CN101665685B - Oil-displacing agent for enhancing crude oil recovery efficiency in tertiary recovery - Google Patents
Oil-displacing agent for enhancing crude oil recovery efficiency in tertiary recovery Download PDFInfo
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- CN101665685B CN101665685B CN2009100704259A CN200910070425A CN101665685B CN 101665685 B CN101665685 B CN 101665685B CN 2009100704259 A CN2009100704259 A CN 2009100704259A CN 200910070425 A CN200910070425 A CN 200910070425A CN 101665685 B CN101665685 B CN 101665685B
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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
- C09K8/588—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 polymers
Abstract
The invention relates to an oil-displacing agent for enhancing crude oil recovery efficiency in tertiary recovery and a preparation method thereof, belonging to the technical field of intensified oil production in oil fields. The surface active agent used in the invention comprises following components in percentage by weight: 0.01-0.3 percent of water soluble high molecular polymer, 0-20 percent of non-ionic surface active agent, 5-65 percent of anion active agent, 0-5 percent of ampholytic active agent, 0.01-1.5 percent of additive and the balance of water. The oil-displacing agent and the polymer are based on a novel intensified oil displacing system which has complementary structure and good compatibility and is obtained by various associations and the interaction among molecules. The system has the performances of high temperature resistance, salt resistance, higher viscosity, ultralow interfacial tension, and the like, is in accordance with the environmental requirement and can obviously enhance the oil recovery efficiency of oil fields after being used for oil-displacing.
Description
Technical field
The invention belongs to technical field of petroleum extraction, relate to the structure that oil three is adopted the pure binary displacement oil system of intensified oil reduction polymkeric substance-tensio-active agent.A kind of binary displacement oil agent that TOR improves oil recovery factor that is used for of saying so more specifically.
Background technology
Traditional oil production is divided into such three phases: primary oil recovery is to lean on reservoir pressure to be sprayed onto ground to crude oil, and RF reaches crude oil standing stock about 15%; Secondary oil recovery is to keep pressure by man-made injection, and crude oil is further exploited, and RF is about about 25%.Through underground crude oil once, behind the secondary recovery, still have substantial oil (40-60%) to be adsorbed in the space, rock stratum and be difficult to exploit with above-mentioned two kinds of methods.Therefore, need with other physico-chemical process it to be extracted from the rock stratum, these methods are referred to as TOR or intensified oil reduction technology.
Along with constantly carrying out of oil production; At present; China's main oilfield has got into high water-cut stage of secondary oil recovery later stage, and underground crude oil is in discontinuous dispersion state, contains big water gaging in the promptly underground crude oil, crude oil can not connect together by sheet; Its technology of reservoir sweep mainly utilizes alkali/polymkeric substance/tensio-active agent ternary composite driving, improves oil recovery factor.
Alkali/polymkeric substance/tensio-active agent ternary oil-displacing agent can increase substantially oil recovery factor, but in the heavy industrialization application process, some problems are also following.The use of alkali causes polyvalent ion deposition, rock forming mineral corrosion, destroys oil reservoir and structure of oil well, badly damaged stratum; Simultaneously, need every barrel that just needed to clean at a distance from 10-15 days, increase cost for oil production; And the existence of alkali not only can increase considerably the usage quantity of polymkeric substance, also can reduce polymer viscoelastic, especially polymer elasticity greatly; In addition, using of alkali also caused extraction liquid as the higher w/o type emulsion of viscosity, both influenced oil well productivity, increased the breakdown of emulsion difficulty again.
Summary of the invention
In order to solve the shortcoming and deficiency that exists in alkali/polymkeric substance/tensio-active agent ternary oil-displacing agent industrial application engineering; Reach the oil increasing precipitation effect; Improve oil recovery factor; The present invention has designed alkali-free low interfacial tension polymkeric substance/tensio-active agent binary displacement oil agent, gives full play to polymer viscoelastic, keeps the system IT 10 simultaneously
-3The mN/m order of magnitude.The invention provides following technical scheme for achieving the above object:
A kind of oil-displacing agent (the pure binary displacement oil system formulation of polymkeric substance-tensio-active agent) that is used for TOR raising oil recovery factor is characterized in that this oil-displacing agent, is made up of following raw materials by weight:
High molecular weight water soluble polymer 0.01～0.3%,
Nonionogenic tenside 0.01～0.2%,
AS 0.05～0.45%,
Zwitterionics 0～0.05%,
Additive 0.01～1.5%,
All the other add water to 100%.
Oil-displacing agent of the present invention, wherein said high molecular weight water soluble polymer are a kind of in SEPIGEL 305, modified polyacrylamide or the XG 550.
Oil-displacing agent of the present invention, wherein said AS are one or more of sulfonated alkylbenzene, sulfonated petro-leum, petroleum carboxylate, side chain sulphonate, succsinic acid sulphonate, poly alkyl alcohol sun Vinyl Ether vitriol, alkyl phenyl sodium sulfonate, pyrrolidyl keto-earboxylic acid sodium, TX10 sodium sulfonate, Gemini surface active agent and sodium carboxymethylcellulose pyce.
Oil-displacing agent of the present invention, wherein said nonionogenic tenside are one or more of AEO, polyoxyethylene nonylphenol, methylcellulose gum M20, Natvosol, hydroxypropylcellulose, Vinylpyrrolidone polymer, Z 150PH, iso-octyl phenolic group Soxylat A 25-7, TX10, polyoxyethylene octyl phenyl ether, aliphatic acid polyethenoxy ether, AEO, polyoxyethylene alkyl amine, sorbyl alcohol and sorbitol acetal verivate.
Oil-displacing agent of the present invention, wherein said zwitterionics are one or more of imidazoline type carboxylate salt, imidazoline type phosphoric acid salt, sulfo group imidazolinium betaine, carboxylic acid trimethyl-glycine, N-amido-carboxylic acid trimethyl-glycine and N-alkylthio carboxylic acid trimethyl-glycine.
Oil-displacing agent of the present invention, wherein water is common clear water or return water.
Oil-displacing agent of the present invention is characterized in that additive therefor is that carbon company commander degree is low-carbon alcohol, low-carbon (LC) ketone or the low-carbon (LC) ether additive of C1-C4.
The present invention further discloses the preparation method of oil-displacing agent, it is characterized in that being undertaken by following method:
With 0.01～0.3% high molecular weight water soluble polymer, 0.01～0.2% nonionogenic tenside, 0.05～0.45% AS; 0～0.05% zwitterionics mixes; Additive 0.01～1.5% joins in the reactor drum that has whipping appts, adds water to 100%; Stir room temperature reaction 1.5～2.5h down, make oil-displacing agent.
Mentality of designing of the present invention is to utilize to have the multiple association of complementary structure and good solubility and the molecular interaction of reactive polymer (hydrogen bond, Coulomb's force, hydrophobic association effect, charge transfer effect etc.) formation polymer composite; Under reservoir condition; Degree of freedom through the compound reduction component polymer of polymer chain; Increase high molecular hydrodynamic volume, make solution obtain HV; Work in coordination with at the kinds of surface promoting agent simultaneously and make under of, reduce the system IT.
Binary displacement oil agent of the present invention is compared with existing alkali/polymkeric substance/tensio-active agent ternary oil-displacing agent technical scheme, has following substantive distinguishing features:
1) alkali-free in the oil-displacing agent involved in the present invention has overcome alkali reduction polymer viscoelastic and alkali and has caused the alkali dirt to destroy problems such as stratal configuration and holddown clean-out service, and promptly compliance with environmental protection requirements has reduced production cost again.This flooding system, the flooding system that is used to improve oil recovery factor makes up.Can be under alkali-free, high temperature, high salinity condition, make between profit IT reduce to 10 by the original 10mN/m order of magnitude
-3The mN/m order of magnitude.
2) compound (like polymkeric substance, tensio-active agent) involved in the present invention is the fine chemicals of suitability for industrialized production, and raw material is easy to get; In addition, employed water promptly can be common clear water in the compound system, also can be return water, and environment protecting is good, also reduces production costs.
3) oil-displacing agent according to the invention confirms through homogeneous rock core oil displacement experiment under high temperature, high salinity condition, can improve oil recovery factor more than 30%.Can know that through viscosity and IT mensuration compound system is at 80 ℃, 25000mg/L (Ca
2++ Mg
2+=552mg/L) under the salinity condition, viscosity reaches 17.1mPa/s, can form 10 with crude oil
-3The mN/m ultra low interfacial tension.
4) experiment showed, under the displacement of reservoir oil condition, through the degree of freedom of main polymer and the compound reduction polymer chain of tensio-active agent; Increase high molecular hydrodynamic volume; Make solution obtain HV, have strong anti-salt property, and; Different kinds of ions tensio-active agent synergy effectively reduces the system IT.
For example: under 70 ℃ of 20000mg/L salinities, polymkeric substance-tensio-active agent binary displacement oil agent and alkali-polymkeric substance-tensio-active agent ternary oil-displacing agent performance comparison:
| Comparing embodiment | Hydrodynamic radius (nm) | Viscosity (mPa/s) | IT (mN/m) |
| The binary displacement oil agent | 600 | 19.1 | 2.2×10 -3 |
| Ternary oil-displacing agent (alkali) | 280 | 11.5 | 2.7×10 -3 |
Embodiment
, and be not used in and also should be interpreted as the restriction to inventing in the listed claim by any way with helping understand the present invention below in conjunction with embodiment.The instrument and the reagent that use in the wherein following instance are following:
(1) use reagent:
SEPIGEL 305, modified polyacrylamide and XG 550, sulfonated petro-leum, petroleum carboxylate, dodecyl phenenyl sulfate, TX10 sodium sulfonate, Gemini surface active agent, TX10, polyoxyethylene octyl phenyl ether, sorbitol acetal verivate, imidazoline type carboxylate salt, imidazoline type phosphoric acid salt, sulfo group imidazolinium betaine, carboxylic acid trimethyl-glycine, N-amido-carboxylic acid trimethyl-glycine and N-alkylthio carboxylic acid trimethyl-glycine (all having commercially available).
(2) use instrument: the TX-500C type changes an interfacial tensimeter, DV-II type Brookfield viscometer (having the UL rotor)
Embodiment 1:
With SEPIGEL 305 18.0g, X 2073 3.0g, Gemini surface active agent 2.0g; Alkyl phenolic group Soxylat A 25-7 5.0g; TX10 sodium sulfonate 10.0g, methyl alcohol 15.0g, clear water 10000g join in the mixing tank that whipping appts is housed; Stirring at room 2.0h makes oil-displacing agent.
In temperature is 80 ℃, salinity 25000mg/L (Ca
2++ Mg
2+=552mg/L), DV-II type Brookfield viscometer (UL joint) is 30 rev/mins of conditions, and recording viscosity is 16.5mPa.S; Use the TX-500C interfacial tensimeter, under 5000 rev/mins of conditions of speed of rotation, minimum IT is 2.6 * 10
-3MN/m.
Embodiment 2:
With modified polyacrylamide 16.0g; Carboxylic acid trimethyl-glycine trimethyl-glycine 2.0g, AEO 2.0g, sulfo group imidazolinium betaine 3.0g; TX10 sodium sulfonate 6.0g; Ethanol 13.0g, clear water 10000g (or return water) joins in the mixing tank that whipping appts is housed, stirring at room 2.5h.Make oil-displacing agent.
In temperature is 80 ℃, salinity 25000mg/L (Ca
2++ Mg
2+=552mg/L), DV-II type Brookfield viscometer (UL joint) is 30 rev/mins of conditions, and recording viscosity is 17.5mPa.S; Use the TX-500C interfacial tensimeter, under 5000 rev/mins of conditions of speed of rotation, minimum IT is 3.1 * 10
-3MN/m.
Embodiment 3:
With XG 550 15.0g, X 2073 3.0g, petroleum carboxylate 6.0g, carboxylic acid trimethyl-glycine 1.5g, sulfo group imidazolinium betaine 2.0g, methyl alcohol 16.0g, clear water 10000g join in the mixing tank that whipping appts is housed, stirring at room 2.5h.Make oil-displacing agent.
In temperature is 80 ℃, salinity 25000mg/L (Ca
2++ Mg
2+=552mg/L), DV-II type Brookfield viscometer (UL joint) is 30 rev/mins of conditions, and recording viscosity is 12.5mPa.S; Use the TX-500C interfacial tensimeter, under 5000 rev/mins of conditions of speed of rotation, minimum IT is 5.0 * 10
-3MN/m.
Embodiment 4:
With modified polyacrylamide 17.0g, sodium laurylsulfonate 3.0g, sulfonated petro-leum 15.2g, TX10 3.0g, clear water 10000g join in the mixing tank that whipping appts is housed, Virahol 12.0g, stirring at room 2h.Make oil-displacing agent.
In temperature is 80 ℃, salinity 25000mg/L (Ca
2++ Mg
2+=552mg/L), DV-II type Brookfield viscometer (UL joint) is 30 rev/mins of conditions, and recording viscosity is 13.0mPa.S; Use the TX-500C interfacial tensimeter, under 5000 rev/mins of conditions of speed of rotation, minimum IT is 5.6 * 10
-3MN/m.
Embodiment 5:
With XG 550 15.0g, sodium laurylsulfonate 3.0g, sulfonated petro-leum 15.2g, TX10 2.8g, clear water 10000g join in the mixing tank that whipping appts is housed, Virahol 12.0g, stirring at room 1.5h.Make oil-displacing agent.
In temperature is 80 ℃, salinity 25000mg/L (Ca
2++ Mg
2+=552mg/L), DV-II type Brookfield viscometer (UL joint) is 30 rev/mins of conditions, and recording viscosity is 15.0mPa.S; Use the TX-500C interfacial tensimeter, under 5000 rev/mins of conditions of speed of rotation, minimum IT is 2.3 * 10
-3MN/m.
Embodiment 6:
With XG 550 16.0g, sulfonated petro-leum 15.0g, TX10 3.0g, polyoxyethylene octyl phenyl ether 3.0g, clear water 10000g join in the mixing tank that whipping appts is housed, acetone 11.0g, stirring at room 2.5h.Make oil-displacing agent.
In temperature is 80 ℃, salinity 25000mg/L (Ca
2++ Mg
2+=552mg/L), DV-II type Brookfield viscometer (UL joint) is 30 rev/mins of conditions, and recording viscosity is 17.0mPa.S; Use the TX-500C interfacial tensimeter, under 5000 rev/mins of conditions of speed of rotation, minimum IT is 3.1 * 10
-3MN/m.
Embodiment 7:
With modified polyacrylamide 17.0g, TX10 sodium sulfonate 2.0g, sulfonated petro-leum 12.0g, aliphatic acid polyethenoxy ether 5.0g, clear water 10000g join in the mixing tank that whipping appts is housed, terepthaloyl moietie 11.0g, stirring at room 2.5h.Make oil-displacing agent.
In temperature is 80 ℃, and salinity 25000mg/L (Ca2++Mg2+=552mg/L), DV-II type Brookfield viscometer (UL joint) are 30 rev/mins of conditions, and recording viscosity is 17.0mPa.S; Use the TX-500C interfacial tensimeter, under 5000 rev/mins of conditions of speed of rotation, minimum IT is 2.7 * 10
-3MN/m.
Embodiment 8:
With modified polyacrylamide 17.0g, TX10 sodium sulfonate 2.0g, sulfonated petro-leum 12.0g; Aliphatic acid polyethenoxy ether vitriol 5.0g; AEO 4.0g, polyoxyethylene octyl phenyl ether 1.0g, clear water 10000g join in the mixing tank that whipping appts is housed; Butanols 11.0g, stirring at room 2.5h.Make oil-displacing agent.
In temperature is 80 ℃, salinity 25000mg/L (Ca
2++ Mg
2+=552mg/L), DV-II type Brookfield viscometer (UL joint) is 30 rev/mins of conditions, and recording viscosity is 19.0mPa.S; Use the TX-500C interfacial tensimeter, under 5000 rev/mins of conditions of speed of rotation, minimum IT is 1.5 * 10
-3MN/m.
Embodiment 9:
With modified polyacrylamide 19.0g, carboxylic acid trimethyl-glycine trimethyl-glycine 4.0g, AEO 1.5g; Sulfo group imidazolinium betaine 1.0g, Vinylpyrrolidone polymer 2.0g, sulfonated petro-leum 17.0g; Ethanol 13.0g; Return water 10000g joins in the mixing tank that whipping appts is housed stirring at room 1.5h.Make oil-displacing agent.
In temperature is 80 ℃, salinity 25000mg/L (Ca
2++ Mg
2+=552mg/L), DV-II type Brookfield viscometer (UL joint) is 30 rev/mins of conditions, and recording viscosity is 12.5mPa.S; Use the TX-500C interfacial tensimeter, under 5000 rev/mins of conditions of speed of rotation, minimum IT is 6.5 * 10
-3MN/m.
Embodiment 10:
With SEPIGEL 305 15.0g, (carboxylic acid trimethyl-glycine trimethyl-glycine+N-amido-carboxylic acid trimethyl-glycine) 4.0g, AEO 1.5g; TX10 1.5g; TX10 sodium sulfonate 2.0g, sulfonated petro-leum 14.0g, terepthaloyl moietie 13.0g; Return water 10000g joins in the mixing tank that whipping appts is housed, stirring at room 1.5h.Make oil-displacing agent.
In temperature is 80 ℃, salinity 25000mg/L (Ca
2++ Mg
2+=552mg/L), DV-II type Brookfield viscometer (UL joint) is 30 rev/mins of conditions, and recording viscosity is 18.0mPa.S; Use the TX-500C interfacial tensimeter, under 5000 rev/mins of conditions of speed of rotation, minimum IT is 2.0 * 10
-3MN/m.
Claims (3)
1. one kind is used for the oil-displacing agent that TOR improves oil recovery factor, it is characterized in that this oil-displacing agent is made up of following raw materials by weight:
High molecular weight water soluble polymer 0.01～0.3%,
Nonionogenic tenside 0.01～0.2%,
AS 0.05～0.45%,
Zwitterionics 0～0.05%,
Additive 0.01～1.5%,
All the other add water to 100%;
Wherein said high molecular weight water soluble polymer is a kind of in SEPIGEL 305, modified polyacrylamide or the XG 550;
Said AS is one or more of sulfonated alkylbenzene, sulfonated petro-leum, petroleum carboxylate, side chain sulphonate, succsinic acid sulphonate, poly alkyl alcohol sun Vinyl Ether vitriol, sodium alkyl benzene sulfonate, pyrrolidyl keto-earboxylic acid sodium, TX10 sodium sulfonate, Gemini surface active agent and sodium carboxymethylcellulose pyce;
Said nonionogenic tenside is one or more of AEO, polyoxyethylene nonylphenol, methylcellulose gum M20, Natvosol, hydroxypropylcellulose, Vinylpyrrolidone polymer, Z 150PH, iso-octyl phenolic group Soxylat A 25-7, TX10, polyoxyethylene octyl phenyl ether, aliphatic acid polyethenoxy ether, AEO, polyoxyethylene alkyl amine, sorbyl alcohol and sorbitol acetal verivate;
Said zwitterionics is one or more of imidazoline type carboxylate salt, imidazoline type phosphoric acid salt, sulfo group imidazolinium betaine, carboxylic acid trimethyl-glycine, N-amido-carboxylic acid trimethyl-glycine and N-alkylthio carboxylic acid trimethyl-glycine;
Described additive is low-carbon alcohol, low-carbon (LC) ketone or the low-carbon (LC) ether of carbon chain lengths C1-C4.
2. the described oil-displacing agent of claim 1, wherein water is common clear water or return water.
3. method for preparing the said oil-displacing agent of claim 1 is characterized in that being undertaken by following method:
With 0.01～0.3% high molecular weight water soluble polymer, 0.01～0.2% nonionogenic tenside, 0.05～0.45% AS; 0～0.05% zwitterionics mixes; Additive 0.01～1.5% joins in the reactor drum that has whipping appts, adds water to 100%; Stir room temperature reaction 1.5～2.5h down, make oil-displacing agent.
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