WO2024001705A1 - 一种生物复合驱油体系的评价与构建方法 - Google Patents
一种生物复合驱油体系的评价与构建方法 Download PDFInfo
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- WO2024001705A1 WO2024001705A1 PCT/CN2023/098747 CN2023098747W WO2024001705A1 WO 2024001705 A1 WO2024001705 A1 WO 2024001705A1 CN 2023098747 W CN2023098747 W CN 2023098747W WO 2024001705 A1 WO2024001705 A1 WO 2024001705A1
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- oil displacement
- displacement system
- lipopeptide
- surfactant
- biological composite
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- 238000006073 displacement reaction Methods 0.000 title claims abstract description 69
- 239000002131 composite material Substances 0.000 title claims abstract description 30
- 238000011156 evaluation Methods 0.000 title claims abstract description 7
- 238000010276 construction Methods 0.000 title abstract description 4
- 239000004094 surface-active agent Substances 0.000 claims abstract description 80
- 108010028921 Lipopeptides Proteins 0.000 claims abstract description 50
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 claims abstract description 15
- 230000000694 effects Effects 0.000 claims abstract description 14
- 239000011259 mixed solution Substances 0.000 claims abstract description 14
- 238000004458 analytical method Methods 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims description 33
- 239000011173 biocomposite Substances 0.000 claims description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 238000001819 mass spectrum Methods 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 238000001514 detection method Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000007921 spray Substances 0.000 claims 1
- 238000002474 experimental method Methods 0.000 abstract description 4
- 230000000295 complement effect Effects 0.000 abstract description 2
- 239000003921 oil Substances 0.000 description 49
- 150000002500 ions Chemical class 0.000 description 22
- 239000003208 petroleum Substances 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 6
- 238000000855 fermentation Methods 0.000 description 5
- 230000004151 fermentation Effects 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 5
- 150000003871 sulfonates Chemical class 0.000 description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 244000063299 Bacillus subtilis Species 0.000 description 3
- 235000014469 Bacillus subtilis Nutrition 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 239000003876 biosurfactant Substances 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229920002401 polyacrylamide Polymers 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 229920001732 Lignosulfonate Polymers 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 238000000944 Soxhlet extraction Methods 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 235000021190 leftovers Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/16—Enhanced recovery methods for obtaining hydrocarbons
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A10/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE at coastal zones; at river basins
- Y02A10/40—Controlling or monitoring, e.g. of flood or hurricane; Forecasting, e.g. risk assessment or mapping
Definitions
- the invention belongs to the technical field of oil extraction and relates to a method for evaluation and construction of a biological composite oil displacement system.
- Oil displacing agents for tertiary oil recovery mainly include petroleum sulfonates, petroleum carboxylates, heavy alkyl benzene sulfonates, ⁇ -olefin sulfonates, lignin sulfonates, etc. These oil displacing agents are not only expensive, but also have poor degradability. They leave residues after use and can easily cause environmental pollution. At the same time, these oil displacing agents need to be compounded with alkali when used, which can easily form alkali scale, causing the formation permeability to decrease, which is not conducive to further exploitation of the remaining oil.
- the purpose of the present invention is to provide a method for evaluation and construction of a biocomposite oil displacement system.
- a method for evaluating a biological composite oil displacement system wherein the biological composite oil displacement system includes a synthetic surfactant and a lipopeptide surfactant.
- the evaluation method includes the following steps:
- Int (+) is the relative intensity of the mass-to-charge ratio under the positive ionization mode scan of the synthetic surfactant
- Int (+) (lipopeptide) is the positive ionization mode of the lipopeptide surfactant.
- the relative intensity of mass-to-charge ratio under scanning is the relative intensity of mass-to-charge ratio under negative ionization mode scanning of synthetic surfactant
- Int (-) (lipopeptide ) is the surface activity of lipopeptide
- step S1 the mass ratio of the synthetic surfactant to the lipopeptide surfactant is 1:10 to 10:1.
- step S1 the concentration of the lipopeptide surfactant in the mixed solution is 0.2g/L to 2.0g/L.
- the solvent is a mixed solvent of methanol or ethanol and water.
- volume content of the methanol or ethanol in the mixed solution is 50% to 100%.
- the electrospray mass spectrometry detection mode is the positive and negative ion detection mode
- the ion source injection voltage is 4.8kV
- the capillary voltage is 15V
- the capillary temperature is 320°C
- the sheath gas is nitrogen. 50arb, auxiliary gas 20arb, full scan mass spectrum range m/z100-1300.
- step S4 for multiple biocomposite oil displacement systems, the one with a larger R (-/+) has a stronger electrical complementarity between its surfactant and lipopeptide, and the system has a better oil displacement effect.
- a method of constructing a biological composite oil displacement system including: for a plurality of biological composite oil displacement systems composed of synthetic surfactants and lipopeptide surfactants of different types and/or different dosage ratios, using the method as claimed in claim 1
- a method of constructing a biological composite oil displacement system including: for a plurality of biological composite oil displacement systems composed of synthetic surfactants and lipopeptide surfactants of different types and/or different dosage ratios, using the method as claimed in claim 1
- the biocomposite oil displacement system at this median is used as a biomass to be used.
- Material composite oil displacement system Furthermore, the biocomposite oil displacement system with the largest R (-/+) is selected as the biocomposite oil displacement system to be used.
- the present invention uses the electrospray mass spectrometry (ESI-MS) method to measure the positive and negative ionization mass spectra of a mixed surfactant solution, and calculates the intensity ratio of the surfactants in the positive ionization mass spectrum and the negative ionization mass spectrum, as well as the positive ion strength.
- the ratio of the ratio to the negative ion intensity ratio Based on this ratio, the positive and negative ionization capabilities of the surfactant are judged, as well as their electrical complementarity in salt-containing systems.
- the larger the R (-/+) value the greater the positive and negative ionization properties.
- the greater the difference the stronger the electrical complementarity in a salt-containing ion atmosphere. Based on this, we can determine the surfactant with the best compounding effect with the lipopeptide biosurfactant, and then select the appropriate surfactant to construct a highly efficient Biocomposite oil displacement system.
- Electrospray mass spectrometry is a method for determining the mass-to-charge ratio of molecules.
- a liquid sample is sprayed into a mist in a vacuum by heating.
- the molecules including surfactants, are rapidly evaporated and dried, the molecules dissociate into ions or combined solutions.
- the ions in the ions have different abilities to form ions, and the mass-to-charge ratio intensity in the mass spectrum is different.
- Different surfactants have different abilities to form positive and negative ions. The greater their difference, one is easier to be negatively ionized and the other is easier to be positively ionized, the stronger their complementarity, the stronger the interaction, and the greater the synergy. The stronger they are, the ratio of their strengths can be used to represent their coordination, and an efficient biocomposite oil displacement system can be optimized.
- the present invention has the following characteristics:
- the invention provides a method for constructing a high-efficiency biological composite oil displacement system. Based on biological surfactant, another surfactant is added, and the mass spectrum of the two different surfactant mixed solutions is measured by electrospray mass spectrometry. , according to the intensity ratio of the surfactant, determine the positive and negative ionization capabilities of the surfactant, and select the appropriate surfactant compound accordingly.
- This method is simple to operate and easy to use. It simultaneously measures the mass spectra of positive and negative ions of surfactants in the same solution system, which facilitates the comparison of positive and negative ion strengths at the same concentration ratio, and thereby determines whether the two surfactants can be electrically complementary. , and quickly screen out surfactants and construct a biocomposite oil displacement system together with lipopeptides, overcoming the shortcomings of existing technologies that require a large number of experiments and a long cycle when selecting compound surfactants.
- Figure 1 is the electrospray mass spectrum in the positive ionization mode of Experimental Group 1 in Example 1;
- Figure 2 is the electrospray mass spectrum of experimental group 1 in the negative ionization mode in Example 1.
- Petroleum sulfonate is an industrial product of petroleum sulfonate produced by Daqing Refinery. It is dried at 130°C to remove water and other volatile matter; the dried solid is dissolved with isopropyl alcohol (v/v, 1:1) and n-pentane. , distribute, remove the unsulfonated matter in the upper layer of n-pentane; after the lower layer is dried, dissolve it with methanol to remove the insoluble salt, and finally dry it to obtain the petroleum sulfonate sample for experiment [Niu Ruixia, Long Biao, Li Bolin. Apply Soxhlet extraction technology Analysis of the composition of industrial petroleum sulfonates. Science, Technology and Engineering, 2011, 11(08).1740-1745.].
- lipopeptide fermentation liquid is obtained after fermentation of Bacillus subtilis; the fermentation liquid undergoes centrifugal sterilization, acidification and precipitation, freeze-drying, extraction with methanol dissolution, and drying to obtain lipopeptide samples [Liu XY, Haddad NIA, Yang SZ et al. Isolation and characterization of a C12-lipopeptide produced by Bacillus subtilis HSO 121. Journal of Peptide Science, 2008, 14: 864–875].
- Surfactant A is commercially available sodium dodecylbenzene sulfonate (AR, Shanghai Lingfeng Chemical Reagent Co., Ltd.).
- Surfactant B is commercially available sodium lauryl sulfate (AR, Shanghai Titan Technology Co., Ltd.).
- the electrospray mass spectrometry was measured using LCT Premier Auxiliary gas 20arb, full scan mass spectrum range m/z100-1300.
- R (+) Int (+) (synthetic surfactant) /Int (+) (lipopeptide) (1)
- R (-) Int (-) (synthetic surfactant) /Int (-) (lipopeptide) (2)
- Int (+) is the relative intensity of the mass-to-charge ratio under the positive ionization mode scan of the synthetic surfactant
- Int (+) (lipopeptide) is the positive ionization mode of the lipopeptide surfactant.
- Int (-) is the relative intensity of mass-to-charge ratio under negative ionization mode scanning of synthetic surfactant
- Int (-) (lipopeptide ) is the surface activity of lipopeptide
- R (-/+) R (-) /R (+) (3)
- the positive and negative ion intensity ratio R (-/+) is calculated according to formula (3).
- petroleum sulfonates and lipopeptides are used to construct a biological composite oil displacement system, and its oil displacement ability is evaluated.
- the specific process is as follows:
- surfactant A and lipopeptide are used to construct a biological composite oil displacement system, and its oil displacement ability is evaluated.
- the specific process is as follows:
- surfactant B and lipopeptide are used to construct a biological composite oil displacement system, and its oil displacement ability is evaluated.
- the specific process is as follows:
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Abstract
本发明涉及一种生物复合驱油体系的评价与构建方法,评价方法包括:首先将合成表面活性剂与脂肽表面活性剂配制成混合溶液,再进行电喷雾质谱分析,并计算正、负离子化模式下的合成表面活性剂与脂肽表面活性剂的质荷比相对强度比R(+)与R(-), R(-/+)=R(-)/R(+) (3) 最后依照式(3)计算正负离子强度比值R(-/+),即代表该生物复合驱油体系的驱油效果。与现有技术相比,本发明简单、快捷,不需要大量的实验,即可判断两种表面活性剂间是否能够电性互补,并据此快速筛选出表面活性剂与脂肽的有效复配,构建生物复合驱油体系。
Description
本发明属于石油开采技术领域,涉及一种生物复合驱油体系的评价与构建方法。
三次采油用驱油剂主要包括石油磺酸盐、石油羧酸盐、重烷基苯磺酸盐、α-烯烃磺酸盐、木质素磺酸盐等。这些驱油剂不仅价格昂贵,而且降解性很差,使用后有残留,易造成环境污染。同时,这些驱油剂在使用时都须要与碱复配,极易形成碱垢,使得地层渗透率下降,不利于剩余油的进一步开采。
大部分的表面活性剂来源于石油,并广泛地应用于石油开采,石油资源又十分紧张,因此采用来源广泛、价格低廉、可再生的生物表面活性剂具有十分重要的意义。食品加工业的边角料等都可以作为生物表面活性剂的原材料。
研究和应用实践证明,复配表面活性剂往往比单一表面活性剂驱油效果更佳。在实践过程中,一般通过实验的方法筛选出两者复配效果最佳的表面活性剂,但该方法存在实验过程复杂、耗时多、结果影响因素多的问题。
发明内容
本发明的目的就是提供一种生物复合驱油体系的评价与构建方法。
本发明的目的可以通过以下技术方案来实现:
一种评价生物复合驱油体系的方法,其中生物复合驱油体系包括合成表面活性剂与脂肽表面活性剂,该评价方法包括以下步骤:
S1:将合成表面活性剂与脂肽表面活性剂配制成混合溶液;
S2:对混合溶液进行电喷雾质谱分析,并分别获得正、负离子化的质谱;
S3:依照式(1)与式(2)分别计算混合溶液的正离子强度比R(+)和负离子强度比R(-);
R(+)=Int(+)(合成表面活性剂)/Int(+)(脂肽) (1)
R(-)=Int(-)(合成表面活性剂)/Int(-)(脂肽) (2)
R(+)=Int(+)(合成表面活性剂)/Int(+)(脂肽) (1)
R(-)=Int(-)(合成表面活性剂)/Int(-)(脂肽) (2)
其中,Int(+)(合成表面活性剂)为合成表面活性剂的正离子化模式扫描下的质荷比相对强度,Int(+)(脂肽)为脂肽表面活性剂的正离子化模式扫描下的质荷比相对强度;Int(-)(合成表面活性剂)为合成表面活性剂的负离子化模式扫描下的质荷比相对强度,Int(-)(脂
肽)为脂肽表面活性剂的负离子化模式扫描下的质荷比相对强度;
S4:
R(-/+)=R(-)/R(+) (3)
R(-/+)=R(-)/R(+) (3)
依照式(3)计算正负离子强度比值R(-/+),即代表该生物复合驱油体系的驱油效果,R(-/+)较大者,代表其驱油效果较好。
进一步地,步骤S1中,所述的合成表面活性剂与脂肽表面活性剂的质量比为1:10~10:1。
进一步地,步骤S1中,所述的混合溶液中,脂肽表面活性剂的浓度为0.2g/L~2.0g/L。
进一步地,步骤S1中,所述的混合溶液中,溶剂为甲醇或乙醇与水的混合溶剂。
进一步地,所述的甲醇或乙醇在混合溶液中的体积含量为50%~100%。
进一步地,步骤S2中,所述的电喷雾质谱分析中,电喷雾质谱检测模式是正、负离子检测模式,离子源喷射电压是4.8kV,毛细管电压是15V,毛细管温度为320℃,鞘气为氮气50arb,辅助气20arb,全扫描质谱范围m/z100-1300。
进一步地,步骤S4中,对于多个生物复合驱油体系,R(-/+)较大者,其表面活性剂与脂肽的电性互补性越强,体系驱油效果较好。
一种构建生物复合驱油体系的方法,包括:对于多个由不同种类和/或不同用量配比的合成表面活性剂与脂肽表面活性剂组成的生物复合驱油体系,采用如权利要求1至7任一项所述的一种评价生物复合驱油体系的方法,计算其R(-/+),并选择R(-/+)≥1的生物复合驱油体系作为待用生物复合驱油体系。
一种构建生物复合驱油体系的方法,包括:对于多个由不同种类和/或不同用量配比的合成表面活性剂与脂肽表面活性剂组成的生物复合驱油体系,采用如权利要求1至7任一项所述的一种评价生物复合驱油体系的方法,计算其R(-/+)以及多个R(-/+)的中位数,选择R(-/+)不低于该中位数的生物复合驱油体系,作为待用生
物复合驱油体系。进一步地,选择R(-/+)最大的生物复合驱油体系作为待用生物复合驱油体系。
本发明利用电喷雾质谱(ESI-MS)法测定混合表面活性剂溶液的正、负离子化的质谱图,计算正离子化质谱图和负离子化质谱图中表面活性剂的强度比,以及正离子强度比与负离子强度比之比值,根据该比值判断表面活性剂的正、负离子化能力,及其在含盐体系中的电性互补性,R(-/+)值越大表示正负离子化电性的差异越大,在含盐离子氛下,电性互补性越强,据此确定与脂肽生物表面活性剂复配效果最佳的表面活性剂,进而选择出合适的表面活性剂以构建高效生物复合驱油体系。
电喷雾质谱是一种测定分子的质荷比的方法,液体样品通过加热在真空中喷成雾状,其中的分子,包括表面活性剂在快速蒸发干燥时,因分子解离成离子或结合溶液中的离子,而形成离子的能力不一样,质谱中的质荷比强度则不同。不同的表面活性剂其形成正、负离子的能力不一样,他们的差异越大,一个更容易负离子化,另一个更容易正离子化,则他们互补性越强,相互作用越强,协同作用也越强,就可以用强度的比例来代表他们的协调作用,优选出高效的生物复合驱油体系。
与现有技术相比,本发明具有以下特点:
本发明提供了一种构建高效生物复合驱油体系的方法,以生物表面活性剂为基础,加入另一种表面活性剂,用电喷雾质谱法测定这两种不同表面活性剂混合溶液的质谱图,根据表面活性剂的强度比,判定表面活性剂的正、负离子化能力,据此选择合适的表面活性剂复配。该方法操作简单、使用方便,同时测定同一溶液体系中表面活性剂的正、负离子化的质谱,便于相同浓度比例下正负离子强度的比较,据此判断两种表面活性剂间是否能够电性互补,并快速筛选出表面活性剂并与脂肽一起构建生物复合驱油体系,克服了现有技术选择复配表面活性剂时需要大量实验,周期长的缺陷。
图1为实施例1中实验组1的正离子化模式下的电喷雾质谱图;
图2为实施例1中实验组1的负离子化模式下的电喷雾质谱图。
下面结合附图和具体实施例对本发明进行详细说明。本实施例以本发明技术方案为前提进行实施,给出了详细的实施方式和具体的操作过程,但本发明的保护范围不限于下述的实施例。
水解聚丙烯酰胺,濮阳市海之源化工实业有限公司的水解聚丙烯酰胺(水解度~15%,标称分子量2500-3000万)
石油磺酸盐系大庆炼化厂生产的石油磺酸盐的工业品,经过130℃烘干除水等易挥发物;干燥固体用水异丙醇(v/v,1:1)和正戊烷溶解、分配,除去上层正戊烷中未磺化物;下层干燥后,用甲醇溶解除去不溶解的盐,最后干燥得到实验用石油磺酸盐样品[牛瑞霞,龙彪,李柏林.应用索氏浸提技术分析工业石油磺酸盐组成.科学技术与工程,2011,11(08).1740-1745.]而得。
脂肽系枯草芽孢杆菌发酵制备:枯草芽孢杆菌发酵后得到脂肽发酵液;发酵液经过离心除菌,酸化沉淀,冷冻干燥,甲醇溶解萃取,干燥除甲醇后得到脂肽样品[Liu XY,Haddad NIA,Yang SZ et al.Isolation and characterization of a C12-lipopeptide produced by Bacillus subtilis HSO 121.Journal of Peptide Science,2008,14:864–875]。
表面活性剂A系市售十二烷基苯磺酸钠(AR,上海凌峰化学试剂有限公司)。
表面活性剂B系市售十二烷基硫酸钠(AR,上海泰坦科技股份有限公司)。
电喷雾质谱测定使用LCT Premier XE(沃特斯公司,USA),检测模式是正、负离子检测模式,离子源喷射电压是4.8kV,毛细管电压是15V,毛细管温度为320℃,鞘气为氮气50arb,辅助气20arb,全扫描质谱范围m/z100-1300。
正离子强度比R(+)和负离子强度比R(-)依照式(1)-(2)进行计算:
R(+)=Int(+)(合成表面活性剂)/Int(+)(脂肽) (1)
R(-)=Int(-)(合成表面活性剂)/Int(-)(脂肽) (2)
R(+)=Int(+)(合成表面活性剂)/Int(+)(脂肽) (1)
R(-)=Int(-)(合成表面活性剂)/Int(-)(脂肽) (2)
其中,Int(+)(合成表面活性剂)为合成表面活性剂的正离子化模式扫描下的质荷比相对强度,Int(+)(脂肽)为脂肽表面活性剂的正离子化模式扫描下的质荷比相对强度;Int(-)(合成表面活性剂)为合成表面活性剂的负离子化模式扫描下的质荷比相对强度,Int(-)(脂
肽)为脂肽表面活性剂的负离子化模式扫描下的质荷比相对强度;
R(-/+)=R(-)/R(+) (3)
R(-/+)=R(-)/R(+) (3)
正负离子强度比值R(-/+)依照式(3)进行计算。
实施例1:
本实施例以石油磺酸盐与脂肽构建生物复合驱油体系,并对其驱油能力进行评价,具体过程如下:
依照表1中的用量配比,将石油磺酸盐与脂肽加入至10mL溶剂中,搅拌溶解混合均匀后,进行电喷雾质谱分析,得到的正、负模式下的质谱图,计算得到正负离子强度比值R(-/+),结果如表1所示。其中,实验组1正、负离子化模式下的质谱图分别如图1与图2所示。
表1
实施例2:
本实施例以表面活性剂A与脂肽构建生物复合驱油体系,并对其驱油能力进行评价,具体过程如下:
依照表2中的用量配比,将表面活性剂A与脂肽加入至10mL溶剂中,搅拌溶解混合均匀后,进行电喷雾质谱分析,得到正、负模式下的质谱图,计算得到正负离子强度比值R(-/+),结果如表2所示。
表2
实施例3:
本实施例以表面活性剂B与脂肽构建生物复合驱油体系,并对其驱油能力进行评价,具体过程如下:
依照表3中的用量配比,将表面活性剂B与脂肽加入至10mL溶剂中,搅拌溶解混合均匀后,进行电喷雾质谱分析,得到正、负模式下的质谱图,计算得到正
负离子强度比值R(-/+),结果如表3所示。
表3
对比表1-3可知,石油磺酸盐与脂肽间有较大的R(-/+),且大于10,而表面活性剂A与脂肽的R(-/+)较小,小于10;表面活性剂B与脂肽的R(-/+)更小,均小于1.0。
实施例4:
依照表4中的质量含量将水解聚丙烯酰胺、表面活性剂、脂肽发酵液、碳酸钠、水混合配制得到复配驱油体系(表中4种组分的百分含量为在驱油体系内的质量含量),并采用“复合驱油体系性能测试方法(SY/T 6424-2000)”的复合驱油体系物理模拟驱油效果测试方法,原油采用大庆采油四厂杏五西脱水脱气原油,人造岩心(Φ25mm*100mm,1000毫达西,孔隙率25-30%,江苏华安科研仪器有限公司),评价试验体系的石油采收率。
取样复配驱油体系0.50mL,于105℃干燥后,甲醇溶解,离心,取上清液用电喷雾质谱测定正、负模式的质谱图,计算正负离子强度比值R(-/+)。
结果如表4所示。
表4
故选用石油磺酸盐与脂肽构建复合驱油体系,石油采收率超过20%,取得了较好的驱油效果。
上述的对实施例的描述是为便于该技术领域的普通技术人员能理解和使用发
明。熟悉本领域技术的人员显然可以容易地对这些实施例做出各种修改,并把在此说明的一般原理应用到其他实施例中而不必经过创造性的劳动。因此,本发明不限于上述实施例,本领域技术人员根据本发明的揭示,不脱离本发明范畴所做出的改进和修改都应该在本发明的保护范围之内。
Claims (10)
- 一种评价生物复合驱油体系的方法,生物复合驱油体系包括合成表面活性剂与脂肽表面活性剂,其特征在于,该评价方法包括以下步骤:S1:将合成表面活性剂与脂肽表面活性剂配制成混合溶液;S2:对混合溶液进行电喷雾质谱分析,并分别获得正、负离子化的质谱;S3:依照式(1)与式(2)分别计算混合溶液的正离子强度比R(+)和负离子强度比R(-);
R(+)=Int(+)(合成表面活性剂)/Int(+)(脂肽) (1)
R(-)=Int(-)(合成表面活性剂)/Int(-)(脂肽) (2)其中,Int(+)(合成表面活性剂)为合成表面活性剂的正离子化模式扫描下的质荷比相对强度,Int(+)(脂肽)为脂肽表面活性剂的正离子化模式扫描下的质荷比相对强度;Int(-)(合成表面活性剂)为合成表面活性剂的负离子化模式扫描下的质荷比相对强度,Int(-)(脂 肽)为脂肽表面活性剂的负离子化模式扫描下的质荷比相对强度;S4:
R(-/+)=R(-)/R(+) (3)依照式(3)计算正负离子强度比值R(-/+),即代表该生物复合驱油体系的驱油效果。 - 根据权利要求1所述的一种评价生物复合驱油体系的方法,其特征在于,步骤S1中,所述的合成表面活性剂与脂肽表面活性剂的质量比为1:10~10:1。
- 根据权利要求1所述的一种评价生物复合驱油体系的方法,其特征在于,步骤S1中,所述的混合溶液中,脂肽表面活性剂的浓度为0.2g/L~2.0g/L。
- 根据权利要求1所述的一种评价生物复合驱油体系的方法,其特征在于,步骤S1中,所述的混合溶液中,溶剂为甲醇或乙醇与水的混合溶剂。
- 根据权利要求4所述的一种评价生物复合驱油体系的方法,其特征在于,所述的甲醇或乙醇在混合溶液中的体积含量为50%~100%。
- 根据权利要求4所述的一种评价生物复合驱油体系的方法,其特征在于,步骤S2中,所述的电喷雾质谱分析中,电喷雾质谱仪检测模式是正、负离子检测模式,离子源喷射电压是4.8kV,毛细管电压是15V,毛细管温度为320℃,鞘 气为氮气50arb,辅助气20arb,全扫描质谱范围m/z100-1300。
- 根据权利要求4所述的一种评价生物复合驱油体系的方法,其特征在于,步骤S4中,对于多个生物复合驱油体系,R(-/+)较大者,驱油效果较好。
- 一种构建生物复合驱油体系的方法,其特征在于,包括:对于多个由不同种类和/或不同用量配比的合成表面活性剂与脂肽表面活性剂组成的生物复合驱油体系,采用如权利要求1至7任一项所述的一种评价生物复合驱油体系的方法,计算其R(-/+),并选择R(-/+)≥1的生物复合驱油体系作为待用生物复合驱油体系。
- 一种构建生物复合驱油体系的方法,其特征在于,该方法包括:对于多个由不同种类和/或不同用量配比的合成表面活性剂与脂肽表面活性剂组成的生物复合驱油体系,采用如权利要求1至7任一项所述的一种评价生物复合驱油体系的方法,计算其R(-/+)以及多个R(-/+)的中位数,选择R(-/+)不低于该中位数的生物复合驱油体系,作为待用生物复合驱油体系。
- 根据权利要求9所述的一种构建生物复合驱油体系的方法,其特征在于,选择R(-/+)最大的生物复合驱油体系作为待用生物复合驱油体系。
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