reactor, and the temperature in anaerobic reactor 3 is 30～40 ℃.Organic waste 2 in the present embodiment is pig manure.In anaerobic reactor 3, mixing by the hollow-fibre membrane aeration between organic waste 2 and coke(oven)gas 1 realizes.Step (c) impurity comprises N
2, H
2, CO, H
2O, CO
2And H
2S, the total mass mark of impurity is less than 10%.
Claims (9)
1. a method that realizes that synchronously coke-oven gas methanation and biogas original position are purified, is characterized in that, the method comprises the following steps:
(a) coke(oven)gas and organic waste are passed in anaerobic reactor;
(b) in anaerobic reactor, organic waste is degraded by microorganisms and generates CH
4And CO
2, the CO of generation
2With the H in coke(oven)gas
2In conjunction with generating CH
4, under microbial process, the CO in coke(oven)gas and CO
2With H
2Generate CH
4, obtain with CH
4Be main biogas;
(c) separate the impurity of removing in step (b) gained biogas, obtain having the Sweet natural gas of high methane content.
2. a kind of method that realizes that synchronously coke-oven gas methanation and biogas original position are purified according to claim 1, is characterized in that, the flow that passes into the coke(oven)gas of anaerobic reactor in step (a) is determined by the following method:
V
Coke(oven)gas=4 * V
CO2/ (P
H2-3 * P
CO-4 * P
CO2)
Wherein, V
Coke(oven)gasBe the flow of coke(oven)gas, V
CO2CO for the anaerobic reactor generation
2Flow, P
H2, P
co, P
CO2Be respectively H
2, CO and CO
2Component in coke(oven)gas.
3. a kind of method that realizes that synchronously coke-oven gas methanation and biogas original position are purified according to claim 1, is characterized in that, the temperature in step (a) or the described anaerobic reactor of step (b) is 30～40 ℃ or 50～60 ℃.
4. a kind of method that realizes that synchronously coke-oven gas methanation and biogas original position are purified according to claim 1, is characterized in that, step (a) or the described anaerobic reactor of step (b) are CSTR reactor or UASB reactor.
5. a kind of method that realizes that synchronously coke-oven gas methanation and biogas original position are purified according to claim 1, is characterized in that, the described organic waste of step (b) is selected from sewage plant sludge, cow dung or pig manure.
6. a kind of method that realizes that synchronously coke-oven gas methanation and biogas original position are purified according to claim 1, it is characterized in that, in anaerobic reactor, mixing by mechanical stirring, gas stirring or hollow-fibre membrane aeration between organic waste and coke(oven)gas realizes.
7. a kind of method that realizes that synchronously coke-oven gas methanation and biogas original position are purified according to claim 1, is characterized in that, the described pressure-variable adsorption that is separated into of step (c) separates or low temperature separation process.
8. a kind of method that realizes that synchronously coke-oven gas methanation and biogas original position are purified according to claim 1, is characterized in that, the described impurity of step (c) comprises N
2, H
2, CO, H
2O, CO
2And H
2S, the total mass mark of impurity is less than 10%.
9. a kind of method that realizes that synchronously coke-oven gas methanation and biogas original position are purified according to claim 1, is characterized in that, the described Sweet natural gas with high methane content of step (c) refers to that the massfraction of methane is the Sweet natural gas more than 98%.
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Cited By (3)
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|---|---|---|---|---|
| CN104926062A (en) * | 2015-07-07 | 2015-09-23 | 云南师范大学 | Enrichment and domestication method of hydrogen nutrition type bacteria groups producing methane |
| CN105463048A (en) * | 2015-03-26 | 2016-04-06 | 高节义 | Method for preparing methane from coal combustion exhaust and device thereof |
| CN105602999A (en) * | 2015-11-13 | 2016-05-25 | 中国石油大学(北京) | System and method used for producing high-quality biological methane gas from biomass |
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Application publication date: 20130522 |