CN103184042B - Gemini surfactant for tertiary oil recovery and preparation and application thereof - Google Patents

Abstract

The invention relates to a gemini surfactant for tertiary oil recovery and preparation and application thereof; firstly, adding alkylbenzene and an alkylation catalyst into a reactor 1, and preheating to 20-50 ℃; dropwise adding halogenated alkane into the reactant, heating to 40-80 ℃, and reacting for 2-5 h; adding anhydride and solvent into the reactor 2, adding acylation catalyst, dripping the reaction product after 30min, and reacting at 20-30 ℃ for 0.5-3 h; adding dilute acid solution and crushed ice, slowly pouring the product of step two into a beaker, uniformly mixing, standing and layering; neutralizing the organic layer with alkaline liquor until the pH value is 7-9, and removing the solvent under reduced pressure to obtain the gemini surfactant; with Na₂CO₃And the minimum use concentration can reach 0 when the water is compounded to be used as an oil displacement agent for tertiary oil recovery.002-0.005%, and the interfacial tension can reach 10% when the concentration of the surfactant is more than 20mg/L^-3mN/m。

Description

A kind of Gemini surface active agent used for tertiary oil recovery and Synthesis and applications thereof

Technical field

The present invention relates to a kind of Gemini surface active agent used for tertiary oil recovery and Synthesis and applications thereof.

Background technology

Tertiary oil recovery (especially compound petroleum driving and recovering) is the important means improving oil recovery factor, and tensio-active agent plays a part very important in combination flooding, direct interfacial tension, oil displacement efficiency and the crude oil demulsifications etc. affected between flooding system/crude oil, therefore about the research of combination flooding tensio-active agent is the research field comparatively enlivened always.The tertiary oil recovery tensio-active agent that current Oil Field is applied is based on sulfonated petro-leum and heavy alkylbenzene sulfonate.

It is the method that heavy alkylbenzene sulfonate prepared by raw material that patent ZL01136653.2, ZL99106077.6, CN1486976A each provide with heavy alkyl benzene, but heavy alkylbenzene sulfonate prepared by these methods is applicable to highly basic NaOH, and working concentration is higher.Patent ZL02140719.3 provides a kind of method of weak base heavy alkylbenzene sulfonate, but the method needs to carry out rectifying cutting, complicated process of preparation to heavy alkyl benzene.Patent CN1426833A provides a kind of preparation method being suitable for the alkyl benzene sulfonate surfactant of weak base, but needs the Virahol of composite 15% ~ 20% in heavy alkylbenzene sulfonate prepared by the method.

Patent CN101185866A provides the preparation method of a kind of pair of alkyl polyoxyethylene ether Gemini anionic surface active agent, the method generates alkyl diphenyl ether with bromoalkane and phenyl ether or generates alkylphenol oxygen Vinyl Ether with alkylphenol and oxygen Vinyl Ether, then carries out sulfonation, neutralization.But the method tensio-active agent preparation cost is higher, alkylphenol degradation property is poor.Patent CN101104794A provides one with ditane, phenyl ether, diphenylethane, lipid acid, thionyl chloride, sulfuric acid for raw material, and the method for the two benzene tensio-active agent of the two alkyl disulfonate of preparation, but the method complicated process of preparation, cost is higher.

Summary of the invention

The object of the present invention is to provide a kind of have active high, working concentration is low, be suitable for Gemini surface active agent used for tertiary oil recovery and Synthesis and applications thereof.This Gemini surface active agent is raw material with alkylbenzene, take halogenated alkane as the two alkylbenzene intermediate of link base preparation, then prepares double type tensio-active agent used for tertiary oil recovery through acidylate; technique is simple; without the need to purification & isolation, tensio-active agent is applicable to weak base formula and uses, and working concentration is low.

The preparation method of Gemini surface active agent used for tertiary oil recovery of the present invention, the starting material needed for it are alkylbenzene, halogenated alkane, acid anhydrides, catalyzer, organic solvent, alkali, mineral acid; The ratio of reactant species amount is: alkylbenzene and halogenated alkane (2 ~ 5): 1, alkylbenzene and acid anhydrides 1: (1 ~ 1.5), catalyzer and halogenated alkane (1 ~ 4): 10;

Concrete grammar is:

1. in reactor 1, add alkylbenzene and alkylation catalyst, mix, and be preheating to 20 DEG C ~ 50 DEG C; Under agitation in reactant, drip halogenated alkane, be added dropwise to complete rear continuation and stir 30min; Then 40 ~ 80 DEG C are heated up, reaction 2h ~ 5h;

2. in reactor 2, add acid anhydrides and solvent, be stirred to dissolving; Slowly add acylation catalyst under stirring cooling, after 30min, drip 1. reaction product, be added dropwise to complete rear continuation and stir 30min; 20 DEG C ~ 30 DEG C reaction 0.5h ~ 3h;

3. in beaker, add dilute acid soln and trash ice, 2. will slowly pour beaker into by product under stirring, mix rear stratification, separating organic layer diluted acid washes 2 times again;

4. organic layer alkali lye is neutralized to pH=7 ~ 9, and decompression is sloughed solvent and namely obtained Gemini surface active agent.

Alkylbenzene used is the alkylbenzene of C10 ~ C24.

Halogenated alkane used is the one in dichloro (bromine, iodine) ethane, dichloro (bromine, iodine) propane, dichloro (bromine, iodine) butane.

Acid anhydrides used is the one in malonic anhydride, Succinic anhydried, MALEIC ANHYDRIDE, Pyroglutaric acid, adipic anhydride.

Catalyzer used is anhydrous AlCl₃, FeCl₃, SbCl₅, BF₃, TiCl₄, ZnCl₂, or HF, H₂sO₄, P₂o₅, H₃pO₄, or acidic oxide SiO₂-Al₂o₃, ionic liquid, one in storng-acid cation exchange resin.

Organic solvent used is the one in methylene dichloride, ethylene dichloride, trichloromethane, tetracol phenixin, hexanaphthene.

Alkali used is the one in sodium hydroxide, potassium hydroxide, ammoniacal liquor, thanomin, diethanolamine, trolamine.

Acid used is hydrochloric acid or sulfuric acid.

This Gemini surface active agent and Na₂cO₃, water is composite as Flooding Agent for EOR, uses formula to be tensio-active agent 0.002% ~ 0.005% weight, Na₂cO₃0.6% ~ 2.0% weight, surplus is distilled water or mineralized water.

The present invention has following characteristics:

1. surfactant activity of the present invention is high: at present, the working concentration of sulfonated petro-leum or heavy alkylbenzene sulfonate is generally more than 0.2%, and the minimum working concentration of tensio-active agent of the present invention can reach 0.002% ~ 0.005%.

2. surfactant product yield of the present invention is high: the present invention has good production repeatability, and product yield is more than 70%.

3. preparation method of the present invention is ripe classical: reaction involved in the present invention is alkylation and acylation reaction, and reaction process is ripe, is easy to realize industrialization.

4. the present invention take alkylbenzene as basic raw material, and tensio-active agent cost is low, is beneficial to and applies.

5. tensio-active agent of the present invention is suitable for and weak base Na₂cO₃composite use.

Accompanying drawing explanation

Fig. 1 CMC of surfactant.

Fig. 2 surfactant interface tension force performance.

Embodiment

Embodiment 1:

The preparation of Gemini surface active agent of the present invention

1. in the reactor of drying, add 36.0g heavy alkyl benzene and 12g hexanaphthene, control temperature, not higher than 30 DEG C, under agitation slowly adds the anhydrous AlCl of 1.07g₃, in reactant, slowly drip 7.5g ethylene dibromide after continuing to stir 30min, be added dropwise to complete rear continuation and stir 30min, be then warming up to 80 DEG C of reaction 2h, stopped reaction cooling down.

2. in another dry reactor, add 12.5g maleic anhydride and 30g ethylene dichloride, be stirred to dissolving; Control temperature, not higher than 30 DEG C, slowly adds the anhydrous AlCl of 31.2g under stirring₃, drip 1. reaction product after 30min, be added dropwise to complete after 30min is stirred in rear continuation and be warming up to 30 DEG C of reaction 2h.

3. in beaker, add dilute hydrochloric acid solution and the trash ice of 5%, 2. will slowly pour beaker into by product under stirring, and mix rear stratification, separate organic layer 5% dilute hydrochloric acid and wash 2 times again.Organic layer 20%NaOH solution is neutralized to pH=7 ~ 9, and solvent is sloughed in decompression and namely water obtain Gemini surface active agent.

Embodiment 2:

The preparation of Gemini surface active agent of the present invention

1. in the reactor of drying, add 72.0g heavy alkyl benzene and 24g hexanaphthene, control temperature, not higher than 30 DEG C, under agitation slowly adds the anhydrous AlCl of 2.14g₃, in reactant, slowly drip 15g ethylene dibromide after continuing to stir 30min, be added dropwise to complete rear continuation and stir 30min, be then warming up to 70 DEG C of reaction 5h, stopped reaction cooling down, pressure reducing and steaming solvent.

2. in another dry reactor, add 21g Succinic anhydried and 30g ethylene dichloride, be stirred to dissolving; Control temperature, not higher than 30 DEG C, slowly adds the anhydrous AlCl of 48.0g under stirring₃, drip 1. reaction product after 30min, be added dropwise to complete after 30min is stirred in rear continuation and be warming up to 30 DEG C of reaction 0.5h.

3. in beaker, add dilute hydrochloric acid solution and the trash ice of 5%, 2. will slowly pour beaker into by product under stirring, and mix rear stratification, separate organic layer 5% dilute hydrochloric acid and wash 2 times again.Organic layer 20%NaOH solution is neutralized to pH=7 ~ 9, and solvent is sloughed in decompression and namely water obtain Gemini surface active agent.

Embodiment 3:

The preparation of Gemini surface active agent of the present invention

1. in the reactor of drying, add 36.0g heavy alkyl benzene and 20g hexanaphthene, control temperature, not higher than 30 DEG C, under agitation slowly adds the anhydrous AlCl of 1.1g₃, in reactant, slowly drip 8.2g dibromopropane after continuing to stir 30min, be added dropwise to complete rear continuation and stir 30min, be then warming up to 70 DEG C of reaction 4h, stopped reaction cooling down, pressure reducing and steaming solvent.

2. in another dry reactor, add 11.5g maleic anhydride and 20g ethylene dichloride, be stirred to dissolving; Control temperature, not higher than 30 DEG C, slowly adds the anhydrous AlCl of 30.0g under stirring₃, drip 1. reaction product after 30min, be added dropwise to complete after 30min is stirred in rear continuation and be warming up to 25 DEG C of reaction 1.0h.

3. in beaker, add dilution heat of sulfuric acid and the trash ice of 5%, 2. will slowly pour beaker into by product under stirring, and mix rear stratification, separate organic layer 5% dilute sulphuric acid and wash 2 times again.Organic layer 20%NaOH solution is neutralized to pH=7 ~ 9, and solvent is sloughed in decompression and namely water obtain Gemini surface active agent.

Embodiment 4:

The preparation of Gemini surface active agent of the present invention

1. in the reactor of drying, the anhydrous AlCl of 1.0g is added₃with 0.8g Triethylammonium chloride, be stirred to dissolving, add 36.0g heavy alkyl benzene, in reactant, slowly drip 3.5ml ethylene dibromide after continuing to stir 30min, be added dropwise to complete rear continuation and stir 30min, be then warming up to 40 DEG C of reaction 4h, stopped reaction cooling down.

2. in another dry reactor, add 11.5g maleic anhydride and 20g ethylene dichloride, be stirred to dissolving; Control temperature, not higher than 30 DEG C, slowly adds the anhydrous AlCl of 30.0g under stirring₃, drip 1. reaction product after 30min, be added dropwise to complete after 30min is stirred in rear continuation and be warming up to 30 DEG C of reaction 3.0h.

3. in beaker, add dilute hydrochloric acid solution and the trash ice of 5%, 2. will slowly pour beaker into by product under stirring, and mix rear stratification, separate organic layer 5% dilute hydrochloric acid and wash 2 times again.Organic layer 20%NaOH solution is neutralized to pH=7 ~ 9, and solvent is sloughed in decompression and namely water obtain Gemini surface active agent.

Embodiment 5:

The preparation of Gemini surface active agent of the present invention

1. in the reactor of drying, the anhydrous AlCl of 1.0g is added₃with 0.8g Triethylammonium chloride, be stirred to dissolving, add 36.0g heavy alkyl benzene, in reactant, slowly drip 3.5ml ethylene dibromide after continuing to stir 30min, be added dropwise to complete rear continuation and stir 30min, be then warming up to 40 DEG C of reaction 5h, stopped reaction cooling down.

2. in another dry reactor, add 11.5g maleic anhydride and 20g ethylene dichloride, be stirred to dissolving; Control temperature, not higher than 30 DEG C, slowly adds the anhydrous AlCl of 30.0g under stirring₃, drip 1. reaction product after 30min, be added dropwise to complete after 30min is stirred in rear continuation and be warming up to 30 DEG C of reaction 1.0h.

3. in beaker, add dilute hydrochloric acid solution and the trash ice of 5%, 2. will slowly pour beaker into by product under stirring, and mix rear stratification, separate organic layer 5% dilute hydrochloric acid and wash 2 times again.

4. above-mentioned organic layer is dissolved in 50g Virahol, under 40 DEG C of agitation conditions, slowly drips the sodium sulfite solution of 50.0g10%, at 60 DEG C of reaction 1h after dripping.

5. above-mentioned product stratification, point sub-cloud inorganic salt, solvent is sloughed in upper strata decompression and namely water obtain Gemini surface active agent.

Embodiment 6

The performance of Gemini surface active agent of the present invention

Get Gemini surface active agent prepared by 10.0g embodiment 1, being dissolved in 40ml volume ratio is in the isopropanol/water mixed solvent of 1: 1, and with n-hexane extraction 3 times, solvent evaporated, obtains pure tensio-active agent.By the CMC value of this tensio-active agent of By Means of Electrical Conductivity, as Fig. 1.The micelle-forming concentration that can obtain tensio-active agent of the present invention from figure is 40mg/L.

Embodiment 7:

The application of Gemini surface active agent of the present invention

With distilled water preparation different concns tensio-active agent of the present invention, add 1.2%Na₂cO₃, measure the interfacial tension of district's crude oil in alkali/surfactant system and In Karamay Oil pseudo-ginseng, surfactant concentration interfacial tension when more than 20mg/L all can reach 10^-3mN/m, as Fig. 2.

Claims (7)

1. a preparation method for Gemini surface active agent used for tertiary oil recovery, is characterized in that: required starting material are alkylbenzene, halogenated alkane, acid anhydrides, catalyzer, organic solvent, alkali, mineral acid; The ratio of reactant species amount is: alkylbenzene and halogenated alkane 2 ~ 5:1, alkylbenzene and acid anhydrides 1:1 ~ 1.5, catalyzer and halogenated alkane 1 ~ 4:10; Concrete grammar is:

1. in reactor 1, add alkylbenzene and alkylation catalyst, mix, and be preheating to 20 DEG C ~ 50 DEG C; Under agitation in reactant, drip halogenated alkane, be added dropwise to complete rear continuation and stir 30min; Reaction 2h ~ 5h; Then 40 ~ 80 DEG C are heated up, reaction 2h ~ 5h;

2. in reactor 2, add acid anhydrides and solvent, be stirred to dissolving; Slowly add acylation catalyst under stirring cooling, after 30min, drip 1. reaction product, be added dropwise to complete rear continuation and stir 30min; 20 DEG C ~ 30 DEG C reaction 0.5h ~ 3h;

3. in beaker, add dilute acid soln and trash ice, 2. will slowly pour beaker into by product under stirring, mix rear stratification, separating organic layer diluted acid washes 2 times again;

4. above-mentioned organic layer alkali lye is neutralized to pH=7 ~ 9, and decompression is sloughed solvent and namely obtained Gemini surface active agent;

Halogenated alkane used is the one in ethylene dibromide, dibromopropane;

Acid anhydrides used is MALEIC ANHYDRIDE;

Alkylbenzene used is heavy alkyl benzene.

2. the preparation method of a kind of Gemini surface active agent used for tertiary oil recovery according to claim 1, is characterized in that: catalyzer used is anhydrous AlCl₃, FeCl₃, SbCl₅, BF₃, TiCl₄, ZnCl₂, or HF, H₂sO₄, P₂o₅, H₃pO₄, or acidic oxide SiO₂-Al₂o₃, ionic liquid, one in storng-acid cation exchange resin.

3. the preparation method of a kind of Gemini surface active agent used for tertiary oil recovery according to claim 1, is characterized in that: organic solvent used is the one in methylene dichloride, ethylene dichloride, trichloromethane, tetracol phenixin, hexanaphthene.

4. the preparation method of a kind of Gemini surface active agent used for tertiary oil recovery according to claim 1, is characterized in that: alkali used is the one in sodium hydroxide, potassium hydroxide, ammoniacal liquor, thanomin, diethanolamine, trolamine.

5. the preparation method of a kind of Gemini surface active agent used for tertiary oil recovery according to claim 1, is characterized in that: mineral acid used is hydrochloric acid or sulfuric acid.

6. a Gemini surface active agent used for tertiary oil recovery, is characterized in that: this tensio-active agent is prepared by the preparation method of Gemini surface active agent used for tertiary oil recovery according to claim 1.

7. an application for Gemini surface active agent used for tertiary oil recovery according to claim 6, is characterized in that: with Na₂cO₃, water is composite as Flooding Agent for EOR, uses formula to be tensio-active agent 0.002% ~ 0.005% weight, Na₂cO₃0.6% ~ 2.0% weight, surplus is distilled water or mineralized water.