CN1184276C - Application of alkylbenzene sulfonate as main surfactant in ternary composite oil-displacing agent - Google Patents

Application of alkylbenzene sulfonate as main surfactant in ternary composite oil-displacing agent Download PDF

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CN1184276C
CN1184276C CNB011368470A CN01136847A CN1184276C CN 1184276 C CN1184276 C CN 1184276C CN B011368470 A CNB011368470 A CN B011368470A CN 01136847 A CN01136847 A CN 01136847A CN 1184276 C CN1184276 C CN 1184276C
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ternary
polymer
slug
viscosity
alkali
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CN1417284A (en
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廖广志
杨振宇
刘奕
韩培慧
伍晓林
周浩
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Petrochina Co Ltd
Daqing Oilfield Co Ltd
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Daqing Oilfield Co Ltd
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Abstract

The present invention relates to an application of alkylbenzene sulfonate as main surfactant to ternary compound oil displacement, which is composed of a ternary main slug, a minor slug and a subsequent protection slug. The three slugs comprise compound system formulas: (1) the ternary main slug: the size is rock core pore volume: injection liquid volume =100: 35 (0.35PV), the formula is surfactant + alkali + polymer =0.2%(efficiency) +1.0%+1800 mg/l, and the viscosity is 45Mpa. S; (2) the ternary minor slug: the size is 0.1PV, the formula is surfactant + alkali + polymer =0.1%(efficiency) +1.0%+1600 mg/l, and the viscosity is 40Mpa. S; (3) the subsequent protection slug: when the polymer is 0.1 pv *1000 mg/L, the viscosity is 35Mpa. S; when the polymer is 0.1 pv*500 mg/L, the viscosity is 15Mpa. S; the alkylbenzene sulfonate is salt of the anionic surfactant, the alkali is NaOH, Na2CO3, Na3PO4 and NaSiO4. H2O, and the polymer is polyacrylamide.

Description

Alkylbenzenesulfonate is the application of first type surface activating agent in the ternary complex oil displacing
Technical field
The present invention relates to a kind of purposes of alkylbenzenesulfonate, relating in particular to alkylbenzenesulfonate is the application of first type surface activating agent in the ternary complex oil displacing.
Background technology
The eighties has been carried out since the ternary combination flooding desk research, and the ternary combination flooding has preferably entered into the pilot field test stage from mechanism research, prescription; Widen gradually in the field of research during the last ten years, and the dynamics of research strengthens gradually, and the paces of field test are also accelerated gradually, and have obtained significant oil increasing precipitation effect; But also should see simultaneously, the difficulty of ternary combination flooding technical research is increasing, remain at the first type surface activating agent determine, prescription is preferred, highly basic is to series of problems such as formation damage, emulsification mechanism and utilization, DP technology and ground surface works are supporting, especially determining of ternary combination flooding first type surface activating agent becomes the key link of restricting current ternary combination flooding technology advances.
Indoor and field test result shows: the influence factor of three-component compound system and crude oil formation ultralow interfacial tension is more, such as colloid, asphalitine content in the crude oil, the mean molecule quantity of crude oil and carbochain distribute, and alkali consumption and bases type and injection water quality etc. are all influential to forming ultralow interfacial tension. But under specific oil property, the principal element that affects ultralow interfacial tension is the first type surface activating agent, when the mean molecule quantity of average equivalent, equivalent distribution and structural property and the crude oil of first type surface activating agent and carbochain distribute when being complementary, could form ultralow interfacial tension. So, to compare with producing polymer, the development of surfactant is relatively complicated, and the ternary combination flooding is also relatively high to the requirement of first type surface activating agent.
According to research, the ternary combination flooding is as follows to the basic demand of first type surface activating agent:
(1) the first type surface activating agent must make oil water interfacial tension reach ultralow
Because the capillary force effect, residual oil is bound by in the pore media with the form of dispersed oil droplets, oil film or oily band, so that general water drive mode is helpless to it. Only have when driving pressure gradient during more than or equal to the capillary pressure gradient, the constraint oil droplet just activates, and namely has:
         dP/dx≥dPc/dL
         Pc＝2σ/Υ
         σ＝0.5·dP/dx·L·Υ
Can be calculated σ=1.1 * 10-3mN/m
This shows under the water drive condition, to only have oil water interfacial tension to reach 1.1 * 10-3During mN/m, the constraint oil droplet could activate and by displacement out. So the first type surface activating agent must make oil water interfacial tension reach 10 in the ternary combination flooding-3The mN/m order of magnitude, and radix is more low better.
(2) ternary system interfacial tension stabilization time is more than 3 months
Ternary system was placed after 3 months, and system still can keep 10-3MN/m order of magnitude ultralow interfacial tension. The adding of polymer can not cause the phase-splitting of system in the ternary system, and little on the interfacial tension impact of system.
(3) adsorbance of first type surface activating agent on rock low (Dynamic Adsorption amount≤0.1mg/g sand, static adsorbance≤1mg/g sand).
(4) ternary system rock core oil displacement efficiency improves 20% than water drive.
(5) first type surface activating agent cost is low.
(6) but the wide suitability for industrialized production of first type surface activating agent raw material sources.
(7) the first type surface activating agent forms requirement as far as possible simply.
The detailed technical indicator of first type surface activating agent sees Table 1.
Table 1 surface active agent for tertiary oil recovery technical target of the product
Sequence number Project Technical indicator
  1 Gross activity thing content ≥51wt％
  2 Interfacial tension Equilibrium interfacial tension in the time of 45 ℃ (2 hours)≤9.9 * 10-3mN/m Surfactant concentration scope under the Different Alkali concentration
NaOH=0.6wt%, activating agent scope 0.05-0.2wt%
NaOH=0.8wt%, activating agent scope 0.1-0.3wt%
NaOH=1.0wt%, activating agent scope 0.1-0.3wt%
NaOH=1.2wt%, activating agent scope 0.1-0.3wt%
  3 Interface performance The interfacial tension mean value of low tension zone is less than 5.0 * 10-3mN/m
  4 The composition of product Product is comprised of homologue as far as possible, and if any other type material, its adsorbance is as far as possible close
  5 The security performance of product Flash-point 〉=30 ℃; Explosion limit 〉=10% (gas volume percentage)
  6 Product average equivalent scope 400-500
  7 Unsulfonated oil content ＜10wt％
  8 The product inorganic salt content ≤3wt％
  9 Dissolubility In the 5-36 ℃ of inherent 1000-10000mg/LNaCl solution of scope, product dispersion rate＞10wt%
  10 Product is mobile Product viscosity＜200mPaS in the time of 5 ℃
  11 The stability of ASP system Under 5-36 ℃ of condition, system is without permanent precipitation in 16 hours
  12 Product stability Under-20-40 ℃ condition, product is without layering and deposited phenomenon (have this phenomenon to produce under at cryogenic conditions, need can dissolve fully in 48 hours in 5-36 ℃ of scope, do not change the performance indications of product).
  13 The pH value of product 8.0-10.0
  14 Three-component compound system stability and compatibility Ternary system was placed after 3 months, and system still can keep 10-3MN/m order of magnitude ultralow interfacial tension. The adding of polymer can not cause the phase-splitting of system in the ternary system, and little on the interfacial tension impact of system.
  15 The indoor rock core displacement of reservoir oil is estimated By " composite displacement system evaluation method ", ASP system oil displacement efficiency improves 20% than water drive.
According to the basic demand of ternary combination flooding to the first type surface activating agent, the first type surface activating agent that adopts in the ternary combination flooding at present is generally the products such as alkylaryl sulfonates, petroleum sulfonate, weak point is unstable product quality, effectively the compatibility between the distribution of the content of active matter and equivalent and the displacement crude oil is poor, the various chemical agent concentration narrow range in the ultralow interfacial tension zone that forms, stationary phase is not long.
Summary of the invention
The object of the present invention is to provide a kind of take alkylbenzenesulfonate as the application of first type surface activating agent in the ternary complex oil displacing.
Provided by the invention take alkylbenzenesulfonate as the application of first type surface activating agent in the ternary complex oil displacing, it successively injects ternary principal piece plug, secondary slug and follow-up protection slug, and the compound system prescription of these three slugs is respectively:
(1) ternary principal piece plug:
Size rock pore volume: injection liquid volume=100: 35, (being 0.35PV)
Formula table surface-active agent+alkali+polymer=0.2% (effectively)+1.0%+1800mg/L;
Viscosity 45mPaS
(2) the secondary slug of ternary:
Size 0.1PV;
Formula table surface-active agent+alkali+polymer=0.1% (effectively)+1.0%+1600mg/L;
Viscosity 40mPaS
(3) follow-up protection slug:
0.1PV * 1000mg/L (polymer), viscosity: 35mPaS
0.1PV * 500mg/L (polymer), viscosity: 15mPaS
The abovementioned alkyl benzene sulfonate is a kind of salt of anion surfactant;
Above-mentioned alkali is NaOH, Na2CO 3、Na 3PO 4、NaSiO 4·H 2Choosing any one kind of them among the O;
Above-mentioned polymer is polyacrylamide.
The present invention with the present ORS-41 that uses (alkylaryl sulfonates of a kind of mixing that the U.S. produces) surfactant as standard, as follows to the evaluation that alkylbenzenesulfonate is done as the various performance indications of surfactant: (unless special explanation is arranged, concentration mentioned in this article is concentration expressed in percentage by weight)
Interfacial tension is estimated
The present invention is with alkylbenzenesulfonate and the contrast of ORS-41 interfacial activity, the result shows that two kinds of surfactants all have larger ultralow interfacial tension zone, the interfacial tension performance of alkylbenzenesulfonate is better than ORS-41 in low alkali, low activity agent concentration scope, and the result as shown in Figure 1.
Ternary system interfacial tension estimation of stability
The present invention is directed to alkylbenzenesulfonate and examined or check the interfacial tension stability of ternary system under 45 ℃ of constant temperatures, examination is the result show, (39 days) this product three-component compound system has preferably interfacial tension stability, result such as Fig. 2, shown in Figure 3 within the existing examination time.
Product stability is estimated
Lab-evaluation is the result show, within the existing examination time (45 days), this surfactant product has preferably stability, and the result is as shown in table 2.
Table 2
Surfactant product standing time (my god) Experimental point (polymer=1200mg/L, commodity concentration)
Pilot product=0.05wt% Pilot product=0.02wt%
 NaOH＝0.6wt％  NaOH＝1.0wt％   NaOH＝0.8wt％   NaOH＝1.0wt％
  1  7.47×10 -4mN/m  5.74×10 -3mN/m   7.85×10 -3mN/m   7.91×10 -4mN/m
  2   1.13×10 -3mN/m
  15  1.91×10 -3mN/m  2.41×10 -3mN/m   3.13×10 -3mN/m   1.00×10 -3mN/m
  30  5.19×10 -3mN/m  3.74×10 -3mN/m   2.10×10 -3mN/m   1.39×10 -3mN/m
  45  2.38×10 -3mN/m  1.57×10 -3mN/m   1.95×10 -3mN/m   8.38×10 -4mN/m
Annotate: product was placed one day, and polymer is 1,600 ten thousand, and other experimental point polymer is 2,500 ten thousand polymer.
Emulsifiability is estimated
Reagent and evaluation method
Reagent: Daqing oil field four factory's dewatered oils, four factory's sewage, alkylbenzenesulfonate (working substance content 50%), ORS-41 (working substance content 50%) analyzes pure NaOH, super high molecular weight polymer (molecular weight 2,500 ten thousand);
Evaluation method: be that four factory's dehydrated oils of 1: 1 and surfactant product monobasic and ternary system are put into color-comparison tube with weight ratio, behind the thermal agitation, place 45 ℃ of insulating boxs, observe upper, middle and lower phase volume and state every day and change.
Evaluation result
A, single surfactant emulsification experimental result as shown in Figure 4, solution composition:
No. 1 S 0.3% (effectively)
No. 2 S 0.2% (effectively)
No. 3 S 0.025% (effectively)
During mentioned solution forms, S-surfactant, the actual percentage composition of effective-surfactant.
As can be seen from Figure 4, alkylbenzenesulfonate is identical with the ORS-41 emulsifying capacity, and namely upper and lower phase volume does not have significant change, and the centre is the canescence film.
B, ternary system emulsification experimental result as shown in Figure 5, ternary system forms:
No. 1 S 0.3% (effectively)+NaOH 1.2%+HPAM 1200mg/L
No. 2 S 0.2% (effectively)+NaOH 1.0%+HPAM 1200mg/L
No. 3 S 0.1% (effectively)+NaOH 1.0%+HPAM 1200mg/L
No. 4 S 0.05% (effectively)+NaOH 1.0%+HPAM 1200mg/L
No. 5 S 0.025% (effectively)+NaOH 1.0%+HPAM 1200mg/L
As can be seen from Figure 5, the upper and lower phase volume of the ternary system of two kinds of surfactants does not have significant change, and the centre is the canescence film still, illustrates that the ternary system emulsifying capacity of two kinds of surfactants is identical, belongs to unsettled emulsion together.
Adsorbance and alkaline consumption are measured
(1) adsorbance
Measured the quiet absorption of alkylbenzenesulfonate at 50-100 order Daqing oil sand, and contrasted with ORS-41. Experimental result shows that both maximal absorptive capacities are basic identical, as shown in Figure 6.
(2) alkaline consumption
The adsorption isotherm of NaOH on the Daqing oil sandstone meets Langmuir absorption rule, and maximum alkali consumption is the 22mg/g oil-sand, as shown in Figure 7.
The physical analogy Displacement Efficiency
(1) artificial homogeneous rock core
Rock core is artificial homogeneous rock core post, overall dimensions 2.5 * 10 (cm). Injection mode: ternary slug 0.3PV, follow-up protection slug 0.2PV. Slug forms: ternary system is 0.2% surfactant+1.0% alkali+1800mg/L polymer, and follow-up is the 1400mg/L polymer. Experimental result sees Table 3.
Table 3
Sequence number Oil saturation, % Waterflood recovery efficiency factor, % Chemical flooding enhanced oil recovery amplitude, % Overall recovery factor % Pattern number Perm-plug method (* 10-3um 2)
  1   82.5   38.8   20.4   59.2   4ta-4    1260
  2   80.9   40.9   22.7   63.6   4ta-6    1241
  3   80.4   42.9   23.8   66.7   4ta-5    1240
  4   76.6   45.6   22.3   67.9   4ta-8    1190
  5   78.6   36.8   25.5   62.3   4ta-18    1163
(2) artificial heterogeneous core
The artificial heterogeneous core coefficient of variation is 0.59, overall dimensions 3.6 * 3.6 * 30 (cm). Injection mode: ternary slug 0.3PV, follow-up protection slug 0.2PV. Slug forms: ternary system is 0.2% surfactant+1.0% alkali+1800mg/L polymer, and follow-up is the 1200mg/L polymer. Experimental result sees Table 4.
Table 4
Sequence number Oil saturation, % Waterflood recovery efficiency factor, % The chemical flooding recovery ratio, % Overall recovery factor % Pattern number Perm-plug method (* 10-3um 2)
  1   76.6   43.9   22.8   66.7   K59-12   867
  2   73.9   40.4   21.2   61.6   K59-13   872
(3) natural core
The natural core post, overall dimensions 2.5 * 10 (cm), injection mode: ternary slug 0.3PV, follow-up protection slug 0.2PV. Slug forms: ternary system is 0.2% surfactant+1.0% alkali+1800mg/L polymer, and follow-up is the 1400mg/L polymer. The result shows that oil displacement efficiency is suitable with ORS-41, and experimental result sees Table 5.
Table 5
Sequence number Oil saturation, % Waterflood recovery efficiency factor, % Chemical flooding enhanced oil recovery amplitude, % Overall recovery factor % Pattern number Perm-plug method (* 10-3um 2) Remarks
  1   67.0   41.2   22.9     64.3     t-123   1051   Sa＝0.3wt％   NaOH＝1.2wt％
  2   73.8   39.8   21.4     61.2     t-63   1356
  3   74.1   39.0   19.0     58.0     t-61   806   Sa＝0.2wt％   NaOH＝1.0wt％
  4   73.9   39.1   16.9     56.0     t-196   1427
  5   68.2   49.3   22.2     71.5     95-4-1   1250   ORS-41＝0.3wt％   NaOH＝1.2wt％
  6   67.3   50.1   16.0     66.1     94-20   1120   ORS-41＝0.2wt％   NaOH＝1.2wt％
From above result, can draw advantage of the present invention has:
1, the surfactant that uses forms ultralow interfacial tension under low concentration and wider alkali range of condition;
2, absorption loss amount and the alkali consumption of the surfactant product of development are suitable with (both at home and abroad) like product;
3, the surfactant that uses has higher oil displacement efficiency.
Description of drawings
Fig. 1 is interfacial activity comparison diagram of the present invention;
Fig. 2 is product ternary system interfacial tension estimation of stability of the present invention;
Fig. 3 is product ternary system interfacial tension estimation of stability of the present invention (dynamic interface tension force);
Fig. 4 is single surfactant solution (monobasic) emulsified state;
Fig. 5 is ternary system emulsification situation;
Fig. 6 is adsorption isotherm;
Fig. 7 is the alkaline consumption curve;
Fig. 8 is ternary combination flooding of the invention process whole district prediction curve;
Fig. 9 is ternary combination flooding of the invention process center well prediction curve.
The specific embodiment
The three-component compound system prescription that the present invention adopts is as follows:
(1) ternary principal piece plug:
Size rock pore volume: injection liquid volume=100: 35, (being 0.35PV)
Formula table surface-active agent+alkali+polymer=0.2% (effectively)+1.0%+1800mg/L;
Viscosity 45mPaS
(2) the secondary slug of ternary:
Size 0.1PV;
Formula table surface-active agent+alkali+polymer=0.1% (effectively)+1.0%+1600mg/L;
Viscosity mPaS
(3) follow-up protection slug:
0.1PV * 1000mg/L (polymer), viscosity: 35mPaS
0.1PV * 500mg/L (polymer), viscosity: 15mPaS
Wherein alkylbenzenesulfonate is a kind of salt of anion surfactant; Alkali can be NaOH, Na2CO 3、Na 3PO 4、NaSiO 4·H 2Choosing any one kind of them among the O adopted NaOH in this example; Polymer is polyacrylamide.
The whole district of Daqing oil field Xing Er district middle part ternary combination flooding flooding Industrial Mine Trial and center well numerical simulation predicted the outcome see Fig. 8, shown in Figure 9. Predicting the outcome shows, when injecting chemical agent slug 0.11PV, comprehensive moisture beginning of the whole district descends, and the whole district is comprehensive moisture after 7.06 (2574 days) reaches 98%, when the time comes, and whole district's accumulation produce oil 49.34 * 104T, ternary combination flooding have a net increase of oil 40.71 * 104T improves recovery ratio 20.18% than water drive; When 9 mouthfuls of center wells arrive moisture 98%, accumulation produce oil 28.06 * 104T has a net increase of oil 21.52 * 104T improves recovery ratio 21.52 than water drive; The center well is during to the whole district comprehensive moisture 98%, tired produce oil 28.19 * 104T has a net increase of oil 23.53 * 104T improves recovery ratio 21.63% than water drive.

Claims (3)

1, a kind of alkylbenzenesulfonate is the application of first type surface activating agent in the ternary complex oil displacing, successively injects ternary principal piece plug, secondary slug and follow-up protection slug, it is characterized in that the compound system prescription of these three slugs is respectively:
(1) ternary principal piece plug:
Size rock pore volume: injection liquid volume=100: 35;
Formula table surface-active agent+alkali+polymer=0.2% (effectively)+1.0%+1800mg/L;
Viscosity 45mPaS;
(2) the secondary slug of ternary:
Size 0.1PV;
Formula table surface-active agent+alkali+polymer=0.1% (effectively)+1.0%+1600mg/L;
Viscosity 40mPaS;
(3) follow-up protection slug:
0.1PV * 1000mg/L (polymer), viscosity: 35mPaS, and
0.1PV * 500mg/L (polymer), viscosity: 15mPaS.
2, alkylbenzenesulfonate according to claim 1 is the application of first type surface activating agent in the ternary complex oil displacing, it is characterized in that, described alkali is NaOH, Na2CO 3、Na 3PO 4、 NaSiO 4·H 2Choosing any one kind of them among the O.
3, alkylbenzenesulfonate according to claim 1 is the application of first type surface activating agent in the ternary complex oil displacing, it is characterized in that, described polymer is polyacrylamide.
CNB011368470A 2001-10-29 2001-10-29 Application of alkylbenzene sulfonate as main surfactant in ternary composite oil-displacing agent Expired - Lifetime CN1184276C (en)

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CN101747884B (en) * 2010-03-08 2011-06-15 大庆浩拓化工有限公司 Efficient compound anti-swelling oil displacement agent and method for preparing same
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