WO2015161470A1 - Composés, compositions associées et procédés d'extraction d'hydrocarbures au moyen desdits composés et compositions - Google Patents

Composés, compositions associées et procédés d'extraction d'hydrocarbures au moyen desdits composés et compositions Download PDF

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WO2015161470A1
WO2015161470A1 PCT/CN2014/076047 CN2014076047W WO2015161470A1 WO 2015161470 A1 WO2015161470 A1 WO 2015161470A1 CN 2014076047 W CN2014076047 W CN 2014076047W WO 2015161470 A1 WO2015161470 A1 WO 2015161470A1
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surfactant
compound
carbon atoms
crude oil
water
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PCT/CN2014/076047
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English (en)
Inventor
Zhijun Wang
Zhenggang CUI
Xiangqiang SHUI
Binglei SONG
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Solvay (Zhangjiagang) Specialty Chemicals Co., Ltd
Jiangnan University
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Application filed by Solvay (Zhangjiagang) Specialty Chemicals Co., Ltd, Jiangnan University filed Critical Solvay (Zhangjiagang) Specialty Chemicals Co., Ltd
Priority to PCT/CN2014/076047 priority Critical patent/WO2015161470A1/fr
Priority to CN201480080261.7A priority patent/CN107001923B/zh
Publication of WO2015161470A1 publication Critical patent/WO2015161470A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • 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

Definitions

  • the present invention relates to a compound, particularly, a betaine
  • Crude oil remains an important energy source. Crude oil producers
  • tertiary recovery also known as “enhanced oil recovery”
  • the mobility control process and chemical process are two commonly used enhanced oil recovery processes.
  • the mobility control process primarily relies on a polymer which can modify the viscosity of fluids.
  • an aqueous fluid comprising the polymer is injected into the underground reservoir so as to develop a favourable mobility ratio between the injected fluid and oil/water bank in the underground reservoir.
  • the purpose is to develop a uniform volumetric sweep of the reservoir, both vertically and areally. This can prevent the water from fingering by the crude oil and enhance the sweep efficiency.
  • the chemical process primarily relies on enhancing the microscopic displacement efficiency of the crude oil. It usually involves injecting a displacing fluid (usually an aqueous fluid) that efficiently displace the crude oil because of the phase behaviour properties, which results in decreasing interfacial tension (I FT) between the displacing fluid and the crude oil.
  • I FT interfacial tension
  • a displacing fluid comprising suitable surfactant(s) and polymer(s) can be used in the tertiary recovery.
  • a displacing fluid possesses a combination of rheological features (e.g., viscosifying properties) and the phase behaviour properties.
  • the displacing fluid may further comprise co-surfactant(s), oil, electrolytes and alkaline.
  • displacing fluids comprising alkaline-surfactant-polymer (ASP) have been used for the tertiary recovery and such technique is called ASP flooding.
  • ASP flooding alkaline-surfactant-polymer
  • anionic surfactants are used in the ASP flooding.
  • the alkaline in the displacing fluid may react with minerals and connate water in the underground reservoir, forming water insoluble substances. This will lead to deposition of precipitates on pipelines and equipment, and blocking of the porous channels in the reservoir as well, which may cause severe damage to the oil wells and jeopardize the crude oil recovery.
  • SP flooding surfactant-polymer
  • CN 101549266 B disclosed that methyl carboxyl betaine having double long hydrocarbon chains (such as didodecyl methyl carboxyl betaine) are suitable surfactants for the alkaline-free SP flooding.
  • the compounds have two long hydrocarbon chains in their molecules, and therefore have poor solubility in water and strong interactions with the sandstone reservoir or the carbonate reservoir, which causes problems in their applications for the SP flooding.
  • a method for extracting hydrocarbons from an underground formation comprising the steps of : (a) delivering a composition comprising water and a compound according to the formula Ri— ( ⁇ ) ⁇ &
  • Ri and R2 are independently linear or branched chain, saturated or unsaturated hydrocarbyl groups containing from 8 to 22 carbon atoms;
  • X and Y are independently alkylene groups containing from 2 to 4 carbon atoms; m and n are independently in the range of 1 to 20;
  • R3 is an alkyl group containing from 1 to 5 carbon atoms
  • R 4 is a carboxyl containing group
  • X and Y are ethylene.
  • Ri and R2 are alkyl groups.
  • Ri and R2 are alkyl groups containing from 8 to 18 carbon atoms.
  • n and n are independently in the range of 1 to 5.
  • R 4 is -CH2COO - .
  • composition for extracting hydrocarbons from an underground formation comprising water, the compound according to the formula
  • Ri and R2 are independently linear or branched chain, saturated or unsaturated hydrocarbyl groups containing from 8 to 22 carbon atoms; the carbon atom numbers of Ri and R2 are same or different; X and Y are independently alkylene groups containing from 2 to 4 carbon atoms; m and n are
  • Px3 is an alkyl group containing from 1 to 5 carbon atoms
  • R 4 is a carboxyl containing group.
  • the viscosifying polymer is a polyacrylamide or a xanthan gum.
  • the composition further comprises a co-surfactant.
  • the co-surfactant is a zwitterionic surfactant or a nonionic
  • the co-surfactant is an alkanol amide.
  • the co-surfactant is a
  • Ri and R2 are independently linear or branched chain, saturated or unsaturated hydrocarbyl groups containing from 8 to 22 carbon atoms; the carbon atom numbers of Ri and R2 are same or different;
  • X and Y are independently alkylene groups containing from 2 to 4 carbon atoms; m and n are
  • R3 is an alkyl group containing from 1 to 5 carbon atoms
  • R 4 is a carboxyl containing group.
  • composition according to the second aspect of the present invention for extracting hydrocarbons from an underground formation.
  • Fig. 1 A shows the molecular mass of the diCi2-uEnA tertiary amine intermediate based on the MS spectra analysis.
  • Fig. 1 B shows the molecular mass of the diCi2-i4EnBproduct based on the
  • Fig. 2 shows the surface tension of aqueous solutions comprising various concentrations of diCi2-uE n B.
  • Fig. 3 shows the interfacial tension (I FT) between an aqueous solution of diCi2-uE n Band /7-akanes and the I FT between an aqueous solution of diCi2-uE n Band the Daqing oilfield crude oil.
  • Fig. 4 shows the dynamic I FT between the Daqing oilfield crude oil and aqueous solutions comprising diC ⁇ uEnB, diCi2B, Ci6betaine and polyacrylamide (PAM).
  • Fig. 5 shows the dynamic I FT between the Daqing oilfield crude oil and aqueous solutions comprising diC ⁇ uEnB, stearyl dimethyl betaine and
  • Fig. 6 shows the dynamic I FT between the Daqing oilfield crude oil and aqueous solutions comprising diCi2-i 4 E n B, palmitoyldiglycol amide (PDGA), and PAM.
  • Fig. 7 shows the dynamic I FT between the Daqing oilfield crude oil and aqueous solutions comprising diC ⁇ uEnB, stearyl dimethyl betaine and PAM after the sandstone adsorption.
  • Fig. 8 shows the dynamic I FT between the Daqing oilfield crude oil and aqueous solutions comprising coconut monoethanol amide, stearyl dimethyl betaine and PAM after the sandstone adsorption.
  • Fig. 9 shows the adsorption isotherm of diCi2-uE n B at the sandstone/water interface in comparison to that of diCi2B.
  • betaine means a chemical compound with a positively charged cationic functional group, such as a quaternary ammonium or phosphoniumcation, which bears no hydrogen atom, and with an anionic group, such as a carboxyl containing group, which may not be adjacent to the cationic site.
  • surfactant means an amphiphilic compound that comprises a hydrophilic moiety and a
  • hydrophobic moiety and that, when present in water, lowers the surface tension of the water.
  • underground formation As used herein, the term “underground formation”, “underground reservoir” or “reservoir” refers to a place where crude hydrocarbons are found in reservoir forms in the Earth's crust.
  • the term "secondary recovery” refers to the process which usually involves the injection of a fluid (usually an aqueous fluid) into the underground reservoir or the formation.
  • the injected fluid and the injection process supplement natural pressure in the reservoir to displace the hydrocarbons to a production well.
  • the secondary recovery is also called “water flooding”.
  • the secondary recovery is usually conducted after the "primary recovery” is completed which mainly relies on the natural pressure present in the underground reservoir for the displacement of the hydrocarbons to the production well.
  • tertiary recovery refers to the process applied by the oil industry to further increase displacement of the hydrocarbons from the underground reservoir in supplement to the primary recovery and the secondary recovery processes.
  • the tertiary recovery techniques encompass thermal processes, mobility control processes and chemical processes, such as heat generation, heat transfer, steam drive, steam soak, polymer flooding, surfactant flooding, surfactant-polymer (SP) flooding, alkaline-surfactant- polymer (ASP) flooding, and use of hydrocarbon solvents, high-pressure hydrocarbon gas, carbon dioxide and nitrogen.
  • the term "displacing fluid” refers to an aqueous fluid used for the tertiary recovery (the enhanced oil recovery) in the underground formation.
  • Ri and R2 are independently linear or branched chain, saturated or unsaturated hydrocarbyl groups containing from 8 to 22 carbon atoms.
  • the carbon atom numbers of Ri and R2 may be same or different.
  • hydrocarbyl groups means a substituent or radical containing hydrogen and carbon atoms.
  • the hydrocarbyl group may have any suitable structures including saturated or unsaturated, straight or branched chain.
  • Illustrative hydrocarbyl groups include, but are not limited to: alkyl, such as methyl, ethyl, isopropyl, octyl, dodecyl, octadecyl and so on;
  • Ri and R2 are independently alkyl groups containing from 8 to 22 carbon atoms. More preferably, Ri and R2 are independently alkyl groups containing from 8 to 18 carbon atoms.
  • X and Y are independently alkylene groups containing from 2 to 4 carbon atoms.
  • X and Y are ethylene or propylene, more preferably, ethylene.
  • Alkoxy moiety in the compound of Formula (I), i.e., (OX)m or (OY)n as illustrated in Formula (I), may comprise a single species of alkylene group, such as ethylene, propylene or butylene.
  • the alkoxy moiety may comprise a mixture of alkylene groups having different carbon atoms numbers, such as a mixture of ethylene and propylene, a mixture of ethylene and butylene, a mixture of propylene and butylene, and a mixture of ethylene, propylene and butylene.
  • the values of m and n are in the range of 1 to 20, preferably 1 to 10, more preferably 1 to 5.
  • the values of m and n may be same or different.
  • the compound of the present invention may not be a single compound containing a certain copy number of alkylene oxide (i.e. OX and OY) as Formula (I) may suggest. Instead, the compound may be a mixture of several homologs which have different copy numbers of the alkylene oxide while the average copy number of the alkylene oxide of the homologs falls within the ranges as described above.
  • R3 is an alkyl group containing from 1 to 5 carbon atoms.
  • R3 is selected from the group consisting of -CH3, -CH2CH3, - CH2CH2CH3, -CH2CH2CH2CH3 and -CH2CH2OH.
  • R 4 is a carboxyl containing group.
  • carboxyl containing group may refer to a hydrocarbyl group in which one hydrogen is substituted by a carboxyl group (i.e., COO ).
  • carboxyl containing groups suitable for the present invention include, but are not limited to -CH2COO - , -CH2CH2COO - , - CH2CH2CH2COO - .
  • the compound of the present invention possesses a surfactant structure.
  • the compound of the present invention has the Formula [0048]
  • Ri , R2 and R3 are as defined in Formula (I).
  • the values of m' and n' are in the range of 1 to 20, preferably 1 to 10, more preferably 1 to 5.
  • the compound of the present invention is typically a betaine compound which has a head group and two fatty alcohol polyalkoxy ether chains linked to the head group.
  • the head group of the compound comprises a cationic site, i.e., the ammonium atom as shown in Formula (I), and an anionic group, i.e., R 4 as shown in Formula (I).
  • each of the fatty alcohol polyalkoxy ether chains possesses a surfactant structure which is composed of lipophilic groups (Ri and R2) and hydrophilic groups (the alkoxy moieties), thus in their designed applications, the performance of the compound is dependent on a balance between the lipophilicity and the hydrophilicity provided by these groups.
  • the compound of the present invention possesses Hydrophilic-Lipophilic Balance (HLB) which is suitable for efficiently reducing interfacial tension (IFT) between crude oil phase and water phase (crude oil-water IFT).
  • HLB Hydrophilic-Lipophilic Balance
  • IFT interfacial tension
  • betaines which have only one fatty alcohol polyalkoxy ether chain
  • the compound of the present invention can be more efficient in reducing the crude oil-water IFT.
  • the compound of the present invention can be used for extracting
  • hydrocarbons more particularly, the crude oil
  • the compound of the present invention can be used for the SP flooding.
  • a composition more particularly, the crude oil, from an underground formation.
  • a displacing fluid comprising the compound may be delivered to the underground formation to facilitate the displacement of the hydrocarbons (e.g., the crude oil).
  • hydrocarbons e.g., the crude oil.
  • a composition more particularly, a displacing fluid, comprising the compound of the present invention as described above.
  • the composition may be an aqueous solution, which may be prepared by mixing the compound of the present invention with water.
  • the composition of the present invention preferably in the form of aqueous solution, may be delivered to the underground formation containing the hydrocarbons (e.g., the crude oil).
  • the composition may be delivered to the underground formation containing the hydrocarbons (e.g., the crude oil).
  • the composition may be delivered to the underground formation containing the hydrocarbons (e.g., the crude oil).
  • the composition can reduce the crude oil-water IFT, forming an oil- water microemulsion locally. This zone of low IFT is then propagated through the underground formation. As a consequence, the hydrocarbons (e.g., the crude oil) trapped in porous sandstone reservoir or porous carbonate reservoir can be displaced, subsequently be recovered through a production system such as a production well.
  • the injection well is same as the production well. It has been found that the composition of the present invention can reduce the crude oil-water IFT to ultralow (below 10 "2 mN/m) without addition of any alkaline or electrolytes in the composition. Hence, by using the composition of the present invention, recovery rate of the crude oil can be significantly increased.
  • the composition of the present invention may optionally comprise a viscosifying polymer.
  • the viscosifying polymer can increase the viscosity of the composition and reduce its mobility in the reservoir. This will enhance the sweeping efficiency and lead to increasing the recovery efficiency of the
  • the displacing fluid when the displacing fluid is delivered to the underground formation, it tends to bypass lower permeability regions, leaving behind a significant volume of the crude oil because the displacing fluid, which is primarily water based, is much more mobile than the crude oil.
  • the difference between the mobility of the displacing fluid and that of the crude oil can be decreased by adding the viscosifying polymer in the displacing fluid, such that the viscosified displacing fluid will not finger by the oil and the sweep efficiency can be therefore enhanced.
  • the viscosifying polymer may also possess surfactant activities, wherein the polymer contributes to reducing the crude oil-water IFT.
  • the composition may be an aqueous solution of the viscosifying polymer, or an aqueous dispersion of the viscosifying polymer.
  • the polymer is substantially evenly distributed within the composition.
  • the polymer may be supplied as a powder.
  • the powder may be used to prepare a mother solution or dispersion of the polymer in water having a polymer concentration of at least 5% by weight, preferably at least 10% by weight, for example, 5 to 20% by weight. Then, the mother solution or dispersion may be dosed into the composition such that the resulting composition has a suitable viscosity for the applications of the present invention.
  • the polymer may be supplied in the form of a concentrated dispersion, e.g., a colloidal dispersion. Then, the concentrated dispersion of the polymer may be dosed into the composition.
  • the polymer may also be supplied in the form of an emulsion comprising a dispersed aqueous phase, in which the polymer is dissolved or dispersed, in a continuous oil phase, e.g., an emulsion in which droplets of the aqueous phase are dispersed in the oil phase.
  • aqueous phase is a highly concentrated solution of the polymer.
  • the final concentration of the viscosifying polymer in the composition may be in the range of 500-2,000 ppm by weight.
  • the viscosifying polymer in the composition may be in the range of 500-2,000 ppm by weight.
  • composition may comprise 1 ,500 ppm, 1 ,250 ppm, 1 ,000 ppm or 700 ppm of the viscosifying polymer by weight.
  • the viscosifying polymers suitable for the present invention include
  • polymers that are known to be useful for the tertiary recovery such as polyacrylamide (including partially hydrolyzed polyacrylamide) and xanthan gum.
  • the composition of the present invention may optionally comprise at least one co-surfactant. It is known that it is in the conditions of formation of the oil-water microemulsion that the crude oil recovery efficiency is highest.
  • the conditions of formation of the oil-water microemulsion depend on the type of the surfactant used, the nature of the crude oil (mainly its content of naphthenates or Alkane Carbon Number (ACN) and its density/viscosity), the salinity of the aqueous phase etc.
  • ACN Alkane Carbon Number
  • the co- surfactant can be included in the composition to optimize the HLB of the resulting composition wherein the optimal HLB is determined based on the characteristics of the oil and of the connate water in the reservoir where the composition will be applied.
  • the co-surfactant may be a small molecule surfactant or a polymeric surfactant.
  • the co-surfactant may be a zwitterionic surfactant, such as a betaine, or a nonionic surfactant, such as an ethoxylated fatty alcohol and an alkanol amide.
  • the composition of the present invention may comprise more than one co- surfactants.
  • the HLB of the composition may also be adjusted by selecting a suitable molar ratio between the compound of the present invention and the co- surfactant(s) in the composition.
  • the molar fraction of the compound of the present invention in the total surfactants is above 0.1 and below 1.0, preferably, in the range of 0.3 to 0.7.
  • composition of the present invention may also comprise other ingredients
  • additives in particular, salts, sacrificial agents and an agent for pH adjustment (for example sodium carbonate).
  • pH adjustment for example sodium carbonate
  • the composition of the present invention may be used for the SP flooding or the ASP flooding, in particular, the SP flooding, in the tertiary recovery.
  • the compound of the present invention may also be used for the secondary recovery.
  • water comprising the compound of the present invention may be injected into the underground reservoir to supplement the natural pressure in the reservoir for displacing the hydrocarbons, at the same time, the solution can reduce the crude oil-water I FT.
  • the present invention also relates to the use of the compound or the
  • composition of the present invention as described above for extracting the hydrocarbons, more particularly, the crude oil, from an underground formation.
  • the present invention provides a suitable compound which may be used as a surfactant for extracting the hydrocarbons from the underground formation, in particular, for the SP flooding.
  • a surfactant for extracting the hydrocarbons from the underground formation, in particular, for the SP flooding.
  • the surfactant should have a sufficient lipophilicity; secondly, the surfactant should have a high adsorption at the oil/water interface; thirdly, the surfactant should have good aqueous solubility so that it will not precipitate easily from the aqueous solution.
  • the compound has poor solubility in water, which may be due to the presence of the two long alkyl chain in the molecule of the compound. Furthermore, it tends to have strong interactions with the sandstone reservoir and/or the carbonate reservoir. This may be problematic when such compound is used for the SP flooding. Surprisingly, it has been found that the compound of the present invention can solve the above mentioned problems associated with the conventional surfactants used for the tertiary recovery.
  • the compound of the present invention exhibits both a strong lipophilicity and a high adsorption at the oil/water interface. Furthermore, the compound has good aqueous solubility.
  • the compound of the present invention exhibit decreased interactions with the sandstones, which may be attributed to the introduction of the alkoxy moieties into the hydrocarbon chains in the molecule of the compound.
  • the compound and the composition of the present invention are particularly suitable for being used for extracting the hydrocarbons (e.g., the crude oil) from the underground formation, the compound and the composition can also be used for other applications wherein the hydrocarbons (e.g., the crude oil) from the underground formation, the compound and the composition can also be used for other applications wherein the hydrocarbons (e.g., the crude oil) from the underground formation, the compound and the composition can also be used for other applications wherein the hydrocarbons (e.g., the crude oil) from the underground formation, the compound and the composition can also be used for other applications wherein the hydrocarbons (e.g., the crude oil) from the underground formation, the compound and the composition can also be used for other applications wherein the hydrocarbons (e.g., the crude oil) from the underground formation, the compound and the composition can also be used for other applications wherein the hydrocarbons (e.g., the crude oil) from the underground formation, the compound and the composition can also be used for other applications wherein the hydrocarbons (
  • Such applications include, but are not limited to detergents, foaming agents, fabric softeners, dyeing and finishing of fabrics, etc..
  • the compound of Formula (I) can be prepared by the following stages :
  • Stage 1 Preparation of fatty alcohol polyalkoxy ether chlorides.
  • fatty alcohol polyalkoxy ether are firstly obtained by reacting fatty alcohols containing 8-22 carbon atoms with ethylene oxide (EO), propylene oxide (PO), butylene oxide (BO) or a mixture thereof by using conventional methods.
  • ethylene oxide (EO) and propylene oxide (PO) is used for the reaction.
  • ethylene oxide (EO) is used for the reaction.
  • Selection of the molar ratio between the alkylene oxide and the fatty alcohol can be determined based on the copy number of the alkylene oxide in the desired reaction product.
  • the present invention may employ a single species of fatty alcohol polyalkoxy ether for the synthesis of the compound of the present invention, in such case, the two fatty alcohol polyalkoxy ether chains in the final product synthesized (e.g., the compound of Formula (I)) will be homogenous.
  • the present invention may employ a mixture of fatty alcohol polyalkoxy ethers for the synthesis of the compound of the present invention, in such case, the two fatty alcohol polyalkoxy ether chains in the final product (e.g., the compound of Formula (I)) will be heterogeneous.
  • certain species of fatty alcohol polyalkoxy ethers are available from commercial sources thus can be directly used as staring materials for the synthesis of the compound of the present invention.
  • a first fatty alcohol polyalkoxy ether chloride i.e. , the
  • the primary alkylamines suitable for the present invention include, but are not limited to NH2CH3, NH2CH2CH3, NH2CH2CH2CH3, NH2CH2CH2CH3 and NH2CH2CH2OH.
  • the reaction can be illustrated in the following equation :
  • the distillated mixture which mainly comprises the secondary amine intermediate (VI) and R3NH3CI, is transferred to a container and water is added to the container to dissolve the R3NH3CI solid salt, which is a by- product of the reaction. Then certain amount of NaOH aqueous solution is added to decompose amine hydrochloride by-products which are possibly produced during the reaction. Subsequently the product mixture is transferred to a funnel and is allowed to separate into two phases. The upper phase which contains the secondary amine intermediate (VI) is collected. The secondary amine intermediate (VI) obtained in this stage can be further purified if necessary.
  • the secondary amine intermediate (VI) obtained in stage (2) is mixed, in a container (e.g., a four-neck flask), with a second fatty alcohol polyalkoxy ether chloride (i.e., the intermediate (IV)) and sodium carbonate.
  • the molar ratio of (VI), (IV) and sodium carbonate is 1 -1.5/1/1 -1.5.
  • the reaction mixture is stirred and heated to 100-200°C, preferably, 150°C to 180°C, and allowed to react at such temperature for 20 to 30 hours to yield the tertiary amine intermediate (VII).
  • a typical reaction time is 24 hours.
  • the tertiary amine intermediate (VII) product may be subject to analysis, such as MS spectra analysis for characterization.
  • Stage 4 Carboxylation of the tertiary amine intermediate (VII).
  • the tertiary amine intermediate (VII) obtained in stage (3) is subject to the carboxylation reaction, wherein a carboxyl containing group is linked to the ammonium atom in the tertiary amine intermediate (VII) so as to yield the compound of Formula (I).
  • the carboxyl containing groups suitable for the reaction include, but are not limited to -CH2COO - , - CH2CH2COO - and -CH2CH2CH2COO - .
  • the tertiary amine intermediate (VII) may be reacted with a carboxylic acid or salt under alkaline condition at a temperature of 70-150°C, notably, to avoid formation of tertiary amine hydrochloride salt in acidic condition.
  • the reaction is carried out in isopropanol/water mixture solvent.
  • reaction may be illustrated in the following equation : CH 2 COO + NaCI
  • the reaction is carried out under alkaline condition at a temperature of 100-150°C.
  • the efficiency of the carboxylation reaction can be increased by adding extra chloroacetic acid and NaOH to the reaction mixture and amount of the unreacted tertiary amine intermediate in the final product can be reduced to below 10%.
  • the final product may be subject to further purification and/or characterization by using technologies well known in the art.
  • Didodecyl methyl carboxyl betaine (denoted as "diCi2B") was obtained from Jiangnan University, China. The synthesis and characterization of diCi 2 B were disclosed in CN101549266 B. diCi 2 B is a methyl carboxyl betaine compound having double C12 alkyl chains.
  • the Daqing oilfield connate water samples were obtained from the Daqing oilfield, China.
  • the Daqing oilfield connate water samples comprise certain amounts of ions, including CO3 2" , HCO3 ,CI ,SO 4 2 ,Ca 2+ ,Mg 2+ ,and Na + .
  • Example 1 Synthesis and characterization of di-coconut alcohol
  • polyoxyethylene ether methyl carboxyl betaine (denoted as diCi2-i4E n B)
  • diCi2 -i 4 E n A obtained in the above step was reacted with chloroacetic acid (CICH2COOH) in the presence of NaOH in aqueous medium at 95-100°C for 8-10 hours, so as to yield the diCi2 -i 4 E n B final product.
  • chloroacetic acid CICH2COOH
  • the molar ratio between chloroacetic acid and di-coconut alcohol polyoxyethylene ether methyl amine was in the range of 1 :1 to 1.3:1 , and the molar ratio between NaOH and chloroacetic acid was 1 :1.
  • the product mixture was neutralized to weak alkaline by using NaOH and dried at vacuum.
  • the dried mixture was dissolved in ethanol and the insoluble salts were removed by filtration.
  • the filtrated mixture was concentrated by evaporation and 5g of the concentrated mixture was dissolved in ethyl acetate (5m L) and passed through a column (40cm x 5cm) filled with chromatograph silica (FCP300-400 mesh, 200g).
  • the molecular mass of the homologues in the diCi2-uE n A intermediate based on MS spectra analysis was shown in Fig. 1A. According to the MS spectra results, it can be derived that the starting material, coconut alcohol polyoxyethylene (2) ethers (AEO), mainly contain C12 and Cu fatty alcohol chains.
  • AEO coconut alcohol polyoxyethylene (2) ethers
  • the diC-12-uEnA intermediate was a mixture of homologs with C12/C12, C12/C14, and C14/C14 fatty alcohol chains.
  • the EO copy numbers in the AEO chains of the homologs in the diCi2-uE n A intermediate varied.
  • the average molecular weight of the AEO was measured to be 283.7 based on the hydroxyl value (197.8) measured, accordingly, the average EO copy number in the AEO chains of the homologs in the diCi2-uE n A intermediate was 2.1 , wherein the calculation is based on that the fatty alcohol present in the diCi2-uE n A intermediate is coconut alcohol
  • the molecular mass of the homologues in the purified diCi2-uE n B based on MS spectra analysis was shown in Fig. 1 B.
  • the diCi2-uE n B product mainly comprises homologs having C12/C12, C12/C14, and Cu/Cu double fatty alcohol chains.
  • the EO copy numbers in the AEO chains of the homologs in diCi2-uE n B varied and the average EO copy number in the AEO chains of the homologs should be same as that of the diC-12-uEnA intermediate, i.e., 2.1.
  • Example 2 Surface activity of diCi2-i4E n B
  • concentrations of diCi2-uE n B were measured at 25°C and the results are shown in Fig. 2. It is found that diCi2-uE n B could efficiently reduce the surface tensions of the aqueous solutions in a dosage dependent manner, and increased concentration of diCi2-uE n B led to decreased surface tension of the aqueous solution.
  • Other parameters such as critical micelle concentration (cmc), effectiveness in reducing surface tension (ycmc) , saturated adsorption at air /water interface (P°) , as well as the cross section area (cr) of a molecule at air/water interface of diCi2-uE n B were measured and the results are listed in Table 1 below.
  • diCi2-uE n B is highly effective and efficient in reducing surface tension (ycmc). Also, compared to typical surfactants, diCi2-uE n B has a high saturated adsorption at air /water interface (P°) and a small cross section area (a°°), indicating that diCi2-uE n B can have a large adsorption at the oil/water interface and form a dense monolayer, which is beneficial for reducing the crude oil-water I FT.
  • Example 3 An aqueous solution of 1 ,000 ppm polyacrylamide (PAM,
  • Example 4 diCi2-uE n B was dissolved in pure water. The final
  • concentration of diCi2-i 4 E n B was 5 mM.
  • Example 5 The aqueous solution of PAM was prepared as in Example 3.
  • diCi2 -i 4 E n B a mixture of diCi2 -i 4 E n B and two zwitterionic co-surfactants, i.e., diCi2B and cetyl dimethyl betaine (Ci6betaine), was dissolved in the above mentioned aqueous solution at varies total surfactant concentrations.
  • the molar fraction of diCi2-uE n B in the total surfactants was 0.6.
  • Example 6 The aqueous solution of PAM was prepared as in Example 3.
  • diCi2-uE n B a mixture of diCi2-uE n B and a zwitterionic co-surfactant, i.e., a stearyl dimethyl betaine was dissolved in the above mentioned aqueous solution at varies total surfactant concentrations.
  • a zwitterionic co-surfactant i.e., a stearyl dimethyl betaine was dissolved in the above mentioned aqueous solution at varies total surfactant concentrations.
  • the molar fraction of diCi2-uEnB in the total surfactants was 0.7.
  • Example 7 The aqueous solution of PAM was prepared as in Example 3.
  • Example 5 As shown in Fig. 4, generally, the dynamic IFTs between all the water phase samples and the Daqing oilfield crude oil were reduced to ultralow (below 10- 2 mN/m) within 30 mins.
  • the equilibrium IFTs between the water phase samples and the Daqing oilfield crude oil were reduced to ultralow (below 10- 2 mN/m) and the equilibrium was reached within 120 mins.
  • the equilibrium IFT between the water phase sample containing the lowest total surfactant concentration (1.25 mM) was also reduced to ultralow (below 10- 2 mN/m), although it took a longer time (approximately 180 mins) to reach the equilibrium.
  • Example 7 As shown in Fig. 6, the equilibrium IFTs between all the water phase samples and the Daqing oilfield crude oil were reduced to ultralow (below 10- 2 mN/m) and the equilibrium was reached within 120 mins.
  • the sandstones in the underground reservoir are usually composed of rocks and clays, most of which are negatively charged in the connate water.
  • anionic and nonionic surfactants have lower adsorption by the sandstones compared to cationic surfactants, and therefore are preferred for the surfactant flooding and surfactant-polymer flooding.
  • One method to examine the effect of adsorption by the sandstones is to add the sandstones in an aqueous surfactant solution and keep the mixture under stirring condition, such that the adsorption of the surfactant by the sandstones will take place. Then after a certain time period, the supernatant containing the un-absorbed surfactant is collected and the dynamic I FT between the surfactant and the crude oil is measured. By doing so, the effects of the adsorption of the surfactant by the sandstones on the surfactant's IFT reducing ability can be examined. Accordingly, such method was employed in the present study.
  • Example 8 The experiments were carried out according to the following step :
  • the sandstones were added to the water phase sample (the sandstones/the water phase sample ratio was 1 :9 by weight).
  • the suspension was kept under stirring at 45 °C for 12 hours for adsorption. Then, the suspension was settled down at 45 °C for about 6 hours to allow the sandstones to sedimentate. Then, the supernatant (containing the un-absorbed surfactants) was collected.
  • steps (b) and (c) were repeated until that the dynamic IFT between the water phase sample and the Daqing oilfield crude oil could no longer reach ultralow (below 10- 2 mN/m).
  • Example 8 the IFT between the water phase samples and the Daqing oilfield crude oil could still reached ultralow (below 10 "2 mN/m) after three times of addition of the sandstones (as shown in Fig. 7).
  • Example 9 the IFT between the water phase samples and the Daqing oilfield crude oil could not reach ultralow after two times of addition of the sandstones (as shown in Fig. 8).
  • Example 10 Adsorption isotherm of the surfactants by the sandstones
  • sandstones/water phase sample ratio was 1 :9 by weight).
  • the suspension was kept under stirring at 45 °C for 12 hours for adsorption. Then, the suspension was settled down at 45 °C for about 6 hours to allow the sandstones to sedimentate. Then, the supernatants (containing the un- absorbed surfactants) were collected and centrifuged to remove the sandstones which did not sedimentate.
  • diCi2B Due to the limited solubility of diCi2B, the adsorption of diCi2B at high concentrations were measured by mixing diCi2B with dodecyl dimethyl carboxyl betaine (a hydrophilic homolog of diCi2B) at different molar fraction, and the adsorption obtained by extrapolated the molar fraction of diCi2B to 1 is taken as the saturated adsorption of diCi2B.
  • dodecyl dimethyl carboxyl betaine a hydrophilic homolog of diCi2B

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Abstract

L'invention concerne un composé, et plus particulièrement un composé de bétaïne doté de chaînes de polyalcoxy éther à double alcool gras, pouvant servir dans l'extraction d'hydrocarbures, en particulier de pétrole brut, à partir d'une formation souterraine. Le composé selon l'invention est particulièrement utile dans des techniques d'inondation par polymères tensioactifs non alcalins dans la récupération tertiaire. L'invention concerne également un procédé de préparation de ce composé, une composition le contenant, ainsi que son utilisation.
PCT/CN2014/076047 2014-04-23 2014-04-23 Composés, compositions associées et procédés d'extraction d'hydrocarbures au moyen desdits composés et compositions WO2015161470A1 (fr)

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CN201480080261.7A CN107001923B (zh) 2014-04-23 2014-04-23 化合物、其组合物以及使用其用于烃提取的方法

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CN116970378A (zh) * 2023-09-25 2023-10-31 四川蜀宏悦能源科技有限公司 微泡修井液及其制备方法

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CN116970378B (zh) * 2023-09-25 2023-12-01 四川蜀宏悦能源科技有限公司 微泡修井液及其制备方法

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