CN103940706B - Definite method of petroleum crude oil three-component compound system - Google Patents
Definite method of petroleum crude oil three-component compound system Download PDFInfo
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Abstract
The invention discloses a kind of quantitative analysis method of petroleum crude oil three-component compound system interfacial tension performance and definite method of this three-component compound system, comprise the steps: to add reference oil in the three-component compound system to be measured preparing, utilize interfacial tensimeter to measure the parameters that calculates interfacial tension, thereby calculate interfacial tension value, draw interfacial tension and be worth time dependent curve, find out the minimum interfacial tension value σ in this curveminWith corresponding ultralow interfacial tension action time Δ t, and then obtain interfacial tension performance index and both incidence relations, for analyzing the interfacial tension performance of three-component compound system; And obtain oil displacement efficiency by interfacial tension performance index, three-component compound system is determined. Method of the present invention has been carried out comprehensive analysis and is provided quantitatively guidance to determining of three-component compound system the interfacial tension performance of three-component compound system by quantitative mode, and process is simple, and result objective science is reproducible.
Description
Technical field
The present invention relates to the analytical method of compound system interfacial tension performance and definite method of this compound system, particularly relate to a kind of quantitative analysis method of petroleum crude oil three-component compound system interfacial tension performance and definite method of this three-component compound system.
Background technology
At present, three-component compound system is a kind of method of injecting stratum together and carry out oil exploitation composite the materials such as the alkali of certain proportioning, surfactant, polymer, is particularly useful for tertiary oil recovery. In oil recovery process, petroleum crude oil and ternary complex tie up to the emulsion liquid that forms profit one under the immixture of underground porous rock and the stirring action of petroleum gas; Locate at oil well restriction, valve and oil pump petroleum pipeline etc., petroleum crude oil and interfacial tension system, through strong collision and friction, also can form emulsion liquid. This method can be brought into play alkali, the effect of surfactant aspect reduction interfacial tension, can bring into play again the effect of polymer profile control and fluidity control, is more conducive to the displacement of reservoir oil. The key of the method is the rational surfactant of How to choose and utilizes the synergy between various chemical substances in emulsion liquid to make interfacial tension between profit reach minimum. Hence one can see that, and the interfacial tension performance of three-component compound system plays very crucial effect to oil displacement efficiency.
In prior art, all analyze the interfacial tension performance of compound system by equilibrium interfacial tension value, stable state interfacial tension value when equilibrium interfacial tension refers to and reaches balance after petroleum crude oil/compound system contact action certain hour, but this analytical method can only be evaluated the interfacial tension performance of the petroleum crude oil/compound system after stable, and be not suitable for profit two-phase and be also in the analysis of the interfacial tension performance of fusion process; And interfacial tension performance is except relevant with interfacial tension value, also relevant with factors such as action times, current method can not be analyzed interfacial tension performance quantitatively, therefore, for Guiding Practice application better, and more scientific theoretical foundation is provided in the time selecting three-component compound system, be badly in need of setting up a kind of quantitative analytical method of interfacial tension performance of the three-component compound system to petroleum crude oil, and instruct definite three-component compound system with it.
Summary of the invention
Main purpose of the present invention is for the technological deficiency existing in prior art, and a kind of quantitative analysis method of petroleum crude oil three-component compound system interfacial tension performance is provided, and the method comprises the following steps:
(1) mensuration of interfacial tension: three-component compound system to be measured and the reference oil that obtained by petroleum crude oil are added in interfacial tensimeter, certain interval of time is measured the reference oil diameter d for calculating interfacial tension, calculate again the interfacial tension value σ of each time point
σ＝5.24×105×Δρ×d3/T2Formula (1)
Wherein, Δ ρ is the density difference of reference oil and three-component compound system to be measured, and T is the rotating speed that interfacial tensimeter is set, and d is reference oil diameter;
(2) calculating of interfacial tension performance index: the interfacial tension value temporal evolution that step (1) is calculated is made an indicatrix, finds out the minimum interfacial tension value σ in this curveminUltralow interfacial tension action time Δ t with corresponding, calculates interfacial tension performance index S:
Wherein, σminFor the minimum interfacial tension value of three-component compound system to be measured;
σStandardFor the minimum interfacial tension value of standard three-component compound system, σStandard＝1.0×10-2mN/m；
Δ t is ultralow interfacial tension action time, and interfacial tension value is less than 1.0 × 10-2The time that mN/m maintains;
(3) utilize interfacial tension performance index S numerical value quantitative analysis three-component compound system interfacial tension to be measured performance, S numerical value is larger, and interfacial tension performance is better.
The preparation process of described reference oil is as follows: get petroleum crude oil in separatory funnel, add organic solvent that petroleum crude oil is all dissolved, add with the petroleum crude oil after the water hydrochloric acid solution that 1:1 mixes by volume adjusting dissolving to pH=2, then extract, get organic phase dehydration, evaporate described organic solvent and obtain reference oil.
In described three-component compound system to be measured and standard three-component compound system, include surfactant, the NaOH of 1.2wt% and the polyacrylamide of 0.15wt% that quality percentage composition is 0.3wt%, formulated by oil field stratum Simulated Water.
Described surfactant is selected from alkylbenzenesulfonate, petroleum sulfonate or petroleum carboxylate.
Described oil field stratum Simulated Water is taken from Daqing oil field the 4th oil recovery factory's sewage, and salinity is 6431.36mmol/L.
Described organic solvent is 120#Unleaded gas.
Another object of the present invention is to provide a kind of definite method of petroleum crude oil three-component compound system, comprehensively determine three-component compound system with the interfacial tension performance index S obtaining in quantitative analysis method described in oil displacement efficiency E and claim 1-6 any one,
E=0.9772LnS+13.241 formula (3)
Wherein, the oil displacement efficiency that E is three-component compound system to be measured;
S is the interfacial tension performance index of three-component compound system to be measured.
It is the three-component compound system of determining that E value is greater than 20% ternary complex.
It is the three-component compound system of determining that S value is greater than 1000 ternary complex.
The present invention has provided the quantitative analysis method of petroleum crude oil three-component compound system interfacial tension performance, and creativeness proposed interfacial tension performance index, the mensuration of above-mentioned analytical method and interfacial tension performance index has direct directive significance for oilfield exploitation with the analysis of three-component compound system interfacial tension performance. Analytical method of the present invention is applicable to the analysis of three-component compound system dynamic interface tension force performance, dynamic interface tension force refers to the instantaneous value of petroleum crude oil/compound system arbitrary moment interfacial tension in contact process, and first interfacial tension performance index and oil displacement efficiency are quantitatively associated, can comprehensively evaluate three-component compound system by quantitative mode like this, and the method is simple, objective, accurate, reproducible, error is little, there is good operability and practicality, for the selection of three-component compound system provides the theoretical foundation of science.
Brief description of the drawings
Figure 1 shows that interfacial tension value temporal evolution figure.
Detailed description of the invention
The quantitative analysis method of a kind of petroleum crude oil three-component compound system interfacial tension performance provided by the invention, to measure minimum interfacial tension value and ultralow interfacial tension action time in three-component compound system by quantitative mode, calculate interfacial tension performance index, the interfacial tension performance of three-component compound system is carried out to Comprehensive Assessment. And then interfacial tension performance index is associated with oil displacement efficiency, with its quantitative analysis instruct three-component compound system determine.
Below in conjunction with specific embodiment, the present invention is described in further detail. Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
Embodiment 1, utilize interfacial tension performance index to carry out quantitative analysis to three-component compound system
1, prepare three-component compound system to be measured
The preparation (concentration is 10wt%) of 1.1 surfactant mother liquors
Get effective content and be 50% sodium alkyl benzene sulfonate 20.0g, add the oil field stratum Simulated Water of 80.0g, shake up. Surfactant can be selected alkylbenzenesulfonate, petroleum sulfonate or petroleum carboxylate etc.
The preparation (concentration is 30wt%) of 1.2 alkali liquors
Get NaOH solid 30.0g in the beaker of clean dried, slowly add oil field stratum Simulated Water 70.0g, be stirred to solid and dissolve completely.
The preparation (concentration is 2000ppm) of 1.3 polymer mother liquors
Get polyacrylamide dry powder (HPAM, molecular weight is 2,500 ten thousand) 2.273g, evenly slowly join while stirring in 997.727g oil field stratum Simulated Water, mixing speed is 400-600r/min, after adding HPAM, continuation stirring 2-4h makes it fully swelling.
The preparation of 1.4 three-component compound systems to be measured
Taking each concentration of component as surfactant 0.3wt%, alkali 1.2wt%, the ternary complex to be measured of polymer 0.15wt% is example:
1.5g surfactant mother liquor, 2.0g alkali liquor and 37.5g polymer mother liquor are mixed, and add 9.0g oil field stratum Simulated Water, stir 30min to dissolving completely, three-component compound system to be measured.
2, the processing of petroleum crude oil---the preparation of reference oil
Get the petroleum crude oil of 40mL object block well head in separatory funnel, add 160～200mL gasoline (all dissolve and be as the criterion with petroleum crude oil), add 30mL1: 1 hydrochloric acid (adjusting pH=2 left and right) extracts. Fully vibrate and exit, leave standstill approximately 2 little layereds (if not layering, add the jolting of 5mL hydrochloric acid several under), collect upper layer of extraction liquid in conical flask, add appropriate anhydrous sodium sulfate (be added to no longer caking till), conical flask is placed more than 2 hours dehydration after jumping a queue. Then filter upper layer of extraction liquid with qualitative filter paper, filtrate is collected in cucurbit, the most of gasoline of Distillation recovery, remaining a small amount of liquid after distillation is proceeded in evaporating dish, in the water bath with thermostatic control of 80 ± 1 DEG C, evaporated after near doing, proceed to while hot in measuring cup, put into 80 ± 1 DEG C of baking ovens and dry to constant weight. Obtain reference oil, put it in drier stand-by.
The petroleum crude oil that the present embodiment is used is Daqing oil field the 4th oil recovery factory's multi-purpose station dehydration petroleum crude oil, and oil field stratum Simulated Water is all taken from Daqing oil field the 4th oil recovery factory's sewage, and salinity is 6431.36mmol/L.
3, the mensuration of interfacial tension
The preparation of 3.1 instruments and sample
The preparation of instrument: the interfacial tensimeter model using in present embodiment is Texas-500C type. Start preheating 5-10min, starts constant temperature system temperature is risen to 45 ± 0.2 DEG C, and fuselage is adjusted to level, opens computer, enters interfacial tension and measures interface, and so far instrument is ready.
The preparation of sample: the three-component compound system to be measured of preparing by method in 1 rinses after interfacial tensimeter capillary 5 times repeatedly, make whole capillary be full of three-component compound system to be measured, reference oil reinjects, ensure that oil droplet is of moderate size and oil droplet height at 0.6mm between 0.8mm, in capillary, must not there is bubble, cover capillary lid, again check in whole capillary and do not have after bubble, preparation of samples completes.
3.2 measure the parameters for calculating interfacial tension
Measure the density of reference oil and three-component compound system to be measured with densitometer, and calculate both density difference DELTA ρ.
Pack ready sample in 3.1 into interfacial tensimeter, setting speed T is 3000-5000r/min, open instrument, now start timing, and take pictures once to sample every 10min, measure length L and the height (being reference oil diameter d) of reference oil in the picture of taking, until the measurement result of continuous three times is less than 0.01mm, stop measuring, obtain the reference oil diameter d numerical value that each time point is corresponding.
3.3 calculating of interfacial tension σ and the drafting of indicatrix
If reference oil length L and height (reference oil diameter d) meet L > 4d, d is brought into formula (1), calculate interfacial tension σ, and draw the time dependent curve of interfacial tension.
σ＝5.24×105×Δρ×d3/T2Formula (1)
In formula: σ-interfacial tension, mN/m;
The density difference of Δ ρ-reference oil and three-component compound system to be measured, g/cm3；
The rotating speed of T-interfacial tensimeter, r/min;
D-reference oil diameter, mm.
In formula (1), for same reference oil and three-component compound system to be measured, Δ ρ immobilizes, and in the present embodiment, the density contrast Δ ρ numerical value of reference oil and three-component compound system to be measured is 0.155g/cm3。
In every batch sample, randomly draw a sample and again detect according to the step in 3.1-3.3, contrast the interfacial tension value that twice meter calculates, the required precision that meets table 1 is qualified data, otherwise again detects.
The requirement of table 1 interfacial tension value accuracy of detection
| σ(mN/m) | Parallel deviation |
| 1.0×10-2≤σ＜1 | ≤±10％ |
| 1.0×10-4≤σ＜1.0×10-2 | ≤±20％ |
| 1.0×10-4＜σ | ≤±30％ |
4, the analysis of three-component compound system interfacial tension performance to be measured
Be worth time dependent curve according to 3.3 interfacial tensions that obtain, obtaining a minimum interfacial tension value and ultralow interfacial tension action time, (is that interfacial tension value is less than 1.0 × 10 by interfacial tension performance index S and minimum interfacial tension value and ultralow interfacial tension action time-2The time that mN/m maintains) associate, obtain formula (2), analyze quantitatively the interfacial tension performance of three-component compound system to be measured by interfacial tension performance index S.
In formula: S-interfacial tension performance index;
σminThe minimum interfacial tension value of-three-component compound system to be measured, mN/m;
σStandardThe minimum interfacial tension value of-standard three-component compound system, numerical value is 1.0 × 10-2mN/m；
Δ t-ultralow interfacial tension action time, interfacial tension value is less than 1.0 × 10-2The time that mN/m maintains, min.
In standard three-component compound system, contain the surfactant of 0.3wt%, the NaOH of 1.2wt%, the HPAM of 2,500 ten thousand molecular weight of 0.15wt%, all the other are oil field stratum Simulated Water, wherein, surfactant adopts sodium alkyl benzene sulfonate, and (this surfactant is the mixture with the sodium alkyl benzene sulfonate of different carbon numbers, its molecular weight is between 400-420, by carbon number in 45wt% alkyl between the sodium alkyl benzene sulfonate of 12-15, in 43wt% alkyl carbon number in the sodium alkyl benzene sulfonate of 16-20 and 12wt% alkyl carbon number between the sodium alkyl benzene sulfonate composition of 21-24), and it is 60% that the equivalent of surfactant distributes with the carbochain distribution matching degree of reference oil. σStandardRecord according to method in 3.
Can draw from above formula, interfacial tension performance index S is with minimum interfacial tension value σminAmplification reciprocal is that linear relationship increases; With the linear increase of increase of ultralow interfacial tension action time Δ t. Therefore, minimum interfacial tension value is larger, and S is less for interfacial tension performance index, and the interfacial tension performance of three-component compound system to be measured is poorer; Minimum interfacial tension is the longest with the time, and S is larger for interfacial tension performance index, and the interfacial tension performance of three-component compound system to be measured is better. Vice versa.
5, the analysis of ASP displacement efficiency to be measured
Further, can, by associated with oil displacement efficiency E interfacial tension performance index S, obtain formula (3), be intended to utilize the interfacial tension performance that quantitative analysis obtains to carry out Comprehensive Assessment to the oil displacement efficiency of three-component compound system to be measured.
E=0.9772LnS+13.241 formula (3)
In formula: E-chemical flooding oil displacement efficiency, %;
S-interfacial tension performance index.
Can find out, oil displacement efficiency E is with the linear increase of increase of interfacial tension performance index S logarithm, and therefore, the interfacial tension performance of three-component compound system to be measured is better, and interfacial tension performance index is larger, and oil displacement efficiency is higher. Vice versa.
By test, quantitative analysis method of the present invention is tested and verified respectively below.
Experimental section: the validity check of interfacial tension performance index
1) prepare reference oil and three kinds of three-component compound systems to be measured 1 that interfacial tension degree is different according to 1 with the method in 2 respectively#、2#、3#; In these three groups of three-component compound systems to be measured, surfactant has just adopted different sodium alkyl benzene sulfonates, and all the other materials are all identical, and (keeping the density contrast of reference oil and every group of three-component compound system to be measured is 0.155g/cm3), this surfactant is the mixture with the sodium alkyl benzene sulfonate of different carbon numbers, its molecular weight is between 400-420, formed between the sodium alkyl benzene sulfonate of 21-24 by the carbon number carbon number in the sodium alkyl benzene sulfonate of 16-20 and 12wt% alkyl in the sodium alkyl benzene sulfonate of 12-15,43wt% alkyl of carbon number in 45wt% alkyl, and the equivalent of surfactant in these three groups of three-component compound systems to be measured distributes and is respectively 60%, 70% and 80% with the carbochain distribution matching degree of reference oil.
2) calculate the interfacial tension value of each time point by the method in 3 and 4, and obtain the time dependent indicatrix of interfacial tension (seeing Fig. 1), find minimum interfacial tension value σminWith ultralow interfacial tension action time Δ t (be that interfacial tension value is less than 1.0 × 10-2The time that mN/m maintains), and then calculate the interfacial tension performance index S of these three kinds of three-component compound systems to be measured;
3) obtain the calculated value of oil displacement efficiency E according to the formula in 5 (3), then these three groups of three-component compound systems to be measured carry out physical simulation experiment respectively and obtain the experiment value of oil displacement efficiency, data are in table 2.
The experiment of table 2 interfacial tension performance index validity and error analysis result
In table 2, calculated value and the experiment value of the oil displacement efficiency that more same group of three-component compound system to be measured obtains, find that both errors are all less than 5%, illustrates that the interfacial tension performance that quantitative analysis method of the present invention is used for evaluating three-component compound system is accurately feasible. And, the numeric ratio by three groups of ASP displacement efficiency to be measured, 1#Three-component compound system to be measured is consistent with the component of standard three-component compound system, utilize the interfacial tension performance index S that the inventive method obtains to approach 1000, oil displacement efficiency approximates 20%, coincide with the parameter of standard three-component compound system, further illustrates quantitative analysis method of the present invention accurately feasible; Numeric ratio by table 2, also shows 2#With 3#The interfacial tension performance of three-component compound system to be measured is all good than standard three-component compound system, and wherein 3#The interfacial tension performance of three-component compound system to be measured is best. According to the experiment of this interfacial tension performance index validity, illustrate that the result that the quantitative analysis method of petroleum crude oil three-component compound system interfacial tension performance of the present invention draws is reliably believable.
Embodiment 2, utilize interfacial tension performance index to determine three-component compound system to be measured
Calculate according to the formula in 5 (3), in the time of oil displacement efficiency E=20%, the interfacial tension performance index S=1000 of three-component compound system, that is to say and want to make oil displacement efficiency E > 20%, the interfacial tension performance index S of three-component compound system wants > 1000. Therefore in the time utilizing interfacial tension performance index to determine three-component compound system to be measured, as long as the interfacial tension performance index S > 1000 calculating, this three-component compound system to be measured is qualified. Associative list 2 is visible, and 1#Three-component compound system to be measured is standard three-component compound system, and 2# and 3# three-component compound system to be measured is qualified three-component compound system.
In order to determine more quickly qualified three-component compound system, carrying out after many experiments, while drawing interfacial tension performance index S=1000, the minimum interfacial tension value σ that three-component compound system is correspondingmin, ultralow interfacial tension action time Δ t data group, be shown in Table 3.
The three-component compound system interfacial tension performance parameter tables of data that table 3 is qualified
Like this, in the time determining three-component compound system, without by the minimum interfacial tension value detecting and ultralow interfacial tension action time substitution formula (2) and formula (3), only use the minimum interfacial tension value recording or ultralow interfacial tension action time compared with data in table, can learn that whether this three-component compound system to be measured is qualified.
For example, 2 in table 2#With 3#Three-component compound system ultralow interfacial tension action time Δ t to be measured is respectively 90.00min and 120min, the minimum interfacial tension value σ reachingminBe respectively 1.55 × 10-3MN/m and 2.39 × 10-4MN/m, tables look-up 3, and the minimum interfacial tension value under this ultralow interfacial tension action time is respectively 8.2 × 10-3MN/m and 8.6 × 10-3MN/m; Because minimum interfacial tension value and interfacial tension performance index are inversely proportional to, 2#With 3#The minimum interfacial tension value 1.55 × 10 of three-component compound system to be measured-3MN/m and 2.39 × 10-4MN/m is less than respectively 8.2 × 10 in table 3-3MN/m and 8.6 × 10-3MN/m, therefore 2#With 3#The interfacial tension performance index S of three-component compound system to be measured exceedes 1000 certainly, and this just means 2#With 3#The oil displacement efficiency of three-component compound system to be measured all exceedes 20% certainly, is qualified three-component compound system. Therefore, the method is for determining that good three-component compound system provides science foundation intuitively.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (9)
1. a definite method for petroleum crude oil three-component compound system, is characterized in that, with oil displacement efficiency E and interfaceTension force performance index S comprehensively determines three-component compound system,
E=0.9772LnS+13.241 formula (3)
Wherein, the oil displacement efficiency that E is three-component compound system to be measured;
S is the interfacial tension performance index of three-component compound system to be measured;
The calculating of the interfacial tension performance index S of three-component compound system comprises the following steps:
(1) mensuration of interfacial tension: three-component compound system to be measured and the reference oil that obtained by petroleum crude oil are added to interfaceIn tensiometer, certain interval of time is measured the reference oil diameter d for calculating interfacial tension, then calculates each time pointInterfacial tension value σ,
σ＝5.24×105×Δρ×d3/T2Formula (1)
Wherein, Δ ρ is the density difference of reference oil and three-component compound system to be measured, and T is the rotating speed that interfacial tensimeter is set,D is reference oil diameter;
(2) calculating of interfacial tension performance index: the interfacial tension value temporal evolution that step (1) is calculatedMake an indicatrix, find out the minimum interfacial tension value σ in this curveminDo with corresponding ultralow interfacial tensionWith time Δ t, calculate interfacial tension performance index S:
Wherein, σminFor the minimum interfacial tension value of three-component compound system to be measured;
σStandardFor the minimum interfacial tension value of standard three-component compound system, σStandard＝1.0×10-2mN/m；
Δ t is ultralow interfacial tension action time, and interfacial tension value is less than 1.0 × 10-2The time that mN/m maintains.
2. determine according to claim 1 method, it is characterized in that, the preparation process of described reference oil is as follows: getPetroleum crude oil, in separatory funnel, adds organic solvent that petroleum crude oil is all dissolved, and adds and water 1:1 by volumePetroleum crude oil after the hydrochloric acid solution adjusting mixing is dissolved, to pH=2, then extracts, and gets organic phase dehydration, steamsSending out organic solvent described obtains reference oil.
3. determine according to claim 2 method, it is characterized in that described three-component compound system to be measured and standard threeUnit include in compound system surfactant that quality percentage composition is 0.3wt%, 1.2wt% NaOH andThe polyacrylamide of 0.15wt%, formulated by oil field stratum Simulated Water.
4. determine according to claim 3 method, it is characterized in that, described surfactant is selected from alkyl benzene sulphonateSalt, petroleum sulfonate or petroleum carboxylate.
5. determine according to claim 4 method, it is characterized in that, described oil field stratum Simulated Water is taken from Daqing oilField the 4th oil recovery factory's sewage, salinity is 6431.36mmol/L.
6. determine according to claim 5 method, it is characterized in that, described organic solvent is 120#Unleaded gas.
7. according to the arbitrary described definite method of claim 1-6, it is characterized in that the tri compound that E value is greater than 20%System is the three-component compound system of determining.
8. determine according to claim 7 method, it is characterized in that the three-component compound system that S value is greater than 1000For the three-component compound system of determining.
9. according to the arbitrary described definite method of claim 1-6, it is characterized in that, it is multiple that S value is greater than 1000 ternaryZoarium is the three-component compound system of determining.
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