CN102492409A - Complex biological oil displacement agent and application thereof - Google Patents
Complex biological oil displacement agent and application thereof Download PDFInfo
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Abstract
The invention discloses a complex biological oil displacement agent, which comprises a biosurfactant and a chemical surfactant which are prepared in a weight ratio of (1:1)-(8:1), wherein the biosurfactant is a rhamnolipid fermentation stock solution, and the chemical surfactant is fatty acid amide sulpho monoester potassium maleate. In the complex biological oil displacement agent, the using amount of the chemical surfactant is low (namely 0.0125 weight percent), and a complex system can reach ultra-low interfacial tension of less than 10<-2>mN/m order of magnitude, so the complex biological oil displacement agent has the advantages of high oil displacement efficiency, simple preparation process, low cost and the like, and is suitable for the popularization and application of the further improvement on a recovery ratio in high-water-content oil fields.
Description
Technical field
The present invention relates to a kind of complex biological oil-displacing agent and the application in the oil displacement of reservoir oil thereof in the tertiary oil recovery technology field.
Background technology
Biological oil-displacing agent is a kind of by mikrobe synthetic, the various surfactant of structure; Mainly be divided into glycolipid class, lipopeptid and lipoprotein, phosphatide and fatty acid, polymeric surfactant and microparticle surfaces promoting agent class five big classes, displacement of reservoir oil bio-surfactant commonly used in oil field belongs to lipopeptid class and glycolipid class.
Biological oil-displacing agent is similar with the chemical oil displacement agent performance, but by contrast, also has many favourable parts: 1. biodegradable, can not cause recontaminate; 2. nontoxic or low toxicity; 3. generally not sensitization, can digest, therefore can be used for the additive of makeup, food and functional food; 4. can use trade refuse production, help environmental pollution improvement; 5. have better Environmental compatibility, higher whipability, better selectivity and specificity under extreme temperature, pH value, salt concn; 6. structure is various, might be applicable to special dimension (Cairns WL1 Biosurfactants andBiotechnology [M] NY:Marcel Dekker Inc, 1987.1).Biological oil-displacing agent also has the performance of good antibacterium, mould and virus, and this is general chemical synthetic tensio-active agent be difficult to be equal to (Jitemdra D D, Ibrahim M B1 Microbio Mol Biol Rev [J], 1997,61 (1): 47～64.).
Biological oil-displacing agent is the same with general bio-surfactant, and it is produced at first to depend on and produces bacterium, and the different production bacterium produces different surface active agents.Owing to recover the oil bio-surfactant is belonged to extensive style, less demanding to the extraction and the purifying of bio-surfactant, therefore the research of oil recovery with bio-surfactant is mainly concentrated in the screening improvement and cultivation of producing bacterium (mikrobe).The present stage research of bio-surfactant mainly concentrates on the generation bacterium of isolation and selection bio-surfactant from the oil reservoir of Oil extraction, then it is cultivated and is used for TOR.
Biological oil-displacing agent is with a wide range of applications as the auxiliary agent of a kind of excellent property in the TOR.The development trend of the tensio-active agent that the oil field displacement of reservoir oil is now used by highly basic to weak base, ternary to two yuan, monobasic development.Along with to raising as the chemical surfactant performance requriements of host; The development difficulty of novel surfactant also strengthens thereupon and cost rises; Biological oil-displacing agent is used as assistant agent and has just in time been remedied the deficiency of existing chemical surfactant on performance; Simultaneously reduce comprehensive cost by a relatively large margin, shown bright development prospect.
According to (state most for Zhang Zihan, Yang Zhenyu to former result of study; The northern combination flooding feasibility of grand celebration Putaohua oil field is inquired into grand celebration petroleum geology and exploitation, 2005; 24 (1): 82～84), many chemical surfactants are like KPS, WXS, MS298, korenyl, TD and NaOH and Na
2CO
3Compound system and the profit in Sa Ertu oil field or oil field, apricot hilllock all have certain flexibility, but carried out finding after a large amount of IT evaluations with the profit of Putaohua oil field, can not form ultra low interfacial tension between these systems and Putaohua oil field crude oil.Particularly inlet surface promoting agent ORS41-NaOH system has obtained good effect in the bio-surfactant combination flooding field test in Daqing oil field Sa Ertu and oil field, apricot hilllock; But be difficult to form ultra low interfacial tension with Putaohua oil field crude oil; The IT of ORS41-NaOH system and grape flower crude oil is seen Fig. 1 (NaOH concentration is respectively 1.0wt%, 1.2wt% and 1.5wt%); And use enzyme and the composite oil displacement experiment of rhamnolipid fermentation liquor to study [Southwest Petrol University's journal (natural science edition); 2008,30 (1): 119～121] show that composite its IT of rhamnolipid fermentation liquor and enzyme reaches 0.41mN/m; And enzyme act as 1.67mN/m separately, and rhamnolipid fermentation liquor is 2.50mN/m.Composite back is all lower than the oil water interfacial tension of effect separately, and explaining acts synergistically helps to reduce IT, but with the index (≤10 of ultralow ultra low interfacial tension
-2MN/m) still have big gap.
In order to improve the interfacial activity of rhanolipid as biosurfactant fermented liquid, need to seek and bio-surfactant the compound property better kind and the product of relevant oil displacement surfactant.The oil property characteristics of Putaohua oil field are that density is low, viscosity is low, saturation pressure is low, asphaltenes low and difference between reservoir pressure and saturation pressure is big, solubility coefficient is big; In addition; The content of natural acid lower (0.06mgKOH/g oil) in the Putaohua oil field crude oil; Acid number is low, makes to utilize the effect of the natural acid formation natural agents in the oil to reduce.Concrete characteristics according to north, Portugal oil reservoir under the condition of alkali-free, require composite chemical surfactant and rhamnolipid to have synergistic effect preferably, can reach the technical indicator (≤10 of ultra low interfacial tension
-2MN/m).IT is one of important indicator that improves RF, and the low more oil displacement efficiency of IT is good more).
At present, the IT of single rhamnolipid system and crude oil is all higher, does not reach ultralow value scope.The IT that rhamnolipid fermentation liquor concentration records when 0.5%～1% scope is between 8.4～9.6mN/m, this shows, makees oil-displacing agent with single rhanolipid as biosurfactant and is difficult to obtain satisfied oil displacement efficiency.
Summary of the invention
The present invention is directed to Daqing oil field reservoir physical property, crude oil, local water, injection aqueous nature, screened a kind of chemical surfactant that has better synergistic effect with rhamnolipid, a kind of complex biological oil-displacing agent is provided.
First aspect present invention provides a kind of complex biological oil-displacing agent, comprises that said bio-surfactant is the rhamnolipid fermenation raw liquid by weight the bio-surfactant and the chemical surfactant of preparation in 1: 1～8: 1; Said chemical surfactant is produced by the outstanding chemical industry of grand celebration richness ltd; Comprise that with the acid of vegetable and animals oils fat, monoethanolamine, MALEIC ANHYDRIDE, potassium sulfite be raw material; Through the synthetic AS that obtains animal oil fatty acid acid amides sulfo group maleic acid monoesters sylvite of series reaction such as amidation, esterification, sulfonation, its structural formula is:
Wherein, wherein R is a Fatty Alcohol(C12-C14 and C12-C18), and the m span is C
8～C
18
Used bio-surfactant adopts the rhamnolipid fermenation raw liquid that Daqing Vertex Chemical Co., Ltd. provides among the present invention; Major ingredient has biomacromolecule protein (mainly containing somatic cells albumen, nucleic acid-protein, polyose albumen etc.), content 12.34-15.12g/L; Glycolipid, content 25.8-27.6g/L; Polysaccharide, content 4.12-5.07g/L; Glyceride, content 22.85-27.02g/L etc.
Said chemical surfactant is 1 with the mixed weight ratio of bio-surfactant fermented liquid: 1-8, making the effective concentration of chemical surfactant in the complex biological oil-displacing agent is 0.1wt%-0.01wt% (below the 0.1wt%).
For obtaining better oil displacement efficiency, also be added with polymkeric substance in the said complex biological oil-displacing agent, be preferably SEPIGEL 305, molecular weight is between 800-1500 ten thousand, and concentration is between 800-1200mg/L, and the flooding system viscosity of preparation is between 15-30mPas.
Said biological oil-displacing agent can also be added with amendment (precrosslink volume expansion grain class amendment), and the adding proportion of polymkeric substance and amendment is 1: 4 (weight ratio), polymer concentration 800～1200mg/L in the dosing, and viscosity is controlled at 15～25mPas.
The application of said biological oil-displacing agent in the oil displacement of reservoir oil also belongs to protection scope of the present invention.
During the displacement of reservoir oil, behind the water drive slug, carry out the displacement of reservoir oil with said complex biological oil-displacing agent preparation slug merely.Perhaps, behind the water drive slug, alternately inject with polymer slug and said complex biological oil-displacing agent preparation slug.Complex biological oil-displacing agent concentration in flooding system is 0.5wt%-2.0wt%, preferred 1.0wt%.
Concrete, can be behind the water drive slug, with below arbitrary scheme proceed the displacement of reservoir oil:
Scheme one: with said complex biological oil-displacing agent preparation slug, complex biological oil-displacing agent concentration is 1.0wt% merely, and consumption is 0.5PV;
Scheme two: with polymkeric substance and complex biological oil-displacing agent mixed preparing slug, complex biological oil-displacing agent concentration 1.0wt%, polymer concentration 0.1wt%, consumption are 0.5PV;
Scheme three: inject 0.1wt% polymkeric substance 0.1PV, 1.0wt% complex biological oil-displacing agent 0.25PV and 0.1wt% polymkeric substance 0.15PV successively.
Here, complex biological oil-displacing agent concentration in flooding system is 1.0wt%, and wherein chemical surfactant effective concentration is 0.125wt%, and rhamnolipid fermenation raw liquid and chemical surfactant weight ratio are 7: 1.
Another concrete combination flooding scheme is behind reservoir water flooding, injects following slug more successively:
Polymkeric substance+amendment, weight ratio 1: 4, slug size 1000m
3
Polymkeric substance+rhamnolipid fermenation raw liquid, weight ratio 1: 12, slug size 10000m
3
Polymkeric substance+amendment, weight ratio 1: 4, slug size 1000m
3
Polymkeric substance+bio-surfactant+chemical surfactant, weight ratio 1: 13: 2, slug size 4000m
3
Polymkeric substance+chemical surfactant, weight ratio 1: 2, slug size 4000m
3
Wherein bio-surfactant, chemical surfactant, polymkeric substance and amendment such as aforementioned.
The present invention has used a kind of chemical surfactant that has better synergistic effect with rhamnolipid.The single product of this chemical surfactant can form 10 with north, Portugal profit below effective concentration 0.1% (wt)
-3The ultra low interfacial tension of the mN/m order of magnitude, and concentration range broad 0.1% (wt)～0.01% (wt).Advantages such as the biological oil-displacing agent that contains chemical surfactant of the present invention has the oil displacement efficiency height, preparation technology is simple and with low cost are fit to the promotion and application that RF is further improved in highly aqueous field.
Below in conjunction with specific embodiment the present invention is explained further details.
Description of drawings
Fig. 1 is the IT figure of ORS41-NaOH system and grape flower crude oil
Figure 1A is biomacromolecule micelle 400 * Electronic Speculum picture
Figure 1B is biological surfactant molecule 1000 * Electronic Speculum picture
Fig. 2 is the relation curve of different concns rhamnolipid fermenation raw liquid and IT
Fig. 3 is the IT detected result of the chemical surfactant of different concns
Fig. 4 is the composite IT detected result of rhamnolipid biological surface activator and chemical surfactant
Fig. 5 is the influence of core permeability to complex biological oil-displacing agent injectability
Fig. 6 is the sticking dense curve of differing mol weight polymers
Fig. 7 is for injecting the sticking dense curve of recovered water preparation complex biological oil-displacing agent
Fig. 8 is the optimum result of rhamnolipid fermenation raw liquid compound system slug and polymer slug injecting scheme
Embodiment
Method therefor is ordinary method if no special instructions among the following embodiment.
Experiment material
1, oil sample
Crude oil sample is taken from the commingled crude of the dehydration degassing of the II of Portugal joint station, and the density that this crude oil is 20 ℃ is 0.7628g/cm
3, 50 ℃ of kinematic viscosities that record are 12.91mPas, and flash-point is 37 ℃, and zero pour is 33 ℃, and molecular weight is 365.3, the distillation ingredients constitute 30.6% before 300 ℃ of the Engler distillation analytical resultss, the oil component analysis sees the following form 1.
The proximate analysis of the II of table 1 Portugal joint station dehydration degassing commingled crude
From crude oil property, wax content is higher, and the viscosity under the formation temperature conditions is 12.9mPas, and the profit ratio of viscosities is higher than the placanticline old liberated area greater than 20.From the PONA analysis result, aromatic hydrocarbons and bitum content also obviously exceed the placanticline old liberated area in the crude oil, explain that this block crude oil property is unique, on screening displacement of reservoir oil formula system, to the compatibleness of crude oil, perform the preferred of oil-displacing agent.
2, water sample
The injection recovered water sample of experiment usefulness is taken from 82-77 of Portugal and the 80-73 of Portugal well respectively.The injection extraction well water matter component difference of the same well group of this block is little, and whether the main water index that detects routine exists notable difference, explains that the flooding system of preparing with this water sample is representative, and the check and analysis result sees table 2.
Table 2 Portugal North Area piece injects the water (concentration unit: mg/L) of extraction well
| Water sample | Pound sign | pH | HCO 3 - | Cl - | SO 4 2- | Br - | I - | Ca 2+ | Mg 2+ |
| Inject water | P82-77 | 7.9 | 3050 | 1060 | 9.61 | 5.18 | 3.81 | 16 | 7.29 |
| Recovered water | P80-73 | 7.1 | 3090 | 1050 | 0 | 5.18 | 5.24 | 16.8 | 9.24 |
| Water sample | Pound sign | K + | Na + | Fe ++ | Mn ++ | Sr ++ | Cu ++ | TDS | |
| Inject water | P82-77 | 9.28 | 1580 | 0.14 | 0.04 | 1.69 | 0.01 | 5950 | |
| Recovered water | P80-73 | 9.28 | 1670 | 0.08 | 0.06 | 2.05 | 0.02 | 5970 |
Analysis Results of Water Quality shows, injects the water meta-alkalescence, and the pH value is 7.9, and total mineralization is 5950mg/L, and recovered water is neutral, and the pH value is 7.1, and total mineralization is 5970mg/L.Various Yin and Yang pair ion ratios in the water quality, recovered water is slightly more higher than the content that injects water.On the whole, injection extraction well water matter component difference is little.
Laboratory apparatus and device
U.S.'s Texas2500 type revolves and drips the ultra low interfacial tension appearance; DV2III+ type Brookfield viscosmeter, electronic balance, TVT2 interfacial tensimeter, the biological inverted microscope of LEICA DMIRB, multi-functional core driving device (production of Hai'an, Jiangsu Province oil plant and instrument factory).
Experimental technique
(1) surface and IT measuring method SY/T 5370-1999;
(2) displacement of reservoir oil is with acrylamide copolymer performance measurement SY/T 5862-1993;
(3) SEPIGEL 305 intrinsic viscosity measuring method GB/T 12005.1-1989 (2004);
(4) rock core routine analysis and thing mould oil displacement experiment method SY/T 5336-2006.
The screening and the optimization of the complex biological oil-displacing agent prescription of test one, suitable test block
IT is one of important indicator that improves RF, and the low more oil displacement efficiency of IT is good more.Experiment is adopted Daqing Vertex Chemical Co., Ltd. to sell the rhamnolipid fermenation raw liquid that provides and (is abbreviated as RH; Bio-surfactant); Major ingredient has: biomacromolecule protein (mainly containing somatic cells albumen, nucleic acid-protein, polyose albumen etc.), glycolipid, polysaccharide; Glyceride, staple is seen table 3.
Existing polar group has non-polar group again in the molecular structure of this bio-surfactant, is one type of neutral the two poles of the earth molecule.Hydrophilic radical is monose, disaccharides, polysaccharide, carboxyl, amino or the peptide chain of non-ionic form, and hydrophobic grouping then is made up of hydroxyl lipid acid.The bio-surfactant molecule (Figure 1B) that this bio-surfactant (rhamnolipid fermenation raw liquid) contains the biological micelle (Figure 1A) of accumulative and has colloidal sol character; The micelle diameter is at micron order; With oil reservoir hole larynx duct coupling, be the irregular shape elastomerics, its quantity is many and be evenly distributed.
Table 3 rhanolipid as biosurfactant fermenation raw liquid main ingredient
Respectively with injecting the aqueous solution of water and recovered water preparation rhamnolipid fermenation raw liquid concentration range 0.01%～10%; Record IT and relation curve (Fig. 2 of concentration of the bio-surfactant of different concns successively; Used crude oil is Portugal's bigeminy gas-free oil; 45 ℃ of experimental temperatures, detecting instrument are the TVT2 interfacial tensimeter).
Detected result shows, no matter is with injection water, or the recovered water preparation, and the IT of single rhamnolipid system and crude oil is all higher, does not reach ultralow value scope.The IT that the rhamnolipid fermentation liquor original liquid concentration records when 0.5%～1% scope is between 8.4～9.6mN/m, this shows that making oil-displacing agent with single rhamnolipid fermentation liquor is difficult to obtain satisfied oil displacement efficiency.
Through repeatedly screening and detecting; Obtain the chemical surfactant fatty acid amide sulfo group maleic acid monoesters sylvite that a kind of and rhamnolipid have better synergistic effect; It is produced by the outstanding chemical industry of grand celebration richness ltd; With the acid of vegetable and animals oils fat, monoethanolamine, MALEIC ANHYDRIDE, potassium sulfite is raw material, synthesizes through series reaction such as amidation, esterification, sulfonation to obtain, and is a kind of AS.Its structural formula is:
Wherein R is Fatty Alcohol(C12-C14 and C12-C18) or is the group that raw material is taken out of with the AEO, and the m span is 8～18.
The single product of this chemical surfactant can form 10 with north, Portugal profit below effective concentration 0.1% (wt)
-3The ultra low interfacial tension of the mN/m order of magnitude; And concentration range broad 0.1% (wt)～0.01% (wt); Fig. 3 is the IT detected result of different concns fatty acid amide sulfo group maleic acid monoesters sylvite, and in actual the use, this chemistry table agent maximum concentration alive can arrive 0.3wt%.Yet this chemical surfactant costs an arm and a leg, and during single use, because consumption is low, the single flooding system of preparation is prone to adsorbed to fall by the clay mineral of oil bearing reservoir in the oil reservoir.The present invention carries out its bio-surfactant with the anti-absorption of cheapness composite, can reduce its adsorptive capacity, and practices thrift cost.
The composite raising oil recovery factor of rhamnolipid biological surface activator and chemical surfactant is based on the similar compatibility principle.Fig. 4 has verified that the fatty acid amide sulfo group maleic acid monoesters sylvite (FJ-1) of screening has synergistic effect preferably with rhamnolipid fermentation liquor (RH); Chemical surfactant effective concentration is decided to be 0.0125wt%; (rhamnolipid concentration is 0.0125wt% and 0.1wt% (like no specified otherwise, concentration of the present invention is meant the final concentration of each composition in composite oil-displacing system) to be mixed with solution by weight 1: 1 and 1: 8 with rhamnolipid biological surface activator respectively.
Detected result shows, rhamnolipid fermenation raw liquid and chemical surfactant all can be less than 10 by the mixed system of 1: 1 and 8: 1
-2The ultra low interfacial tension of the mN/m order of magnitude so just can make composite flooding system satisfy the technical indicator of ultra low interfacial tension, and wherein the consumption of chemical surfactant can very low (0.0125wt%).
To above-mentioned complex biological oil-displacing agent, also detected the IT stability under 45 ℃ of constant temperatures.Detected result shows that this complex biological oil-displacing agent system has IT stability preferably, and balance and dynamic interface tension force all show stability preferably.
The present invention is further through lab screening and evaluation; Chemical surfactant fatty acid amide sulfo group maleic acid monoesters sylvite concentration range is between 0.01wt%～0.25wt% in final definite complex biological oil-displacing agent system; Any assembly of the ratio range of rhamnolipid fermenation raw liquid and chemical surfactant between 1: 1 to 8: 1 all can reach 10
-2The ultra low interfacial tension of the mN/m order of magnitude, and have IT stability preferably.
The compatibility test in test two, complex biological oil-displacing agent and oil field, north, Portugal
(1) oil displacement efficiency of reservoir temperature, pressure, rate of permeation and complex biological oil-displacing agent
Temperature: for confirming the influence of reservoir temperature to composite flooding system; With complex biological oil-displacing agent system (chemical surfactant 0.0125wt%; The weight ratio of rhamnolipid fermenation raw liquid and chemical surfactant is between 1: 1～8: 1; See table 4) concentration be divided into 0.025%, 0.1% and 1% 3 series, under differing temps, measure the variation of IT successively.
From detected result (table 4), temperature variation has significant difference to the IT influence of complex biological displacing surfactant system.It is little wherein to change difference for the IT influence of the flooding system of lower concentration, but the IT influence of high density flooding system is changed obviously.Analyzing reason mainly is the chemical surfactant solvability difference under differing temps that adds, and temperature is high, then solubility enhanced; Otherwise, then be the result of variation.Through data investigation (the composite oil displacement experiment research of enzyme and rhamnolipid fermentation liquor; Southwest Petrol University's journal (natural science edition); 2008,30 (1): 119～121), north, Portugal is oil field reservoir temperature 40-50 ℃ at present; Under this temperature, the compound system that optimizes all can reach ultra low interfacial tension.
Table 4 reservoir temperature is to the influence of complex biological oil-displacing agent system IT
Pressure: since the preparation of site operation and medicament all normal pressure carries out on ground, so pressure to the influence of complex biological flooding system, can be ignored.And behind the flooding system entering oil reservoir; Pressure can be used for reference the data of other combination flooding test in places (the northern Feasibility of Polymer Flood research of Putaohua oil field, grand celebration petroleum geology and exploitation at present to the influence of complex biological flooding system; 2001,20 (2): 80～82).
Rate of permeation: rate of permeation shows (practice of Daqing oil field tertiary oil recovery technology and understanding, Daqing oil field geology and exploitation, 2001,20 (2): 1～8) in the variation of injecting handling capacity to the influence of complex biological flooding system.Oil field, north, Portugal belongs to the thin poor reservoir of fault block, influenced by the oil reservoir non-homogeneous degree, and there is some difference for the growth of well group oil reservoir, in the design of individual well displacement strength of solution, need carry out personalized design according to actual injectability between each well group.
In order to test complex biological flooding system (concentration 0.1wt%; Contain chemical surfactant 0.0125wt%; The weight ratio of rhamnolipid fermenation raw liquid and chemical surfactant is 8: 1) injection handling capacity in oil reservoir, natural core is adopted in experiment, and rate of permeation is respectively 118 * 10
-3μ m
2, 184 * 10
-3μ m
2With 285 * 10
-3μ m
2Consider the actual exploitation situation of test in place district injection well, the complex biological oil-displacing agent is mixed with the solution that viscosity is 25mPas, the displacement slug of design is 0.5PV, and displacing velocity is decided to be 0.2mL/min.Wherein the injection multiple in water drive stage is between 3.0～3.5PV, and complex biological oil-displacing agent displacement slug is 0.5PV, is the follow-up water drive stage afterwards.
(three kinds of core permeabilities are respectively 118 * 10 Fig. 5 from the displacement test result
-3μ m
2, 184 * 10
-3μ m
2With 285 * 10
-3μ m
2, lines are distinguished with numerical value among the figure), when rate of permeation less than 200 * 10
-3μ m
2The time, when the complex biological flooding system passes through rock core, can form higher pressure gradient " wall ", pressure amplification surpasses 2.0MPa, helps flooding system to enlarge swept volume, also makes the irreducible oil enrichment that is gone out by displacement become " band " simultaneously, further improves RF.When rate of permeation greater than 200 * 10
-3μ m
2The time, the pressure gradient of formation is obviously on the low side, and pressure amplification only has 0.5MPa, though the handling capacity of flooding system has improved under this situation, the zone of involving the irreducible oil position is limited, influences the extraction effect greatly.Therefore, in conjunction with the on-the-spot injection pressure of well and the difference between the oil reservoir parting pressure injected, the viscosity of appropriate design flooding system and injection speed have important directive significance to the oil displacement efficiency of improving the complex biological oil-displacing agent.
(2) the complex biological oil-displacing agent is to the oil displacement efficiency of test block rock core
Because the experiment of the thing mould of complex biological oil-displacing agent is to confirm to provide important basis for each item design parameter value in the Site Test Scheme.The design of the indoor physical simulation experimental program of therefore, carrying out to the different tests block (experiment condition, influence factor) is particularly important too.For the oil displacement efficiency and the mechanism of action of better checking complex biological oil-displacing agent, carried out natural core thing mould oil displacement experiment, this test also provides parameter for the formulating of recipe of complex biological displacement of reservoir oil rig-site utilization simultaneously.
1. experiment basis parameter
The complex biological flooding system concentration 0.1wt% of experiment usefulness contains chemical surfactant 0.0125wt%, and the weight ratio of rhamnolipid fermenation raw liquid and chemical surfactant is 8: 1.Experimental temperature is 45 ℃.Displacing velocity is 0.2mL/min, is equivalent to that seepage velocity is 1m/d in the stratum.
2. microbial oil displacement experimental procedure
Rock core is found time oily (making the irreducible water) → water drive of the oil well produced local water of saturated seven factories → saturation simulation to moisture 98% end, calculates waterflood recovery efficiency factor → injection complex biological oil-displacing agent slug, and maintenance constant temperature → water drive extremely moisture 98% finishes again.
Three groups of natural cores are adopted in experiment, and the rate of permeation section is respectively less than 100 * 10
-3μ m
2Section, 150 * 10
-3μ m
2Section and 200 * 10
-3μ m
2Section, the oil displacement experiment result sees table 5.
The complex biological oil-displacing agent experimental result of the different core permeabilities of table 5
Through injecting complex biological oil-displacing agent slug, find amplitude that three groups of cores improve RF all more than 5% (OOIP), wherein rate of permeation is less than 150 * 10
-3μ m
2The time the RF value be higher than rate of permeation greater than 200 * 10
-3μ m
2The RF value.Explain that complex biological oil-displacing agent of the present invention is applicable to that rate of permeation is less than 150 * 10
-3μ m
2Oil reservoir, the oil displacement efficiency of acquisition is higher relatively.
The optimization of test three, complex biological oil-displacing agent slug and polymer slug injecting scheme
Indoor thing mould oil displacement test mainly study injectant preferred and reasonable injection mode, inject confirming of slug, implantation concentration, IR, injection length, and inject the back effect prediction.
(1) complex biological oil-displacing agent consumption improves the RF effect
In order to investigate complex biological oil-displacing agent concentration to improving the influence of RF; Carried out complex biological oil-displacing agent concentration optimization experiment; Complex biological oil-displacing agent concentration is respectively 0.5wt% (FJ-1 concentration 0.1wt%; RH: FJ-1 is 4: 1), 1.0wt% (FJ-1 concentration 0.125wt%, RH: FJ-1 are 7: 1), 2.0wt% (FJ-1 concentration 0.25wt%, RH: FJ-1 are 7: 1)
Complex biological oil-displacing agent oil displacement experiment result under table 6 different concns
Can find out from experimental result (table 6); Complex biological oil-displacing agent concentration improved the RF value all between 5～7% at 0.5%, 1.0%, 2.0% o'clock; Difference is little; This is because the complex biological oil-displacing agent except having the oil water interfacial tension of reduction, also has good solubilising, emulsification and reduces the effects such as adhesive power of crude oil at rock surface.Take all factors into consideration the diluting effect influence of experiment effect and local water, confirm that finally the concentration that compound system (complex biological oil-displacing agent) adopts is 1.0wt%.
(2) polymkeric substance is to the influence of oil displacement efficiency
Whether raising RF project successfully reaches the key that whether has an economic benefit is farthest to improve the oil reservoir sweep efficiency, so should be towards the direction effort that improve the oil reservoir sweep area to greatest extent with the fluid that injects.Consider the nonuniformity of test site, north, Portugal oil reservoir, design should add preposition polymkeric substance profile control slug before injecting the compound system slug, can further improve the oil displacement efficiency of bio-surfactant like this.Preposition polymkeric substance profile control slug design relates to confirming of polymericular weight and concentration.
1. molecular weight confirms (the northern Feasibility of Polymer Flood research of Putaohua oil field, grand celebration petroleum geology and exploitation, 2001,20 (2): 80～82)
Adopt clear water prepared polymer mother liquor and solution, polymer solution concentration adopts 1000mg/L.Use molecular weight 800 * 10
4～1500 * 10
4Polyacrylamide polymers, polymer solution viscosity is 17～37mPas (table 7).
Table 7 is with the viscosity correspondence table of north, Portugal local water preparation differing mol weight polymers
According to the oil displacement experiment result, reservoir permeability is low more, and the polymkeric substance relative molecular mass that can inject is low more, polymer flooding effect poor more (seeing table 8).
Table 8 polymer flooding experimental result
Therefore, when the selective polymer relative molecular mass, should select the polymkeric substance of high molecular weight as far as possible, so that under the identical situation of other conditions, obtain better oil displacement efficiency, suggestion adopts 800～1500 * 10
4The polymkeric substance of molecular weight (narrow sand body oil field cross-linked polymer depth profile control FS, grand celebration petroleum geology and exploitation, 2002,21 (6): 55～57).
2. polymer concentration confirms
According to thing mould oil displacement experiment result, the viscosity ratio of injecting fluid viscosity and crude oil at 3: 1 above oil displacement efficiency better.The underground viscosity of crude of test block is 6.9mPas, and the underground activities viscosity of injection system should be more than 20.7mPas.
Previous investigation thinks that the viscosity when polymers soln arrives oil reservoir through uphole equipment with injection well shaft bottom will approximately lose 52.6%, and therefore the injection well injection system well head viscosity of test requires to reach more than the 30mPas.
Consider that the oil reservoir RF increases in the complex biological oil-displacing agent injection process, the practical situation that injectability descends in the individual well design process, are confirmed the implantation concentration of individual well according to the actual needs of individual well.In concrete injection process; Will be under the condition that guarantees preposition polymeric system viscosity; According to the injection situation of reality, suitably adjust polymer concentration, guarantee to inject well injection system well head viscosity and require to reach more than the 30mPas; Injection pressure is as the criterion below the oil reservoir parting pressure, referring to Fig. 6 and Fig. 7.
Comprehensive each item index confirms that finally preferred polymkeric substance is a SEPIGEL 305, and molecular weight is between 800-1500 ten thousand, and concentration is between 600-1200mg/L, and the flooding system viscosity of preparation is between 15-30mPas.
(3) slug Combination Optimized
Composite biological oil-displacing agent (1.0wt%, FJ-1 concentration 0.125wt%, RH: FJ-1 are 7: 1) slug and polymer slug injecting scheme are optimized.(three kinds of schemes have been carried out the rock core oil displacement test six times to experimental result altogether in the his-and-hers watches 9 respectively; RF in the test, moisture and pressure dependence are shown in A-F among Fig. 8;) show; Scheme one [is injected a slug of simple biological oil-displacing agent; 1.0% complex biological oil-displacing agent 0.5PV] improve RF amplitude 5.5%, and scheme two [polymer injection and slug of complex biological oil-displacing agent blended, (1.0% complex biological oil-displacing agent+0.1% polymkeric substance) 0.5PV] and scheme three [injection of polymer, complex biological oil-displacing agent, three slugs of polymkeric substance successively; (0.1% polymkeric substance) 0.1PV+1.0% complex biological oil-displacing agent 0.25PV+ (0.1% polymkeric substance) 0.15PV] effect all be better than scheme one; The amplitude that improves RF obviously exceeds 2.8% and 3.5% respectively 8.3% and 9.0%, and wherein scheme three (polymkeric substance and complex biological oil-displacing agent slug alternately inject respectively) improves RF 0.7% than scheme two (polymkeric substance and biological oil-displacing agent mixed water injection slug) again.
The biological oil-displacing agent combination flooding of table 9 injection mode optimization experiment result
Test four, the design of complex biological oil-displacing agent system (1wt%, FJ-1 concentration 0.125wt%, RH: FJ-1 are 7: 1) injection parameter
(1) complex biological oil-displacing agent slug size confirms
It is that 2 notes 9 are adopted well group that biological oil-displacing agent drives the test site, and well spacing is 300m * 300m, oil-bearing area 0.72km
2, average individual well is penetrated out sandstone thickness 11.0m, penetrates to have to imitate thickness 9.05m, and the stratum average pore is 23%.Volume of voids through initial estimate whole test district is 140 * 10
4m
3Average day reservoir quantity 150m of the two mouthfuls of injection wells in test site
3, not changing under the original production system condition in test site, the concentration of on-the-spot complex biological oil-displacing agent displacing fluid is by 1% preparation, and the biological oil-displacing agent slug size and the dosing of different schemes are seen table 10.
The biological oil-displacing agent slug size in table 10 test site is confirmed
Can find out that from above-mentioned 5 schemes the dosing of scheme 1 is difficult to the warranty test effect very little, and the medicament of scheme 4 and 5 not only consumption is too big, and the injection cycle more than 7 months, therefore do not do alternative.Have only the dosing of scheme 2 and 3 more suitable,, can save reagent cost, shorten construction period, can satisfy on-the-spot effect again through contrasting back preferred version 2.The complex biological oil-displacing agent that on-the-spot preparation is 200 tons needs to inject water 20000m
3, the volume size that can confirm biological oil-displacing agent slug thus is 2.0 * 10
4m
3
(2) complex biological oil-displacing agent flooding system consumption is confirmed
On the basis of confirming biological oil-displacing agent slug size; Consider and also have other auxiliary chemical agents in the complex biological oil-displacing agent flooding system; Comprise chemical surfactant, polymkeric substance and a certain proportion of amendment; Amendment is specially precrosslink volume expansion grain amendment (product of the model WT-1 that is for example sold by grand celebration ten thousand Tonghua worker ltds), and polymkeric substance and amendment are prepared in the ratio of 1: 4 (weight ratio).In conjunction with the injection allocation situation of two mouthfuls of injection wells, the consumption of design is seen table 11.
Table 11 test site chemical agent consumption statistics
Host: (biological table agent, i.e. rhamnolipid fermenation raw liquid alive), 140 tons of consumptions, compound concentration are 1%, slug size 10000m
3
Assistant agent 1 (polymkeric substance): 16 tons of consumptions, dosing concentration 600-1000mg/L, molecular weight 1000-1500 ten thousand, the dosing viscosity is controlled at 15-30mPas.
Assistant agent 2 (amendment): 6 tons of consumptions, dosing concentration 2000-4000mg/L, the dosing viscosity is controlled at 15-25mPas, slug size 2000m
3
Assistant agent 3 (chemical surfactant): 16 tons of consumptions, dosing concentration 2000mg/L, the dosing viscosity is controlled at 15-25mPas, slug size 8000m
3
(3) injection mode of complex biological oil-displacing agent
Experimental result in the reference chamber, whole oil displacement process is designed to five slugs, and required medicament composition, proportioning, consumption and the size of each slug specifically seen table 12.
Table 12 test site chemical agent slug size and proportioning
On the slug injection mode, considered the exploitation situation of test site, and local water is to the dilution effect and the adsorption losses of biological oil-displacing agent in oil reservoir of biological oil-displacing agent.For improving biological oil-displacing agent utilising efficiency, added the stifled slug of two little accent, through adjustment water drive passage, change the flow direction, make biological oil-displacing agent can involve wider surplus oil zone, reach the purpose of further raising RF.Adopt above-mentioned different big pill combination and replace injection mode, can obtain higher oil displacement efficiency, experimental result, RF improves more than 5 percentage points.
(4) effect prediction of complex biological oil-displacing agent
According to indoor thing mould oil displacement experiment result,, under the condition of implantation concentration 1%, can improve 6 percentage points of RF injecting biological oil-displacing agent slug 0.4PV.As by injecting biological oil-displacing agent slug 0.015PV, calculate under the condition of implantation concentration 1%, improving RF should be more than 0.2 percentage point.Therefore, the test site adopts the biological oil-displacing agent displacement of reservoir oil, and expectation can increase oil more than 2000 tons.With reference to present world market oil price, by 50 dollars of the oil that increase per ton, the output value that increases oil per ton is 50 * 6.82 * 7.35=2506 unit, and the output value that then increases 2000 tons of oil is: ten thousand yuan of 2506 * 2000=501.2.And this time the input expense of test in place then drops into the extraction ratio and reaches 1: 2.5 at 2,000,000 yuan.
Claims (10)
1. complex biological oil-displacing agent; Comprise by weight the bio-surfactant and the chemical surfactant of preparation in 1: 1～8: 1; Said bio-surfactant is the rhamnolipid fermenation raw liquid; Said chemical surfactant is a fatty acid amide sulfo group maleic acid monoesters sylvite, and its structural formula is:
Wherein R is Fatty Alcohol(C12-C14 and C12-C18) or is the group that raw material obtains with the AEO, and the m span is 8～18.
2. according to the said complex biological oil-displacing agent of claim 1, it is characterized in that the effective concentration of said chemical surfactant in the complex biological oil-displacing agent is 0.25wt%-0.01wt%, preferred 0.01wt%-0.125%.
3. according to claim 1 or 2 said complex biological oil-displacing agents, it is characterized in that the content of said rhamnolipid fermenation raw liquid in the complex biological oil-displacing agent is 0.01wt%～2.0wt%, preferred 0.01wt%～1.0wt%.
4. complex biological oil-displacing agent according to claim 3; It is characterized in that; Biomacromolecule albumen in the said rhamnolipid fermenation raw liquid (comprising somatic cells albumen, nucleic acid-protein, polyose albumen etc.) content 12.34-15.12g/L; Glycolipid content is 25.8-27.6g/L, and polysaccharide content is 4.12-5.07g/L, and glyceride content is 22.85-27.02g/L.
5. according to claim 1 or 2 or 3 or 4 described complex biological oil-displacing agents; It is characterized in that: also be added with polymkeric substance, said polymkeric substance is preferably SEPIGEL 305, and molecular weight is 800-1500 ten thousand; Concentration is between the 800-1200mg/L in the complex biological oil-displacing agent, and viscosity is 15-30mPas.
6. complex biological oil-displacing agent according to claim 5 is characterized in that: also be added with amendment, polymkeric substance and amendment weight ratio are 1: 4, and said amendment is the precrosslink volume expansion grain.
7. the application of the arbitrary described complex biological oil-displacing agent of claim 1-6 in the oil displacement of reservoir oil, complex biological oil-displacing agent concentration in flooding system is 0.5wt%-2.0wt%, preferred 1.0wt%.
8. application according to claim 7; It is characterized in that; Said complex biological oil-displacing agent concentration in flooding system is 1.0wt%, and wherein chemical surfactant effective concentration is 0.125wt%, and rhamnolipid fermenation raw liquid and chemical surfactant weight ratio are 7: 1.
9. application according to claim 8 is characterized in that: behind the water drive slug, with below arbitrary scheme proceed the displacement of reservoir oil:
Scheme one: with said complex biological oil-displacing agent preparation slug, complex biological oil-displacing agent concentration is 1.0wt% merely, and consumption is 0.5PV;
Scheme two: with polymkeric substance and complex biological oil-displacing agent mixed preparing slug, complex biological oil-displacing agent concentration 1.0wt%, polymer concentration 0.1wt%, consumption are 0.5PV;
Scheme three: inject 0.1wt% polymkeric substance 0.1PV, 1.0wt% complex biological oil-displacing agent 0.25PV and 0.1wt% polymkeric substance 0.15PV successively.
10. combination flooding method is characterized in that: behind the reservoir water flooding, inject following slug more successively:
Polymkeric substance+amendment, proportioning 1: 4, slug size 1000m
3
Polymkeric substance+rhamnolipid fermenation raw liquid, weight ratio 1: 12, slug size 10000m
3
Polymkeric substance+amendment, weight ratio 1: 4, slug size 1000m
3
Polymkeric substance+bio-surfactant+chemical surfactant, weight ratio 1: 13: 2, slug size 4000m
3
Polymkeric substance+chemical surfactant, weight ratio 1: 2, slug size 4000m
3
Wherein, said bio-surfactant, chemical surfactant, polymkeric substance and amendment such as aforementioned claim are said.
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Application publication date: 20120613 |