CN102952531B - Surfactant for displacing oil of offshore oilfield and preparation method thereof - Google Patents
Surfactant for displacing oil of offshore oilfield and preparation method thereof Download PDFInfo
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Abstract
The invention relates to surfactant for displacing the oil of an offshore oilfield and a preparation method thereof, and the surfactant and the preparation method thereof belong to the technical field of surfactants. The surfactant for displacing the oil of the offshore oilfield comprises the following components: hydroxypropyl sulfo betaine type amphoteric surfactant is adopted as the main agent and alkylphenol polyoxyethylene ether non-ionic surfactant serves as the auxiliary agent. The preparation method comprises the following steps that 1) the main agent is prepared: (1) water is adopted as the solvent to react with sodium hydrogen sulfite, sodium sulfite and epoxy chloropropane, and 3-chloro-2-hydroxypropyl sodium sulfonate is prepared; (2) low-carbon alcohol is adopted as the solvent, the product in the step (1) and emulsifier are dissolved, 12/14 tertiary amine is dripped in, and reflux reaction is carried out; (3) the tertiary amine and the solvent which do not react are removed, recrystallized and filtered; 2) assistant agent is selected; and 3) the main agent and the auxiliary agent are prepared by the mass ratio of 30 to 50: 30 to 90. The surfactant for displacing the oil of the offshore oilfield and the preparation method thereof have the advantages of ultra-low interfacial tension and good performance of emulsified crude oil, no toxin, no harm to the stratum, good compatibility, cooperation with polymer, microorganism and other flooding agent to displace oil and the like.
Description
Technical field
The invention belongs to technical field of surfactant, particularly relate to a kind of offshore oilfield surfactant oil displacement and preparation method thereof.
Background technology
Tensio-active agent, by adsorbing on water-oil interface, reduces oil water interfacial tension and emulsified crude oil, thereby improves oil recovery factor.The displacement of reservoir oil widely used tensio-active agent in oil field is sulfonated petro-leum analog anion surfactants.Although its raw material is easy to get, water-soluble better, this class surfactant interface activity is lower, is generally difficult to reach ultralow oil water interfacial tension; And most sulfonated petro-leums can not emulsified crude oil, and after oil mixing with water, crude oil is difficult to be dispersed in surfactant soln, profit layering, the crude oil promoting agent upper strata of floating on the surface.Mahogany acid salt resistance is poor in addition, particularly, in the time that divalent-metal ion content exceedes 400mg/L, sulfonated petro-leum can form precipitation or go to oil phase, and interfacial activity reduces greatly, and fouling in stratum, thereby cause larger injury to affect Sustainable Exploitation on stratum.
Oil displacement efficiency, for improving surfactant properties, is improved in oil field, by alkali, polymkeric substance and tensio-active agent synergistic application, forms ternary composite driving.Alkali can produce tensio-active agent on the spot with petroleum acid, with synthetic surfactant synergy, further reduces oil water interfacial tension and improves the emulsifying effectiveness of tensio-active agent to crude oil.But ternary composite driving easily forms alkali dirt containing alkali, can cause the problem such as reservoir choke, oil-water pipeline burn into production fluid breakdown of emulsion difficulty; Especially offshore oilfield, plugging removal effect is poor, replacing tubing string difficulty, and the existence of alkali can have a strong impact on normal production.
Summary of the invention
The present invention provides a kind of offshore oilfield surfactant oil displacement and preparation method thereof for solving the technical problem existing in known technology.
One of object of the present invention is to provide under a kind of condition that does not rely on alkaline agent, there is the performance that reaches ultra low interfacial tension and emulsified crude oil, and nontoxic, do not injure stratum, compatibleness is good, can drive the collaborative displacement of reservoir oil of agent with polymkeric substance, microorganism etc., improve the offshore oilfield surfactant oil displacement of the features such as chemical flooding oil displacement efficiency.
Tensio-active agent of the present invention, existing without alkaline agent under low consistency conditions, can be reduced to 2 × 10 by oil water interfacial tension
-4mN/m, and crude oil is had to good emulsifying effect, thus avoid adding alkali in oil-displacing agent, eliminate the impact of alkaline agent on reservoir and pipeline.
The technical scheme that offshore oilfield surfactant oil displacement of the present invention is taked for the technical problem existing in solution known technology is:
A kind of offshore oilfield surfactant oil displacement, is characterized in: offshore oilfield surfactant oil displacement comprises two kinds of tensio-active agents, host is that molecular weight is the hydroxypropyl sultaine class amphoterics of 350-410, and mass parts is 30-50; Assistant agent is that molecular weight is the alkylphenol polyoxyethylene class nonionogenic tenside of 600-640, and mass parts is 30-90.
Offshore oilfield surfactant oil displacement of the present invention can also adopt following technical scheme:
Described offshore oilfield surfactant oil displacement, is characterized in: hydroxypropyl sultaine structural formula is as follows:
Wherein R
n=C
12or C
14.
Described offshore oilfield surfactant oil displacement, is characterized in: one or more of polyoxyethylene octylphenol ether-10, polyoxyethylene octylphenol ether-9, polyoxyethylene octylphenol ether-8 or polyoxyethylene nonylphenol ether-10 that alkylphenol polyoxyethylene class class nonionogenic tenside is straight chain;
The structure of alkylphenol polyoxyethylene class class nonionogenic tenside is as follows:
R
n<O?>O(CH
2?CH
2?O)
nH
Wherein R
n=C
8or C
9, n=8,9,10.
Described offshore oilfield surfactant oil displacement, is characterized in: the low carbon chain alcohol that offshore oilfield surfactant oil displacement contains 2-6 C atom.
The preparation method of the offshore oilfield surfactant oil displacement of the features such as two of object of the present invention is to provide one, and to have technique simple, and preparation is convenient, and production efficiency is high, and product oil displacement efficiency is good.
The technical scheme that the preparation method of offshore oilfield surfactant oil displacement of the present invention takes for the technical problem existing in solution known technology is:
A kind of preparation method of offshore oilfield surfactant oil displacement, be characterized in: the preparation process of offshore oilfield surfactant oil displacement comprises that host molecular weight is the hydroxypropyl sultaine class amphoterics preparation of 350-410, the alkylphenol polyoxyethylene class nonionogenic tenside process for preparation that host and assistant agent molecular weight are 600-640:
1) preparation process of hydroxypropyl sultaine class amphoterics:
(1), taking distilled water as solvent, sodium bisulfite, S-WAT, epoxy chloropropane feed intake by the mol ratio of 3:1:2, under 18 ~ 30 DEG C of bath temperatures, and reaction 2h; Obtain the chloro-2-hydroxypropyl azochlorosulfonate acid sodium of lenticular intermediate product 3-;
(2) taking low-carbon alcohol as solvent, by step (1) gained intermediate product and emulsifying agent intensification stirring and dissolving, in the time that reaching 75 ~ 80 DEG C, temperature drips while stirring 12/14 tertiary amines, add rear steady temperature back flow reaction; In the time of PH=7-7.5, add basic catalyst, total reaction time 7 ~ 8h;
(3) reaction product step (2) being obtained, removes unreacted tertiary amine and solvent, then uses dehydrated alcohol recrystallization, and filtered while hot falls not dissolved salt, obtains light yellow liquid transparent liquid alkyl hydroxypropyl sultaine amphoterics;
2) assistant agent alkylphenol polyoxyethylene class nonionogenic tenside is chosen one or more of polyoxyethylene octylphenol ether-10, polyoxyethylene octylphenol ether-9, polyoxyethylene octylphenol ether-8 or polyoxyethylene nonylphenol ether-10 of straight chain;
3) process for preparation of offshore oilfield surfactant oil displacement:
The host alkyl hydroxypropyl sultaine amphoterics making and the assistant agent of choosing, in the ratio preparation of quality 30-50:30 ~ 90, obtain offshore oilfield surfactant oil displacement.
The preparation method of offshore oilfield surfactant oil displacement of the present invention can also take following technical scheme:
The preparation method of described offshore oilfield surfactant oil displacement, is characterized in: basic catalyst is sodium carbonate.
The preparation method of described offshore oilfield surfactant oil displacement, is characterized in: when the preparation of offshore oilfield surfactant oil displacement is entered, solution is heated to 40 ~ 55 DEG C, under agitation condition, dissolves.
The preparation method of described offshore oilfield surfactant oil displacement, is characterized in: when the preparation of offshore oilfield surfactant oil displacement is entered, add the Virahol auxiliary agent of quality proportioning 2-8.
Option table surfactant system assistant agent of the present invention polyoxyethylene octylphenol ether-8,9,10 or the one of polyoxyethylene nonylphenol ether, be made into certain density solution by above mass percent by Oil Field water or Simulated Water with the host hydroxypropyl sultaine of preparation, obtain displacement of reservoir oil ultra low interfacial tension surfactant system.The amount ranges of surfactant system is 0.1 ~ 1.0%(massfraction), resistance to salinity scope 0 ~ 50000ppm, PH=8 ~ 8.5.
When preparation table surfactant system: if 1. will shorten the dosing time, solution stirring heating at 40 ~ 55 DEG C of temperature can be dissolved; 2. the application requiring to oil-displacing agent according to oil reservoir, can add low carbon chain alcohol to make auxiliary agent, further optimization system performance.
Advantage and positively effect that the present invention has are:
Offshore oilfield surfactant oil displacement and preparation method thereof, owing to having adopted the brand-new technical scheme of the present invention, compared with prior art, has following characteristics:
1. the host of surfactant system of the present invention is a kind of structurally-modified betaines amphoterics, and major-minor dose acts synergistically, under wider concentration range, oil water interfacial tension can be reached to 10 in profit system
-3the ultra low levels of mN/m.
2. system of the present invention has good emulsifying viscosity reducing effect to crude oil especially viscous crude, and crude oil can be fine powdered and be dispersed in surfactant soln, forms oil-in-water emulsion, and viscosity of crude can reduce more than 80%;
3. system alkali-free of the present invention agent, has effectively avoided the impact of alkaline agent fouling on reservoir and oil production equipment;
4. system nontoxicity of the present invention, do not injure stratum, compatibleness is good, can with other chemical oil displacement agent Application of composite, improve oil recovery factor.
Brief description of the drawings
Accompanying drawing 1 is that surfactant concentration prepared by embodiment 4 is the dynamic interface tensammetric curve between 0.1%, 0.3%, 0.5% solution and crude oil.(crude oil: SZ 36-1 Field H block dehydration gas-free oil; Salinity 9281mg/L, calcium magnesium 850mg/L; Temperature: 60 DEG C).
Accompanying drawing 2 is surfactant concentration prepared by embodiment 4 viscosity break ratio histograms (temperature 50 C, testing tool: DV-II rotational viscosimeter) to crude oil while being 0.1 ~ 0.5%.
Accompanying drawing 3 is tensio-active agent imitation oil displacement experiment effects that concentration prepared by embodiment 4 is 0.3%.(temperature 60 C, the high 1400mD that oozes of simulation core, hypotonic 500mD, porosity 25%; Water drive crude oil turns surfactant flooding during to water ratio 65%).
Embodiment
For further understanding summary of the invention of the present invention, Characteristic, hereby exemplify following examples, and coordinate accompanying drawing to be described in detail as follows:
Consult accompanying drawing 1, Fig. 2 and Fig. 3.
Embodiment 1
A kind of offshore oilfield surfactant oil displacement, comprises two kinds of tensio-active agents, and host is that molecular weight is the hydroxypropyl sultaine class amphoterics of 350-410, quality 40Kg; Assistant agent is that molecular weight is the alkylphenol polyoxyethylene class nonionogenic tenside of 600-640, and quality is 60kg.
Hydroxypropyl sultaine structural formula is as follows:
Wherein R
n=C
12or C
14.
Polyoxyethylene octylphenol ether-10 that alkylphenol polyoxyethylene class nonionogenic tenside is straight chain.
Embodiment 2
A kind of offshore oilfield surfactant oil displacement, comprises two kinds of tensio-active agents, and host is that molecular weight is the hydroxypropyl sultaine class amphoterics of 350-410, quality 30Kg; Assistant agent is that molecular weight is the alkylphenol polyoxyethylene class nonionogenic tenside of 600-640, and quality is 65Kg; Auxiliary agent Virahol quality is 5Kg.
Embodiment 3
The preparation method of offshore oilfield surfactant oil displacement, comprises following technological process:
1. the preparation process of surfactant system host:
A, in there-necked flask, add 15.6g sodium bisulfite, 6.3g S-WAT, taking distilled water as solvent, be stirred to completely and dissolve; Then drip 9.25g epoxy chloropropane, keeping bath temperature is 18 ~ 30 DEG C, dropwises rear reaction 2h, observes adularescent crystal and separates out.After reaction finishes, ageing, suction filtration, the dry chloro-2-hydroxypropyl azochlorosulfonate acid sodium of lenticular intermediate product 3-that to obtain.
B, with 10%1,2-propylene glycol for solvent, in there-necked flask, add the chloro-2-hydroxypropyl azochlorosulfonate acid sodium of 25.5g 3-, heat up to be stirred to completely and dissolve.In the time that temperature is increased to 75 DEG C, drip while stirring 22.7g lauryl dimethyl tertiary amine, dropwise rear constant temperature back flow reaction 4h; Then add appropriate basic catalyst (sodium carbonate) to regulate PH in the mode dripping, keep the weakly alkaline of system, continue reaction 7h and finish.
C, by n-hexane extraction unreacted tertiary amine for b step products, de-1,2-PD to the greatest extent, evaporating water; Use again dehydrated alcohol recrystallization, and filter insoluble salt, finally obtain target product: lauryl dimethyl hydroxypropyl sultaine (light yellow liquid transparent liquid), reaction conversion ratio >=93%, active matter content is more than or equal to 35%.
Embodiment 4
Surfactant system is the application in tertiary oil production in oil field at sea:
A, offshore oilfield test site oil reservoir overview
Test site is SZ 36-1 Field H block, is positioned at Southern Liaodong Bay marine site, the Bohai Sea; This block ground crude oil mean density 0.965g/cm
3, viscosity 1754mPas, gum asphalt average content 23%, belongs to heavy highly viscous crude.Test site water filling is chloride-calcium type, and total mineralization is 9000 ~ 10000ppm approximately, calcium ions and magnesium ions content 800 ~ 900ppm.Test site reservoir mean permeability 1300mD, net porosity 25%, belongs to middle and high infiltration reservoir.
The preparation of b, surfactant oil displacement system
A kind of offshore oilfield surfactant oil displacement system, its main component and content are: (wt%)
Host I lauryl dimethyl hydroxypropyl sultaine: 30
Assistant agent II polyoxyethylene octylphenol ether-10:65
Auxiliary agent Virahol 5
By host I, assistant agent II, auxiliary agent, with above-mentioned mass percent 30:65:5, using Oil Field water to be made into concentration is 0.1 ~ 0.5% surfactant system, makes a kind of offshore oilfield surfactant oil displacement system.
The performance of c, surfactant oil displacement system
1) interfacial activity of surfactant system test
It is 0.1 ~ 0.5% solution that the offshore oilfield surfactant system of above-mentioned preparation is made into concentration, minimum interfacial tension and the dynamic interface tensammetric curve of test crude oil/water.
Interfacial tensimeter (SY/T5370-1999) is dripped in test testing tool: TX-500C rotation; Temperature 60 C; Crude oil: SZ 36-1 Field H block dehydration gas-free oil, density 0.965g/cm
3; Dosing water: SZ 36-1 Field H block hole condition recovered water, the about 9000mg/L of salinity, calcium ions and magnesium ions 850mg/L.
Minimum oil water interfacial tension sees the following form 1, and profit dynamic interface tensammetric curve as shown in Figure 1.Surfactant system concentration is oil water interfacial tension can be reduced to 10 in 0.1% ~ 0.5% scope
-3mN/m, in the time that concentration is greater than 0.3%, in 60min, minimum oil water interfacial tension reaches 10
-4mN/m, and continue in time to reduce.
The minimum interfacial tension of table 1 embodiment 4 surfactant solns and oil field, Suizhong H block crude oil
2) reducing viscosity by emulsifying of surfactant system test
For investigating the reducing viscosity by emulsifying performance of surfactant system of above-mentioned preparation, first test SZ36-1H block dehydration gas-free oil viscosity at 50 DEG C; Then the surfactant soln equal-volume that is 0.1 ~ 0.5% by crude oil with concentration mixes, and vibration shakes up; Observe the emulsifying effect of tensio-active agent to crude oil and the viscosity break ratio of crude oil.
The emulsifying property of crude oil and viscosity break ratio are in table 2, accompanying drawing 2.After Suizhong block viscous crude mixes with surfactant soln, to observe crude oil and be dispersed in surfactant soln with fine powdered, test emulsion type is oil-in-water emulsion; Tensio-active agent can reduce viscosity of crude more than 80% as can be seen from Table 2 simultaneously, and along with concentration raises, viscosity break ratio increases, maximum viscosity break ratio 88.9%.
The viscosity break ratio of table 2 embodiment 4 surfactant systems to Suizhong block crude oil
3) surfactant system imitation oil displacement experiment experiment
By the displacing surfactant system of above-mentioned preparation, carry out synthetic core displacement of reservoir oil simulated experiment, test this system and improve oil recovery factor value; Wherein synthetic core rate of permeation, nonuniformity, porosity etc. are with reference to the reservoir properties design (in table 3) of SZ 36-1 Field H block.Water drive, to the current water ratio 65 ~ 70% of this block, then turns surfactant flooding, and test surfaces surfactant flood improves oil recovery factor; Design 3 thing mould displacement tests as follows:
1# experiment: water drive, to water ratio 65%, continues water drive to 5PV, finishes (blank);
2# experiment: water drive, to water ratio 65%, is injected the surfactant system that 0.5PV concentration is 0.3%, continues water drive to 5PV;
3# experiment: repeat 2# experiment.
Rock core displacement the results are shown in Table 3, accompanying drawing 3.The surfactant system that can find out above-mentioned preparation improves respectively oil recovery factor 14.25%, 13.49% than water drive, improves recovery ratio average 13.87%, and oil displacement efficiency is obvious.
Table 3 core physical simulation surfactant flooding oil displacement experiment data
Illustrate that by embodiment surfactant system of the present invention can be reduced to oil water interfacial tension ultra low interfacial tension (≤10 above
-3mN/m), and crude oil is had to good emulsifying viscosity reducing effect, the highest viscosity break ratio 88.9%, and system alkali-free, do not injure stratum, compatibleness is good.It is average 13.87% that laboratory core simulated experiment improves waterflood recovery efficiency factor, and oil increasing effect is obvious, for tertiary oil recovery provides a kind of efficient without nocuous displacing surfactant system.
Claims (2)
1. an offshore oilfield surfactant oil displacement, is characterized in that: offshore oilfield surfactant oil displacement comprises two kinds of tensio-active agents, and host is that molecular weight is the hydroxypropyl sultaine class amphoterics of 350-410, and mass parts is 30-50; Assistant agent is that molecular weight is the alkylphenol polyoxyethylene class nonionogenic tenside of 600-640, and mass parts is 30-90;
Hydroxypropyl sultaine structural formula is as follows:
Wherein R
nfor carbon 12 or carbon 14 alkyl.
2. according to offshore oilfield surfactant oil displacement claimed in claim 1, it is characterized in that: one or more of polyoxyethylene octylphenol ether-10, polyoxyethylene octylphenol ether-9, polyoxyethylene octylphenol ether-8 or polyoxyethylene nonylphenol ether-10 that alkylphenol polyoxyethylene class nonionogenic tenside is straight chain;
The structure of alkylphenol polyoxyethylene class nonionogenic tenside is as follows:
Wherein R
nfor carbon 8 or carbon 9 alkyl, n=8,9,10.
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Effective date of registration: 20200624 Address after: 066000 Lulong County, Hebei Province under the village Zhai Zhai village Co-patentee after: Beijing Yingu Rainbow Technology Co.,Ltd. Patentee after: Qinhuangdao normanke Chemical Technology Co., Ltd Address before: 300384 in Tianjin Binhai high tech Zone Huayuan Industrial Park (outer ring) six Haitai development road 6 Haitai green industry base M2 Patentee before: E-TECH ENERGY TECHNOLOGY DEVELOPMENT Corp. |