CN102051164A - Surfactant for oil field and preparation method of surfactant - Google Patents
Surfactant for oil field and preparation method of surfactant Download PDFInfo
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Abstract
The invention relates to a tertiary oil recovery displacement agent modified petroleum sulfonate and a preparation method thereof. The preparation method comprises the following steps: introducing a non-ion group polyoxygen alkyl group in a raw material oil molecular, wherein vacuum cut 2 distillate, vacuum cut 3 distillate. or furfural refined extract oil are used as raw material oils, and then carrying out sulfonation with sulfur trioxide, so that a non-ion group (polyoxygen alkyl group) and an anion group (sulfo group) are in the same surfactant molecular. The modified petroleum sulfonate takes an effect of combination and prevents chromatograph, and has the advantages of non-ion surfactants and anion surfactants as well as good salt resistance and high-temperature resistance capabilities. The prepared modified petroleum sulfonate serving as the surfactant for displacing oil can be used in surfactant displacement or compound displacement.
Description
Technical field
The present invention relates to a kind of tertiary oil recovery oil-displacing agent modification sulfonated petro-leum and preparation method thereof, belong to a kind of negatively charged ion-nonionic surface active agent and preparation method thereof.
Background technology
The chemical combined flooding technology is a tertiary oil recovery new technology, is to adopt organic compound between alkali, tensio-active agent and the high molecular polymer, increases substantially oil displacement efficiency.Sulfonated petro-leum is most widely used tertiary oil recovery tensio-active agent.Sulfonated petro-leum is to be raw material synthetic aniorfic surfactant with crude oil that is rich in aromatic hydrocarbons or distillate, and main component is the monosulfonate of aromatic hydroxy compound.The preparation method of petroleum sulfonate for tertiary oil recovery, Chinese patent has 98101774.6,99107580.3,01129677.1,01110282.9,02125840.6,200610111622.7,200680052521.5 etc., and United States Patent (USP) has US Pat4144266-1979, US Pat4148821-1979, USPat4541940-1985, US Pat4541939-1985, US Pat4614623-1986, USPat4557840-1985 etc.The sulfonated petro-leum raw material sources are wide, production technique is simple, cost is lower, and sulfonated petro-leum and the crude oil compatibleness is good, good water solubility, so be subjected to extensive attention always, are considered to the tertiary oil recovery tensio-active agent of tool commercial promise.But sulfonated petro-leum exists the shortcoming of salt tolerance difference.In oil displacement process, sulfonated petro-leum can react with the multivalent metal cation in the stratum and generate precipitation.Sedimentary formation not only can cause the loss of tensio-active agent, but also can stop up blowhole, even can reduce the performance of displacing surfactant system.Therefore sulfonated petro-leum uses at the high salinity oil reservoir and is restricted.By using the effect that can play salt tolerant with other surfactant compound, but the compounded surfactant system is easy in the migration process of stratum serious " chromatographic separation " phenomenon takes place, thereby cause composite inefficacy.
Summary of the invention
The technical problem to be solved in the present invention is:
At the deficiencies in the prior art, the purpose of this invention is to provide a kind of oil field tensio-active agent and preparation method thereof, improve the anti-salt property of sulfonated petro-leum, this tensio-active agent has good salt tolerant and heat-resisting ability, and then preparation can be used for the modification petroleum sulfonate surfactant of high salinity oil reservoir.
Product technology scheme of the present invention is:
A kind of oil field tensio-active agent, it is the modification sulfonated petro-leum of (1) formula for structural formula,
In (1) formula,
General structure for stock oil; The scope of n is 2～7;
Described stock oil is selected from a kind of in following: refinery second line of distillation distillate, refinery subtract three-way distillate or oil is extracted in the refinery furfural treatment out, and the molecular weight of described stock oil is 200～600, and the aromaticity content in the described stock oil is 20%～80%.
Preparation method's technical scheme of the present invention is:
In the 1st step, stock oil is selected from a kind of in following: refinery second line of distillation distillate, refinery subtract three-way distillate or oil is extracted in the refinery furfural treatment out, and the molecular weight of described stock oil is 200～600, and the aromaticity content in the described stock oil is 20%～80%.
Solvent is a kind of in following: ethylene dichloride, Glacial acetic acid or solvent oil, and preferred described solvent is the 200# solvent oil;
Catalyzer is a kind of in following: aluminum trichloride (anhydrous) or Zinc Chloride Anhydrous;
In molar ratio,
Stock oil: solvent: catalyzer=1: 3～6: 0.5～1,
Described stock oil, described solvent and described catalyzer are added in first reaction vessel, add Paraformaldehyde 96 again, feed hydrogen chloride gas simultaneously, 40 ℃～80 ℃ following stirring reactions 1～4 hour;
In molar ratio,
Stock oil: Paraformaldehyde 96=1: 1.5～2.5,
Stock oil: hydrogenchloride=1: 1.25～1.5,
Isolate upper organic phase after the cooling, use alkali aqueous solution and water washing to neutral successively, underpressure distillation removes and desolvates, and obtains the intermediate product of thickness oily liquids;
Preferred described alkali aqueous solution is: aqueous sodium carbonate or aqueous sodium hydroxide solution, mass concentration 10%～50%;
The 1st step reaction equation is as follows:
Wherein:
Be described stock oil general structure.
Alkali aqueous solution washing, water washing, underpressure distillation all can be adopted known routine techniques.
The 2nd step added multicondensed ethylene glycol in second reaction vessel, add the sodium sheet, in molar ratio,
Sodium: stock oil=0.25～0.5: 1;
Be heated to 80 ℃ dissolve fully to sodium after, behind the reheat to 110 ℃～150 ℃, step reaction gained intermediate product in the adding;
Reacted 12～16 hours, and added entry after the cooling, use extracted with diethyl ether again, repeat 2～5 times, merge upper solution, use acid and water washing to neutral successively upper organic phase solution, use anhydrous magnesium sulfate drying, ether is removed in distillation, obtains the distillate modified product;
Preferred described acid is: the hydrochloric acid of concentration 2～8mol/L;
The 2nd step reaction equation is as follows:
Pickling, washing, drying, distillation all can be adopted known routine techniques.
In the 3rd step, step reaction gained distillate modified product adds ethylene dichloride simultaneously before adding in sulfonation reactor;
Press mass ratio, the distillate modified product: ethylene dichloride=1: 1～3,
With dry air sulphur trioxide is diluted to concentration 2%～6% back and feeds sulfonation reactor, reacted 1～4 hour down at 30 ℃～60 ℃,
In molar ratio, the distillate modified product: sulphur trioxide=1: 1.0～1.5,
Reaction product is after 0.5～2 hour burin-in process of insulated and stirred, and being neutralized to the pH value with the aqueous sodium hydroxide solution of mass concentration 20%～50% is 9～10;
Again with the extraction of volumetric concentration 30%～50% aqueous ethanolic solution; The distillation of aqueous ethanolic solution extract layer except that desolvating, is obtained modification sulfonated petro-leum product, be the oil field surfactant product of structural formula for (1) formula;
The 3rd step reaction equation is as follows:
The modification sulfonated petro-leum prepared by above method is mixed with the aqueous solution, measures the oil water interfacial tension of itself and crude oil, and interfacial tension can reach ultralow value (≤10
-3MN/m).
The said products can be used in the high temperature and high salt oil deposit tertiary oil recovery surfactant flooding as oil-displacing agent, or with the binary or ternary composite driving of polymkeric substance, the compound use of alkali in.
The displacing fluid system consists of: the mass concentration of modification sulfonated petro-leum is 0.01%～3%; The mass concentration of polymkeric substance is 0～2%; The mass concentration of alkali is 0～2%.
Beneficial effect of the present invention:
The present invention introduces non-ionic group polyoxy alkyl in the stock oil molecule, carry out sulfonation with sulphur trioxide then, thereby in sulfonate molecules, introduced non-ionic group polyoxy alkyl, non-ionic group (polyoxy alkyl) and anionic group (sulfonic group) are designed in a surfactant molecule, no longer are single hydrophilic radical in molecular structure.Can play composite effect, can prevent " chromatographic separation " phenomenon again, have the advantage of nonionic and anion surfactant concurrently, have good salt tolerant and heat-resisting ability.And then prepare the modification petroleum sulfonate surfactant that can be used for high salinity oil reservoir excellent property.
Description of drawings
Fig. 1 is the sulfonation reaction device sketch.
Fig. 2 is the infrared spectrogram of product of the present invention.
Embodiment
Embodiment 1:
The 1st step, (molecular-weight average is 295 to take by weighing 590g second line of distillation distillate, aromaticity content is 30.9%) place the there-necked flask that thermometer, agitator, prolong (drying tube is housed) are housed, add 200g Glacial acetic acid, 82g Zinc Chloride Anhydrous (0.6mol), add 36g Paraformaldehyde 96 (1.2mol), start agitator, feed the 1.2mol hydrogen chloride gas simultaneously, 70 ℃ of following stirring reactions 2 hours.Pour in the separating funnel after reacting the cooling that finishes, separate obtaining the upper strata organism.Use the sodium carbonate solution of concentration 20% and water washing to PH=7 successively, underpressure distillation obtains brown thickness oily liquids.
The 2nd step added 292g tetraethylene-glycol (about 1.5mol) in the there-necked flask that thermometer, dropping funnel, agitator are housed, add 7g sodium, was heated to 80 ℃ of sodium and dissolved fully.Drip 103g (about 0.3mol) with dropping funnel and go up step reaction gained intermediate product, 120 ℃ of following stirring reactions 14 hours, reaction finishes and cools off back adding 50ml water, use the 100ml extracted with diethyl ether, triplicate like this, merging upper solution, is 7 with concentration 3mol/L hydrochloric acid and water washing solution to pH value.After the adding anhydrous magnesium sulfate dewatered, ether was removed in distillation, obtains second line of distillation distillate modified product.
The 3rd step, second line of distillation distillate modified product 50g (about 0.1mol) adding is equipped with in the sulfonation reactor of thermometer, agitator, gas distributor and prolong, add the 50g ethylene dichloride simultaneously.The oleum heating obtains gaseous sulfur trioxide, enters by gas distributor to concentration 3.5% with dry air dilution sulphur trioxide and carries out sulfonation reaction in the reactor.Gas speed is controlled by gas meter, and sulphur trioxide and stock oil mol ratio are 1.2: 1.40 ℃ of following stirring reactions 1 hour.After having led to sulphur trioxide, the product that obtains of reaction continues insulation reaction and wore out in 0.5 hour, and the product after the burin-in process adds 50% aqueous sodium hydroxide solution, and to be neutralized to pH value be 9, pours in the insulation separating funnel to extract with the 200ml50% aqueous ethanolic solution.The underpressure distillation of aqueous ethanolic solution extract layer except that desolvating, is obtained modification sulfonated petro-leum product after the oven dry.
Adopt Nicolet Nexus 470 class Fourier transformation infrared spectrometer (U.S. Nicolet company) that synthetic modification sulfonated petro-leum product is carried out Infrared spectroscopy, see Fig. 2.Analytical results is as shown in table 1.The examination of infrared spectrum result shows that the constitutional features of institute's synthetic product meets the constitutional features of target compound.
The results of IR of table 1 synthetic product
| Absorption peak position (cm -1) | Group |
| 1105.7 | Fatty ether C-O-C unsymmetrically stretching vibration absorption peak |
| 3426.6 | Hydroxyl O-H stretching vibration absorption peak |
| 1610.6、1512.0 | Aromatic ring C=C stretching vibration absorption peak |
| 832.1、625.8 | Aromatic ring C-H flexural vibration absorption peak |
| 1351.8、1187.2 | Sulfonic acid SO 2Base stretching vibration absorption peak |
| 2956.8、2926.5、2872.1 | -CH 3、-CH 2-stretching vibration absorption peak |
Sulfonation reaction device as shown in Figure 1, among the figure: 1,2-cock; 3-oleum storage tank; 4,8,14-water bath with thermostatic control; 5,6-under meter; 7-cushions primary heater unit; The 9-gas distributor; The 10-agitator; The 11-sulfonation reactor; The 12-vapor pipe; The 13-thermometer; The 14-water-bath.
With the product preparation water phase surfactant mixture of this embodiment preparation, measure oil water interfacial tension with crude oil system.Preparation water is the higher high salinity simulated formation water of calcium ions and magnesium ions content, and its composition sees Table 1.Crude oil is the Shengli Oil Field dewatered oil.Modification mahogany acid salt concn is 1500mg/L.Measuring temperature is 80 ℃, and surveying instrument is a TX500C gamut interfacial tension survey meter, and minute is 1 hour.The interfacial tension measured value sees Table 3.
The composition of table 2 simulated formation water
| Ionic species | Ca 2+ | Mg 2+ | Na ++K + | Cl - | Total mineralization |
| Ion content (mg/L) | 700 | 576 | 11438 | 20602 | 33316 |
Embodiment 2:
The 1st step, take by weighing and subtract three-way distillate 530g (molecular-weight average 325, aromaticity content is 36.8%) place the there-necked flask that thermometer, agitator, prolong (drying tube is housed) are housed, add 200g Glacial acetic acid, 82g Zinc Chloride Anhydrous (0.6mol), add 36g Paraformaldehyde 96 (1.2mol), start agitator, feed the 1.2mol hydrogen chloride gas simultaneously, 70 ℃ of following stirring reactions 2 hours.Pour in the separating funnel after reacting the cooling that finishes, separate obtaining the upper strata organism.Use the sodium carbonate solution of concentration 20% and water washing to PH=7 successively, underpressure distillation obtains brown thickness oily liquids.
The 2nd step added 292g tetraethylene-glycol (about 1.5mol) in the there-necked flask that thermometer, dropping funnel, agitator are housed, add 7g sodium, was heated to 80 ℃ of sodium and dissolved fully.Drip 112g (about 0.3mol) with dropping funnel and go up step reaction gained intermediate product, 120 ℃ of following stirring reactions 14 hours, the reaction cooling back that finishes added 50ml water, use the 100ml extracted with diethyl ether, triplicate like this, merging upper solution.With concentration 3mol/L hydrochloric acid and water washing solution to pH value is 7.After the adding anhydrous magnesium sulfate dewatered, ether was removed in distillation, obtains subtracting three-way distillate modified product.
The 3rd step will subtract three-way distillate modified product 53g (about 0.1mol) adding and be equipped with in the sulfonation reactor of thermometer, agitator, gas distributor and prolong, add the 53g ethylene dichloride simultaneously.The oleum heating obtains gaseous sulfur trioxide, enters by gas distributor to concentration 4% with dry air dilution sulphur trioxide and carries out sulfonation reaction in the reactor.Gas speed is controlled by gas meter, and sulphur trioxide and stock oil mol ratio are 1.25: 1.40 ℃ of following stirring reactions 1 hour.After having led to sulphur trioxide, the product that obtains of reaction continues insulation reaction and wore out in 0.5 hour, and the product after the burin-in process adds 50% aqueous sodium hydroxide solution, and to be neutralized to pH value be 9, pours in the insulation separating funnel to extract with the 200ml50% aqueous ethanolic solution.The underpressure distillation of aqueous ethanolic solution extract layer except that desolvating, is obtained modification sulfonated petro-leum product after the oven dry.
With this product preparation water phase surfactant mixture, measure oil water interfacial tension with crude oil system.Condition determination is with embodiment 1, and measurement result sees Table 3.
Embodiment 3:
The 1st step, take by weighing furfural treatment and extract oily 394g (molecular-weight average 405 out, aromaticity content is 61.8%), place the there-necked flask that thermometer, agitator, prolong (drying tube is housed) are housed, add 200g Glacial acetic acid, 82g Zinc Chloride Anhydrous (0.6mol), add 36g Paraformaldehyde 96 (1.2mol), start agitator, feed the 1.2mol hydrogen chloride gas simultaneously, 70 ℃ of following stirring reactions 2 hours.Pour in the separating funnel after reacting the cooling that finishes, separate obtaining the upper strata organism.Use the sodium carbonate solution of concentration 20% and water washing to PH=7 successively, underpressure distillation obtains brown thickness oily liquids.
The 2nd step added 292g tetraethylene-glycol (about 1.5mol) in the there-necked flask that thermometer, dropping funnel, agitator are housed, add 7g sodium, was heated to 80 ℃ of sodium and dissolved fully.Drip 136g (about 0.3mol) with dropping funnel and go up step reaction gained intermediate product, 120 ℃ of following stirring reactions 14 hours, the reaction cooling back that finishes added 50ml water, use the 100ml extracted with diethyl ether, triplicate like this, merging upper solution.With concentration 3mol/L hydrochloric acid and water washing solution to pH value is 7.After the adding anhydrous magnesium sulfate dewatered, ether was removed in distillation, obtains the furfural extract oil modified product.
The 3rd step, furfural extract oil modified product 61g (about 0.1mol) adding is equipped with in the sulfonation reactor of thermometer, agitator, gas distributor and prolong, add the 61g ethylene dichloride simultaneously.The oleum heating obtains gaseous sulfur trioxide, enters by gas distributor to concentration 4.5% with dry air dilution sulphur trioxide and carries out sulfonation reaction in the reactor.Gas speed is controlled by gas meter, and sulphur trioxide and stock oil mol ratio are 1.3: 1.40 ℃ of following stirring reactions 1 hour.After having led to sulphur trioxide, the product that obtains of reaction continues insulation reaction and wore out in 0.5 hour, and the product after the burin-in process adds 50% aqueous sodium hydroxide solution, and to be neutralized to pH value be 9, pours in the insulation separating funnel to extract with the 200ml50% aqueous ethanolic solution.The underpressure distillation of aqueous ethanolic solution extract layer except that desolvating, is obtained modification sulfonated petro-leum product after the oven dry.
With this product preparation water phase surfactant mixture, measure oil water interfacial tension with crude oil system.Condition determination is with embodiment 1, and measurement result sees Table 3.
Embodiment 4:
The 1st step, (molecular-weight average is 295 to take by weighing 590g second line of distillation distillate, aromaticity content is 30.9%) place the there-necked flask that thermometer, agitator, prolong (drying tube is housed) are housed, add 200g Glacial acetic acid, 82g Zinc Chloride Anhydrous (0.6mol), add 36g Paraformaldehyde 96 (1.2mol), start agitator, feed the 1.2mol hydrogen chloride gas simultaneously, 70 ℃ of following stirring reactions 2 hours.Pour in the separating funnel after reacting the cooling that finishes, separate obtaining the upper strata organism.Use the sodium carbonate solution of concentration 20% and water washing to PH=7 successively, underpressure distillation obtains brown thickness oily liquids.
The 2nd step added 226g triethylene glycol (about 1.5mol) in the there-necked flask that thermometer, dropping funnel, agitator are housed, add 7g sodium, was heated to 80 ℃ of sodium and dissolved fully.Drip 103g (about 0.3mol) with dropping funnel and go up step reaction gained intermediate product, 120 ℃ of following stirring reactions 14 hours, the reaction cooling back that finishes added 50ml water, use the 100ml extracted with diethyl ether, triplicate like this, merging upper solution.With concentration 3mol/L hydrochloric acid and water washing solution to pH value is 7.After the adding anhydrous magnesium sulfate dewatered, ether was removed in distillation, obtains second line of distillation distillate modified product.
The 3rd step, second line of distillation distillate modified product 50g (about 0.1mol) adding is equipped with in the sulfonation reactor of thermometer, agitator, gas distributor and prolong, add the 50g ethylene dichloride simultaneously.The oleum heating obtains gaseous sulfur trioxide, enters by gas distributor to concentration 3.5% with dry air dilution sulphur trioxide and carries out sulfonation reaction in the reactor.Gas speed is controlled by gas meter, and sulphur trioxide and stock oil mol ratio are 1.2: 1.40 ℃ of following stirring reactions 1 hour.After having led to sulphur trioxide, the product that obtains of reaction continues insulation reaction and wore out in 0.5 hour, and the product after the burin-in process adds 50% aqueous sodium hydroxide solution, and to be neutralized to pH value be 9, pours in the insulation separating funnel to extract with the 200ml50% aqueous ethanolic solution.The underpressure distillation of aqueous ethanolic solution extract layer except that desolvating, is obtained modification sulfonated petro-leum product after the oven dry.
With this product preparation water phase surfactant mixture, measure oil water interfacial tension with crude oil system.Condition determination is with embodiment 1, and measurement result sees Table 3.
Embodiment 5:
The 1st step, take by weighing and subtract three-way distillate 530g (molecular-weight average 325, aromaticity content is 36.8%) place the there-necked flask that thermometer, agitator, prolong (drying tube is housed) are housed, add 200g Glacial acetic acid, 82g Zinc Chloride Anhydrous (0.6mol), add 36g Paraformaldehyde 96 (1.2mol), start agitator, feed the 1.2mol hydrogen chloride gas simultaneously, 70 ℃ of following stirring reactions 2 hours.Pour in the separating funnel after reacting the cooling that finishes, separate obtaining the upper strata organism.Use the sodium carbonate solution of concentration 20% and water washing to PH=7 successively, underpressure distillation obtains brown thickness oily liquids.
The 2nd step added 226g triethylene glycol (about 1.5mol) in the there-necked flask that thermometer, dropping funnel, agitator are housed, add 7g sodium, was heated to 80 ℃ of sodium and dissolved fully.Drip 112g (about 0.3mol) with dropping funnel and go up step reaction gained intermediate product, 120 ℃ of following stirring reactions 14 hours, the reaction cooling back that finishes added 50ml water, use the 100ml extracted with diethyl ether, triplicate like this, merging upper solution.With concentration 3mol/L hydrochloric acid and water washing solution to pH value is 7.After the adding anhydrous magnesium sulfate dewatered, ether was removed in distillation, obtains subtracting three-way distillate modified product.
The 3rd step will subtract three-way distillate modified product 53g (about 0.1mol) adding and be equipped with in the sulfonation reactor of thermometer, agitator, gas distributor and prolong, add the 53g ethylene dichloride simultaneously.The oleum heating obtains gaseous sulfur trioxide, enters by gas distributor to concentration 4% with dry air dilution sulphur trioxide and carries out sulfonation reaction in the reactor.Gas speed is controlled by gas meter, and sulphur trioxide and stock oil mol ratio are 1.25: 1.40 ℃ of following stirring reactions 1 hour.After having led to sulphur trioxide, the product that obtains of reaction continues insulation reaction and wore out in 0.5 hour, and the product after the burin-in process adds 50% aqueous sodium hydroxide solution, and to be neutralized to pH value be 9, pours in the insulation separating funnel to extract with the 200m150% aqueous ethanolic solution.The underpressure distillation of aqueous ethanolic solution extract layer except that desolvating, is obtained modification sulfonated petro-leum product after the oven dry.
With this product preparation water phase surfactant mixture, measure oil water interfacial tension with crude oil system.Condition determination is with embodiment 1, and measurement result sees Table 3.
Embodiment 6:
The 1st step, take by weighing furfural treatment and extract oily 394g (molecular-weight average 405 out, aromaticity content is 61.8%), place the there-necked flask that thermometer, agitator, prolong (drying tube is housed) are housed, add 200g Glacial acetic acid, 82g Zinc Chloride Anhydrous (0.6mol), add 36g Paraformaldehyde 96 (1.2mol), start agitator, feed the 1.2mol hydrogen chloride gas simultaneously, 70 ℃ of following stirring reactions 2 hours.Pour in the separating funnel after reacting the cooling that finishes, separate obtaining the upper strata organism.Use the sodium carbonate solution of concentration 20% and water washing to PH=7 successively, underpressure distillation obtains brown thickness oily liquids.
The 2nd step added 226g triethylene glycol (about 1.5mol) in the there-necked flask that thermometer, dropping funnel, agitator are housed, add 7g sodium, was heated to 80 ℃ of sodium and dissolved fully.Drip 136g (about 0.3mol) with dropping funnel and go up step reaction gained intermediate product, 120 ℃ of following stirring reactions 14 hours, the reaction cooling back that finishes added 50ml water, use the 100ml extracted with diethyl ether, triplicate like this, merging upper solution.With concentration 3mol/L hydrochloric acid and water washing solution to pH value is 7.After the adding anhydrous magnesium sulfate dewatered, ether was removed in distillation, obtains the furfural extract oil modified product.
The 3rd step, furfural extract oil modified product 61g (about 0.1mol) adding is equipped with in the sulfonation reactor of thermometer, agitator, gas distributor and prolong, add the 61g ethylene dichloride simultaneously.The oleum heating obtains gaseous sulfur trioxide, enters by gas distributor to concentration 4.5% with dry air dilution sulphur trioxide and carries out sulfonation reaction in the reactor.Gas speed is controlled by gas meter, and sulphur trioxide and stock oil mol ratio are 1.3: 1.40 ℃ of following stirring reactions 1 hour.After having led to sulphur trioxide, the product that obtains of reaction continues insulation reaction and wore out in 0.5 hour, and the product after the burin-in process adds 50% aqueous sodium hydroxide solution, and to be neutralized to pH value be 9, pours in the insulation separating funnel to extract with the 200ml50% aqueous ethanolic solution.The underpressure distillation of aqueous ethanolic solution extract layer except that desolvating, is obtained modification sulfonated petro-leum product after the oven dry.
With this product preparation water phase surfactant mixture, measure oil water interfacial tension with crude oil system.Condition determination is with embodiment 1, and measurement result sees Table 3.
The oil water interfacial tension value of table 3 modification mahogany acid salt brine solution and crude oil
| Modification mahogany acid product salt | Interfacial tension * 10 -4/(mN/m) |
| |
4.9 |
| |
5.8 |
| Embodiment 3 | 10.1 |
| |
5.5 |
| Embodiment 5 | 7.2 |
| |
16.8 |
By table 2, table 3 as seen, with the modification mahogany acid salt brine solution that calcium, magnesium ion total content are prepared greater than the high salinity simulated formation water of 30000mg/L greater than 1000mg/L, total mineralization, the oil water interfacial tension value with crude oil system under 80 ℃ hot conditions can reach ultra low interfacial tension value (10
-3MN/m) below.Therefore, product of the present invention is a kind of surfactant oil displacement of excellent property of heat-resistant salt-resistant.
Claims (5)
1. oil field tensio-active agent is characterized in that:
It is the modification sulfonated petro-leum of (1) formula for structural formula,
In (1) formula,
General structure for stock oil; The scope of n is 2～7;
Described stock oil is selected from a kind of in following: refinery second line of distillation distillate, refinery subtract three-way distillate or oil is extracted in the refinery furfural treatment out, and the molecular weight of described stock oil is 200～600, and the aromaticity content in the described stock oil is 20%～80%.
2. the described oil field of a claim 1 is characterized in that: may further comprise the steps with the preparation method of tensio-active agent:
In the 1st step, stock oil is selected from a kind of in following: refinery second line of distillation distillate, refinery subtract three-way distillate or oil is extracted in the refinery furfural treatment out, and the molecular weight of described stock oil is 200～600, and the aromaticity content in the described stock oil is 20%～80%;
Solvent is a kind of in following: ethylene dichloride, Glacial acetic acid or solvent oil;
Catalyzer is a kind of in following: aluminum trichloride (anhydrous) or Zinc Chloride Anhydrous;
In molar ratio,
Stock oil: solvent: catalyzer=1: 3～6: 0.5～1,
Described stock oil, described solvent and described catalyzer are added in first reaction vessel, add Paraformaldehyde 96 again, feed hydrogen chloride gas simultaneously, 40 ℃～80 ℃ following stirring reactions 1～4 hour;
In molar ratio,
Stock oil: Paraformaldehyde 96=1: 1.5～2.5,
Stock oil: hydrogenchloride=1: 1.25～1.5,
Isolate upper organic phase after the cooling, use alkali aqueous solution and water washing to neutral successively, underpressure distillation removes and desolvates, and obtains the intermediate product of thickness oily liquids;
The 2nd step added multicondensed ethylene glycol in second reaction vessel, add the sodium sheet, in molar ratio,
Sodium: stock oil=0.25～0.5: 1;
Be heated to 80 ℃ dissolve fully to sodium after, behind the reheat to 110 ℃～150 ℃, step reaction gained intermediate product in the adding;
Reacted 12～16 hours, and added entry after the cooling, use extracted with diethyl ether again, repeat 2～5 times, merge upper solution, use acid and water washing to neutral successively upper organic phase solution, use anhydrous magnesium sulfate drying, ether is removed in distillation, obtains the distillate modified product;
In the 3rd step, step reaction gained distillate modified product adds ethylene dichloride simultaneously before adding in sulfonation reactor;
Press mass ratio, the distillate modified product: ethylene dichloride=1: 1～3,
With dry air sulphur trioxide is diluted to concentration 2%～6% back and feeds sulfonation reactor, reacted 1～4 hour down at 30 ℃～60 ℃,
In molar ratio, the distillate modified product: sulphur trioxide=1: 1.0～1.5,
Reaction product is after 0.5～2 hour burin-in process of insulated and stirred, and being neutralized to the pH value with the aqueous sodium hydroxide solution of mass concentration 20%～50% is 9～10;
Again with the extraction of volumetric concentration 30%～50% aqueous ethanolic solution; The distillation of aqueous ethanolic solution extract layer except that desolvating, is obtained modification sulfonated petro-leum product, be the oil field surfactant product of structural formula for (1) formula.
3. preparation method according to claim 2 is characterized in that:
In the 1st step, described solvent is the 200# solvent oil.
4. according to the described preparation method of one of claim 2 to 3, it is characterized in that:
In the 1st step, the alkali aqueous solution of washing usefulness is: aqueous sodium carbonate or aqueous sodium hydroxide solution, mass concentration 10%～50%.
5. according to the described preparation method of one of claim 2 to 3, it is characterized in that:
In the 2nd step, preferred, the acid of washing usefulness is: the hydrochloric acid of concentration 2～8mol/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910236762.0A CN102051164B (en) | 2009-10-30 | 2009-10-30 | Surfactant for oil field and preparation method of surfactant |
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| CN102553490A (en) * | 2010-12-10 | 2012-07-11 | 江南大学 | Synthetic method of furfural surfactant |
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| CN104946226A (en) * | 2015-07-14 | 2015-09-30 | 中国石油化工股份有限公司 | Thick oil sulfonate preparing method |
| CN105419764A (en) * | 2014-09-17 | 2016-03-23 | 中国石油化工股份有限公司 | High-temperature-resistant and high-salinity-resistant furfural extract oil sulphonate system and preparation method thereof |
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| US4144266A (en) * | 1973-07-05 | 1979-03-13 | Marathon Oil Company | Sulfonation of crude oils to produce petroleum sulfonates |
| US4266610A (en) * | 1978-11-28 | 1981-05-12 | Phillips Petroleum Company | Sulfonate-cosurfactant mixtures for use in hard brines during oil recovery operations |
| CN100489054C (en) * | 2006-06-15 | 2009-05-20 | 中国石化股份胜利油田分公司地质科学研究院 | Highly effective mixed oil expellant applied to tertiary oil recovery and its preparation method |
| 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 |
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| CN105419764A (en) * | 2014-09-17 | 2016-03-23 | 中国石油化工股份有限公司 | High-temperature-resistant and high-salinity-resistant furfural extract oil sulphonate system and preparation method thereof |
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| CN110835313A (en) * | 2018-08-17 | 2020-02-25 | 中国石油化工股份有限公司 | Water-soluble oil washing agent for thick oil and preparation method thereof |
| CN110835313B (en) * | 2018-08-17 | 2021-10-22 | 中国石油化工股份有限公司 | Water-soluble oil washing agent for thick oil and preparation method thereof |
| CN110157404A (en) * | 2019-05-30 | 2019-08-23 | 济南市坤鹏技术开发中心 | A kind of ecological environment-friendly type oil field oil displacement system |
| CN110157404B (en) * | 2019-05-30 | 2020-11-13 | 东北石油大学 | Ecological environment-friendly oil field displacement of reservoir oil system |
| CN111560252A (en) * | 2020-05-09 | 2020-08-21 | 中国石油大学(华东) | Method for cleaning high-concentration naphthenic crude oil polluted soil |
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