CN102051164B - 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 Flooding Agent for EOR Modified Petroleum Sulfonate and preparation method thereof, belong to a kind of Anionic-nonionic type tensio-active agent and preparation method thereof.
Background technology
The chemical combined flooding technology is a tertiary oil recovery new technology, is the organic composite that adopts 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 rich in the crude oil of aromatic hydrocarbons or distillate is the synthetic aniorfic surfactant of raw material, 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, thus always in widespread attention, be considered to the tertiary oil recovery tensio-active agent of tool commercial promise.But sulfonated petro-leum exists the poor shortcoming of salt tolerance.In oil displacement process, sulfonated petro-leum can with the stratum in multivalent metal cation react and generate precipitation.The formation of precipitation 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 high salinity reservoirs was and is restricted.By using the effect that can play salt tolerant with other surfactant compound, but composite surfactant system is easy in the migration process of stratum serious " chromatographic separation " phenomenon occurs, thereby cause composite inefficacy.
Summary of the invention
The technical problem to be solved in the present invention is:
For the deficiencies in the prior art, the purpose of this invention is to provide a kind of Surfactants Used for Oil field 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 Modified Petroleum Sulfonate tensio-active agent of high salinity reservoirs was.
Product technology scheme of the present invention is:
A kind of Surfactants Used for Oil field, it is the Modified Petroleum Sulfonate 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 Light lube oil, refinery subtract three line distillates or refinery furfural extract oil, 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 Light lube oil, refinery subtract three line distillates or refinery furfural extract oil, 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 the first reaction vessel, add again Paraformaldehyde 96, pass into simultaneously hydrogen chloride gas, 40 ℃～80 ℃ lower 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 successively alkali aqueous solution and water washing to neutral, the underpressure distillation desolventizing 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 the 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, reheat after 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 successively acid and water washing to neutral 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;
In mass ratio, the distillate modified product: ethylene dichloride=1: 1～3,
Pass into sulfonation reactor after with dry air sulphur trioxide being diluted to concentration 2%～6%, 30 ℃～60 ℃ lower reactions 1～4 hour,
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; With aqueous ethanolic solution extract layer distillation desolventizing, obtain the Modified Petroleum Sulfonate product, be structural formula and be the Surfactants Used for Oil field product of (1) formula;
The 3rd step reaction equation is as follows:
The Modified Petroleum Sulfonate 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, alkali compound use in.
The displacing fluid composing system is: the mass concentration of Modified Petroleum Sulfonate is 0.01%～3%; Polymer mass concentration 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 feedstock, then carry out sulfonation with sulphur trioxide, 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 again " chromatographic separation " phenomenon, have the advantage of nonionic and anion surfactant concurrently, have good salt tolerant and heat-resisting ability.And then prepare the Modified Petroleum Sulfonate tensio-active agent that can be used for the high salinity reservoirs was 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 the 590g Light lube oil, 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, pass into simultaneously the 1.2mol hydrogen chloride gas, 70 ℃ of lower stirring reactions 2 hours.Pour in the separating funnel after reacting complete cooling, separate obtaining the upper strata organism.Use successively the sodium carbonate solution of concentration 20% and water washing to PH=7, 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 the upper step reaction of 103g (about 0.3mol) gained intermediate product with dropping funnel, 120 ℃ of lower stirring reactions 14 hours, add 50ml water after reacting complete cooling, 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 the Light lube oil modified product.
The 3rd step, Light lube oil modified product 50g (about 0.1mol) adding is equipped with in the sulfonation reactor of thermometer, agitator, gas distributor and prolong, add simultaneously the 50g ethylene dichloride.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 lower 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.With aqueous ethanolic solution extract layer underpressure distillation desolventizing, obtain the Modified Petroleum Sulfonate product after the oven dry.
Adopt Nicolet Nexus 470 class Fourier transformation infrared spectrometer (U.S. Nicolet company) that synthetic Modified Petroleum Sulfonate 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 configuration water phase surfactant mixture of this embodiment preparation, measure the 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.Modified Petroleum Sulfonate concentration is 1500mg/L.Measuring temperature is 80 ℃, and surveying instrument is 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 line 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, pass into simultaneously the 1.2mol hydrogen chloride gas, 70 ℃ of lower stirring reactions 2 hours.Pour in the separating funnel after reacting complete cooling, separate obtaining the upper strata organism.Use successively the sodium carbonate solution of concentration 20% and water washing to PH=7, 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 the upper step reaction of 112g (about 0.3mol) gained intermediate product with dropping funnel, 120 ℃ of lower stirring reactions 14 hours, add 50ml water after reacting complete cooling, use the 100ml extracted with diethyl ether, triplicate like this, merging upper solution.Be 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 subtracting three line distillate modified products.
The 3rd step will subtract three line distillate modified product 53g (about 0.1mol) adding and be equipped with in the sulfonation reactor of thermometer, agitator, gas distributor and prolong, add simultaneously the 53g ethylene dichloride.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 lower 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.With aqueous ethanolic solution extract layer underpressure distillation desolventizing, obtain the Modified Petroleum Sulfonate product after the oven dry.
With this product configuration water phase surfactant mixture, measure the 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 extract oil 394g (molecular-weight average 405, 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, pass into simultaneously the 1.2mol hydrogen chloride gas, 70 ℃ of lower stirring reactions 2 hours.Pour in the separating funnel after reacting complete cooling, separate obtaining the upper strata organism.Use successively the sodium carbonate solution of concentration 20% and water washing to PH=7, 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 the upper step reaction of 136g (about 0.3mol) gained intermediate product with dropping funnel, 120 ℃ of lower stirring reactions 14 hours, add 50ml water after reacting complete cooling, use the 100ml extracted with diethyl ether, triplicate like this, merging upper solution.Be 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 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 simultaneously the 61g ethylene dichloride.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 lower 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.With aqueous ethanolic solution extract layer underpressure distillation desolventizing, obtain the Modified Petroleum Sulfonate product after the oven dry.
With this product configuration water phase surfactant mixture, measure the 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 the 590g Light lube oil, 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, pass into simultaneously the 1.2mol hydrogen chloride gas, 70 ℃ of lower stirring reactions 2 hours.Pour in the separating funnel after reacting complete cooling, separate obtaining the upper strata organism.Use successively the sodium carbonate solution of concentration 20% and water washing to PH=7, 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 the upper step reaction of 103g (about 0.3mol) gained intermediate product with dropping funnel, 120 ℃ of lower stirring reactions 14 hours, add 50ml water after reacting complete cooling, use the 100ml extracted with diethyl ether, triplicate like this, merging upper solution.Be 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 the Light lube oil modified product.
The 3rd step, Light lube oil modified product 50g (about 0.1mol) adding is equipped with in the sulfonation reactor of thermometer, agitator, gas distributor and prolong, add simultaneously the 50g ethylene dichloride.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 lower 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.With aqueous ethanolic solution extract layer underpressure distillation desolventizing, obtain the Modified Petroleum Sulfonate product after the oven dry.
With this product configuration water phase surfactant mixture, measure the 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 line 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, pass into simultaneously the 1.2mol hydrogen chloride gas, 70 ℃ of lower stirring reactions 2 hours.Pour in the separating funnel after reacting complete cooling, separate obtaining the upper strata organism.Use successively the sodium carbonate solution of concentration 20% and water washing to PH=7, 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 the upper step reaction of 112g (about 0.3mol) gained intermediate product with dropping funnel, 120 ℃ of lower stirring reactions 14 hours, add 50ml water after reacting complete cooling, use the 100ml extracted with diethyl ether, triplicate like this, merging upper solution.Be 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 subtracting three line distillate modified products.
The 3rd step will subtract three line distillate modified product 53g (about 0.1mol) adding and be equipped with in the sulfonation reactor of thermometer, agitator, gas distributor and prolong, add simultaneously the 53g ethylene dichloride.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 lower 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.With aqueous ethanolic solution extract layer underpressure distillation desolventizing, obtain the Modified Petroleum Sulfonate product after the oven dry.
With this product configuration water phase surfactant mixture, measure the 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 extract oil 394g (molecular-weight average 405, 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, pass into simultaneously the 1.2mol hydrogen chloride gas, 70 ℃ of lower stirring reactions 2 hours.Pour in the separating funnel after reacting complete cooling, separate obtaining the upper strata organism.Use successively the sodium carbonate solution of concentration 20% and water washing to PH=7, 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 the upper step reaction of 136g (about 0.3mol) gained intermediate product with dropping funnel, 120 ℃ of lower stirring reactions 14 hours, add 50ml water after reacting complete cooling, use the 100ml extracted with diethyl ether, triplicate like this, merging upper solution.Be 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 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 simultaneously the 61g ethylene dichloride.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 lower 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.With aqueous ethanolic solution extract layer underpressure distillation desolventizing, obtain the Modified Petroleum Sulfonate product after the oven dry.
With this product configuration water phase surfactant mixture, measure the 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 the table 3 Modified Petroleum Sulfonate aqueous solution and crude oil
| The Modified Petroleum Sulfonate product | 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, as seen from Table 3, with the Modified Petroleum Sulfonate aqueous 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 (4)
1. the preparation method of a Surfactants Used for Oil field is characterized in that: may further comprise the steps:
In the 1st step, stock oil is selected from a kind of in following: refinery Light lube oil, refinery subtract three line distillates or refinery furfural extract oil, 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 the first reaction vessel, add again Paraformaldehyde 96, pass into simultaneously hydrogen chloride gas, 40 ℃～80 ℃ lower 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 successively alkali aqueous solution and water washing to neutral, the underpressure distillation desolventizing obtains the intermediate product of thickness oily liquids;
The 2nd step added multicondensed ethylene glycol in the 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, reheat after 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 successively acid and water washing to neutral 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;
In mass ratio, distillate modified product: ethylene dichloride=1:1～3,
Pass into sulfonation reactor after with dry air sulphur trioxide being diluted to concentration 2%～6%, 30 ℃～60 ℃ lower reactions 1～4 hour,
In molar ratio, 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; With aqueous ethanolic solution extract layer distillation desolventizing, obtain structural formula and be the Modified Petroleum Sulfonate product of (1) 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 Light lube oil, refinery subtract three line distillates or refinery furfural extract oil, and the molecular weight of described stock oil is 200～600, and the aromaticity content in the described stock oil is 20%～80%;
Be described Surfactants Used for Oil field product.
2. preparation method according to claim 1 is characterized in that:
In the 1st step, described solvent is the 200# solvent oil.
3. according to claim 1 to one of 2 described preparation methods, 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%.
4. according to claim 1 to one of 2 described preparation methods, it is characterized in that:
In the 2nd step, preferred, the acid of washing usefulness is: the hydrochloric acid of concentration 2～8mol/L.
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| CN102807503B (en) * | 2011-06-01 | 2015-02-11 | 中国石油化工股份有限公司 | Polymerizable monomer with surface activity and tackifying copolymer with surface activity as well as preparation methods and application thereof |
| CN105419764B (en) * | 2014-09-17 | 2018-08-07 | 中国石油化工股份有限公司 | A kind of resisting high temperature, high salt furfural extract oil sulfonate systems alone and preparation method thereof |
| 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 |
| 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 |
| CN110157404B (en) * | 2019-05-30 | 2020-11-13 | 东北石油大学 | Ecological environment-friendly oil field displacement of reservoir oil system |
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