CN101397494A - Method for preparing surfactants for displacement of oil - Google Patents
Method for preparing surfactants for displacement of oil Download PDFInfo
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- CN101397494A CN101397494A CNA2008102239717A CN200810223971A CN101397494A CN 101397494 A CN101397494 A CN 101397494A CN A2008102239717 A CNA2008102239717 A CN A2008102239717A CN 200810223971 A CN200810223971 A CN 200810223971A CN 101397494 A CN101397494 A CN 101397494A
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- alkylbenzene
- oil
- sulfonation reaction
- oil displacement
- alkyl benzene
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Abstract
The invention relates to a preparation method of a surfactant used for oil displacement, belonging to the field of tertiary oil recovery. The previously researched single agent can achieve good interfacial activity only by being compounded and prepared by more than two types of surfactants, has poor field application effect, and can only carry out oil displacement under high injected alkali concentration. The invention overcomes the problems in the prior art that the speed of sulfonation reaction process is difficult to control, the mixing is uneven, and the like; applies high gravity technology into the sulfonation reaction process, meets the needs of fast response and micromixing of the sulfonation reaction, and provides a method for continuously and industrially preparing alkylbenzene sulfonate surfactant which has high efficiency, short production cycle and high product quality. The prepared alkylbenzene sulfonate is a single type surfactant used for oil displacement, and the single agent has good interfacial activity and low using concentration, and can lead the oil-water interfacial tension to be ultra-low (10<-3>mN/m order of magnitude) in wider and lower alkali concentration range.
Description
Technical field
The present invention relates to a kind of high-gravity technology that adopts and prepare the preparation method of oil field, belong to the tertiary oil recovery field with tensio-active agent.
Background technology
Hypergravity refers under the environment more much bigger than earth gravity acceleration (9.8m/s2), the suffered power research material of material under the hypergravity environment physics and the utilisation technology of chemical change process high-gravity technology.As a kind of high and new technology, high-gravity technology has a great application prospect industrial.Under the hypergravity environment, molecular diffusion between different sized molecules and alternate transmittance process be faster than under the conventional gravity field all, liquid-liquid two-phase under the hypergravity environment bigger hundreds of times to thousands of times than earth gravity field porous medium or the duct in the contact of produce flowing, great shear forces is torn into liquid liquid film, brin and the drop of micron to nano grade, produce huge and phase interface fast updating, make 1～3 order of magnitude of raising in the interphase mass transfer speed ratio tradition tower, microcosmic mixes and mass transfer process is greatly strengthened.The short-cut method of realizing the hypergravity environment is to produce centrifugal principle and the rotating equipment hypergravity machine (Rotating Packed Bed) of particular design by rotation.Utilize mass transfer process highly enriched under the hypergravity environment and micro mixing characteristic, the huge chemical tower equipment up to tens meters often can be substituted with the hypergravity machine not as good as two meters.Hypergravity machine has following characteristics: greatly dwindled equipment size and weight; Greatly strengthened transmittance process; Extremely short (100ms～1s) of the residence time of material in equipment; Can be vertically, level or any direction install; Rapid and uniform microcosmic mixes or the like.Based on above characteristics, high-gravity technology can be applicable to following special process: the processing of heat-sensitive material (utilizing residence time weak point); The processing of expensive material or poisonous material (utilizing less residue in the machine); The production of high quality nano material (utilizing Rapid and uniform microcosmic mixed characteristic).Because the conspicuous advantage of high-gravity technology, since late 1970s, first hypergravity machine occurred, many in the world big chemical companies all competitively developed research to this technology, and have carried out certain pilot scale or industry research.At home, Beijing University of Chemical Technology's hypergravity Engineering Research Center, the application of high-gravity technology was carried out the research in a plurality of fields, preparation comprising nanometer grade powder material, promptly utilize high-strength high speed microcosmic blended characteristics in the hypergravity machine, make nano level (30nm) calcium carbonate superfine powder of controllable granularity, narrow diameter distribution, utilized overweight force method also to prepare more than ten kind of powder products such as nano strontium carbonate, nano-aluminum hydroxide, nano barium carbonate and nano silicon.High-gravity technology makes important progress in the applied research of field of chemical engineering in recent years.
Along with Development of Tertiary Oil Recovery Technology, generally believe that at present adopting chemical combined flooding to carry out tertiary oil recovery is effective means, ternary composite driving is meant that alkali and tensio-active agent and high molecular polymer (ASP system) carry out the displacement of reservoir oil after organically compound.The medicament of most critical is a tensio-active agent in the combination flooding, and the basic demand that is fit to do the tensio-active agent of ternary composite driving is: can make oil water interfacial tension reach ultralow (10
-3The mN/m order of magnitude) below; The working concentration of tensio-active agent is less than 0.6% (wt), and all can form ultra low interfacial tension in the surfactant concentration scope of broad, and the composition of tensio-active agent is single relatively, guarantees not take place in displacement process serious chromatographic separation.
The surfactant oil displacement of former studies mainly stresses prescription and auxiliary agent at research several types tensio-active agent, has ignored the performance of single type tensio-active agent, and the single agent of most of former studies can only make oil water interfacial tension reach 10
-2MN/m, thereby can only just can reach the good interface activity by the surfactant compound more than two types.For example use heavy alkylbenzene sulfonate and petroleum carboxylate composite, and for example composite etc. with sulfonated petro-leum and nonionogenic tenside, although the tensio-active agent after composite can make oil water interfacial tension reach ultralow, but because surfactant types difference, variant on the structure, the compound surfactant system owing to differences such as absorption losses, the chromatographic separation phenomenon can occur in the combination flooding oil displacement process, destroy original optimum formula system, thereby cause effect of field application poor.In addition, the surfactant interface activity that has is good under high-alkalinity, and poor activity under the low alkaline concentration, interfacial tension do not reach ultralow (10
-3Thereby compound system can only (1.2-1.5wt%) times displacement of reservoir oils be as ORS-41, WPS tensio-active agent at high injection alkali concn the mN/m order of magnitude).Because alkali can generate dirty crystallization with calcium, the magnesium plasma reaction in the bottom, or can generate the crystallization of sial dirt with clay mineral (kaolin, feldspar, polynite) effect in the stratum, the oil reservoir hole is stopped up in these dirty crystallization meetings, the spread area of displacing agent is reduced, recovery ratio reduces, and make oil reservoir receive injury, it is high more to inject alkali concn, big more to the injury of oil reservoir.Therefore if ultra low interfacial tension alkali concn scope can be moved to low alkaline concentration, it is favourable using for ternary composite driving.
In addition,,, promptly reduce consumption in ternary composite driving if in the ternary built system, reduce surfactant concentrations because the tensio-active agent price of using at present generally is more expensive, just on certain meaning reduced the tensio-active agent cost.
Summary of the invention
The present invention has overcome in the prior art sulfonation reaction process speed and has been difficult to control, mixes unequal problem, high-gravity technology is applied to the sulfonation reaction process, the rapid reaction and the microcosmic blended needs that adapt to sulfonation reaction provide a kind of efficient height, with short production cycle, method that continuous industryization that quality product is high prepares alkyl benzene sulfonate surfactant.Prepared alkylbenzene sulfonate is a kind of surfactant oil displacement of single type, and the interfacial activity of single agent is good, and working concentration is low, can make oil water interfacial tension reach ultralow (10 at broad and lower alkali concn scope
-3The mN/m order of magnitude).
Because sulfonation reaction is quick moment reaction, must make reaction raw materials moment in reactor reach intermolecular uniform mixing is the microcosmic mixing, just can avoid the heterogeneity of reactive component in the reactor, thereby make product avoid oversulfonate.Therefore, must adopt special charging and hybrid mode just can reach the microcosmic melange effect, and in the reactor amplification process, be consistent.And hypergravity machine just in time can satisfy these requirements, is the ideal reactor of sulfonation reaction.
The alkylbenzene that the present invention selects for use is the alkylbenzene between the C9-C22, adopt rotating packed bed reactor, under the hypergravity environment, with oleum mixing sulfonation, greatly strengthening microcosmic mixes, high strength is carried out mass transfer, hypergravity makes the effect of surface tension of liquid become insignificant, under great shear forces and bump, liquid is drawn into film as thin as a wafer, tiny silk and small drop produce huge alternate contact area, and swiftly flowing liquid can be at filling surface formation liquid film as thin as a wafer simultaneously, violent disturbance makes the reactant contact surface constantly more disconnected again, like this, the transmittance process of material is strengthened greatly, and rate of mass transfer improves greatly, processing power also increases greatly, shortens the reaction times greatly.
The invention provides a kind of method that adopts high-gravity technology to prepare alkyl benzene sulfonate surfactant, it is characterized in that: may further comprise the steps:
(1) sulfonation: under 30 ℃-80 ℃, it in oleum and alkylbenzene mass ratio 0.3-1.2 ratio, alkylbenzene between the C9-C22 and oleum solution are transported in the supergravity reactor rotating packed bed simultaneously continuously, high-gravity rotating bed mixing speed is 200rpm/min to 2000rpm/min, alkylbenzene and oleum mix in rotating packed bed and carry out sulfonation reaction 1～20s, left standstill 1.0～4 hours under 60～80 ℃ from rotating packed bed bottom distilled product, isolate organic phase, i.e. alkyl benzene sulphonate (ABS);
(2) neutralization: at normal temperatures, with in the alkaline solution with alkyl benzene sulphonate (ABS) to pH value be 8-9, obtain alkylbenzene sulfonate; Described alkali lye is sodium hydroxide or yellow soda ash;
(3) composite: under 10 ℃-30 ℃, add the alcohol that accounts for final product total amount weight percent 5%-25% in above-mentioned alkylbenzene sulfonate, described alcohol is Virahol or propyl carbinol; Obtain the final product surfactant oil displacement.
Further, high-gravity rotating bed mixing speed carries out under 800rpm to 1500rpm in the step 1).
Advantage of the present invention is as follows:
(a) with supergravity reactor technology first Application in the sulfonation reaction process, be fit to the sulfonation reaction rapid reaction and and microcosmic blended needs, fortification substance transmittance process greatly, the raising rate of mass transfer has improved reaction efficiency;
(b) speed of response is fast, and the reaction times is no more than 1 minute, and is energy-conservation, simultaneously batch between the repeatability of product good;
(c) adopt the present invention produce alkylbenzene sulfonate composite after, show more excellent interfacial tension and displacement of reservoir oil performance, reach best oil displacement efficiency.
Embodiment
Below in conjunction with specific embodiment, technology contents of the present invention is elaborated:
Embodiment 1:
Alkylbenzene between the C9-C22 is that the oleum of 20% (wt) is that 0.3:1 squeezes in the rotating packed bed reactor that treatment capacity is 3L by mass ratio with concentration, the hypergravity machine rotating speed is 700 rev/mins, rotating speed of agitator is 800 rev/mins, sulfonation temperature is 30 ℃, sulfonation reaction is instantaneous successive reaction, sulfonation reaction time 5s.
Divide acid: in alkyl benzene sulphonate (ABS) and vitriolic mixture, add the water that accounts for total amount 5% (wt), divide 60 ℃ of sour temperature, divide acid time 1h, isolate the upper strata alkyl benzene sulphonate (ABS).
The neutralization: among the NaOH of concentration 25% (wt) and isolated alkyl benzene sulphonate (ABS) to pH value 8～9.
Composite: as under 20 ℃, in product, to add the Virahol that accounts for total amount 5% (wt).
Utilize the prepared alkyl benzene sulfonate surfactant in composite back, be configured to a kind of three-component compound system that is suitable for the weak base alkyl benzene sulfonate surfactant, experiment showed, and obtained ultra low interfacial tension (seeing Table 1) between this ternary composite displacement system and the crude oil.
Interfacial tension between table 1 weak base alkyl benzene sulfonate surfactant/alkali systems and the crude oil
Embodiment 2:
Alkylbenzene between the C9-C22 is that 50% oleum is that 0.5:1 squeezes in the rotating packed bed reactor that treatment capacity is 3L by mass ratio with concentration, the hypergravity machine rotating speed is 2000 rev/mins, sulfonation temperature is 50 ℃, and sulfonation reaction is instantaneous successive reaction, sulfonation reaction time 10s.
Divide acid: in alkyl benzene sulphonate (ABS) and vitriolic mixture, add the water that accounts for total amount 10% (wt), divide 70 ℃ of sour temperature, divide acid time 2h, isolate the upper strata alkyl benzene sulphonate (ABS).
Neutralization: the NaCO of concentration 25% (wt)
3Neutralize isolated alkyl benzene sulphonate (ABS) to pH value 8～9.
Composite: as under 20 ℃, in product, to add the propyl carbinol that accounts for total amount 15% (wt).
Other is with embodiment 1, test result such as table 2.
Interfacial tension between table 2 weak base alkyl benzene sulfonate surfactant/alkali systems and the crude oil
Embodiment 3:
Alkylbenzene between the C9-C22 is that 20% oleum is that 0.8:1 squeezes in the rotating packed bed reactor that treatment capacity is 3L by mass ratio with concentration, the hypergravity machine rotating speed is 200 rev/mins, sulfonation temperature is 60 ℃, and sulfonation reaction is instantaneous successive reaction, sulfonation reaction time 15s.
Divide acid: in alkyl benzene sulphonate (ABS) and vitriolic mixture, add the water that accounts for total amount 20% (wt), divide 70 ℃ of sour temperature, divide acid time 3h, isolate the upper strata alkyl benzene sulphonate (ABS).
Composite: as under 20 ℃, in product, to add the propyl carbinol that accounts for total amount 10% (wt).
Other is with embodiment 1, test result such as table 3.
Interfacial tension between table 3 weak base alkyl benzene sulfonate surfactant/alkali systems and the crude oil
Embodiment 4:
Alkylbenzene between the C9-C22 is that 20% oleum is that 1.2:1 squeezes in the rotating packed bed reactor that treatment capacity is 3L by mass ratio with concentration, the hypergravity machine rotating speed is 1500 rev/mins, sulfonation temperature is 80 ℃, and sulfonation reaction is instantaneous successive reaction, sulfonation reaction time 20s.
Divide acid: in alkyl benzene sulphonate (ABS) and vitriolic mixture, add the water that accounts for total amount 15% (wt), divide 60 ℃ of sour temperature, divide acid time 4h, isolate the upper strata alkyl benzene sulphonate (ABS).
Composite: as under 20 ℃, in product, to add the Virahol that accounts for total amount 15% (wt).
Other is with embodiment 1, test result such as table 4.
Interfacial tension between table 4 weak base alkyl benzene sulfonate surfactant/alkali systems and the crude oil
Claims (1)
1. the preparation method of a surfactant oil displacement is characterized in that, comprises the steps:
(1) sulfonation: under 30 ℃-80 ℃, it in oleum and alkylbenzene mass ratio 0.3-1.2 ratio, alkylbenzene between the C9-C22 and oleum solution are transported in the supergravity reactor rotating packed bed simultaneously continuously, high-gravity rotating bed mixing speed is 200rpm/min to 2000rpm/min, alkylbenzene and oleum mix in rotating packed bed and carry out sulfonation reaction 1～20s, left standstill 1.0～4 hours under 60～80 ℃ from rotating packed bed bottom distilled product, isolate organic phase, i.e. alkyl benzene sulphonate (ABS);
(2) neutralization: at normal temperatures, with in the alkaline solution with alkyl benzene sulphonate (ABS) to pH value be 8-9, obtain alkylbenzene sulfonate; Described alkali lye is sodium hydroxide or yellow soda ash;
(3) composite: under 10 ℃-30 ℃, add the alcohol that accounts for final product total amount weight percent 5%-25% in above-mentioned alkylbenzene sulfonate, described alcohol is Virahol or propyl carbinol; Obtain the final product surfactant oil displacement.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008102239717A CN101397494A (en) | 2008-10-10 | 2008-10-10 | Method for preparing surfactants for displacement of oil |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008102239717A CN101397494A (en) | 2008-10-10 | 2008-10-10 | Method for preparing surfactants for displacement of oil |
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| CN101397494A true CN101397494A (en) | 2009-04-01 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102304069A (en) * | 2011-06-23 | 2012-01-04 | 东北石油大学 | Method for synthesizing saturated cardanol sulfonate surfactant for oil displacement |
| CN103450056A (en) * | 2013-08-09 | 2013-12-18 | 王晓晨 | Mahogany petroleum sulfonate preparation method for oil exploitation |
| CN103865508A (en) * | 2014-03-07 | 2014-06-18 | 荆州市国洋化工有限公司 | Plasticizer for displacing oil during oilfield exploitation |
| CN106966930A (en) * | 2017-04-24 | 2017-07-21 | 北京化工大学 | A kind of method that supergravity reactor Green synthesizes petroleum sulfonate for tertiary oil recovery |
| CN110882674A (en) * | 2019-10-12 | 2020-03-17 | 北京化工大学 | Coupling reaction separation and absorption supergravity sulfonate continuous production system and method |
-
2008
- 2008-10-10 CN CNA2008102239717A patent/CN101397494A/en not_active Withdrawn
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102304069A (en) * | 2011-06-23 | 2012-01-04 | 东北石油大学 | Method for synthesizing saturated cardanol sulfonate surfactant for oil displacement |
| CN103450056A (en) * | 2013-08-09 | 2013-12-18 | 王晓晨 | Mahogany petroleum sulfonate preparation method for oil exploitation |
| CN103865508A (en) * | 2014-03-07 | 2014-06-18 | 荆州市国洋化工有限公司 | Plasticizer for displacing oil during oilfield exploitation |
| CN103865508B (en) * | 2014-03-07 | 2017-03-15 | 湖北国洋科技有限公司 | A kind of plasticizer for the oilfield exploitation displacement of reservoir oil |
| CN106966930A (en) * | 2017-04-24 | 2017-07-21 | 北京化工大学 | A kind of method that supergravity reactor Green synthesizes petroleum sulfonate for tertiary oil recovery |
| CN110882674A (en) * | 2019-10-12 | 2020-03-17 | 北京化工大学 | Coupling reaction separation and absorption supergravity sulfonate continuous production system and method |
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Open date: 20090401 |