CN1123620C - Three-element built-up composition containing lignosulfonate surfactant and its application in tertiary petroleum recovery - Google Patents
Three-element built-up composition containing lignosulfonate surfactant and its application in tertiary petroleum recovery Download PDFInfo
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- CN1123620C CN1123620C CN 00120985 CN00120985A CN1123620C CN 1123620 C CN1123620 C CN 1123620C CN 00120985 CN00120985 CN 00120985 CN 00120985 A CN00120985 A CN 00120985A CN 1123620 C CN1123620 C CN 1123620C
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Abstract
The present invention relates to a ternary compounding composition which contains lignosulphonate surfactant. The present invention comprises components by weight: 0.05 to 0.8 part of lignosulphonate compound surfactant, 0.6 to 1.6 parts of alkali and 0.08 to 1.8 parts of polymer in 100 parts of water, wherein lignosulphonate is respectively compounded with petroleum carboxylate and alkylbenzene sulfonate according to the ratio of 1: 1 to 3: 1. The present invention simultaneously discloses the application of the compounding composition as an oil displacement injection agent to tertiary oil recovery. The compatibility of the compounding composition of the present invention and oilfields is good, and the oil displacement effect is obvious.
Description
The present invention relates to oil field displacement of reservoir oil injection system, be specifically related in the ternary composite driving a kind of complex composition and as the application of displacement of reservoir oil injecting in tertiary oil recovery.
The application surface promoting agent recovers the oil to study and originates in early thirties in petro-technology, so far the history in existing more than 60 year.Six during the last ten years, all obtained very big development in the theory and practice.At present, following several injection systems have been formed basically.(1) active water drive; (2) micellar solution flooding; (3) the low interfacial tension system is recovered the oil; (4) ternary composite driving.Wherein ternary composite driving (alkali-polymkeric substance-tensio-active agent) is a kind of novel method that improves recovery ratio that the eighties just grows up in this century, because this method still can obtain higher oil displacement efficiency under the situation of low surfactant consumption significantly, therefore, it becomes the new technology in economic and technical raising recovery ratio that can both be successful.
After the oil field enters high water-cut stage, surplus oil with discontinuous oil clot by trap in the reservoir rocks hole, two main power that act on the oil droplet are viscap.As use suitable surfactant system, reduce the interfacial tension between profit, just reduced the resistance that the oil droplet distortion is brought when using irreducible oil to move, thus oil displacement efficiency improved.
Xylogen is the by product that produces in the paper industry, and its source is wide, cheap.The conventional sulfonated lignin that with the xylogen are raw material production are the most frequently used tensio-active agents both at home and abroad, but its surfactivity is relatively poor, is mainly used in the dispersion agent of liquid-solid dispersion system, generally, the surface tension of its aqueous solution is about 50mN/m, and micelle-forming concentration is very high.The sulfonated lignin of modification, in structure, introduce lipophilic ingredient after, have higher water-soluble, but use can not form ultra low interfacial tension with crude oil separately, can not be directly used in the displacement of reservoir oil.
The object of the present invention is to provide a kind of ternary recompounded composite that has excellent compatibility and can form the sulfonated lignin cheap with crude oil than containing of low interfacial tension.
Another purpose of the present invention is to provide above-mentioned ternary built displacement of reservoir oil composition as the application of displacement of reservoir oil injecting in tertiary oil recovery.
For achieving the above object, the present invention takes following technical scheme:
A kind of ternary recompounded composite that contains lignin sulfonate surfactant, its each component concentration are to contain in 100 parts of weight water:
Sulfonated lignin complexed surfactant 0.05-0.8 weight part
Alkali 0.6-1.6 weight part
Polymkeric substance 0.08-1.8 weight part
The ternary recompounded composite that contains lignin sulfonate surfactant recited above, described sulfonated lignin complexed surfactant be sulfonated lignin and alkylbenzene sulfonate in 1: 1-4: the complexed surfactant of 1 ratio preparation.
The ternary recompounded composite that contains lignin sulfonate surfactant recited above, described sulfonated lignin complexed surfactant be sulfonated lignin and petroleum carboxylate in 1: 1-3: the complexed surfactant of 1 ratio preparation.
The ternary recompounded composite that contains lignin sulfonate surfactant recited above, described sulfonated lignin are modified lignin mahogany sulfonate.
Below technology of the present invention is described further.
Ternary recompounded composite of the present invention, what adopt is sulfonated lignin complexed surfactant-alkali-polymer ternary displacement system, wherein, alkaline agent main effect be the charge property that changes rock surface, tensio-active agent that protective price is more expensive and polymkeric substance reduce them and lose in the stratum; The principle of the alkali displacement of reservoir oil is that it can have surface-active material with organic carboxyl acid or other the effective acidic components reaction generation in the crude oil simultaneously, cause interfacial tension lowering, emulsification wettability reversal, make oil droplet or the oil droplet that is in dispersion state that be captured in the stratum breast crack start, assemble, the rich oil band that formation can continuous flow and by extraction.
In the ternary displacement system, the adding of polymkeric substance increases the viscosity of solution, thereby the basic component of aqueous phase can be contacted with more oil phase, form more surfactant, help reducing water termination tension force, displacement goes out more irreducible oil, also make simultaneously displacing fluid sweep and the oil reservoir volume increase, the surplus oil of energy extraction drive than independent alkali or polymer flooding more.
General lignin sulfonate surface activity is relatively poor, and generally the surface tension of its aqueous solution is about 50mN/m, and micelle-forming concentration is very high, does not reach the live requirement of agent of ternary composite displacement system his-and-hers watches.Therefore, the used sulfonated lignin of the present invention are modified lignin mahogany sulfonate, and it has very high water-soluble, mainly is to introduce lipophilic ingredient in its structure.Concrete approach can obtain by alkylation process, Mannich reaction method and condensation reaction method, and concrete reaction path is as follows with chemical formulation:
(1) alkylation process:
(2) Mannich reaction method:
(3) condensation reaction method:
The present invention includes following accompanying drawing:
Fig. 1 illustrates the ternary recompounded composite interfacial tension of the embodiment of the invention five;
Fig. 2 is the active figure in interface between the ternary recompounded composite of the embodiment of the invention nine and crude oil;
Fig. 3 illustrates the ternary recompounded composite interfacial tension of the embodiment of the invention 11;
Fig. 4 illustrates the ternary recompounded composite interfacial tension of the embodiment of the invention 16;
Fig. 5 is the active figure in interface between the ternary recompounded composite of the embodiment of the invention 15 and crude oil
Below in conjunction with the drawings and specific embodiments, specify ternary recompounded composite provided by the invention with and the remarkable technique effect that brings.
If no special instructions, reagent and the testing tool that uses in embodiment and the test experiments is as follows:
One, use reagent:
The plain sulfonate WNS of wood pulp alkali: the product of Dalian University of Technology;
Straw pulp alkali lignin sulfonate GNS: Dalian University of Technology's product;
Heavy alkylbenzene sulfonate HS: the sintetics of Dalian University of Technology;
Petroleum carboxylate WGN: Jianghan Petroleum College's development, the organic chemical industry's head factory pilot scale of Fuxin, Liaoning is amplified;
Alkylbenzene sulfonate ORS: U.S. SCI company produces;
Polymkeric substance: polyacrylamide, PAM, the grand celebration auxiliary reagent factory produces, molecular weight 1000～2,500 ten thousand.
Alkali: sodium hydroxide NaOH is the technical pure commodity.
Crude oil: Daqing oil field dewatered oil.
Two, use instrument:
Interfacial tensimeter is dripped in the rotation of Model-500 type: Texas, USA university produces, 45 ℃ of experimental temperatures;
Automatic density instrument: the automatic digital density instrument of the DA-101B type of kyoto, Japan Electronics Co., Ltd.;
Rock core displacement of reservoir oil device: French Geomecanique company makes High Temperature High Pressure oil displacement test device;
Embodiment one～embodiment 17: the indoor natural core oil displacement experiment result of the specifically ternary recompounded composite prescription of Shi Shiing, and part embodiment, see table 1 for details.
Table 1 ternary recompounded composite and interfacial tension thereof and oil displacement experiment result
| Embodiment | Promoting agent total amount wt% | The promoting agent ratio | Alkali consumption wt% | Polymer loading mg/l | Complex composition interfacial tension mN/m | Improve recovery ratio % than water drive |
| OOIP | ||||||
| One | 0.6 | GNS∶ORS＝1∶1 | 1.2 | 1200 | 10 -3mN/m | 18.76 |
| Two | 0.8 | GNS∶ORS＝3∶2 | 1.2 | 1500 | 10 -4mN/m | 21.23 |
| Three | 0.6 | WNS∶ORS＝4∶1 | 1.0 | 1200 | 10 -3mN/m | 16.27 |
| Four | 0.8 | WNS∶ORS＝3∶1 | 1.2 | 1200 | 10 -3mN/m | 18.32 |
| Five | 0.6 | WNS∶ORS＝3∶1 | 0.8-1.6 | 1800 | 10 -4mN/m | 18.90 |
| Six | 0.8 | WNS∶ORS＝3∶1 | 1.2 | 1800 | 10 -3mN/m | 20.00 |
| Seven | 0.05-0.6 | WNS∶HS＝1∶1 | 1.2 | 1500 | 10 -3mN/m | |
| Eight | 0.4 | WNS∶HS＝4∶1 | 1.2 | 1200 | 10 -3mN/m | |
| Nine | 0.05-0.6 | WNS∶HS＝1∶1 | 0.8-1.5 | 1800 | 10 -3mN/m | |
| Ten | 0.2 | WNS∶HS＝3∶2 | 0.9-1.5 | 1800 | 10 -3mN/m | |
| 11 | 0.1-0.8 | GNS∶HS＝3∶2， 2∶3，4∶1，1∶1 | 1.2 | 1500 | 10 -3mN/m | |
| 12 | 0.2 | GNS∶HS＝3∶2 | 0.9-1.4 | 1500 | 10 -4mN/m | |
| 13 | 0.6 | WNS∶WGN＝2∶1 | 1.2 | 1500 | 10 -3mN/m | 18.6 |
| 14 | 0.8 | WNS∶WGN＝2∶1 | 1.2 | 1500 | 10 -3mN/m | 20.00 |
| 15 | 0.1-0.8 | WNS∶WGN＝2∶1 | 0.6-1.2 | 1500 | 10 -3mN/m | |
| 16 | 0.4 | WNS∶WGN＝2∶1， 1.5∶1，3∶1 | 0.8 | 1500 | 10 -3mN/m |
Fig. 1 has studied the interfacial tension of complex composition under Different Alkali concentration of embodiment five, and as can be seen, NaOH can both form ultra low interfacial tension with crude oil in the 0.8-1.6wt% scope, and during for 1.2wt%, interfacial tension reaches 10
-4The mN/m order of magnitude.
Fig. 2 studies the interfacial activity of complex composition when composite reactive agent total concn and alkali concn variation of embodiment nine, as can be seen, system reaches promoting agent and alkali concn a wider range of ultra low interfacial tension, surfactant concentration scope 0.05-0.6wt%, NaOH concentration range 0.8-1.5wt%, wherein, the interfacial tension of subregion system and crude oil can reach 10
-4The mN/m order of magnitude.
Fig. 3 has studied the interfacial tension of complex composition under different GNS and HS proportioning of embodiment 11, as can be seen, GNS: HS is active always to the influence of concentration interfacial tension by 2: 3,4: 1,3: 2,1: 1 o'clock, wherein, ratio is 3: 2 o'clock best results, and the promoting agent total concn can both form ultra low interfacial tension with crude oil in the 0.1-0.8wt% scope.
Fig. 4 has studied the interfacial tension of complex composition under different WNS and WGN proportioning of embodiment 16, as can be seen, WNS: WGN is 1.5: 1-3: can both make system and crude oil form ultra low interfacial tension at 1 o'clock, wherein ratio is 2: 1 o'clock, the interfacial tension effect is more excellent, makes the interfacial tension of system and crude oil can reach 10
-4The mN/m order of magnitude.
Fig. 5 is WNS and WGN composite table agent alive-alkali interfacial activity figure of embodiment 15, the result shows, in big regional extent, promoting agent total concn 0.1-0.8wt%, in the NaOH 0.6-1.2wt% scope, system all can form ultra low interfacial tension with crude oil, illustrates that WNS and WGN have good synergistic, and compound system has compatibleness preferably with oil, glassware for drinking water.
Ternary recompounded composite rock core oil displacement efficiency
The factor that influences chemical displacement of reservoir oil effect is a lot, and as the moving hold-up of chemical agent, therefore the compatibleness of system etc., come the oil displacement efficiency of evaluating combined system by model test of the reservoir sweep, have carried out the oil displacement efficiency evaluation of sulfonated lignin on rock core, experimental procedure:
The saturation water of now natural core being found time, again with the saturated crude oil of rock core of saturation water, make irreducible water saturation, water drive crude oil then, to moisture 98% o'clock, begin to inject complex composition, follow-up slug then reinjects, use water drive at last, improve the increased value of recovery ratio after writing down waterflood recovery efficiency factor and injecting composition.
Injecting program:
1, water drive;
2, inject complex composition;
3、1275A 800ppm 0.2PV；
4, water drive.
Experimental result sees Table 1.
Show by displacement of reservoir oil evaluation result, inject complex composition recovery ratio average specific water drive and improve more than 15%, illustrate that complex composition of the present invention and oil field have compatibleness preferably.Simultaneously, owing to use the agent of living of cheap lignin surfactant and other table compound, oil displacement efficiency is shown agent oil displacement efficiency alive when identical with being used alone, can cost saving, and the saving ratio is about 30-60%.
Claims (6)
1, a kind of ternary recompounded composite that contains lignin sulfonate surfactant, its each component concentration are to contain in 100 parts of weight water:
Sulfonated lignin complexed surfactant 0.05-0.8 weight part,
Alkali 0.6-1.6 weight part, and
Polyacrylamide polymers 0.08-1.8 weight part;
Wherein, described sulfonated lignin complexed surfactant be sulfonated lignin and alkylbenzene sulfonate in 1: 1-4: the complexed surfactant of any ratio preparation in 1 the weight ratio.
2, a kind of ternary recompounded composite that contains lignin surfactant, its each component concentration are to contain in 100 parts of weight water:
Sulfonated lignin complexed surfactant 0.05-0.8 weight part,
Alkali 0.6-1.6 weight part, and
Polyacrylamide polymers 0.08-1.8 weight part;
Wherein, described sulfonated lignin complexed surfactant be sulfonated lignin and petroleum carboxylate in 1: 1-3: the complexed surfactant of any ratio preparation in 1 the weight ratio.
3, the ternary recompounded composite that contains lignin sulfonate surfactant according to claim 1 and 2 is characterized in that, described sulfonated lignin are modified lignin mahogany sulfonate.
4, the ternary recompounded composite that contains lignin sulfonate surfactant according to claim 1 is characterized in that, its each component concentration is to contain in 100 parts of weight water:
Sulfonated lignin complexed surfactant 0.05-0.6 weight part, wherein, sulfonated lignin and alkylbenzene sulfonate weight ratio are 3: 1;
Alkali 0.8-1.5 weight part, and
Polyacrylamide polymers 1.2-1.8 weight part.
5, the ternary recompounded composite that contains lignin sulfonate surfactant according to claim 2 is characterized in that, its each component concentration is to contain in 100 parts of weight water:
Sulfonated lignin complexed surfactant 0.1-0.8 weight part, wherein, sulfonated lignin and petroleum carboxylate weight ratio are 2: 1;
Alkali 0.6-1.2 weight part, and
Polyacrylamide polymers 1.2-1.5 weight part.
6, the described ternary recompounded composite of lignin sulfonate surfactant that contains of one of claim 1 to 5 is as the application of displacement of reservoir oil injecting in tertiary oil recovery.
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| CN 00120985 CN1123620C (en) | 2000-08-07 | 2000-08-07 | Three-element built-up composition containing lignosulfonate surfactant and its application in tertiary petroleum recovery |
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