CN110872357A - Polypeptide surfactant and preparation and application thereof - Google Patents

Polypeptide surfactant and preparation and application thereof Download PDF

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CN110872357A
CN110872357A CN201911074549.4A CN201911074549A CN110872357A CN 110872357 A CN110872357 A CN 110872357A CN 201911074549 A CN201911074549 A CN 201911074549A CN 110872357 A CN110872357 A CN 110872357A
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glutamyl
glycine
cysteinyl
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CN110872357B (en
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侯庆锋
王源源
王哲
郑晓波
沈健
莫宏
付磊
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Petrochina Co Ltd
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    • C07—ORGANIC CHEMISTRY
    • C07K—PEPTIDES
    • C07K5/00—Peptides containing up to four amino acids in a fully defined sequence; Derivatives thereof
    • C07K5/02—Peptides containing up to four amino acids in a fully defined sequence; Derivatives thereof containing at least one abnormal peptide link
    • C07K5/0215—Peptides containing up to four amino acids in a fully defined sequence; Derivatives thereof containing at least one abnormal peptide link containing natural amino acids, forming a peptide bond via their side chain functional group, e.g. epsilon-Lys, gamma-Glu
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    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
    • C09K8/584—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific surfactants
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Abstract

The invention discloses a polypeptide surfactant and preparation and application thereof. The structural formula of the polypeptide surfactant is as follows:
Figure DDA0002262010390000011
wherein
Figure DDA0002262010390000012
Are amino acid residues. The polypeptide surfactant can be used as an ion response oil displacement agent, the oil displacement agent is suitable for clean and efficient oil displacement of various oil fields, the problems that the existing chemical oil displacement agent is serious in residual pollution, difficult in demulsification, incapable of being recycled and the like are solved, and the environmental pollution and the problems of demulsification of the later-stage oil displacement agent and post-treatment of the oil displacement agent are reduced. The oil phase is the same as the chemical oil displacement agent widely used at presentCompared with the prior art, the oil displacement agent has the outstanding advantages of small environmental pollution, convenient emulsification-demulsification and convenient recovery and reuse, and can be used as an oil displacement agent for cleaning and high efficiency of various oil fields.

Description

Polypeptide surfactant and preparation and application thereof
Technical Field
The invention relates to the technical field of oil exploitation; in particular to a polypeptide surfactant and preparation and application thereof.
Background
Petroleum is one of the most important global strategic materials, and the stable yield and the high yield of the petroleum are one of the determinants related to the national safety and economic development speed.
Currently, the oil extraction field of China enters a tertiary oil displacement stage, and a large amount of anionic surfactants are used for oil displacement of oil fields. Although these chemical oil-displacing agents effectively improve the recovery efficiency of oil fields, they also cause severe pollution to the formation and water quality. In addition, most of anionic surfactants have good emulsification effect, but also have the serious defects of difficult demulsification and incapability of being reused, thereby causing the problems of huge subsequent treatment difficulty of produced liquid, difficult pollution treatment of the produced liquid and high treatment cost.
The design of a high-efficiency and environment-friendly oil displacement agent which is environment-friendly, convenient for emulsification-demulsification and reusable has become a key point and a hotspot of research in related fields.
The polypeptide surfactant is a kind of polypeptide molecule which is composed of amino acid residues and has the structural characteristics and properties of the surfactant. Compared with common amino acid surfactants, the polypeptide surfactant has higher molecular chain length, can form stronger steric hindrance, and realizes good stability of an emulsification system.
And various different chemical properties and spatial structures are arranged according to a preset design, so that the complementary advantages of different amino acid surfactants can be realized, and the effect which cannot be achieved by the common amino acid surfactants can be achieved. Compared with other types of surfactants, the polypeptide surfactant has better environmental friendliness and adjustability based on the structural characteristics of amino acid and the multi-selectivity of spatial arrangement combination, and is convenient for various targeted molecular designs and chemical modifications to meet the requirements of different practical applications.
How to realize good emulsification effect on crude oil through reasonable molecular design, and realizing demulsification and recycling of an oil displacement agent through a simple method, and realizing good emulsification-demulsification and recycling while exerting the environment-friendly advantage of the polypeptide surfactant is a reliable way for solving the current chemical problems.
Disclosure of Invention
Based on the background technology, the invention provides a polypeptide surfactant and preparation and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a polypeptide surfactant having the following structural formula:
Figure BDA0002262010370000021
wherein
Figure BDA0002262010370000022
Are amino acid residues.
In the preferred embodiment 2 of the present invention, the
Figure BDA0002262010370000023
Is composed of
Figure BDA0002262010370000024
Namely, the polypeptide surfactant is lauroyl sarcosine-gamma-L-glutamyl-L-cysteinyl-glycine polypeptide, and the structural formula is as follows:
Figure BDA0002262010370000025
in the preferred embodiment 3 of the present invention, the
Figure BDA0002262010370000026
Is oleoyl amino acid sodium (ramination A, C)17H33CONHCH3(CONHCH2CH3)6COONa), i.e. the polypeptide surfactant is oleoyl amino acid- γ -L-glutamyl-L-cysteinyl-glycine polypeptide, of the formula:
Figure BDA0002262010370000031
in a second aspect, the present invention provides a method for preparing the above polypeptide surfactant, comprising the steps of:
oxidized form of gamma-L-glutamyl-L-cysteinyl-glycine and
Figure BDA0002262010370000032
and heating the corresponding sodium amino acid serving as a raw material under an acidic condition to react to generate the polypeptide surfactant.
Preferably, the oxidized forms of gamma-L-glutamyl-L-cysteinyl-glycine and
Figure BDA0002262010370000033
the concrete steps of the reaction of the corresponding sodium amino acid comprise:
oxidized gamma-L-glutamyl-L-cysteinyl-glycine and
Figure BDA0002262010370000034
dissolving the corresponding sodium amino acid in water, adding acid, and heating and refluxing for reaction.
Preferably, the oxidized forms of gamma-L-glutamyl-L-cysteinyl-glycine and
Figure BDA0002262010370000035
mols of the corresponding sodium amino acidThe molar ratio is 1: 1.
Preferably, the acid is sulfuric acid, hydrochloric acid or nitric acid.
Preferably, the acid is concentrated sulfuric acid, and the volume of the added concentrated sulfuric acid is 15% of the volume of water.
Preferably, the reaction is carried out for 2h under heating and reflux. During the specific reaction process, judging
Figure BDA0002262010370000036
The reaction was terminated until the amount of the corresponding sodium amino acid was no longer reduced.
In the preferred embodiment 2 of the present invention, the corresponding preparation method is:
the oxidized gamma-L-glutamyl-L-cysteinyl-glycine and sodium lauroyl sarcosine are used as raw materials, and are heated to react under an acidic condition to generate the polypeptide surfactant, wherein the reaction formula is as follows:
Figure BDA0002262010370000041
in the preferred embodiment 3 of the present invention, the corresponding preparation method is:
oxidized form of gamma-L-glutamyl-L-cysteinyl-glycine and sodium oleoyl-amino acid (Ramipron A, C)17H33CONHCH3(CONHCH2CH3)6COONa) as a raw material, and heating the raw material under an acidic condition to react to generate the polypeptide surfactant, wherein the reaction formula is as follows:
Figure BDA0002262010370000042
preferably, the oxidized gamma-L-glutamyl-L-cysteinyl-glycine is obtained by oxidizing reduced gamma-L-glutamyl-L-cysteinyl-glycine serving as a raw material with hydrogen peroxide under an alkaline condition; the reaction formula is as follows:
Figure BDA0002262010370000043
preferably, the reduced γ -L-glutamyl-L-cysteinyl-glycine is prepared by the following steps:
firstly, 2- [ N- (N-benzyl-prolyl) amino ] benzophenone 1 (namely, a hand type auxiliary agent BPB), nickel chloride hexahydrate and L-glutamic acid react to obtain a glutamic acid Schiff base Ni (II) complex 2;
then, the compound is reacted with S-benzyl-L-cysteine by a diisopropyl carbodiimide (DIC)/1-hydroxy-benzotriazole (HOBt) compound condensing agent method to obtain an S-benzyl-gamma-L-glutamyl-L-cysteine Schiff base Ni (II) complex 3;
then, the same DIC/HOBt composite condensing agent method is adopted to react with glycine to obtain an S-benzyl-gamma-L-glutamyl-L-cysteinyl-glycine Schiff base Ni (II) complex 4;
then dilute acid hydrolyzes the complex 4 to obtain S-benzyl-gamma-L-glutamyl-L-cysteinyl-glycine 5;
and finally, removing S-benzyl by adopting ammonium formate catalytic transfer hydrogenation to obtain the gamma-L-glutamyl-L-cysteinyl-glycine 6.
The reaction formula is as follows:
Figure BDA0002262010370000051
the second aspect of the invention provides the application of the polypeptide surfactant in oil displacement of oil fields.
Preferably, the polypeptide surfactant acts as an ion-responsive oil-displacing agent, or as an oil-displacing agent component.
The polypeptide surfactant can be used as an ion response oil displacement agent, the oil displacement agent is suitable for clean and efficient oil displacement of various oil fields, the problems that the existing chemical oil displacement agent is serious in residual pollution, difficult in demulsification, incapable of being recycled and the like are solved, and the environmental pollution and the problems of demulsification of the later-stage oil displacement agent and post-treatment of the oil displacement agent are reduced. Compared with the chemical oil displacement agent which is widely used at present, the oil displacement agent has the outstanding advantages of small environmental pollution, convenient emulsification-demulsification and convenient recovery and reuse, and can be used as an oil displacement agent for cleaning and high efficiency of various oil fields.
Drawings
FIG. 1 is an IR spectrum of lauroyl sarcosine- γ -L-glutamyl-L-cysteinyl-glycine polypeptide prepared in example 2.
Figure 2 is a graph of the results of an epitonia test of different concentrations of lauroylsarcosine-gamma-L-glutamyl-L-cysteinyl-glycine polypeptide.
Figure 3 is a graph of viscosity measurements of lauroylsarcosine-gamma-L-glutamyl-L-cysteinyl-glycine polypeptides at various concentrations.
FIG. 4 shows the results of measurement of the emulsifying effect of lauroyl sarcosine- γ -L-glutamyl-L-cysteinyl-glycine polypeptide at a water content of 10%.
FIG. 5 shows the results of measurement of the emulsifying effect of lauroyl sarcosine- γ -L-glutamyl-L-cysteinyl-glycine polypeptide at a water content of 20%.
FIG. 6 shows the results of measurement of the emulsifying effect of lauroyl sarcosine- γ -L-glutamyl-L-cysteinyl-glycine polypeptide at a water content of 30%.
FIG. 7 shows the results of measurement of the emulsifying effect of lauroyl sarcosine- γ -L-glutamyl-L-cysteinyl-glycine polypeptide at a water content of 40%.
FIG. 8 is a photograph showing the emulsification effect of lauroyl sarcosine-gamma-L-glutamyl-L-cysteinyl-glycine polypeptide at 30 ℃ under different pH conditions.
FIG. 9 shows the foaming ratio of lauroyl sarcosine-gamma-L-glutamyl-L-cysteinyl-glycine polypeptide at 30 ℃ under different pH values.
FIG. 10 is a photograph showing the emulsification effect of lauroyl sarcosine-gamma-L-glutamyl-L-cysteinyl-glycine polypeptide at 70 ℃ under different pH conditions.
FIG. 11 shows the foaming ratio of lauroyl sarcosine- γ -L-glutamyl-L-cysteinyl-glycine polypeptide at 70 ℃ under different pH conditions.
FIG. 12 shows the recovery rates of lauroyl sarcosine-gamma-L-glutamyl-L-cysteinyl-glycine polypeptide oil-displacing agents at different pH values.
FIG. 13 is an IR spectrum of oleoyl amino acid- γ -L-glutamyl-L-cysteinyl-glycine polypeptide prepared in example 3.
Figure 14 is the results of an epitension test of various concentrations of oleoyl amino acid-gamma-L-glutamyl-L-cysteinyl-glycine polypeptide.
Figure 15 is the results of viscosity measurements of oleoyl amino acid- γ -L-glutamyl-L-cysteinyl-glycine polypeptides at different concentrations.
FIG. 16 shows the results of measurement of the emulsifying effect of oleoyl amino acid-gamma-L-glutamyl-L-cysteinyl-glycine polypeptide at a water content of 10%.
FIG. 17 shows the results of measurement of the emulsifying effect of oleoyl amino acid-gamma-L-glutamyl-L-cysteinyl-glycine polypeptide at a water content of 20%.
FIG. 18 shows the results of measurement of the emulsifying effect of oleoyl amino acid-gamma-L-glutamyl-L-cysteinyl-glycine polypeptide at a water content of 30%.
FIG. 19 shows the results of measurement of the emulsifying effect of oleoyl amino acid-gamma-L-glutamyl-L-cysteinyl-glycine polypeptide at a water content of 40%.
FIG. 20 is a photograph showing the emulsification effect of oleoyl amino acid-gamma-L-glutamyl-L-cysteinyl-glycine polypeptide at 30 ℃ under different pH conditions.
FIG. 21 shows the foaming ratio of oleoyl amino acid-gamma-L-glutamyl-L-cysteinyl-glycine polypeptide at 30 ℃ under different pH conditions.
FIG. 22 is a photograph showing the effect of oleoyl amino acid-gamma-L-glutamyl-L-cysteinyl-glycine polypeptide emulsification at 70 ℃ under different pH conditions.
FIG. 23 shows the foaming ratio of oleoyl amino acid-gamma-L-glutamyl-L-cysteinyl-glycine polypeptide at 70 ℃ under different pH conditions.
FIG. 24 shows the recovery rates of oleoyl amino acid-gamma-L-glutamyl-L-cysteinyl-glycine polypeptide oil-displacing agents at different pH values.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
Example 1
This example synthesizes oxidized form gamma-L-glutamyl-L-cysteinyl-glycine according to the following reaction formula:
Figure BDA0002262010370000081
1) synthesis of glutamic acid Schiff base Ni (II) complex 2
2- [ N- (N-benzyl-prolyl) amino ] benzophenone (namely, the chiral auxiliary BPB) (1.92g), nickel chloride hexahydrate (2.38g) and L-glutamic acid (3.68g) are dissolved in 17.5mL of methanol, stirred under the protection of nitrogen and heated to 40-50 ℃. Adding a potassium hydroxide (4.49g dissolved in 15mL of MeOH) solution, stirring at 55-65 ℃ for reacting for 2h, cooling to room temperature, and pouring the mixture into 200mL of water (4.6 mL containing glacial acetic acid) under stirring to precipitate a large amount of crystals. Filtration and washing of the crystals twice with water. Recrystallizing the crude product by using acetone, and drying the crude product in vacuum at 60 ℃ to obtain the glutamic acid Schiff base Ni (II) complex 2.
2) Synthesis of S-benzyl-gamma-L-glutamyl-L-cysteine Schiff base Ni (II) complex 3
Dissolving the complex 2(2.85g) in 20mL of N, N-Dimethylformamide (DMF), stirring and dissolving at room temperature under the protection of nitrogen, adding DIC (N, N' -diisopropylcarbodiimide, 1.01mL) and HOBt (1-hydroxybenzotriazole, 0.68g), reacting at room temperature for 8h, and filtering to obtain a filtrate, namely an activated ester solution. S-benzyl-L-cysteine (1.06g) was dissolved in 20mL DMF (N, N-dimethylformamide) and about 3mL N, O-bistrimethylsilylacetamide (BSA, C)8H21NOSi2) And (3) dissolving, slightly heating until the solution is basically clear, slowly dropwise adding the solution into the activated ester solution, and reacting for 1 hour at room temperature. The mixture was filtered, and the filtrate was poured into 100mL of water to precipitate a large amount of crystals. Filtration and washing of the crystals twice with water. Purifying the crude product by silica gel column chromatography, eluting V (acetone) to V (normal hexane) to V (glacial acetic acid) at the ratio of 6 to 4 to 0.7, and drying in vacuum at 60 ℃ to obtain the S-benzyl-gamma-L-glutamyl-L-cysteine Schiff base Ni (II) complex 3.
3) Synthesis of S-benzyl-gamma-L-glutamyl-L-cysteinyl-glycine Schiff base Ni (II) complex 4
Dissolving the complex 3(3.82g) in 20mL of DMF (dimethyl formamide), stirring and dissolving at room temperature under the protection of nitrogen, adding DIC (1.01mL) and HOBt (0.68g), reacting at room temperature for 2h, and filtering to obtain a filtrate, namely the activated ester solution. Glycine (0.38g) was added to the above activated ester solution and reacted at room temperature for 1 hour. The mixture was filtered, and the filtrate was poured into 100mL of water to precipitate a large amount of crystals. Filtration and washing of the crystals twice with water. Purifying the crude product by silica gel column chromatography, eluting with V V (acetone) to V (n-hexane) to V (glacial acetic acid) at the ratio of 6: 4: 1, and vacuum drying at 60 ℃ to obtain the S-benzyl-gamma-L-glutamyl-L-cysteinyl-glycine Schiff base Ni (II) complex 4.
4) Synthesis of S-benzyl-gamma-L-glutamyl-L-cysteinyl-glycine 5
Complex 4(4.10g) was dissolved in 20mL MeOH and slowly added dropwise to 20mL of 70 deg.C mixture [ V (3mol L)-1Hydrochloric acid (HCl) to (V) (MeOH) 1:1]Stirring, reacting until red color disappears, evaporating to remove the solvent, adding to pH 7, adding chloroform for extraction, evaporating to remove the solvent in an organic phase, recrystallizing with anhydrous ethanol, recovering the chiral auxiliary 1, transferring water to a cation exchange column, leaching with water, leaching with ammonia water, collecting the solution, evaporating to dryness, recrystallizing with water, and drying at 60 ℃ to obtain S-benzyl-gamma-L-glutamyl-L-cysteinyl-glycine 5.
5) Synthesis of reduced gamma-L-glutamyl-L-cysteinyl-glycine 6
Dissolving the complex 5(0.40g) in 20mL of MeOH, adding 0.20g of 10% palladium-carbon hydrogenation catalyst (Pd/C) and ammonium formate (0.13g) into the MeOH for five times, heating and refluxing for 10h, cooling and filtering the reaction product, washing the Pd/C twice with the MeOH, combining the filtrates, evaporating the solvent, dissolving the crude product in 5mL of water, transferring the crude product into a cation exchange column, leaching the cation exchange column with water, leaching the cation exchange column with ammonia water, collecting the solution, evaporating the solution to dryness, recrystallizing the crude product with water, and drying the recrystallization product in vacuum at 60 ℃ to obtain the reduced gamma-L-glutamyl-L-cysteinyl-glycine 6.
6) Synthesis of oxidized gamma-L-glutamyl-L-cysteinyl-glycine 7
The method comprises the steps of taking reduced gamma-L-glutamyl-L-cysteinyl-glycine 6 as a raw material, and oxidizing the raw material by hydrogen peroxide under an alkaline condition to obtain oxidized gamma-L-glutamyl-L-cysteinyl-glycine 7.
Example 2
This example synthesizes lauroyl sarcosine-gamma-L-glutamyl-L-cysteinyl-glycine polypeptide according to the following reaction formula:
Figure BDA0002262010370000101
taking 6.12g of oxidized gamma-L-glutamyl-L-cysteinyl-glycine and 2.93g of sodium lauroyl sarcosine as raw materials, dissolving the raw materials in 100mL of water, adding 15mL of concentrated sulfuric acid, and refluxing for 2h by introducing condensed water at 100 ℃. The final product is lauroyl sarcosine-gamma-L-glutamyl-L-cysteinyl-glycine polypeptide.
FIG. 1 is an IR spectrum of lauroyl sarcosine-gamma-L-glutamyl-L-cysteinyl-glycine polypeptide 3000-3600cm-1The absorption peaks of (1) are N-H and water peaks (sample is easy to absorb moisture and contains a small amount of water), 1645cm-1The absorption peak at (A) is C ═ O, 705cm-1The absorption peak at (A) is-OH.
And (3) performance testing:
firstly, the surface tension of lauroyl sarcosine-gamma-L-glutamyl-L-cysteinyl-glycine polypeptide under different concentrations is measured
The surface tension of the solution was measured by a surface tension meter by adding the above-mentioned oil-displacing agent at various concentrations to 100mL of water, and the measurement results were averaged over 3 effective samples, as shown in fig. 2, from which it was seen that the addition of the ion-responsive surfactant caused a significant decrease in the surface tension of the solution.
Secondly, the viscosity of lauroyl sarcosine-gamma-L-glutamyl-L-cysteinyl-glycine polypeptide is measured under different concentrations
The oil displacement agent is prepared by mixing 50% of water and 50% of white oil (volume ratio), measuring the viscosity of the oil displacement agent at different concentrations by a rotational viscometer at 25 ℃, and taking the average value of 3 effective samples, wherein the measurement result is shown in figure 3, and as can be seen from figure 3, the addition of the ion response surfactant can obviously reduce the oil/water interfacial viscosity and the interfacial aging phenomenon.
Thirdly, the emulsification effect of lauroyl sarcosine-gamma-L-glutamyl-L-cysteinyl-glycine polypeptide is measured at different water contents
Simulated ion water in Daqing is used to replace underground water, and white oil is used to replace crude oil. Emulsifying by adding 0.3% surfactant at different oil-water ratio and mechanically stirring for 2min, and observing the emulsifying effect under microscope, wherein the emulsifying effect is shown in fig. 4-7.
As can be seen from the microscopic image, the foam size is obviously increased as the water content is increased, and when the water content of the system is more than 20%, the foam surface also presents an obvious emulsion layer. Therefore, the polypeptide surfactant has a good emulsifying effect and can be used as a high-efficiency oil displacement agent.
Fourth, testing pH value at 30 ℃ on emulsification effect
In the experiment, Daqing simulated ionic water is used for replacing underground water (the mineralization degree is 10000), and white oil is used for replacing crude oil. The oil displacement agent is emulsified in a mode of adding 0.3% of surfactant according to the oil-water ratio of 1:1, mechanically stirring for 2min, recording the foaming ratio, standing for 48 hours, observing the height change of an emulsion layer in different time periods, and effectively analyzing the oil displacement effect of the oil displacement agent according to the height of the emulsion layer and the height of foam, wherein the higher the height of the emulsion layer and the height of the foam is, the better the emulsion effect is, the higher the oil displacement efficiency is, and the more difficult the emulsion breaking is.
The photograph of the emulsification effect at 30 ℃ under different pH values is shown in FIG. 8, wherein the pH values are 2, 4, 6, 8, 10 and 12 from left to right; FIG. 9 shows the foaming ratios at 30 ℃ and different pH values.
As can be seen from fig. 8 and 9, the oil displacement agent has a good emulsification effect when the pH value is about 10, and has a good oil displacement effect when the foaming capacity is 229%, but when the pH value of the system is 2 or 4, the height of the emulsification layer and the height of the foam are low, so that the emulsification stability is poor, the emulsion breaking is easy, and the good emulsification-emulsion breaking effect can be realized only by reasonably adjusting the H ion concentration of the system.
Fifth, test of pH value at 70 deg.C to emulsification effect
Ground water (degree of mineralization 10000) is replaced by Daqing simulated ion water, and crude oil is replaced by white oil. The oil displacement agent is emulsified in a mode of adding 0.3% of surfactant according to the oil-water ratio of 1:1, mechanically stirring for 2min, recording the foaming ratio, standing for 48 hours, observing the height change of an emulsion layer in different time periods, and effectively analyzing the oil displacement effect of the oil displacement agent according to the height of the emulsion layer and the height of foam, wherein the higher the height of the emulsion layer and the height of the foam is, the better the emulsion effect is, the higher the oil displacement efficiency is, and the more difficult the emulsion breaking is.
The photograph of the emulsification effect at 70 ℃ under different pH values is shown in FIG. 10, and the pH values are 2, 4, 6, 8, 10 and 12 from left to right; FIG. 11 shows the foaming ratios at 70 ℃ and different pH values.
As can be seen from fig. 10 and 11, the oil displacement agent has a good emulsification effect when the pH value is about 10, and has a foaming capacity of 170.67% and a good oil displacement effect, but when the pH value of the system is 2 or 4, the height of the emulsification layer and the height of the foam are low, so that the emulsification stability is poor, the emulsion breaking is easy, and the good emulsification-emulsion breaking effect can be achieved by only reasonably adjusting the H ion concentration of the system.
The combination of the performance tests of four and (30 ℃) and five (70 ℃) shows that under the conditions of low temperature and medium and high temperature, the oil displacement agent can realize good emulsification-demulsification effect by adjusting the concentration of H ions, namely, good recovery effect. The recovery rate is calculated according to the foaming capacity of the emulsifier under different pH values, the recovery curve is shown in figure 12, the recovery rate is increased and then decreased along with the change of the pH value of the system, and the recovery rate can reach 77 percent when the pH value of the system is 10 and is slightly alkaline.
Example 3
This example synthesizes oleoyl amino acid-gamma-L-glutamyl-L-cysteinyl-glycine polypeptide according to the following reaction formula:
Figure BDA0002262010370000121
taking 6.12g of oxidized gamma-L-glutamyl-L-cysteinyl-glycine and 7.1g of oleoyl sodium amino acid as raw materials, dissolving in 100mL of water, adding 15mL of concentrated sulfuric acid, and refluxing for 2h at 100 ℃ by introducing condensed water. The final product is oleoyl amino acid-gamma-L-glutamyl-L-cysteinyl-glycine polypeptide.
Wherein n is 5-7, and n is 6, R'＝CH3，R”＝CH2CH3。
FIG. 13 is an IR spectrum of oleoyl amino acid-gamma-L-glutamyl-L-cysteinyl-glycine polypeptide, 3000-3600cm-1The absorption peaks of (1) are N-H and water peaks (sample is easy to absorb moisture and contains a small amount of water), 2123cm-1The absorption peak of (A) is-CH2，1656cm-1The absorption peak is C ═ O, 1232cm-1The absorption peak at (A) is C-O.
And (3) performance testing:
firstly, the surface tension of oleoyl amino acid-gamma-L-glutamyl-L-cysteinyl-glycine polypeptide under different concentrations is measured
The above-mentioned oil displacing agents were added to 100mL of water at different concentrations, and the surface tension of the solution was measured by a surface tension meter, and the results were averaged out from 3 effective samples, and the measurement results are shown in fig. 14. As can be seen from fig. 14, the addition of the ion-responsive surfactant significantly reduced the surface tension of the solution.
Secondly, the viscosity of the oleoyl amino acid-gamma-L-glutamyl-L-cysteinyl-glycine polypeptide is measured under different concentrations
The oil displacement agent is prepared by mixing 50% of water and 50% of white oil (volume ratio), measuring the viscosity of the oil displacement agent at different concentrations by a rotary viscometer at 25 ℃, and taking the average value of 3 effective samples, wherein the measurement result is shown in figure 15, and as can be seen from figure 15, the addition of the ion response surfactant can obviously reduce the oil/water interfacial viscosity and the interfacial aging phenomenon.
Thirdly, the emulsification effect of the oleoyl amino acid-gamma-L-glutamyl-L-cysteinyl-glycine polypeptide is measured when different water contents are carried out
Simulated ion water in Daqing is used to replace underground water, and white oil is used to replace crude oil. Emulsifying by adding 0.3% surfactant at different oil-water ratio and mechanically stirring for 2min, and observing the emulsifying effect under microscope, wherein the emulsifying effect is shown in figures 16-19.
As can be seen from the microscopic image, the foam size is obviously increased as the water content is increased, and when the water content of the system is more than 20%, the foam surface also presents an obvious emulsion layer. Therefore, the polypeptide surfactant has a good emulsifying effect and can be used as a high-efficiency oil displacement agent.
Fourth, testing pH value at 30 ℃ on emulsification effect
In the experiment, Daqing simulated ionic water is used for replacing underground water (the mineralization degree is 10000), and white oil is used for replacing crude oil. The oil displacement agent is emulsified in a mode of adding 0.3% of surfactant according to the oil-water ratio of 1:1, mechanically stirring for 2min, recording the foaming ratio, standing for 48 hours, observing the height change of an emulsion layer in different time periods, and effectively analyzing the oil displacement effect of the oil displacement agent according to the height of the emulsion layer and the height of foam, wherein the higher the height of the emulsion layer and the height of the foam is, the better the emulsion effect is, the higher the oil displacement efficiency is, and the more difficult the emulsion breaking is.
The photograph of the emulsification effect at 30 ℃ under different pH values is shown in FIG. 20, wherein the pH values are 2, 4, 6, 8, 10 and 12 from left to right; FIG. 21 shows the foaming ratios at 30 ℃ and different pH values.
As can be seen from fig. 20 and 21, the oil displacement agent has good emulsification effect at a pH value of more than 6, i.e., good oil displacement effect, and has a foaming capacity of 290.33% at a pH value of 10. However, when the pH value of the system is 2, the height of an emulsion layer and the height of foam are lower, so that the emulsion stability is poor, and the emulsion breaking is easy, so that the good emulsion-emulsion breaking effect can be realized only by reasonably adjusting the H ion concentration of the system.
Fifth, test of pH value at 70 deg.C to emulsification effect
Ground water (degree of mineralization 10000) is replaced by Daqing simulated ion water, and crude oil is replaced by white oil. The oil displacement agent is emulsified in a mode of adding 0.3% of surfactant according to the oil-water ratio of 1:1, mechanically stirring for 2min, recording the foaming ratio, standing for 48 hours, observing the height change of an emulsion layer in different time periods, and effectively analyzing the oil displacement effect of the oil displacement agent according to the height of the emulsion layer and the height of foam, wherein the higher the height of the emulsion layer and the height of the foam is, the better the emulsion effect is, the higher the oil displacement efficiency is, and the more difficult the emulsion breaking is.
The photograph of the emulsification effect at 70 ℃ under different pH values is shown in FIG. 22, wherein the pH values are 2, 4, 6, 8, 10 and 12 from left to right; FIG. 23 shows the foaming ratios at 70 ℃ and different pH values.
As can be seen from fig. 22 and 23, the oil displacement agent has a good emulsification effect at a pH of about 6 or 10, and the foaming capacities are 222% and 248.67%, respectively. The oil displacement agent has good oil displacement effect, but when the pH value of the system is 2, the height of an emulsion layer and the height of foam are lower, so that the emulsion stability is poor, and the emulsion breaking is easy, so that the good emulsion-emulsion breaking effect can be realized only by reasonably adjusting the H ion concentration of the system.
The combination of the performance tests of four and (30 ℃) and five (70 ℃) shows that under the conditions of low temperature and medium and high temperature, the oil displacement agent can realize good emulsification-demulsification effect by adjusting the concentration of H ions, namely, good recovery effect. The recovery rate is calculated according to the foaming capacity of the emulsifier under different pH values, the recovery curve is shown in figure 24, the recovery rate is increased and then decreased along with the change of the pH value of the system, and the recovery rate can reach as high as 78.5 percent when the pH value of the system is 10 and is slightly alkaline.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.

Claims (13)

1. A polypeptide surfactant, characterized in that it has the following structural formula:
Figure FDA0002262010360000011
wherein
Figure FDA0002262010360000012
Are amino acid residues.
2. The polypeptide surfactant of claim 1, wherein the polypeptide surfactant is a mixture of two or more of the above
Figure FDA0002262010360000013
Is composed of
Figure FDA0002262010360000014
3. A method for preparing the polypeptide surfactant of claim 1 or 2, comprising the steps of:
oxidized form of gamma-L-glutamyl-L-cysteinyl-glycine and
Figure FDA0002262010360000015
and heating the corresponding sodium amino acid serving as a raw material under an acidic condition to react to generate the polypeptide surfactant.
4. The method according to claim 3, wherein the oxidized forms of γ -L-glutamyl-L-cysteinyl-glycine and
Figure FDA0002262010360000016
the concrete steps of the reaction of the corresponding sodium amino acid comprise:
oxidized gamma-L-glutamyl-L-cysteinyl-glycine and
Figure FDA0002262010360000017
dissolving the corresponding sodium amino acid in water, adding acid, and heating and refluxing for reaction.
5. The method according to claim 4, wherein the oxidized forms of γ -L-glutamyl-L-cysteinyl-glycine and
Figure FDA0002262010360000018
corresponding amino acidThe molar ratio of sodium is 1: 1.
6. The method according to claim 4, wherein the acid is sulfuric acid, hydrochloric acid or nitric acid.
7. The method according to claim 4, wherein the acid is concentrated sulfuric acid, and the concentrated sulfuric acid is added in an amount of 15% by volume based on the volume of water.
8. The method according to claim 4, wherein the reaction is carried out under reflux for 2 hours.
9. The production method according to claim 3,
Figure FDA0002262010360000021
the corresponding sodium amino acid is sodium lauroyl sarcosinate.
10. The preparation method according to claim 3, wherein the oxidized γ -L-glutamyl-L-cysteinyl-glycine is obtained by oxidizing reduced γ -L-glutamyl-L-cysteinyl-glycine with hydrogen peroxide under alkaline conditions.
11. The method according to claim 10, wherein the reduced form of γ -L-glutamyl-L-cysteinyl-glycine is prepared by:
firstly, 2- [ N- (N-benzyl-prolyl) amino ] benzophenone, nickel chloride hexahydrate and L-glutamic acid react to obtain a glutamic acid Schiff base Ni (II) complex;
then, the compound condensing agent method of diisopropylcarbodiimide/1-hydroxy-benzotriazole is adopted to react with S-benzyl-L-cysteine to obtain an S-benzyl-gamma-L-glutamyl-L-cysteine Schiff base Ni (II) complex;
then, the compound is reacted with glycine by a diisopropyl carbodiimide/1-hydroxy-benzotriazole compound condensing agent method to obtain an S-benzyl-gamma-L-glutamyl-L-cysteinyl-glycine Schiff base Ni (II) complex;
then hydrolyzing the S-benzyl-gamma-L-glutamyl-L-cysteinyl-glycine Schiff base Ni (II) complex by dilute acid to obtain S-benzyl-gamma-L-glutamyl-L-cysteinyl-glycine;
and finally, removing S-benzyl by adopting ammonium formate catalytic transfer hydrogenation to obtain the gamma-L-glutamyl-L-cysteinyl-glycine.
12. Use of the polypeptide surfactant of claim 1 or 2 in oil displacement in oil fields.
13. The use according to claim 12, wherein the polypeptide surfactant is used as an ion-responsive oil-displacing agent, or as an oil-displacing agent component.
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