Tall oil-based surfactant as well as preparation method and application thereof

Abstract

The invention belongs to the field of oil and gas fields, and provides a tall oil-based surfactant and a preparation method and application thereof.The preparation method of the tall oil-based surfactant comprises the steps that S1, tall oil acid and diethanol amine serve as raw materials and are subjected to an amidation reaction under the action of a solid base catalyst, and tall oil diethanolamide is obtained; s2, carrying out esterification reaction on the tall oil diethanolamide and maleic anhydride which serve as raw materials under the action of a solid acid catalyst and a negative pressure condition to obtain tall oil diethanolamide succinic acid monoester; and S3, mixing the tall oil diethanolamide succinic acid monoester and a sodium sulfite solution, reacting, adding ethanol after the reaction is completed, stirring, and filtering to obtain a liquid which is the tall oil-based surfactant. The tall oil-based surfactant disclosed by the invention can be independently used as a surfactant for an oil-displacing agent, and the chromatographic separation effect caused by different adsorbability of each component after a traditional compound oil-displacing agent system enters a stratum is overcome.

Description

Technical Field

[0001] The invention belongs to the field of oil and gas fields and relates to a tall oil-based surfactant and a preparation method and application thereof. Background Art

[0002] The process of crude oil extraction generally goes through primary oil recovery, secondary oil recovery and tertiary oil recovery. Primary oil recovery can utilize the natural energy of the oil layer itself and has a lower extraction cost, but due to the exhaustion or insufficiency of natural energy, the recovery rate is extremely limited. Secondary oil recovery uses water injection or gas injection to purposefully replenish the formation energy, restore or maintain the formation pressure to increase the recovery rate. The average recovery rate of secondary oil recovery is about 35%. For oil fields with good quality, the recovery rate can only reach 45%. For oil fields with poor quality, 90% of the crude oil will remain underground. In order to increase the recovery rate, the use of chemicals to improve the performance of oil, gas, water and rock has gradually been valued, which is called tertiary oil recovery.

[0003] Tertiary oil recovery refers to the process of injecting other fluids to change the properties of reservoir rocks and fluids by physical, chemical, thermal, biological and other methods to increase the recovery rate of crude oil after water flooding. Chemical flooding, gas miscible flooding, thermal oil recovery and microbial oil recovery are all methods of enhanced oil recovery (EOR). In the process of tertiary oil recovery, a large amount of money must be invested to build injection equipment for injecting chemicals, heat-carrying fluids and miscible gases, and a large amount of money is also needed to inject fluids. Due to the large scale of tertiary oil recovery, the recovery rate of tertiary oil recovery has increased significantly. After the oil reservoir has undergone tertiary oil recovery, the recovery rate can reach 50%~90%.

[0004] At present, chemical flooding has become an important means to significantly improve the recovery rate of medium and high permeability oil reservoirs. Chemical flooding is to improve the recovery rate by injecting some chemical agents. It is mainly divided into alkali flooding, surfactant flooding, polymer flooding and composite flooding. Since the oil recovery performance of existing single-component surfactants is very poor and cannot meet the requirements of oil recovery agents when used alone, surfactant flooding usually uses several surfactant components in combination. In order to overcome the problem of poor oil recovery performance of single-component surfactants, surfactants can also be used in combination with polymers and / or alkalis, that is, composite flooding. The method of using the synergistic effect of surfactants and polymers to flood oil is called binary composite flooding. The method of using the synergistic effect of alkali, surfactants and polymers to flood oil is called ternary composite flooding (ASP). Whether it is ternary composite flooding, binary composite flooding, or surfactant flooding, the oil recovery agent system is composed of at least two components. Due to the differences in the adsorption performance of rocks in the formation to different components, the oil recovery agent system has a chromatographic separation effect, which leads to a low actual crude oil recovery rate, and the recovery rate decreases faster over time.

[0005] For example, Chinese invention patent CN106566511B discloses a surfactant micellar oil-displacing agent, which is a mixture of lauryl amide propyl betaine, sodium lauryl sulfate, nano silica sol, sodium chloride and excess water. Although the micellar oil-displacing agent can improve the recovery rate to a certain extent, it belongs to a composite type, and there is a relatively obvious chromatographic separation effect in actual use, resulting in the final actual recovery rate being limited. Chinese invention patent CN104910024B discloses a surfactant for oil displacement, which is tetradecyl allyl dibromide tetramethylethylenediamine, which has a poor effect when used alone, and must be compounded with sodium monolauryl phthalate to significantly improve the recovery rate, but there is a relatively obvious chromatographic separation effect after compounding. Chinese invention patent CN102690641B discloses a sulfonate surfactant, which cannot be used alone and needs to be compounded with polyacrylamide and Na2CO3 to form a ternary composite oil-displacing agent. The compounded ternary composite oil-displacing agent has a relatively obvious chromatographic separation effect when used.

[0006] Therefore, it becomes very urgent to develop a single-component oil-displacing agent. Summary of the invention

[0007] In order to solve the above-mentioned problems of the prior art, the present invention provides a tall oil-based surfactant and a preparation method and application thereof. The tall oil-based surfactant can be used alone as a surfactant in an oil displacement agent, thereby overcoming the chromatographic separation effect caused by the different adsorption properties of the components of the traditional compound oil displacement agent system after entering the formation.

[0008] The present invention is achieved through the following technical solutions: The present invention provides a method for preparing a tall oil-based surfactant, comprising the following steps: S1, using tall oil acid and diethanolamine as raw materials, carrying out an amidation reaction under the action of a solid base catalyst to obtain tall oil diethanolamide; S2, using tall oil diethanolamide and maleic anhydride as raw materials, carrying out an esterification reaction under negative pressure under the action of a solid acid catalyst to obtain tall oil diethanolamide succinic acid monoester; S3, tall oil diethanolamide succinic acid monoester and sodium sulfite solution are mixed and reacted, and after the reaction is completed, ethanol is added, stirred and filtered, and the obtained liquid is a tall oil-based surfactant.

[0009] In the preparation method of the tall oil-based surfactant of the present invention, the preparation method of the solid base catalyst used in S1 is: impregnating aluminum oxide in a potassium hydroxide solution, then separating the solid and drying and calcining it in sequence to obtain a solid base catalyst.

[0010] Among them, the aluminum oxide is preferably columnar aluminum oxide, the mass concentration of the potassium hydroxide solution is preferably 15%~20%, and the mass ratio of aluminum oxide to potassium hydroxide solution is preferably (5~6):1.

[0011] In the preparation method of the solid base catalyst, the impregnation temperature is preferably 45-55°C, the time is preferably 4-6 hours, the specific drying method is preferably: vacuum drying at 75-85°C for 2-3 hours, and the calcination is preferably: vacuum calcination at 750-850°C for 3-5 hours.

[0012] In some embodiments of the present invention, in S1, the mass ratio of the tall oil acid to diethanolamine is (3.0-3.2):1, and the mass of the solid base catalyst is 1%-2% of the total mass of the tall oil acid and diethanolamine.

[0013] The quality of the tall oil acid used in the present invention, measured by mass percentage, meets the following requirements: the total content of oleic acid and linoleic acid is 72% to 75%, the content of rosin acid is 25% to 30%, and the content of unsaponifiable matter is less than or equal to 3%.

[0014] In some embodiments of the present invention, in S1, the reaction temperature of the amidation reaction is 90-95° C., the reaction time is 3-4 h, and the amidation reaction is carried out under normal pressure.

[0015] The conventional amidation reaction uses liquid alkali as a catalyst, which has low reaction efficiency and a diethanolamine conversion rate of less than 70%, resulting in a large amount of free diethanolamine residue, and free diethanolamine has a relatively obvious carcinogenic effect, and the carcinogenic activity is proportional to the proportion of free diethanolamine; at the same time, due to the presence of fatty acids in tall oil acid, the acid value of tall oil acid is too high, resulting in excessive consumption of liquid alkali, obvious saponification phenomenon, and then resulting in too high viscosity of tall oil diethanolamide, darkening of color, and poor oil washing effect. The solid base catalyst obtained by impregnation and high-temperature calcination in the present invention is a mixture of integrated metal oxides and has high catalytic activity. The present invention uses a solid base catalyst to catalyze the amidation reaction, with high reaction efficiency, high raw material conversion rate, less free diethanolamine residue, and an amide content of more than 90% in the amidation reaction product. In addition, the use of a solid base catalyst reduces the reaction temperature compared to the conventional amidation reaction, so that the amidation reaction can be carried out under milder conditions. At the same time, the solid base catalyst can be removed by solid-liquid separation.

[0016] In the preparation method of the tall oil-based surfactant of the present invention, the preparation method of the solid acid catalyst used in S2 is: immersing aluminum oxide in a p-toluenesulfonic acid solution, then separating the solid and drying and calcining it in sequence to obtain a solid acid catalyst.

[0017] The alumina is preferably columnar alumina, the mass concentration of the p-toluenesulfonic acid solution is preferably 20% to 25%, and the mass ratio of alumina to p-toluenesulfonic acid solution is preferably (8 to 10):1.

[0018] In the preparation method of the solid acid catalyst, the impregnation temperature is preferably 45-55°C, the time is preferably 2-4h, the specific drying method is preferably: vacuum drying at 75-85°C for 2-3h, and the calcination is preferably: vacuum calcination at 750-850°C for 3-5h.

[0019] In some embodiments of the present invention, in S2, the mass ratio of tall oil diethanolamide to maleic anhydride is (3.0-3.2):1, and the mass of the solid acid catalyst is 3%-6% of the total mass of tall oil diethanolamide and maleic anhydride.

[0020] In some embodiments of the present invention, in S2, the reaction temperature of the esterification reaction is 60-80° C., the reaction time is 4-6 h, and the negative pressure condition is -0.08-0.1 MPa.

[0021] The present invention adopts a solid acid catalyst to catalyze the esterification reaction, which has high catalytic activity, the esterification rate of tall oil diethanolamide is greater than 95%, and the reaction conditions are mild. Compared with liquid acid catalysts, solid acid catalysts not only have high catalytic activity, but are also easy to separate, recyclable, and environmentally friendly.

[0022] In some embodiments of the present invention, in S3, the mass ratio of tall oil diethanolamide succinic acid monoester to the solute in the sodium sulfite solution is (3.0-4.2):1.

[0023] In some embodiments of the present invention, in S3, the reaction temperature is controlled at 70-80° C., the reaction is carried out under normal pressure, the reaction time is 2-3 h, and the iodine value is less than or equal to 10 mg / g as the basis for judging the reaction endpoint.

[0024] The tall oil-based surfactant obtained by the above preparation method of the present invention has an active ingredient comprising a compound of the following structural formula:

[0025] Where R1 is ( Z )-9-heptadecanediyl, R2 is cis, cis-9,12-heptadecanediyl, R3 is , in R3 is the bonding position.

[0026] The present invention also provides the use of the tall oil-based surfactant as a surfactant in oil field recovery, especially in tertiary oil recovery.

[0027] Specifically, the tall oil-based surfactant of the present invention can be used alone as a surfactant for oil field flooding without being compounded with other substances, that is, the tall oil-based surfactant is compounded with water into an oil displacement agent and injected into the formation for oil displacement.

[0028] Although the tall oil-based surfactant of the present invention can be used alone as a surfactant in oil field flooding to achieve a good oil recovery effect, if necessary, the tall oil-based surfactant can also be compounded with a polymer for use, and the present invention does not impose any particular limitation on this.

[0029] Compared with the prior art, the present invention has the following beneficial effects: The preparation method of the tall oil-based surfactant of the present invention comprises the following steps: taking tall oil acid and diethanolamine as raw materials for an amidation reaction to prepare tall oil diethanolamide; then taking tall oil diethanolamide and maleic anhydride as raw materials for an esterification reaction to obtain tall oil diethanolamide succinic acid monoester; and finally carrying out a sulfiting reaction with sodium sulfite to obtain the tall oil-based surfactant. Firstly, the tall oil-based surfactant obtained by taking tall oil acid as raw material of the present invention has very strong surface activity, and can fully meet the requirements of the oil displacement agent when used alone, and does not need to be used in combination with other surfactants or polymers and alkalis, thereby overcoming the chromatographic separation effect caused by the inconsistent adsorption of different components on the rock surface of the formation in the traditional compound oil displacement agent, and improving the oil displacement efficiency and durability of the oil displacement agent. At the same time, the tall oil-based surfactant prepared by the present invention contains a disodium structure formed by the compound of -COONa and -SO3Na, which can be complexed with divalent metal ions (such as calcium ions and magnesium ions) in the formation to provide salt resistance; the active component structure of the tall oil-based surfactant contains a hydroxyl group, so that it has good temperature resistance. Secondly, the present invention adopts a solid base catalyst to catalyze the amidation reaction. The solid base catalyst has high catalytic activity, so that the raw material conversion rate is high, the product yield is high, and the free diethanolamine content in the finished product is extremely low, which reduces the carcinogenicity; and the use of the solid base catalyst can avoid the saponification phenomenon caused by the liquid base catalyst, and improve the reaction activity of tall oil diethanolamide. Thirdly, a solid acid catalyst is used to catalyze the esterification reaction. The solid acid catalyst has high catalytic activity for the esterification reaction, which can improve the raw material conversion rate and product yield. Then, the solid acid catalyst and the solid base catalyst are easy to separate, and can be reused after drying and regeneration, which is safe and environmentally friendly. Finally, the present invention carries out the esterification reaction under negative pressure conditions. Compared with normal pressure, the negative pressure condition can reduce the temperature required for the reaction, reduce the required intermolecular activation energy, and increase the probability and rate of relative intermolecular collisions. Therefore, the reaction rate is faster, so that the raw material conversion rate and product yield are improved. In addition, the preparation method of the present invention has a wide range of raw material sources and has a large-scale promotion value.

[0030] Furthermore, due to the use of a solid base catalyst, the amidation reaction of the present invention can be carried out under relatively mild conditions, with a reaction temperature below 100° C. and low energy consumption.

[0031] Furthermore, due to the use of a solid acid catalyst, the esterification reaction of the present invention can be carried out under relatively mild conditions, with a reaction temperature below 100° C. and low energy consumption.

[0032] The tall oil-based surfactant provided by the present invention has very strong surface activity and strong crude oil emulsification ability, and can reduce the oil-water interfacial tension to 10 -4 mN / m, reaching ultra-low interfacial tension, and can fully meet the requirements of oil-displacing agents when used alone. Therefore, the tall oil-based surfactant of the present invention can be used alone as a surfactant to prepare an oil-displacing agent, and does not need to be used in combination with other surfactants or polymers and alkalis, and the adsorption amount of the tall oil-based surfactant on the rock surface is extremely low, so that the chromatographic separation effect caused by the inconsistent adsorption of different components on the rock surface of the formation of the traditional compound oil-displacing agent can be overcome, and the oil displacement efficiency and durability of the oil-displacing agent can be improved, and the crude oil recovery rate can be greatly improved. At the same time, the tall oil-based surfactant provided by the present invention has good salt resistance, because the disodium structure formed by the compound of -COONa and -SO3Na in the tall oil-based surfactant can be complexed with divalent metal ions (such as calcium ions and magnesium ions) in the formation to form a more stable complex structure. Therefore, the tall oil-based surfactant has excellent salt resistance, and when used in a formation with a high content of divalent metal ions (such as calcium ions and magnesium ions), the oil-water interfacial tension can still be kept stable, and the oil displacement effect can be maintained for a long time. In addition, the tall oil-based surfactant of the present invention contains a hydroxyl group in its compound structure. The presence of the hydroxyl group ensures the stability of the structure, thereby enabling it to have good temperature resistance.

[0033] The invention uses a tall oil-based surfactant as a surfactant to carry out oil displacement, which can overcome the chromatographic separation effect caused by the inconsistent adsorption of different components on the rock surface in the formation caused by the traditional compound oil displacement agent, greatly improve the crude oil recovery rate, and can stably displace oil in the formation with high salt content. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0035] Figure 1The infrared spectra of tall oil acid, tall oil diethanolamide and tall oil-based surfactant obtained in Example 1 are shown. DETAILED DESCRIPTION

[0036] The following describes the embodiments of the present invention through specific examples, and those skilled in the art can easily understand other advantages and effects of the present invention from the contents disclosed in this specification. The present invention can also be implemented or applied through other different specific embodiments, and the details in this specification can also be modified or changed in various ways based on different viewpoints and applications without departing from the spirit of the present invention.

[0037] It should be noted that the process equipment or devices not specifically specified in the following embodiments are all conventional equipment or devices in the art.

[0038] It should be noted that the terms "include" and "have" and any variations thereof are intended to cover non-exclusive inclusions. For example, a process, method, system, product or device that includes a series of steps or units is not necessarily limited to those steps or units clearly listed, but may include other steps or units that are not clearly listed or inherent to these processes, methods, products or devices. Moreover, unless otherwise specified, the numbering of each method step is only a convenient tool for identifying each method step, and is not intended to limit the order of arrangement of each method step or to define the scope of the present invention. Changes or adjustments in their relative relationships should also be regarded as the scope of the present invention without substantially changing the technical content.

[0039] The preparation examples of the solid base catalyst and the solid acid catalyst used in the following examples and comparative examples of the present invention are as follows.

[0040] Preparation Example 1 Preparation of solid base catalyst: 50 g of columnar alumina was immersed in 9 mL of 18% potassium hydroxide solution at 50°C for 4 h, and then the solid was separated, vacuum dried at 80°C for 2 h, and vacuum calcined at 800°C for 4 h to obtain a solid base catalyst.

[0041] Preparation Example 2 Preparation of solid acid catalyst: 50 g of columnar alumina was rotary immersed in 5 mL of 20% p-toluenesulfonic acid solution at 50 ° C for 2 h, with a forward and reverse rotation interval of 30 min and a rotation speed of 50 rpm. The solid was then separated, vacuum dried at 80 ° C for 2 h, and vacuum calcined at 800 ° C for 4 h to obtain a solid acid catalyst.

[0042] Example 1 S101: Weigh 24 g of tall oil acid, 8 g of diethanolamine and 0.3 g of a solid base catalyst, place in a closed reactor, stir at a low speed of 400 r / min, control the temperature at 92° C., react for 4 h at normal pressure, and obtain highly active tall oil diethanolamide.

[0043] S102: 30 g of tall oil diethanolamide and 10 g of maleic anhydride were stirred and mixed, and the temperature was raised to 75° C., 1.2 g of a solid acid catalyst was added, and an esterification reaction was carried out at a pressure of -0.09 MPa. The reaction time was 5 h. The reaction was terminated when the acid value reached 76 mg / g to obtain tall oil diethanolamide succinic acid monoester.

[0044] S103: 41 g of tall oil diethanolamide succinic acid monoester was added to a condensing reflux device, and a sodium sulfite solution prepared by dissolving 12 g of sodium sulfite in 20 g of water was added, the stirring speed was adjusted to 1000 r / min, the temperature was controlled at 75°C, the reaction was carried out at normal pressure for 3 hours, and the end point was reached when the iodine value was 5 mg / g, the temperature was lowered to room temperature, 24.5 g of ethanol was added for phase inversion, and after stirring for 10 minutes, the solid was removed by filtering to obtain a tall oil-based surfactant. The tall oil acid conversion rate was 99.5%, and the yield of the tall oil-based surfactant was 98.9%.

[0045] Example 2 S201: Weigh 24 g of tall oil acid, 7.5 g of diethanolamine and 0.3 g of a solid base catalyst, place in a closed reactor, stir at a low speed of 400 r / min, control the temperature at 92° C., react for 4 hours at normal pressure to obtain high-activity tall oil diethanolamide.

[0046] S202: 30 g of tall oil diethanolamide and 10 g of maleic anhydride were stirred and mixed, and the temperature was raised to 75° C., 1.2 g of a solid acid catalyst was added, and an esterification reaction was carried out at a pressure of -0.09 MPa. The reaction time was 5 h. The reaction was terminated when the acid value reached 76 mg / g to obtain tall oil diethanolamide succinic acid monoester.

[0047] S203: 41 g of tall oil diethanolamide succinic acid monoester was added to a condensing reflux device, and a sodium sulfite solution obtained by dissolving 12 g of sodium sulfite in 20 g of water was added, the stirring speed was adjusted to 1000 r / min, the temperature was controlled at 75°C, the reaction was carried out at normal pressure for 3 hours, and the end point was reached when the iodine value was 5 mg / g, the temperature was lowered to room temperature, 24.5 g of ethanol was added for phase inversion, and after stirring for 10 minutes, the solid was removed by filtering to obtain a tall oil-based surfactant. The tall oil acid conversion rate was 95.2%, and the yield of the tall oil-based surfactant was 98.3%.

[0048] Example 3 S301: 24 g of tall oil acid, 8 g of diethanolamine and 0.6 g of a solid base catalyst were weighed and placed in a closed reactor. The mixture was stirred at a low speed of 400 r / min, the temperature was controlled at 92° C., and the mixture was reacted at normal pressure for 4 h to obtain high-activity tall oil diethanolamide.

[0049] S302: 30 g of tall oil diethanolamide and 10 g of maleic anhydride were stirred and mixed, and the temperature was raised to 75° C., 1.2 g of a solid acid catalyst was added, and an esterification reaction was carried out at a pressure of -0.09 MPa. The reaction time was 5 h. The reaction was terminated when the acid value reached 76 mg / g to obtain tall oil diethanolamide succinic acid monoester.

[0050] S303: 41 g of tall oil diethanolamide succinic acid monoester was added to a condensing reflux device, and a sodium sulfite solution prepared by dissolving 12 g of sodium sulfite in 20 g of water was added, the stirring speed was adjusted to 1000 r / min, the temperature was controlled at 75°C, the reaction was carried out at normal pressure for 3 hours, and the end point was reached when the iodine value was 5 mg / g, the temperature was lowered to room temperature, 24.5 g of ethanol was added for phase inversion, and after stirring for 10 minutes, the solid was removed by filtration to obtain a tall oil-based surfactant. The tall oil acid conversion rate was 99.4%, and the yield of the tall oil-based surfactant was 99.1%.

[0051] Example 4 S401: Weigh 24 g of tall oil acid, 8 g of diethanolamine and 0.3 g of a solid base catalyst, place in a closed reactor, stir at a low speed of 400 r / min, control the temperature at 92° C., react for 4 hours at normal pressure to obtain high-activity tall oil diethanolamide.

[0052] S402: 30 g of tall oil diethanolamide and 10 g of maleic anhydride were stirred and mixed, and the temperature was raised to 75° C., 2.4 g of solid acid catalyst was added, and esterification reaction was carried out at a pressure of -0.09 MPa. The reaction time was 5 h. The reaction was terminated when the acid value reached 76 mg / g to obtain tall oil diethanolamide succinic acid monoester.

[0053] S403: 41 g of tall oil diethanolamide succinic acid monoester was added to a condensing reflux device, and a sodium sulfite solution prepared by dissolving 12 g of sodium sulfite in 20 g of water was added, the stirring speed was adjusted to 1000 r / min, the temperature was controlled at 75°C, the reaction was carried out at normal pressure for 3 hours, and the end point was reached when the iodine value was 5 mg / g, the temperature was lowered to room temperature, 24.5 g of ethanol was added for phase inversion, and after stirring for 10 minutes, the solid was removed by filtering to obtain a tall oil-based surfactant. The tall oil acid conversion rate was 99.4%, and the yield of the tall oil-based surfactant was 98.5%.

[0054] Example 5 S501: Weigh 24 g of tall oil acid, 8 g of diethanolamine and 0.3 g of a solid base catalyst, place in a closed reactor, stir at a low speed of 400 r / min, control the temperature at 95° C., react for 4 hours at normal pressure to obtain high-activity tall oil diethanolamide.

[0055] S502: 30 g of tall oil diethanolamide and 10 g of maleic anhydride were stirred and mixed, and the temperature was raised to 75° C., 1.2 g of solid acid catalyst was added, and esterification reaction was carried out at a pressure of -0.09 MPa. The reaction time was 5 h. The reaction was terminated when the acid value reached 76 mg / g to obtain tall oil diethanolamide succinic acid monoester.

[0056] S503: 41g of tall oil diethanolamide succinic acid monoester was added to a condensing reflux device, and a sodium sulfite solution obtained by dissolving 12g of sodium sulfite in 20g of water was added, the stirring speed was adjusted to 1000r / min, the temperature was controlled at 75°C, the reaction was carried out at normal pressure for 3h, and the end point was reached when the iodine value was 5mg / g, the temperature was lowered to room temperature, 24.5g of ethanol was added for phase inversion, and after stirring for 10min, the solid was removed by filtration to obtain a tall oil-based surfactant. The tall oil acid conversion rate was 96.8%, and the yield of the tall oil-based surfactant was 98.5%.

[0057] Example 6 S601: Weigh 24g of tall oil acid, 8g of diethanolamine and 0.3g of solid base catalyst, place in a closed reactor, stir at a low speed of 400r / min, control the temperature at 92°C, react for 3h at normal pressure to obtain high-activity tall oil diethanolamide.

[0058] S602: 30 g of tall oil diethanolamide and 10 g of maleic anhydride were stirred and mixed, and the temperature was raised to 75° C., 1.2 g of solid acid catalyst was added, and esterification reaction was carried out at a pressure of -0.09 MPa. The reaction time was 5 h. The reaction was terminated when the acid value reached 76 mg / g to obtain tall oil diethanolamide succinic acid monoester.

[0059] S603: 41g of tall oil diethanolamide succinic acid monoester was added to a condensing reflux device, and a sodium sulfite solution prepared by dissolving 12g of sodium sulfite in 20g of water was added, the stirring speed was adjusted to 1000r / min, the temperature was controlled at 75°C, the reaction was carried out at normal pressure for 3h, and the end point was reached when the iodine value was 5mg / g, the temperature was lowered to room temperature, 24.5g of ethanol was added for phase inversion, and after stirring for 10min, the solid was removed by filtration to obtain a tall oil-based surfactant. The tall oil acid conversion rate was 95.8%, and the yield of the tall oil-based surfactant was 98.4%.

[0060] Example 7 S701: Weigh 24g of tall oil acid, 8g of diethanolamine and 0.3g of solid base catalyst, place in a closed reactor, stir at a low speed of 400r / min, control the temperature at 92°C, react for 4h at normal pressure to obtain high-activity tall oil diethanolamide.

[0061] S702: 30 g of tall oil diethanolamide and 9.4 g of maleic anhydride were stirred and mixed, and the temperature was raised to 75° C., 1.2 g of solid acid catalyst was added, and esterification reaction was carried out at a pressure of -0.09 MPa. The reaction time was 5 h. The reaction was terminated when the acid value reached 76 mg / g to obtain tall oil diethanolamide succinic acid monoester.

[0062] S703: 41g of tall oil diethanolamide succinic acid monoester was added to a condensing reflux device, and a sodium sulfite solution prepared by dissolving 12g of sodium sulfite in 20g of water was added, the stirring speed was adjusted to 1000r / min, the temperature was controlled at 75°C, the reaction was carried out at normal pressure for 3h, and the end point was reached when the iodine value was 5mg / g, the temperature was lowered to room temperature, 24.5g of ethanol was added for phase inversion, and after stirring for 10min, the solid was removed by filtration to obtain a tall oil-based surfactant. The tall oil acid conversion rate was 99.1%, and the yield of the tall oil-based surfactant was 99.2%.

[0063] Example 8 S801: Weigh 24g of tall oil acid, 8g of diethanolamine and 0.3g of solid base catalyst, place in a closed reactor, stir at a low speed of 400r / min, control the temperature at 92°C, react for 4h at normal pressure to obtain high-activity tall oil diethanolamide.

[0064] S802: 30 g of tall oil diethanolamide and 10 g of maleic anhydride were stirred and mixed, and the temperature was raised to 62° C., 1.2 g of solid acid catalyst was added, and esterification reaction was carried out at a pressure of -0.09 MPa. The reaction time was 5 h. The reaction was terminated when the acid value reached 76 mg / g to obtain tall oil diethanolamide succinic acid monoester.

[0065] S803: 41g of tall oil diethanolamide succinic acid monoester was added to a condensing reflux device, and a sodium sulfite solution prepared by dissolving 12g of sodium sulfite in 20g of water was added, the stirring speed was adjusted to 1000r / min, the temperature was controlled at 75°C, the reaction was carried out at normal pressure for 3h, and the end point was reached when the iodine value was 5mg / g, the temperature was lowered to room temperature, 24.5g of ethanol was added for phase inversion, and after stirring for 10min, the solid was removed by filtration to obtain a tall oil-based surfactant. The tall oil acid conversion rate was 98.8%, and the yield of the tall oil-based surfactant was 97.5%.

[0066] Example 9 S901: Weigh 24g of tall oil acid, 8g of diethanolamine and 0.3g of solid base catalyst, place in a closed reactor, stir at a low speed of 400r / min, control the temperature at 92°C, react for 4h at normal pressure to obtain high-activity tall oil diethanolamide.

[0067] S902: 30 g of tall oil diethanolamide and 10 g of maleic anhydride were stirred and mixed, and the temperature was raised to 75° C., 1.2 g of solid acid catalyst was added, and esterification reaction was carried out at a pressure of -0.09 MPa. The reaction time was 4 h. The reaction was terminated when the acid value reached 76 mg / g to obtain tall oil diethanolamide succinic acid monoester.

[0068] S903: 41g of tall oil diethanolamide succinic acid monoester was added to a condensing reflux device, and a sodium sulfite solution prepared by dissolving 12g of sodium sulfite in 20g of water was added, the stirring speed was adjusted to 1000r / min, the temperature was controlled at 75°C, the reaction was carried out at normal pressure for 3h, and the end point was reached when the iodine value was 5mg / g, the temperature was lowered to room temperature, 24.5g of ethanol was added for phase inversion, and after stirring for 10min, the solid was removed by filtration to obtain a tall oil-based surfactant. The tall oil acid conversion rate was 98.9%, and the yield of the tall oil-based surfactant was 96.1%.

[0069] Example 10 S1001: Weigh 24g of tall oil acid, 8g of diethanolamine and 0.3g of solid base catalyst, place in a closed reactor, stir at a low speed of 400r / min, control the temperature at 92°C, react for 4h at normal pressure to obtain high-activity tall oil diethanolamide.

[0070] S1002: 30 g of tall oil diethanolamide and 10 g of maleic anhydride were stirred and mixed, and the temperature was raised to 75° C., 1.2 g of solid acid catalyst was added, and esterification reaction was carried out at a pressure of -0.09 MPa. The reaction time was 6 h. The reaction was terminated when the acid value reached 76 mg / g to obtain tall oil diethanolamide succinic acid monoester.

[0071] S1003: 41g of tall oil diethanolamide succinic acid monoester was added to a condensing reflux device, and a sodium sulfite solution prepared by dissolving 12g of sodium sulfite in 20g of water was added, the stirring speed was adjusted to 1000r / min, the temperature was controlled at 75°C, the reaction was carried out at normal pressure for 3h, and the end point was reached when the iodine value was 5mg / g, the temperature was lowered to room temperature, 24.5g of ethanol was added for phase inversion, and after stirring for 10min, the solid was removed by filtration to obtain a tall oil-based surfactant. The tall oil acid conversion rate was 99.1%, and the yield of the tall oil-based surfactant was 99.0%.

[0072] Embodiment 11 S1101: Weigh 24 g of tall oil acid, 8 g of diethanolamine and 0.3 g of a solid base catalyst, place in a closed reactor, stir at a low speed of 400 r / min, control the temperature at 92°C, react for 4 hours at normal pressure, and obtain highly active tall oil diethanolamide.

[0073] S1102: 30 g of tall oil diethanolamide and 10 g of maleic anhydride were stirred and mixed, and the temperature was raised to 75° C., 1.2 g of solid acid catalyst was added, and esterification reaction was carried out at a pressure of -0.09 MPa. The reaction time was 5 h. The reaction was terminated when the acid value reached 76 mg / g to obtain tall oil diethanolamide succinic acid monoester.

[0074] S1103: 41g of tall oil diethanolamide succinic acid monoester was added to a condensing reflux device, and a sodium sulfite solution prepared by dissolving 12g of sodium sulfite in 10g of water was added, the stirring speed was adjusted to 1000r / min, the temperature was controlled at 75°C, the reaction was carried out at normal pressure for 3h, and the end point was reached when the iodine value was 5mg / g, the temperature was lowered to room temperature, 24.5g of ethanol was added for phase inversion, and after stirring for 10min, the solid was removed by filtration to obtain a tall oil-based surfactant. The tall oil acid conversion rate was 98.2%, and the yield of the tall oil-based surfactant was 95.2%.

[0075] Comparative Example 1 S1201: Weigh 24 g of tall oil acid, 8 g of diethanolamine and 0.2 g of potassium hydroxide, place in a closed reactor, stir at a low speed of 400 r / min, control the temperature at 92° C., react for 4 hours at normal pressure to obtain tall oil diethanolamide.

[0076] S1202: 30 g of tall oil diethanolamide and 10 g of maleic anhydride were stirred and mixed, and the temperature was raised to 75°C. 1.2 g of solid acid catalyst was added, and esterification reaction was carried out at a pressure of -0.09 MPa. The reaction time was 5 h. The reaction was terminated when the acid value reached 76 mg / g to obtain tall oil diethanolamide succinic acid monoester.

[0077] S1203: 41g of tall oil diethanolamide succinic acid monoester was added to a condensing reflux device, and a sodium sulfite solution obtained by dissolving 12g of sodium sulfite in 20g of water was added, the stirring speed was adjusted to 1000r / min, the temperature was controlled at 75°C, the reaction was carried out at normal pressure for 3h, and the end point was reached when the iodine value was 5mg / g, the temperature was lowered to room temperature, 24.5g of ethanol was added for phase inversion, and after stirring for 10min, the solid was removed by filtration to obtain a tall oil-based surfactant. The tall oil acid conversion rate was 79.8%, and the yield of the tall oil-based surfactant was 82.4%.

[0078] Comparative Example 2 S1301: Weigh 24g of tall oil acid, 8g of diethanolamine and 0.3g of solid base catalyst, place in a closed reactor, stir at a low speed of 400r / min, control the temperature at 92°C, react for 4h at normal pressure to obtain high-activity tall oil diethanolamide.

[0079] S1302: 30 g of tall oil diethanolamide and 10 g of maleic anhydride were stirred and mixed, and the temperature was raised to 75° C., 0.7 g of p-toluenesulfonic acid was added, and an esterification reaction was carried out at a pressure of -0.09 MPa. The reaction time was 5 h. The reaction was terminated when the acid value reached 76 mg / g to obtain tall oil diethanolamide succinic acid monoester.

[0080] S1303: 41g of tall oil diethanolamide succinic acid monoester was added to a condensing reflux device, and a sodium sulfite solution prepared by dissolving 12g of sodium sulfite in 20g of water was added, the stirring speed was adjusted to 1000r / min, the temperature was controlled at 75°C, the reaction was carried out at normal pressure for 3h, and the end point was reached when the iodine value was 5mg / g, the temperature was lowered to room temperature, 24.5g of ethanol was added for phase inversion, and after stirring for 10min, the solid was removed by filtration to obtain a tall oil-based surfactant. The tall oil acid conversion rate was 98.8%, and the yield of the tall oil-based surfactant was 75.8%.

[0081] Comparative Example 3 S1401: 24 g of tall oil acid, 8 g of diethanolamine and 0.3 g of a solid base catalyst were weighed and placed in a closed reactor, stirred at a low speed of 400 r / min, the temperature was controlled at 92° C., and reacted at normal pressure for 4 hours to obtain high-activity tall oil diethanolamide.

[0082] S1402: 30 g of tall oil diethanolamide and 10 g of maleic anhydride were stirred and mixed, and the temperature was raised to 75° C., 1.2 g of solid acid catalyst was added, and an esterification reaction was carried out under normal pressure. The reaction time was 5 h. The reaction was terminated when the acid value reached 76 mg / g, and tall oil diethanolamide succinic acid monoester was obtained.

[0083] S1403: 41g of tall oil diethanolamide succinic acid monoester was added to a condensing reflux device, and a sodium sulfite solution prepared by dissolving 12g of sodium sulfite in 20g of water was added, the stirring speed was adjusted to 1000r / min, the temperature was controlled at 75°C, the reaction was carried out at normal pressure for 3h, and the end point was reached when the iodine value was 5mg / g, the temperature was lowered to room temperature, 24.5g of ethanol was added for phase inversion, and after stirring for 10min, the solid was removed by filtration to obtain a tall oil-based surfactant. The tall oil acid conversion rate was 98.7%, and the yield of the tall oil-based surfactant was 79.4%.

[0084] Comparative Example 4 S1501: Weigh 24 g of oleic acid, 8 g of diethanolamine and 0.3 g of a solid base catalyst, place in a closed reactor, stir at a low speed of 400 r / min, control the temperature at 92° C., react for 4 h at normal pressure, and obtain high-activity tall oil diethanolamide.

[0085] S1502: 30 g of oleic acid diethanolamide and 10 g of maleic anhydride were stirred and mixed, and the temperature was raised to 75°C. 1.2 g of solid acid catalyst was added, and esterification reaction was carried out at a pressure of -0.09 MPa. The reaction time was 5 h. The reaction was terminated when the acid value reached 76 mg / g to obtain oleic acid diethanolamide succinic acid monoester.

[0086] S1503: 41g of oleic acid diethanolamide succinic acid monoester was added to a condensing reflux device, and a sodium sulfite solution prepared by dissolving 12g of sodium sulfite in 20g of water was added, the stirring speed was adjusted to 1000r / min, the temperature was controlled at 75°C, the reaction was carried out at normal pressure for 3h, and the end point was reached when the iodine value was 5mg / g, the temperature was lowered to room temperature, 24.5g of ethanol was added for phase inversion, and after stirring for 10min, the solid was removed by filtering to obtain disodium oleic acid diethanolamide succinic acid monoester. The oleic acid conversion rate was 97.5%, and the yield of disodium oleic acid diethanolamide succinic acid monoester was 85.8%.

[0087] Comparative Example 5 S1601: Weigh 24 g of tall oil acid, 6 g of diethanolamine and 0.3 g of a solid base catalyst, place in a closed reactor, stir at a low speed of 400 r / min, control the temperature at 92° C., react for 4 h at normal pressure to obtain tall oil diethanolamide.

[0088] S1602: 30 g of tall oil diethanolamide and 10 g of maleic anhydride were stirred and mixed, and the temperature was raised to 75°C. 1.2 g of solid acid catalyst was added, and esterification reaction was carried out at a pressure of -0.09 MPa. The reaction time was 5 h. The reaction was terminated when the acid value reached 76 mg / g to obtain tall oil diethanolamide succinic acid monoester.

[0089] S1603: 41g of tall oil diethanolamide succinic acid monoester was added to a condensing reflux device, and a sodium sulfite solution prepared by dissolving 12g of sodium sulfite in 20g of water was added, the stirring speed was adjusted to 1000r / min, the temperature was controlled at 75°C, the reaction was carried out at normal pressure for 3h, and the end point was reached when the iodine value was 5mg / g, the temperature was lowered to room temperature, 24.5g of ethanol was added for phase inversion, and after stirring for 10min, the solid was removed by filtration to obtain a tall oil-based surfactant. The tall oil acid conversion rate was 91.5%, and the yield of the tall oil-based surfactant was 90.8%.

[0090] Figure 1This is the infrared spectrum of the tall oil-based surfactant obtained in Example 1. Figure 1 Medium, 4000~3000cm -1 It is the stretching vibration region of -CH, -NH and -OH. The stretching vibration absorption peaks of -CH, -NH and -OH exist simultaneously, indicating that one hydroxyl group in tall oil diethanolamide is retained during the reaction, and the generated tall oil-based surfactant is a monoester compound. -1 The characteristic peak at 1642 cm is the symmetric stretching vibration absorption peak of -CH2-. -1 The characteristic peak at 1550cm is the stretching vibration absorption peak of -C=O- -1 The characteristic peak at 2000~1500cm is the stretching vibration absorption peak of -C=C-. -1 Compared with the spectrum of tall oil diethanolamide, the spectrum of tall oil-based surfactants showed the stretching vibration absorption peak of -C=O-, indicating that maleic anhydride underwent a ring-opening reaction to form -C=O-, and made tall oil diethanolamide have a peak at 2900~3500cm -1 The -CH stretching vibration absorption peak in the range is enhanced, and the position of the -OH stretching vibration absorption peak is shifted. -1 The area is the single bond area, 1100~1115cm -1 The characteristic peak at 900~1000cm is the stretching vibration absorption peak of -CN- -1 and 600~700cm -1 The characteristic peak at 1632cm is the stretching vibration absorption peak of -OS-, indicating the presence of -SO3Na in the compound structure of tall oil-based surfactant. -1 The characteristic peak at 1251cm is the stretching vibration absorption peak of -COO-. -1 The characteristic peak at is the stretching vibration absorption peak of -NCO-. The infrared spectrum of the tall oil-based surfactant shows that the target product is prepared in the present invention.

[0091] The products finally obtained in the above examples and comparative examples were used as surfactants to test the oil-water interfacial tension, emulsifying power, salt resistance, temperature resistance and oil washing rate.

[0092] The test methods are as follows: Oil-water interfacial tension: According to the provisions of SY / T 6424-2000, the tall oil-based surfactant was added with water to prepare a surfactant solution with a concentration of 0.2%. The crude oil sample was kerosene. The instrument used was a TX-500C spinning drop interfacial tension meter. The instrument temperature was set to 50°C and the instrument speed was set to 5000r / min.

[0093] Emulsifying power: in accordance with the provisions of Q / SY 1583-2013.

[0094] Oil washing rate: in accordance with the provisions of Q / SY 1583-2013.

[0095] Salt resistance: According to the mineralized water ratio specified in SY / T 6424-2014. Specifically: weigh 42.50g (accurate to 0.01g) sodium chloride, 1.40g (accurate to 0.01g) magnesium chloride hexahydrate, 6.00g (accurate to 0.01g) calcium chloride, dissolve in a beaker with 600mL deionized water, transfer to a 1000mL volumetric flask after stirring, and wash three times with deionized water. All the washings are transferred to the volumetric flask, and deionized water is added to the scale to obtain mineralized water; according to the mass concentration of 0.05%, each product finally obtained in the embodiment and the comparative example is prepared into a surfactant solution with the above-mentioned mineralized water, and the oil-water interfacial tension is tested. And the mineralized water is used as a control to test the oil-water interfacial tension under the condition of mineralized water without any surfactant.

[0096] Temperature resistance: Refer to the above test method for oil-water interfacial tension, except that the instrument temperature is set to 80°C.

[0097] The test results of the above oil-water interfacial tension, emulsifying power, salt resistance, temperature resistance and oil washing rate are shown in Table 1.

[0098] Table 1 Performance test results of surfactants

[0099] By comparing Example 1 with Comparative Example 1, it can be seen that, compared with a liquid alkali catalyst, the amidation reaction of tall oil acid and diethanolamine catalyzed by a solid alkali catalyst can improve the conversion rate of tall oil acid and the yield of the tall oil-based surfactant in the final product, thereby greatly reducing the oil-water interfacial tension when the tall oil-based surfactant is used as a surfactant, and improving the emulsifying power, salt resistance, temperature resistance and oil washing rate of the tall oil-based surfactant.

[0100] By comparing Example 1 with Comparative Example 2, it can be seen that, compared with a liquid acid catalyst, the use of a solid acid catalyst to catalyze the esterification reaction of tall oil diethanolamide and maleic anhydride can improve the conversion rate of tall oil diethanolamide and the yield of the tall oil-based surfactant in the final product, thereby reducing the oil-water interfacial tension when the tall oil-based surfactant is used as a surfactant, and improving the emulsifying power, salt resistance, temperature resistance and oil washing rate of the tall oil-based surfactant.

[0101] By comparing Example 1 with Comparative Example 3, it can be seen that when tall oil diethanolamide and maleic anhydride are subjected to esterification reaction under normal pressure, the yield of tall oil-based surfactant in the product is relatively low, resulting in a high corresponding oil-water interfacial tension, poor emulsifying power, salt resistance, temperature resistance and oil washing rate. In Example 1 of the present invention, tall oil diethanolamide and maleic anhydride are subjected to esterification reaction under negative pressure conditions, and the yield of tall oil-based surfactant in the product is significantly increased, thereby significantly reducing the corresponding oil-water interfacial tension, and significantly improving the emulsifying power, salt resistance, temperature resistance and oil washing rate.

[0102] By comparing Example 1 with Comparative Example 4, it can be seen that the oil-water interfacial tension of the tall oil-based surfactant prepared with tall oil acid as the raw material is significantly lower than that of disodium oleic acid diethanolamide succinate prepared with oleic acid as the raw material, and the emulsifying power, salt resistance, temperature resistance and oil washing rate of the corresponding tall oil-based surfactant are also stronger than those of disodium oleic acid diethanolamide succinate. This is because tall oil acid contains various fatty acids, especially rosin acid, which makes the obtained tall oil-based surfactant have stronger lipophilicity to crude oil, so that the tall oil-based surfactant has a higher oil washing rate.

[0103] By comparing Example 1 with Comparative Example 5, it can be seen that the dosage relationship of tall oil acid and diethanolamine has a relatively obvious influence on the yield and performance of the final product tall oil-based surfactant. When the dosage of diethanolamine is too low, the yield of the tall oil-based surfactant will also be relatively low, resulting in relatively poor performance of the final product. Within the dosage relationship range of tall oil acid and diethanolamine defined in the present invention, a relatively high yield of tall oil-based surfactant can be obtained, and it has better surface activity, emulsifying power, salt resistance, temperature resistance and oil washing rate.

Claims

1. A method for preparing a tall oil-based surfactant, characterized in that: The following steps are involved: S1, using tall oil acid and diethanolamine as raw materials, carrying out an amidation reaction under the action of a solid base catalyst to obtain tall oil diethanolamide; S2, using tall oil diethanolamide and maleic anhydride as raw materials, carrying out an esterification reaction under negative pressure under the action of a solid acid catalyst to obtain tall oil diethanolamide succinic acid monoester; S3, tall oil diethanolamide succinic acid monoester and sodium sulfite solution are mixed and reacted, and after the reaction is completed, ethanol is added, stirred and filtered, and the obtained liquid is a tall oil-based surfactant.

2. The method for preparing a tall oil-based surfactant according to claim 1, characterized in that: In S1, the preparation method of the solid base catalyst is: impregnating aluminum oxide in a potassium hydroxide solution, then separating the solid and sequentially drying and calcining to obtain the solid base catalyst.

3. The method for preparing a tall oil-based surfactant according to claim 1, characterized in that: In S1, the mass ratio of the tall oil acid to diethanolamine is (3.0-3.2):1, and the mass of the solid base catalyst is 1%-2% of the total mass of the tall oil acid and diethanolamine.

4. The method for preparing a tall oil-based surfactant according to claim 1, characterized in that: In S1, the reaction temperature of the amidation reaction is 90-95° C., and the reaction time is 3-4 h.

5. The method for preparing a tall oil-based surfactant according to claim 1, characterized in that: In S2, the preparation method of the solid acid catalyst is: impregnating aluminum oxide in a p-toluenesulfonic acid solution, then separating the solid and sequentially drying and calcining to obtain the solid acid catalyst.

6. The method for preparing a tall oil-based surfactant according to claim 1, characterized in that: In S2, the mass ratio of the tall oil diethanolamide to maleic anhydride is (3.0-3.2):1, and the mass of the solid acid catalyst is 3%-6% of the total mass of the tall oil diethanolamide and maleic anhydride.

7. The method for preparing a tall oil-based surfactant according to claim 1, characterized in that: In S2, the reaction temperature of the esterification reaction is 60-80°C, the reaction time is 4-6h, and the negative pressure condition is -0.08-0.1MPa.

8. The method for preparing a tall oil-based surfactant according to claim 1, characterized in that: In S3, the mass ratio of tall oil diethanolamide succinic acid monoester and the solute in the sodium sulfite solution is (3.0~4.2):

1.

9. A tall oil-based surfactant obtained by the preparation method according to any one of claims 1 to 8, characterized in that: The active ingredients of the tall oil-based surfactant include compounds of the following structural formula: Where R1 is ( Z )-9-heptadecanediyl, R2 is cis, cis-9,12-heptadecanediyl, R3 is , in R3 is the bonding position.

10. Use of the tall oil-based surfactant according to claim 9 as a surfactant in oil field flooding.

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