CN106010494A - Low-permeability reservoir oil-displacement surfactant as well as preparation method and product thereof - Google Patents
Low-permeability reservoir oil-displacement surfactant as well as preparation method and product thereof Download PDFInfo
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Abstract
The invention provides a low-permeability reservoir oil-displacement surfactant as well as a preparation method and a product thereof. The preparation method comprises the following steps: in the presence of a basic catalyst with a non-ionic surfactant, carrying out a reaction between a non-ionic surfactant and a glycidyl ether compound which serve as raw materials by taking an organic solvent as a reaction solvent, so as to obtain a reaction solution; hydrolyzing the reaction solution in the presence of a pH adjuster; carrying out a reaction between the hydrolyzed product and a metal-organic compound under an alkaline condition, so as to obtain the low-permeability reservoir oil-displacement surfactant, wherein the molar ratio of the non-ionic surfactant to the glycidyl ether compound to the metal-organic compound to the basic catalyst to the pH adjuster is 8:4:4:1:2. The low-permeability reservoir oil-displacement surfactant provided by the invention can be used independently or in combination with other surfactants, has an anti-swelling effect while reducing oil-water interfacial tension and changing wettability, can increase the number of displacement fluid capillary tubes, and reduce the injection pressure, and has a good prospect in improving the water flooding effect and improving the oil recovery of low-permeability reservoirs.
Description
Technical field
The invention belongs to oil field chemical production field, specifically, relate to a kind of LOW PERMEABILITY RESERVOIR oil displacement surfactant
And prepare and product.
Background technology
China's land low permeability oil field is distributed widely in national 20 Duo Geyou districts, since the nineties grand celebration, Jilin,
The main oilfield such as the Liaohe River, triumph, long celebrating are found that many low-permeability oil deposits successively.According to statistics, verifying in recent years
Not employing in petroleum-in-place, the reserves of low-permeability oil deposit account for 58%, and in the petroleum-in-place verified, low
The petroleum-in-place proportion of infiltration oil reservoir is up to 60～70%.Low-permeability oil deposit is the most considerably long one section of China
The Main Resources basis produced in increasing the storage in time.
Particularity and complexity due to LOW PERMEABILITY RESERVOIR reservoir so that such reservoir water production efficiency is relatively low.In water filling
In development process, owing to the reservoir properties of low-permeability oil deposit is poor, complex pore structure, porosity is low, and pore throat radius is little,
Capillary pressure is high, and matrix permeability is low, and clay mineral content is high, and reservoir sensitivity particularly water-sensitive is serious, and water is locked
Effect highlights, and easily causes formation damage in drilling completion and development process.
Reservoir exploitation effect is had a great impact by the imbibition effect of low-permeability oil deposit reservoir.Owing to surfactant can
From reducing oil water interfacial tension, changing the rock wettability flowable crude oil of increase, improve aqueous phase relative permeability, reduce
Water injection pressure, improves the recovery ratio of LOW PERMEABILITY RESERVOIR, and therefore, the filtrational resistance existed for oil reservoir is big, water injection pressure is high
And the problem such as waterflood recovery efficiency factor is on the low side, what oil field at home was taked more adds based on surfactant in injecting water
Chemical system carrys out improving ecology effect.
The anionic petroleum sulfonate surfactant of the general displacement of reservoir oil, due to by adsorption losses amount and himself tied
The impact of structure characteristic, is not enough to increase substantially oil recovery factor in LOW PERMEABILITY RESERVOIR.Wherein use more be cloudy from
Subtype surfactant and the big class of nonionic surfactant two, and anionic and nonionic type surfactant is due to its molecule
In be compounded with the hydrophilic group that polyoxyethylene is different with anion two class, so this kind of surfactant has good boundary
Surface properties and anti-swollen performance, especially have in tertiary oil recovery field in the exploitation of low-permeability oil deposit and high salinity reservoirs
Have broad application prospects.
The problem that the reservoir characteristics complicated for LOW PERMEABILITY RESERVOIR and waterflooding extraction exist, develops one and has reduction
Oil water interfacial tension, change reservoir wettability have the efficient oil displacement system of antiexpanding action concurrently, can solve to a certain extent
LOW PERMEABILITY RESERVOIR oil extraction problem, improves oil recovery factor, has great answering to the oil recovery factor improving such oil reservoir
By value.
Summary of the invention
It is an object of the present invention to provide the preparation method of a kind of LOW PERMEABILITY RESERVOIR oil displacement surfactant；The present invention's
Purpose be big for LOW PERMEABILITY RESERVOIR filtrational resistance, water injection pressure is high and waterflood recovery efficiency factor is on the low side, and the one proposed fit
Close the surfactant of such oil reservoir.The dominant mechanism of the surfactant that this preparation method produces gained is to reduce profit
Interfacial tension and raising displacement efficiency.
Another object of the present invention is to the LOW PERMEABILITY RESERVOIR oil-displacement surface activity providing described preparation method to prepare
Agent.
A further object of the present invention is to provide a kind of LOW PERMEABILITY RESERVOIR oil displacement surfactant composition system.
For reaching above-mentioned purpose, on the one hand, the invention provides the preparation method of a kind of LOW PERMEABILITY RESERVOIR oil displacement surfactant,
Wherein, described method includes: with organic solvent as reaction dissolvent, in the presence of base catalyst, with non-ionic surface
Activating agent and (+)-2,3-Epoxy-1-propanol ether compound are that raw material reacts, and have reacted and have obtained reaction solution, and reaction solution is in acid
Hydrolyze under the conditions of property, then react with metal organic salt and obtain described LOW PERMEABILITY RESERVOIR oil displacement surfactant；Wherein, non-
Ionic surface active agent, (+)-2,3-Epoxy-1-propanol ether compound, metal organic salt, base catalyst and pH adjusting agent mole
Ratio is 8～80:4～40:4～40:1.
According to some specific embodiments of the present invention, wherein, described metal organic salt consumption is to be adjusted by reaction solution pH
Joint is 8-10.
It is to say, by controlling to add the amount of metal organic salt so that reaction solution is in the range of 8-10 at pH
React with metal organic salt and obtain described LOW PERMEABILITY RESERVOIR oil displacement surfactant.
According to some specific embodiments of the present invention, wherein, described with nonionic surfactant and (+)-2,3-Epoxy-1-propanol ethers
Compound is that to carry out reaction be to react under reflux to raw material；The most preferably react 2-8h；
According to some specific embodiments of the present invention, wherein, nonionic surfactant and (+)-2,3-Epoxy-1-propanol ether compound
Carrying out reaction is that the two mixture is first preheating to 30-90 DEG C, then back flow reaction；
According to some specific embodiments of the present invention, wherein, nonionic surfactant and (+)-2,3-Epoxy-1-propanol ether compound
Carrying out reaction is that the two mixture keeps at 30-90 DEG C 0.5h～2h, then back flow reaction.
According to some specific embodiments of the present invention, wherein, reaction solution is the hydrolyzed under acidic conditions at pH 3-5,
Then react with metal organic salt and obtain described LOW PERMEABILITY RESERVOIR oil displacement surfactant.
According to some specific embodiments of the present invention, wherein, regulation reaction solution be acid condition be this area routine behaviour
Make, acid such as can be used to be adjusted, be adjusted as added hydrochloric acid, sulphuric acid or acetum.
According to some specific embodiments of the present invention, wherein, described react with metal organic salt in the basic conditions anti-
Answering temperature is 30～90 DEG C；The most preferably react 3-9h.
According to some specific embodiments of the present invention, wherein, described react with metal organic salt in the basic conditions anti-
Answering temperature is 60～70 DEG C.
According to some specific embodiments of the present invention, wherein, described react with metal organic salt in the basic conditions anti-
It is 6-7h between Ying Shi.
According to some specific embodiments of the present invention, wherein, described react with metal organic salt in the basic conditions be
6-7h is reacted at 60～70 DEG C.
According to some specific embodiments of the present invention, wherein, described (+)-2,3-Epoxy-1-propanol ether compound is to drip mode to add
Enter；Preferably rate of addition is that 8-12 drips/min.
According to some specific embodiments of the present invention, wherein, described method comprises the steps:
(1) nonionic surfactant is dissolved in organic solvent, obtains nonionic surfactant solution；
(2) in the nonionic surfactant that step (1) obtains, add base catalyst, and drip (+)-2,3-Epoxy-1-propanol
Ether compound, drips and finishes, stirring reaction, has reacted and has obtained reaction solution；
(3) in the reaction solution of step (2), pH adjusting agent regulation pH value is added to acidity, hydrolysis, hydrolysis
Regulating reacting solution pH value after end the most neutral, add metal organic salt, reaction obtains described LOW PERMEABILITY RESERVOIR displacement of reservoir oil table
Face activating agent.
According to some specific embodiments of the present invention, wherein, described nonionic surfactant selected from alkanolamide,
Fatty alcohol-polyoxyethylene ether, alkylphenol polyoxyethylene or polyxyethylated acyl hydramine.
According to some specific embodiments of the present invention, wherein, described (+)-2,3-Epoxy-1-propanol ether compound contracts selected from pi-allyl
Water glycerin ether compounds, diglycidyl ether of ethylene glycol compounds or phenyl glycidyl ether compounds.
According to some specific embodiments of the present invention, wherein, described metal organic salt is alkaline metal organic salt；
According to other specific embodiments of the present invention, wherein, described metal organic salt is sodium organic salt；
According to other specific embodiments of the present invention, wherein, described metal organic salt be sodium acetate, sodium benzoate or
One in sodium chloroacetate.
According to some specific embodiments of the present invention, wherein, described organic solvent is methanol, ethanol, acetone and ether
In one or more.
According to some specific embodiments of the present invention, wherein, described base catalyst be sodium hydroxide, potassium hydroxide or
One in sodium carbonate.
According to some specific embodiments of the present invention, wherein, step (3) adds in the reaction solution of step (2)
PH adjusting agent regulation pH value hydrolyzes to 3-5.
According to some specific embodiments of the present invention, wherein, step (3) adds to the reaction solution of step (2)
It is at 80～100 DEG C, hydrolyze 1～3h after pH adjusting agent.
According to some specific embodiments of the present invention, wherein, step (3) after the end of the hydrolysis be use inorganic base or
Alkaline, inorganic salts regulation pH is to neutral.
Wherein said inorganic base can be inorganic base commonly used in the art, such as potassium hydroxide or sodium hydroxide；
Described alkaline, inorganic salts can be alkaline, inorganic salts commonly used in the art, the most alkali-metal hydrochlorate or
Bicarbonate, such as sodium carbonate, potassium carbonate, sodium bicarbonate or potassium bicarbonate.
According to some specific embodiments of the present invention, wherein, step (3) is anti-with metal organic salt in the basic conditions
After should terminating, also include removing metal organic salt with washing, filtering and the step of distillation of reducing pressure.
According to some specific embodiments of the present invention, wherein, step (3) is to remove metal with absolute ethanol washing to have
Machine salt, and obtain described LOW PERMEABILITY RESERVOIR oil displacement surfactant.
According to some specific embodiments of the present invention, wherein, the washing of step (3), the step of filtration repeat 2-3
Secondary.
According to some specific embodiments of the present invention, wherein, after step (3) adds metal organic salt, it is at pH
Under conditions of 8-10, reaction obtains described LOW PERMEABILITY RESERVOIR oil displacement surfactant.
According to some specific embodiments of the present invention, wherein, preparation method of the present invention comprises the steps:
(1) weigh a certain amount of nonionic surfactant and add appropriate organic solvent, stir；
(2) reaction solution in (1) adds appropriate base catalyst, take the ethers speed with 10/min
The stirring of degree dropping limit, limit, after dropping, increases the temperature to about 60 DEG C, and back flow reaction 6h at a constant temperature；
(3) in reaction system, pH adjusting agent is added, hydrolysis, adjust pH value to neutral afterwards, add and nonionic
The organic salt that type surfactant is proportional, in the basic conditions, heated and stirred, continues reaction 6h, reaction
Complete, with absolute ethanol washing, to filter, decompression distillation obtains product.
The outward appearance of the present invention is the faint yellow uniform liquid to yellow, has preferable water solublity.
The mentality of designing of the present invention is the advantage by combining nonionic surfactant and anion surfactant, and
And utilize ether can form hydrogen bond with hydroxylated clay, play antiexpanding action, form one and be suitable for LOW PERMEABILITY RESERVOIR exploitation
Surfactant oil displacement.
System of the present invention can be used alone or use compounding with other surface agents, for low-permeability oil deposit, to improve water
Drive formula.
On the other hand, present invention also offers the LOW PERMEABILITY RESERVOIR oil-displacement surface activity that described preparation method prepares
Agent.
According to some specific embodiments of the present invention, wherein, the Weight-average molecular of described LOW PERMEABILITY RESERVOIR oil displacement surfactant
Amount is 600-10 ten thousand.
Another aspect, present invention also offers a kind of LOW PERMEABILITY RESERVOIR oil displacement surfactant composition system, wherein, institute
State surface activator composition system and at least contain LOW PERMEABILITY RESERVOIR oil displacement surfactant of the present invention.
According to some specific embodiments of the present invention, wherein, described surface activator composition system possibly together with include to
Few a kind of nonionic and/or other surfactants of anion surfactant, wherein said LOW PERMEABILITY RESERVOIR displacement of reservoir oil table
Face activating agent and other surfactant weight ratios are 2:1-10:1.
Wherein it is understood that other surfactants described here, refer to except low permeability of the present invention
Hide other surfactants commonly used in the art of oil displacement surfactant, and other described surfactants are
Including at least one nonionic surfactant and/or anion surfactant.
According to some specific embodiments of the present invention, wherein, other described surfactants are non-selected from least one
Ionic surface active agent and/or anion surfactant.
According to some specific embodiments of the present invention, wherein, described surface activator composition system be possibly together with
One or both are selected from nonionic and/or other surfactants of anion surfactant.
According to some specific embodiments of the present invention, wherein, described nonionic is selected from polyoxyethylene ether series surface activity
Agent；Described anion surfactant is selected from carboxylate surfactant.
Described polyoxyethylene ether series of surfactants can be polyoxyethylene ether series surface commonly used in the art
Activating agent, such as can be fatty alcohol polyethenoxy ether class surfactant or the work of alkylphenol polyoxyethylene surface
Property agent.
Described carboxylate surfactant can be carboxylate surfactant commonly used in the art, such as may be used
To be the potassium salt of higher fatty acids, sodium salt, triethanolamine salt or ammonium salt.
The LOW PERMEABILITY RESERVOIR oil displacement surfactant composition system of the present invention is in use, molten with prepared time handled
Liquid gross weight (pending target solution adds surfactant system gross weight) is 100% meter, the described LOW PERMEABILITY RESERVOIR displacement of reservoir oil
Surface-active contents is 0.1%～0.5%.
The LOW PERMEABILITY RESERVOIR oil displacement surfactant of the present invention can be used alone or use compounding with other surface agents, in fall
Have antiexpanding action concurrently while low oil water interfacial tension, change wettability, by increasing capacitance it is possible to increase displacement fluid capillary number, reduce
Injection pressure, has a good application prospect to LOW PERMEABILITY RESERVOIR improving ecology and raising oil recovery factor.
In sum, the invention provides a kind of LOW PERMEABILITY RESERVOIR oil displacement surfactant and preparation thereof and product.The present invention
Surfactant have the advantage that
A surfactant oil displacement that () present invention produces, can reduce oil water interfacial tension, is changing wettability
Have antiexpanding action concurrently, by increasing capacitance it is possible to increase displacement fluid capillary number simultaneously, reduce injection pressure；
B () uses the LOW PERMEABILITY RESERVOIR surfactant oil displacement that the present invention produces, make with other surfactant compounds
With, show interfacial tension and the washing oil ability of excellence；
C () uses the surfactant oil displacement that the present invention produces, use with other surfactant compounds, carry out
Oil displacement experiment, has higher oil displacement efficiency, has reached preferably oil displacement efficiency.
Accompanying drawing explanation
Fig. 1 compound system (0.1%GJ agent+0.05%YJ) changes over figure with the interfacial tension of crude oil.Abscissa
Being the time, vertical coordinate is the interfacial tension of compound system and crude oil.
Fig. 2 prevents swollen henchnmrk test device schematic diagram.
Bentonitic moistening volume schematic diagram over time in Fig. 3 different solutions.
Detailed description of the invention
Implementation process and the beneficial effect of generation of the present invention is described in detail, it is intended to help to read below by way of specific embodiment
Reader is more fully understood that essence and the feature of the present invention, not as can the restriction of practical range to this case.
Instrument and medicament
(1) reagent is used:
Host A, host B, host C, anionic and nonionic surfactant GJ agent, polyethenoxy ether class surface activity
Agent (YJ), quartz sand, PROCESS OF FLOWING TEST, bentonite, wherein GJ agent is laboratory self-control；Hyposmosis people
The lithogenesis heart provides for Chinese Petroleum Univ.；Remaining reagent is commercially available.
(2) instrument is used:
JJ2000B type rotates and drips interfacial tension measuring instrument, DCAT21 type surface tension/contact angle instrument, infiltration glass
Glass pipe, ultrasonic oscillator, DHG thermostatic drying chamber, laboratory simulation flooding device.
Embodiment 1:
Weigh 0.4mol alkanolamide to be placed in flask, after adding proper amount of methanol solvent, add base catalyst
0.05mol sodium hydroxide, weighs 0.2mol allyl glycidyl ether, is slowly added dropwise and stirs, after dropping,
Increase the temperature to 30 DEG C and keep 1h, be then refluxed for reacting 8h；Adding sulfur acid for adjusting pH again in reaction system is 3-5,
Being heated to 80 DEG C of reaction 1h, add sodium hydroxide after having hydrolyzed again in reaction system, regulation pH is the most neutral,
Addition 0.2mol sodium acetate, in the basic conditions, continuation heated and stirred at 30 DEG C, reaction 3h, after completion of the reaction,
With absolute ethanol washing, filtering, decompression distillation prepares GJ-1 agent.
Embodiment 2:
Weigh 0.5mol alkanolamide to be placed in flask, after adding ethanol in proper amount solvent, add 0.05mol hydroxide
Potassium, weighs 0.25mol diglycidyl ether of ethylene glycol compounds, is slowly added dropwise and stirs, and after dropping, raises
Temperature to 40 DEG C keeps 1h, is then refluxed for reacting 2h；Adding salt acid for adjusting pH again in reaction system is 3-5,
Being heated to 80 DEG C of DEG C of reaction 2h, add potassium hydroxide after having hydrolyzed again in reaction system, regulation pH is the most neutral,
Add 0.25mol sodium benzoate, in the basic conditions, continue heated and stirred at 40 DEG C, react 9h, react complete
After, with absolute ethanol washing, to filter, decompression distillation prepares GJ-2 agent.
Embodiment 3:
Weigh 0.5mol polyxyethylated acyl hydramine to be placed in flask, after adding proper amount of acetone solvent, add
0.05mol sodium carbonate, weighs 0.25mol phenyl glycidyl ether compounds, is slowly added dropwise and stirs, drip
Bi Hou, increases the temperature to 50 DEG C and keeps 1h, is then refluxed for reacting 7h；Acetic acid regulation is added again in reaction system
PH is 3-5, is heated to 80 DEG C of reaction 3h, adds sodium carbonate again, regulate pH after having hydrolyzed in reaction system
To neutral, add 0.25mol sodium chloroacetate, in the basic conditions, continue heated and stirred at 50 DEG C, react 4h,
After completion of the reaction, with absolute ethanol washing, filtering, decompression distillation prepares GJ-3 agent.
Embodiment 4:
Weigh 0.4mol fatty alcohol-polyoxyethylene ether to be placed in flask, after adding appropriate ether solvent, add 0.05mol
Sodium hydroxide, weighs 0.2mol allyl glycidyl ether compounds, is slowly added dropwise and stirs, after dropping,
Increase the temperature to 60 DEG C and keep 1h, be then refluxed for reacting 3h；Adding sulfur acid for adjusting pH again in reaction system is 3-5,
Being heated to 90 DEG C of reaction 1h, add sodium hydroxide after having hydrolyzed again in reaction system, regulation pH is the most neutral,
Addition 0.2mol sodium benzoate, in the basic conditions, continuation heated and stirred at 60 DEG C, reaction 8h, after completion of the reaction,
With absolute ethanol washing, filtering, decompression distillation prepares GJ-4 agent.
Embodiment 5:
Weigh 0.5mol fatty alcohol-polyoxyethylene ether to be placed in flask, after adding proper amount of methanol solvent, add 0.05mol
Potassium hydroxide, weighs 0.25mol diglycidyl ether of ethylene glycol compounds, is slowly added dropwise and stirs, after dropping,
Increase the temperature to 70 DEG C and keep 1h, be then refluxed for reacting 6h；Adding salt acid for adjusting pH again in reaction system is 3-5,
Being heated to 90 DEG C of reaction 2h, add potassium hydroxide after having hydrolyzed again in reaction system, regulation pH is the most neutral,
Addition 0.25mol sodium acetate, in the basic conditions, continuation heated and stirred at 70 DEG C, reaction 5h, after completion of the reaction,
With absolute ethanol washing, filtering, decompression distillation prepares GJ-5 agent.
Embodiment 6:
Weigh 0.5mol polyxyethylated acyl hydramine to be placed in flask, after adding ethanol in proper amount solvent, add
0.05mol sodium carbonate, weighs 0.25mol phenyl glycidyl ether compounds, is slowly added dropwise and stirs, drip
Bi Hou, increases the temperature to 80 DEG C and keeps 1h, is then refluxed for reacting 4h；Acetic acid regulation is added again in reaction system
PH is 3-5, is heated to 90 DEG C of reaction 3h, adds sodium carbonate again, regulate pH after having hydrolyzed in reaction system
To neutral, add 0.25mol sodium acetate, in the basic conditions, at 80 DEG C, continue heated and stirred, react 7h, instead
After Ying, with absolute ethanol washing, filtering, decompression distillation prepares GJ-6 agent.
Embodiment 7:
Weigh 0.4mol alkylphenol polyoxyethylene to be placed in flask, after adding proper amount of acetone solvent, add 0.05mol
Sodium hydroxide, weighs 0.2mol allyl glycidyl ether compounds, is slowly added dropwise and stirs, after dropping,
Increase the temperature to 90 DEG C and keep 1h, be then refluxed for reacting 5h；Adding sulfur acid for adjusting pH again in reaction system is 3-5,
Being heated to 100 DEG C of reaction 1h, add sodium hydroxide after having hydrolyzed again in reaction system, regulation pH is the most neutral,
Addition 0.2mol sodium chloroacetate, in the basic conditions, continuation heated and stirred at 90 DEG C, reaction 6h, after completion of the reaction,
With absolute ethanol washing, filtering, decompression distillation prepares GJ-7 agent.
Embodiment 8:
Weigh 0.4mol alkylphenol polyoxyethylene to be placed in flask, after adding appropriate ether solvent, add 0.05mol
Potassium hydroxide, weighs 0.2mol diglycidyl ether of ethylene glycol compounds, is slowly added dropwise and stirs, after dropping,
Increase the temperature to 60 DEG C and keep 1h, be then refluxed for reacting 6h；Adding salt acid for adjusting pH again in reaction system is 3-5,
Being heated to 100 DEG C of reaction 2h, add potassium hydroxide after having hydrolyzed again in reaction system, regulation pH is the most neutral,
Addition 0.2mol sodium chloroacetate, in the basic conditions, continuation heated and stirred at 60 DEG C, reaction 4h, after completion of the reaction,
With absolute ethanol washing, filtering, decompression distillation prepares GJ-8 agent.
Embodiment 9:
Weigh 0.5mol alkanolamide to be placed in flask, after adding proper amount of acetone solvent, add 0.05mol sodium carbonate,
Weigh 0.25mol phenyl glycidyl ether compounds, be slowly added dropwise and stir, after dropping, increase the temperature to
70 DEG C keep 1h, are then refluxed for reacting 7h；Adding vinegar acid for adjusting pH again in reaction system is 3-5, is heated to 100
DEG C reaction 3h, adds sodium carbonate again in reaction system after hydrolyze, regulation pH to neutral, addition 0.25mol
Sodium benzoate, in the basic conditions, continues heated and stirred, reacts 7h, after completion of the reaction, use anhydrous second at 70 DEG C
Alcohol washs, and filters, and decompression distillation prepares GJ-9 agent.
Embodiment 10:
The GJ agent of in embodiment 1～embodiment 9 0.1% as host, conventional surfactants YJ (ten of 0.05%
Dialkyl phenol polyoxyethylene ether), compound for auxiliary agent, form surfactant compound system (0.1%GJ agent
+ 0.05%YJ) (compound system is 100%, and GJ accounts for 0.1%, and YJ accounts for 0.05%, and other compositions are to need to be lowered
Surface or the solution of interfacial tension).Embodiment 10-1 in table 1 below, 10-2,10-3 ... be to represent in embodiment
Embodiment 1, embodiment 2, embodiment 3 is used ... wait the surfactant of preparation in 10.
Table 1 embodiment table corresponding with surfactant
Embodiment 11: interfacial activity evaluation
According to the rotation dripping method in " SY/T 5370-1999 surface and interfacial tension assay method " to embodiment 1～reality
The interfacial activity executing the GJ agent in example 9 and the compound system in embodiment 10 (0.1%GJ agent+0.05%YJ) is entered
Row is evaluated.Wherein compound system changes over (embodiment 10-9) as shown in Figure 1 with the interfacial tension of crude oil.
Experiment condition: temperature is 50 DEG C, rotary speed is 5000r/min；Instrument: JJ2000B type rotates and drips interface
Tensiometer.
Simplified process: injecting aqueous phase in cleaned capillary tube, the capillary tube that will be equipped with aqueous solution preheats, and
Drive bubble in pipe away；With in microsyringe note 3 μ L crude oil aqueous phase in pipe, in injection process guarantees pipe
Bubble-free；Ready capillary tube is put into rotation drip in interfacial tensimeter, rotating speed is adjusted to 5000r/min, start
Instrument starts, and deposits the image that under different time, oil droplet is stretched in test process；After being completed, input profit two
Phase density is poor, calculates oil water interfacial tension the most in the same time.
Table 2 surfactant system oil water interfacial tension measurement result
As shown in Table 2, the LOW PERMEABILITY RESERVOIR surfactant oil displacement of embodiment 1～9 preparation has good surface property,
After the surfactant that in embodiment 10 prepared by the present invention is compounding with conventional surfactants, surface property is strengthened.
Synergism between response time and temperature and reactant all can cause the nature difference of product, embodiment
8, in 9, reaction temperature controls at 60～70 DEG C, and constant temperature return time is to occur more preferably between 6～7h, and reactant
Synergism.
Therefore, can be that reaction temperature controls at 60～70 DEG C by experimental condition optimization, constant temperature return time be 6～7h.
Embodiment 12: wettability evaluation
According to the contact angle method in " SY/T 5153-2007 reservoir rocks wettability determination method ", to embodiment 1～9
In GJ agent (0.1%) and the wettability of compound system (0.1%GJ agent+0.05%YJ) in embodiment 10
It is evaluated.
Experiment condition: temperature is 20 DEG C；Instrument: DCAT21 type surface/contact angle instrument.
Simplified process: sliver is placed at 80 DEG C impregnation process 10d in crude oil, forms oil-wetted surface, respectively will
Immersion 8h put in deionized water, surfactant solution by sliver, reaches adsorption equilibrium, measure respectively GJ agent and
The compound system contact angle to oily wet sliver；Recording undressed sliver contact angle in experiment is 76.80 °.
Table 3 surfactant system wettability measurement result
As shown in Table 3, the LOW PERMEABILITY RESERVOIR surfactant oil displacement of embodiment 1～9 preparation has good wettability,
After the surfactant that in embodiment 10 prepared by the present invention is compounding with conventional surfactants, wettability is strengthened.
Embodiment 13: anti-swollen performance evaluation
Use Washburn dynamic method investigated clay 0.1% GJ agent solution and compound system (0.1%GJ agent
+ 0.05%YJ) expansion character in solution imbibition.Accompanying drawing 2 is shown in by experiment schematic diagram.
Simplified process: bentonite filled by the glass tubing putting into filter paper to bottom, the most repeatedly doses, doses guarantor every time
Card equal amount bentonite is to identical graduation line；Populated glass tubing is put in the sample fixer of torsion balance；?
Glass sample pond adds the GJ agent solution of 0.1%, is placed in pallet, start to measure, measure temperature and be set to 20 DEG C.
Expansion rate, anti-dilative is calculated by bentonite expansion volume in GJ agent solution and deionized water.Calculate public affairs
Formula is as follows:
Expansion rate:
Anti-dilative:
Wherein: Δ V bentonite expansion volume in deionized water or solution, mL；
V0Bentonite dry volume, mL；
PR bentonite expansion rate in deionized water, in experiment, measured value is 12.86%；
PR1Bentonite expansion rate in the solution.
Swollen Evaluation results prevented by table 4
As shown in Table 4, the LOW PERMEABILITY RESERVOIR surfactant oil displacement of embodiment 1～9 preparation has the most anti-swollen performance,
After the surfactant that in embodiment 10 prepared by the present invention is compounding with conventional surfactants, anti-swollen performance is strengthened.
Embodiment 14: Oil Displacing Capacity evaluation
Imitation oil displacement experiment experiment 1
The GJ agent of in embodiment 1 0.1%, the long 6 dehydration degassed crudes of long celebrating, as Experimental Flowing Object, carry out oil displacement efficiency
Evaluate, at constant temperature 60 DEG C, after the saturated crude oil of rock core, carry out lab simulation water drive oil, surfactant body respectively
It it is oil displacement experiment.
Experiment condition:
Rock core size: the long 6.806cm of rock core, diameter 2.530cm；
Core parameters: pore volume 8.06cm3, water surveys permeability 27.11 × 10-3μm2, oil saturation 63.40%；
Temperature: 60 DEG C.
Oil displacement experiment installation drawing is shown in accompanying drawing 3.
Test simplified process: rock core is loaded in clamper, by rock core saturation water after evacuation 60min；Inject long
The long 6 dehydration degassed crudes of celebrating make rock core to irreducible water state；Then water drive oil is to rock core production fluid aqueous 98%；
It is then poured into the GJ agent of 0.1%, after GJ agent oil displacement system Duan Sai is fully injected into, continues water drive aqueous to production fluid
98%；Calculate water drive, surfactant flooding and overall recovery factor respectively.Result of calculation is shown in Table 5.
Table 5 single GJ oil displacement experiment result
As shown in Table 5, the LOW PERMEABILITY RESERVOIR surfactant oil displacement of embodiment 1～9 preparation has preferable mother oil displacement
Efficiency.
Imitation oil displacement experiment experiment 2
With the compound system (0.1%GJ+0.05%YJ) in embodiment 2, the long 6 dehydration degassed crudes of long celebrating for experiment stream
Body, carries out oil displacement efficiency evaluation, at constant temperature 60 DEG C, after the saturated crude oil of rock core, carries out lab simulation water drive respectively
Oil, surfactant system oil displacement experiment.
Experiment condition:
Rock core size: the long 6.780cm of rock core, diameter 2.518cm；
Core parameters: hole system 7.35cm3, water surveys permeability 25.05 × 10-3μm2, oil saturation 60.15%.
Temperature: 60 DEG C.
Test simplified process: test 1 with imitation oil displacement experiment, except that, when agent is driven, the surfactant body of injection
System is compound system i.e. 0.1%GJ+0.05%YJ；Calculate water drive, surfactant flooding and overall recovery factor respectively.Meter
Calculation the results are shown in Table 6.
Table 6 compound system oil displacement experiment result
As shown in Table 6, after surfactant prepared by the present invention is compounding with conventional surfactants, have the most former
Oil displacement efficiency, and displacement efficiency is more than single GJ displacement of reservoir oil displacement efficiency.
Claims (10)
1. a preparation method for LOW PERMEABILITY RESERVOIR oil displacement surfactant, wherein, described method includes: with organic molten
Agent is reaction dissolvent, in the presence of base catalyst, with nonionic surfactant with (+)-2,3-Epoxy-1-propanol ether compound is
Raw material reacts, and has reacted and has obtained reaction solution, and reaction solution hydrolyzes in acid condition, then organic with metal
Reactant salt obtains described LOW PERMEABILITY RESERVOIR oil displacement surfactant；Wherein, nonionic surfactant, (+)-2,3-Epoxy-1-propanol ethers
Compound, metal organic salt, base catalyst molar ratio range are 8～80:4～40:4～40:1；The most preferably react molten
Liquid is at the hydrolyzed under acidic conditions of pH3-5；Preferably metal organic salt consumption is to be 8-10 by reaction solution pH regulator；
Preferably described nonionic surfactant is selected from alkanolamide, fatty alcohol-polyoxyethylene ether, alkyl phenol polyoxy second
Alkene ether or polyxyethylated acyl hydramine；
Carrying out reaction with (+)-2,3-Epoxy-1-propanol ether compound for raw material with nonionic surfactant described in preferably is in backflow
Under react；The most preferably react 2-8h；
The most further preferably nonionic surfactant and (+)-2,3-Epoxy-1-propanol ether compound carry out reaction is by the two mixture
First it is preheating to 30-90 DEG C, then back flow reaction；Wherein it is more preferably at 30-90 DEG C, keeps 0.5h～2h, then backflow is anti-
Should；
The reaction temperature reacted with metal organic salt in the basic conditions described in preferably is 30-90 DEG C；The most preferably react
3-9h；The most more preferably reaction temperature is 60-70 DEG C, response time 6-7h.
Preparation method the most according to claim 1, wherein, described (+)-2,3-Epoxy-1-propanol ether compound is with dropping
Mode adds, and preferably rate of addition is that 8-12 drips/min.
Preparation method the most according to claim 1, wherein, described method comprises the steps:
(1) nonionic surfactant is dissolved in organic solvent, obtains nonionic surfactant solution；
(2) in the nonionic surfactant that step (1) obtains, add base catalyst, and drip (+)-2,3-Epoxy-1-propanol
Ether compound, drips and finishes, stirring reaction, has reacted and has obtained reaction solution；
(3) in the reaction solution of step (2), add pH adjusting agent regulation pH value the most acid, be preferably adjusted to
PH is 3-5, hydrolysis, preferably hydrolyzes 1～3h at 80～100 DEG C, and hydrolysis regulates reacting solution pH value extremely after terminating
Neutrality, is preferably used inorganic base or alkaline, inorganic salts regulation pH is the most neutral, adds metal organic salt, and reaction obtains institute
State LOW PERMEABILITY RESERVOIR oil displacement surfactant.
4. according to the preparation method described in claims 1 to 3 any one, wherein, have with metal in the basic conditions
After machine reactant salt terminates, also include removing metal organic salt with washing, filtering and the step of distillation of reducing pressure, preferably use
Absolute ethanol washing removes metal organic salt, and the step more preferably wash, filtered repeats 2-3 time, and obtains described low
Permeability hides oil displacement surfactant.
5. according to the preparation method described in claims 1 to 3 any one, wherein, described (+)-2,3-Epoxy-1-propanol ethers
Compound is selected from allyl glycidyl ether, diglycidyl ether of ethylene glycol or phenyl glycidyl ether.
6. according to the preparation method described in claims 1 to 3 any one, wherein, described metal organic salt is alkali gold
Belong to organic salt；It is preferably sodium organic salt；The more preferably one in sodium acetate, sodium benzoate or sodium chloroacetate.
7. according to the preparation method described in claims 1 to 3 any one, wherein, described organic solvent be methanol,
One or more in ethanol, acetone and ether.
8. according to the preparation method described in claims 1 to 3 any one, wherein, described base catalyst is hydrogen-oxygen
Change the one in sodium, potassium hydroxide or sodium carbonate.
9. the LOW PERMEABILITY RESERVOIR oil displacement surfactant that the preparation method described in claim 1～8 any one prepares；
The weight average molecular weight of the most described LOW PERMEABILITY RESERVOIR oil displacement surfactant is 600-10 ten thousand.
10. a LOW PERMEABILITY RESERVOIR oil displacement surfactant composition system, wherein, described surface activator composition body
The LOW PERMEABILITY RESERVOIR oil displacement surfactant described in claim 9 is at least contained in system；The most described surface activator composition
System possibly together with including other surfactants of at least one nonionic and/or anion surfactant, Qi Zhongsuo
Stating LOW PERMEABILITY RESERVOIR oil displacement surfactant with other surfactant weight ratios is 2:1～10:1；Wherein preferably possibly together with
One or both be selected from nonionic and/or other surfactants of anion surfactant, the most described non-from
Son is selected from carboxylate surfactants selected from polyoxyethylene ether series of surfactants, described anion surfactant
Agent.
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| CN109266321A (en) * | 2018-10-11 | 2019-01-25 | 中国石油化工股份有限公司 | Wettability modification oil film removal relative permeability modifier and preparation method thereof |
| CN113372896A (en) * | 2021-06-02 | 2021-09-10 | 宁波锋成先进能源材料研究院有限公司 | Imbibition oil displacement agent and preparation method thereof |
| CN113390759A (en) * | 2021-04-27 | 2021-09-14 | 清华大学 | Evaluation method for representing wettability influence based on oil reservoir chip |
| CN116023923A (en) * | 2021-10-25 | 2023-04-28 | 中国石油化工股份有限公司 | Composition for preventing and/or relieving water lock effect, and preparation method and application thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109266321A (en) * | 2018-10-11 | 2019-01-25 | 中国石油化工股份有限公司 | Wettability modification oil film removal relative permeability modifier and preparation method thereof |
| CN113390759A (en) * | 2021-04-27 | 2021-09-14 | 清华大学 | Evaluation method for representing wettability influence based on oil reservoir chip |
| CN113372896A (en) * | 2021-06-02 | 2021-09-10 | 宁波锋成先进能源材料研究院有限公司 | Imbibition oil displacement agent and preparation method thereof |
| CN113372896B (en) * | 2021-06-02 | 2023-06-20 | 宁波锋成先进能源材料研究院有限公司 | Imbibition oil displacement agent and preparation method thereof |
| CN116023923A (en) * | 2021-10-25 | 2023-04-28 | 中国石油化工股份有限公司 | Composition for preventing and/or relieving water lock effect, and preparation method and application thereof |
| CN116023923B (en) * | 2021-10-25 | 2024-03-12 | 中国石油化工股份有限公司 | Composition for preventing and/or relieving water lock effect, and preparation method and application thereof |
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