CN102408887A - Oil reservoir endogenous microorganism high-efficient activator and effect evaluation method thereof - Google Patents
Oil reservoir endogenous microorganism high-efficient activator and effect evaluation method thereof Download PDFInfo
- Publication number
- CN102408887A CN102408887A CN2011102669149A CN201110266914A CN102408887A CN 102408887 A CN102408887 A CN 102408887A CN 2011102669149 A CN2011102669149 A CN 2011102669149A CN 201110266914 A CN201110266914 A CN 201110266914A CN 102408887 A CN102408887 A CN 102408887A
- Authority
- CN
- China
- Prior art keywords
- activator
- oil
- activation
- reservoir
- effect
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Abstract
The invention relates to an oil reservoir endogenous microorganism high-efficient activator and an effect evaluation method thereof. The method comprises: the evaluation of activator components based on the economic and technical feasibility of the application of the activator; the evaluation of the activation effect of the activator based on the selective activation of oil reservoir endogenous microorganisms, the changes of biochemical indexes of oil and water samples, and the extent of the improvement of the crude oil recovery efficiency by physical simulation oil displacement experiments; the construction of detailed scoring rules of the activator and its effect with respect to the economic and technical feasibility, the selective activation of endogenous microorganisms, the biochemical indexes of oil and water samples, and physical simulation oil displacement; the construction of grade division methods of the activator and its effect based on the scoring conditions of each index. The evaluation method of the invention has the advantages of systemic and comprehensive evaluation indexes, low operation cost, and subsequent referential evaluation indexes, solves the current problems of the lack of an oil reservoir endogenous microorganism high-efficient activator and its standardized evaluation method, and provides an systemic and effective evaluation method for the smooth oil field application of the oil reservoir endogenous microorganism high-efficient activator.
Description
Technical field
The present invention relates to efficient activator of reservoir endogenous micro-organisms and Evaluation on effect method thereof, belong to microorganism biological technology and resource environment biological technical field.
Background technology
Along with many main oilfield in the world get into high water-cut stages; Be faced with problems such as the exploitation difficulty is big, cost of winning height; The microbe oil production technology is low with its cost, flexibility strong, payzone is hanged down advantages such as injury and non-environmental-pollution; Especially oil reservoir behind chemical flooding and exhausted oil reservoir carry out the great potential of intensified oil reduction once more, have caused the generally attention of countries in the world.Compare with the inoculating microbe oil recovery technique; The endogenous microbes oil recovery technique need not inject mikrobe in the stratum, only need to inject nutrition agent to oil reservoir, and inject the mikrobe that air in certain amount directly activates the stratum; Large-scale ground equipment need not added in the scene; Drop into lower, remarkable benefit, thereby have more wide application prospect.
Divide by function, reservoir endogenous micro-organisms mainly comprise hydrocarbon oxidation bacterium, aerobic saprophytic microorganism, anaerobically fermenting bacterium, nitrate reduction bacterium, sulphate reducing bacteria and methanogen etc.In oil reservoir, inject suitable activator nutrition system and aerated water can activate it through WIW, act on reservoir media, thereby improve oil recovery factor through these mikrobes itself and meta-bolites thereof.Therefore, target reservoir endogenous microbes ecologic structure is being investigated, confirmed under the prerequisite of displacement of reservoir oil technology, selecting suitable activator to activate the key link that the target flora becomes the endogenous microbes oil recovery technique.
Result of study shows at present, and many countries filter out multiple activator component to specific oil reservoir, and these systems mainly comprise small molecules carbon source, nitrogenous source, phosphorus source, growth factor and sulphate reducing bacteria supressor.The growth and breeding that is incorporated as reservoir endogenous micro-organisms of these activator provides available nutritive substance, and acts on oil reservoir through these mikrobes itself and meta-bolites thereof, considerable raising oil recovery factor.But, activator and the Evaluation on effect thereof that screens do not formed a cover efficient ways.
Summary of the invention
The present invention seeks to be system's effectively evaluating reservoir endogenous micro-organisms activator and effect thereof, a cover efficient activator of reservoir endogenous micro-organisms and an effect evaluation method thereof is provided.
The present invention is to be evaluated as main body structure efficient activator of reservoir endogenous micro-organisms and activation effect evaluation method thereof to the evaluation of activator component with to the activator activation effect.Improve four aspects of RF amplitude from economic and technical feasibility, reservoir endogenous micro-organisms selectively activate index, profit appearance biochemical index and physical simulation oil displacement experiment and made up activator and activation effect scoring detailed rules and regulations and activator and gradation of effects division methods thereof.
Efficient activator of reservoir endogenous micro-organisms provided by the invention and effect evaluation method thereof by forming to the evaluation of activator component with to evaluation two portions of activator activation effect, comprise the steps:
1st, the economic and technical feasibility of using according to activator is estimated the activator component;
Described economic and technical feasibility index comprises: the transportation of activator source, activator price, activator, storage, mining site use the influence that receives season, with compatibleness, activator aqueous solution filtration characteristic and the activation cycle of oil reservoir;
2nd, improve the RF amplitude according to reservoir endogenous micro-organisms selectively activate index, profit appearance biochemical index and physical simulation oil displacement experiment, the activator activation effect is estimated;
2.1st, the selectively activated evaluation index of reservoir endogenous micro-organisms comprises: total bacterium is dense, the quantity of hydrocarbon oxidation bacterium and methanogen increases, and sulphate reducing bacteria quantity increasing degree reduces less than an one magnitude or sulphate reducing bacteria quantity;
2.2nd, profit appearance biochemical index comprises: water sample activates back emulsification of crude oil dispersion effect, reducing crude oil viscosity, product acid and aerogenesis;
2.3rd, physical simulation oil displacement experiment raising oil recovery factor amplitude is in the simulating oil deposit rate of permeation, porosity, and oil saturation, under WS, the pressure and temperature parameter condition, oil recovery factor difference before and after activator adds; The physical simulation oil displacement experiment is with reference to SY-T 6424-2000. composite oil-displacing system performance test methods.
3rd, improve four aspects of RF amplitude from economic and technical feasibility, reservoir endogenous micro-organisms selectively activate index, profit appearance biochemical index and physical simulation oil displacement experiment and make up activator and activation effect scoring detailed rules and regulations thereof;
4th, according to the score situation of the 3rd each index of step, make up activator and gradation of effects division methods thereof.
More than the activator mining site described in the 1st step use and be meant by the influence in season: activator be difficult for because of the microbiological contamination of summer temp height corrupt, not because of the low and mobile variation influence field mix of winter temperature;
Activator and the compatibleness of oil reservoir described in the 1st step be meant, institute's component of inorganic salts of screen not with local water in divalent-metal ion Ca2+ and the Mg2+ formation that reacts precipitate, one side causes the waste of nutritive substance, stops up reservoir on the other hand; The measuring method of the compatibleness of activator and local water carries out with reference to GB 13200-91 " mensuration of water turbidity ";
Activator aqueous solution filtration characteristic described in the 1st step is with how many expressions of activator solid water insolubles content, and the mensuration of activator solid water insolubles content recommends index and analytical procedure to carry out according to SY/T 5329-94 petroclastic rock reservoir water water quality.
The activation of hydrocarbon oxidation bacterium described in the 2.1st step is meant that hydrocarbon oxidation bacterium quantity increases the 1-3 one magnitude or reaches 107cells/l in the water sample;
The effective inhibition to sulphate reducing bacteria described in the 2.1st step is meant that reservoir endogenous micro-organisms is after activator activates, and sulphate reducing bacteria quantity increasing degree reduces less than an one magnitude or sulphate reducing bacteria quantity;
The activation of the methanogen described in the 2.1st step is meant that methanogen quantity increases by 1 one magnitude in the water sample.
Total bacterium is dense, the mensuration of hydrocarbon oxidation bacterium, sulphate reducing bacteria and methanogen adopts the bacterium test bottle, carries out with reference to SY/T0532-93 oilfield injection water bacteria analyzing method disappearance dilution method.
Activation water sample emulsification of crude oil dispersion effect described in the 2.2nd step is meant degree of scatter, stability and the oil droplet size size of crude oil in water sample;
Described in the 2.2nd step reducing crude oil viscosity is meant the reduction amplitude of profit appearance viscosity of crude after activating, the mensuration of viscosity of crude is carried out with reference to SY/T 0520-1993. viscosity of crude mensuration-rotational viscosimeter method.
How much representing with pH of product acid amount described in the 2.2nd step, acetate and Determination on content employing HPLC are carried out.
The power of gas deliverability described in the 2.2nd step representes with factor of created gase,
The gas volume of factor of created gase=generation/activation liquid is long-pending,
The mensuration of gaseous fraction is carried out with reference to the compositional analysis vapor-phase chromatography of GB/T 13610-2003. Sweet natural gas.
Activator described in the 3rd step and activation effect scoring detailed rules and regulations thereof are shown in following table 1:
Annotate: T-activation cycle; A, total dense log value of bacterium before and after the A-water sample activates; B, hydrocarbon oxidation bacterium quantity log before and after the B-water sample activates; The activation water sample emulsification of crude oil degree of scatter that the C-observation is demarcated; The V-viscosity of crude reduces amplitude (per-cent); D-activates back profit appearance pH value; E, acetic acid content before and after the E-water sample activates; F-activates the volume of water sample; The F-water sample activates the gas volume that the back produces; G-activates the methane volume that water sample produces; R improves the RF amplitude.
Activator described in the 4th step and gradation of effects division methods thereof are shown in following table 2:
The activator described in the 4th step and the step of gradation of effects division methods thereof specifically comprise:
1) at first the back is activated and activated to activator component and oil reservoir compatibility, aqueous solution filtration characteristic, alkane degradation bacterium whether and have or not the viscosity reduction effect to estimate to crude oil, one of four are not up to standard, and this activator promptly is regarded as defective;
2), improve the RF amplitude and, it is divided into I-1 class, I-2 class, II-1 class, II-2 class, III-1 class and the agent of III-2 Class Activation the inhibition situation of sulphate reducing bacteria according to the physical simulation oil displacement experiment for qualified activator component.
3) in same Class Activation agent component, each item evaluation index score is added and carries out activator and Evaluation on effect thereof in the same rank.
This method is applicable to efficient activator of waterflooding reservoir endogenous microbes and Evaluation on effect thereof.
Advantage of the present invention and beneficial effect:
The present invention be directed to and activate efficient activator of reservoir endogenous micro-organisms and Evaluation on effect method thereof in the reservoir endogenous micro-organisms oil recovery technique, have that the evaluation index system is comprehensive, running cost is low and evaluating can be used as advantages such as subsequent reference.Solved the problem of efficient activator of present reservoir endogenous micro-organisms and effect standard evaluation method thereof disappearance, for the smooth mining site of the efficient activator of reservoir endogenous micro-organisms is used the system's effectively evaluating method that provides.
Description of drawings
Fig. 1 is efficient activator of reservoir endogenous micro-organisms and effect assessment schema thereof;
Fig. 2 is one group of different activator prescription activated profit appearance emulsification of crude oil dispersion effect; Wherein, (a) (b) (d) (e) (f) emulsification of crude oil dispersion effect " ++ ++ " of emulsification of crude oil dispersion effect " +++" of emulsification of crude oil dispersion effect " ++ " of emulsification of crude oil dispersion effect control group (c) emulsification of crude oil dispersion effect "+" of emulsification of crude oil dispersion effect "-";
Fig. 3 is stained with 3 profit appearance oil droplet under opticmicroscope after the activator activation to distribute and the crude oil emulsion type;
Fig. 4 is stained with 3 profit appearance oil droplet size distribution statistics after activator activates to learn description;
Fig. 5 is stained with 3 profit appearance oil droplet size distribution histogram after activator activates;
Fig. 6 is stained with 3 profit appearance emulsification of crude oil dispersion effect after activator activates;
Fig. 7 be stained with 3 profit appearance after activator activates middle level solution transmittance with the change curve of settling time;
Fig. 8 is the acetate high-efficient liquid phase chromatogram; Wherein, (a) standard small molecules acid high-efficient liquid phase chromatogram (b) profit appearance is activated preceding acetate high-efficient liquid phase chromatogram (c) profit appearance and is activated back acetate high-efficient liquid phase chromatogram;
Fig. 9 is stained with 3 profit appearance gaseous fraction relative content after activator activates to change.
Embodiment
Be stained with 3 efficient activator of high-heat heavy crude reservoir endogenous micro-organisms (Dried Corn Steep Liquor Powder 0.33%, Secondary ammonium phosphate 0.3 and saltpetre 0.2%) with Shengli Oil Field below and effect assessment is an example, the present invention is elaborated.% is m/V, i.e. activator quality/volume of water sample; Estimate schema and see accompanying drawing 1.
Embodiment 1 activator solid water insolubles content is measured
Reference standard SY/T 5329-94 petroclastic rock reservoir water water quality recommends index and analytical procedure to carry out.Filter membrane is put into zero(ppm) water soak 30min, and with distillation washing 3-4 time; Take out filter membrane and be placed in the baking oven, 90 ℃ of following 30min put into moisture eliminator and are cooled to room temperature after the taking-up, weigh; Activator (Dried Corn Steep Liquor Powder 0.33%, Secondary ammonium phosphate 0.3 and the saltpetre 0.2%) aqueous solution is packed in the filtering with microporous membrane tester; The filter membrane of constant weight is installed on the millipore filter after with water-wet; Vacuumize, make suction filtration device internal pressure remain on 0.1-0.15MPa, filter, and the record efflux volume; Weigh from filter taking-up filter membrane and oven dry with tweezers; Bringing formula into, to calculate the solid water insolubles content be 4mg/l.
The economic and technical feasibility that embodiment 2 activator are used
It all is solid powder particles that Shengli Oil Field is stained with 3 activation of block agent components, is convenient to transportation and storage, and it is poor to have solved the mobile property of liquid starting material in winter, problems such as batching difficulty; Solid water insolubles content 4mg/l meets oil-field flooding water water quality requirement; Selected component is composite nutrient, and has the effect of certain buffer pH, for microbial growth provides good nutrition and breeding environment; Activator component kind is few, has reduced buying and transit link; At present, 2500 yuan of t of Dried Corn Steep Liquor Powder market value
-1, 4000 yuan of t of Secondary ammonium phosphate
-1, 2800 yuan of t of SODIUMNITRATE
-1, being stained with 3 activation of block agent (Dried Corn Steep Liquor Powder 0.33%, Secondary ammonium phosphate 0.3% and saltpetre 0.2%) raw materials cost is 26.33 yuan of t
-1Nutritive medium.Through estimating, Shengli Oil Field is stained with the requirement that 3 activation of block agent meet economic and technical feasibility.
With reference to SY/T0532-93 oilfield injection water bacteria analyzing method disappearance dilution method, adopt that the bacterium test bottle is dense to total bacterium, the quantity of hydrocarbon oxidation bacterium, sulphate reducing bacteria and methanogen measures.
Shengli Oil Field is stained with 3 profit appearance after activator activates, and biological community structure is is obviously tightened and improved (seeing table 3): always bacterium is dense reaches 10
8Cellsml
-1, alkane degradation bacterium quantity increases to 10
7Cellsml
-1, methanogen quantity increases to 10
4Cellsml
-1, sulphate reducing bacteria quantity is effectively controlled.
Microbe population changed before and after table 3 profit appearance was activated
Visual inspection activates profit appearance emulsification of crude oil dispersion effect, and it is divided into "-" to " ++ ++ " five grades.The situation that has just added crude oil with the crude oil substratum is contrast, if crude oil is close to bottle wall or become a bulk of floating on to activate in the profit appearance, not only and fermented liquid in do not contain the former oil particles of dissolved, the more clarification that becomes is on the contrary then demarcated and is "-"; If crude oil is close to bottle wall or become a bulk of floating on to activate in the profit appearance, but contains dissolved crude oil small-particle in the fermented liquid, then demarcating is "+"; Activate in the profit appearance if crude oil is dissolved in a large number, but still exist more larger oil droplet to float on the fermented liquid liquid level, then demarcating is " ++ "; Activate in the profit appearance if crude oil is dissolved in a large number, and only exist a spot of little oil droplet to float on the fermented liquid liquid level, then demarcate and be " +++"; Activate in the profit appearance if crude oil is dissolved in a large number, and tiny evenly, the oscillation energy of wall built-up, particle does not form even suspension liquid and is the prepared Chinese ink shape, then demarcate and be " ++ ++ ".Instance is seen accompanying drawing 2.
According to this method; Shengli Oil Field is stained with 3 profit appearance after activator (Dried Corn Steep Liquor Powder 0.33%, Secondary ammonium phosphate 0.3 and saltpetre 0.2%) activates; Crude oil is dissolved in fermented liquid in a large number, and tiny evenly, the oscillation energy of wall built-up, particle does not form even suspension liquid and is the prepared Chinese ink shape.Therefore, being stained with 3 profit appearance activates back emulsification of crude oil dispersion effect through activator and demarcates and be " ++ ++ ".
In the oilfield water extraction process, the emulsification of crude oil and the reduction of oil water interfacial tension can improve profit biphase mobility ratio, improve the water displacing oil sweep efficiency; Simultaneously; Surfactant adsorbs in oil droplets, makes oil droplet be difficult for adhering to again the oil reservoir rock stratum, improves displacement efficiency.
Content of crude oil is carried out the certain multiple dilution to the crude oil fermented liquid in the based on crude substratum; Get 2ml in centrifuge tube after mixing gently; Add get after the dyeing of little water dissolubility or oil soluble staining fluid mixing a little on the slide glass under opticmicroscope, through microscopic analysis systems measurement statistics oil droplet size, (opticmicroscope is observed down to observe the crude oil emulsion type; Do not add deckglass, in order to avoid milk sap compressive strain or crush is split).
Be stained with 3 profit appearance microscopic examination result after activator activates dyeing and show and formed O/W type milk sap, see accompanying drawing 3.Oil droplet size statistic analysis result (seeing accompanying drawing 4) shows, oil droplet size minimum value 13.21 μ m, peak 83.65 μ m; Average 43.3658 μ m; Extreme difference 70.44 μ m, wherein 50% oil droplet size is less than 41.6340 μ m, and 97% oil droplet size is less than 76.2246 μ m.The oil droplet size distribution histogram is seen accompanying drawing 5.
Embodiment 6 colorimetric method for determining crude oil emulsions stability
Sedimentation or rising under action of gravity in the O/W type profit mixed system is separated inside and outside causing, and the settling velocity of phase is followed Stokes equation v=2r in the milk sap
2(ρ
2-ρ
1) g/9 η, v is the settling velocity of disperse phase, r is the radius of dispersed phase drop, ρ
2, ρ
1Be the density of disperse phase and dispersion medium, η is the viscosity of dispersion medium
[61]Can find out by formula, square being directly proportional of settling velocity and dispersant liquid drop radius, therefore, the disperse phase particle diameter is more little, and mixed system is stable more, and separation time is long more.
Testing sample requires: the emulsification degree of scatter that observation is demarcated crude oil in the crude oil fermented liquid is " +++" or " ++ ++ ".
Be stained with 3 profit appearance crude oil homodisperse in whole fermented liquid medium after activator activates; And tiny evenly, the oscillation energy of wall built-up, particle does not form even suspension liquid and is the prepared Chinese ink shape; The emulsification dispersion effect that demarcate to activate crude oil in the profit appearance according to observation is " ++ ++ ", sees accompanying drawing 6.Measuring result's (seeing accompanying drawing 7) shows; Crude oil Granula Subsidence Time and middle level solution transmittance curve show absorbancy basically with time relation in direct ratio; Explain that the milk sap particle diameter ratio that forms is less than homogeneous and granularity, oil-water mixture has stability preferably.
The mensuration of experiment of embodiment 7 reducing crude oil viscosities and viscosity
Add 30g crude oil to the 250ml Erlenmeyer flask, 30ml activates water sample, the activation substratum of the fresh oil reservoir local water preparation of 40ml; The simulating oil deposit reservoir temperature; The 150r/min concussion was cultivated 15 days, and the leachate body is measured viscosity with BROOKFIELD CAP-2000+ viscometer down in FT after the crude oil centrifuge dehydration; With water replace water sample to shake bottle (autoclaving) be control group, the calculating viscosity break ratio.
Be stained with 3 crude oil initial viscosity 1007.25mPas, behind the viscosity reduction, viscosity of crude is 630.67mPas, and viscosity break ratio reaches 37.39%.Viscosity of crude reduces, its flowing property be improved significantly; Simultaneously, because the oil-water two-phase flow degree has increased the swept volume of displacing fluid to a certain extent than reducing, be beneficial to the extraction of more crude oil
Embodiment 8 produces the efficient liquid phase chromatographic analysis of acidimetric estimation and acetate
Produce how much representing of acid amount, measure the pH value with pH meter with pH; Acetate and Determination on content adopt HPLC to carry out.
(1) liquid-phase chromatographic analysis condition chromatographic column: Eclipse XDB-C18 reversed-phase column, 150mm * 4.6mm; Moving phase: 0.015mol/L potassium dihydrogen phosphate buffer solution-acetonitrile solution (98: 2, V/V), regulate pH to 2.30 (the reagent water is a ultrapure water) with phosphoric acid; Flow velocity: 1mL/min; Sample size: 20 μ L; Detect wavelength: 210nm;
(2) sample preparation
The oil field water sample: accurately measure 300ml oil field water sample, 40 ℃ of underpressure distillation are analyzed with carrying out HPLC behind the 0.45 μ m membrane filtration to 30ml.
Activate profit appearance: get and activate profit appearance 20mL, remove crude oil with common filter paper filtering, the centrifugal 10min of 10000rpm, supernatant carry out the HPLC analysis after with the membrane filtration of 0.45 μ m.
Be stained with 3 profit appearance after activator activates, pH reduces to 6.5 by initial 7.2; Profit appearance is after activator activates, and acetic acid content increases to 200mg/l by initial 30mg/l.The acetic acid high-efficient liquid phase chromatogram is seen accompanying drawing 8.
The acidic substance of microorganisms mainly are some short chain organic acids such as formic acid, acetate, propionic acid, butyric acid, valeric acid and isomery thereof the low molecular weight acid that becomes to grade.These acidic substance can dissolve sedimentary carbonate in the oil reservoir rock hole effectively, increase the porosity and the rate of permeation of oil reservoir, improve the flowing environment of crude oil.Acid is reacted the CO that produces with carbonatite
2Can increase sand pressure; Portion gas is dissolved in and makes its expansion in the crude oil, can reduce viscosity of crude, improves its flowability, thereby improves the RF of crude oil.
Acetate is that multiple mikrobe common metabolic produces and the synthesis result that consumes in anaerobic environment, is the important indicator of reaction reservoir endogenous micro-organisms growth metabolism.Acetate be the meta-bolites of anaerobion also be the important substrate of further synthesizing methane, the variation of acetic acid content can reflect the dynamic change of reservoir endogenous micro-organisms in the profit appearance activation process indirectly.
The gas chromatographic analysis of embodiment 9 gas production rate mensuration and gaseous fraction
Collect the gas that produces in the mikrobe activation process through the gas collection bag, with the power of factor of created gase (gas volume of generation/activation liquid is long-pending) expression gas deliverability.
The mensuration of gaseous fraction is carried out with reference to the compositional analysis vapor-phase chromatography of GB/T 13610-2003. Sweet natural gas.
(1) standard gas and composition are seen table 4
(2) detection method-vapor-phase chromatography
O
2And CO
2Detect with the TCD detector.Testing conditions: gac packed column (2m); Carrier gas 99.99% nitrogen, flow rate of carrier gas 50ml/min; 200 ℃ of injector temperatures, 150 ℃ of detector temperatures, 150 ℃ of column temperatures, electric current 75uA; Sample size 1ml.
CH
4, C
2H
6And C
4H
10Detect with fid detector.Testing conditions: Vitabiosol packed column (4m); Carrier gas: 99.99% nitrogen, flow rate of carrier gas 30ml/min, air velocity 0.5kg/cm2, hydrogen flow rate 0.7kg/cm2; 200 ℃ of injector temperatures, 200 ℃ of detector temperatures, 100 ℃ of column temperatures; Sample size 1ml.
Be stained with 3 profit appearance after activator activates, factor of created gase (gas volume of generation/activation liquid is long-pending) 50%; Compare O with control group
2Reduce to 0.2%, CO by 1.6%
2Rise to 46.5%, CH by 2.6%
4Rise to 2.26% by 0.02%.See accompanying drawing 9.
The gas that the reservoir endogenous micro-organisms metabolism produces mainly contains CO
2, CH
4, H
2And N
2, these gases can exist with mixed phase or non-mixed phase form in oil reservoir.When reservoir pressure was higher, these gases mainly were dissolved in the oil phase, can reduce the viscosity of oil phase, improved the crude oil flow ability.When reservoir pressure was low, biogas had part again and exists with the free gas form, has increased the saturation ratio of non-wetting phase, has improved the relative permeability of oil phase.Simultaneously, the Jamin effect of bubble also can increase flow resistance, improves and injects ripples and efficient.
Methanogen is one type of ancient bacterium of extreme anaerobism; Common and other bacteriums form a kind of special syntrophism relation; Can inorganic or organic cpds anaerobically fermenting be changed into methane and carbonic acid gas, be in the least significant end of anaerobe chain, comparatively common in the anaerobic environment of oil reservoir depths.Therefore, the generation of methane is a whole reservoir endogenous micro-organisms ecological chain activated index effectively indirectly.
The purpose of physical simulation experiment research is further formula system to be optimized, and confirms parameters such as activator IR, air IR through experimental study, for overall experimental program provides optimum parameter.
(1) laboratory apparatus
20cm * 2.5cm sand-packed model, LB-10 constant-flux pump, piston-type intermediate receptacle, thermostat container, precision pressure table, gas meter, graduated cylinder, stopwatch, range 5mL scale test tube etc.
(2) fluid is used in activator and experiment
Activator soln: the result prepares activator soln according to shake flat experiment, measuring density, viscosity, pH and surface tension.
Displacing fluid: test block produced liquid in oil well (coarse filter paper filtration).Carry out the microorganism concn analysis, guarantee to have the mikrobe of enough concentration, require to shake a bottle activation experiment evaluation and have preferably after the effect effective.
Crude oil: test block dewatered oil needs measuring density, viscosity, the content of wax and zero pour before using.
(3) saturated local water
Regulation with reference to the saturated standard SY/T5336 of natural rock sample is carried out.
(4) experiment basis parameter measurement
Volume of voids, porosity, perm-plug method, water are surveyed the measurement of underlying parameters such as rate of permeation, oil survey rate of permeation, initial oil saturation and are carried out with reference to conventional oil displacement experiment method.
(5) displacement of reservoir oil flow process
1) sand-packed model: with reference to the oil reservoir rate of permeation, confirm silica sand proportioning and compaction pressure, adopt and wetly to fill out the method compacting and fill and present model, Guan Chong behind record dry sand amount, the water yield, blank pipe weight and the filling damp sand.
Consolidated core: with reference to the oil reservoir rate of permeation, choose the approaching rock core of gas-phase permeation rate, claim dry weight, add the 4.5MPa ring and press.
2) vacuumize 1 hour, the saturated local water of constant voltage (sand-packed model 3MPa, synthetic core is pressed with ring), 1ml/min water is surveyed rate of permeation, and the title weight in wet base is calculated volume of voids, porosity.
3) the single pump of 0.2ml/min, is observed pressure and is suitably raised speed to seeing oil two-tube saturated oil, continues displacement to almost no longer water outlet, calculates SWB.
4) 0.1ml/min survey oil oozes, pressure when record is stablized.
5) build the pressure to oily consolidation pressure, wellblock injection water drive is replaced, and to double water ratio 98%, injects 0.2PV and activates prescription and 0.2PV air (vapour-liquid ratio 1: 1).(normal pressure is the metering gas vol down: open exit end, close exit end behind the injection 0.1PV air, continue to annotate the 0.1PV air)
(6) Data Processing in Experiment
1) oil displacement efficiency calculation formula
In the formula: η-oil displacement efficiency, %;
N
p-cumulative recovery, ml;
The original oleaginousness of N-, ml.
2) draw injection pressure, RF and water ratio and injection pore volume multiple relation curve.
3 oil reservoirs and fluid condition are stained with in simulation, adopt the back-up sand core under FT (60 ℃) and reservoir pressure (13.0MPa), carry out the physical simulation oil displacement experiment to being stained with 3 efficient activator of reservoir endogenous micro-organisms.Physical simulation oil displacement experiment model parameter is seen table 5.
Table 5 physical simulation oil displacement experiment model parameter
Table 6 can be found out; The physical simulation oil displacement experiment shows that raising RF amplitude is between 5%-7%; The oil displacement efficiency of endogenous microbes (6.9%) is superior to the effect (5.8%) of not distribution after the distribution, and this possibly be because the displacement of reservoir oil effect of hydrocarbon oxidation bacterium has been strengthened in the supply of air causes.
Table 6 physical simulation oil displacement experiment improves the RF effect
Annotate: Physical Experiment model and experimental data are from Oil Mined Technology Research Inst., Shengli Oil Field microbe oil production center
3 activation of block agent are stained with by embodiment 11 Shengli Oil Fields and gradation of effects is divided
Carry out grade classification according to activator and effect thereof scoring detailed rules and regulations and activator and gradation of effects division methods thereof to being stained with 3 activation of block agent and effect thereof, see table 7 for details.The result shows that the activator that screens is the agent of I-1 Class Activation, score 81 minutes.
Table 7 is optimized activator component each index score and grade
Claims (8)
1. efficient activator of reservoir endogenous micro-organisms and effect evaluation method thereof is characterized in that this method comprises the steps: by forming to the evaluation of activator component with to evaluation two portions of activator activation effect
1st, the economic and technical feasibility of using according to activator is estimated the activator component;
Described economic and technical feasibility index comprises: the transportation of activator source, activator price, activator, storage, mining site use the influence that receives season, with compatibleness, activator aqueous solution filtration characteristic and the activation cycle of oil reservoir;
2nd, improve the RF amplitude according to reservoir endogenous micro-organisms selectively activate index, profit appearance biochemical index and physical simulation oil displacement experiment, the activator activation effect is estimated;
2.1st, the selectively activated evaluation index of reservoir endogenous micro-organisms comprises: total bacterium is dense, the quantity of hydrocarbon oxidation bacterium and methanogen increases, and sulphate reducing bacteria quantity increasing degree reduces less than an one magnitude or sulphate reducing bacteria quantity;
2.2nd, profit appearance biochemical index comprises: water sample activates back emulsification of crude oil dispersion effect, reducing crude oil viscosity, product acid and aerogenesis;
2.3rd, physical simulation oil displacement experiment raising oil recovery factor amplitude is under simulating oil deposit rate of permeation, porosity, oil saturation, WS, pressure and temperature parameter condition, oil recovery factor difference before and after activator adds;
3rd, improve four aspects of RF amplitude from economic and technical feasibility, reservoir endogenous micro-organisms selectively activate index, profit appearance biochemical index and physical simulation oil displacement experiment and make up activator and activation effect scoring detailed rules and regulations thereof;
4th, according to the score situation of the 3rd each index of step, make up activator and gradation of effects division methods thereof.
2. method according to claim 1 is characterized in that,
Activator mining site described in the 1st step is used and be meant by the influence in season: activator is difficult for because of summer temp height microbiological contamination corruption, not because of the low and mobile variation influence field mix of winter temperature;
The 1st the step described in activator and oil reservoir compatibleness be meant, the component of inorganic salts of screening not with the oil reservoir local water in divalent-metal ion Ca
2+And Mg
2+React and form deposition; The measuring method of the compatibleness of activator and local water carries out with reference to the mensuration of GB 13200-91 water turbidity;
Activator aqueous solution filtration characteristic described in the 1st step is with how many expressions of activator solid water insolubles content, and the mensuration of activator solid water insolubles content recommends index and analytical procedure to carry out according to SY/T 5329-94 petroclastic rock reservoir water water quality.
3. method according to claim 1 is characterized in that,
The activation of hydrocarbon oxidation bacterium described in the 2.1st step is meant that hydrocarbon oxidation bacterium quantity increases the 1-3 one magnitude or reaches 10 in the water sample
7Cells/l;
The effective inhibition to sulphate reducing bacteria described in the 2.1st step is meant that reservoir endogenous micro-organisms is after activator activates, and sulphate reducing bacteria quantity increasing degree reduces less than an one magnitude or sulphate reducing bacteria quantity;
The activation of the methanogen described in the 2.1st step is meant that methanogen quantity increases by 1 one magnitude in the water sample;
Total bacterium is dense, the mensuration of hydrocarbon oxidation bacterium, sulphate reducing bacteria and methanogen adopts the bacterium test bottle, carries out with reference to SY/T0532-93 oilfield injection water bacteria analyzing method disappearance dilution method.
4. method according to claim 1 is characterized in that,
Profit appearance described in the 2.2nd step is activated back emulsification of crude oil dispersion effect and is meant degree of scatter, stability and the oil droplet size size of crude oil in water sample;
Described in the 2.2nd step reducing crude oil viscosity is meant the reduction amplitude of profit appearance viscosity of crude after activating, the mensuration of viscosity of crude is carried out with reference to SY/T 0520-1993. viscosity of crude mensuration-rotational viscosimeter method;
How much representing with pH of product acid amount described in the 2.2nd step, acetate and Determination on content employing HPLC are carried out;
The power of gas deliverability described in the 2.2nd step representes with factor of created gase,
The gas volume of factor of created gase=generation/activation liquid is long-pending,
The mensuration of gaseous fraction is carried out with reference to the compositional analysis vapor-phase chromatography of GB/T 13610-2003. Sweet natural gas.
5. method according to claim 1 is characterized in that, activator described in the 3rd step and activation effect scoring detailed rules and regulations thereof are as shown in the table:
In the table, T-activation cycle; A, total dense log value of bacterium before and after the A-water sample activates; B, hydrocarbon oxidation bacterium quantity log before and after the B-water sample activates; The activation water sample emulsification of crude oil degree of scatter that the C-observation is demarcated; The V-viscosity of crude reduces amplitude (per-cent); D-activates back profit appearance pH value; E, acetic acid content before and after the E-water sample activates; F-activates the volume of water sample; The F-water sample activates the gas volume that the back produces; G-activates the methane volume that water sample produces; R improves the RF amplitude.
6. method according to claim 1 is characterized in that, activator and the gradation of effects division methods thereof described in the 4th step is as shown in the table:
7. method according to claim 1 is characterized in that, the activator described in the 4th step and the concrete steps of gradation of effects division methods thereof comprise:
1) at first the back is activated and activated to activator component and oil reservoir compatibility, activator aqueous solution filtration characteristic, hydrocarbon oxidation bacterium whether and have or not the viscosity reduction effect to estimate to crude oil, one of four are not up to standard, and this activator promptly is regarded as defective;
2), improve the RF amplitude and, it is divided into I-1 class, I-2 class, II-1 class, II-2 class, III-1 class and the agent of III-2 Class Activation the inhibition situation of sulphate reducing bacteria according to the physical simulation oil displacement experiment for qualified activator component;
3) in same Class Activation agent component, each item evaluation index score is added and carries out activator and Evaluation on effect thereof in the same rank.
8. the method for claim 1 is characterized in that, this method is applicable to efficient activator of waterflooding reservoir endogenous microbes and Evaluation on effect thereof.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011102669149A CN102408887A (en) | 2011-09-09 | 2011-09-09 | Oil reservoir endogenous microorganism high-efficient activator and effect evaluation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011102669149A CN102408887A (en) | 2011-09-09 | 2011-09-09 | Oil reservoir endogenous microorganism high-efficient activator and effect evaluation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102408887A true CN102408887A (en) | 2012-04-11 |
Family
ID=45911243
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011102669149A Pending CN102408887A (en) | 2011-09-09 | 2011-09-09 | Oil reservoir endogenous microorganism high-efficient activator and effect evaluation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102408887A (en) |
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103805153A (en) * | 2012-11-12 | 2014-05-21 | 中国石油天然气股份有限公司 | Nucleus-containing nutritional gel |
| CN104404086A (en) * | 2014-10-27 | 2015-03-11 | 中国石油化工股份有限公司 | Method for regulating and controlling oil-reservoir microbe metabolism for producing biogas |
| CN104502524A (en) * | 2014-10-27 | 2015-04-08 | 中国石油化工股份有限公司 | Screening method of indigenous microbe activator with profile control function |
| CN104695919A (en) * | 2015-02-15 | 2015-06-10 | 南开大学 | Method for selectively activating main beneficial bacteria in oil deposit and keeping high concentration |
| CN105156083A (en) * | 2015-10-23 | 2015-12-16 | 中国石油化工股份有限公司 | Indigenous microorganism drive reservoir adaptability evaluating method |
| CN105255988A (en) * | 2015-10-23 | 2016-01-20 | 中国石油化工股份有限公司 | Screening method of microorganism long-acting activating agent for oil extraction |
| CN105255734A (en) * | 2015-09-28 | 2016-01-20 | 中国石油化工股份有限公司 | Endogenous microbial activator with profile control function and effect evaluation method thereof |
| CN105350947A (en) * | 2015-09-28 | 2016-02-24 | 中国石油化工股份有限公司 | Method for evaluating microorganism oil-displacement field test effects |
| CN106226196A (en) * | 2016-07-14 | 2016-12-14 | 中国石油大学(北京) | The screening technique of endogenous microbes activator and application thereof under High Temperature High Pressure system |
| CN107558971A (en) * | 2016-07-01 | 2018-01-09 | 中国石油化工股份有限公司 | A kind of method that medium to high permeable reservoir endogenous micro-organisms recover the oil |
| CN107795307A (en) * | 2016-08-30 | 2018-03-13 | 中国石油化工股份有限公司 | A kind of method that heavy oil wells endogenous microbes improve well yield |
| CN107795305A (en) * | 2016-08-30 | 2018-03-13 | 中国石油化工股份有限公司 | A kind of method that regulation and control reservoir endogenous micro-organisms diversity improves recovery ratio |
| CN108219765A (en) * | 2018-01-11 | 2018-06-29 | 侯岱言 | A kind of reservoir endogenous micro-organisms activator and its flooding method based on inorganic salts |
| CN109358157A (en) * | 2018-09-29 | 2019-02-19 | 陕西延长石油(集团)有限责任公司研究院 | CO2The screening of the endogenous microbes activator of oil reservoirs and activation effect evaluation method and application |
| CN110739032A (en) * | 2019-10-28 | 2020-01-31 | 中国石油化工股份有限公司 | Evaluation method of active bottom water heavy oil reservoir microorganism huff-puff injection agent |
| CN110805417A (en) * | 2019-11-04 | 2020-02-18 | 中国石油化工股份有限公司 | Method for regulating and controlling growth and metabolism rules of endogenous microorganisms in oil reservoir |
| CN110863809A (en) * | 2019-10-22 | 2020-03-06 | 中国石油化工股份有限公司 | Method for compositely displacing oil by utilizing electric field and microorganisms |
| CN111985735A (en) * | 2019-05-05 | 2020-11-24 | 中国石油天然气股份有限公司 | Endogenous microbial oil displacement oil reservoir screening and evaluating method |
| CN112576229A (en) * | 2020-12-11 | 2021-03-30 | 大庆油田有限责任公司 | Method for producing methane from underground crude oil by utilizing microbial action |
| CN112983367A (en) * | 2021-03-15 | 2021-06-18 | 西北大学 | Application of toxoplasma bacteria in evaluation of microbial oil displacement field test effect and method thereof |
| CN114427400A (en) * | 2020-09-21 | 2022-05-03 | 中国石油化工股份有限公司 | Method for improving development effect of biological limestone oil reservoir by utilizing acid-producing microorganisms |
| CN116285927A (en) * | 2023-03-28 | 2023-06-23 | 华东理工大学 | Method for improving metabolism activity of microorganisms in thickened oil and application |
-
2011
- 2011-09-09 CN CN2011102669149A patent/CN102408887A/en active Pending
Non-Patent Citations (2)
| Title |
|---|
| 《化工学报》 20110715 高配科等 "胜利油田沾3区块内源微生物激活剂的筛选、优化及效果评价" 第2005-2012页 1-9 第62卷, 第7期 * |
| 高配科等: ""胜利油田沾3区块内源微生物激活剂的筛选、优化及效果评价"", 《化工学报》 * |
Cited By (31)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103805153B (en) * | 2012-11-12 | 2016-06-08 | 中国石油天然气股份有限公司 | Containing core nutrition frozen glue |
| CN103805153A (en) * | 2012-11-12 | 2014-05-21 | 中国石油天然气股份有限公司 | Nucleus-containing nutritional gel |
| CN104404086A (en) * | 2014-10-27 | 2015-03-11 | 中国石油化工股份有限公司 | Method for regulating and controlling oil-reservoir microbe metabolism for producing biogas |
| CN104502524A (en) * | 2014-10-27 | 2015-04-08 | 中国石油化工股份有限公司 | Screening method of indigenous microbe activator with profile control function |
| CN104695919A (en) * | 2015-02-15 | 2015-06-10 | 南开大学 | Method for selectively activating main beneficial bacteria in oil deposit and keeping high concentration |
| CN104695919B (en) * | 2015-02-15 | 2018-02-16 | 南开大学 | A kind of method for selectively activating the main beneficial bacterium of oil reservoir and keeping high concentration |
| CN105255734A (en) * | 2015-09-28 | 2016-01-20 | 中国石油化工股份有限公司 | Endogenous microbial activator with profile control function and effect evaluation method thereof |
| CN105350947A (en) * | 2015-09-28 | 2016-02-24 | 中国石油化工股份有限公司 | Method for evaluating microorganism oil-displacement field test effects |
| CN105350947B (en) * | 2015-09-28 | 2017-10-03 | 中国石油化工股份有限公司 | A kind of evaluation method of microbial oil displacement field test results |
| CN105156083B (en) * | 2015-10-23 | 2017-07-18 | 中国石油化工股份有限公司 | A kind of evaluation method of endogenous microbes oil reservoirs adaptability |
| CN105255988A (en) * | 2015-10-23 | 2016-01-20 | 中国石油化工股份有限公司 | Screening method of microorganism long-acting activating agent for oil extraction |
| CN105156083A (en) * | 2015-10-23 | 2015-12-16 | 中国石油化工股份有限公司 | Indigenous microorganism drive reservoir adaptability evaluating method |
| CN107558971B (en) * | 2016-07-01 | 2019-07-23 | 中国石油化工股份有限公司 | A kind of method that medium to high permeable reservoir endogenous micro-organisms recover the oil |
| CN107558971A (en) * | 2016-07-01 | 2018-01-09 | 中国石油化工股份有限公司 | A kind of method that medium to high permeable reservoir endogenous micro-organisms recover the oil |
| CN106226196A (en) * | 2016-07-14 | 2016-12-14 | 中国石油大学(北京) | The screening technique of endogenous microbes activator and application thereof under High Temperature High Pressure system |
| CN107795307A (en) * | 2016-08-30 | 2018-03-13 | 中国石油化工股份有限公司 | A kind of method that heavy oil wells endogenous microbes improve well yield |
| CN107795305A (en) * | 2016-08-30 | 2018-03-13 | 中国石油化工股份有限公司 | A kind of method that regulation and control reservoir endogenous micro-organisms diversity improves recovery ratio |
| CN107795307B (en) * | 2016-08-30 | 2019-08-23 | 中国石油化工股份有限公司 | A kind of method that heavy oil wells endogenous microbes improve well yield |
| CN108219765A (en) * | 2018-01-11 | 2018-06-29 | 侯岱言 | A kind of reservoir endogenous micro-organisms activator and its flooding method based on inorganic salts |
| CN109358157A (en) * | 2018-09-29 | 2019-02-19 | 陕西延长石油(集团)有限责任公司研究院 | CO2The screening of the endogenous microbes activator of oil reservoirs and activation effect evaluation method and application |
| CN111985735A (en) * | 2019-05-05 | 2020-11-24 | 中国石油天然气股份有限公司 | Endogenous microbial oil displacement oil reservoir screening and evaluating method |
| CN110863809A (en) * | 2019-10-22 | 2020-03-06 | 中国石油化工股份有限公司 | Method for compositely displacing oil by utilizing electric field and microorganisms |
| CN110863809B (en) * | 2019-10-22 | 2022-01-28 | 中国石油化工股份有限公司 | Method for compositely displacing oil by utilizing electric field and microorganisms |
| CN110739032A (en) * | 2019-10-28 | 2020-01-31 | 中国石油化工股份有限公司 | Evaluation method of active bottom water heavy oil reservoir microorganism huff-puff injection agent |
| CN110739032B (en) * | 2019-10-28 | 2022-04-15 | 中国石油化工股份有限公司 | Evaluation method of microbial huff-puff injection agent for active side-bottom water heavy oil reservoir |
| CN110805417A (en) * | 2019-11-04 | 2020-02-18 | 中国石油化工股份有限公司 | Method for regulating and controlling growth and metabolism rules of endogenous microorganisms in oil reservoir |
| CN110805417B (en) * | 2019-11-04 | 2021-09-24 | 中国石油化工股份有限公司 | Method for regulating and controlling growth and metabolism rules of endogenous microorganisms in oil reservoir |
| CN114427400A (en) * | 2020-09-21 | 2022-05-03 | 中国石油化工股份有限公司 | Method for improving development effect of biological limestone oil reservoir by utilizing acid-producing microorganisms |
| CN112576229A (en) * | 2020-12-11 | 2021-03-30 | 大庆油田有限责任公司 | Method for producing methane from underground crude oil by utilizing microbial action |
| CN112983367A (en) * | 2021-03-15 | 2021-06-18 | 西北大学 | Application of toxoplasma bacteria in evaluation of microbial oil displacement field test effect and method thereof |
| CN116285927A (en) * | 2023-03-28 | 2023-06-23 | 华东理工大学 | Method for improving metabolism activity of microorganisms in thickened oil and application |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102408887A (en) | Oil reservoir endogenous microorganism high-efficient activator and effect evaluation method thereof | |
| Scott et al. | Thermogenic and secondary biogenic gases, San Juan Basin, Colorado and New Mexico—implications for coalbed gas producibility | |
| Rice | Composition and origins of coalbed gas | |
| CN104087534A (en) | Activator for activating endogenous microbial oil displacement in polymer-displaced oil reservoir | |
| Brown et al. | An ombrotrophic bog as a methane reservoir | |
| CN108414385B (en) | Device and method for evaluating carbon dioxide huff and puff recovery ratio of shale oil | |
| Clayton et al. | Alteration of natural gas during leakage from a North Sea salt diapir field | |
| CN105239977A (en) | Method for increasing petroleum production rate of low-permeability oil reservoir through air and microorganism flooding | |
| CN107288590A (en) | One kind note CO2Improve the experimental method of Recovery of Gas Condensate Reservoirs | |
| CN104695919A (en) | Method for selectively activating main beneficial bacteria in oil deposit and keeping high concentration | |
| Wenzhi et al. | Enrichment factors of movable hydrocarbons in lacustrine shale oil and exploration potential of shale oil in Gulong Sag, Songliao Basin, NE China | |
| Li et al. | Factors controlling the distribution of oil shale layers in the Eocene Fushun Basin, NE China | |
| Wang et al. | Effect of permafrost properties on gas hydrate petroleum system in the Qilian Mountains, Qinghai, Northwest China | |
| Miao et al. | Geochemistry and organic petrology of middle permian source rocks in taibei sag, Turpan-Hami Basin, China: Implication for organic matter enrichment | |
| Pashin | Coal as a petroleum source rock and reservoir rock | |
| CN101412980B (en) | Spindle bacillus and use thereof | |
| Lu et al. | The investigation of the connections among hydrogeological factors and the emissions of two greenhouse gases in lake sediment | |
| CN109358157A (en) | CO2The screening of the endogenous microbes activator of oil reservoirs and activation effect evaluation method and application | |
| CN110566168A (en) | method for activating endogenous microorganism to enhance oil recovery or pollution treatment by injecting Dietzia | |
| Ehrlich et al. | Microbial populations in a jet-fuel-contaminated shallow aquifer at Tustin, California | |
| US3033761A (en) | Hydrocarbon prospecting | |
| CN107459999A (en) | A kind of condensate demulsification water purification agent and preparation method thereof | |
| Stephens et al. | The utilization of the microflora indigenous to and present in oil-bearing formations to selectively plug the more porous zones thereby increasing oil recovery during waterflooding, Class 1 | |
| CN111763240A (en) | Sodium lauroyl sarcosinate-diglucoside peptide compound and composite oil displacement agent | |
| Rose et al. | Nitrogen‐15‐Labeled Nitrate Transport in a Soil with Fissured Shale Substratum |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20120411 |