CN104531118A - Method for preparing intelligent nanometer oil-displacing agent - Google Patents
Method for preparing intelligent nanometer oil-displacing agent Download PDFInfo
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- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
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- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
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- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/588—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
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Abstract
The invention discloses a method for preparing an intelligent nanometer oil-displacing agent. The method comprises the following steps: grafting a temperature-sensitive polymer, a hydrophilic polymer and a hydrophobic polymermer to the surfaces of nanoparticles by virtue of a covalent bond so as to prepare composite nanoparticles with temperature sensitive characteristic; and compounding the composite nanoparticles with alkali and surfactants, thereby obtaining the intelligent nanometer oil-displacing agent with temperature response characteristic. The nanometer oil-displacing agent has the characteristics that according to change of displacing fluid along with temperature in the using process, the hydrophilic and oleophylic performances of the nanometer oil-displacing agent can be regulated. The formation temperature is high, the nanometer oil-displacing agent is oleophylic, crude oil is conveniently stripped from the rock surface, and the recovery ratio is improved. The formation temperature is low, the nanometer oil-displacing agent is hydrophilic, and oil-water separation can be rapidly realized without a demulsifying agent. Moreover, the sizes of the nanoparticles correspondingly change along with temperature difference, and controllable dual effects of plugging and profile control and plug removal are achieved in the formation.
Description
Technical field
The present invention relates to oil-gas field and improve recovery ratio function field of nanometer material technology, especially relate to a kind of preparation method of intelligent nano oil-displacing agent.
Background technology
Nanoparticle is the molecule of size between 1-100nm.Nano particle diameter is little, and specific surface area is large, and surfactivity is high.In recent years, the application of nanoparticle in oil-gas field field starts to be paid close attention to, and nanometer displacement agent is paid much attention to due to the Oil Displacing Capacity of its uniqueness.Nanometer displacement agent has very large specific surface area and surface energy, significantly can reduce oil water interfacial tension, and make to inject fluid and be easy to the crude oil of blowhole to peel off, driven liquid displacement out.Meanwhile, the micro-pore of nanoparticle formation rock has temporary occlusion effect, can expand swept volume, and big area oil reservoir is obtained displacement, so greatly can improve recovery ratio.
Nanometer displacement agent achieves good effect in oil displacement process, improve oil recovery factor, but the subject matter still existed at present has: hydrophilic, the oleophylic performance of (1) nanoparticle are difficult to regulation and control, if nanoparticle wetting ability is too strong, then weak to the displacement ability to function of crude oil, if nanoparticle lipophilicity is strong, then reclaim in crude oil containing more nanoparticle, be difficult to removing, affect crude quality; (2) regulation and control of nano particle diameter size, need the nanoparticle by synthesizing different-grain diameter to carry out composite, preparation process is loaded down with trivial details.Therefore, there is the change of environmentally condition, auto-control nanometer displacement agent is hydrophilic, oleophylic performance, the research and development of the flooding system of auto-control nanometer displacement agent size, has great importance to the raising of nanometer displacement agent oil displacement efficiency and further genralrlization application.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of intelligent nano oil-displacing agent, the oil-displacing agent finished product prepared can the change of environmentally condition, automatically regulates hydrophilic, oleophylic performance and grain size size, and then realizes higher oil displacement efficiency.
For achieving the above object, the present invention can take following technical proposals:
The preparation method of intelligent nano oil-displacing agent of the present invention comprises the following steps:
The first step, 10 ~ 45 parts of nanoparticles and 1 ~ 15 part of double bond silane coupling agent are dissolved in reaction medium, react 2 ~ 8 hours at ambient temperature, then by 1 ~ 35 part of hydrophilic monomer, 0 ~ 30 part of hydrophobic monomer, 3 ~ 35 parts of function monomers, add above-mentioned system, then add 0.1 ~ 2 part of initiator, be warmed up to 60 ~ 90 DEG C, react 2 ~ 10 hours, obtained Intelligent Composite nanoparticle;
Second step, adds in above-mentioned composite nanoparticle dispersion liquid successively by 2 ~ 25 parts of alkali, 1 ~ 32 part of tensio-active agent, at ambient temperature, stirs 3 ~ 10 hours, i.e. obtained intelligent nano oil-displacing agent.
Described nanoparticle is selected from one or more in Nano particles of silicon dioxide, silicon nano, calcium carbonate nano particle, calcium oxide nanoparticle, graphite composite powder, copper oxide nano particle, zinc oxide nano-particle.
Described double bond silane coupling agent is selected from one or more in γ-methacryloxypropyl trimethoxy silane coupling agent, γ-methacryloxypropyl coupling agent, vinyltrimethoxy silane coupling agent and vinyltriethoxysilane coupling agent.
Described reaction medium is selected from one or more mixed solvents of methyl alcohol, ethanol, Virahol, propyl carbinol, DMF, acetone, butanone, tetrahydrofuran (THF) and water.
Described hydrophilic monomer is selected from one or more in acrylamide, vinylformic acid, sodium acrylate, sodium methacrylate, methacrylic acid, hydroxyethyl methacrylate, Hydroxyethyl Acrylate.
Described hydrophobic monomer is selected from one or more in methyl methacrylate, β-dimethyl-aminoethylmethacrylate, butyl methacrylate, pentylmethacrylate, methyl acrylate, ethyl propenoate, butyl acrylate, amyl acrylate, vinylbenzene or other hydrophobic monomers.
Described function monomer is selected from one or more in NIPA, N,N-DMAA, N, N-acrylamide.
Described initiator is selected from the one in Potassium Persulphate, ammonium persulphate, Sodium Persulfate, Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), hydrogen peroxide-ferric sulfate, hydrogen peroxide-iron(ic) chloride.
Described alkali is selected from the one in sodium hydroxide, potassium hydroxide, sodium carbonate, salt of wormwood, sodium bicarbonate, saleratus.
Described tensio-active agent is selected from the one in sodium lauryl sulphate, sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, Trimethyllaurylammonium bromide, dodecylphenyl ditallowdimethyl ammonium bromide.
For current nanometer displacement agent in use Problems existing, the intelligent polymer and hydrophilic polymer, hydrophobic polymer with environmental stimulus sensitivity characteristic are grafted to nanoparticle surface by the present invention simultaneously, prepare intelligent nano particle, then with alkali, surfactant compound, the nanometer flooding system with intelligent response characteristic is obtained.
The advantage of intelligent nano oil-displacing agent prepared by the present invention is:
(1) hydrophilic, the oleophylic performance controllable of nanometer displacement agent: by the change of temperature, hydrophilic, oleophylic performance can be regulated and controled.When running on stratum, envrionment temperature is high, and nanometer displacement agent shows as lipophilicity, tends to be combined with oil, promotes oil reservoir and moves forward, realize the displacement of reservoir oil at water-oil interface; When displacing fluid returns to ground, envrionment temperature reduces, and nanometer displacement agent changes wetting ability into, enters water layer from water-oil interface, realizes oil and water sharp separation, a large amount of emulsion splitter need not be used can to realize crude oil recovery fast.
(2) the size controllable of nanometer displacement agent: according to the difference of formation temperature, intelligent control size of particles size.In the earth formation, temperature is high, and size of particles becomes large, can shout carry out temporary transient shutoff to rock pore, and then expands swept volume, make not by the mother oil displacement that feeds through to out to reach raising oil displacement efficiency; When involve mention produce a desired effect time, by regulate fluid temperature (F.T.), size of particles is diminished, removes the shutoff that rock pore is shouted, so reduce injection pressure, reduce energy consumption.
(3) according to the requirement of Different Strata, can by selecting type and the molecular size range of nanoparticle surface polymkeric substance, regulation and control can regulate and control the parent/hydrophobic transition temperature of intelligent nano particle.This nanometer displacement agent can require to design targetedly, prepare according to stratum, applied widely.
Embodiment
Describe the specific embodiment of the present invention below in conjunction with embodiment, but the present invention is not confined to following examples.
embodiment 1:
15g nano silicon, 10mL vinyltrimethoxy silane coupling agent are dissolved in 120mL ethanol, stir 2 hours.Take 5g acrylamide, 15g NIPA is dissolved in 150mL water, until completely dissolved, adds above-mentioned mixed system, then adds 1.8g Potassium Persulphate, be warmed up to 70 DEG C, reacts 5 hours, obtained Intelligent Composite nanoparticle dispersion liquid;
Then 15g sodium hydroxide, 25g sodium lauryl sulphate are added above-mentioned nanoparticle dispersion liquid successively, under room temperature condition, stir 6 hours, be i.e. obtained intelligent nano oil-displacing agent.
embodiment 2:
25g nano silicon, 35mL vinyltriethoxysilane coupling agent are dissolved in 140mL DMF, stir 3 hours.Take 3g acrylamide, 1g methyl methacrylate, 28g NIPA is dissolved in 200mL water, until completely dissolved, add above-mentioned mixed system, then add 2.5g ammonium persulphate, be warmed up to 80 DEG C, react 4 hours, obtained Intelligent Composite nanoparticle dispersion liquid;
Then 23g sodium carbonate, 18g sodium lauryl sulphate are added in above-mentioned nanoparticle dispersion liquid successively, under room temperature condition, stir 5 hours, be i.e. obtained intelligent nano oil-displacing agent.
embodiment 3:
20g nano-calcium carbonate, 25mL γ-methacryloxypropyl trimethoxy silane coupling agent are dissolved in 120mL water and alcohol mixed solution, stir 5 hours.Take 10g acrylamide, 2g butyl methacrylate, 35g N,N-DMAA is dissolved in 300mL ethanol, until completely dissolved, add above-mentioned mixed system, then add 2.5g Sodium Persulfate, be warmed up to 80 DEG C, react 5 hours, obtained Intelligent Composite nanoparticle dispersion liquid;
15g salt of wormwood, 12g Sodium dodecylbenzene sulfonate are added in above-mentioned nanoparticle dispersion liquid successively, at ambient temperature, stirs 8 hours, be i.e. obtained intelligent nano oil-displacing agent.
embodiment 4:
25g nano silicon, 20mL γ-methacryloxypropyl coupling agent are dissolved in 180mL acetone, stir 4 hours.Take 8g acrylamide, 30g NIPA is dissolved in 300mL water, until completely dissolved, adds above-mentioned mixed system, then adds 2.5g Sodium Persulfate, be warmed up to 70 DEG C, reacts 8 hours, obtained Intelligent Composite nanoparticle dispersion liquid;
20g salt of wormwood, 15g Trimethyllaurylammonium bromide are added in above-mentioned nanoparticle dispersion liquid successively, at ambient temperature, stirs 8 hours, be i.e. obtained intelligent nano oil-displacing agent.
embodiment 5:
35g nano-silicon particle, 52mL γ-methacryloxypropyl coupling agent are dissolved in 180mL acetone, stir 4 hours.Take 18g acrylamide, 40g NIPA is dissolved in 350mL water, until completely dissolved, adds above-mentioned mixed system, then adds 4.8g ammonium persulphate, be warmed up to 85 DEG C, reacts 6 hours, obtained Intelligent Composite nanoparticle dispersion liquid;
25g salt of wormwood, 19g dodecylphenyl ditallowdimethyl ammonium bromide are added in above-mentioned nanoparticle dispersion liquid successively, at ambient temperature, stirs 15 hours, be i.e. obtained intelligent nano oil-displacing agent.
Claims (10)
1. a preparation method for intelligent nano oil-displacing agent, is characterized in that comprising the following steps:
The first step, 10 ~ 45 parts of nanoparticles and 1 ~ 15 part of double bond silane coupling agent are dissolved in reaction medium, react 2 ~ 8 hours at ambient temperature, then by 1 ~ 35 part of hydrophilic monomer, 0 ~ 30 part of hydrophobic monomer, 3 ~ 35 parts of function monomers, add above-mentioned system, then add 0.1 ~ 2 part of initiator, be warmed up to 60 ~ 90 DEG C, react 2 ~ 10 hours, obtained Intelligent Composite nanoparticle;
Second step, adds in above-mentioned composite nanoparticle dispersion liquid successively by 2 ~ 25 parts of alkali, 1 ~ 32 part of tensio-active agent, at ambient temperature, stirs 3 ~ 10 hours, i.e. obtained intelligent nano oil-displacing agent.
2. the preparation method of intelligent nano oil-displacing agent according to claim 1, is characterized in that: described nanoparticle is selected from one or more in Nano particles of silicon dioxide, silicon nano, calcium carbonate nano particle, calcium oxide nanoparticle, graphite composite powder, copper oxide nano particle, zinc oxide nano-particle.
3. the preparation method of intelligent nano oil-displacing agent according to claim 1, is characterized in that: described double bond silane coupling agent is selected from one or more in γ-methacryloxypropyl trimethoxy silane coupling agent, γ-methacryloxypropyl coupling agent, vinyltrimethoxy silane coupling agent and vinyltriethoxysilane coupling agent.
4. the preparation method of intelligent nano oil-displacing agent according to claim 1, it is characterized in that: described reaction medium is selected from one or more mixed solvents of methyl alcohol, ethanol, Virahol, propyl carbinol, DMF, acetone, butanone, tetrahydrofuran (THF) and water.
5. the preparation method of intelligent nano oil-displacing agent according to claim 1, is characterized in that: described hydrophilic monomer is selected from one or more in acrylamide, vinylformic acid, sodium acrylate, sodium methacrylate, methacrylic acid, hydroxyethyl methacrylate, Hydroxyethyl Acrylate.
6. the preparation method of intelligent nano oil-displacing agent according to claim 1, is characterized in that: described hydrophobic monomer is selected from one or more in methyl methacrylate, β-dimethyl-aminoethylmethacrylate, butyl methacrylate, pentylmethacrylate, methyl acrylate, ethyl propenoate, butyl acrylate, amyl acrylate, vinylbenzene or other hydrophobic monomers.
7. the preparation method of intelligent nano oil-displacing agent according to claim 1, is characterized in that: described function monomer is selected from one or more in NIPA, N,N-DMAA, N, N-acrylamide.
8. the preparation method of intelligent nano oil-displacing agent according to claim 1, is characterized in that: described initiator is selected from the one in Potassium Persulphate, ammonium persulphate, Sodium Persulfate, Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), hydrogen peroxide-ferric sulfate, hydrogen peroxide-iron(ic) chloride.
9. the preparation method of intelligent nano oil-displacing agent according to claim 1, is characterized in that: described alkali is selected from the one in sodium hydroxide, potassium hydroxide, sodium carbonate, salt of wormwood, sodium bicarbonate, saleratus.
10. the preparation method of intelligent nano oil-displacing agent according to claim 1, is characterized in that: described tensio-active agent is selected from the one in sodium lauryl sulphate, sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, Trimethyllaurylammonium bromide, dodecylphenyl ditallowdimethyl ammonium bromide.
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