CN102863948A - Hydroxysulfobetaine amphoteric surfactant for flooding and preparation method of hydroxysulfobetaine amphoteric surfactant - Google Patents

Abstract

The invention relates to a hydroxysulfobetaine amphoteric surfactant for flooding and a preparation method of the hydroxysulfobetaine amphoteric surfactant, wherein the hydroxysulfobetaine amphoteric surfactant for flooding has a structural formula shown in the specification, in which R is selected from one of C6H5 phenyl, C7H7 tolyl, C8H9 o-xylyl, m-xylyl, p-xylyl, ethylphenyl, mixed xylyl, and C9H11 isopropylphenyl. The hydroxysulfobetaine amphoteric surfactant for flooding provided by the invention has good thermal stability and preferable resistance to high temperature and salt, can generate super low interfacial tension at a high temperature, can be suitable to be used at a large formation temperature range, specially for high-temperature high-salt oil fields, and has a good application prospect.

Description

A kind of hydroxysulfobetaine amphoteric surfactant for oil displacement and preparation method thereof

1. Technical field:

The invention relates to a surfactant used in oilfield tertiary oil recovery, in particular to a hydroxysultaine amphoteric surfactant for oil displacement and a preparation method thereof.

2. Background technology:

The internal salt structure of betaine-type surfactant makes it have good temperature resistance and salt resistance. In addition, it has good interfacial properties in a wide pH range. Prerequisites for application in the system. At present, there are few literatures about the application of betaine in oil fields. Interfacial Tension Reduction Performance Surfactants enhance oil recovery by reducing interfacial tension between oil and water, reducing the start-up resistance of residual oil, and improving microscopic oil displacement efficiency. Therefore, the research on the interfacial properties of surfactants has always been the focus of screening surfactants for chemical composite flooding.

At present, surfactants used in oilfield tertiary oil recovery, such as petroleum carboxylate, are unstable at high temperatures due to the relatively small bond energy of molecules, and are sensitive to high temperatures, resulting in deactivation of surfactants; in addition, in high salinity, especially high calcium Magnesium ion conditions are easy to form precipitates, and are sensitive to salt, resulting in the loss of surfactants. These put forward higher requirements for surfactants both technically and economically. Therefore, it is very important to study the salt-resistant properties of surfactants for their applicable range.

3. Contents of the invention:

An object of the present invention is to provide a kind of hydroxysulfobetaine amphoteric surfactant for oil displacement, which is used to solve the problem that the surface activity such as petroleum carboxylate is not good in resistance to salt; another aspect of the present invention One object is the preparation method of the hydroxysultaine amphoteric surfactant for oil displacement.

The technical solution adopted by the present invention to solve its technical problems is: the structural formula of this oil displacement hydroxysultaine amphoteric surfactant is:

Among them: R is taken from C ₆ H ₅ phenyl, C ₇ H ₇ tolyl, C ₈ H ₉ o-xylyl, m-xylyl, p-xylyl, ethyl phenyl, mixed xylyl, C ₉ H Any one of ₁₁ cumyl groups.

The preparation method of the above-mentioned oil displacement hydroxysultaine amphoteric surfactant:

The first step is to prepare aryl methyl oleate by alkylation of methyl oleate and aromatic hydrocarbon;

The second step is to prepare aryl oleyl alcohol by hydrogenation reduction of aryl oleic acid methyl ester;

The third step is to prepare aryl oleyl glycidyl ether by etherification reaction of aryl oleyl alcohol and epichlorohydrin;

In the fourth step, the aryl oleyl glycidyl ether is aminated with an aminating reagent to obtain a tertiary amine;

In the fifth step, the tertiary amine is subjected to a quaternization reaction with a quaternary amination reagent to obtain the hydroxysultaine amphoteric surfactant for oil displacement.

In the above scheme, the aminating reagent is dimethylamine or diethylamine or diethanolamine or n-butylamine or N,N-dimethyl-1,3-propanediamine.

In the above scheme, the process of preparing aryl methyl oleate by alkylation of methyl oleate and aromatic hydrocarbon is as follows: using methanesulfonic acid as a catalyst, put methyl oleate, aromatic hydrocarbon and methanesulfonic acid into the reaction kettle, and feed N ₂ for 30 minutes , react at 80°C for 10 hours, distill off unreacted aromatic hydrocarbons under reduced pressure, and recrystallize three times with absolute ethanol to obtain methyl aryl oleate, wherein the aromatic hydrocarbons are selected from benzene, toluene, xylene, ethylbenzene, and cumene any of the .

The process of preparing aryl oleyl alcohol by hydrogenation reduction of aryl oleic acid methyl ester in the above scheme is as follows: put 500g aryl oleic acid methyl ester and 2.5g catalyst into the reaction kettle, first replace with _N2 , then replace with _{H2 and} then stir Heat up, pressure 0.1MPa, stirring speed 500r/min; after the temperature reaches 230°C, raise the system pressure to 1.1MPa, start timing, take samples at regular intervals to measure the iodine value, until the iodine value no longer drops, cool down and decompress and discharge .

In the above scheme, the process of preparing aryl oleyl glycidyl ether by etherification reaction between aryl oleyl alcohol and epichlorohydrin is as follows: weigh aryl oleyl alcohol and epichlorohydrin in a molar ratio of 1:1, and weigh The final aryl oleyl alcohol, epichlorohydrin, sodium hydroxide solution with a mass percentage concentration of 30%, and tetrabutylammonium bromide are placed in a four-necked bottle equipped with an electric stirrer and a condensing device, and the epoxy chloride is added dropwise. Propane, the temperature is controlled at 40-70°C, and the dropping time is 5-10h; the temperature is raised to 80-100°C, and the reaction is 5-8h; cooled and filtered, washed with distilled water at 70-80°C until neutral, and the upper layer is collected after liquid separation Dark liquid; dry with anhydrous sodium sulfate, remove excess epichlorohydrin, a small amount of water and solvent toluene by rotary evaporation under reduced pressure.

In the above scheme, the process of amination reaction of aryl oleyl glycidyl ether and amination reagent is as follows: weigh aryl oleyl glycidyl ether and amination reagent according to the molar ratio of 1:1, and mix the amination reagent and ethanol solution Put it into a four-necked bottle equipped with a condensing device, a stirring device and a thermometer, keep the temperature at 40-80°C, start to slowly add aryl glycidyl ether dropwise, after the dropwise addition, raise the temperature to 50-80°C, maintain The temperature is reacted for 4-10 hours, the reaction is completed, the unreacted ethanol and amination reagent are removed by rotary evaporation, and the product tertiary amine is obtained after drying.

In the above scheme, the process of the quaternization reaction between the tertiary amine and the quaternary amination reagent is that the quaternary amination reagent is 3-chloro 2-hydroxyl-propanesulfonate sodium, and the tertiary amine and 3-chloro 2-hydroxyl-propanesulfonate are weighed Sodium acid, the molar ratio of tertiary amine and 3-chloro 2-hydroxyl-propanesulfonate sodium is 1.2:1.0, and the quaternization reagent is placed in a four-necked flask equipped with an electric stirrer and a condensing device, and the volume ratio is 70% ethanol solution to dissolve it, raise the temperature to 70-80°C, start to slowly add tertiary amine dropwise, after the dropwise addition, keep the temperature at 80-90°C, pH at 8-9, react for 9-12 hours, and end the reaction; After cooling, solids appear in the reactant, filter with suction, extract with petroleum ether to remove unreacted tertiary amine, recover the liquid by rotary evaporation to remove ethanol and water, and obtain a yellow viscous product; wash the product with ethyl acetate, filter with suction, and dry Obtain the hydroxysulfobetaine amphoteric surfactant for oil displacement, recrystallize with ethanol, and dry to obtain a white powdery solid product.

In the above scheme, the process of quaternization reaction between tertiary amine and quaternary ammonizing agent is as follows: The molar ratio of chemical reagents is 1:1. Add 0.1mol tertiary amine to a four-necked bottle equipped with a reflux condenser, a magnetic stirrer, a constant pressure dropping funnel, and a thermometer, dissolve it in 100-200ml acetone, and weigh 0.1 mol (propane sultone or butane sultone) of sultone was slowly added dropwise to a four-necked flask at room temperature, slowly added dropwise at 0-15°C, and after the dropwise addition was completed, the temperature was raised to reflux for 24-48h, and the reaction After the end, cool the system to room temperature, filter out the solid matter, wash it with acetone several times, and then recrystallize it with a mixture of acetone and methanol to obtain a white crystal, and dry it under vacuum at 60-80°C to obtain a white powdery solid, which is used for oil displacement. betaine-based amphoteric surfactant.

The synthetic principle of hydroxysultaine amphoteric surfactant for oil displacement of the present invention is as follows:

1. Synthesis of methyl aryl oleate:

R=C ₆ H ₆ (benzene); R=C ₇ H ₈ (toluene); R=C ₈ H ₁₀ (o-xylene, m-xylene, p-xylene, ethylbenzene, mixed xylene); R=C ₉ H ₁₂ (cumene)

2. Synthesis of aryl oleyl alcohol:

3. Synthesis of aryl oleyl glycidyl ether:

4. Amination reaction:

5. Quaternization reaction:

Beneficial effect:

1. The hydroxysulfobetaine amphoteric surfactant for oil displacement provided by the present invention has good thermal stability, has good high temperature resistance and salt resistance, can produce ultra-low interfacial tension at relatively high temperatures, and is applicable to the formation temperature range Wide, especially suitable for high-temperature and high-salt oil fields, and has a good application prospect.

2. The hydroxysulfobetaine amphoteric surfactant for oil displacement provided by the present invention has small static adsorption loss and is not easily deactivated. the

3. The method for preparing the hydroxysultaine amphoteric surfactant for oil displacement provided by the present invention has a simple synthesis process and the product is non-toxic and harmless.

4. Description of drawings:

Fig. 1 is the graph of interfacial tension of hydroxysultaine amphoteric surfactant for oil displacement of the present invention;

Fig. 2 is a graph of the influence of alkali on the interfacial properties of the hydroxysultaine amphoteric surfactant for oil displacement of the present invention;

Fig. 3 is a graph showing the influence of temperature on the adsorption performance of the hydroxysultaine amphoteric surfactant for oil displacement of the present invention.

5. Specific implementation methods:

Below in conjunction with accompanying drawing, the present invention will be further described:

Example 1:

1. Put 296g of methyl oleate, 117g of benzene, and 1g of methanesulfonic acid as catalysts into the reaction kettle, feed N ₂ for 30min, react at 80°C for 10h, distill off unreacted aromatics under reduced pressure, and recrystallize with absolute ethanol The aryl oleic acid methyl ester can be obtained three times, and the yield is 91.3%.

2. Put 250g of methyl aryl oleate and 2.5g of catalyst palladium carbon into the reactor, first replace with N ₂ , then replace with H ₂ , then stir and raise the temperature, the pressure is 0.1MPa, and the stirring speed is 500r/min. After the temperature reaches 230°C, raise the system pressure to 1.1MPa, start timing, take samples at regular intervals to measure the iodine value, until the iodine value no longer drops, cool down and depressurize the material, and the yield is 97.3%.

3. Weigh aryl oleyl alcohol and epichlorohydrin, 134g of 30% sodium hydroxide solution, and 1g of tetrabutylammonium bromide in a molar ratio of 1:1, and place them in a four-necked bottle equipped with an electric mixer and a condensing device. Add 92.5g of epichlorohydrin dropwise, the temperature is controlled at 60°C, and the dropping time is 8h; the temperature is raised to 80°C, and the reaction is 6h; cooled and filtered, washed with distilled water at 80°C until neutral, and the upper dark liquid is collected after liquid separation; It was dried with anhydrous sodium sulfate, and the excess epichlorohydrin, a small amount of water and the solvent toluene were removed by rotary evaporation under reduced pressure. The yield was 78.6%.

4. Weigh 112.5g of dimethylamine aqueous solution according to the etheramine molar ratio of 1:1, put 100ml of ethanol into a four-necked bottle equipped with a condensation device, a stirring device and a thermometer, maintain the temperature at 70°C, and start slowly adding aryl After the addition of glycidyl ether (1 mol), the temperature was raised to 80°C, and the temperature was maintained for 8 hours to complete the reaction. Unreacted ethanol and amination reagent were removed by rotary evaporation, and the product was weighed dry, and the calculated yield was 91.5%.

5. Take the molar feed ratio of tertiary amine and 3-chloro 2-hydroxy-propanesulfonate as 1.2:1.0, put 196.5g of 3-chloro 2-hydroxy-propanesulfonate in a room equipped with electric stirrer and condensing device In a four-neck flask, dissolve it with 100ml of 70% ethanol solution, raise the temperature to 80°C, start to slowly add 1.2mol of tertiary amine dropwise, after the dropwise addition, keep the temperature at 90°C, pH at 8-9, and react for 12 hours , to end the reaction. After cooling, solids appeared in the reactant, filtered by suction, extracted with petroleum ether to remove unreacted tertiary amine, recovered liquid was rotary evaporated to remove ethanol and water, and obtained a yellow viscous product. Wash the product with ethyl acetate, filter it with suction, and dry it to obtain the product. Recrystallization was carried out with ethanol, and the calculated yield was 78.2% after drying.

Example 2:

1. Put 296g of methyl oleate, 158g of mixed xylene, and 1g of methanesulfonic acid as a catalyst into the reactor, feed N ₂ for 30min, react at 80°C for 10h, distill off unreacted aromatics under reduced pressure, and use absolute ethanol Methyl aryl oleate can be obtained by recrystallization three times with a yield of 92.5%.

2. Put 250g of methyl aryl oleate and 2.5g of catalyst into the reactor, replace with N ₂ first, then replace with H ₂ , then stir and raise the temperature, the pressure is 0.1MPa, and the stirring speed is 500r/min. After the temperature reaches 230°C, raise the system pressure to 1.1MPa, start timing, take samples at regular intervals to measure the iodine value, until the iodine value no longer drops, cool down and depressurize, and discharge, with a yield of 98.1%.

3. Weigh aryl oleyl alcohol and epichlorohydrin, 134g of 30% sodium hydroxide solution, and 1g of tetrabutylammonium bromide in a molar ratio of 1:1, and place them in a four-necked bottle equipped with an electric mixer and a condensing device. Add 92.5g of epichlorohydrin dropwise, the temperature is controlled at 60°C, and the dropping time is 8h; the temperature is raised to 80°C, and the reaction is 6h; cooled and filtered, washed with distilled water at 80°C until neutral, and the upper dark liquid is collected after liquid separation; It was dried with anhydrous sodium sulfate, and the excess epichlorohydrin, a small amount of water and the solvent toluene were removed by rotary evaporation under reduced pressure, and the yield was 78.5%.

4. Weigh 73g of diethylamine aqueous solution according to the etheramine molar ratio of 1:1, put 100ml of ethanol into a four-necked bottle equipped with a condensation device, a stirring device and a thermometer, keep the temperature at 70°C, and start to slowly add aryl shrinkage Glyceryl ether (1mol), after the dropwise addition, the temperature was raised to 80°C, and the reaction was maintained at this temperature for 8 hours, and the reaction was terminated. Unreacted ethanol and amination reagent were removed by rotary evaporation, and the product was weighed dry, and the calculated yield was 91.2%.

5. Add 0.1mol tertiary amine to a four-neck flask equipped with a reflux condenser, a magnetic stirrer, a constant pressure dropping funnel, and a thermometer, dissolve it in 100ml acetone, weigh 12.214g of 0.1mol propane sultone, and slowly Add it dropwise to a four-necked flask, slowly drop it at 0°C, and heat up to reflux for 24 hours after the dropwise addition. After the reaction, cool the system to room temperature, filter out the solid matter, wash it with acetone several times, and then wash it with acetone and methanol The mixed solution was recrystallized to obtain white crystals, which were dried under vacuum at 60°C to obtain a white powdery solid, and the calculated yield after drying was 71.6%.

Example 3:

1. Put 296g of methyl oleate, 138g of toluene, and 1g of methanesulfonic acid as catalysts into the reaction kettle, feed N ₂ for 30 minutes, react at 80°C for 10 hours, distill off unreacted aromatics under reduced pressure, and recrystallize with absolute ethanol Three times to get methyl aryl oleate.

2. Put 500g of methyl aryl oleate and 2.5g of catalyst into the reactor, replace with N ₂ first, then replace with H ₂ , then stir and raise the temperature, the pressure is 0.1MPa, and the stirring speed is 500r/min. After the temperature reaches 230°C, raise the system pressure to 1.1MPa, start timing, take samples at regular intervals to measure the iodine value, until the iodine value no longer drops, then cool down and decompress and discharge.

3. Weigh aryl oleyl alcohol and epichlorohydrin, 134g of 30% sodium hydroxide solution, and 1g of tetrabutylammonium bromide in a molar ratio of 1:1, and place them in a four-necked bottle equipped with an electric mixer and a condensing device. Add 92.5g of epichlorohydrin dropwise, the temperature is controlled at 40°C, and the dropping time is 5h; the temperature is raised to 90°C, and the reaction is 5h; cooling and suction filtration, washing with distilled water at 70°C until neutral, and collecting the upper dark liquid after liquid separation; It was dried with anhydrous sodium sulfate, and the excess epichlorohydrin, a small amount of water and the solvent toluene were removed by rotary evaporation under reduced pressure. The yield was 78.8%.

4. Weigh 73g of diethylamine aqueous solution according to the etheramine molar ratio of 1:1, put 100ml of ethanol into a four-necked bottle equipped with a condensation device, a stirring device and a thermometer, keep the temperature at 40°C, and start slowly adding aryl shrinkage Glyceryl ether (1mol), after the dropwise addition, the temperature was raised to 50°C, and the reaction was maintained at this temperature for 4 hours, and the reaction was terminated. Unreacted ethanol and amination reagent were removed by rotary evaporation, and the product was weighed dry, and the calculated yield was 91.2%.

5. Take the molar feed ratio of tertiary amine and 3-chloro 2-hydroxy-propanesulfonate as 1.2:1.0, put 196.5g of 3-chloro 2-hydroxy-propanesulfonate in a room equipped with electric stirrer and condensing device In the four-neck flask, dissolve it with 100ml of 70% ethanol solution, raise the temperature to 70°C, start to slowly add 1.2mol of tertiary amine dropwise, after the dropwise addition, keep the temperature at 80°C, pH at 8, react for 9 hours, end reaction. After cooling, solids appeared in the reactant, filtered by suction, extracted with petroleum ether to remove unreacted tertiary amine, recovered liquid was rotary evaporated to remove ethanol and water, and obtained a yellow viscous product. Wash the product with ethyl acetate, filter it with suction, and dry it to obtain the product. Recrystallization was carried out with ethanol, and the calculated yield was 78.6% after drying.

Example 4:

1. Put 296g of methyl oleate, 159g of ethylbenzene, and 1g of methanesulfonic acid as catalysts into the reactor, feed _N2 for 30min, react at 80°C for 10h, distill off the unreacted aromatic hydrocarbons under reduced pressure, and weigh them with absolute ethanol Crystallize three times to get methyl aryl oleate.

2. Put 500g of methyl aryl oleate and 2.5g of catalyst into the reactor, replace with N ₂ first, then replace with H ₂ , then stir and raise the temperature, the pressure is 0.1MPa, and the stirring speed is 500r/min. After the temperature reaches 230°C, raise the system pressure to 1.1MPa, start timing, take samples at regular intervals to measure the iodine value, until the iodine value no longer drops, then cool down and decompress and discharge.

3. Weigh aryl oleyl alcohol and epichlorohydrin, 134g of 30% sodium hydroxide solution, and 1g of tetrabutylammonium bromide in a molar ratio of 1:1, and place them in a four-necked bottle equipped with an electric mixer and a condensing device. Add 92.5g of epichlorohydrin dropwise, the temperature is controlled at 70°C, and the dropping time is 10h; the temperature is raised to 100°C, and the reaction is carried out for 85h; cooling and suction filtration, washing with distilled water at 75°C until neutral, and collecting the upper dark liquid after liquid separation; It was dried with anhydrous sodium sulfate, and the excess epichlorohydrin, a small amount of water and the solvent toluene were removed by rotary evaporation under reduced pressure. The yield was 79.1%.

4. Weigh 73g of diethylamine aqueous solution according to the etheramine molar ratio of 1:1, put 100ml of ethanol into a four-necked bottle equipped with a condensation device, a stirring device and a thermometer, keep the temperature at 60°C, and start slowly adding aryl shrinkage Glyceryl ether (1mol), after the dropwise addition, the temperature was raised to 70°C, and the reaction was maintained at this temperature for 10 hours, and the reaction was terminated. The unreacted ethanol and amination reagent were removed by rotary evaporation, and the product was weighed dry, and the calculated yield was 91%.

5. Take the molar feed ratio of tertiary amine and 3-chloro 2-hydroxy-propanesulfonate as 1.2:1.0, put 196.5g of 3-chloro 2-hydroxy-propanesulfonate in a room equipped with electric stirrer and condensing device In the four-neck flask, dissolve it with 100ml of 70% ethanol solution, raise the temperature to 80°C, start to slowly add 1.2mol of tertiary amine dropwise, after the dropwise addition, keep the temperature at 90°C, pH at 9, react for 10 hours, and end reaction. After cooling, solids appeared in the reactant, filtered by suction, extracted with petroleum ether to remove unreacted tertiary amine, recovered liquid was rotary evaporated to remove ethanol and water, and obtained a yellow viscous product. Wash the product with ethyl acetate, filter it with suction, and dry it to obtain the product. Recrystallization was carried out with ethanol, and the calculated yield was 79.2% after drying.

Example 5:

1. Put 296g of methyl oleate, 159g of xylene, and 1g of methanesulfonic acid as catalysts into a reaction kettle, feed N ₂ for 30 minutes, and react at 80°C for 10 hours. Unreacted aromatics are distilled out under reduced pressure and weighed with absolute ethanol. The methyl aryl oleate can be obtained by crystallization three times, and the yield is 91.6%.

2. Put 250g of methyl aryl oleate and 2.5g of catalyst palladium carbon into the reactor, first replace with N ₂ , then replace with H ₂ , then stir and raise the temperature, the pressure is 0.1MPa, and the stirring speed is 500r/min. After the temperature reaches 230°C, raise the system pressure to 1.1MPa, start timing, take samples at regular intervals to measure the iodine value, until the iodine value no longer drops, cool down and depressurize, and discharge, with a yield of 97.5%.

3. Weigh aryl oleyl alcohol and epichlorohydrin, 134g of 30% sodium hydroxide solution, and 1g of tetrabutylammonium bromide in a molar ratio of 1:1, and place them in a four-necked bottle equipped with an electric mixer and a condensing device. Add 92.5g of epichlorohydrin dropwise, the temperature is controlled at 60°C, and the dropping time is 8h; the temperature is raised to 80°C, and the reaction is 6h; cooled and filtered, washed with distilled water at 80°C until neutral, and the upper dark liquid is collected after liquid separation; It was dried with anhydrous sodium sulfate, and the excess epichlorohydrin, a small amount of water and the solvent toluene were removed by rotary evaporation under reduced pressure. The yield was 78.4%.

4. Weigh 112.5g of dimethylamine aqueous solution according to the etheramine molar ratio of 1:1, put 100ml of ethanol into a four-necked bottle equipped with a condensation device, a stirring device and a thermometer, maintain the temperature at 70°C, and start slowly adding aryl After the addition of glycidyl ether (1 mol), the temperature was raised to 80°C, and the temperature was maintained for 8 hours to complete the reaction. Unreacted ethanol and amination reagent were removed by rotary evaporation, and the product was weighed dry, and the calculated yield was 91.5%.

5. Take the molar feed ratio of tertiary amine and 3-chloro 2-hydroxy-propanesulfonate as 1.2:1.0, put 196.5g of 3-chloro 2-hydroxy-propanesulfonate in a room equipped with electric stirrer and condensing device In a four-neck flask, dissolve it with 100ml of 70% ethanol solution, raise the temperature to 80°C, start to slowly add 1.2mol of tertiary amine dropwise, after the dropwise addition, keep the temperature at 90°C, pH at 8-9, and react for 12 hours , to end the reaction. After cooling, solids appeared in the reactant, filtered by suction, extracted with petroleum ether to remove unreacted tertiary amine, recovered liquid was rotary evaporated to remove ethanol and water, and obtained a yellow viscous product. Wash the product with ethyl acetate, filter it with suction, and dry it to obtain the product. Recrystallization was carried out with ethanol, and the calculated yield was 74.7% after drying.

Embodiment 6:

1. Put 296g of methyl oleate, 180g of cumene, and 1g of methanesulfonic acid as catalysts into the reaction kettle, feed N ₂ for 30min, react at 80°C for 10h, distill off unreacted aromatics under reduced pressure, and use absolute ethanol Recrystallization three times can obtain aryl oleic acid methyl ester, yield 91%.

2. Put 250g of methyl aryl oleate and 2.5g of catalyst palladium carbon into the reactor, first replace with N ₂ , then replace with H ₂ , then stir and raise the temperature, the pressure is 0.1MPa, and the stirring speed is 500r/min. After the temperature reaches 230°C, raise the system pressure to 1.1MPa, start timing, take samples at regular intervals to measure the iodine value, until the iodine value no longer drops, cool down and depressurize the material, and the yield is 97.1%.

3. Weigh aryl oleyl alcohol and epichlorohydrin, 134g of 30% sodium hydroxide solution, and 1g of tetrabutylammonium bromide in a molar ratio of 1:1, and place them in a four-necked bottle equipped with an electric mixer and a condensing device. Add 92.5g of epichlorohydrin dropwise, the temperature is controlled at 60°C, and the dropping time is 8h; the temperature is raised to 80°C, and the reaction is 6h; cooled and filtered, washed with distilled water at 80°C until neutral, and the upper dark liquid is collected after liquid separation; It was dried with anhydrous sodium sulfate, and the excess epichlorohydrin, a small amount of water and the solvent toluene were removed by rotary evaporation under reduced pressure. The yield was 78.2%.

4. Weigh 112.5g of dimethylamine aqueous solution according to the etheramine molar ratio of 1:1, put 100ml of ethanol into a four-necked bottle equipped with a condensation device, a stirring device and a thermometer, maintain the temperature at 70°C, and start slowly adding aryl After the addition of glycidyl ether (1 mol), the temperature was raised to 80°C, and the temperature was maintained for 8 hours to complete the reaction. Unreacted ethanol and amination reagent were removed by rotary evaporation, and the product was weighed dry, and the calculated yield was 91.8%.

5. Take the molar feed ratio of tertiary amine and 3-chloro 2-hydroxy-propanesulfonate as 1.2:1.0, put 196.5g of 3-chloro 2-hydroxy-propanesulfonate in a room equipped with electric stirrer and condensing device In a four-neck flask, dissolve it with 100ml of 70% ethanol solution, raise the temperature to 80°C, start to slowly add 1.2mol of tertiary amine dropwise, after the dropwise addition, keep the temperature at 90°C, pH at 8-9, and react for 12 hours , to end the reaction. After cooling, solids appeared in the reactant, filtered by suction, extracted with petroleum ether to remove unreacted tertiary amine, recovered liquid was rotary evaporated to remove ethanol and water, and obtained a yellow viscous product. Wash the product with ethyl acetate, filter it with suction, and dry it to obtain the product. Recrystallization was carried out with ethanol, and the calculated yield was 75.% after drying.

Embodiment 7:

1. Put 296g of methyl oleate, 158g of mixed xylene, and 1g of methanesulfonic acid as a catalyst into the reactor, feed N ₂ for 30min, react at 80°C for 10h, distill off unreacted aromatics under reduced pressure, and use absolute ethanol Methyl aryl oleate can be obtained by recrystallization three times with a yield of 92.5%.

2. Put 250g of methyl aryl oleate and 2.5g of catalyst into the reactor, replace with N ₂ first, then replace with H ₂ , then stir and raise the temperature, the pressure is 0.1MPa, and the stirring speed is 500r/min. After the temperature reaches 230°C, raise the system pressure to 1.1MPa, start timing, take samples at regular intervals to measure the iodine value, until the iodine value no longer drops, cool down and depressurize, and discharge, with a yield of 98.1%.

3. Weigh aryl oleyl alcohol and epichlorohydrin, 134g of 30% sodium hydroxide solution, and 1g of tetrabutylammonium bromide in a molar ratio of 1:1, and place them in a four-necked bottle equipped with an electric mixer and a condensing device. Add 92.5g of epichlorohydrin dropwise, the temperature is controlled at 60°C, and the dropping time is 8h; the temperature is raised to 80°C, and the reaction is 6h; cooled and filtered, washed with distilled water at 80°C until neutral, and the upper dark liquid is collected after liquid separation; It was dried with anhydrous sodium sulfate, and the excess epichlorohydrin, a small amount of water and the solvent toluene were removed by rotary evaporation under reduced pressure, and the yield was 78.5%.

4. Weigh 73g of diethylamine aqueous solution according to the etheramine molar ratio of 1:1, put 100ml of ethanol into a four-necked bottle equipped with a condensation device, a stirring device and a thermometer, keep the temperature at 70°C, and start to slowly add aryl shrinkage Glyceryl ether (1mol), after the dropwise addition, the temperature was raised to 80°C, and the reaction was maintained at this temperature for 8 hours, and the reaction was terminated. Unreacted ethanol and amination reagent were removed by rotary evaporation, and the product was weighed dry, and the calculated yield was 91.2%.

5. Add 0.1mol tertiary amine to a four-neck flask equipped with a reflux condenser, a magnetic stirrer, a constant pressure dropping funnel, and a thermometer, dissolve it in 200ml acetone, and weigh 13.617g of 0.1mol butane sultone at room temperature Slowly add dropwise to the four-necked bottle, slowly dropwise at 15°C, after the dropwise addition is completed, the temperature is raised to reflux for 48 hours, after the reaction, the system is cooled to room temperature, the solid matter is filtered out, washed with acetone several times, and then washed with acetone and The methanol mixture was recrystallized to obtain white crystals, which were dried under vacuum at 80°C to obtain white powdery solids, and the calculated yield after drying was 71.6%.

Utilize above-mentioned embodiment to carry out the interfacial tension test of hydroxysultaine amphoteric surfactant for oil displacement, obtain the interfacial tension curve of hydroxysultaine amphoteric surfactant for oil displacement as shown in Figure 1, and Fig. 1 reflects this displacement Hydroxysultaine amphoteric surfactant for oil can produce ultra-low interfacial tension at higher temperature.

Utilize above-mentioned embodiment simultaneously to carry out the test of the influence of alkali on the interfacial properties of the hydroxysultaine amphoteric surfactant for oil displacement, and obtain the influence curve of alkali on the interface performance of the hydroxysultaine amphoteric surfactant for oil displacement as shown in Figure 2 , Figure 2 reflects that alkali has little effect on the interfacial properties of this hydroxysultaine amphoteric surfactant for oil displacement.

Also utilize above-mentioned embodiment to carry out the impact test of temperature on the adsorption performance of hydroxysultaine amphoteric surfactant for oil displacement, obtain the influence curve of temperature on the adsorption performance of hydroxysultaine amphoteric surfactant for oil displacement as shown in the figure 3, it can be seen that this kind of hydroxysulfobetaine amphoteric surfactant for oil displacement has good thermal stability and good high temperature and salt resistance.

In addition, using the above-mentioned examples, the effect of the adsorption performance of the hydroxysultaine amphoteric surfactant for oil displacement was also tested on the oil displacement effect. The test results are shown in Table 1.

                                                            

Claims (9)

1. displacement of reservoir oil hydroxy sulfo lycine amphoterics, it is characterized in that: this displacement of reservoir oil with the structural formula of hydroxy sulfo lycine amphoterics is:

Wherein: R takes from C ₆H ₅Phenyl, C ₇H ₇Tolyl, C ₈H ₉O-Xylol base, m-xylene base, p-Xylol base, ethylbenzene, xylol base, C ₉H ₁₁In the cumyl any one.

2. the displacement of reservoir oil claimed in claim 1 is characterized in that with the preparation method of hydroxy sulfo lycine amphoterics: the described displacement of reservoir oil is with the preparation method of hydroxy sulfo lycine amphoterics:

The first step prepares the aryl Witconol 2301 by Witconol 2301 and alkylating aromatic hydrocarbon;

Second step prepares the aryl oleyl alcohol by aryl Witconol 2301 hydrogenating reduction;

In the 3rd step, prepare aryl oleyl alcohol glycidyl ether by aryl oleyl alcohol and epoxy chloropropane through etherification reaction;

In the 4th step, aryl oleyl alcohol glycidyl ether and amination reagent are carried out amination reaction obtain tertiary amine;

In the 5th step, tertiary amine and quaternary ammonium reagent are carried out quaternary ammonium reaction obtain described displacement of reservoir oil hydroxy sulfo lycine amphoterics.

3. the displacement of reservoir oil according to claim 2 is with the preparation method of hydroxy sulfo lycine amphoterics, it is characterized in that: the process that described Witconol 2301 and alkylating aromatic hydrocarbon prepare the aryl Witconol 2301 is: take methylsulfonic acid as catalyzer, with Witconol 2301 and aromatic hydrocarbons and methylsulfonic acid, drop into reactor, pass into N ₂30min, 80 ℃ of lower reaction 10h, unreacted aromatic hydrocarbons is gone out in underpressure distillation, can obtain the aryl Witconol 2301 for three times with the dehydrated alcohol recrystallization, and wherein aromatic hydrocarbons is selected from any one in benzene,toluene,xylene, ethylbenzene, the isopropyl benzene.

4. the displacement of reservoir oil according to claim 2 is with the preparation method of hydroxy sulfo lycine amphoterics, it is characterized in that: the process that described aryl Witconol 2301 hydrogenating reduction prepares the aryl oleyl alcohol is, 500g aryl Witconol 2301,2.5g catalyzer are dropped into reactor, use first N ₂H is used in displacement again ₂Stir after the displacement and heat up pressure 0.1MPa, mixing speed 500r/min; Temperature rises to 1.1MPa with system pressure after arriving 230 ℃, the beginning timing, and sampling and measuring iodine value at regular intervals, until till iodine value no longer descends, the cooling decompression discharging.

5. the displacement of reservoir oil according to claim 2 is with the preparation method of hydroxy sulfo lycine amphoterics, it is characterized in that: described aryl oleyl alcohol and epoxy chloropropane through the process that etherification reaction prepares aryl oleyl alcohol glycidyl ether are, molar ratio by 1:1 takes by weighing aryl oleyl alcohol and epoxy chloropropane, with aryl oleyl alcohol and the epoxy chloropropane after taking by weighing, mass percent concentration is 30% sodium hydroxide solution, Tetrabutyl amonium bromide places electric blender is housed, in the four-hole bottle of condensing works, drip epoxy chloropropane, temperature is controlled at 40-70 ℃, and time for adding is 5-10h; Be warmed up to 80-100 ℃, reaction 5-8h; The cooling suction filtration to neutral, is collected the upper strata adopting dark liquid with 70-80 ℃ of distilled water wash behind the separatory; Use anhydrous sodium sulfate drying, vacuum rotary steam is removed excessive epoxy chloropropane, a small amount of water and solvent toluene.

6. the displacement of reservoir oil according to claim 5 is with the preparation method of hydroxy sulfo lycine amphoterics, it is characterized in that: the described process that aryl oleyl alcohol glycidyl ether and amination reagent are carried out amination reaction is, take by weighing aryl oleyl alcohol glycidyl ether and amination reagent according to mol ratio 1:1, amination reagent and ethanolic soln put into condensing works is housed, in the four-hole bottle of whipping appts and thermometer, holding temperature is at 40-80 ℃, beginning slowly drips arylolycidyl ethers, dropwise, temperature is elevated to 50-80 ℃, kept this thermotonus 4-10 hour, finish reaction, revolve to steam and remove unreacted ethanol and amination reagent, get the product tertiary amine after the drying.

7. the displacement of reservoir oil according to claim 6 is with the preparation method of hydroxy sulfo lycine amphoterics, it is characterized in that: the process that described tertiary amine and quaternary ammonium reagent carry out quaternary ammonium reaction is, quaternary ammonium reagent is 3-chlorine 2-hydroxyl-propanesulfonate, take by weighing tertiary amine and 3-chlorine 2-hydroxyl-propanesulfonate, the mol ratio of tertiary amine and 3-chlorine 2-hydroxyl-propanesulfonate is 1.2:1.0, quaternary ammonium reagent placed electric mixer is housed, in the four-hole boiling flask of condensing works, be that 70% ethanolic soln makes its dissolving with volume ratio, be warming up to 70-80 ℃, beginning slowly drips tertiary amine, dropwise, holding temperature is at 80-90 ℃, and pH is at 8-9, reacted 9-12 hour, and finished reaction; Have solid to occur in the cooling afterreaction thing, suction filtration is removed unreacted tertiary amine with petroleum ether extraction, and recovering liquid is revolved to steam and removed the second alcohol and water, obtains yellow thick product; Wash product with ethyl acetate, suction filtration, drying obtains displacement of reservoir oil hydroxy sulfo lycine amphoterics, carries out recrystallization with ethanol, dry white powder solid phase prod.

8. the displacement of reservoir oil according to claim 6 is with the preparation method of hydroxy sulfo lycine amphoterics, it is characterized in that: the process that described tertiary amine and quaternary ammonium reagent carry out quaternary ammonium reaction is, quaternary ammonium reagent is propane sultone or butane sultone, take by weighing tertiary amine and quaternary ammonium reagent, the mol ratio of tertiary amine and quaternary ammonium reagent is 1:1, reflux condensing tube is being housed, magnetic stirring apparatus, constant pressure funnel, add the 0.1mol tertiary amine in the four-hole bottle of thermometer, be dissolved in the 100-200ml acetone, take by weighing and slowly be added drop-wise in the four-hole bottle under the sultone room temperature of 0.1mol (propane sultone or butane sultone), 0-15 ℃ of lower slowly dropping, be warming up to back flow reaction 24-48h after dropwising, after reaction finishes, system is cooled to room temperature, filter out solid matter, repeatedly wash with acetone, then obtain white crystal with acetone and methyl alcohol mixed liquor recrystallization, 60-80 ℃ of lower vacuum-drying gets the white powder solid, displacement of reservoir oil hydroxy sulfo lycine amphoterics.

9. the displacement of reservoir oil according to claim 2 is with the preparation method of hydroxy sulfo lycine amphoterics, and it is characterized in that: described amination reagent is dimethylamine or diethylamine or diethanolamine or n-Butyl Amine 99 or N, N-dimethyl-1,3-propylene diamine.

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