CN1131292C - Surfactant composition for increasing recovery ratio of crude and its application - Google Patents
Surfactant composition for increasing recovery ratio of crude and its application Download PDFInfo
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- CN1131292C CN1131292C CN 01109055 CN01109055A CN1131292C CN 1131292 C CN1131292 C CN 1131292C CN 01109055 CN01109055 CN 01109055 CN 01109055 A CN01109055 A CN 01109055A CN 1131292 C CN1131292 C CN 1131292C
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Abstract
The present invention relates to a surfactant composition for improving crude oil recovery rate in tertiary oil recovery, which is composed of alkyl benzene sulfonate and heavy alkyl benzene sulfonate with known carbon number. The present invention can be used under the condition of low basicity for improving crude oil recovery rate. The present invention also introduces an application method for improving crude oil recovery rate in tertiary oil recovery by utilizing an oil displacing system which is composed of the surfactant composition.
Description
The present invention relates to a kind of surfactant composition that is used to improve oil recovery factor, the invention still further relates to the displacing surfactant system that is used to improve oil recovery factor with this surfactant composition preparation.
Oil belongs to Nonrenewable resources, thus how under satisfying the prerequisite of economic benefit fully the recover petroleum resource become problem eternal in the oilfield development process.Along with the continuity of water flooding process, the recovery ratio in some highly aqueous fields also has only about 40%, and still about 60% petroleum-in-place remains in the blowhole of oil reservoir in addition.Therefore press for a kind of new oil recovery technique and come further recover petroleum resource.
Find that after deliberation the oil that remains in the blowhole of oil reservoir can improve displacement efficiency by injecting suitable tensio-active agent, alkali, polymer ternary system, can enlarge swept volume again, has realized the purpose of further raising recovery ratio.Usually, surfactant waterflooding is extraction volume increase oil from oilbearing stratum effectively, but because the solution viscosity of tensio-active agent is low excessively, in oil displacement process, easily cause " fingering " phenomenon, recovery ratio is a greater impact, therefore, in water phase surfactant mixture, add the viscosity that small amount of polymer increases oil-displacing agent.In addition, in oil-displacing agent, add the displacement of reservoir oil solution that alkali forms alkalescence, can in and the acidic component of crude oil and the neutral compound of at least a a large amount of existence in the reservoir, improve oil-displacing agent and contain the oil displacement efficiency of petroleum acid soap surfactant system, thereby formed widely used ternary composite driving in tertiary oil recovery now in reservoir formation.
But, in the ternary composite driving that we find to use in most of oil fields, the alkali consumption that share with tensio-active agent and polymkeric substance very big (ORS-41 that is using as Daqing oil field), for reach improve recovery ratio purpose, though when using, obtained some effects, but use alkali not only the visco-elasticity of polymkeric substance to be had considerable influence in a large number, and easily cause many drawbacks such as oil well fouling.
An object of the present invention is to provide a kind of surfactant composition under the low alkali composition situation in the ternary composite driving that is suitable for.
Another object of the present invention provides the displacing surfactant system that is used to improve oil recovery factor that a kind of application surface surfactant composition is made into.
The alkylbenzene sulfonate of the known carbonatoms among the present invention, its molecular formula is
Wherein M is basic metal, ammonium or amine, and R is C
10～C
24A kind of alkylbenzene sulfonate.Technologies such as present industrialized alkylbenzene production technique has that normal paraffin dehydrogenation, chlorination, paraffin wax cracking, tetrapropylene are superimposed, normal paraffin chlorination-dehydrochlorination and ethylene oligomerization.We can use the alpha-olefin or the haloalkane of the synthetic known carbon number of above-mentioned various production technique, and the present invention only introduces a kind of production technique-by the C of wax destructive distillation
10～C
24Alpha-olefin and the benzene alkylation alkylbenzene sulfonate of producing known carbon number, the technological process of production is summarized as follows:
(1) preparation of alchlor complex compound
(2) alkylated reaction
(3) alkylation liquefied ammonia neutralization, washing process
(4) fractionation process
(5) alkylbenzene is refining
(6) alkylbenzene sulfonation reaction
(7) in the alkyl benzene sulphonate (ABS) and salify
Here the alkylbenzene sulfonate of known carbonatoms can be according to the different carbon number distribution of adjusting alkylbenzene sulfonate of various places crude oil carbon number distribution.
Heavy alkylbenzene sulfonate is synthesized by present sophisticated production technique among the present invention, it is complicated, diversified that its carbon number is formed, wherein contain partial impurities, use the mixture of its main composition A, B, C, D through separation, extraction, technology such as the centrifugal back of purifying:
The molecular formula of A:
The molecular formula of B:
The molecular formula of C:
(n is a positive integer of 0～17)
The molecular formula of D:
Wherein M is basic metal, ammonium or amine, R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8Be identical or different C
1～C
20In alkyl.
Utilize the alkylbenzene sulfonate of known carbonatoms to mix with heavy alkylbenzene sulfonate, and the alkylbenzene sulfonate of known carbonatoms accounts for 15%～98% (weight) in composition, be generally 20%～98% (weight), be preferably 30%～90% (weight), be preferably 40%～60% (weight); Corresponding heavy alkylbenzene sulfonate accounts for 2%～85% (weight) in composition, be generally 2%～80% (weight), is preferably 10%～70% (weight), is preferably 40%～60% (weight).Coordinative role by their different carbon numbers has reached balance, the compound system carbon number distribution ideal between the individual component, can and crude oil between form 10
-3The ultra low interfacial tension of mN/m, the velocity ratio that has reached balance, profit between the profit reaches consistent, thereby the recovery ratio of crude oil can be improved about 25%.
The alkylbenzene sulfonate of known carbon number of the present invention is generally the benzene sulfonamide acid amide of the alkyl benzene sulphonate (ABS) ammonium of the alkyl benzene sulphonate (ABS) lithium of the alkyl benzene sulphonate (ABS) potassium of the sodium alkyl benzene sulfonate of known carbon number, known carbon number, known carbon number, known carbon number, known carbon number, the sodium alkyl benzene sulfonate of known carbon number preferably, its average molecular weight range is preferably between 325～500 between 275～600.The linear alkylbenzene sulfonate of known carbon number used in this invention or branch-alkylbenzene sulfonate can be ten sodium alkyl benzene sulfonates, Sodium dodecylbenzene sulfonate, tetradecyl benzene sulfonic acid sodium salt, hexadecyl benzene sulfonic acid sodium salt, octadecyl benzene sulfonic acid sodium salt, eicosyl benzene sulfonic acid sodium salt, docosyl benzene sulfonic acid sodium salt, tetracosyl benzene sulfonic acid sodium salt, wherein preferably tetradecyl benzene sulfonic acid sodium salt～eicosyl benzene sulfonic acid sodium salt, most preferably octadecyl benzene sulfonic acid sodium salt.
Can add partially hydrolyzed polyacrylamide in flooding system, content is 0.03%～1.0% (weight), can also further add cosurfactant C
1～C
8Alcohol be 0.05%～30% (weight).Cosurfactant can improve the solubleness of tensio-active agent, improves the flowability of solution.Therefore, add the action effect that suitable cosurfactant helps to improve tensio-active agent.The cosurfactant that the present invention uses is C
1～C
8Alcohol, generally be methyl alcohol, ethanol, Virahol, propyl carbinol, amylalcohol, hexanol, octanol and composition thereof.Preferably ethanol, Virahol, propyl carbinol and composition thereof.
The present invention compares with domestic and international oil-displacing agent, topmost advantage is that it can be when improving oil recovery factor 25%, reduced the consumption of alkali dramatically, make the alkali consumption in oil field reach Schwellenwert, thereby effectively avoided the injury of alkali for the stratum, this flooding system can keep splendid oil displacement efficiency always to some months in several minutes simultaneously.In addition, another advantage of the present invention is exactly that its crude oil scope of adapting to is wider, under the various geologic conditions, the oil reservoir of various character all has good displacement effect.
A kind of western B-100 ternary composite oil-displacing system of using of flooding system and grand celebration district that is used for improving the tensio-active agent of oil recovery factor of the present invention, ORS-41 ternary composite oil-displacing system that grand celebration Xing Wu district uses are in formation 10
-3The contrast of the alkali scope that is suitable for during the following low interfacial tension of mN/m, see following table 1 for details:
Table 1
Annotate: 1275A is the partially hydrolyzed polyacrylamide that allied colloid is produced.
| Title | Composition concentration scope (weight percent) | Alkali concn scope (weight percent) | Best form (weight percent) |
| A kind of flooding system that is used to improve oil recovery factor of the present invention | 0.05％～1.0％ | 0.1％-0.7％(NaOH) | 0.3% constituent+0.5%NaOH+1.2% Virahol+1200mg/L1275A |
| The B-100 ternary composite oil-displacing system | 0.05％～0.6％ | 0.76％～1.7％(Na 2CO 3) | 0.3％B-100+1.25％Na 2CO 3+1200mg/L1275A |
| The ORS-41 ternary composite oil-displacing system | 0.05％～0.6％ | 0.8％～1.4％(NaOH) | 0.3％ORS-41+1.2％NaOH +1200mg/L1275A |
In the table 1, laboratory apparatus is U.S. Texas 500 type interfacial tensimeters, and oil is Daqing crude oil, and water is the grand celebration local water.The concentration owing to alkali is too high in the ORS-41 ternary composite oil-displacing system that western B-100 ternary composite oil-displacing system of using in district and grand celebration Xing Wu district use in the grand celebration as seen from Table 1, causes many drawbacks such as polymer viscoelastic decline, oil reservoir and oil well scale problems are serious.And the suitable alkali concn of the flooding system that uses surfactant composition of the present invention to be mixed with is low, oil reservoir and oil well do not have obvious fouling, and, advantages such as flowability very good, speed of action fast, injection back stable performance, operation nothing injury less to the visco-elasticity influence of polymkeric substance can increase substantially oil recovery factor.
Further describe the present invention with the embodiment that has illustrative and can not limit protection domain of the present invention below.
Embodiment
Embodiment 1
This example has been described the concrete process for preparation of the composition of tensio-active agent:
(1) preparation of the alkylbenzene sulfonate of known carbon number:
Here only introduce the C of a kind of production technique one by wax destructive distillation
18Alpha-olefin and the benzene alkylation alkylbenzene sulfonate of producing known carbon number, the technological process of production is summarized as follows:
(1) preparation of alchlor complex compound
Benzene and C
18Alpha-olefin, alchlor, HCL by 1: 2: 2: the proportioning of 1 (mol ratio), temperature are controlled to be 50 ℃, stir, and the reaction times is 2 hours.
(2) alkylated reaction
Benzene and C
18Alpha-olefin, alchlor complex compound by 8: 1: 0.02 proportionings, temperature is controlled to be 50 ± 5 ℃, stirs, the reaction times is 1 hour.
(3) alkylation liquefied ammonia neutralization, washing process
Alkylate and liquefied ammonia neutralization, get rid of waste water, wash with water more than 5 times, standing demix is discharged waste water.
(4) fractionation process
The alkylate fractionation after the washing, remove unreacted benzene.
(5) alkylbenzene is refining
Product utilization carclazytes after the fractionation etc. are refining.
(6) alkylbenzene sulfonation reaction
Alkylbenzene is at SO
3Sulfonation in the film reactor, 40 ℃ of temperature of reaction
(7) in the alkyl benzene sulphonate (ABS) and salify
Octadecyl Phenylsulfonic acid and NaOH are neutralized into the octadecyl benzene sulfonic acid sodium salt, and its molecular formula is:
(2) preparation of heavy alkylbenzene sulfonate:
Heavy alkylbenzene sulfonic acid and NaOH are neutralized into heavy alkylbenzene sulfonic acid sodium.
(3) process for preparation of surfactant composition:
The octadecyl benzene sulfonic acid sodium salt that is synthesized is mixed by a certain percentage, stirs with heavy alkylbenzene sulfonic acid sodium, obtain surfactant composition.
(4) see Table 2 by the concrete prescription of the different surfactant composition of above-mentioned steps preparation
Table 2
| Prescription | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 |
| The weight percent of octadecyl benzene sulfonic acid sodium salt in composition | 15 | 20 | 30 | 40 | 50 | 60 | 70 | 80 | 90 | 98 |
| The weight percent of heavy alkylbenzene sulfonic acid sodium in composition | 85 | 80 | 70 | 60 | 50 | 40 | 30 | 20 | 10 | 2 |
Annotate: according to the characteristics of Daqing crude oil carbon number distribution, preferably octadecyl benzene sulfonate, most preferably octadecyl benzene sulfonic acid sodium salt.
Embodiment 2～21
Embodiment 2～21 improves wherein 20 kinds of prescriptions of the displacing surfactant system of oil recovery factor for being used to of being made into ten kinds of prescriptions among the embodiment 1, and sees Table 3:
Table 3
| Prescription | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | ||||||||||
| Embodiment | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12 | 13 | 14 | 15 | 16 | 17 | 18 | 19 | 20 | 21 |
| The weight percent of composition in the flooding system | 0.3 | 0.05 | 0.3 | 0.05 | 0.3 | 0.05 | 0.3 | 0.05 | 0.3 | 0.05 | 0.3 | 0.05 | 0.3 | 0.05 | 0.3 | 0.05 | 0.3 | 0.05 | 0.3 | 0.05 |
| The weight percent of Virahol in the flooding system | 1.2 | 0.2 | 1.2 | 0.2 | 1.2 | 0.2 | 1.2 | 0.2 | 1.2 | 0.2 | 1.2 | 0.2 | 1.2 | 0.2 | 1.2 | 0.2 | 1.2 | 0.2 | 1.2 | 0.2 |
| Surplus | Water | |||||||||||||||||||
The interfacial tension of the flooding system of embodiment 2～21 under different N aOH concentration conditions sees the following form 4:
Table 4
In the table 4, laboratory apparatus is U.S. Texas 500 type interfacial tensimeters, and oil is Daqing crude oil oil, and water is the grand celebration local water.As seen from Table 4, the content of the octadecyl benzene sulfonic acid sodium salt of the surfactant composition of a kind of displacing surfactant system that is used for improving oil recovery factor of the present invention is during greater than 40% (weight), the concentration of NaOH be 0.2%～0.7% (weight) can both and crude oil between form 10
-3The ultra low interfacial tension of mN/m, thus reach the purpose that increases substantially oil recovery factor.
Embodiment 22
Because it is a lot of to influence the factor of chemical displacement of reservoir oil effect, as the anti-dilution capacity of system, the moving hold-up of tensio-active agent etc., only the quality of estimating the flooding system prescription according to interfacial tension is not enough, so, also must estimate the oil displacement efficiency of best system formulation by displacement of reservoir oil simulated experiment under near the oil field physical condition.We have carried out utilizing the ternary composite oil-displacing system that surfactant composition of the present invention is made into and the contrast oil displacement experiment of U.S. ORS-41 ternary composite oil-displacing system on the natural core of Daqing oil field.Its flooding system prescription 1 is:
(1) surfactant composition concentration 0.3% (weight)
(2) NaOH 0.5% (weight)
(3) partially hydrolyzed polyacrylamide (1275A) 1200 mg/litre
(4) Virahol 1.2% (weight)
(5) surplus is that water displacing oil system formulation 2 is:
(1) ORS-41 concentration 0.3% (weight)
(2) NaOH 1.2% (weight)
(3) partially hydrolyzed polyacrylamide (1275A) 1200 mg/litre
(4) surplus is a water
Core character sees Table 5:
Table 5
| The core numbering | Length (cm) | Diameter (cm) | Sectional area (cm 2) | Rate of permeation (md) | Volume of voids (cm 3) |
| 2000-11 | 9.85 | 2.45 | 4.71 | 476 | 11.67 |
| 2000-12 | 9.70 | 2.45 | 4.71 | 380 | 12.18 |
The saturated local water of at first core being found time, saturated then grand celebration gas-free oil is set up irreducible water.Afterwards core was worn out three days under 45 ℃ of conditions, to recover the former initial wetting of core.After this carry out water-drive oil recovery, when the moisture displacement of reservoir oil slug that injects surfactant compound system of the present invention after 98% that reaches.And then inject water at last, finished until moisture 98% o'clock.The result shows by the core oil displacement experiment, and prescription 1 forms oily wall in oil displacement process, moisture dropping to below 50%, and ultimate recovery factor improves about 25% than water drive.In addition, the pressure reduction explicit declaration, in the whole oil displacement process, the mobility control of slug is better, does not produce and breaks through.And 2 ultimate recovery factoies of filling a prescription improve about 20% than water drive.This shows, form 10 between displacing surfactant system energy of the present invention and the crude oil
-3The mNm/m ultra low interfacial tension so can increase substantially recovery ratio, under equal cost, is compared with the ORS-41 ternary composite oil-displacing system of the U.S., has the advantage of low alkali, low injury, high investment output ratio.
Claims (23)
1, a kind of surfactant composition that is used to improve oil recovery factor, mainly form by following material:
A kind of alkylbenzene sulfonate of (1) 15%～98% (weight), its molecular formula is:
Wherein M is basic metal, ammonium or amine, and R is C
10～C
24In a kind of alkyl.
The heavy alkylbenzene sulfonate of (2) 2%～85% (weight).
2, surfactant composition according to claim 1, the main composition that it is characterized in that said heavy alkylbenzene sulfonate are the mixtures of A, B, C, D:
The molecular formula of A is:
The molecular formula of B is:
The molecular formula of C is:
(n is a positive integer of 0～17)
The molecular formula of D is:
Wherein M is basic metal, ammonium or amine, R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8Be identical or different C
1～C
20In alkyl.
3, surfactant composition according to claim 1 is characterized in that said basic metal can be sodium or potassium or lithium.
4, surfactant composition according to claim 1 is characterized in that said alkylbenzene sulfonate is alkyl benzene sulphonate (ABS) ammonium or benzene sulfonamide acid amide, and heavy alkylbenzene sulfonate is heavy alkylbenzene sulfonic acid ammonium or heavy alkylbenzene sulfonic acid amine.
5, surfactant composition according to claim 1 is characterized in that said alkylbenzene sulfonate is a sodium alkyl benzene sulfonate.
6, surfactant composition according to claim 1, the R that it is characterized in that said alkylbenzene sulfonate is C
12～C
22In a kind of alkyl.
7, surfactant composition according to claim 1, the R that it is characterized in that said alkylbenzene sulfonate is C
14～C
20In a kind of alkyl.
8, surfactant composition according to claim 1, the R that it is characterized in that said alkylbenzene sulfonate is C
18Alkyl.
9, surfactant composition according to claim 1, the content that it is characterized in that alkylbenzene sulfonate in composition are 20%～98% (weight), and the content of heavy alkylbenzene sulfonate is 2%～80% (weight).
10, surfactant composition according to claim 1, the content that it is characterized in that alkylbenzene sulfonate in composition are 30%～90% (weight), and the content of heavy alkylbenzene sulfonate is 10%～70% (weight).
11, surfactant composition according to claim 1, the content that it is characterized in that alkylbenzene sulfonate in composition are 40%～60% (weight), and the content of heavy alkylbenzene sulfonate is 40%～60% (weight).
12, the displacing surfactant system of preparing with the surfactant composition of claim 1 that is used to improve oil recovery factor is characterized in that this flooding system comprises following several component:
(1) NaOH is 0.1%～0.7% (weight);
(2) surfactant composition is 0.05%～1% (weight); This tensio-active agent mainly is made up of following material:
1. a kind of alkylbenzene sulfonate of 15%～98%, its molecular formula is:
Wherein M is basic metal, ammonium or amine, and R is C
10～C
24In a kind of alkyl.
2. 2%～85% heavy alkylbenzene sulfonate
(3) cosurfactant C
1～C
8Alcohol be 0.05%～30% (weight).
(4) surplus is a water.
13, according to the said displacing surfactant system that is used to improve oil recovery factor of claim 12, wherein the main composition of heavy alkylbenzene sulfonate is the mixture of A, B, C, D:
The molecular formula of A is:
The molecular formula of B is:
The molecular formula of C is:
(n is a positive integer of 0～17)
The molecular formula of D is:
Wherein M is basic metal, ammonium or amine, R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8Be identical or different C
1～C
20In alkyl.
14, according to the said displacing surfactant system that is used to improve oil recovery factor of claim 12, it is characterized in that further adding partially hydrolyzed polyacrylamide, content is 0.03%～1.0% (weight).
15,, it is characterized in that said basic metal can be sodium or potassium or lithium according to the said displacing surfactant system that is used to improve oil recovery factor of claim 12.
16,, it is characterized in that said alkylbenzene sulfonate is a sodium alkyl benzene sulfonate according to the said displacing surfactant system that is used to improve oil recovery factor of claim 12.
17, according to the said displacing surfactant system that is used to improve oil recovery factor of claim 12, it is characterized in that said alkylbenzene sulfonate is alkyl benzene sulphonate (ABS) ammonium or benzene sulfonamide acid amide, heavy alkylbenzene sulfonate is heavy alkylbenzene sulfonic acid ammonium or heavy alkylbenzene sulfonic acid amine.
18, according to the said displacing surfactant system that is used to improve oil recovery factor of claim 12, the R that it is characterized in that said alkylbenzene sulfonate is C
12～C
22In a kind of alkyl.
19, according to the said displacing surfactant system that is used to improve oil recovery factor of claim 12, the R that it is characterized in that said alkylbenzene sulfonate is C
14～C
20In a kind of alkyl.
20, according to the said displacing surfactant system that is used to improve oil recovery factor of claim 12, the R that it is characterized in that said alkylbenzene sulfonate is C
18Alkyl.
21, according to the said displacing surfactant system that is used to improve oil recovery factor of claim 12, the content that it is characterized in that alkylbenzene sulfonate in composition is 20%～98% (weight), and the content of heavy alkylbenzene sulfonate is 2%～80% (weight).
22, according to the said displacing surfactant system that is used to improve oil recovery factor of claim 12, the content that it is characterized in that alkylbenzene sulfonate in composition is 30%～90% (weight), and the content of heavy alkylbenzene sulfonate is 10%～70% (weight).
23, according to the said displacing surfactant system that is used to improve oil recovery factor of claim 12, the content that it is characterized in that alkylbenzene sulfonate in composition is 40%～60% (weight), and the content of heavy alkylbenzene sulfonate is 40%～60% (weight).
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| CN100404439C (en) * | 2005-05-20 | 2008-07-23 | 中国石油天然气股份有限公司 | Oil displacement agent |
| CN102766448B (en) * | 2012-07-12 | 2016-08-03 | 天津市瑞德赛恩新材料开发有限公司 | A kind of foam flooding oil preparation |
| CN109796953A (en) * | 2019-03-26 | 2019-05-24 | 黑龙江信维源化工有限公司 | A kind of glycine betaine complex oil displacing composition |
| CN112011326B (en) * | 2020-09-09 | 2021-09-14 | 中国科学院兰州化学物理研究所 | Compound surfactant with ultralow oil-water interfacial tension and preparation method thereof |
| CN114933560B (en) * | 2022-06-16 | 2023-11-10 | 寿光新海能源技术有限公司 | Surfactant for improving crude oil recovery ratio and preparation method and application thereof |
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