CN1128006C - Petroleum sulfonate surfactant for oil field, its preparation process and use in tertiary oil recovery - Google Patents
Petroleum sulfonate surfactant for oil field, its preparation process and use in tertiary oil recovery Download PDFInfo
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- CN1128006C CN1128006C CN99107580.3A CN99107580A CN1128006C CN 1128006 C CN1128006 C CN 1128006C CN 99107580 A CN99107580 A CN 99107580A CN 1128006 C CN1128006 C CN 1128006C
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Abstract
The present invention relates to a method for preparing surface active agents of petroleum sulfonate, which comprises the following steps: pressure reducing distillate oil whose molecular weight is from 320 to 380 is selected as raw materials; the sulfonation temperature is from 60 to 90 DEG C, the molar ratio of SO3 to aromatic hydrocarbon is 1.0 to 2.0: 1, and the gas concentration of the SO3 is from 2.0% to 10.0%; mahogany acid is neutralized by 15 to 40 % of alkali liquor until the pH value is form 7 to 8; 40 to 70% of alcohol whose solvent ration is 1: 1 is used for extracting to the obtain water solution of surface active agents, and petroleum ether whose solvent ratio is 0.5 to 0.6: 1 at the temperature of 60 to 90 DEG C is used for reverse extraction; alcohol water solution is distilled off under the conditions of at the temperature of 40 to 100 DEG C and a distillation method; the petroleum ether at the temperature of 60 to 90 DEG C is used for extracting and separating unreacted oil. The petroleum sulfonate can be used as oil displacement agents in the tertiary oil recovery.
Description
The present invention relates to oil field (displacement of reservoir oil) with surfactant and preparation and application, specifically, for petroleum sulfonate surfactant for oil field, its preparation method and as the application of oil displacement agent in tertiary oil recovery.
As the petroleum sulfonate that the displacement of reservoir oil is used,, be to improve the surfactant that oil recovery rate is preferentially selected for use owing to wide, cheap, the steady performance of raw material sources.The petroleum sulfonate price of using is more expensive at present, and itself and oil field compatibility are not fine, and many limitation are arranged in use.
Purpose of the present invention is to provide the tool low interfacial tension that can be applied in the oil field and good compatibility, petroleum sulfonate surfactant with low cost;
Another object of the present invention is to provide a kind of method of simple, the practical above-mentioned petroleum sulfonate surfactant of preparation;
A further object of the present invention is to provide above-mentioned petroleum sulfonate surfactant as the application of oil displacement agent in tertiary oil recovery;
An also purpose of the present invention is to provide above-mentioned petroleum sulfonate surfactant as composite dose of application in tertiary oil recovery in the ternary composite driving.
Technical solution of the present invention comprises that the molecular weight with following method preparation is the petroleum sulfonate surfactant of 380-450, and described preparation method may further comprise the steps:
A) selecting molecular weight for use is raw material at the vacuum distillate of 320-380;
B) membrane-type sulfonation-sulfonation temperature is at 60-90 ℃,
SO
3With the aromatic hydrocarbons mol ratio be 1.0-2.0: 1,
SO
3Gas concentration is 2.0%-10.0%;
C) among the neutralization-usefulness alkali lye 15-40%NaOH and mahogany acid to pH7-8;
D) the ethanol extraction ratio of solvent of extract and separate-employing 50% is 1: 1, and the gained aqueous surfactant solution is used 60-90 ℃ of benzinum again, and ratio of solvent is 0.5-0.6: 1 strips;
E) concentrate-under 40-100 ℃ of condition, the ethanol water distillation is removed;
F) make with extra care-after with 60-90 ℃ of benzinum unreacted oil being extracted, be product.
Technical solution of the present invention also comprises the method that the above-mentioned oil sulphur of preparation is got salt surfactant, comprises the steps:
A) selecting molecular weight for use is raw material at the vacuum distillate of 320-380;
B) membrane-type sulfonation-sulfonation temperature is at 60-90 ℃,
SO
3With the aromatic hydrocarbons mol ratio be 1.0-2.0: 1,
SO
3Gas concentration is 2.0%-10.0%;
C) among the neutralization-usefulness alkali lye 15-40%NaOH and mahogany acid to pH7-8;
D) the ethanol extraction ratio of solvent of extract and separate-employing 50% is 1: 1, and the gained aqueous surfactant solution is used 60-90 ℃ of benzinum again, and ratio of solvent is 0.5-0.6: 1 strips;
E) concentrate-under 40-100 ℃ of condition, the ethanol water distillation is removed;
F) make with extra care-unreacted oil is extracted, promptly get product with 60-90 ℃ of benzinum.
Technical solution of the present invention also comprises:
Among the above-mentioned preparation method, between the step a) intermediate distillates molecular weight 320-380.
Among the above-mentioned preparation method, sulfonation temperature is 75 ℃-80 ℃ in the step b).
Among the above-mentioned preparation method, step b) SO
3With certain hydrocarbon mol ratio be 1.3-1.8: 1.
Among the above-mentioned preparation method, SO in the step b)
3% is 4.0-8.0%.
Among the above-mentioned preparation method, used alkali lye is potassium hydroxide or NaOH in the step c).
Technical solution of the present invention further comprises: described petroleum sulfonate surfactant is as the application of oil displacement agent in tertiary oil recovery, and described petroleum sulfonate surfactant is as composite application in tertiary oil recovery.
The present invention includes following accompanying drawing:
Fig. 1 is a petroleum sulfonate surfactant preparation technology flow chart of the present invention;
Fig. 2 is a petroleum sulfonate surfactant liquid chromatogram of the present invention;
Fig. 3 is adding alkali lye rear interface tension detection curve for petroleum sulfonate surfactant of the present invention;
The ternary complex that Fig. 4 forms for petroleum sulfonate surfactant of the present invention ties up to oil displacement experiment result curve on the natural core.
Fig. 5 is mahogany acid salt assitant of the present invention (the effluent analysis chart of the three-component compound system displacement crude oil of generation.
Below in conjunction with the drawings and specific embodiments, describe in detail technology contents of the present invention with and the significant technique effect that brings.
The preparation of petroleum sulfonate
1. this example adopts dragon and phoenix general petrochemical works, Daqing to produce decompression workshop section fraction oil, and fraction oiling properties sees Table 1
Table 1 feedstock oil physico-chemical property
| Molecular weight | 45 ℃ of viscosity | Freezing point | Flash-point |
| 340 | 31mPa·s | -18℃ | 242℃ |
| Saturated hydrocarbons | Aromatic hydrocarbons | Nonhydrocarbon | Asphalitine |
| 80.0 | 12.4 | 6.5 | 1.1 |
2. sulfonating reaction is carried out in the falling film type device.The fundamental reaction of sulfonation is aromatic hydrocarbons and the SO in the fraction oil
3Between carrying out.
Sulfonation fundamental reaction principle
Main reaction:
Side reaction:
Ageing step:
R and Ar represent alkyl and aryl respectively in the following formula.
Referring to Fig. 1, its technological process can be carried out with reference to prior art, and 1000 kilograms of reaction masses in the silo squeeze into reactor, and oleum are squeezed into stripping tower by the sulfuric acid constant displacement pump through the metering of fraction oil constant displacement pump, produce SO
3Gas, SO
3Gas is behind the dryness of air tower, again through spinner flowmeter control, the SO by 5%
3The dense 1000 kilograms of oleums (mol ratio 1.5: 1) of in reactor, putting into of gas, temperature of reactor is controlled at 60 ℃ by Water Tank with Temp.-controlled, and the reaction time is 30-50 second.Obtaining product is mahogany acid, and its composition is measured with following method:
(1) mensuration of arene content
Carry out with reference to petroleum department's analytical standard compilation " adsorption charomatography is measured arene content in the fraction oil ".
(2) mensuration of active matter content
Adopt solvent extraction and separation, measure active matter content with standard anion diphasic titration method then.
(3) mensuration of single sulfonic acid and disulfonic acid
Adopt Waters510 type high performance liquid chromatograph to analyze.
(4) calculating of conversion ratio
(5) byproduct acid sludge cubage
(6) calculating of effective active content
Test result is listed in table 2.
3. hydrolysis neutralization.Product is mixed with 20%NaOH product solution, and transfer to NaOH, pH is 8 o'clock, and hydrolysis neutralization reaction mechanism is:
4. extraction.With 0.8 kilogram of 50% ethanolic solution extraction petroleum sodium sulfonate, and then with 0.3 kilogram benzinum, 60 ℃ of reextraction down.
5. concentrate---under 40 ℃ of-60 ℃ of conditions, remove ethanol water with distillating method;
6. make with extra care---after with 60-90 ℃ of benzinum unreacted oil being extracted, be product.
With the preparation flow of embodiment 1, wherein, except that sulfonation temperature is controlled at 90 ℃, other and the embodiment 1 identical petroleum sulfonate that obtains.
Embodiment 3
Preparation technology is with embodiment 1, wherein, and SO when removing sulfonation
3Concentration is controlled to be outside 4.25%, and other is identical with embodiment 1, makes petroleum sulfonate.
Embodiment 4
Preparation technology is with embodiment 1, wherein, and SO when removing sulfonation
3Concentration is controlled to be outside 6.24%, and other is identical with embodiment 1, makes petroleum sulfonate.
Embodiment 5
Preparation technology wherein, removes and uses 5% SO with embodiment 1
30.3 outside the kilogram, other is identical with embodiment 1, makes petroleum sulfonate.
Embodiment 6
Preparation technology wherein, removes and uses 5% SO with embodiment 1
30.6 outside the kilogram, other is identical with embodiment 1, makes petroleum sulfonate.
Embodiment 7
Preparation technology wherein, is that molecular weight is the fraction oil of A1000g except that adopting raw material with embodiment 1, and other is identical with embodiment 1, makes petroleum sulfonate.
Embodiment 8
Preparation technology wherein, is that molecular weight is the fraction oil of B1000g except that adopting raw material with embodiment 1, and other is identical with embodiment 1, makes petroleum sulfonate.
Preparation technology is with embodiment 1, and wherein, in the potassium hydroxide aqueous solution of use 40% and the mahogany acid, other is identical with embodiment 1, makes petroleum sulfonate.
Preparation technology is with embodiment 1, and wherein, except that adopting benzinum as the extractant, other is identical with embodiment 1, makes petroleum sulfonate.
Embodiment 11
Preparation technology is with embodiment 1, and wherein, except that sulfonation temperature is 75%, other is identical with embodiment 1, makes petroleum sulfonate.
With embodiment 12
The technological process of embodiment 1 is wherein in sulfonation process, through the SO of vaporization
3Remove moisture with air compressor, silicic acid drying, enter SO through the gas flow meter again
3Stripping tower, enter the sulphonator top.Fraction oil is pumped to the film sulfonator top with metering, with SO after 60 ℃ of preheatings
3-air also flows and descends, and form film along inside pipe wall and react, the sulphonator hot water thermal insulating, reaction temperature is 80 ℃, sulphonator periphery inventory is 3.05kg/hrcm, about 26 seconds of reaction time.Treating capacity is 25kg/hr.The sulphonator structure is φ 38 * 3 stainless steel tubes, effective length 4.95m.The acid-soluble oil that comes out from sulphonator separates acid sludge and acid-soluble oil through sedimentation 4 hours, and acid-soluble oil stirs neutralization at normal temperatures with the NaOH of 20% concentration, keeps pH=7-8, extracts petroleum sulfonate with 50% ethanol water afterwards.Then ethanol and petroleum sulfonate are concentrated, slough the second alcohol and water after, be product.By analysis, drawn the composition of product.
Table 3 product is formed table
| Title | Active matter % | Mineral oil % | Volatile matter % | Inorganic salts % | Average equivalent |
| Embodiment 12 | 57.6 | 9.3 | 29 | 4.1 | 427 |
This product through high-speed liquid phase chromatogram analysis, is drawn the composition (see figure 2) of monosulfonate and disulfonate in the product.Find out by Fig. 2, the mahogany acid product salt that adopts above-mentioned process for sulfonation condition to be synthesized, the selectivity of monosulfonate is greater than more than 90%.
Table 2 mahogany acid composition
| Conversion ratio | Acid sludge amount in the sulfonated products | Water-soluble sulfonate/oil-soluble sulfonic | |
| Embodiment | |||
| 1 | 76.0％ 92.0％ 39.9％ 49.2％ 35.2％ 81.3％ 79.4％ 80.5％ 79.7％ 41.1％ | 4.3 5.76 6.9 8.4 0.64 9.0 6.4 5.5 6.1 6.7 | 7.46 2.43 12.3 23.1 21.1 19.7 16.4 2.22 |
Embodiment 13 petroleum sulfonates application of the present invention-be used for tertiary oil recovery as oil displacement agent.
Embodiment 12 products are added the alkali of 1.0wt%,,, obtained 10 when mahogany acid salinity during at 0.1-1.6wt% through experiment
-3The ultralow interfacial tension value (referring to Fig. 3) of mN/m and the contrast of the B100 surfactant of the imported product U.S., the result will get well than the imported product performance.
The application of the embodiment 14 petroleum sulfonates of the present invention-ingredients of writing in reply is used for tertiary oil recovery.
Embodiment 12 products are formed compound system according to prescription, carry out the test of compound system oil displacement efficiency.
A, petroleum sulfonate 1.0wt% of the present invention
NaOH 1.0wt％
V
228Or 333OS 100-2000mg/L
B、PS-D
2 1.0wt％
Na
2CO
31.2wt％
V
228Or 333OS 1000-2000mg/L
Oil displacement test carries out on the natural core of grand celebration.The displacement of reservoir oil mode of salinity gradient has been considered in the design of oil displacement test, and promptly the at first saturated stratum of rock core connate water (salt content 7000mg/L) behind the saturated oils, is used and injected water (1200mg/L).If salt content raises (being that chloride ion content increases) then shows that swept volume has increased in the extraction liquid like this, experimental result is listed in table 4.As seen, the oil displacement efficiency of petroleum sulfonate compound system is:
1, reduce moisture content significantly, the rich oil band is relatively concentrated, formed to produce oil.The core oil displacement test shows, general moisture content drops to below 50% from 98%, and oil productivity is above freezing being raised to more than 50% near, is up to 80%.See Fig. 4.
2, the core oil displacement test shows, when injecting the 0.3PV slug, average recovery ratio improves more than 28% than water drive.
3, mobility control is that pressure reduction by the rock core two ends detects, when injecting PS-D
2Behind the compound system, discrete oil phase begins to flow, and oil film, oil droplet progressively form the rich oil band, and after the oil band was broken through, pressure reduction descended.
4, the mensuration of effluent interfacial tension.Using the rotation method of dripping measures the interfacial tension of effluent and crude oil.Surface as a result, the minimum interfacial tension of effluent and crude oil is 10
-2The mN/m order of magnitude (Fig. 5) illustrates that combination flooding by behind the rock core hole seepage flow, still has a large amount of surface-actives and alkali with the effluent extraction.
Simultaneously, the analysis showed that of rock core test effluent, under the condition that adds alkali, the moving Damage for Detention of petroleum sulfonate is less,＜1mg/g sand, alkaline consumption also＜1mg/g sand.
Table 4 oil displacement experiment is summary sheet as a result
| The experiment sequence number | The core numbering | Voids volume cm 3 | Saturated oils | Water drive | Combination flooding | Damage for Detention (chemical agent) | Core is put mode | The chemistry slug is formed percentage by weight | |||||||||||
| Oil saturation % | Bundle is full to be tied up and water degree % | Profit is full to be driven and the surplus % of residual degree | Waterflood recovery efficiency factor % | Slug consumption Vp | The highest oil content % | Chemical flooding improves recovery ratio % (OOIP) | Water drive and chemical flooding ultimate recovery % (OOIP) | Surplus carburetion is full drive and the back degree residual | Surfactant | ||||||||||
| Total total notes that stagnate are always adopted to be detained to annotate to adopt to stay into the amount of measuring amount and are entered output mg mg mg/g amount amount mg/g mg mg | |||||||||||||||||||
| 1 | 39 | 14.05 | 62.9 | 37.4 | 30.8 | 51.2 | 0.31 | 49.8 | 32.8 | 83.8 | 16.2 | 23.96 | 9.49 | 0.170 | 43.56 | 10.73 | 0.384 | Vertically | Inject water PSD-2=1.0% [NaOH]=1.0% [V 228]＝2000ppm |
| 2 | 42 | 14.6 | 76.5 | 23.5 | 37.8 | 50.5 | 0.516 | 54.4 | 26.5 | 76.9 | 23.1 | 41.8 | 75.9 | 24.0 | 0.632 | Level | Inject water PSD-2=1.0% [NaOH]=1.0% [v 228]＝2000mg/L | ||
| 3 | E9 0- 32 | 14.76 | 75.9 | 24.1 | 47.3 | 52.7 | 0.772 | 46.7 | 29.7 | 82.4 | 17.6 | 62.5 | 24.4 | 0.48 | 113.7 | 48.36 | 0.829 | Level | Inject water PSD-2=1.0% [NaOH]=1.0% [V 228]＝2000mg/L |
| 4 | 37 | 14.37 | 67.9 | 32.1 | 27.6 | 59.6 | 4.74 | 52.3 | 26.7 | 86.3 | 13.7 | Level | Inject water PSD-2=1.0% [NaOH]=1.0% [v 228]＝2000mg/l | ||||||
Claims (9)
1. the molecular weight with the preparation of following method is the petroleum sulfonate surfactant between the 380-450, and described preparation method comprises down with step:
A) selecting molecular weight for use is raw material at the vacuum distillate of 320-380;
B) membrane-type sulfonation-sulfonation temperature is at 60-90 ℃,
SO
3With the aromatic hydrocarbons mol ratio be 1.0-2.0: 1,
SO
3Gas concentration is 2.0%-10.0%;
C) in the alkali lye of neutralization-be 15-40% with concentration with mahogany acid to pH7-8;
D) the ethanol extraction ratio of solvent of extract and separate-employing 40%-70% is 1: 1, and the gained aqueous surfactant solution is used 60-90 ℃ of benzinum again, and ratio of solvent is 0.5-0.6: 1 strips;
E) concentrating-adopt the way of distillation steams ethanol water under 40-100 ℃ of condition;
F) make with extra care-, the unreacted oil extract and separate is fallen with 60-90 ℃ of benzinum.
2. petroleum sulfonate surfactant according to claim 1 is characterized in that, described preparation method's step a) intermediate distillates molecular weight is between 320-380.
3. petroleum sulfonate surfactant according to claim 1 is characterized in that, sulfonation temperature is 75 ℃-80 ℃ in described preparation method's step b).
4. petroleum sulfonate surfactant according to claim 1 is characterized in that, described preparation method's step b) SO
3With the aromatic hydrocarbons mol ratio be 1.3-1.8: 1.
5. petroleum sulfonate surfactant according to claim 1 is characterized in that, SO in described preparation method's step b)
3% is 4-8%.
6. petroleum sulfonate surfactant according to claim 1 is characterized in that, used alkali lye is potassium hydroxide or NaOH in described preparation method's step c).
7. the preparation method of the described petroleum sulfonate surfactant of claim 1 may further comprise the steps:
A) selecting molecular weight for use is raw material at the vacuum distillate of 320-380;
B) membrane-type sulfonation-sulfonation temperature is at 60-90 ℃,
SO
3With the aromatic hydrocarbons mol ratio be 1.0-2.0: 1,
SO
3Gas concentration is 2.0%-10.0%;
C) in the alkali lye of neutralization-be 15-40% with concentration with mahogany acid to pH7-8;
D) the ethanol extraction ratio of solvent of extract and separate-employing 40%-70% is 1: 1, and the gained aqueous surfactant solution is used 60-90 ℃ of benzinum again, and ratio of solvent is 0.5-0.6: 1 strips;
E) concentrate-under 40-100 ℃ of condition, the ethanol water distillation is removed;
F) make with extra care-unreacted oil is extracted the back products obtained therefrom with 60-90 ℃ of benzinum.
8. the described petroleum sulfonate surfactant of claim 1 is the application of oil displacement agent in tertiary oil recovery.
9. the described petroleum sulfonate surfactant of claim 1 is as the composite dose of application in tertiary oil recovery.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99107580.3A CN1128006C (en) | 1999-05-27 | 1999-05-27 | Petroleum sulfonate surfactant for oil field, its preparation process and use in tertiary oil recovery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99107580.3A CN1128006C (en) | 1999-05-27 | 1999-05-27 | Petroleum sulfonate surfactant for oil field, its preparation process and use in tertiary oil recovery |
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| CN1128006C true CN1128006C (en) | 2003-11-19 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101455950B (en) * | 2007-12-12 | 2011-09-07 | 中国石油天然气股份有限公司 | Preparation method and application of sulfonate surfactant |
| CN101402592B (en) * | 2008-11-21 | 2013-10-09 | 北京天颐格润新能源技术开发有限公司 | Stone oil sulphonic acid, its salt, preparation method and uses thereof |
| CN101955451A (en) * | 2010-09-03 | 2011-01-26 | 中国石油大学(华东) | Method for preparing petroleum sulfonate surfactant by falling film sulfonation |
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1999
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