CN112707865B - Zwitterionic surfactant and preparation method thereof - Google Patents
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Abstract
The invention relates to a zwitterionic surfactant and a preparation method thereof. Mainly solves the problems of poor oil displacement effect of surfactant as an oil displacement agent and corrosion and scaling of alkali to stratum in ternary complex flooding in the prior production technology. The invention adopts a hydrocarbon imidazoline polyoxypropylene polyoxyethylene ether carboxylate zwitterionic surfactant, and the molecular general formula is as follows: in the formula (1), R 1 Is C 8 ‑C 22 Is a hydrocarbon group of (2); m is the polymerization degree of polyethylene polyamine, x is the polymerization degree of polyoxypropylene, y is the polymerization degree of polyoxyethylene, m=any one integer from 0 to 6, x=any one number from 0 to 20, and y=any one number from 1 to 20; m is selected from a cation or cationic group that charge balances formula (1); the technical scheme that n is the reciprocal of the absolute value of the M valence state solves the problem well and can be used in the enhanced oil recovery production of oil fields.
Description
Technical Field
The invention relates to a zwitterionic surfactant and a preparation method thereof.
Background
After decades of exploitation, many oil fields in China enter a high water content stage, the yield is faced to be reduced, and the development of tertiary oil recovery is an important way for improving the oil recovery. Tertiary oil recovery is compared with primary oil recovery and secondary oil recovery. In the early stage of oil exploitation, the natural energy of stratum is only utilized to exploit oil, which is called primary oil exploitation, and the recovery rate is only about 10%. Methods of recovering oil, such as water injection, gas injection, etc., by supplementing the formation with energy are known as secondary recovery. At present, a large number of oil fields in the world adopt a secondary oil extraction method, but the recovery rate can only reach about 25 to 40 percent. Tertiary oil recovery is a method for continuously exploiting underground residual petroleum by means of physical, chemical, biological and the like, thereby improving the recovery ratio of crude oil. The research of oil extraction by using surfactants in oil exploitation starts in the beginning of thirty of the twentieth century, and has been developed so far, which is an important means for improving the recovery efficiency in oil fields, and has been greatly progressed in theory and practice. Currently, the following injection systems are basically formed: active water flooding, foam flooding, low interfacial tension system flooding and the like.
The main mechanism of using surfactant to increase crude oil recovery is: after the oil field enters the high water content period, the residual oil is trapped in the pores of the oil reservoir rock in a discontinuous oil film, and two main forces acting on the oil droplets are viscous force and capillary force, if a proper surfactant system is selected, the interfacial tension between the oil and the water is reduced, so that the interfacial tension between the oil and the water of the oil reservoir is reduced from 20 mN/m to 30mN/m to a lower or ultra-low value (10 -3 ～10 -4 mN/m), the resistance caused by deformation of the oil droplets when the residual oil moves can be reduced, thereby greatly improving the oil displacement efficiency.
At present, most tertiary oil recovery surfactants at home and abroad are surfactants (CN 1203935A, CN1566258A and CN 1426833A) modified by petroleum sulfonate, heavy alkylbenzenesulfonate and other oil refining byproducts, and the surfactants are characterized by wide material availability and low cost. However, these surfactants also have a series of problems such as insufficient stability, poor salt tolerance, particularly divalent cation tolerance, and the like, and cannot be applied to high-temperature and high-mineralization oilfield blocks. Therefore, the development of the novel surfactant has extremely important significance for the tertiary oil recovery industry in China. At present, surfactants have been successfully used in common oil reservoirs (first and second oil reservoirs) (CN 1458219A), but for high-temperature and high-mineralization oil reservoirs, surfactants with better effects on the first and second oil reservoirs cannot effectively reduce interfacial tension, and are characterized by changeable chemical structures, serious chromatographic separation and the like, so that the surfactant is insufficient. The invention relates to a hydrocarbon imidazoline polyoxypropylene polyoxyethylene ether carboxylate zwitterionic surfactant which is a novel amphoteric surfactant, has high interfacial activity, can well solve the problems, and has good application prospect.
Disclosure of Invention
One of the technical problems to be solved by the invention is the problem of poor oil displacement efficiency of an oil displacement agent containing a surfactant in the prior art, and a novel hydrocarbon-based imidazoline polyoxypropylene polyoxyethylene ether carboxylate zwitterionic surfactant is provided. The alkyl imidazoline polyoxypropylene polyoxyethylene ether carboxylate zwitterionic surfactant has high interfacial activity, and can reach 10 under the condition of no alkali and high mineralization degree -3 The advantage of ultra-low interfacial tension of mN/m, thereby improving the recovery ratio of crude oil. The second technical problem to be solved by the invention is to provide a preparation method of the alkyl imidazoline polyoxypropylene polyoxyethylene ether carboxylate zwitterionic surfactant corresponding to the first technical problem. The method has the characteristics of simple process, mild reaction conditions, low equipment requirement and the like. The invention aims to solve the third technical problem that the alkyl imidazoline polyoxypropylene polyoxyethylene ether carboxylate zwitterionic surfactant corresponding to one of the technical problems is applied to the improvement of the crude oil recovery ratio in the oil field.
In order to solve one of the problems, the invention adopts the following technical scheme: a hydrocarbon imidazoline polyoxypropylene polyoxyethylene ether carboxylate zwitterionic surfactant has a molecular general formula:
in the formula (1), R 1 Is C 8 -C 22 Is a hydrocarbon group of (2); m is the polymerization degree of polyethylene polyamine, x is the polymerization degree of polyoxypropylene, y is the polymerization degree of polyoxyethylene, m=any one integer from 0 to 6, x=any one number from 0 to 20, and y=any one number from 1 to 20; m is selected from a cation or cationic group that charge balances formula (1); n is the reciprocal of the absolute value of the M valence; x is a halogen ion.
In the above technical solution, R is 1 Preferably C 12 ～C 16 Alkyl, C of (2) 12 ～C 16 Alkenyl, C 12 ～C 16 At least one of the aryl groups of (a).
In the above technical solution, the value range of m is preferably 0 to 2.
In the above technical solution, M is preferably any one selected from ammonium ion, alkali metal ion, and alkaline earth metal ion, and when M is ammonium ion or alkali metal ion, n is 1; when M is an alkaline earth metal, n is 0.5; further preferably, the alkali metal ion is preferably selected from any of sodium ion and potassium ion, and the alkaline earth metal ion is preferably selected from any of calcium ion and magnesium ion.
In the above technical solution, the X is preferably Cl.
In order to solve the second technical problem, the invention adopts the following technical scheme: the preparation method of the alkyl imidazoline polyoxypropylene polyoxyethylene ether carboxylate zwitterionic surfactant in any one of the technical schemes solves the technical problems comprises the following steps:
a) With hydrocarbon radicals R 1 According to the mol ratio of 1:1.05, under the reaction temperature of 85-160 ℃ and the action of an alkaline catalyst, the generated methanol is distilled out while reacting, and the reaction is carried out for 1-10 hours, so as to obtain the alkyl imidazoline;
b) Under the action of an alkaline catalyst, reacting the alkyl imidazoline with the required amount of propylene oxide and ethylene oxide to obtain alkyl imidazoline polyoxypropylene polyoxyethylene ether;
c) Dissolving the alkyl imidazoline polyoxypropylene polyoxyethylene ether obtained in the step a) into a solvent, adding alkali according to the molar ratio of 1 (2-4), carrying out an alkalization reaction, and then adding a carboxylation reagent according to the molar ratio of 1 (2-4), and carrying out a carboxylation reaction to obtain the alkyl imidazoline polyoxypropylene polyoxyethylene ether carboxylate zwitterionic surfactant.
In the above technical solution, the alkaline catalyst in step a) and/or step c) is at least one of an alkali metal hydroxide or an alkaline earth metal hydroxide.
In the technical scheme, the reaction temperature of the methyl alkyl acid ester and polyethylene polyamine in the step a) is 120-150 ℃ and the reaction time is 6-8 hours.
In the above technical scheme, the solvent in the step c) is selected from benzene, the alkali is selected from sodium hydroxide, the alkalizing temperature is 30-80 ℃, preferably 40-60 ℃, and the reaction time is 0.5-3 hours, preferably 1-2 hours; the carboxylation reaction temperature is 50-100 ℃, preferably 60-80 ℃, and the reaction time is 6-18 hours, preferably 6-10 hours.
The obtained alkyl imidazoline polyoxypropylene polyoxyethylene ether carboxylate zwitterionic surfactant has good surface and interface activity and salt resistance, and can form lower interfacial tension on an oil-water interface, so that the alkyl imidazoline polyoxypropylene polyoxyethylene ether carboxylate zwitterionic surfactant is used for chemical flooding enhanced oil recovery and has wide application prospect and practical significance.
In order to solve the third technical problem of the invention, the technical scheme adopted by the invention is as follows: the application of the alkyl imidazoline polyoxypropylene polyoxyethylene ether carboxylate zwitterionic surfactant in the oil field for improving the crude oil recovery ratio is provided.
In the above technical solution, the application is not particularly limited, and for example, a specific method may be to inject an oil-displacing agent comprising 1 part by weight of the alkyl imidazoline polyoxypropylene polyoxyethylene ether carboxylate zwitterionic surfactant and 10 to 2000 parts by weight of water into an oil-containing stratum. The water used may be any one or more of deionized water, oilfield injection water, formation water, sea water, rainwater, river water and the like with the total degree of mineralization ranging from 0 to 300000mg/L, preferably water with the total degree of mineralization ranging from 1000 to 50000mg/L, and more preferably oilfield injection water from the aspects of convenience in construction, water conservation, and the like, for example, victory oilfield injection water used in the embodiment of the invention has the composition shown in table 1. In order to increase the oil displacement effect, the oil displacement agent of the invention can also comprise additives commonly used in the field, such as small molecule alcohols, DMSO, diethanolamine, CTAC and the like.
By adopting the technical scheme of the inventionThe interfacial tension between the alkyl imidazoline polyoxypropylene polyoxyethylene ether carboxylate zwitterionic surfactant and crude oil of Shengli oil field can reach 10 under the condition that the total degree of mineralization is 0-300000mg/L and the temperature is 70-90 DEG C -4 mN/m, on the basis of water flooding, can further improve the recovery ratio by more than 11.9%, and obtain better technical effect.
The invention is further illustrated by the following examples.
Drawings
FIG. 1 is an infrared spectrum of a hexadecyl imidazoline polyoxyethylene (5) ether carboxylate zwitterionic surfactant of example 2.
Detailed Description
[ example 1 ]
1. Synthesis of laurylimidazoline polyoxyethylene (2) ether carboxylate
a) Methyl laurate and diethylenetriamine are reacted for 8 hours under the action of potassium hydroxide catalyst at the reaction temperature of 145 ℃ according to the mol ratio of 1:1.05, and the generated methanol is distilled off at the same time to obtain the lauryl imidazoline.
b) Adding the lauryl imidazoline synthesized in the step a) into a reactor provided with a condensing device, a stirring device and a gas disperser, adding 1% sodium hydroxide by weight, heating to 85 ℃ while introducing nitrogen, and stirring for reaction for 1 hour. Starting a vacuum system, vacuumizing and dehydrating for 1 hour at 90 ℃, purging with nitrogen for 4 times, then adjusting the reaction temperature of the system to 150 ℃, slowly introducing ethylene oxide according to the molar ratio of 1:2, and controlling the pressure to be less than or equal to 0.40MPa for reaction; after the reaction, the system is purged with nitrogen, and is neutralized and dehydrated after being cooled, thus obtaining the lauryl imidazoline polyoxyethylene (2) ether.
c) Dissolving the product obtained in the step b) into a benzene solvent, adding sodium hydroxide according to a molar ratio of 1:3, alkalizing for 1 hour at 60 ℃, adding sodium chloroacetate serving as a carboxylation reagent according to a molar ratio of 1:2.5, and reacting for 8 hours to obtain the lauryl imidazoline polyoxyethylene (2) ether carboxylate zwitterionic surfactant.
2. Evaluation of surfactant Performance
And (3) preparing an oil displacement agent:
and (3) mixing 1 part by weight of the surfactant with 600 parts by weight of the winning injection water of the winning oil field to obtain the oil displacement agent for interfacial tension evaluation and oil displacement experiments. The compositions of the winning injection water for the winning fields used in all examples and comparative examples of the present invention are shown in Table 1. The compositions of the oil-displacing agents are listed in Table 2 for comparison.
Interfacial tension evaluation:
the interfacial tension results between the oil displacement agent and dehydrated crude oil of the victory oil field were measured using a TX-500C rotary drop interfacial tensiometer produced by texas university, usa at 80 ℃ and a rotational speed of 4500 rpm, and are shown in table 3.
[ example 2 ]
1. Synthesis of hexadecyl imidazoline polyoxyethylene (5) ether carboxylate
a) Methyl oleate and diethylenetriamine are reacted for 8 hours under the action of potassium hydroxide catalyst at the reaction temperature of 145 ℃ according to the mol ratio of 1:1.05, and the generated methanol is distilled out at the same time of reaction, so that the oil-based imidazoline is obtained.
b) Adding the hexadecyl imidazoline synthesized in the step a) into a reactor provided with a condensing device, a stirring device and a gas disperser, adding 1% sodium hydroxide by weight, heating to 85 ℃ while introducing nitrogen, and stirring for reaction for 1 hour. Starting a vacuum system, vacuumizing and dehydrating for 1 hour at 90 ℃, purging with nitrogen for 4 times, then adjusting the reaction temperature of the system to 150 ℃, slowly introducing ethylene oxide according to the molar ratio of 1:5, and controlling the pressure to be less than or equal to 0.40MPa for reaction; after the reaction is finished, the nitrogen is used for blowing the system, and the hexadecyl imidazoline polyoxyethylene (5) ether is obtained after the system is cooled, neutralized and dehydrated.
c) Dissolving the product obtained in the step b) into a benzene solvent, adding sodium hydroxide according to a molar ratio of 1:3, alkalizing for 1 hour at 60 ℃, adding sodium chloroacetate serving as a carboxylation reagent according to a molar ratio of 1:2.5, and reacting for 8 hours to obtain the hexadecyl imidazoline polyoxyethylene (5) ether carboxylate zwitterionic surfactant.
2. Structural characterization
The infrared spectrum of hexadecyl imidazoline polyoxyethylene ether carboxylate is shown in figure 1, and is prepared fromAs can be seen from the figure, 3454.9cm -1 A telescopic vibration absorption peak of-OH; 2922.4 and 2856.3cm -1 The telescopic vibration absorption peaks of-CH 3 and-CH 2-upper C-H are positioned; 1734.5cm -1 A telescopic vibration absorption peak at-c=o; 1649.0cm -1 At-c=n-stretching vibration absorption peak; 1458.8cm -1 The bending vibration absorption peak of saturated-C-H; 1097.1cm -1 The telescopic vibration absorption peak of-C-O is shown.
3. Evaluation of surfactant Performance
The performance evaluation method was the same as in example 1, except that the oil-displacing agent composition was different. For comparison, the compositions of the oil-displacing agents are shown in Table 2, and the evaluation results are shown in Table 3.
[ example 3 ]
1. Synthesis of octyl imidazoline carboxylate
a) Methyl octanoate and triethylene tetramine are reacted for 8 hours under the action of potassium hydroxide catalyst at the reaction temperature of 145 ℃ according to the mol ratio of 1:1.05, and methanol generated during the reaction is distilled out, so that the octyl imidazoline is obtained.
b) Adding the octyl imidazoline synthesized in the step a) into a reactor provided with a condensing device, a stirring device and a gas disperser, adding 1% sodium hydroxide, heating to 85 ℃ while introducing nitrogen, and stirring for reaction for 1 hour. Starting a vacuum system, vacuumizing and dehydrating for 1 hour at 90 ℃, purging with nitrogen for 4 times, then adjusting the reaction temperature of the system to 150 ℃, slowly introducing propylene oxide according to the molar ratio of 1:10, then slowly introducing ethylene oxide according to the molar ratio of 1:20, and controlling the pressure to be less than or equal to 0.40MPa for reaction; after the reaction is finished, the nitrogen is used for blowing the system, and after cooling, the system is neutralized and dehydrated, thus obtaining the octyl imidazoline polyoxypropylene (10) polyoxyethylene (20) ether.
c) Dissolving the product obtained in the step b) into a benzene solvent, adding sodium hydroxide according to a molar ratio of 1:3, alkalizing for 1 hour at 60 ℃, adding sodium chloroacetate serving as a carboxylation reagent according to a molar ratio of 1:2.5, and reacting for 8 hours to obtain the octyl imidazoline polyoxypropylene (10) polyoxyethylene (20) ether carboxylate zwitterionic surfactant.
2. Evaluation of surfactant Performance
The performance evaluation method was the same as in example 1, except that the oil-displacing agent composition was different. For comparison, the compositions of the oil-displacing agents are shown in Table 2, and the evaluation results are shown in Table 3.
[ example 4 ]
1. Synthesis of behenyl imidazoline carboxylate
a) And (3) according to the molar ratio of the methyl docosylate to the diethylenetriamine of 1:1.05, under the reaction temperature of 145 ℃ and the action of a potassium hydroxide catalyst, the generated methanol is distilled off while reacting, and the reaction is carried out for 8 hours, so as to obtain the docosanyl imidazoline.
b) Adding the synthesized twenty-two alkyl imidazoline in the step a) into a reactor provided with a condensing device, a stirring device and a gas disperser, adding 1% sodium hydroxide, heating to 85 ℃ while introducing nitrogen, and stirring for reaction for 1 hour. Starting a vacuum system, vacuumizing and dehydrating for 1 hour at 90 ℃, purging with nitrogen for 4 times, then adjusting the reaction temperature of the system to 150 ℃, slowly introducing propylene oxide according to the molar ratio of 1:3, then slowly introducing ethylene oxide according to the molar ratio of 1:7, and controlling the pressure to be less than or equal to 0.40MPa for reaction; after the reaction is finished, the nitrogen is used for blowing the system, and the system is cooled, neutralized and dehydrated to obtain the behenyl imidazoline polyoxypropylene (3) polyoxyethylene (7) ether.
c) Dissolving the product obtained in the step b) into a benzene solvent, adding sodium hydroxide according to the molar ratio of 1:3, alkalizing for 1 hour at 60 ℃, adding sodium chloroacetate serving as a carboxylation reagent according to the molar ratio of 1:2.5, and reacting for 8 hours to obtain the didodecyl imidazoline polyoxypropylene (3) polyoxyethylene (7) ether carboxylate zwitterionic surfactant.
2. Evaluation of surfactant Performance
The performance evaluation method was the same as in example 1, except that the oil-displacing agent composition was different. For comparison, the compositions of the oil-displacing agents are shown in Table 2, and the evaluation results are shown in Table 3.
[ example 5 ]
1. Surfactant preparation
The surfactant synthesized in example 2 was used, except for the concentration of formulation.
2. Evaluation of oil-displacing agent Performance
The performance evaluation method was the same as in example 1, except that the oil-displacing agent composition was different. For comparison, the compositions of the oil-displacing agents are shown in Table 2, and the evaluation results are shown in Table 3.
[ example 6 ]
According to the physical simulation oil displacement effect test of the compound oil displacement system in the SY/T6424-2000 compound oil displacement system performance test method, the length is 30cm, the diameter is 2.5cm, and the permeability is 1.5m at 80 DEG C 2 And (3) carrying out a simulated oil displacement experiment on the core. Firstly, water flooding is carried out by using winning injection water of a winning oil field until the water content reaches 98%, after the water flooding is finished, 0.3pv (core pore volume) of the oil displacement agent is transferred, then the water flooding is carried out until the water content reaches 98%, and the crude oil recovery ratio is calculated and improved.
Oil displacement experiment evaluation is carried out on the oil displacement agents prepared in the method (example 2) and the oil displacement agent prepared in the method (example 5), and the oil recovery ratio of the oil is improved by 9.5% and 11.9% respectively
[ comparative example 1 ]
Evaluation method the same as in example 2 except that sodium petroleum sulfonate (Daqing refinery) was used instead of the cetylimidazoline imidazoline polyoxyethylene (4) ether carboxylate zwitterionic surfactant in example 2, the remainder being the same, an interfacial tension of 0.024mN/m was established between this composition and the crude oil of the victory oilfield.
The composition prepared above was subjected to oil displacement in the same manner as in example 6, and an increase in crude oil recovery of 3.8% was measured.
TABLE 1 victory oilfield injection water
Table 2 examples 1-5 oil-displacing agent composition
TABLE 3 interfacial tension Properties of oil-displacing agents examples 1-5
| Examples | Interfacial tension (mN/m) |
| 1 | 0.0033 |
| 2 | 0.00028 |
| 3 | 0.0085 |
| 4 | 0.0066 |
| 5 | 0.00013 |
Claims (10)
1. A hydrocarbon imidazoline polyoxypropylene polyoxyethylene ether carboxylate zwitterionic surfactant has a molecular general formula:
r in formula (1) 1 Is C 8 Alkyl of C12-C16, alkyl of C 22 Alkyl of (a); m is the polymerization degree of polyethylene polyamine, x is the polymerization degree of polyoxypropylene, y is the polymerization degree of polyoxyethylene, m=0-2, and m is not 0, x=0 to 20, y=2 to 20; m is selected from a cation or cationic group that charge balances formula (1); n is the reciprocal of the absolute value of the M valence; x is a halogen ion; the M is selected from ammoniumAny one of a root ion, an alkali metal ion, and an alkaline earth metal ion.
2. The hydrocarbylimidazoline polyoxypropylene polyoxyethylene ether carboxylate zwitterionic surfactant of claim 1, wherein when M is an ammonium ion or an alkali metal ion, n is 1; when M is an alkaline earth metal, n is 0.5.
3. The alkyl imidazoline polyoxypropylene polyoxyethylene ether carboxylate zwitterionic surfactant of claim 2, wherein the alkali metal ions are selected from sodium ions and potassium ions, and the alkaline earth metal ions are selected from calcium ions and magnesium ions.
4. A process for preparing the hydrocarbylimidazoline polyoxypropylene polyoxyethylene ether carboxylate zwitterionic surfactant of any one of claims 1-3, comprising the steps of:
a) With hydrocarbon radicals R 1 According to the mole ratio of 1 (1-1.5), under the reaction temperature of 85-160 ℃ and the action of an alkaline catalyst, the generated methanol is distilled out while reacting, and the reaction is carried out for 1-10 hours, so as to obtain the alkyl imidazoline;
b) Under the action of an alkaline catalyst, reacting the alkyl imidazoline with the required amount of propylene oxide and ethylene oxide to obtain alkyl imidazoline polyoxypropylene polyoxyethylene ether;
c) Dissolving the alkyl imidazoline polyoxypropylene polyoxyethylene ether obtained in the step b) into a solvent, adding alkali according to the molar ratio of 1 (2-4), carrying out an alkalization reaction, and then adding a carboxylation reagent according to the molar ratio of 1 (2-4), and carrying out a carboxylation reaction to obtain the alkyl imidazoline polyoxypropylene polyoxyethylene ether carboxylate zwitterionic surfactant.
5. The method for preparing a zwitterionic surfactant of a hydrocarbon-based imidazoline polyoxypropylene polyoxyethylene ether carboxylate as claimed in claim 4, wherein the basic catalyst in the step a) and/or the step c) is at least one of alkali metal hydroxide or alkaline earth metal hydroxide.
6. The method for preparing a zwitterionic surfactant of a hydrocarbon-based imidazoline polyoxypropylene polyoxyethylene ether carboxylate as claimed in claim 4, wherein the reaction temperature of the methyl ester of hydrocarbon-based acid and polyethylene polyamine in the step a) is 120-150 ℃ and the reaction time is 6-8 hours.
7. The process for preparing a zwitterionic surfactant of a hydrocarbyl imidazoline polyoxypropylene polyoxyethylene ether carboxylate according to claim 4, wherein step c) the solvent is selected from benzene, the base is selected from sodium hydroxide, the alkalization temperature is 30-80 ℃ and the reaction time is 0.5-3 hours; the carboxylation reaction temperature is 50-100 ℃ and the reaction time is 6-18 hours.
8. The process for preparing a zwitterionic surfactant of a hydrocarbyl imidazoline polyoxypropylene polyoxyethylene ether carboxylate according to claim 7, characterized in that in step c) the alkalizing temperature is 40-60 ℃ and the reaction time is 1-2 hours; the carboxylation reaction temperature is 60-80 ℃ and the reaction time is 6-10 hours.
9. Use of a hydrocarbyl imidazoline polyoxypropylene polyoxyethylene ether carboxylate zwitterionic surfactant of any one of claims 1-3 to enhance crude oil recovery.
10. The use according to claim 9, characterized by comprising the step of injecting an oil-displacing agent containing 1 part by weight of the surfactant and 10 to 2000 parts by weight of water into an oil-bearing formation.
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