CN104109518A - Oil displacement composition used for low permeability oil reservoirs, and preparation method thereof - Google Patents
Oil displacement composition used for low permeability oil reservoirs, and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an oil displacement composition used for low permeability oil reservoirs, and a preparation method thereof, and mainly solves the problems of easy stratum obstruction and difficult injection in the low permeability oil reservoir oil displacement process of present composite flooding polymers. The oil displacement composition contains a long carbon chain betaine surfactant and an inorganic salt, wherein the long carbon chain betaine surfactant is anyone selected from long chain carboxylic acid betaine and sulfonic acid betaine, the carbon chain is a C14-C40 alkyl or alkenyl group, the inorganic salt is anyone of or a composition of CaCl2, MgCl2, NaCl and NaHCO3, and a mass ratio of the long carbon chain betaine surfactant to the inorganic salt is 1:(1-100). The oil displacement composition has the advantages of formation of oil-water ultralow interface tension, decompression and augmented injection, and simple system, well solves the problems, and can be used in the intensified oil production process of the low permeability oil reservoirs.
Description
Technical field
The present invention relates to a kind of displacement of reservoir oil composition and method of making the same for low-permeability oil deposit.
Background technology
The most of main force in China land oil field enters the tail period stage, and water content and oil field produced degree are more and more higher, under these circumstances, employs and to have developed low-permeability oil deposit extremely urgent.Because low-permeability oil deposit ubiquity that pore throat is tiny, non-darcy flow and trigger pressure high, surface molecular power and capillary force action are strong, while only having the larger displacement pressure of existence, liquid could flow.Therefore, step-down augmented injection is to improve the vital factor of these oil recoveries.
The flooding method of applying in current Oil extraction can be divided into four large classes: the one, and heating power drives, and comprises steam flood, combustion in situ etc.; The 2nd, mixed phase drives, and comprises CO
2mixed phase, hydrocarbon mixed phase and other rare gas element mixed phases drive; The 3rd, chemical flooding; The 4th, microbe oil production, comprises that biological polymer, MICROBIAL SURFACTANT drive.Wherein, chemical flooding is the technology of extremely important in intensified oil reduction and extensive enforcement, comprises the multiple combination technology of polymer flooding, surfactant flooding, caustic waterflooding etc. and polymkeric substance, alkali, tensio-active agent.
The effect of chemical flooding is the result of physical action and chemical action, and physical action refers to the effect that involves of displacing fluid, and chemical action refers to the microcosmic oil drive effect of displacing fluid.The core of chemical action is to reduce the interfacial tension of displacing fluid and crude oil.Tensio-active agent is owing to having oleophylic (hydrophobic) and hydrophilic (oleophobic) character concurrently, and in the time that tensio-active agent is water-soluble, molecule is mainly distributed on water-oil interface, can significantly reduce oil water interfacial tension.The reduction of oil water interfacial tension means that surfactant system can overcome the force of cohesion between crude oil, and larger oil droplet is dispersed into little oil droplet, thereby improves the percent of pass of crude stream in the time of pore throat.Physical action is realized by polymkeric substance, and the polymkeric substance of high molecular can improve the viscosity of injection liquid, improves the mobility ratio of profit phase, and then improves sweep efficiency.Chemical combined flooding can be given full play to the synergy of various chemical reagent, increases substantially oil displacement efficiency.But chemical combined flooding flooding system exists some problems, the polymkeric substance in chemical flooding, because molecule is larger, is easy to stop up duct, causes and injects difficulty, is difficult to successful Application in low-permeability oil deposit.Therefore, development of low-permeability oil reservoir is a great problem, and the average recovery ratio that Sinopec has been developed low-permeability oil deposit unit is 22.2%, lower by 4.1% than the average recovery ratio of foreign same type oil reservoir.
At present, improve development of low-permeability oil reservoir situation and conventionally adopt several method: the one, physical mechanical way, i.e. infilled well pattern, and/or bulk fracture treatment and pit shaft lift technique etc.; The 2nd, whether gas drive, by realizing mixed phase or non-mixed phase the mother oil displacement in stratum out, reservoir pressure, exist the conditions such as crack to bring very large impact to tar productivity; The 3rd, in chemical flooding system, add low-molecular-weight polymkeric substance, the common <5000000 of molecular weight.As at document " oilfield chemistry " 2008, in vol25, mention a kind of sultaine with aromatic ring and can form ultralow interfacial tension with crude oil, composite with low-molecular-weight polyacrylamide (4800000), adopt synthetic core, rock core mean permeability is 29 ~ 46mD, tensio-active agent 1000mg/L, when polymkeric substance 400mg/L, improve recovery ratio 10%, tensio-active agent 1000mg/L, though can improve recovery ratio to 16% when polymkeric substance 800mg/L, but inject difficulty.
Recently, viscoelastic surfactant because of its molecular weight little, under high-shear, viscosity is very low, viscosity rise under low shearing, the easily row of returning, can, to features such as stratum damage, not cause oilfielder's concern gradually.As patent CN101182411A mentions the displacement of reservoir oil composition of the vermiculate glues that a kind of anion surfactant forms, under alkaline condition, induce sodium oleate to make with the ionogen containing sodium ion, can improve to a certain extent recovery ratio.In said composition, there is no polymkeric substance, can be applied in low permeability pay oil displacement process, document " China University Of Petroleum Beijing's journal " 2009, vol33 adopts oleic acid trimethyl-glycine can form highly viscous fluid in the 2%HCl aqueous solution, etc.But in above-mentioned composition, contain mineral alkali or acid, bring injury to stratum, and the viscoelastic composition of report all only focuses on its aggregate structure in the aqueous solution, can not simultaneously form ultralow interfacial tension with crude oil.
For this reason, the invention provides a kind of displacement of reservoir oil composition of the alkali-free of growing carbochain beet alkali surface activator and inorganic salt composition, make body have mutually high viscosity by the self-assembly of control surface promoting agent, tensio-active agent itself has high interfacial activity simultaneously, thereby improves the recovery ratio of low-permeability oil deposit.
Summary of the invention
One of technical problem to be solved by this invention is that the polymkeric substance in existing chemical combined flooding easily causes reservoir choke for low-permeability oil deposit oil displacement process, inject difficult problem, be provided for the displacement of reservoir oil composition of low-permeability oil deposit, this displacement of reservoir oil composition is in forming profit ultra low interfacial tension, there is step-down augmented injection, the simple advantage of system.
Two of technical problem to be solved by this invention is to provide a kind of preparation method of the displacement of reservoir oil composition corresponding with one of technical solution problem.
Three of technical problem to be solved by this invention is to provide a kind of flooding method corresponding with one of above-mentioned technical problem.
For one of solving the problems of the technologies described above, the technical solution used in the present invention is as follows: for the displacement of reservoir oil composition of low-permeability oil deposit, comprise long carbochain beet alkali surface activator, inorganic salt, described long carbochain beet alkali surface activator is selected from any one in long-chain carboxylic acid's betaine salt, sulfonate trimethyl-glycine, and inorganic salt are selected from CaCl
2, MgCl
2, NaCl, NaHCO
3in at least one;
Long-chain carboxylic acid's betaine salt general molecular formula is:
Long-chain sulfonate betaine salt general molecular formula is:
Described R is C
14~ C
40alkyl, thiazolinyl in any one, described R ' is C
1~ C
5alkylidene group, R ' ' is C
1~ C
5alkylidene group, hydroxyl substituted alkylene in any one, the mass ratio of described long-chain beet alkali surface activator and described inorganic salt is 1:(1 ~ 100).
R described in technique scheme is preferably C
16~ C
30between alkyl or alkenyl.The mass ratio of described long-chain beet alkali surface activator and described inorganic salt is preferably 1:(2 ~ 50).
The present composition can solid form supply, all right paste or the supply of solution form.When with solid or paste form for seasonable, those skilled in the art will know that with after water dissolution for the displacement of reservoir oil.
Convenient for rig-site utilization, the present composition preferably includes water.Now more preferably in described displacement of reservoir oil composition by weight described displacement of reservoir oil composition be (0.55 ~ 16) with the ratio of water: 100.
For two of above-mentioned technical problem, technical scheme of the present invention is as follows: the preparation method of the described displacement of reservoir oil composition for low-permeability oil deposit, comprises the following steps:
A) lipid acid or its ester and required amidation reagent are added to reactor, in 140 ~ 170 DEG C of reactions 8 ~ 20 hours; Then add sulfonated reagent or carboxylation reagent, continue to react 3 ~ 10 hours in 75 ~ 95 DEG C, obtain alkyl betaine; According to starting raw material meter, lipid acid or its ester: amidation reagent: the mol ratio of sulfonated reagent or carboxylation reagent is 1:(1 ~ 3): (1 ~ 3);
B) beet alkali surface activator inorganic salt and step a being obtained is dissolved in the water and mixes, and obtains required composition.
Amidation reagent general molecular formula described in technique scheme is preferably
, wherein R ' is C
1~ C
5alkylidene group, described sulfonated reagent general molecular formula is preferably
, described carboxylation reagent molecule general formula is preferably
, R ' ' is preferably C
1~ C
5alkylidene group, hydroxyl substituted alkylene in any one.
For solve the problems of the technologies described above three, technical scheme of the present invention is as follows: a kind of flooding method of low-permeability oil deposit, comprises that the displacement of reservoir oil composition of described solution form is injected to low-permeability oil deposit carries out the displacement of reservoir oil.
The rate of permeation of low-permeability oil deposit described in technique scheme is preferably 1 ~ 40mD, more preferably 2 ~ 30mD.
In displacement of reservoir oil composition of the present invention, do not contain macromolecular polymkeric substance, the small molecules aggregate that relies on tensio-active agent and inorganic salt to form regulates the viscosity of composition, in improving sweep efficiency, reach the object of step-down augmented injection, and tensio-active agent can reduce oil, water termination tension force simultaneously, thereby effectively overcome the force of cohesion between crude oil, be conducive to former oil-out, and then significantly improve oil displacement efficiency.
In low-permeability oil deposit enhanced oil recovery process, adopt displacement of reservoir oil composition of the present invention, there is interfacial activity high: surfactant composition consumption is can form 10 with the underground crude oil in Henan under 0.01 ~ 0.5% condition
-3~ 10
-4mN/m ultra low interfacial tension; Adopt rate of permeation be 30 millidarcies fill out sand tube model, injection pressure only has 80% of water injection pressure, can continue to improve recovery ratio 12% on the basis of water drive.
Below by embodiment, the present invention is further elaborated.
Embodiment
[embodiment 1]
By 9-octadecenoic acid and N, N-dimethyl-Putriscine drops in reactor according to mol ratio 1:1.5, at 165 DEG C, stir 8h, rear 165 DEG C of oil pumps vacuumize removes unreacted N, N-dimethyl-1,4-butanediamine is 99.0wt% through liquid chromatogram measuring octadecylene acid amides butanediamine content.In above-mentioned system, be that 1:1.5 adds 4-chloro-butyric acid sodium according to 9-octadecenoic acid and 4-chloro-butyric acid sodium mol ratio again, react 6h with 85 DEG C, after reaction finishes, remove unreacted 4-chloro-butyric acid sodium with absolute ethanol washing, after steaming desolventizes, obtain octadecylene acid amides butyrobetaine, content is 97.0wt%.
Octadecylene acid amides butyrobetaine is mixed to composition displacement of reservoir oil composition with NaCl according to mass ratio 1:10, this displacement of reservoir oil composition mixes according to mass ratio 5.5:100 with water, while measuring 25 DEG C with Ma Erwen dynamic light scattering particle instrument Nano ZS90, the micella size of its formation, the results are shown in Table 1.
At 75 DEG C, drip interfacial tensimeter with TX-500C rotation and measure the oil water interfacial tension between composition and the Henan crude oil of octadecylene acid amides butyrobetaine, NaCl and water composition, the results are shown in Table 1.
It is 30 centimetres in length, diameter is 2.5 centimetres, rate of permeation is to carry out oil displacement test on the rock core of 20 bold and unconstrained darcies, temperature is 75 DEG C, first water is driven to moisture 98wt%, metaideophone 0.3pv(rock pore volume) octadecylene acid amides butyrobetaine, NaCl and the composition of water composition after, be driven to moisture 100wt%, composition drives injection pressure and the results are shown in Table 1 with water drive injection pressure ratio and raising oil recovery factor.
[embodiment 2]
By 12-tetracosenoic acid and N, N-dimethyl-1,2-quadrol drops in reactor according to mol ratio 1:3, at 160 DEG C, stir 10h, rear 165 DEG C of oil pumps vacuumize removes unreacted N, N-dimethyl-1，2-diaminoethane is 98.9wt% through liquid chromatogram measuring two tetradecene acid amides quadrol content.In above-mentioned system, be that 1:3 adds 2-chloroethyl sodium sulfonate according to 12-tetracosenoic acid and 2-chloroethyl sodium sulfonate mol ratio again, react 10h with 80 DEG C, after reaction finishes, remove unreacted 2-chloroethyl sodium sulfonate with absolute ethanol washing, after steaming desolventizes, obtain two tetradecene acid amides ethyl trimethyl-glycines, content is 97.1wt%.
By two tetradecene acid amides ethyl trimethyl-glycine and CaCl
2mix composition displacement of reservoir oil composition according to mass ratio 1:5, this displacement of reservoir oil composition mixes according to mass ratio 3:100 with water, and while measuring 25 DEG C with Ma Erwen dynamic light scattering particle instrument Nano ZS90, the micella size of its formation, the results are shown in Table 1.
At 75 DEG C, drip interfacial tensimeter with TX-500C rotation and measure two tetradecene acid amides ethyl trimethyl-glycines, CaCl
2and the oil water interfacial tension between composition and the Henan crude oil of water composition, the results are shown in Table 1.
Be 30 centimetres in length, diameter is 2.5 centimetres, and rate of permeation is to carry out oil displacement test on the rock core of 10 bold and unconstrained darcies, and temperature is 75 DEG C, and first water is driven to moisture 98wt%, metaideophone 0.3pv(rock pore volume) two tetradecene acid amides ethyl trimethyl-glycines, CaCl
2after the composition of water composition, be driven to moisture 100wt%, composition drives injection pressure and the results are shown in Table 1 with water drive injection pressure ratio and raising oil recovery factor.
[embodiment 3]
By 7,15-lumequeic acid and N, N-dimethyl-1,2-quadrol drops in reactor according to mol ratio 1:2, at 170 DEG C, stir 20h, rear 165 DEG C of oil pumps vacuumize removes unreacted N, N-dimethyl-1,2-quadrol is 99.0wt% through liquid chromatogram measuring 30 alkene acid amides quadrol content.Again in above-mentioned system according to 7,15-lumequeic acid and chloromethane sodium sulfonate mol ratio are that 1:1.5 adds chloromethane sodium sulfonate, react 3h with 95 DEG C, after reaction finishes, remove unreacted chloromethane sodium sulfonate with absolute ethanol washing, after steaming desolventizes, obtain 30 alkene acid amides ethyl trimethyl-glycines, content is 97.3wt%.
By 30 alkene acid amides ethyl trimethyl-glycine and NaHCO
3mix composition displacement of reservoir oil composition according to mass ratio 1:2, this displacement of reservoir oil composition mixes according to mass ratio 0.55:100 with water, and while measuring 25 DEG C with Ma Erwen dynamic light scattering particle instrument Nano ZS90, the micella size of its formation, the results are shown in Table 1.
At 75 DEG C, drip interfacial tensimeter with TX-500C rotation and measure 30 alkene acid amides ethyl trimethyl-glycines, NaHCO
3and the oil water interfacial tension between composition and the Henan crude oil of water composition, the results are shown in Table 1.
Be 30 centimetres in length, diameter is 2.5 centimetres, and rate of permeation is to carry out oil displacement test on the rock core of 30 bold and unconstrained darcies, and temperature is 75 DEG C, and first water is driven to moisture 98wt%, metaideophone 0.3pv(rock pore volume) 30 alkene acid amides ethyl trimethyl-glycines, NaHCO
3after the composition of water composition, be driven to moisture 100wt%, composition drives injection pressure and the results are shown in Table 1 with water drive injection pressure ratio and raising oil recovery factor.
[embodiment 4]
By hexadecyl carboxylate methyl ester and N, N-dimethyl-1,5-pentamethylene diamine drops in reactor according to mol ratio 1:1.5, at 140 DEG C, stir 20h, rear 175 DEG C of oil pumps vacuumize removes unreacted N, N-dimethyl-1,5-pentamethylene diamine, is 99.2wt% through liquid chromatogram measuring hexadecyl acid amides pentamethylene diamine content.In above-mentioned system, be that 1:1 adds 4-chloro-3-hydroxyl Sodium propanecarboxylate according to hexadecyl carboxylate methyl ester and 4-chloro-3-hydroxyl Sodium propanecarboxylate mol ratio again, react 10h with 80 DEG C, after reaction finishes, remove unreacted 4-chloro-3-hydroxyl Sodium propanecarboxylate with absolute ethanol washing, after steaming desolventizes, obtain hexadecyl acid amides amyl group trimethyl-glycine, content is 97.0wt%.
By hexadecyl acid amides amyl group trimethyl-glycine and MgCl
2mix composition displacement of reservoir oil composition according to mass ratio 1:50, this displacement of reservoir oil composition mixes according to mass ratio 2.5:100 with water, and while measuring 25 DEG C with Ma Erwen dynamic light scattering particle instrument Nano ZS90, the micella size of its formation, the results are shown in Table 1.
At 75 DEG C, drip interfacial tensimeter with TX-500C rotation and measure hexadecyl acid amides amyl group trimethyl-glycine, MgCl
2and the oil water interfacial tension between composition and the Henan crude oil of water composition, the results are shown in Table 1.
Be 30 centimetres in length, diameter is 2.5 centimetres, and rate of permeation is to carry out oil displacement test on the rock core of 2 bold and unconstrained darcies, and temperature is 75 DEG C, and first water is driven to moisture 98wt%, metaideophone 0.3pv(rock pore volume) hexadecyl acid amides amyl group trimethyl-glycine, MgCl
2after the composition of water composition, be driven to moisture 100wt%, composition drives injection pressure and the results are shown in Table 1 with water drive injection pressure ratio and raising oil recovery factor.
[embodiment 5]
By 5,10-eicosenoic acid and N, N-dimethyl-1,3-propylene diamine drops in reactor according to mol ratio 1:1, at 165 DEG C, stirs 20h, and rear 165 DEG C of oil pumps vacuumize removes unreacted N, N-dimethyl-1,3-propylene diamine, is 98.9wt% through liquid chromatogram measuring icosa alkene acid amides propylene diamine content.In above-mentioned system, be that 1:1.5 adds sodium chloroacetate according to 5,10-eicosenoic acid and sodium chloroacetate mol ratio again, react 3h with 90 DEG C, after reaction finishes, remove unreacted sodium chloroacetate with absolute ethanol washing, after steaming and desolventizing, obtain icosa alkene amido propyl betaine, content is 97.6wt%.
By icosa alkene amido propyl betaine, NaCl, CaCl
2mix composition displacement of reservoir oil composition according to mass ratio 1:27:3, this displacement of reservoir oil composition mixes according to mass ratio 16:100 with water, and while measuring 25 DEG C with Ma Erwen dynamic light scattering particle instrument Nano ZS90, the micella size of its formation, the results are shown in Table 1.
At 75 DEG C, drip interfacial tensimeter with TX-500C rotation and measure icosa alkene amido propyl betaine, NaCl, CaCl
2and the oil water interfacial tension between composition and the Henan crude oil of water composition, the results are shown in Table 1.
Be 30 centimetres in length, diameter is 2.5 centimetres, and rate of permeation is to carry out oil displacement test on the rock core of 15 bold and unconstrained darcies, and temperature is 75 DEG C, and first water is driven to moisture 98wt%, metaideophone 0.3pv(rock pore volume) icosa alkene amido propyl betaine, NaCl, CaCl
2after the composition of water composition, be driven to moisture 100wt%, composition drives injection pressure and the results are shown in Table 1 with water drive injection pressure ratio and raising oil recovery factor.
[embodiment 6]
By octadecyl carboxylate methyl ester and N, N-dimethyl methyl diamines drops in reactor according to mol ratio 1:1.5, at 140 DEG C, stirs 20h, and rear 160 DEG C of oil pumps vacuumize removes unreacted N, N-dimethyl methyl diamines is 99.0wt% through liquid chromatogram measuring octadecyl acid amides methanediamine content.In above-mentioned system, be that 1:3 adds 3-chloro-2-hydroxypropanesulfonacid acid sodium salt according to octadecyl carboxylate methyl ester and 3-chloro-2-hydroxypropanesulfonacid acid sodium salt mol ratio again, react 10h with 80 DEG C, after reaction finishes, remove unreacted 3-chloro-2-hydroxypropanesulfonacid acid sodium salt with absolute ethanol washing, after steaming desolventizes, obtain octadecyl acid amides methyl betaine, content is 97.1wt%.
By octadecyl acid amides methyl betaine, MgCl
2, CaCl
2mix composition displacement of reservoir oil composition according to mass ratio 1:1.5:1.5, this displacement of reservoir oil composition mixes according to mass ratio 1:100 with water, and while measuring 25 DEG C with Ma Erwen dynamic light scattering particle instrument Nano ZS90, the micella size of its formation, the results are shown in Table 1.
At 75 DEG C, drip interfacial tensimeter with TX-500C rotation and measure octadecyl acid amides methyl betaine, MgCl
2, CaCl
2and the oil water interfacial tension between composition and the Henan crude oil of water composition, the results are shown in Table 1.
Be 30 centimetres in length, diameter is 2.5 centimetres, and rate of permeation is to carry out oil displacement test on the rock core of 10 bold and unconstrained darcies, and temperature is 75 DEG C, and first water is driven to moisture 98wt%, metaideophone 0.3pv(rock pore volume) octadecyl acid amides methyl betaine, MgCl
2, CaCl
2after the composition of composition, be driven to moisture 100wt%, composition drives injection pressure and water drive injection pressure ratio and improves oil recovery factor and the results are shown in Table 1.
[embodiment 7]
By pentadecyl carboxylate methyl ester and N, N-dimethyl-1,5-pentamethylene diamine drops in reactor according to mol ratio 1:1.5, at 140 DEG C, stir 20h, rear 175 DEG C of oil pumps vacuumize removes unreacted N, N-dimethyl-1,5-pentamethylene diamine, is 99.0wt% through liquid chromatogram measuring pentadecyl acid amides pentamethylene diamine content.In above-mentioned system, be that 1:2 adds 6-chlorine Sodium n-caproate according to pentadecyl carboxylate methyl ester and 6-chlorine Sodium n-caproate mol ratio again, react 10h with 80 DEG C, after reaction finishes, remove unreacted 6-chlorine Sodium n-caproate with absolute ethanol washing, after steaming desolventizes, obtain pentadecyl acid amides amyl group trimethyl-glycine, content is 97.1wt%.
Pentadecyl acid amides amyl group trimethyl-glycine is mixed to composition displacement of reservoir oil composition with NaCl according to mass ratio 1:100, this displacement of reservoir oil composition mixes according to mass ratio 16:100 with water, while measuring 25 DEG C with Ma Erwen dynamic light scattering particle instrument Nano ZS90, the micella size of its formation, the results are shown in Table 1.
At 75 DEG C, drip interfacial tensimeter with TX-500C rotation and measure the oil water interfacial tension between composition and the Henan crude oil of pentadecyl acid amides amyl group trimethyl-glycine, NaCl and water composition, the results are shown in Table 1.
It is 30 centimetres in length, diameter is 2.5 centimetres, rate of permeation is to carry out oil displacement test on the rock core of 20 bold and unconstrained darcies, temperature is 75 DEG C, first water is driven to moisture 98wt%, metaideophone 0.3pv(rock pore volume) pentadecyl acid amides amyl group trimethyl-glycine, NaCl and the composition of water composition after, be driven to moisture 100wt%, composition drives injection pressure and the results are shown in Table 1 with water drive injection pressure ratio and raising oil recovery factor.
[embodiment 8]
By 10,20,30-40 carbon enoic acids and N, N-dimethyl-Putriscine drops in reactor according to mol ratio 1:1.5, at 165 DEG C, stirs 8h, rear 165 DEG C of oil pumps vacuumize removes unreacted N, N-dimethyl-Putriscine is 98.9wt% through liquid chromatogram measuring 40 alkene acid amides butanediamine content.Again in above-mentioned system according to 10,20,30-40 carbon enoic acids and 4-chloro-butyric acid sodium mol ratio are that 1:1.5 adds 4-chloro-butyric acid sodium, react 6h with 85 DEG C, after reaction finishes, remove unreacted 4-chloro-butyric acid sodium with absolute ethanol washing, after steaming and desolventizing, obtain 40 alkene acid amides butyrobetaines, content is 97.1wt%.
40 alkene acid amides butyrobetaines are mixed to composition displacement of reservoir oil composition with NaCl according to mass ratio 1:10, this displacement of reservoir oil composition mixes according to mass ratio 5.5:100 with water, while measuring 25 DEG C with Ma Erwen dynamic light scattering particle instrument Nano ZS90, the micella size of its formation, the results are shown in Table 1.
At 75 DEG C, drip interfacial tensimeter with TX-500C rotation and measure the oil water interfacial tension between composition and the Henan crude oil of 40 alkene acid amides butyrobetaines, NaCl and water composition, the results are shown in Table 1.
It is 30 centimetres in length, diameter is 2.5 centimetres, rate of permeation is to carry out oil displacement test on the rock core of 20 bold and unconstrained darcies, temperature is 75 DEG C, first water is driven to moisture 98wt%, metaideophone 0.3pv(rock pore volume) 40 alkene acid amides butyrobetaines, NaCl and the composition of water composition after, be driven to moisture 100wt%, composition drives injection pressure and the results are shown in Table 1 with water drive injection pressure ratio and raising oil recovery factor.
[embodiment 9]
By 9-octadecenoic acid and N, N-dimethyl-Putriscine drops in reactor according to mol ratio 1:1.5, at 165 DEG C, stir 8h, rear 165 DEG C of oil pumps vacuumize removes unreacted N, N-dimethyl-1,4-butanediamine is 99.0wt% through liquid chromatogram measuring octadecylene acid amides butanediamine content.In above-mentioned system, be that 1:1.5 adds 5-chlorine penta sodium sulfonate according to 9-octadecenoic acid and 5-chlorine penta sodium sulfonate mol ratio again, react 6h with 85 DEG C, after reaction finishes, remove unreacted 5-chlorine penta sodium sulfonate with absolute ethanol washing, after steaming desolventizes, obtain octadecylene acid amides butyrobetaine, content is 97.0wt%.
Octadecylene acid amides butyrobetaine is mixed to composition displacement of reservoir oil composition with NaCl according to mass ratio 1:1, this displacement of reservoir oil composition mixes according to mass ratio 1:100 with water, while measuring 25 DEG C with Ma Erwen dynamic light scattering particle instrument Nano ZS90, the micella size of its formation, the results are shown in Table 1.
At 75 DEG C, drip interfacial tensimeter with TX-500C rotation and measure the oil water interfacial tension between composition and the Henan crude oil of octadecylene acid amides butyrobetaine, NaCl and water composition, the results are shown in Table 1.
It is 30 centimetres in length, diameter is 2.5 centimetres, rate of permeation is to carry out oil displacement test on the rock core of 20 bold and unconstrained darcies, temperature is 75 DEG C, first water is driven to moisture 98wt%, metaideophone 0.3pv(rock pore volume) octadecylene acid amides butyrobetaine, NaCl and the composition of water composition after, be driven to moisture 100wt%, composition drives injection pressure and the results are shown in Table 1 with water drive injection pressure ratio and raising oil recovery factor.
[comparative example 1]
By tridecyl carboxylate methyl ester and N, N-dimethyl-1,4-butanediamine drops in reactor according to mol ratio 1:1.5, at 165 DEG C, stir 8h, rear 165 DEG C of oil pumps vacuumize removes unreacted N, N-dimethyl-Putriscine is 99.0wt% through liquid chromatogram measuring tridecyl acid amides butanediamine content.In above-mentioned system, be that 1:1.5 adds 4-chloro-butyric acid sodium according to tridecyl carboxylic acid and 4-chloro-butyric acid sodium mol ratio again, react 6h with 85 DEG C, after reaction finishes, remove unreacted 4-chloro-butyric acid sodium with absolute ethanol washing, after steaming desolventizes, obtain tridecyl acid amides butyrobetaine, content is 97.0wt%.
Tridecyl acid amides butyrobetaine is mixed to composition displacement of reservoir oil composition with NaCl according to mass ratio 1:10, this displacement of reservoir oil composition mixes according to mass ratio 5.5:100 with water, while measuring 25 DEG C with Ma Erwen dynamic light scattering particle instrument Nano ZS90, the micella size of its formation, the results are shown in Table 1.
At 75 DEG C, drip interfacial tensimeter with TX-500C rotation and measure the oil water interfacial tension between composition and the Henan crude oil of tridecyl acid amides butyrobetaine, NaCl and water composition, the results are shown in Table 1.
It is 30 centimetres in length, diameter is 2.5 centimetres, rate of permeation is to carry out oil displacement test on the rock core of 20 bold and unconstrained darcies, temperature is 75 DEG C, first water is driven to moisture 98wt%, metaideophone 0.3pv(rock pore volume) tridecyl acid amides butyrobetaine, NaCl and the composition of water composition after, be driven to moisture 100wt%, composition drives injection pressure and the results are shown in Table 1 with water drive injection pressure ratio and raising oil recovery factor.
[comparative example 2]
By 9-octadecenoic acid and N, N-dimethyl-Putriscine drops in reactor according to mol ratio 1:1.5, at 165 DEG C, stir 8h, rear 165 DEG C of oil pumps vacuumize removes unreacted N, N-dimethyl-1,4-butanediamine is 99.0wt% through liquid chromatogram measuring octadecylene acid amides butanediamine content.In above-mentioned system, be that 1:1.5 adds 4-chloro-butyric acid sodium according to 9-octadecenoic acid and 4-chloro-butyric acid sodium mol ratio again, react 6h with 85 DEG C, after reaction finishes, remove unreacted 4-chloro-butyric acid sodium with absolute ethanol washing, after steaming desolventizes, obtain octadecylene acid amides butyrobetaine, content is 97.0wt%.
Octadecylene acid amides butyrobetaine is mixed according to mass ratio 0.5:100 with water.
At 75 DEG C, drip interfacial tensimeter with TX-500C rotation and measure the oil water interfacial tension between octadecylene acid amides butyrobetaine and composition and the Henan crude oil of water composition, the results are shown in Table 1.
It is 30 centimetres in length, diameter is 2.5 centimetres, rate of permeation is to carry out oil displacement test on the rock core of 20 bold and unconstrained darcies, temperature is 75 DEG C, first water is driven to moisture 98wt%, metaideophone 0.3pv(rock pore volume) octadecylene acid amides butyrobetaine and the composition of water composition after, be driven to moisture 100wt%, composition drives injection pressure and the results are shown in Table 1 with water drive injection pressure ratio and raising oil recovery factor.
[comparative example 3]
The polyacrylamide of dodecyl carboxylic acid trimethyl-glycine, molecular weight 4800000, NaCl are mixed to composition displacement of reservoir oil composition according to mass ratio 1:0.5:10, this displacement of reservoir oil is mixed according to mass ratio 1.15:100 with water with composition.
At 75 DEG C, drip interfacial tensimeter with TX-500C rotation and measure the oil water interfacial tension between composition and the Henan crude oil of the polyacrylamide of empgen BB, molecular weight 4800000, NaCl and water composition, the results are shown in Table 1.
It is 30 centimetres in length, diameter is 2.5 centimetres, rate of permeation is to carry out oil displacement test on the rock core of 20 bold and unconstrained darcies, temperature is 75 DEG C, first water is driven to moisture 98wt%, metaideophone 0.3pv(rock pore volume) the composition of polyacrylamide, NaCl and water composition of empgen BB, molecular weight 4800000 after, be driven to moisture 100wt%, composition drives injection pressure and the results are shown in Table 1 with water drive injection pressure ratio and raising oil recovery factor.
1(is continued for table) aggregate size that forms of composition in embodiment and comparative example,
And compare and recovery ratio result with Henan crude oil interfacial tension, injection pressure
1(is continuous for table) aggregate size that forms of composition in embodiment and comparative example,
And compare and recovery ratio result with Henan crude oil interfacial tension, injection pressure
Claims (10)
1. for the displacement of reservoir oil composition of low-permeability oil deposit, comprise long carbochain beet alkali surface activator, inorganic salt, described long carbochain beet alkali surface activator is selected from any one in long-chain carboxylic acid's betaine salt, sulfonate trimethyl-glycine, and inorganic salt are selected from CaCl
2, MgCl
2, NaCl, NaHCO
3in at least one;
Long-chain carboxylic acid's betaine salt general molecular formula is:
Long-chain sulfonate betaine salt general molecular formula is:
Described R is C
14~ C
40alkyl, thiazolinyl in any one, described R ' is C
1~ C
5alkylidene group, R ' ' is C
1~ C
5alkylidene group, hydroxyl substituted alkylene in any one, the mass ratio of described long-chain beet alkali surface activator and described inorganic salt is 1:(1 ~ 100).
2. according to claim 1 for the displacement of reservoir oil composition of low-permeability oil deposit, it is characterized in that described R is C
16~ C
30between alkyl or alkenyl.
3. according to claim 1 for the displacement of reservoir oil composition of low-permeability oil deposit, the mass ratio that it is characterized in that described long-chain beet alkali surface activator and described inorganic salt is 1:(2 ~ 50).
4. according to the displacement of reservoir oil composition for low-permeability oil deposit described in any one in claims 1 to 3, it is characterized in that described composition comprises water.
5. displacement of reservoir oil composition according to claim 4, is characterized in that in described displacement of reservoir oil composition that described displacement of reservoir oil composition is (0.55 ~ 16) with the ratio of water by weight: 100.
6. according to the preparation method for the displacement of reservoir oil composition of low-permeability oil deposit described in claim 4 or 5, comprise the following steps:
A) lipid acid or its ester and required amidation reagent are added to reactor, in 140 ~ 170 DEG C of reactions 8 ~ 20 hours; Then add sulfonated reagent or carboxylation reagent, continue to react 3 ~ 10 hours in 75 ~ 95 DEG C, obtain alkyl betaine; According to starting raw material meter, lipid acid or its ester: amidation reagent: the mol ratio of sulfonated reagent or carboxylation reagent is 1:(1 ~ 3): (1 ~ 3);
B) beet alkali surface activator inorganic salt and step a being obtained is dissolved in the water and mixes, and obtains required composition.
7. according to claim 6 for the preparation method of the displacement of reservoir oil composition of low-permeability oil deposit, it is characterized in that described amidation reagent general molecular formula is
, wherein R ' is C
1~ C
5alkylidene group, described sulfonated reagent general molecular formula is
, described carboxylation reagent molecule general formula is
, R ' ' is C
1~ C
5alkylidene group, hydroxyl substituted alkylene in any one.
8. a flooding method for low-permeability oil deposit, comprises that displacement of reservoir oil composition described in any one in claim 4 or 5 is injected to low-permeability oil deposit carries out the displacement of reservoir oil.
9. the flooding method of low-permeability oil deposit according to claim 8, the rate of permeation that it is characterized in that described low-permeability oil deposit is 1 ~ 40mD.
10. the flooding method of low-permeability oil deposit according to claim 9, the rate of permeation that it is characterized in that described low-permeability oil deposit is 2 ~ 30mD.
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