CN104694106B - One is suitable for Weak Base ASP Flood oil sulfosalt surfactant and application - Google Patents
One is suitable for Weak Base ASP Flood oil sulfosalt surfactant and application Download PDFInfo
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- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
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Abstract
What the present invention relates to is that one is suitable for Weak Base ASP Flood oil sulfosalt surfactant and application, and this Weak Base ASP Flood oil sulfosalt surfactant that is suitable for is prepared by the following method: select C
12~ C
24alkylaryl compounds, molecular-weight average are the C of 310
20~ C
28mixing alpha-olefin, mixing; Sulfonation reaction: adopt falling film sulfonator to carry out sulfonation reaction, material molar ratio is 1.0 ~ 2.0: 1, and sulfonation reaction temperature is 30 DEG C ~ 80 DEG C, SO
3does is gas concentration 2.0g/L ~ 6.0%? g/L, the overall control of protection air quantity is 2000L/h, does is the ratio of First air and secondary air 500/1500L? / h ~ 600/1400L/h; Aging and neutralization: the water above-mentioned sulfonated products being added under sulfonation temperature 2.0% ~ 4.0% is hydrolyzed and aging 0.5h ~ 1.5h, add alcohol, then use the alkaline solution of 20% to be neutralized to pH=8 ~ 9 at 30 DEG C ~ 60 DEG C, namely obtain being suitable for Weak Base ASP Flood oil sulfosalt surfactant.The present invention is little to reservoir injury, low to oil well pipe, oil well pump corrosion and scaling, and comparable water drive improves oil recovery factor more than 20%.
Description
Technical field
The present invention relates to the tensio-active agent used in tertiary oil production in oil field, be specifically related to one and be suitable for Weak Base ASP Flood oil sulfosalt surfactant and application.
Background technology
Alkylaryl sulphonate is the surfactant oil displacement of the excellent property of generally acknowledging both at home and abroad, is mainly used in the combination flooding technology of tertiary oil production in oil field.Ternary composite driving (namely by alkali, surfactant and polymer three kinds of chemical systems) is by the combination of chemical agent and synergy thereof, improve oil recovery factor better, carried out on-the-spot Pilot trial in grand celebration, triumph and Xinjiang Oilfield, recovery ratio improves more than 20%.Combination flooding technology has become cost-effective tertiary oil recovery and has improved recovery efficiency technique method.Tensio-active agent plays an important role in tertiary oil recovery process.It mainly reaches by reducing oil water interfacial tension and improving capillary number the object improving recovery ratio.Indoor and mining site research shows, alkali/Surfactant/Polymer (ASP) ternary composite driving recovery ratio can improve more than 20% again on water drive basis, has good oil increasing precipitation effect.In ternary composite driving application, highly basic (NaOH, KOH), though can react with active ingredient in crude oil and generate natural surface active agent, produces with applying surface promoting agent and acts synergistically, significantly reduce oil-water interfacial tension; And reduce surfactant adsorption amount, combination flooding cost is declined.But highly basic uses and brings site construction technology complexity, oil extraction system fouling, recovery well liquid-producing capacity declines, pump detection period shortens, Produced Liquid breaking emulsion and dewatering difficulty, polymers soln visco-elasticity reduce and cause degradation series of problems under zone permeability because of stratum clay dispersion and migration, and finally restricts ternary composite driving industrial application.Therefore, strengthen weak base, low the alkali even research of alkali-free flooding system are imperative.Although have the ternary composite driving tensio-active agent being suitable for weak base at present, but normally sulfonated petro-leum or the tensio-active agent by composite preparation, there is composition complicated, the defect that particularly unsulfonated oil content is high, poorly soluble, active matter content is low, make its unstable properties, bring problems to production and application.
Summary of the invention
The object of this invention is to provide one and be suitable for Weak Base ASP Flood oil sulfosalt surfactant, this Weak Base ASP Flood oil sulfosalt surfactant that is suitable for is for solving the problem of the problem such as highly basic formation injury in existing ternary composite driving, and another object of the present invention is to provide this application being suitable for Weak Base ASP Flood oil sulfosalt surfactant.
The technical solution adopted for the present invention to solve the technical problems is: this to be suitable for Weak Base ASP Flood oil sulfosalt surfactant be by C
12~ C
24alkylaryl compounds, C
20~ C
28after blend alpha-olefin, carry out sulfonation reaction, aging hydrolysis, then add alcohol, then neutralization is obtained, and in described obtained sulfosalt surfactant, the average equivalent of alkylaryl sulphonate is 400 ~ 500, and concrete preparation method is as follows:
(1) select C
12~ C
24alkylaryl compounds, molecular-weight average are the C of 310
20~ C
28mixing alpha-olefin, mixes as sulfonation raw material, wherein C
12~ C
24the weight percentage of alkylaryl compounds is 50% ~ 90%, C
20~ C
28the weight percentage of mixing alpha-olefin is 10% ~ 50%; (2) sulfonation reaction: adopt the sulfonation raw material of falling film sulfonator to above-mentioned mixing to carry out sulfonation reaction, reaction process condition is: reaction raw materials mol ratio is 1.0 ~ 2.0: 1, and sulfonation reaction temperature is 30 DEG C ~ 80 DEG C, SO
3gas concentration is 2.0g/L ~ 6.0%g/L, and the overall control of protection air quantity is 2000L/h, and the ratio of First air and secondary air is 500/1500L/h ~ 600/1400L/h; Reaction raw materials mol ratio is SO
3with the mol ratio of the sulfonation raw material mixed;
(3) aging and neutralization: the water above-mentioned sulfonated products being added under sulfonation temperature massfraction 2.0% ~ 4.0% is hydrolyzed and aging 0.5h ~ 1.5h, add alcohol, then with mass percent concentration be 20% alkaline solution at 30 DEG C ~ 60 DEG C, be neutralized to pH=8 ~ 9, namely obtain being suitable for Weak Base ASP Flood oil sulfosalt surfactant, the add-on of above-mentioned alcohol is 10% ~ 20% of the product gross weight of last gained.
Further C in step in such scheme (1)
12~ C
24the weight percentage of alkylaryl compounds is 65% ~ 85%, C
20~ C
28the weight percentage of mixing alpha-olefin is 15% ~ 35%; In step (2), reaction raw materials mol ratio is 1.15 ~ 1.65: 1, and sulfonation reaction temperature is 35 DEG C ~ 65 DEG C, SO
3gas concentration is 3.0g/L ~ 5.5%g/L.
That optimum is C in step in such scheme (1)
12~ C
24the weight percentage of alkylaryl compounds is 70% ~ 75%, C
20~ C
28the weight percentage of mixing alpha-olefin is 25% ~ 30%; In step (2), reaction raw materials mol ratio is 1.3 ~ 1.45: 1, and sulfonation reaction temperature is 45 DEG C ~ 55 DEG C, SO
3gas concentration is 4.0g/L ~ 4.5%g/L.
C in such scheme
12~ C
24alkylaryl compounds is the mixture of alkylbenzene, alkyl toluene, alkyl xylene, alkyl isopropyl benzene one of them or they.
In such scheme, alcohol is the mixture of n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, primary isoamyl alcohol one of them or they.
In such scheme alkaline solution can be sodium hydroxide solution, potassium hydroxide solution and solution of ammonium hydroxide one of them.
The above-mentioned Weak Base ASP Flood oil sulfosalt surfactant that is suitable for is applied in the weak base compound flooding tertiary oil recovery of oil field as built agent.
The present invention has following beneficial effect:
1, raw material of the present invention is easy to get, and preparation technology is simple, and product composition is controlled, stable performance.Adopt between the ternary composite oil-displacing system of weak base, water-soluble polymers and this kind of tensio-active agent composition and Daqing crude oil and can form ultra low interfacial tension, laboratory core experiment shows, comparable water drive improves oil recovery factor more than 20%, little to reservoir injury, low to oil well pipe, oil well pump corrosion and scaling, be conducive to oil field spread.
2, this Static Adsorption loss being suitable for Weak Base ASP Flood oil sulfosalt surfactant provided by the invention is little, better heat stability.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated, and protection scope of the present invention is not limited to following embodiment.
embodiment 1:
It is this that to be suitable for Weak Base ASP Flood oil sulfosalt surfactant be by C
12~ C
24alkylaryl compounds, C
20~ C
28after blend alpha-olefin, carry out sulfonation reaction, aging hydrolysis, add alcohol again, then neutralization is obtained, described obtained this being suitable for, comprises alkylaryl sulphonate and α olefin sulfonate in Weak Base ASP Flood oil sulfosalt surfactant, wherein the average equivalent of alkylaryl sulphonate is 400 ~ 500, and concrete preparation method is as follows:
(1) select alkylbenzene, molecular-weight average be 310 C
20~ C
28mixing alpha-olefin, mix as sulfonation raw material, wherein the weight percentage of alkylbenzene is 50% ~ 90%, C
20~ C
28the weight percentage of mixing alpha-olefin is 10% ~ 50%; (2) sulfonation reaction: adopt the sulfonation raw material of falling film sulfonator to above-mentioned mixing to carry out sulfonation reaction, reaction process condition is: reaction raw materials mol ratio is 1.0 ~ 2.0: 1, and sulfonation reaction temperature is 30 DEG C ~ 80 DEG C, SO
3gas concentration is 2.0g/L ~ 6.0%g/L, and the overall control of protection air quantity is 2000L/h, and the ratio of First air and secondary air is 500/1500L/h ~ 600/1400L/h; Reaction raw materials mol ratio is SO
3with the mol ratio of the sulfonation raw material mixed;
(3) aging and neutralization: the water above-mentioned sulfonated products being added under sulfonation temperature massfraction 2.0% ~ 4.0% is hydrolyzed and aging 0.5h ~ 1.5h, add n-propyl alcohol, then with mass percent concentration be 20% sodium hydroxide solution at 30 DEG C ~ 60 DEG C, be neutralized to pH=8 ~ 9, namely obtain being suitable for Weak Base ASP Flood oil sulfosalt surfactant, the add-on of above-mentioned n-propyl alcohol is 10% ~ 20% of the product gross weight of last gained, and the product of last gained is and is suitable for Weak Base ASP Flood oil sulfosalt surfactant.
embodiment 2:
It is this that to be suitable for the concrete preparation method of Weak Base ASP Flood oil sulfosalt surfactant as follows:
(1) select alkyl xylene, molecular-weight average be 310 C
20~ C
28mixing alpha-olefin, mix as sulfonation raw material, wherein the weight percentage of alkyl xylene is 65% ~ 85%, C
20~ C
28the weight percentage of mixing alpha-olefin is 15% ~ 35%; (2) sulfonation reaction: adopt the sulfonation raw material of falling film sulfonator to above-mentioned mixing to carry out sulfonation reaction, reaction process condition is: reaction raw materials mol ratio is 1.3 ~ 1.45: 1, and sulfonation reaction temperature is 45 DEG C ~ 55 DEG C, SO
3gas concentration is 4.0g/L ~ 4.5%g/L, and the overall control of protection air quantity is 2000L/h, and the ratio of First air and secondary air is 500/1500L/h ~ 600/1400L/h; Reaction raw materials mol ratio is SO
3with the mol ratio of the sulfonation raw material mixed;
(3) aging and neutralization: the water above-mentioned sulfonated products being added under sulfonation temperature massfraction 2.0% ~ 4.0% is hydrolyzed and aging 0.5h ~ 1.5h, add isopropylcarbinol, then with mass percent concentration be 20% solution of ammonium hydroxide at 30 DEG C ~ 60 DEG C, be neutralized to pH=8 ~ 9, namely obtain being suitable for Weak Base ASP Flood oil sulfosalt surfactant, the add-on of above-mentioned isopropylcarbinol is 10% ~ 20% of the product gross weight of last gained.
embodiment 3:
Be suitable for the performance test of Weak Base ASP Flood oil sulfosalt surfactant.
What to utilize in embodiment 1 preparation is suitable for Weak Base ASP Flood oil sulfosalt surfactant, and prepare weak base three-component compound system by table 1 institute is routine, method is: tensio-active agent (effective concentration) and alkali are all first mixed with 5wt% mother liquor.Polymkeric substance adopts deeply treating wastewater to be mixed with 5000mg/L solution, stirs 2-3 hour, slaking 12 hours during prepared polymer solution under rotating speed is 1000RPM condition.Ternary system preparation time with dilution of sewage 5000mg/L solution to respective concentration.First add according to the few person of amount during ternary system preparation and tensio-active agent and alkali will separate the principle of application of sample, the addition sequence of various chemical agent should be: surfactant and polymer-sewage-alkali.Weighing will be accurate to 0.001 gram, and the ternary system of preparation will stir, and the time is no less than 30 minutes.
Test experiments result shows, this sulfosalt surfactant defines ultra low interfacial tension with Daqing crude oil under weak base condition, minimumly reaches 3.73 × 10
-4mN/m, and the equilibrium interfacial tension in wider surfactant concentration (0.05 ~ 0.3wt%) and alkali concn (0.6 ~ 1.2wt%) scope between ternary system and crude oil obtains ultralow value.Instead of highly basic sodium hydroxide owing to employing weak base sodium carbonate, this system will alleviate injury and other undesirable action of the formation that highly basic brings.
Table 1 is suitable for Weak Base ASP Flood oil sulfosalt surfactant interfacial tension check point
Note: 1. crude oil is well head dehydration gas-free oil, and water is deeply treating wastewater
2. experimental temperature is 45 DEG C
3. testing tool: University of Texas rotates drips interfacial tensimeter, and model is TX-500C
embodiment 4:
Be suitable for weak base combination flooding sulfosalt surfactant ternary system physical contradictions.
Experimental technique:
Experiment is all carried out under 45 DEG C of conditions.
(1) by the core model of having cast (ground homogeneous core model loads in core holding unit and adds ring pressure), find time 3.5h, saturated synthetic salt solution metering orifice porosity;
(2) the model of saturated synthetic salt solution is placed in 45 DEG C of thermostat containers, constant temperature 12h;
(3) use simulated oil expelling water to mold exit not water outlet, determine original in saturation ratio;
With the rate of displacement water drive of the left and right of 1m/d to mold exit moisture more than 98%, calculate waterflood recovery efficiency factor;
(5) carry out the chemical displacement of reservoir oil according to chemical flooding scheme, after chemical agent has all injected, continue water drive to mold exit moisture more than 98%, calculational chemistry drives recovery ratio and overall recovery factor.
Ternary composite driving experimental program:
Experimental program lists in table 2.
Table 2 chemical flooding experimental program
Oil displacement efficiency:
The results are shown in Table 3 for oil displacement experiment.
Table 3 weak base three-component compound system Displacement Efficiency
Core oil-displacement test shows, Weak Base ASP Flood oil systems improves 18.2% ~ 27.6% than water drive, and average recovery ratio, more than 20%, reaches 21.55%.
The present embodiment result shows, the displacement of reservoir oil of weak base three-component compound system is suitable with strong base ternary compound system displacement of reservoir oil heavy alkylbenzene sulfonate oil displacement efficiency under sulfosalt surfactant indoor physical simulation oil displacement experiment and the same terms, provides support on technology and material by entering mining site practical application for Weak Base ASP Flood oil systems.
Claims (7)
1. be suitable for a Weak Base ASP Flood oil sulfosalt surfactant, it is characterized in that: this to be suitable for Weak Base ASP Flood oil sulfosalt surfactant be by C
12~ C
24alkylaryl compounds, C
20~ C
28after blend alpha-olefin, carry out sulfonation reaction, aging hydrolysis, then add alcohol, then neutralization is obtained, and in described obtained sulfosalt surfactant, the molecular-weight average of alkylaryl sulphonate is 400 ~ 500, and concrete preparation method is as follows:
(1) select C
12~ C
24alkylaryl compounds, molecular-weight average are the C of 310
20~ C
28mixing alpha-olefin, mixes as sulfonation raw material, wherein C
12~ C
24the weight percentage of alkylaryl compounds is 50% ~ 90%, C
20~ C
28the weight percentage of mixing alpha-olefin is 10% ~ 50%;
(2) sulfonation reaction: adopt the sulfonation raw material of falling film sulfonator to above-mentioned mixing to carry out sulfonation reaction, reaction process condition is: reaction raw materials mol ratio is 1.0 ~ 2.0: 1, and sulfonation reaction temperature is 30 DEG C ~ 80 DEG C, SO
3gas concentration is 2.0g/L ~ 6.0%g/L, and the overall control of protection air quantity is 2000L/h, and the ratio of First air and secondary air is 500/1500L/h ~ 600/1400L/h; Reaction raw materials mol ratio is SO
3with the mol ratio of the sulfonation raw material mixed;
(3) aging and neutralization: the water above-mentioned sulfonated products being added under sulfonation temperature its massfraction 2.0% ~ 4.0% is hydrolyzed and aging 0.5h ~ 1.5h, add alcohol, then with mass percent concentration be 20% alkaline solution at 30 DEG C ~ 60 DEG C, be neutralized to pH=8 ~ 9, namely obtain being suitable for Weak Base ASP Flood oil sulfosalt surfactant, the add-on of above-mentioned alcohol is 10% ~ 20% of the product gross weight of last gained.
2. be according to claim 1ly suitable for Weak Base ASP Flood oil sulfosalt surfactant, it is characterized in that: C in described step (1)
12~ C
24the weight percentage of alkylaryl compounds is 65% ~ 85%, C
20~ C
28the weight percentage of mixing alpha-olefin is 15% ~ 35%; In step (2), reaction raw materials mol ratio is 1.15 ~ 1.65: 1, and sulfonation reaction temperature is 35 DEG C ~ 65 DEG C, SO
3gas concentration is 3.0g/L ~ 5.5%g/L.
3. be according to claim 2ly suitable for Weak Base ASP Flood oil sulfosalt surfactant, it is characterized in that: C in described step (1)
12~ C
24the weight percentage of alkylaryl compounds is 70% ~ 75%, C
20~ C
28the weight percentage of mixing alpha-olefin is 25% ~ 30%; In step (2), reaction raw materials mol ratio is 1.3 ~ 1.45: 1, and sulfonation reaction temperature is 45 DEG C ~ 55 DEG C, SO
3gas concentration is 4.0g/L ~ 4.5%g/L.
4. be according to claim 3ly suitable for Weak Base ASP Flood oil sulfosalt surfactant, it is characterized in that: described C
12~ C
24alkylaryl compounds is the mixture of alkylbenzene, alkyl toluene, alkyl xylene, alkyl isopropyl benzene one of them or they.
5. be according to claim 4ly suitable for Weak Base ASP Flood oil sulfosalt surfactant, it is characterized in that: described alcohol is the mixture of n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, primary isoamyl alcohol one of them or they.
6. be according to claim 5ly suitable for Weak Base ASP Flood oil sulfosalt surfactant, it is characterized in that: described alkaline solution can be sodium hydroxide solution, potassium hydroxide solution, solution of ammonium hydroxide one of them.
7. the application being suitable for Weak Base ASP Flood oil sulfosalt surfactant according to claim 6, is characterized in that: this Weak Base ASP Flood oil sulfosalt surfactant that is suitable for is applied in the weak base compound flooding tertiary oil recovery of oil field as built agent.
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| CN112111261B (en) * | 2020-09-09 | 2022-07-26 | 长江大学 | CO (carbon monoxide) 2 Shale oil-based channeling sealing agent for flooding and preparation method thereof |
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| CN102086389A (en) * | 2010-12-31 | 2011-06-08 | 上海大学 | Temperature-resistant salt-resistant composite foam oil displacement agent for tertiary oil recovery and preparation method thereof |
| CN103031120B (en) * | 2011-09-29 | 2014-10-15 | 中国石油化工股份有限公司 | Foaming agent composition containing alkylphenol ethoxylate benzene sulfonate and application |
| CN103254884A (en) * | 2013-05-27 | 2013-08-21 | 上海大学 | High-efficient foam compound flooding agent for tertiary oil recovery and preparation method thereof |
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