CN107413191A - A kind of method for catching of organic exhaust gas - Google Patents
A kind of method for catching of organic exhaust gas Download PDFInfo
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- CN107413191A CN107413191A CN201710238060.0A CN201710238060A CN107413191A CN 107413191 A CN107413191 A CN 107413191A CN 201710238060 A CN201710238060 A CN 201710238060A CN 107413191 A CN107413191 A CN 107413191A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/84—Biological processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/72—Organic compounds not provided for in groups B01D53/48 - B01D53/70, e.g. hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N1/00—Microorganisms, e.g. protozoa; Compositions thereof; Processes of propagating, maintaining or preserving microorganisms or compositions thereof; Processes of preparing or isolating a composition containing a microorganism; Culture media therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2256/00—Main component in the product gas stream after treatment
- B01D2256/24—Hydrocarbons
- B01D2256/245—Methane
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/59—Biological synthesis; Biological purification
Abstract
The present invention relates to a kind of method for catching of organic exhaust gas, comprise the following steps S1:Methane phase bacterium solution is well mixed with crude oil, obtains absorbing liquid;S2:The absorbing liquid is added in the simulator of stratum;S3:Organic exhaust gas is passed into the stratum simulator and handled, the temperature in the stratum simulator is 55 58 DEG C, and initial pressure is 9.8 10.2Mp.The present invention, which proposes, is passed through organic exhaust gas in discarded oil reservoir so that organic exhaust gas is preferably handled, while the method for promoting the microorganism gasification methane phase of residual oil in oil reservoir, is realized the efficient utilization of waste, is reached sustainable development truly.
Description
Technical field
The invention belongs to environmental protection and microorganism gasification technical field, and in particular to a kind of seizure side of organic exhaust gas
Method.
Background technology
Organic exhaust gas refers to the organic compound for including carbon hydrocarbon compound, benzene and benzene homologues, alcohols, ketone, phenols etc..It is main
To come from the generation of the industry such as vehicle exhaust, electronics, chemical industry, petrochemical industry, coating, printing, application, furniture, leather.Organic exhaust gas
Be usually present it is inflammable and explosive, poisonous and harmful, not soluble in water, be dissolved in organic solvent, the characteristics of intractability is big.It is organic handling
During waste gas generally using organic exhaust gas active-carbon adsorption treatment method, Production by Catalytic Combustion Process, catalytic oxidation, acid-base neutralization method,
A variety of principles such as plasma method.But these ways simply simply eliminate the harm of organic exhaust gas, but can not effectively carry
Rise the utilization rate of organic exhaust gas.
With the growth of world population, between the reduction of increase and Global Oil resource of the people to fossil energy demand
Contradiction increasingly highlight, and the irreducible oil in most of discarded oil reservoir has due to the increase rate of current recovery efficiency technique at present
Limit is without being utilized better, and in order to solve this problem, people have done substantial amounts of research, 2004 Oklahoma days in the end of the year
Report University of Oklahoma Suflita professor research work, i.e., by using microorganism species in itself and its metabolism
The comprehensive function of product and reservoir rockses, fluid, residual oil in oil reservoir is converted into natural gas, it is this directly to exploit or store up on the spot
The residual oil microorganism gasification technology deposited can make old filed come back to life;The LUCA companies of Colorado carry out coal or
Oil is converted into the research of natural gas, wherein showing Monument Butte oil fields result of study, the oil and water sample of the oil reservoir exist
When cultivating together, due to microbial action, there is a considerable amount of methane to produce in 60 days most started, then at 297 days,
Methane production reaches maximum, and this is similar in general microculture growth curve.Therefore how to be gasified using microorganism
Technology carries out deep development to old filed, and improve oil recovery factor has turned into the central task of current old filed exploitation.
It data show under natural endowment hydrocarbon and nonhydrocarbon biodegradation first order kinetics in oil measure layer
It is about 10 to learn speed constant-6-10-7It is more hydrocarbon than anaerobism in superficial underground environment (such as soot or superficial subterranean layer) between/year
Slow 10000 to 100000 times of the speed of degradation, therefore, in order under anaerobic by micro- life in oil reservoir by oil
Thing degraded produces the methane of commercial quantities, it is necessary to accelerate the technology of methane generation speed.
Because the process of alkane anaerobic biodegradation methane phase is a variety of bacterium participations, the reaction of multi-step, entirely degraded
The influence factor of journey reaction rate is very more, and most important influence factor includes:1st, the chemical property of hydrocarbon, particularly dissolubility,
Therefore it is exactly the intake ability for increasing microorganism to petroleum hydrocarbon to accelerate one of feasible method of crude oil anaerobic degradation speed, but micro-
Biology is lived in aqueous phase mostly, is implemented and is had any problem;2nd, the activity and richness of microorganism, in whole anaerobic degradation mistake
Cheng Zhong, related functional flora play key player, the whole degradation rate of abundance and activity influence of these functional microorganisms,
Therefore the rich of them can be increased to activate functional flora by adding nutriment in microbial augmentation oil exploitation technology
Fu Du, so as to accelerate the speed of crude oil anaerobic biodegradation, reach the Expected Results for improving oil utilization rate;3rd, the generation of microorganism
Thank to required electron acceptor, due to the gaseous metabolism of microorganism often need some electron acceptors (such as oxygen, nitrate, sulfate,
Ferric iron, organic acid etc.) participation, therefore the content for increasing electron acceptor is also to improve one of method of oil utilization rate;4、
The suppression of intermediate product is released, reaction is carried out and improve the key factor of hydrocarbon anaerobic degradation rate towards favourable direction.
At present, it is common mainly to be swashed using microorganism gasification technology raising recovery ratio field test technique by what is screened
Agent living and air by certain injection rate is continuous or slug formula in a manner of in injection testing block well, but do not consider crude oil,
The physics of stratum water and Rock Matrix, chemical composition and maintain micropopulation activity overall ecological environment but only by
The nutriment that injection original place Institute of Micro-biology needs is come to accelerate microorganism gas producing efficiency be that have ignored subsurface deposit is than relatively low
One complex environment, it can not effectively realize and allow microorganism aerogenesis on the spot in the earth formation, to improve the oil recovery of microorganism;
In addition tradition used in activator (such as glucose, starch, Dried Corn Steep Liquor Powder, diammonium hydrogen phosphate) largely be it is quick-acting,
Depletion rate is too fast, and the activator of injection is largely consumed near wellbore zone, and it is less to migrate to the amount of oil deposit deep part, causes oil
Tibetan medium and deep is facultative and anaerobic bacteria can not fully be activated.
Therefore, how organic exhaust gas to be combined with microorganism gasification technology, can efficiently utilizes organic exhaust gas, realized
Make the best use of everything, it is the purpose of the present invention that and can, which promotes the efficiency of Anaerobic Biodegradation of Hydrocarbon methane phase,.
The content of the invention
In view of this, it is an object of the invention to overcome the deficiencies of the prior art and provide a kind of seizure side of organic exhaust gas
Organic exhaust gas is passed through in discarded oil reservoir by method, this method, and not only organic exhaust gas preferably can be handled, while also promotes
The microorganism gasification methane phase efficiency of residual oil, realizes the efficient utilization of waste in oil reservoir, reach truly can
Sustainable development.
To realize object above, the present invention adopts the following technical scheme that:
A kind of method for catching of organic exhaust gas, comprises the following steps:
S1:Methane phase bacterium solution is well mixed with crude oil, obtains absorbing liquid;
S2:The absorbing liquid is added in the simulator of stratum;
S3:Organic exhaust gas is passed into the stratum simulator and handled, the temperature in the stratum simulator is
55-58 DEG C, initial pressure 9.8-10.2Mp.
Preferably:Methane phase bacterium solution described in S1 includes minimal medium and methane phase inoculum, and the methane phase connects
The preparation method of kind thing includes step:From production wellhead pumping oil water mixture, and it is enriched with the environment of sterile anaerobism
Culture, until when the environment of the sterile anaerobism has methane generation, obtain methane phase inoculum.
Preferably:The minimal medium includes the raw material of following parts by weight:
KH2PO4,5.0g;K2HPO4,5.0g;NH4Cl, 5.0g;NaCl, 10g;MgCl2,2.0g;CaCl2,0.1g;It is micro-
Secondary element solution, 5g;Deionized water is settled to 1L; pH:7.0-7.2;Resazurin, 1g;Boil deoxygenation, and with Hungate devices
High pure nitrogen is passed through, until culture medium is become colorless by pink colour, and adds Na2S9H2O (0.5g) and NaHCO3 (2.5g).
Further:The preparation method of the minimal medium comprises the following steps:
(1) it is the potassium dihydrogen phosphate, dipotassium hydrogen phosphate, ammonium chloride, sodium chloride, magnesium chloride, calcium chloride, trace element is molten
Liquid and resazurin are well mixed, and obtain mixed material;
(2) mixed material is settled to 1L with deionized water, and adjusts its pH value to 7.0-7.2, obtain mixed liquor;
(3) mixed liquor is boiled into deoxidation, then passes to high pure nitrogen, until the mixed liquor becomes colorless, finally
Add the nine water vulcanized sodium and sodium acid carbonate to stir, produce minimal medium.
Further:The volume ratio of methane inoculum and the minimal medium is 0.9- in the methane phase bacterium solution
1.2∶2。
Further:The volume ratio of methane phase inoculum described in S1 and the crude oil is 0.9-1.2: 2.
Preferably:Stratum simulator described in S2 includes:
Main reactor, for housing the absorbing liquid;
The pressure sensor and temperature sensor set is connected with the main reactor inwall;
The air inlet and gas liquid sampler body mouth being in fluid communication with the main reactor;
And it is coated on the heater on the outside of the main reactor.
Preferably:The temperature control scope of the stratum simulator is 35-70 DEG C, and temperature-controlled precision is ± 0.1 DEG C;Pressure control scope is
0-14MPa, pressure control precision are ± 0.1MPa.
Preferably:Temperature described in S3 is 55 DEG C, initial pressure 10Mpa, processing time 450d.
Beneficial effects of the present invention:
1st, the present invention, which proposes, is passed through organic exhaust gas in discarded oil reservoir so that organic exhaust gas is preferably handled, together
When promote residual oil in oil reservoir microorganism gasification methane phase method, realize the efficient utilization of waste, reach real meaning
Sustainable development in justice;
2nd, methane phase bacterium solution of the invention comes from the endogenous microbes in oil reservoir, because having it suitable for specific oil reservoir
Endogenous functional flora, secondly under the conditions of oil reservoir simulate, microorganism can with degrading crude oil generation methane, ethane, normal butane,
The organic gas such as iso-butane, furthermore organic gas is soluble in oil and promotes the generation of methane and the degraded of oil,
The composition of organic exhaust gas also significantly changes simultaneously.
3rd, the present invention establishes stratum simulator, and set stratum simulator temperature control scope be 35-70 DEG C because herein
The active highest of methanogen under temperature range, stratum simulator of the invention is also with pressure control effect in addition, the present invention's
The degraded methane phase of residual oil can be carried out in the simulator of stratum using the indigenous microorganism in crude oil completely, forefathers are compensate for and grind
Study carefully and focus mostly on analog temperature, and have ignored the influence of pressure in oil reservoir.
Brief description of the drawings
, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical scheme of the prior art
The required accompanying drawing used is briefly described in embodiment or description of the prior art.
Fig. 1 is the changes of contents of the methane of O1 control groups over time (ordinate is methane content, and abscissa is the time);
Fig. 2 is that (A wellblocks sample point, ordinate contain the changes of contents of methane over time for methane in Different treatments
Amount, abscissa is the time);
Fig. 3 is that (B wellblocks sample point, ordinate contain the changes of contents of methane over time for methane in Different treatments
Amount, abscissa is the time);
Fig. 4 is oil saturated hydrocarbon gas chromatography-mass spectrogram of sample point WYO2 processing in B wellblocks before simulation;
Fig. 5 is oil saturated hydrocarbon gas chromatography-mass spectrogram of sample point WYO2 processing in B wellblocks after simulation;
Embodiment
To make the object, technical solutions and advantages of the present invention clearer, technical scheme will be carried out below
Detailed description.Obviously, described embodiment is only part of the embodiment of the present invention, rather than whole embodiments.Base
Embodiment in the present invention, those of ordinary skill in the art are resulting on the premise of creative work is not made to be owned
Other embodiment, belong to the scope that the present invention is protected.
Crude oil and oil water mixture in the following embodiments of the present invention are all from pungent fault block oil well area of Shengli Oil Tiandong County, oil well
Using polymer displacement of reservoir oil production technique.Characteristics of reservoirs:Big terrestrial facies, sandstone, porosity 27.0 ± 1.0%, 65 DEG C -75 of formation temperature
DEG C, 3.5 DEG C/100m of geothermal gradient.9.98 ± 0.1MPa of difference between reservoir pressure and saturation pressure.0.9354 ± 0.02g/cm of oil density3, viscosity
221.4 ± 5.0mPas, saturation point 33.9 ± 0.7%, fragrance point 32.7 ± 0.7%, colloid 28.6 ± 0.6%, asphalitine
4.9 ± 0.1%.
Embodiment 1
A kind of method for catching of organic exhaust gas, comprises the following steps:
(1) methane phase inoculum is prepared:From production wellhead pumping oil water mixture, the oil water mixture after collection is in 4 DEG C
It is sealed, carries out enrichment culture after the completion of collection immediately;The concrete operations of enrichment culture are to take 50mL oil water mixtures to inject
Into the sterile anaerobism bottles of 120mL, while the oxygen retained in high pure nitrogen removal bottle is passed through with Hungate devices, then uses rubber
Plug stoppers bottleneck, is at strictly anaerobic state.And progress lucifuge culture in constant incubator is positioned over, used after 100 days
High pressure liquid phase tests and analyzes headspace gas, and when having detected methane generation, the methane phase using liquid in this bottle as enrichment culture connects
Kind thing;
(2) minimal medium is prepared:KH2PO4, 5.0g;K2HPO4, 5.0g;NH4Cl, 5.0g;NaCl, 10g;MgCl2,
2.0g;CaCl2, 0.1g;Trace element solution, 5g;Deionized water is settled to 1L;pH:7.0-7.2;Resazurin, 1g;Boil and remove
Oxygen, and high pure nitrogen is passed through with Hungate devices, until culture medium is become colorless by pink colour, obtain mixed liquor;By the mixing
Liquid boils deoxidation, then passes to high pure nitrogen, until the mixed liquor becomes colorless, be eventually adding 0.5g nine water vulcanized sodium and
2.5g sodium acid carbonate stirs, and produces minimal medium;
(3) above-mentioned methane phase inoculum is forwarded in minimal medium by 0.9: 2 volume ratio, obtains methanogen
Liquid, methane phase bacterium solution is well mixed with crude oil sample by 0.9: 2 volume ratio, absorbing liquid is obtained, the absorbing liquid is added to
Volume is in 115mL stratum simulator;
(4) organic exhaust gas is passed into the stratum simulator and handled, control the temperature in the simulator of stratum to be
55 DEG C, initial pressure 9.8Mp, and react 450d at this temperature and initial pressure.
Embodiment 2
A kind of method for catching of organic exhaust gas, comprises the following steps:
(1) methane phase inoculum is prepared:From production wellhead pumping oil water mixture, the oil water mixture after collection is in 4 DEG C
It is sealed, carries out enrichment culture after the completion of collection immediately;The concrete operations of enrichment culture are to take 50mL oil water mixtures to inject
Into the sterile anaerobism bottles of 120mL, while the oxygen retained in high pure nitrogen removal bottle is passed through with Hungate devices, then uses rubber
Plug stoppers bottleneck, is at strictly anaerobic state.And progress lucifuge culture in constant incubator is positioned over, used after 100 days
High pressure liquid phase tests and analyzes headspace gas, and when having detected methane generation, the methane phase using liquid in this bottle as enrichment culture connects
Kind thing;
(2) minimal medium is prepared:KH2PO4, 5.0g;K2HPO4, 5.0g;NH4Cl, 5.0g;NaCl, 10g;MgCl2,
2.0g;CaCl2, 0.1g;Trace element solution, 5g;Deionized water is settled to 1L;pH:7.0-7.2;Resazurin, 1g;Boil and remove
Oxygen, and high pure nitrogen is passed through with Hungate devices, until culture medium is become colorless by pink colour, obtain mixed liquor;By the mixing
Liquid boils deoxidation, then passes to high pure nitrogen, until the mixed liquor becomes colorless, be eventually adding 0.5g nine water vulcanized sodium and
2.5g sodium acid carbonate stirs, and produces minimal medium;
(3) above-mentioned methane phase inoculum is forwarded in minimal medium by 1: 2 volume ratio, obtains methanogen
Liquid, methane phase bacterium solution is well mixed with crude oil sample by 1: 2 volume ratio, absorbing liquid is obtained, the absorbing liquid is added to appearance
Product is in 125mL stratum simulator;
(4) organic exhaust gas is passed into the stratum simulator and handled, control the temperature in the simulator of stratum to be
55 DEG C, initial pressure 10Mp, and react 450d at this temperature and initial pressure.
Embodiment 3
A kind of method for catching of organic exhaust gas, comprises the following steps:
(1) methane phase inoculum is prepared:From production wellhead pumping oil water mixture, the oil water mixture after collection is in 4 DEG C
It is sealed, carries out enrichment culture after the completion of collection immediately;The concrete operations of enrichment culture are to take 50mL oil water mixtures to inject
Into the sterile anaerobism bottles of 120mL, while the oxygen retained in high pure nitrogen removal bottle is passed through with Hungate devices, then uses rubber
Plug stoppers bottleneck, is at strictly anaerobic state.And progress lucifuge culture in constant incubator is positioned over, used after 100 days
High pressure liquid phase tests and analyzes headspace gas, and when having detected methane generation, the methane phase using liquid in this bottle as enrichment culture connects
Kind thing;
(2) minimal medium is prepared:KH2PO4, 5.0g;K2HPO4, 5.0g;NH4Cl, 5.0g;NaCl, 10g;MgCl2,
2.0g;CaCl2, 0.1g;Trace element solution, 5g;Deionized water is settled to 1L;pH:7.0-7.2;Resazurin, 1g;Boil and remove
Oxygen, and high pure nitrogen is passed through with Hungate devices, until culture medium is become colorless by pink colour, obtain mixed liquor;By the mixing
Liquid boils deoxidation, then passes to high pure nitrogen, until the mixed liquor becomes colorless, be eventually adding 0.5g nine water vulcanized sodium and
2.5g sodium acid carbonate stirs, and produces minimal medium;
(3) above-mentioned methane phase inoculum is forwarded in minimal medium by 1.2: 2 volume ratio, obtains methanogen
Liquid, methane phase bacterium solution is well mixed with crude oil sample by 1.2: 2 volume ratio, absorbing liquid is obtained, the absorbing liquid is added to
Volume is in 125mL stratum simulator;
(4) organic exhaust gas is passed into the stratum simulator and handled, control the temperature in the simulator of stratum to be
58 DEG C, initial pressure 10.2Mp, and react 450d at this temperature and initial pressure.
In addition present invention also offers a kind of stratum simulator, including:Main reactor, for housing the absorbing liquid;With
The pressure sensor and temperature sensor that the main reactor inwall connection is set;The air inlet being in fluid communication with the main reactor
Mouth and gas liquid sampler body mouth;And it is coated on the heater on the outside of the main reactor.The temperature control model of the stratum simulator
Enclose for 35-70 DEG C, temperature-controlled precision is ± 0.1 DEG C;Pressure control scope is 0-14MPa, and pressure control precision is ± 0.1MPa.
3 groups of experimental examples are carried out below to verify with the experiment effect to the embodiment of the present invention 2:
The code name for setting reaction condition is as follows:
Be passed through by pressurized gas source into reactor the mixture of nitrogen and organic gas to 10Mp initial pressures be (W),
The specific composition of wherein organic gas has:Nitrogen, ethane, ethene, propane, normal butane, iso-butane, butylene, maleic -2, anti-fourth
Alkene -2 etc. (such as table 1,2);
Only be passed through by pressurized gas source into reactor nitrogen to 10Mp initial pressures be (M);
It is (Y) to add crude oil;
It is (N) to be added without crude oil;
Unsterilised is (O2);
Sterilize as (O1);
Eight processing are set according to the setting of above-mentioned code name, are followed successively by:WYO2 (embodiment 2), the WYO1 (blank pair of embodiment 2
According to);WNO2 (control group 1), WNO1 (blank control of control group 1);MYO2 (control group 2), MYO1 (blank control of control group 2);
MNO2 (control group 3), MNO1 (blank control of control group 3).And eight processing are prepared according to same method, sterilize blank
Control need to pass through continuous several times autoclaving.All processing have multigroup repetition, control 55 DEG C of temperature to be cultivated respectively.
In analogue reactor, 450d simulation culture is carried out to microbial degradation petroleum hydrocarbon, after simulation culture is completed
Analysis is sampled, carries out interpretation of result with GC-2010 gas chromatographs and GC-MS, concrete outcome is as Figure 1-5:
As shown in Figure 1, by the continuous culture of 450 days, control group WYO1, methane content by sterilizing remain
0 μm of ol, it is seen that in the presence of no microorganism, organic exhaust gas can not be captured, and oil can not be degraded to methane.
As shown in Figure 2, when cultivating early stage methane growing amount very little, beyond the determination limit of chromatogram, and can only be qualitative
Analysis.The microorganism of each processing after the laundering period of about 150 days starts that the growing amount of methane can be detected.WYO2 and
MYO2 has a quick period for producing methane, and methane production is very big;And WNO2 and MNO2 also have a quick generation
Methane period but methane production very little.WYO2 was wherein understood 175-375 days when by slope, methane is kept at a high speed
Generating rate, methane content is finally reached 1340 μm of ol.The final only about 50 μm of ol methane contents of WNO2, and and
MNO2 final methane content is close, and difference is not notable (P < 0.01).By slope learn MYO2 225-325 days when
Wait, methane keeps the generating rate of high speed, and compared with WYO2, methane content is finally 1140 μm of ol, WYO2 and MYO2 differences show
Write.
And in other groups of analogue reactor, by 450d culture, from figure 3, it can be seen that all processing are in early stage
A less methane can all be presented when 150d and produce speed, and one quick methane phase period can be undergone after which.
Wherein WYO2 remain high speed methane phase speed at 225-425 days, and the final content of culture methane passed through 450 days reaches about
2500μmol;And MYO2 microorganism kept higher methane phase speed at 250-425 days after one section of laundering period, pass through
The final methane content of continuous culture of 450 days reaches about 1700 μm of ol, the significant difference compared with WYO2 processing;Simultaneously
WNO2 and MNO2 processing also has a quick generation methane period about at 225-300 days, but methane production very little, most
Whole methane content is 190 μm of ol respectively, and 195 μm of ol differences are not notable.
The conclusion drawn from B wellblocks and A wellblocks is unanimous on the whole, and wherein WYO2, MYO2 and WNO2, MNO2 are respectively compared difference
It is extremely notable;WYO2 and MYO2 comparing differences are notable;WNO2 and MNO2 comparing differences are not notable.And from figure 1 it appears that through
The control group O1 methane contents for the continuous culture sterilizing for spending 450 days remain 0 μm of ol.We are from the WYO2 processing of B wellblocks
Saturated hydrocarbons GC-MS Tic are schemed knowable to (such as Fig. 4,5) before and after simulation, and WYO2 handles the obvious of the gaschromatographic mass spectrometry figure before degraded
Peak band is from left to right C11-C37 successively, and is distributed completely, and all alkane Abundances are higher, have content compared with horn of plenty
Saturated hydrocarbons, wherein branched paraffin and distribution of normal alkanes is intact, and such as, aromatic component is more for some complex advanced components
The series compounds such as PAH component preserve also more complete.And it was found from the collection of illustrative plates after degraded, the oil in analogue reactor
Receive the serious degraded of microorganism, the n-alkane overwhelming majority in saturated hydrocarbon component is disappeared, and branched paraffin is also partly disappeared
Consume, higher alkane series is very low by a certain degree of degraded, abundance.Crude oil saturated alkane chromatogram before anaerobic degradation with
Crude oil saturated alkane chromatogram after degraded is compared to there is notable difference, Pr and Ph abundance does not significantly change before and after degraded.
Table 1
The gas of principal component is passed through into analogue reactor by pressurized gas source to initial pressure, wherein WNO1, WNO2,
WYO1, WYO2 are passed through the mixture of nitrogen and organic gas, and wherein nitrogen accounts for major part;And MNO1, MNO2, MYO1, MYO2 are only
Nitrogen is passed through to identical initial pressure.As it can be seen from table 1 WNO1, WNO2, WYO1, WYO2 Ethane initial values all phases
Together, difference pole is not notable, and its value is 2.5mmol;And at the beginning of their Ethylene, Propane, n-Butane, iso-Butane
Initial value is also essentially identical, and difference pole is not notable, respectively 2mmol, 9.5mmol, 2.5mmol, 4.5mmol.
Ethane by 450d culture final WNO1, WNO2 does not change for 2.5mmol, and WYO1, WYO2
Ethane is respectively 2mmol, 3mmol, MYO2 0.5mmol, and this explanation Ethane is soluble in oil, while micro- life
Thing degraded oil generates Ethane again, and the control group to sterilize does not have Ethane generations;This front and rear change phase with Propane
Seemingly, the final contents of WNO1, WNO2 Propane are 9.3mmol, WYO1 8mmol, illustrate that it has been dissolved in oil, WYO2
For 9mmol, MYO2 0.5mmol, illustrate that by the degraded of microorganism Propane can be produced;
WNO1, WNO2 final contents of Ethylene are 2mmol, and WYO1, WYO2 final contents of Ethylene are respectively
1.3mmol, 1.1mmol, MYO2 0mmol, illustrate for Ethylene, and microbial degradation oil does not produce
Ethylene, and Ethylene is soluble in oil, and the effect of microorganism promotes Ethylene dissolving;And
The front and rear change of the n-Butane respectively handled, iso-Butane value and similar, the WNO1 of change before and after Ethylene value, WNO2's
N-Butane end values are 2.5mmol, and WYO1, WYO2 n-Butane end values are respectively 1.5mmol, 1.2mmol, MYO2
For 0.2mmol.This explanation n-Butane is soluble in oil, and microbial degradation oil can produce a small amount of n-
Butane, and the effect of microorganism promotes n-Butane and is dissolved in oil;WNO1, WNO2 iso-Butane are final
It is worth for 4.2mmol, WYO1, WYO2 iso-Butane end values are respectively 2.5mmol, 2mmol, MYO2 0.2mmol.This
Illustrate that iso-Butane is soluble in oil, and microbial degradation oil can produce a small amount of iso-Butane, and
And the effect of microorganism promotes iso-Butane and is dissolved in oil again.
From table 2 it can be seen that WNO1, WNO2, WYO1, WYO2 Butylene initial values are all identical, difference pole is not notable,
Its value is 8.8mmol;And their Trans-2-Butene, Cis-2-Butene, n-Pentane, iso-Pentane are initial
Value is also essentially identical, and difference pole is not notable, respectively 8.6mmol, 8.2mmol, 8.5mmol, 8.5mmol.By 450d training
Support, final WNO1, WNO2 Butylene values do not change for 8.8mmol, and WYO1, WYO2 Butylene are respectively
3.5mmol, 3mmol, MYO2 0.2mmol, this explanation Butylene is soluble in oil, while microbial degradation oil
Butylene is generated again, and the control group that the effect of microorganism promotes Ethylene dissolving and sterilized does not have
Butylene is produced;This n-Pentane with each processing, iso-Pentane front and rear change is similar, WNO1, WNO2 n-
The final content of Pentane, iso-Pentane is respectively 8.3mmol, 8.5mmol, WYO1 n-Pentane, iso-Pentane
Final content is respectively 3.5mmol, 3.5mmol, the final content of WYO2 n-Pentane, iso-Pentane be respectively 2mmol,
The final content of 3mmol, MYO2 n-Pentane, iso-Pentane is respectively 0.2mmol, 0.2mmol, and this illustrates n-
Pentane, iso-Pentane are soluble in oil, and microbial degradation oil can produce a small amount of n-
Pentane, iso-Pentane, and the effect of microorganism promotes n-Pentane, and iso-Pentane is dissolved in oil
In.
WNO1, WNO2 final content of Trans-2-Butene, Cis-2-Butene are respectively 8.6mmol, 8.2mmol,
The WYO1 final content of Trans-2-Butene, Cis-2-Butene is respectively 4mmol, 4.2mmol, WYO2 Trans-2-
The final content of Butene, Cis-2-Butene is respectively 4mmol, 4.2mmol, MYO2 Trans-2-Butene, Cis-2-
The final contents of Butene are respectively < 0.1mmol, < 0.2mmol, are illustrated for Trans-2-Butene, Cis-2-Butene
For, microbial degradation oil generates a small amount of Trans-2-Butene, Cis-2-Butene, and Trans-2-Butene,
Cis-2-Butene is soluble in oil.
Table 2
To sum up, the embodiment of the present invention 2 is by injecting the processing (WYO2) of the mixture of nitrogen and organic gas, with being only passed through
The processing (MYO2) of nitrogen is contrasted, while using sterilization treatment (O1) as control, show that the final methane of WYO2 processing contains
Amount illustrates that the addition of organic exhaust gas promotes microbial degradation petroleum hydrocarbon, so as to produce more methane gas apparently higher than MYO2
Body (such as Fig. 1,2).The injection with organic exhaust gas, Ethylene, iso-Pentane, n- can also be found out from (table 1,2)
The organic gas such as Pentane, Cis-2-Butene have been dissolved in oil, and this may change the property of petroleum hydrocarbon, so as to have
Beneficial to degraded aerogenesis of the microorganism to petroleum hydrocarbon, while the content of organic gas is also changed, and is largely had before and after degraded
Machine gas is reduced, methane content increase, significant difference.Be advantageous to the purification of organic gas, while preferably utilize organic gas
Reduce the discharge of pollution, and it can also be seen that coming before and after WYO2 processing petroleum hydrocarbon degradations to change significantly, from figure from Fig. 4,5
In it can be seen that crude oil in isoprenoid pristane (Pr) and phytane (Ph) structure it is more stable, often with n-heptadecane/
Pristane (nC17/Pr), the ratio of n-octadecane/phytane (nC18/Ph) determine the degraded situation of petroleum hydrocarbon, can be with from figure
Ratio is obviously reduced before and after finding out degraded, shows that the petroleum hydrocarbon of WYO2 processing is sufficiently degraded.
The foregoing is only a specific embodiment of the invention, but protection scope of the present invention is not limited thereto, any
Those familiar with the art the invention discloses technical scope in, change or replacement can be readily occurred in, should all be contained
Cover within protection scope of the present invention.Therefore, protection scope of the present invention should be based on the protection scope of the described claims.
Claims (9)
1. a kind of method for catching of organic exhaust gas, it is characterised in that comprise the following steps:
S1:Methane phase bacterium solution is well mixed with crude oil, obtains absorbing liquid;
S2:The absorbing liquid is added in the simulator of stratum;
S3:Organic exhaust gas is passed into the stratum simulator and handled, the temperature in the stratum simulator is 55-58
DEG C, initial pressure 9.8-10.2Mp.
2. the method for catching of organic exhaust gas according to claim 1, it is characterised in that methane phase bacterium solution described in S1 includes nothing
Machine salt culture medium and methane phase inoculum, the preparation method of the methane phase inoculum include step:From production wellhead pumping oil
Aqueous mixtures, and enrichment culture is carried out in the environment of sterile anaerobism, until when the environment of the sterile anaerobism has methane generation,
Obtain methane phase inoculum.
3. the method for catching of organic exhaust gas according to claim 1, it is characterised in that the minimal medium includes following
The raw material of parts by weight:
KH2PO4, 5.0g;K2HPO4, 5.0g;NH4Cl, 5.0g;NaCl, 10g;MgCl2, 2.0g;CaCl2, 0.1g;Trace element is molten
Liquid, 5g;Deionized water is settled to 1L;pH:7.0-7.2;Resazurin, 1g;Deoxygenation is boiled, and is passed through with Hungate devices high-purity
Nitrogen, until culture medium is become colorless by pink colour, and add Na2S·9H2O (0.5g) and NaHCO3(2.5g)。
4. the method for catching of organic exhaust gas according to claim 3, it is characterised in that the preparation side of the minimal medium
Method comprises the following steps:
(1) by the potassium dihydrogen phosphate, dipotassium hydrogen phosphate, ammonium chloride, sodium chloride, magnesium chloride, calcium chloride, trace element solution and
Resazurin is well mixed, and obtains mixed material;
(2) mixed material is settled to 1L with deionized water, and adjusts its pH value to 7.0-7.2, obtain mixed liquor;
(3) mixed liquor is boiled into deoxidation, then passes to high pure nitrogen, until the mixed liquor becomes colorless, be eventually adding
The nine water vulcanized sodium and sodium acid carbonate stir, and produce minimal medium.
5. the method for catching of organic exhaust gas according to claim 4, it is characterised in that methane is inoculated with the methane phase bacterium solution
The volume ratio of thing and the minimal medium is 0.9-1.2: 2.
6. the method for catching of organic exhaust gas according to claim 5, it is characterised in that methane phase inoculum described in S1 and institute
The volume ratio for stating crude oil is 0.9-1.2: 2.
7. the method for catching of organic exhaust gas according to claim 1, it is characterised in that stratum simulator described in S2 includes:
Main reactor, for housing the absorbing liquid;
The pressure sensor and temperature sensor set is connected with the main reactor inwall;
The air inlet and gas liquid sampler body mouth being in fluid communication with the main reactor;
And it is coated on the heater on the outside of the main reactor.
8. the method for catching of organic exhaust gas according to claim 1, it is characterised in that the temperature control scope of the stratum simulator
For 35-70 DEG C, temperature-controlled precision is ± 0.1 DEG C;Pressure control scope is 0-14MPa, and pressure control precision is ± 0.1MPa.
9. the method for catching of organic exhaust gas according to claim 1, it is characterised in that temperature described in S3 is 55 DEG C, initially
Pressure is 10Mpa, processing time 450d.
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