A tall oil-based surfactant, its preparation method and application

Abstract

The present invention belongs to the field of oil and gas fields, and provides a tall oil-based surfactant, a preparation method thereof and an application. The preparation method of the tall oil-based surfactant comprises: S1, using tall oil fatty acid and diethanolamine as raw materials, and 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, and 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, mixing the tall oil diethanolamide succinic acid monoester and a sodium sulfite solution, carrying out a reaction, after the reaction is completed, adding ethanol, stirring and then filtering, and the obtained liquid is the tall oil-based surfactant. The tall oil-based surfactant of the present invention can be used alone as a surfactant for an oil displacement agent, and overcomes the chromatographic separation effect caused by different adsorption properties of each component of the traditional compound oil displacement agent system after entering the formation.

Description

Technical Field

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

[0002] The oil production process generally goes through primary oil recovery, secondary oil recovery, and tertiary oil recovery. Primary oil recovery can utilize the natural energy of the oil reservoir itself, with relatively low production costs. However, due to the exhaustion or insufficiency of natural energy, the recovery rate is extremely limited. Secondary oil recovery is a method of injecting water or gas to artificially replenish the formation energy, restore or maintain the formation pressure, and improve the recovery rate purposefully. The average recovery rate of secondary oil recovery is about 35%. For oil fields with good quality, the recovery rate can only reach 45%, and for oil fields with poor quality, 90% of the crude oil will remain underground. To improve the recovery rate, the use of chemicals to improve the performance between oil, gas, water, and rock has gradually been taken seriously, which is called tertiary oil recovery.

[0003] Tertiary oil recovery refers to changing the properties of reservoir rocks and fluids by injecting other fluids and using physical, chemical, thermal, biological and other methods to improve the crude oil recovery rate after water flooding. Chemical flooding, gas miscible flooding, thermal oil recovery, and microbial oil recovery are all methods to improve the enhanced oil recovery (EOR). During the tertiary oil recovery process, a large amount of capital needs to be invested in building injection equipment for injecting chemical agents, heat-carrying fluids, and miscible gases, and a large amount of capital is also required for the injected fluids. Due to the large scale of tertiary oil recovery, the recovery rate can be increased significantly. After the oil reservoir undergoes 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 reservoirs. Chemical flooding is to improve the recovery rate by injecting some chemical agents, mainly including alkali flooding, surfactant flooding, polymer flooding, and composite flooding. Since the oil displacement performance of existing single-component surfactants is very poor and cannot meet the requirements of oil displacement agents alone, surfactant flooding usually uses a combination of several surfactant components. To overcome the problem of poor oil displacement performance of single-component surfactants, surfactants can also be combined with polymers and / or alkalis, that is, composite flooding. The method of using the synergistic effect of surfactants and polymers to displace oil is called binary composite flooding. The method of using the synergistic effect of alkalis, surfactants, and polymers to displace oil is called alkaline-surfactant-polymer flooding (ASP). Whether it is ASP, binary composite flooding, or surfactant flooding, the oil displacement agent system is composed of at least two components in combination. Due to the different adsorption properties of rocks in the formation for different components, chromatographic separation effects occur in the oil displacement agent system, resulting in a relatively low actual crude oil recovery rate, and over time, the rate of decline in the recovery rate accelerates.

[0005] For example, Chinese invention patent CN106566511B discloses a surfactant micelle flooding agent, which is composed of lauramidopropyl betaine, sodium dodecyl sulfate, nano-silica sol, sodium chloride and the balance of water. Although this micelle flooding agent can improve the recovery rate to a certain extent, it belongs to a compound type and has an obvious chromatographic separation effect in actual use, resulting in limited actual recovery rate. Chinese invention patent CN104910024B discloses a surfactant for oil displacement, which is tetradecyl allyl dimethyl ethylenediamine dibromide. Its single use effect is poor, and it must be compounded with sodium monolauryl phthalate to significantly improve the recovery rate, but there is an 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 Na 2 CO 3 to form a ternary composite flooding agent by compounding, and the ternary composite flooding agent formed by compounding has an obvious chromatographic separation effect during application.

[0006] Therefore, it has become very urgent to develop a single-component flooding agent. Summary of the Invention

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

[0008] The present invention is achieved through the following technical solutions:

[0009] The present invention provides a preparation method of a tall oil-based surfactant, including the following steps:

[0010] S1, using tall oil fatty acid and diethanolamine as raw materials, under the action of a solid base catalyst, carrying out amidation reaction to obtain tall oil diethanolamide;

[0011] S2, using tall oil diethanolamide and maleic anhydride as raw materials, under the action of a solid acid catalyst, carrying out esterification reaction under negative pressure conditions to obtain tall oil diethanolamide succinic acid monoester;

[0012] S3, mixing tall oil diethanolamide succinic acid monoester and sodium sulfite solution, carrying out reaction, after the reaction is completed, adding ethanol, stirring and then filtering, and the obtained liquid is the tall oil-based surfactant.

[0013] In the preparation method of the above-mentioned tall oil-based surfactant of the present invention, the preparation method of the solid base catalyst used in S1 is as follows: alumina is impregnated in a potassium hydroxide solution, and then the solid is separated and dried and calcined in sequence to obtain the solid base catalyst.

[0014] Among them, preferably columnar alumina is used for alumina, the mass concentration of the potassium hydroxide solution is preferably 15% - 20%, and the mass ratio of alumina to the potassium hydroxide solution is preferably (5 - 6):1.

[0015] In the preparation method of the solid base catalyst, the temperature of the impregnation treatment is preferably 45 - 55°C, the time is preferably 4 - 6 h, the specific drying method is preferably: vacuum drying at 75 - 85°C for 2 - 3 h, and the specific calcination is preferably: vacuum calcination at 750 - 850°C for 3 - 5 h.

[0016] In some embodiments of the present invention, in S1, the mass ratio of the tall oil fatty 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 fatty acid and diethanolamine.

[0017] The tall oil fatty acid used in the present invention, by mass percentage, its quality meets: the total content of oleic acid and linoleic acid is 72% - 75%, the rosin acid content is 25% - 30%, and the unsaponifiable matter content is less than or equal to 3%.

[0018] 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.

[0019] The traditional amidation reaction uses a liquid base as a catalyst, with low reaction efficiency, a conversion rate of diethanolamine less than 70%, resulting in a relatively large residue of free diethanolamine, 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 the tall oil fatty acid, the acid value of the tall oil fatty acid is too high, resulting in a large consumption of the liquid base, obvious saponification phenomenon, and then resulting in too high viscosity and darker color of the tall oil diethanolamide, and the oil washing effect becomes worse. 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 residue of free diethanolamine, and the amide content in the amidation reaction product is greater than 90%. Moreover, the use of the solid base catalyst reduces the reaction temperature compared with the traditional amidation reaction, enabling the amidation reaction to be carried out under milder conditions. At the same time, the solid base catalyst can be removed by solid-liquid separation.

[0020] In the preparation method of the above-mentioned tall oil-based surfactant of the present invention, the preparation method of the solid acid catalyst used in S2 is as follows: Alumina is impregnated in a p-toluenesulfonic acid solution, and then the solid is separated and dried and calcined in sequence to obtain the solid acid catalyst.

[0021] Among them, the alumina preferably uses columnar alumina, the mass concentration of the p-toluenesulfonic acid solution is preferably 20% - 25%, and the mass ratio of alumina to the p-toluenesulfonic acid solution is preferably (8 - 10):1.

[0022] In the preparation method of the solid acid catalyst, the temperature of the impregnation treatment is preferably 45 - 55°C, the time is preferably 2 - 4 h, the specific drying method is preferably: vacuum drying at 75 - 85°C for 2 - 3 h, and the specific calcination is preferably: vacuum calcination at 750 - 850°C for 3 - 5 h.

[0023] In some embodiments of the present invention, 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.

[0024] 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.

[0025] The present invention uses a solid acid catalyst to catalyze the esterification reaction, which has high catalytic activity, the esterification rate of the tall oil diethanolamide is greater than 95%, and the reaction conditions are mild. Compared with the liquid acid catalyst, the solid acid catalyst not only has high catalytic activity, but also is easy to separate, recyclable, and environmentally friendly in the process.

[0026] In some embodiments of the present invention, in S3, the mass ratio of the tall oil diethanolamide succinic acid monoester to the solute in the sodium sulfite solution is (3.0 - 4.2):1.

[0027] 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 less than or equal to 10 mg / g is used as the judgment basis for the reaction end point.

[0028] The tall oil-based surfactant obtained by the above preparation method of the present invention has an active ingredient including a compound with the following structural formula:

[0029]

[0030] Among them, R 1 is ( Z )-9-heptadecenyl, R 2 is cis,cis-9,12-heptadecadienyl, R 3 is , R 3 in is the bonding position.

[0031] The present invention also provides the application of the above-mentioned tall oil-based surfactant as a surfactant in oil displacement in oil fields, especially in tertiary oil recovery.

[0032] Specifically, the tall oil-based surfactant of the present invention can be used alone as a surfactant in oil displacement in oil fields without the need for compounding with other substances. That is, the tall oil-based surfactant is formulated with water into an oil displacement agent and injected into the formation for oil displacement.

[0033] Although the tall oil-based surfactant of the present invention can be used alone as a surfactant in oil displacement in oil fields and already achieves a good oil displacement effect, if necessary, the tall oil-based surfactant can also be compounded with a polymer for use. In this regard, the present invention does not make any special restrictions.

[0034] Compared with the prior art, the present invention has the following beneficial effects:

[0035] The preparation method of the tall oil-based surfactant of the present invention uses tall oil fatty acid and diethanolamine as raw materials for amidation reaction to prepare tall oil diethanolamide; then uses tall oil diethanolamide and maleic anhydride as raw materials for esterification reaction to obtain tall oil diethanolamide succinic acid monoester; finally, it is sulfonated with sodium sulfite to obtain the tall oil-based surfactant. First, the tall oil-based surfactant obtained from tall oil fatty acid as a raw material in the present invention has very strong surface activity and can completely meet the requirements of the oil displacement agent when used alone without the need for compounding with other surfactants, polymers, or alkalis. Thus, it can overcome the chromatographic separation effect caused by inconsistent adsorption of different components on the surface of formation rocks in traditional compound oil displacement agents and improve the oil displacement efficiency and persistence of the oil displacement agent. At the same time, the tall oil-based surfactant prepared in the present invention contains -COONa and -SO 3The disodium structure formed by the combination of Na can chelate with divalent metal ions (such as calcium ions and magnesium ions) in the formation to provide salt tolerance; the active ingredient structure of the tall oil-based surfactant contains a hydroxyl group, which endows it with good temperature resistance. Secondly, in the present invention, a solid base catalyst is used to catalyze the amidation reaction. The solid base catalyst has high catalytic activity, resulting in high raw material conversion rate, high product yield, and extremely low content of free diethanolamine in the finished product, reducing carcinogenicity; moreover, the use of the solid base catalyst can avoid the saponification phenomenon caused by liquid base catalysts 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 esterification reaction of the present invention is carried out under negative pressure conditions. Compared with normal pressure, the negative pressure conditions can reduce the temperature required for the reaction, lower the intermolecular activation energy required, and increase the probability and rate of intermolecular collisions. Therefore, the reaction rate is faster, resulting in higher raw material conversion rate and product yield. In addition, the raw materials for the preparation method of the present invention are widely available, and it has great promotion value.

[0036] Furthermore, due to the use of the solid base catalyst, the amidation reaction of the present invention can be carried out under relatively mild conditions, with the reaction temperature below 100 °C and low energy consumption.

[0037] Furthermore, due to the use of the solid acid catalyst, the esterification reaction of the present invention can be carried out under relatively mild conditions, with the reaction temperature below 100 °C and low energy consumption.

[0038] The tall oil-based surfactant provided by the present invention has very strong surface activity and strong crude oil emulsifying ability. It can reduce the oil-water interfacial tension to 10 -4 mN / m, reaching an ultra-low interfacial tension. Alone, it can fully meet the requirements of an oil displacement agent. Therefore, the tall oil-based surfactant of the present invention can be used alone as a surfactant to prepare an oil displacement agent without the need to be compounded with other surfactants or polymers and alkalis. Moreover, the adsorption amount of the tall oil-based surfactant on the rock surface is extremely low, thereby overcoming the chromatographic separation effect caused by inconsistent adsorption of different components of traditional compound oil displacement agents on the formation rock surface, improving the oil displacement efficiency and persistence of the oil displacement agent, and greatly increasing the crude oil recovery rate. At the same time, the tall oil-based surfactant provided by the present invention has good salt tolerance because -COONa and -SO 3The disodium structure formed by the combination of Na can complex 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 tolerance and can still maintain the stability of the oil-water interfacial tension and achieve a long-term oil displacement effect when used in formations with a high content of divalent metal ions (such as calcium ions and magnesium ions). In addition, the compound structure of the tall oil-based surfactant of the present invention contains a hydroxyl group, and the presence of the hydroxyl group ensures the stability of the structure, thereby enabling it to have good temperature resistance performance.

[0039] In the present invention, a tall oil-based surfactant is used as the surfactant for oil displacement, which can overcome the chromatographic separation effect caused by the inconsistent adsorption of different components on the rock surface in the formation of traditional compound oil displacement agents, greatly improve the crude oil recovery rate, and can stably displace oil in formations with a high salt content. BRIEF DESCRIPTION OF THE DRAWINGS

[0040] In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings required for the description of the embodiments or the prior art. Obviously, the drawings in the following description are some embodiments of the present invention. For those of ordinary skill in the art, other drawings can be obtained based on these drawings without creative efforts.

[0041] Figure 1 They are the infrared spectra of tall oil acid, the tall oil diethanolamide obtained in Example 1, and the tall oil-based surfactant. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0042] The following specific examples illustrate the embodiments of the present invention. Those skilled in the art can easily understand other advantages and effects of the present invention from the content disclosed in this specification. The present invention can also be implemented or applied through other different specific embodiments, and various details in this specification can also be modified or changed based on different viewpoints and applications without departing from the spirit of the present invention.

[0043] It should be noted that the process equipment or devices not specifically noted in the following examples are all conventional equipment or devices in the art.

[0044] It should be noted that the terms "comprising" and "having" and any variations thereof are intended to cover non-exclusive inclusion. For example, a process, method, system, product or device that comprises a series of steps or units need not be limited to those steps or units clearly listed, but may include other steps or units 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, rather than restricting the arrangement order of each method step or limiting the scope in which the present invention can be implemented. Changes or adjustments to their relative relationships, without substantial changes in the technical content, should also be regarded as the scope in which the present invention can be implemented.

[0045] 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.

[0046] Preparation Example 1

[0047] Preparation of the solid base catalyst: 50 g of columnar alumina was impregnated in 9 mL of 18% potassium hydroxide solution at 50 °C for 4 h, then the solid was separated, vacuum dried at 80 °C for 2 h, and vacuum calcined at 800 °C for 4 h to obtain the solid base catalyst.

[0048] Preparation Example 2

[0049] Preparation of the solid acid catalyst: 50 g of columnar alumina was subjected to rotary impregnation 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 r / min. Then the solid was separated, vacuum dried at 80 °C for 2 h, and vacuum calcined at 800 °C for 4 h to obtain the solid acid catalyst.

[0050] Example 1

[0051] S101: Weigh 24 g of tall oil fatty acid, 8 g of diethanolamine, and 0.3 g of the solid base catalyst, place them in a closed reactor, stir at a low speed of 400 r / min, control the temperature at 92 °C, and react at normal pressure for 4 h to obtain highly active tall oil diethanolamide.

[0052] S102: Stir and mix 30 g of tall oil diethanolamide and 10 g of maleic anhydride, heat to raise the temperature to 75 °C, add 1.2 g of the solid acid catalyst, and carry out an esterification reaction at a pressure of -0.09 MPa. The reaction time is 5 h, and the reaction ends when the acid value reaches 76 mg / g to obtain tall oil diethanolamide succinic acid monoester.

[0053] S103: Add 41 g of tall oil diethanolamide succinic acid monoester into a condensing reflux device, and add the sodium sulfite solution prepared by dissolving 12 g of sodium sulfite in 20 g of water in advance. Adjust the stirring speed to 1000 r / min, control the temperature at 75 °C, and react for 3 h under normal pressure. When the iodine value reaches 5 mg / g, it reaches the end point. Lower the temperature to room temperature, add 24.5 g of ethanol for phase inversion, stir for 10 min, and then filter to remove solids to obtain a tall oil-based surfactant. The conversion rate of tall oil acid is 99.5%, and the yield of the tall oil-based surfactant is 98.9%.

[0054] Example 2

[0055] S201: Weigh 24 g of tall oil acid, 7.5 g of diethanolamine and 0.3 g of solid base catalyst, place them in a closed reactor, stir at a low speed of 400 r / min, control the temperature at 92 °C, and react for 4 h under normal pressure to obtain highly active tall oil diethanolamide.

[0056] S202: Stir and mix 30 g of tall oil diethanolamide and 10 g of maleic anhydride, heat to raise the temperature to 75 °C, add 1.2 g of solid acid catalyst, and carry out an esterification reaction under a pressure of -0.09 MPa. The reaction time is 5 h, and when the acid value reaches 76 mg / g, the reaction ends to obtain tall oil diethanolamide succinic acid monoester.

[0057] S203: Add 41 g of tall oil diethanolamide succinic acid monoester into a condensing reflux device, and add the sodium sulfite solution prepared by dissolving 12 g of sodium sulfite in 20 g of water in advance. Adjust the stirring speed to 1000 r / min, control the temperature at 75 °C, and react for 3 h under normal pressure. When the iodine value reaches 5 mg / g, it reaches the end point. Lower the temperature to room temperature, add 24.5 g of ethanol for phase inversion, stir for 10 min, and then filter to remove solids to obtain a tall oil-based surfactant. The conversion rate of tall oil acid is 95.2%, and the yield of the tall oil-based surfactant is 98.3%.

[0058] Example 3

[0059] S301: Weigh 24 g of tall oil acid, 8 g of diethanolamine and 0.6 g of solid base catalyst, place them in a closed reactor, stir at a low speed of 400 r / min, control the temperature at 92 °C, and react for 4 h under normal pressure to obtain highly active tall oil diethanolamide.

[0060] S302: Stir and mix 30 g of tall oil diethanolamide and 10 g of maleic anhydride, heat to raise the temperature to 75 °C, add 1.2 g of solid acid catalyst, and carry out an esterification reaction under a pressure of -0.09 MPa. The reaction time is 5 h, and when the acid value reaches 76 mg / g, the reaction ends to obtain tall oil diethanolamide succinic acid monoester.

[0061] S303: Add 41 g of tall oil diethanolamide succinic acid monoester into a condensing reflux device, and add the sodium sulfite solution prepared by dissolving 12 g of sodium sulfite in 20 g of water in advance. Adjust the stirring speed to 1000 r / min, control the temperature at 75 °C, and react for 3 h under normal pressure. When the iodine value reaches 5 mg / g, it reaches the end point. Lower the temperature to room temperature, add 24.5 g of ethanol for phase inversion, stir for 10 min, and then filter to remove solids to obtain a tall oil-based surfactant. The conversion rate of tall oil acid is 99.4%, and the yield of the tall oil-based surfactant is 99.1%.

[0062] Example 4

[0063] S401: Weigh 24 g of tall oil acid, 8 g of diethanolamine, and 0.3 g of solid base catalyst, place them in a closed reactor, stir at a low speed of 400 r / min, control the temperature at 92 °C, and react for 4 h under normal pressure to obtain highly active tall oil diethanolamide.

[0064] S402: Stir and mix 30 g of tall oil diethanolamide and 10 g of maleic anhydride, heat to raise the temperature to 75 °C, add 2.4 g of solid acid catalyst, and carry out an esterification reaction under a pressure of -0.09 MPa for 5 h. When the acid value reaches 76 mg / g, the reaction ends to obtain tall oil diethanolamide succinic acid monoester.

[0065] S403: Add 41 g of tall oil diethanolamide succinic acid monoester into a condensing reflux device, and add the sodium sulfite solution prepared by dissolving 12 g of sodium sulfite in 20 g of water in advance. Adjust the stirring speed to 1000 r / min, control the temperature at 75 °C, and react for 3 h under normal pressure. When the iodine value reaches 5 mg / g, it reaches the end point. Lower the temperature to room temperature, add 24.5 g of ethanol for phase inversion, stir for 10 min, and then filter to remove solids to obtain a tall oil-based surfactant. The conversion rate of tall oil acid is 99.4%, and the yield of the tall oil-based surfactant is 98.5%.

[0066] Example 5

[0067] S501: Weigh 24 g of tall oil acid, 8 g of diethanolamine, and 0.3 g of solid base catalyst, place them in a closed reactor, stir at a low speed of 400 r / min, control the temperature at 95 °C, and react for 4 h under normal pressure to obtain highly active tall oil diethanolamide.

[0068] S502: Stir and mix 30 g of tall oil diethanolamide and 10 g of maleic anhydride, heat to raise the temperature to 75 °C, add 1.2 g of solid acid catalyst, carry out the esterification reaction under a pressure of -0.09 MPa, with a reaction time of 5 h. When the acid value reaches 76 mg / g, the reaction ends to obtain tall oil diethanolamide succinic acid monoester.

[0069] S503: Add 41 g of tall oil diethanolamide succinic acid monoester to the condensation reflux device, and add the sodium sulfite solution prepared by dissolving 12 g of sodium sulfite in 20 g of water in advance. Adjust the stirring speed to 1000 r / min, control the temperature at 75 °C, and react for 3 h under normal pressure. When the iodine value reaches 5 mg / g, it reaches the end point. Lower the temperature to room temperature, add 24.5 g of ethanol for phase inversion, stir for 10 min, and then filter to remove solids to obtain the tall oil-based surfactant. The conversion rate of tall oil acid is 96.8%, and the yield of the tall oil-based surfactant is 98.5%.

[0070] Example 6

[0071] S601: Weigh 24 g of tall oil acid, 8 g of diethanolamine and 0.3 g of solid base catalyst, place them in a closed reactor, stir at a low speed of 400 r / min, control the temperature at 92 °C, and react for 3 h under normal pressure to obtain highly active tall oil diethanolamide.

[0072] S602: Stir and mix 30 g of tall oil diethanolamide and 10 g of maleic anhydride, heat to raise the temperature to 75 °C, add 1.2 g of solid acid catalyst, carry out the esterification reaction under a pressure of -0.09 MPa, with a reaction time of 5 h. When the acid value reaches 76 mg / g, the reaction ends to obtain tall oil diethanolamide succinic acid monoester.

[0073] S603: Add 41 g of tall oil diethanolamide succinic acid monoester to the condensation reflux device, and add the sodium sulfite solution prepared by dissolving 12 g of sodium sulfite in 20 g of water in advance. Adjust the stirring speed to 1000 r / min, control the temperature at 75 °C, and react for 3 h under normal pressure. When the iodine value reaches 5 mg / g, it reaches the end point. Lower the temperature to room temperature, add 24.5 g of ethanol for phase inversion, stir for 10 min, and then filter to remove solids to obtain the tall oil-based surfactant. The conversion rate of tall oil acid is 95.8%, and the yield of the tall oil-based surfactant is 98.4%.

[0074] Example 7

[0075] S701: Weigh 24 g of tall oil acid, 8 g of diethanolamine and 0.3 g of solid base catalyst, place them in a closed reactor, stir at a low speed of 400 r / min, control the temperature at 92 °C, and react for 4 h under normal pressure to obtain highly active tall oil diethanolamide.

[0076] S702: Stir and mix 30 g of tall oil diethanolamide and 9.4 g of maleic anhydride, heat to raise the temperature to 75 °C, add 1.2 g of solid acid catalyst, carry out the esterification reaction under a pressure of -0.09 MPa, with a reaction time of 5 h. When the acid value reaches 76 mg / g, the reaction ends to obtain tall oil diethanolamide succinic acid monoester.

[0077] S703: Add 41 g of tall oil diethanolamide succinic acid monoester to the condensation reflux device, and add the sodium sulfite solution prepared by dissolving 12 g of sodium sulfite in 20 g of water in advance. Adjust the stirring speed to 1000 r / min, control the temperature at 75 °C, and react for 3 h under normal pressure. When the iodine value reaches 5 mg / g, it reaches the end point. Lower the temperature to room temperature, add 24.5 g of ethanol for phase inversion, stir for 10 min, and then filter to remove solids to obtain the tall oil-based surfactant. The conversion rate of tall oil fatty acid is 99.1%, and the yield of the tall oil-based surfactant is 99.2%.

[0078] Example 8

[0079] S801: Weigh 24 g of tall oil fatty acid, 8 g of diethanolamine and 0.3 g of solid base catalyst, place them in a closed reactor, stir at a low speed of 400 r / min, control the temperature at 92 °C, and react for 4 h under normal pressure to obtain highly active tall oil diethanolamide.

[0080] S802: Stir and mix 30 g of tall oil diethanolamide and 10 g of maleic anhydride, heat to raise the temperature to 62 °C, add 1.2 g of solid acid catalyst, carry out the esterification reaction under a pressure of -0.09 MPa, with a reaction time of 5 h. When the acid value reaches 76 mg / g, the reaction ends to obtain tall oil diethanolamide succinic acid monoester.

[0081] S803: Add 41 g of tall oil diethanolamide succinic acid monoester to the condensation reflux device, and add the sodium sulfite solution prepared by dissolving 12 g of sodium sulfite in 20 g of water in advance. Adjust the stirring speed to 1000 r / min, control the temperature at 75 °C, and react for 3 h under normal pressure. When the iodine value reaches 5 mg / g, it reaches the end point. Lower the temperature to room temperature, add 24.5 g of ethanol for phase inversion, stir for 10 min, and then filter to remove solids to obtain the tall oil-based surfactant. The conversion rate of tall oil fatty acid is 98.8%, and the yield of the tall oil-based surfactant is 97.5%.

[0082] Example 9

[0083] S901: Weigh 24 g of tall oil fatty acid, 8 g of diethanolamine and 0.3 g of solid base catalyst, place them in a closed reactor, stir at a low speed of 400 r / min, control the temperature at 92 °C, and react for 4 h under normal pressure to obtain highly active tall oil diethanolamide.

[0084] S902: Stir and mix 30 g of tall oil diethanolamide and 10 g of maleic anhydride, heat to raise the temperature to 75 °C, add 1.2 g of solid acid catalyst, carry out the esterification reaction under a pressure of -0.09 MPa, with a reaction time of 4 h. When the acid value reaches 76 mg / g, the reaction ends to obtain tall oil diethanolamide succinic acid monoester.

[0085] S903: Add 41 g of tall oil diethanolamide succinic acid monoester to a condensation reflux device, and add a sodium sulfite solution prepared by dissolving 12 g of sodium sulfite in 20 g of water in advance. Adjust the stirring speed to 1000 r / min, control the temperature at 75 °C, and react for 3 h under normal pressure. When the iodine value reaches 5 mg / g, it reaches the end point. Lower the temperature to room temperature, add 24.5 g of ethanol for phase inversion, stir for 10 min, and then filter to remove solids to obtain a tall oil-based surfactant. The conversion rate of tall oil acid is 98.9%, and the yield of the tall oil-based surfactant is 96.1%.

[0086] Example 10

[0087] S1001: Weigh 24 g of tall oil acid, 8 g of diethanolamine and 0.3 g of solid base catalyst, place them in a closed reactor, stir at a low speed of 400 r / min, control the temperature at 92 °C, and react for 4 h under normal pressure to obtain highly active tall oil diethanolamide.

[0088] S1002: Stir and mix 30 g of tall oil diethanolamide and 10 g of maleic anhydride, heat to raise the temperature to 75 °C, add 1.2 g of solid acid catalyst, carry out the esterification reaction under a pressure of -0.09 MPa, with a reaction time of 6 h. When the acid value reaches 76 mg / g, the reaction ends to obtain tall oil diethanolamide succinic acid monoester.

[0089] S1003: Add 41 g of tall oil diethanolamide succinic acid monoester to a condensation reflux device, and add a sodium sulfite solution prepared by dissolving 12 g of sodium sulfite in 20 g of water in advance. Adjust the stirring speed to 1000 r / min, control the temperature at 75 °C, and react for 3 h under normal pressure. When the iodine value reaches 5 mg / g, it reaches the end point. Lower the temperature to room temperature, add 24.5 g of ethanol for phase inversion, stir for 10 min, and then filter to remove solids to obtain a tall oil-based surfactant. The conversion rate of tall oil acid is 99.1%, and the yield of the tall oil-based surfactant is 99.0%.

[0090] Example 11

[0091] S1101: Weigh 24 g of tall oil fatty acid, 8 g of diethanolamine, and 0.3 g of solid base catalyst, place them in a closed reactor, stir at a low speed of 400 r / min, control the temperature at 92 °C, and react for 4 h under normal pressure to obtain highly active tall oil diethanolamide.

[0092] S1102: Stir and mix 30 g of tall oil diethanolamide and 10 g of maleic anhydride, heat to raise the temperature to 75 °C, add 1.2 g of solid acid catalyst, carry out an esterification reaction under a pressure of -0.09 MPa, with a reaction time of 5 h, and end the reaction when the acid value reaches 76 mg / g to obtain tall oil diethanolamide succinic acid monoester.

[0093] S1103: Add 41 g of tall oil diethanolamide succinic acid monoester to a condensing reflux device, and add a sodium sulfite solution prepared by dissolving 12 g of sodium sulfite in 10 g of water in advance. Adjust the stirring speed to 1000 r / min, control the temperature at 75 °C, and react for 3 h under normal pressure. When the iodine value reaches 5 mg / g, reach the end point. Lower the temperature to room temperature, add 24.5 g of ethanol for phase inversion, stir for 10 min, and then filter to remove solids to obtain a tall oil-based surfactant. The conversion rate of tall oil fatty acid is 98.2%, and the yield of the tall oil-based surfactant is 95.2%.

[0094] Comparative Example 1

[0095] S1201: Weigh 24 g of tall oil fatty acid, 8 g of diethanolamine, and 0.2 g of potassium hydroxide, place them in a closed reactor, stir at a low speed of 400 r / min, control the temperature at 92 °C, and react for 4 h under normal pressure to obtain tall oil diethanolamide.

[0096] S1202: Stir and mix 30 g of tall oil diethanolamide and 10 g of maleic anhydride, heat to raise the temperature to 75 °C, add 1.2 g of solid acid catalyst, carry out an esterification reaction under a pressure of -0.09 MPa, with a reaction time of 5 h, and end the reaction when the acid value reaches 76 mg / g to obtain tall oil diethanolamide succinic acid monoester.

[0097] S1203: Add 41 g of tall oil diethanolamide succinic acid monoester to a condensing reflux device, and add a sodium sulfite solution prepared by dissolving 12 g of sodium sulfite in 20 g of water in advance. Adjust the stirring speed to 1000 r / min, control the temperature at 75 °C, and react for 3 h under normal pressure. When the iodine value reaches 5 mg / g, reach the end point. Lower the temperature to room temperature, add 24.5 g of ethanol for phase inversion, stir for 10 min, and then filter to remove solids to obtain a tall oil-based surfactant. The conversion rate of tall oil fatty acid is 79.8%, and the yield of the tall oil-based surfactant is 82.4%.

[0098] Comparative Example 2

[0099] S1301: Weigh 24 g of tall oil fatty acid, 8 g of diethanolamine and 0.3 g of solid base catalyst, place them in a closed reactor, stir at a low speed of 400 r / min, control the temperature at 92 °C, and react under normal pressure for 4 h to obtain highly active tall oil diethanolamide.

[0100] S1302: Stir and mix 30 g of tall oil diethanolamide and 10 g of maleic anhydride, heat to raise the temperature to 75 °C, add 0.7 g of p-toluenesulfonic acid, and carry out an esterification reaction under a pressure of -0.09 MPa for 5 h. When the acid value reaches 76 mg / g, the reaction ends to obtain tall oil diethanolamide succinic acid monoester.

[0101] S1303: Add 41 g of tall oil diethanolamide succinic acid monoester to a condensation reflux device, and add a sodium sulfite solution prepared by dissolving 12 g of sodium sulfite in 20 g of water in advance. Adjust the stirring speed to 1000 r / min, control the temperature at 75 °C, and react under normal pressure for 3 h. When the iodine value reaches 5 mg / g, it reaches the end point. Lower the temperature to room temperature, add 24.5 g of ethanol for phase inversion, stir for 10 min, and then filter to remove solids to obtain a tall oil-based surfactant. The conversion rate of tall oil fatty acid is 98.8%, and the yield of the tall oil-based surfactant is 75.8%.

[0102] Comparative Example 3

[0103] S1401: Weigh 24 g of tall oil fatty acid, 8 g of diethanolamine and 0.3 g of solid base catalyst and place them in a closed reactor, stir at a low speed of 400 r / min, control the temperature at 92 °C, and react under normal pressure for 4 h to obtain highly active tall oil diethanolamide.

[0104] S1402: Stir and mix 30 g of tall oil diethanolamide and 10 g of maleic anhydride, heat to raise the temperature to 75 °C, add 1.2 g of solid acid catalyst, and carry out an esterification reaction under normal pressure for 5 h. When the acid value reaches 76 mg / g, the reaction ends to obtain tall oil diethanolamide succinic acid monoester.

[0105] S1403: Add 41 g of tall oil diethanolamide succinic acid monoester to a condensation reflux device, and add a sodium sulfite solution prepared by dissolving 12 g of sodium sulfite in 20 g of water in advance. Adjust the stirring speed to 1000 r / min, control the temperature at 75 °C, and react under normal pressure for 3 h. When the iodine value reaches 5 mg / g, it reaches the end point. Lower the temperature to room temperature, add 24.5 g of ethanol for phase inversion, stir for 10 min, and then filter to remove solids to obtain a tall oil-based surfactant. The conversion rate of tall oil fatty acid is 98.7%, and the yield of the tall oil-based surfactant is 79.4%.

[0106] Comparative Example 4

[0107] S1501: Weigh 24 g of oleic acid, 8 g of diethanolamine, and 0.3 g of solid base catalyst, place them in a closed reactor, stir at a low speed of 400 r / min, control the temperature at 92 °C, and react for 4 h under normal pressure to obtain highly active tall oil diethanolamide.

[0108] S1502: Stir and mix 30 g of oleic acid diethanolamide and 10 g of maleic anhydride, heat to raise the temperature to 75 °C, add 1.2 g of solid acid catalyst, carry out an esterification reaction under a pressure of -0.09 MPa, with a reaction time of 5 h. When the acid value reaches 76 mg / g, the reaction ends to obtain oleic acid diethanolamide succinic acid monoester.

[0109] S1503: Add 41 g of oleic acid diethanolamide succinic acid monoester to a condensing reflux device, and add a sodium sulfite solution prepared by dissolving 12 g of sodium sulfite in 20 g of water in advance. Adjust the stirring speed to 1000 r / min, control the temperature at 75 °C, and react for 3 h under normal pressure. When the iodine value reaches 5 mg / g, it reaches the end point. Lower the temperature to room temperature, add 24.5 g of ethanol for phase inversion, stir for 10 min, and then filter to remove solids to obtain disodium oleic acid diethanolamide succinate. The conversion rate of oleic acid is 97.5%, and the yield of disodium oleic acid diethanolamide succinate is 85.8%.

[0110] Comparative Example 5

[0111] S1601: Weigh 24 g of tall oil fatty acid, 6 g of diethanolamine, and 0.3 g of solid base catalyst, place them in a closed reactor, stir at a low speed of 400 r / min, control the temperature at 92 °C, and react for 4 h under normal pressure to obtain tall oil diethanolamide.

[0112] S1602: Stir and mix 30 g of tall oil diethanolamide and 10 g of maleic anhydride, heat to raise the temperature to 75 °C, add 1.2 g of solid acid catalyst, carry out an esterification reaction under a pressure of -0.09 MPa, with a reaction time of 5 h. When the acid value reaches 76 mg / g, the reaction ends to obtain tall oil diethanolamide succinic acid monoester.

[0113] S1603: Add 41 g of tall oil diethanolamide succinic acid monoester to a condensing reflux device, and add a sodium sulfite solution prepared by dissolving 12 g of sodium sulfite in 20 g of water in advance. Adjust the stirring speed to 1000 r / min, control the temperature at 75 °C, and react for 3 h under normal pressure. When the iodine value reaches 5 mg / g, it reaches the end point. Lower the temperature to room temperature, add 24.5 g of ethanol for phase inversion, stir for 10 min, and then filter to remove solids to obtain a tall oil-based surfactant. The conversion rate of tall oil fatty acid is 91.5%, and the yield of the tall oil-based surfactant is 90.8%.

[0114] Figure 1 The infrared spectrum of the tall oil-based surfactant obtained in Example 1. Figure 1 In the range of 4000 - 3000 cm -1 is the region of stretching vibrations of -C-H, -N-H, and -O-H. The stretching vibration absorption peaks of -C-H, -N-H, and -O-H coexist, indicating that during the reaction, one hydroxyl group in tall oil diethanolamide is retained, and the resulting tall oil-based surfactant is a monoester compound. The characteristic peak at 2933 cm -1 is the symmetric stretching vibration absorption peak of -CH 2 -, and the characteristic peak at 1642 cm -1 is the stretching vibration absorption peak of -C=O-, and the characteristic peak at 1550 cm -1 is the stretching vibration absorption peak of -C=C-. The range of 2000 - 1500 cm -1 is the region of stretching vibrations of -C=C- and -C=O-. Compared with the spectrum of tall oil diethanolamide, the stretching vibration absorption peak of -C=O- appears in the spectrum of the tall oil-based surfactant, indicating that maleic anhydride undergoes a ring-opening reaction to form -C=O-, and makes the -C-H stretching vibration absorption peak of tall oil diethanolamide in the range of 2900 - 3500 cm -1 enhanced, and at the same time makes the position of the -O-H stretching vibration absorption peak shift. The region below 1500 cm -1 is the single-bond region. The characteristic peak at 1100 - 1115 cm -1 is the stretching vibration absorption peak of -C-N-, and the characteristic peaks at 900 - 1000 cm -1 and 600 - 700 cm -1 are the stretching vibration absorption peaks of -O-S-, indicating that -SO 3 Na exists in the compound structure of the tall oil-based surfactant. The characteristic peak at 1632 cm -1 is the stretching vibration absorption peak of -COO-, and the characteristic peak at 1251 cm -1 is the stretching vibration absorption peak of -N-C-O-. The infrared spectrum of the tall oil-based surfactant indicates that the target product is prepared in this invention.

[0115] Taking the products finally obtained in the above examples and comparative examples as surfactants, tests on oil-water interfacial tension, emulsifying power, salt tolerance, temperature resistance, and oil washing rate are carried out.

[0116] The test methods are as follows:

[0117] Oil-water interfacial tension: It is carried out according to the regulations in SY / T 6424-2000. The tall oil-based surfactant is added with water to prepare a surfactant solution with a concentration of 0.2%. Kerosene is used for the crude oil sample, and a TX-500C spinning drop interfacial tensiometer is used for the instrument. The instrument temperature is set at 50 °C, and the instrument rotation speed is set at 5000 r / min.

[0118] Emulsifying power: It is carried out according to the regulations in Q / SY 1583-2013.

[0119] Oil washing rate: It is carried out according to the regulations in Q / SY 1583-2013.

[0120] Salt tolerance: It is carried out according to the proportion of mineralized water specified in SY / T 6424-2014. Specifically: Weigh 42.50 g (accurate to 0.01 g) of sodium chloride, 1.40 g (accurate to 0.01 g) of magnesium chloride hexahydrate, and 6.00 g (accurate to 0.01 g) of calcium chloride. Dissolve them in 600 mL of deionized water in a beaker, stir well, then transfer them to a 1000 mL volumetric flask, and wash three times with deionized water. All the washing solutions are transferred into the volumetric flask, and deionized water is added to make up to the scale line to obtain the mineralized water. According to a mass concentration of 0.05%, the final products obtained in the examples and comparative examples are used to prepare surfactant solutions with the above-mentioned mineralized water, and the oil-water interfacial tension is measured. And taking the said mineralized water as a control, the oil-water interfacial tension under the condition of mineralized water without adding any surfactant is measured.

[0121] Temperature tolerance: Referring to the above test method for oil-water interfacial tension, only the instrument temperature is set at 80 °C.

[0122] The test results of the above oil-water interfacial tension, emulsifying power, salt tolerance, temperature tolerance and oil washing rate are shown in Table 1.

[0123] Table 1 Performance test results of surfactants

[0124]

[0125] By comparing Example 1 with Comparative Example 1, it can be seen that compared with the liquid base catalyst, using a solid base catalyst to catalyze the amidation reaction of tall oil fatty acid and diethanolamine can improve the conversion rate of tall oil fatty acid and the yield of 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 tolerance, temperature tolerance and oil washing rate of the tall oil-based surfactant.

[0126] Comparing Example 1 with Comparative Example 2, it can be seen that, compared with the liquid acid catalyst, using 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 tall oil-based surfactant in the final product. Furthermore, it reduces the oil-water interfacial tension of the tall oil-based surfactant as a surfactant and improves the emulsifying power, salt tolerance, temperature resistance, and oil washing rate of the tall oil-based surfactant.

[0127] Comparing Example 1 with Comparative Example 3, it can be seen that when the esterification reaction of tall oil diethanolamide and maleic anhydride is carried out under atmospheric pressure, the yield of tall oil-based surfactant in the product is relatively low, resulting in a relatively high corresponding oil-water interfacial tension, and poor emulsifying power, salt tolerance, temperature resistance, and oil washing rate. In Example 1 of the present invention, the esterification reaction of tall oil diethanolamide and maleic anhydride is carried out under negative pressure, and the yield of tall oil-based surfactant in the product increases significantly, so that the corresponding oil-water interfacial tension decreases significantly, and the emulsifying power, salt tolerance, temperature resistance, and oil washing rate also increase significantly.

[0128] Comparing Example 1 with Comparative Example 4, it can be seen that the oil-water interfacial tension of the tall oil-based surfactant prepared from tall oil fatty acid as a raw material is significantly lower than that of sodium oleic diethanolamide succinate prepared from oleic acid as a raw material. Correspondingly, the emulsifying power, salt tolerance, temperature resistance, and oil washing rate of the tall oil-based surfactant are also stronger than those of sodium oleic diethanolamide succinate. This is because tall oil fatty acid contains various fatty acids, especially rosin acid, which makes the obtained tall oil-based surfactant have stronger lipophilicity for crude oil, so that the tall oil-based surfactant has a higher oil washing rate.

[0129] Comparing Example 1 with Comparative Example 5, it can be seen that the dosage relationship between tall oil fatty 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 tall oil-based surfactant will also be relatively low, resulting in relatively poor performance of the final product. Within the range of the dosage relationship between tall oil fatty 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 tolerance, 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, the reaction temperature is 90-95° C., to obtain tall oil diethanolamide; the mass ratio of the tall oil acid to the diethanolamine is (3.0-3.2):1; 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; the mass ratio of the tall oil diethanolamide to maleic anhydride is (3.0-3.2):1; 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 of the solid base catalyst is 1% to 2% of the total mass of 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 time of the amidation reaction is 3 to 4 hours.

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 of the solid acid catalyst is 3% to 6% of the total mass of 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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