CN109401744A - Displacement of reservoir oil fluid containing adsorption inhibitor and the application in tertiary oil recovery - Google Patents
Displacement of reservoir oil fluid containing adsorption inhibitor and the application in tertiary oil recovery Download PDFInfo
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/584—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific surfactants
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/588—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific polymers
Abstract
The present invention relates to a kind of displacement of reservoir oil fluid containing adsorption inhibitor and the applications in tertiary oil recovery, mainly solve in the prior art as the surfactant of the displacement of reservoir oil fluid main component when containing petroleum-bearing formation, the especially high displacement of reservoir oil of oil bearing bed containing clay because oil displacement system oil displacement efficiency caused by concentration caused by being adsorbed and/or ratio variation declines problem.The present invention is by adopting the displacement of reservoir oil fluid containing adsorption inhibitor, in terms of mass fraction, including following components: 1) 1 part of oil displacement agent；2) 0.001~10 part of adsorption inhibitor；Wherein, contain surfactant in the oil displacement agent；The adsorption inhibitor is the technical solution of at least one of the small molecule compound containing carboxyl, the polymer of molecular weight 1000~500000 and alkali compounds or two or more mixtures, it preferably solves the problems, such as this, can be used in tertiary oil recovery production.
Description
Technical field
The present invention relates to a kind of displacement of reservoir oil fluid containing adsorption inhibitor and the applications in tertiary oil recovery.
Background technique
Chemical flooding is to change the physicochemical properties and rheological property of injection fluid by adding chemical agent in aqueous solution
And a kind of enhancements of recovery ratio are improved with the interaction characteristic of reservoir rock, it is able to fast development in China,
Main cause is that China's reservoir is that continental deposit heterogeneity is stronger, and terrestrial origin of petroleum Crude viscosity is higher, more suitable in EOR method
Together in chemical flooding.
With polymer phase ratio, surfactant is easier to be adsorbed on rock surface, and its cost is often higher than polymer, because
This, surfactant number of adsorbance in stratum is the economy major part of entire oil displacement system, studies oil displacement agent
Absorption loss is one of the key factor for being related to chemical displacement of reservoir oil success or failure.Mainly there is rock medium in the reason of causing oil displacement agent to lose
Absorption, reacted with tradable multivalent ion in water flooding, clay and in residual oil distribution etc., surfactant is in clay
After adsorbing on mineral, the loss of surfactant can be caused, and also great changes will take place for the property of clay particle.It is hydrocarbon
Absorption of the class surfactant on clay mineral, the country has done a lot of work at present in tertiary oil recovery, such as Yang Cheng
Will et al. systematically has studied absorption rule of the neopelex on different clays, carbonatite, quartz and natural core
It is found after rule, each clay mineral adsorbance maximum value sequence is montmorillonite, kaolin, sodium kaolin and illite.Shandong is big
It is small in the lonely east of Shengli Oil Field to polymer Flooding Systems Based On Natural Mixed Carboxylic Acids (salt) composite oil-displacing system to learn chemical institute's gelatinization research institute prune assistant et al.
Well spacing 52+3It is found after layer progress Static Adsorption (solid-liquid ratio is 1:5) research, carboxylic acid (salt) type anionic surfactant SDC-
Quickly, the rear rate of adsorption tends to balance for 24 hours, and static adsorbance is 6.60mg/g sand for the rate of adsorption increase when 3 beginning, compares nonionic
The static adsorbance (5.47mg/g sand) of surfactant Tween80 is bigger, and the static state than cationicsurfactants is inhaled
Attached amount (36.22mg/g sand) is small.Yu Baoyu et al. the suction of chemical agent on lonely eastern oil-sand in research ternary composite oil-displacing system
The discovery of additional loss time-consuming, when nonionic surface active agent OP-10 initial concentration increases to 7000mg/L by 2000mg/L,
Adsorbance increases to 6.7mg/g sand by 2.0mg/g sand；OP-10 when OP-10 initial concentration is less than 5000mg/L, in liquid phase
Almost adsorbed entirely by oil-sand.Yue Xiangan et al. is living at research petroleum carboxylate/heavy alkylbenzene sulfonate/alkali compound system interface
Property and when characterization of adsorption find that the adsorbance of heavy alkylbenzene sulfonate ORS-41 is 7.581mg/g oil-sand, ORS- in compound system
41 saturated extent of adsorption are 6.741mg/g oil-sand, therefore propose that cheap petroleum oxidation soap, which is added, reduces heavy alkylbenzene sulfonate
Adsorbance.Zhao Puchun et al. has found when studying nonionic surfactant NS in the absorption on Wenmingzhai oil-sand and rock core, non-
Solid-to-liquid ratio is 1:10, adsorbance is about 5.2mg/g oil-sand on the sand for crossing 40 meshes, adsorbance rises ionic surface active agent NS
Just increase with concentration and increase sharply, the increase of adsorbance becomes smaller in certain concentration range, finally becomes very slowly.Week
Refined duckweed et al. study Chemical Flooding Fluids in each component in Static Adsorption (solid-to-liquid ratio 1:9) feature on oil-sand surface when send out
Existing, the adsorbance of non-ionic surfactant is 14.8mg/g oil-sand, it is believed that due to surfactant molecular weight compare it is larger, so
Absorption loss on rock surface is larger.Yick-Mone Shum points out, interior of the alkylbenzene sulfonate on Berea sandstone
Experiment adsorbance is 2.5mg/g rock, and the adsorbance on the rock core sand in the oil field Texas Manvel is 3.56mg/g sand,
Damage for Detention is then respectively 1.38mg/g, 1.85mg/g.
Although the anionic surfactants such as alkylbenzene sulfonate, heavy alkylbenzene sulfonate are widely used in tertiary oil recovery
In the process, but there are still absorption problem bigger than normal is lost；Amphoteric ionic surfactant, such as glycine betaine because intramolecular contains two
No matter when sandstone formation or carbonate strata are as the oil displacement agent displacement of reservoir oil adsorbance all there is in the opposite hydrophilic head base of a electrical property
Larger problem；Cationic surfactant is generally not used for adopting three times because it easily adsorbs or generate precipitating by sandstone formation
Oil, if but compound cationic surfactant with electrically opposite anionic surfactant, utilize zwitterion table
Many outstanding advantages of face activating agent mixed system, especially superelevation interfacial activity, the disadvantages of overcoming it easily to precipitate, the yin of formation
Cationic complexed surfactant can obviously reduce absorption loss of the cationic surfactant on rock core, so that cation form
Face activating agent is possibly realized as oil displacement agent component, in this respect, the researchers such as Li Yingcheng of Shanghai Petroleum Chemical Engineering Institute
Chinese invention patent of the more than one piece in relation to zwitterion complexed surfactant, displacement composition and flooding method is applied for, such as
ZL201210150216.7, ZL201210239983.5, ZL 201210240014.1, ZL201210325051.2, but contain in height
The stratum of clay, however it remains Adsorption And Retention problem need to further decrease oil displacement system to obtain higher oil displacement efficiency
Adsorbance.
Summary of the invention
The first technical problem to be solved by the present invention is living as the surface of displacement of reservoir oil fluid main component in the prior art
Property agent contain petroleum-bearing formation, the especially high displacement of reservoir oil of oil bearing bed containing clay when because concentration caused by being adsorbed and/or ratio change
Oil displacement system oil displacement efficiency caused by change declines problem, provides a kind of new displacement of reservoir oil fluid containing adsorption inhibitor.The drive
Flow of oil in oil displacement system by using adding more cheap adsorption inhibitor as oil displacement agent in oil displacement process, tool
Have the advantages that anti-adsorption capacity is strong, oil displacement efficiency is high.
The second technical problem to be solved by the present invention is to provide described in a kind of one of above-mentioned technical problem containing absorption suppression
The preparation method of the displacement of reservoir oil fluid of preparation.
The third technical problem to be solved by the present invention is to provide described in a kind of one of solution above-mentioned technical problem containing inhaling
The application of the displacement of reservoir oil fluid of attached inhibitor.
One of in order to solve the above-mentioned technical problem, The technical solution adopted by the invention is as follows: one kind contains adsorption inhibitor
Displacement of reservoir oil fluid, include: in terms of mass fraction
1) 1 part of oil displacement agent；
2) 0.001~10 part of adsorption inhibitor；
Wherein, contain surfactant in the oil displacement agent；The adsorption inhibitor is the small molecule chemical combination containing carboxyl
At least one of object, the polymer of molecular weight 1000~500000 and alkali compounds.
In above-mentioned technical proposal, the displacement of reservoir oil fluid is preferably the surfactant flooding that oil displacement agent is surfactant
Fluid, oil displacement agent are that polymer-surfactant binary displacement oil fluid, the oil displacement agent of polymer and surfactant are polymerization
At least one of the polymer-surfactant of object, surfactant and alkali-alkali ternary oil displacement fluid.
In above-mentioned technical proposal, the surfactant be preferably nonionic surfactant, anionic surfactant,
At least one of cationic surfactant, amphoteric ionic surfactant；More preferably zwitterion composite surface is living
At least one of property agent, amphoteric ionic surfactant.
In above-mentioned technical proposal, the zwitterion complexed surfactant is further preferably by cation surface activating
Agent and containing polyoxyethylene, polyethenoxy ether segment anionic surfactant composition.
In above-mentioned technical proposal, the amphoteric ionic surfactant is preferably beet alkali surface activator.
In above-mentioned technical proposal, the polymer-surfactant binary displacement oil fluid, polymer-surfactant-alkali
Polymer in ternary oil displacement fluid can be each quasi polymer commonly used in the art, and be not particularly limited, such as but not limit
It is described at least one of partially hydrolyzed polyacrylamide (PHPA), modified polyacrylamide, polymer microballoon, biomass polymers
Modified polyacrylamide can be anion-polyacrylamide, hydrophobically associated polyacrylamide, temperature-resistant anti-salt modified poly- third
Acrylamide.
In above-mentioned technical proposal, the polyacrylamide of the partial hydrolysis, molecular weight is preferably 500~25,000,000, hydrolysis
Degree is 15~25%；The hydrophobic associated polymer is preferably copolymerized by acrylamide, temperature-resistant anti-salt monomer and hydrophobic monomer；
The temperature-resistant anti-salt modified polyacrylamide is preferably copolymerized by acrylamide, temperature-resistant anti-salt monomer；The polymer microballoon
It is preferred that using initial particle made from alcohol-water system dispersion polymerization processes for sub-micron to micron order, with the resistance to of monodispersity
Warm salt resistance acrylamide polymer microballoon；Temperature-resistant anti-salt monomer or hydrophobic monomer can be well-known to those skilled in the art contain
There are monomer (such as styrene sulfonic acid, N- alkyl maleimide, the acrylamido chain alkyl sulphur of big side group or rigid side group
Acid, chain alkyl allyl dimethyl base ammonium halide, 3- acrylamido -3 Methylbutanoic acid etc.), the monomer containing resistance to salt groups (such as
2- acrylamide-2-methylpro panesulfonic acid), the monomer (such as N- alkyl acrylamide) of the group containing hydrolysis, containing can inhibit amide
At least one of the monomer (such as N- vinylpyrrolidone) of group of base hydrolysis, monomer containing hydrophobic grouping, temperature-resistant anti-salt
Monomer is preferably 2- acrylamide-2-methylpro panesulfonic acid, and hydrophobic monomer is preferably 2- acrylamido dodecyl sodium sulfonate.
In above-mentioned technical proposal, acrylamide and temperature-resistant anti-salt monomer and hydrophobic monomer in the hydrophobic associated polymer
Molar ratio be preferably (0.1~40): 1:(0.001~0.05), viscosity-average molecular weight be 500~25,000,000；More preferably propylene
The molar ratio of amide and temperature-resistant anti-salt monomer and hydrophobic monomer is (0.1~20): 1: (0.001~0.01), viscosity-average molecular weight are
1200~22,000,000.
In above-mentioned technical proposal, acrylamide and temperature-resistant anti-salt monomer rubs in the temperature-resistant anti-salt modified polyacrylamide
You are than being preferably (0.1~40): 1.
In above-mentioned technical proposal, the preferred acrylamide of the hydrophobic associated polymer, 2- acrylamido -2- methyl-prop
Sulfonic acid and 2- acrylamido dodecyl sodium sulfonate are copolymerized, acrylamide, 2- acrylamide-2-methylpro panesulfonic acid and 2-
Acrylamido dodecyl sodium sulfonate molar ratio is preferably (0.1~40): 1:(0.001~0.05), more preferably (0.1~20)
: 1: (0.001~0.01).
In above-mentioned technical proposal, the temperature-resistant anti-salt modified polyacrylamide is preferably by acrylamide, 2- acrylamido-
2- methyl propane sulfonic acid is copolymerized, and acrylamide and 2- acrylamide-2-methylpro panesulfonic acid molar ratio are preferably (0.1~40)
: 1, the viscosity-average molecular weight of modified polyacrylamide is preferably 800~25,000,000.
In above-mentioned technical proposal, the alkali in the polymer-surfactant-alkali ternary oil displacement fluid is preferably alkali metal
Hydroxide, alkaline earth metal hydroxide, alkali carbonate, alkali silicate, alkali metal phosphate, alkali borate
Or at least one of short carbon chain organic amine；Further preferred: alkali metal hydroxide is in sodium hydroxide, potassium hydroxide
At least one, alkaline earth metal hydroxide are selected from least one of magnesium hydroxide, calcium hydroxide, and alkali carbonate is selected from carbon
At least one of sour sodium or sodium bicarbonate, alkali silicate are selected from least one of sodium metasilicate or potassium silicate, alkali metal
Phosphate is selected from least one of sodium phosphate/potassium or sodium polyphosphate/potassium, and alkali borate is selected from Boratex or potassium borate
At least one of；Short carbon chain organic amine be preferably in molecule containing in primary amine groups, secondary amine, tertiary amine groups, quaternary ammonium base extremely
Few one kind, further preferably at least one of ethanol amine, diethanol amine, triethanolamine or triethylamine.
In above-mentioned technical proposal, the adsorption inhibitor is preferably the small molecule compound containing carboxyl, further preferably
The carboxylic acid containing hydroxyl of carboxylic acid and/or salt, carbochain lower than 8 and/or salt, carbochain from carbochain lower than 8 contain amino lower than 8
Carboxylic acid and/or salt, carbochain lower than 8 saccharide compound at least one of.
In above-mentioned technical proposal, the small molecule compound containing carboxyl is further preferably from formic acid and/or salt, acetic acid
And/or salt, propionic acid and/or salt, malonic acid and/or salt, butyric acid and/or salt, succinic acid and/or salt, valeric acid and/or salt, penta 2
Acid and/or salt, caproic acid and/or salt, adipic acid and/or salt, citric acid and/or salt, tartaric acid and/or salt, alanine and/or
At least one of salt, glutamic acid and/or salt, monosaccharide.
In above-mentioned technical proposal, the adsorption inhibitor can be preferably the polyacrylic acid of molecular weight 3000~200000 again
And/or at least one of salt and/or ester.
In above-mentioned technical proposal, the adsorption inhibitor can also be preferably without containing the compound of carboxylate radical, e.g., alkalinity
Compound, in preferred alkali metal hydroxide, alkaline earth metal hydroxide, alkali carbonate and short carbon chain organic amine at least
It is a kind of；Further preferred alkali metal hydroxide is selected from least one of sodium hydroxide, potassium hydroxide, alkaline-earth metal hydroxide
Object be selected from least one of magnesium hydroxide, calcium hydroxide, alkali carbonate in sodium carbonate or sodium bicarbonate at least
One kind, alkali silicate are selected from least one of sodium metasilicate or potassium silicate, and alkali metal phosphate is selected from sodium phosphate/potassium or more
At least one of polyphosphate sodium/potassium, alkali borate are selected from least one of Boratex or potassium borate；Short carbon chain is organic
Amine is preferably in molecule containing at least one of primary amine groups, secondary amine, tertiary amine groups, quaternary ammonium base, further preferably ethyl alcohol
At least one of amine, diethanol amine, triethanolamine or triethylamine.
In above-mentioned technical proposal, the adsorption inhibitor is also preferably at least two mixture in alkali compounds,
Or the carboxylic acid containing hydroxyl of carboxylic acid of the carbochain lower than 8 and/or salt, carbochain lower than 8 and/or salt, carbochain contain ammonia lower than 8
The saccharide compound of the carboxylic acid and/or salt of base, carbochain lower than 8 at least one of it is mixed at least one of alkali compounds
It closes the carboxylic acid containing hydroxyl of the carboxylic acid of object or carbochain lower than 8 and/or salt, carbochain lower than 8 and/or salt, carbochain is lower than 8
Carboxylic acid and/or salt, carbochain containing amino lower than 8 saccharide compound at least one of with molecular weight 3000~200000
Polyacrylic acid and/or at least one of salt and/or ester mixture；Various ingredients have preferable synergistic work at this time
With, to reduce SURFACTANT ADSORPTION amount, improve oil displacement efficiency have the function of synergy.
In above-mentioned technical proposal, the mass ratio of the displacement of reservoir oil fluid and adsorption inhibitor is preferably 1:(0.1~4).
To solve above-mentioned technical problem two, the technical solution adopted in the present invention is as follows: a kind of to solve above-mentioned technology and ask
The preparation method of any displacement of reservoir oil fluid containing adsorption inhibitor in technical solution described in one of topic, including following step
It is rapid:
The desired amount of oil displacement agent and adsorption inhibitor are uniformly mixed, or by the desired amount of oil displacement agent, adsorption inhibitor and
Water is uniformly mixed, and obtains the displacement of reservoir oil fluid containing adsorption inhibitor.
In above-mentioned technical proposal, surfactant flooding fluid, polymer-surface can be configured to using conventional method
Activating agent binary displacement oil fluid or polymer-surfactant-alkali ternary oil displacement fluid, one of preferred embodiment include following step
It is rapid:
(a) preparation of cationic surfactant:
Work as a=1, when b=0, cationic surfactant is single-stranded quaternary ammonium salt, can be by being commercially available；Work as a=1, b=1
When, cationic surfactant is double-chain quaternary ammonium salt, preparation process are as follows: by fatty amine and Y01CH2(CH2)fCH2Y02By required
Molar ratio mixes in short carbon chain alcohol aqueous solution, is warming up to back flow reaction 2~100 hours, and it is living to obtain required cationic surface
Property agent aqueous solution or short carbon chain alcohol aqueous solution；Wherein, the concentration of short carbon chain alcohol aqueous solution is 0~100wt%, and short carbon chain alcohol is selected from
C1~C5Fatty alcohol, Y01、Y02Selected from chlorine, bromine or iodine, f=0~2；
(b) preparation of yin-yang complexed surfactant:
1. in the presence of basic catalyst, long-chain alcohol or long-chain amine successively with aequum ethylene oxide, propylene oxide, epoxy
Ethane reacts to obtain polyether compound；
2. product and Y that step (b) is 1. obtained03R01COOR01And alkali metal hydroxide or alkali metal alcoholates are to rub
You are than 1:(1~5): (1~10) mixing is reacted 3~15 hours under stirring in 50~120 DEG C of reaction temperature, without separation, is continued
Water is added and carries out saponification, after reflux 1~10 hour, be added step (a) obtained aqueous solution of cationic surfactant active or
Short carbon chain alcohol aqueous solution is warming up to 40~100 DEG C and stirs 1~5 hour, obtains required yin-yang compound surfactant；Its
In, Y03Selected from chlorine, bromine or iodine, R01Selected from C1~C5Alkylidene or at least one of hydroxyl substituted alkylene, R01Selected from C1
~C8Alkyl.
(c) based on the mass fraction, yin-yang complexed surfactant and polymer and/or alkali that step (b) is obtained
It is uniformly mixed, obtains the oil displacement agent.
(d) oil displacement agent prepared by adsorption inhibitor, step (c) is configured to certain density mother with oil field simulation salt water
Liquid is uniformly mixed in required ratio and obtains the displacement of reservoir oil fluid containing adsorption inhibitor.
In above-mentioned technical proposal, the preparation of the anionic and nonionic surfactant in the yin-yang complexed surfactant may be used also
To be reacted to obtain with nonionic surfactant using common carboxy methylation reagent or sulfonated reagent, carboxy methylation reagent
Example have but be not limited to halogenated acetic acids salt (such as sodium chloroacetate, bromoacetic acid sodium), halogenated acetic acids (such as monoxone, bromoacetic acid)
Deng；Sulfonated reagent has but is not limited to halogenosulfonic acid salt (such as 2- chloroethanes sodium sulfonate, 2- bromoethane sodium, 3- chlorine-2-hydroxyl
The bromo- 2- hydroxypropionate sodium of propanesulfonate, 3-) etc..
In above-mentioned technical proposal, the mass ratio of surfactant and polymer and alkaline matter is excellent in the displacement composition
It is selected as 1: (0.1~2): (0~5).
Displacement of reservoir oil fluid of the present invention can also contain foaming agent commonly used in the art, small organic molecule (such as isopropanol, second
Glycol monobutyl ether, DMSO etc.) etc. oil recoveries auxiliary agent.
In above-mentioned technical proposal, the displacement of reservoir oil fluid containing adsorption inhibitor can using various conventional mixing methods according to
Aequum each component is mixed to get, and dissolves to obtain oil displacement agent for the displacement of reservoir oil with water according to required concentration when for the displacement of reservoir oil；It can be with
According to the concentration of required oil displacement agent, it is dissolved in water each component in the displacement of reservoir oil fluid to obtain displacement of reservoir oil fluid and is used to drive
Oil.Water used in preparation can be tap water, river water, seawater, oil field stratum water；Preferred water is: simulation oil field water flooding,
Total salinity is preferably 3000~300000 mg/litres.
In order to solve the above-mentioned technical problem three, the technical solution adopted by the present invention is as follows: in a kind of above-mentioned technical proposal
Application of any displacement of reservoir oil fluid containing adsorption inhibitor in tertiary oil production in oil field production.
In above-mentioned technical proposal, the displacement of reservoir oil fluid applies preferred high-temperature oil reservoir, and formation temperature is 60~120 DEG C, stratum
3000~300000mg/L of total salinity of salt water.
Displacement of reservoir oil fluid prepared by the present invention containing adsorption inhibitor, by clay to the elecrtonegativity in adsorption inhibitor from
Son (e.g., COO-、OH-、SiO3 2-、BO3 3-Deng) effective absorption, the electropositive of clay end face is regulated to elecrtonegativity, Ke Yiyou
Effect reduces the absorption to anionic surfactant.In addition, by structure to anionic-cationic compound surfactant and
The adjusting of ratio, so that cationic head base is in internal layer in yin-yang mixed micelle, anion head base is in outer layer and keeps system total
Body is in elecrtonegativity, and Electrostatic Absorption of the cationic surfactant on bear electricity sandstone and modified clay surface obtains effectively
Shielding, significantly reduces cationic surfactant in the adsorbance on bear electric material surface, solves surfactant in height
The low technical problem of clay content oil reservoir large amount of adsorption, oil displacement efficiency.It, can be with by adding relatively relatively inexpensive adsorption inhibitor
Modification surface of stratum itself is adsorbed to surface of stratum, to reduce or eliminate surfactant adsorption, further decreases drive
The higher surfactant usage amount of price in flow of oil and the oil displacement efficiency for maintaining its good, greatly enhance displacement of reservoir oil fluid economy
Property.
Using the displacement of reservoir oil fluid of the invention containing adsorption inhibitor, it to be used for 60~120 DEG C of formation temperature, salinity 3000
The simulation salt water and crude oil of~300000 mg/litres, the adsorption inhibitor of 0.1~4 part of addition, can make in every part of displacement of reservoir oil fluid
Obtain SURFACTANT ADSORPTION amount decline 30%~70% in displacement of reservoir oil fluid.Through physical analogy displacement experiment Lab-evaluation, and it is not added
The displacement of reservoir oil fluid of adsorption inhibitor improves oil recovery factor on the basis of water drive and compares, and reaches as high as 22.95%, achieves preferably
Technical effect.
Specific embodiment
[embodiment 1]
(1) preparation of surfactant S01
(a) Shuangzi cation quaternary ammonium salt type surfactant (10-6-10,2Cl-)
By 213.0 grams of decyl diethyl tertiary amine (1 mole) and 77.5 grams of (0.5 mole) 1,6- dichloro hexanes, isopropanols 600
It gram is mixed in the four-hole boiling flask of 2000 milliliters equipped with mechanical stirring, thermometer and reflux condensing tube, is heated to back flow reaction
60 hours, stop reflux.Isopropanol is evaporated off, sampling is with the titration of tetraphenylboron sodium standard solution, gemini cationic surfactant
(10-6-10,2Cl-) content be 96.5%, remaining sample is not handled, spare.
(b) preparation of anion and compound surfactant S01
1. gram 276 grams of (1 mole) dodecyl benzylalcohols, 4.6 grams are added into the 2L pressure reactor equipped with agitating device
Potassium hydroxide, when being heated to 80~90 DEG C, open vacuum system, under a high vacuum be dehydrated 1 hour, then with nitrogen displacement 3~
4 times, system reaction temperature is adjusted to 150 DEG C and is slowly passed through 585.8 grams of (10.1 moles) propylene oxide, control pressure≤
0.60MPa adjusts the temperature to 140 DEG C again after reaction to propylene oxide and is slowly passed through 90.2 grams of (2.05 moles) epoxy second
Alkane controls pressure≤0.40MPa.After reaction, 90 DEG C are cooled to, low-boiling-point substance is removed in vacuum, neutralizes, dehydration, obtains after cooling
898.7 grams of ether of dodecyl benzylalcohol polyoxypropylene (10) polyoxyethylene (2), yield 95.2%.
2. being added with stirring step in 5000 milliliters of the reaction flask equipped with mechanical stirring, thermometer and reflux condensing tube
Suddenly (b) (1) synthesis 472 grams of ether of dodecyl benzylalcohol polyoxypropylene (10) polyoxyethylene (2) (0.5 mole) and 48.0 grams
(1.2 moles) sodium hydroxide is slowly dropped into 108.6 grams of (0.6 mole) acetic acid n-propyl bromides, controls 90 DEG C of reaction temperature reactions 4
Hour, 700 grams of water and 100 gram of 95% ethyl alcohol is added after cooling, continues to be heated to back flow reaction 3 hours.40 DEG C are cooled to, is added
Shuangzi cation quaternary ammonium salt type surfactant (the 10-6-10,2Cl of the preparation containing 55.2 grams of (0.095 mole) steps (a)-) it is different
Propanol mixture continues at 45 DEG C and stirs 3 hours, obtains required combined surfactant S01, by percentage to the quality, yin
Positive surfactant 35.37%, sodium bromide 3.85%, glycolic sodium 0.62%, mixed alcohol (ethyl alcohol+normal propyl alcohol+isopropanol)
15.42%, water 44.74%.
(2) aqueous surfactant solution containing adsorption inhibitor is prepared respectively with 0.5wt%NaCl analog salt water, with 3:1
Liquid-solid ratio mixed with the quartz sand containing clay, concussion for 24 hours, is centrifugated after cooling, supernatant liquor is taken, using high-efficient liquid phase color
Compose the concentration of (HPLC) analysis measurement Anionic Surfactant and cation, the adsorbance of gauging surface activating agent, unit mg/
G, the results are shown in Table 1.Wherein, adsorbate I is 5wt% kaolin+95wt%100~200 mesh quartz sand containing clay quartz
Sand；Adsorbate II is the mesh of 92wt%200~300 quartz sand+5.6wt% kaolin+2.4wt% sodium bentonite containing clay stone
Sand, clay total content are 8%；Adsorbate III is 15wt% kaolin+85wt%100~200 mesh quartz sand containing clay stone
Sand；Adsorption temp is 80 DEG C.
[embodiment 2]
(1) surfactant S02
(a) cationic surfactant is dodecyl benzyl dimethyl ammonium chloride, commercial goods, content 45%, solvent
For water.
(b) preparation of anion and complexed surfactant S03
Wherein, R=iso-C13H27。
1. 200 grams of (1 mole) isomerous tridecanols, 4 grams of potassium hydroxide are added into the pressure reactor equipped with agitating device
With 2.6 grams of Anhydrous potassium carbonate, when being heated to 80~90 DEG C of reaction temperature, vacuum system is opened, is dehydrated 1 hour under a high vacuum,
Then it is replaced 3~4 times with nitrogen, system reaction temperature is adjusted to 150 DEG C and is slowly passed through 701.8 grams of (12.1 moles) epoxies third
Alkane controls pressure≤0.50MPa, and after reaction to propylene oxide, cooling, being slowly passed through 88.0 grams in 130 DEG C, (2.0 rub
You) ethylene oxide, control pressure≤0.60MPa.After reaction, it is post-processed with [embodiment 1], obtains isomerous tridecanol polyoxy third
955.5 grams of ether of alkene (12) polyoxyethylene (2), yield 97.1%.
2. being added with stirring step in 5000 milliliters of the reaction flask equipped with mechanical stirring, thermometer and reflux condensing tube
Suddenly (b) (1) synthesis 492 grams of ether of isomerous tridecanol polyoxypropylene (12) polyoxyethylene (2) (0.5 mole) and 60.0 gram (1.5
Mole) sodium hydroxide, 79.6 grams of (0.65 mole) ethyl chloroacetates are slowly dropped into, 90 DEG C of reaction temperature is controlled and reacts 4 hours, it is cold
But 600 grams of water and 200 gram of 95% ethyl alcohol are added afterwards, continues to be heated to back flow reaction 5 hours.40 DEG C are cooled to, is added and contains 85.0
The aqueous solution of gram (0.25 mole) dodecyl benzyl dimethyl ammonium chloride continues at 40 DEG C and stirs 4 hours, obtains required answer
Surfactant S03 is closed, by percentage to the quality, yin-yang surfactant 38.02%, sodium chloride 1.81%, glycolic sodium
0.9%, sodium hydroxide 0.49%, ethyl alcohol 13.57%, water 45.21%.
(2) with 3.2wt%NaCl+0.1wt%CaCl2+ 0.05wt%MgCl2Analog salt water is prepared respectively to be inhibited containing absorption
The aqueous solution of the surfactant of agent carries out adsorption experiment with [embodiment 1] (2), the results are shown in Table shown in 2.Wherein, adsorption temp
It is 90 DEG C, adsorbate IV is the mesh of 11.7wt%30~40 mesh of+14.7wt%40~60 mesh of+26.4wt%60~80+23.4wt%
80~100 kaolinic quartz sands containing clay of the mesh of mesh+10.3wt%100~150 mesh of+4.4wt%200~300+9.1wt%.
[embodiment 3]
(1) surfactant S03
By sodium laurate and dodecyl trimethyl ammonium chloride, 15:1 is added in reaction flask in molar ratio, with 10wt% isopropyl
Alcohol solution is solvent, is warming up to 80 DEG C of stirrings 2 hours to being completely dissolved, vacuum distillation removal isopropanol obtains required yin
Positive system surfactant, wherein surfactant total content is 40.8% by percentage to the quality.
(2) aqueous solution of the surfactant containing adsorption inhibitor is prepared respectively with 0.5wt%NaCl analog salt water, together
[embodiment 1] (2) carry out adsorption experiment, the results are shown in Table shown in 3.Wherein, adsorption temp is 83 DEG C.
[embodiment 4]
(1) surfactant S04
(a) synthesis of docosyl polyoxypropylene (m=8) polyoxyethylene (n=2) ether acetic acid sodium
By 439 grams of ether of docosyl polyoxypropylene (m=8) polyoxyethylene (n=2) (0.5 mole) with 60 grams (1.5 rub
You) sodium hydroxide, 70.0 grams of (0.6 mole) sodium chloroacetates and 1200 milliliters of acetone be mixed in equipped with mechanical stirring, thermometer and
In 2000 milliliters of reaction kettle of reflux condensing tube, it is heated to back flow reaction 8 hours.It is cooling, with the acidification of 25wt% hydrochloric acid, divides and go
Water and inorganic salts, upper organic phase are neutralized with the sodium hydroxide of 40wt%, and acetone is evaporated off, and 60 DEG C of vacuum drying obtain 22
Alkyl polyoxypropylene (m=8) polyoxyethylene (n=2) ether acetic acid sodium.
(b) 191.6 gram (0.2 of sodium of docosyl polyoxypropylene (m=8) polyoxyethylene (n=2) ether acetic acid of synthesis is taken
Mole), 10.5 grams of dodecyltriethylammonium ammonium bromide (0.03 mole), isopropyl alcohol concentration be 10wt% isopropoxide aqueous solution
500 grams of the sodium-chloride water solution of 10wt% (salt water be) sequentially adds in reaction flask, is warming up to 80 DEG C and stirs 2 hours, decompression is steamed
It evaporates except isopropanol, obtains required yin-yang system surfactant, wherein surfactant total content is by percentage to the quality
For 31.2wt%.
(2) with total salinity for 9000 mg/litres, Mg2++Ca2+The analog salt water of 36 mg/litres is prepared respectively containing absorption
The aqueous solution of the surfactant of inhibitor carries out adsorption experiment with [embodiment 1] (2), the results are shown in Table shown in 4.Wherein, it adsorbs
Temperature is 83 DEG C.
[embodiment 5]
(1) surfactant S05
(a) Shuangzi cation quaternary ammonium salt type surfactant (10-6-10,2Cl-) preparation with [embodiment 1].
(b) preparation of anion and compound surfactant S-10
1. 330 grams of 2,4- dicumyl phenols (1 mole), 3.8 grams are added into the 2L pressure reactor equipped with agitating device
Potassium hydroxide, when being heated to 80~90 DEG C, open vacuum system, under a high vacuum be dehydrated 1 hour, then with nitrogen displacement 3~
4 times, system reaction temperature is adjusted to 140 DEG C and is slowly passed through 532.4 grams of (12.1 moles) ethylene oxide, control pressure≤
0.60MPa after reaction, is cooled to 90 DEG C, and low-boiling-point substance is removed in vacuum, neutralizes, dehydration after cooling, obtains 2,4- dicumyl phenol
833.1 grams of ether of polyoxyethylene (12), yield 97.1%.
2. being added with stirring step in 2000 milliliters of the reaction flask equipped with mechanical stirring, thermometer and reflux condensing tube
Suddenly 2,4- dicumyl phenol polyoxyethylene (12) ether 429 grams (0.5 moles) and 87.0 grams of (1.5 moles) hydrogen of (b) (1) synthesis
Potassium oxide is slowly dropped into 102.4 grams of (0.75 mole) isopropyl chloracetates, controls 100 DEG C of reaction temperature and reacts 3 hours, cooling
300 grams of water and 300 gram of 95% ethyl alcohol are added afterwards, continues to be heated to back flow reaction 3 hours.40 DEG C are cooled to, is added 45.9 grams
(0.25 mole) Cetyltrimethylammonium bromide continues at 40 DEG C and stirs 5 hours, obtains required combined surfactant
S05, by percentage to the quality, yin-yang surfactant 41.51%, potassium chloride 3.05%, glycolic sodium 2.32%, mixed alcohol
(ethyl alcohol+isopropanol) 26.48%, water 26.64%.
(2) aqueous solution of the surfactant containing adsorption inhibitor is prepared respectively with 25.0wt%NaCl analog salt water, together
[embodiment 1] (2) carry out adsorption experiment, the results are shown in Table shown in 5.Wherein, adsorption temp is 95 DEG C.
[embodiment 6]
It the results are shown in Table 6 institutes the difference is that surfactant is betaine type amphoteric surfactant S06 with [embodiment 1]
Show.
[embodiment 7]
Oil displacement experiment process: by rock core constant temperature drying to constant weight, the gas permeability of rock core is measured；With above-mentioned simulation oil field
Water flooding saturated core calculates its pore volume, and at a temperature of the displacement of reservoir oil, with crude oil saturated core, record is saturated the volume of crude oil,
Water flooding is pumped into the speed of 0.2mL/min again, is driven to aqueous up to 100%, calculates the recovery ratio that water drive improves crude oil, then with
Speed metaideophone 0.1~1PV (rock pore volume) displacement of reservoir oil fluid of 0.15mL/min, with the speed water drive of 0.2mL/min to containing
Water 100% calculates the percentage that oil recovery factor is improved on the basis of water drive.
S01, adsorption inhibitor and modified polyacrylamide polymer (P1, copolymerization AM/ of [embodiment 1] are prepared respectively
Molar ratio=1/0.05 AMPS, the ten thousand) aqueous solution of viscosity-average molecular weight 2500, remixes dilution and obtains uniform displacement of reservoir oil fluid, measures
Oil water interfacial tension of the system at 80 DEG C, crude oil are east oilfields dewatered oil (viscosity 2.3mPa.s), the results are shown in Table 7 institutes
Show.Interfacial tension is measured by the TX500 type rotating interfacial tensimeter that Texas ,Usa university produces.
Imitation oil displacement experiment experiment is carried out on Φ 38*1000 (unit: millimeter) fill out sand tube, displacement of reservoir oil temperature is 80 DEG C, injection rate
For 0.3PV (rock pore volume), the percentage for improving oil recovery factor on the basis of water drive is calculated, is shown in Table 7.
[embodiment 8]
With [embodiment 7] carry out oil displacement experiment, the difference is that oil field dewatered oil be east crude oil, 90 DEG C
When apparent viscosity be 35mPa.s, simulation salt water be 3.2wt%NaCl+0.1wt%CaCl2+ 0.05wt%MgCl2, measure boundary
Face tension and the temperature of the displacement of reservoir oil are 90 DEG C, surfactant S02, and polymer is that (P2 is copolymerized AM/ to hydrophobic associated polymer P2
Ten thousand) AMPS/2- acrylamido dodecyl sodium sulfonate molar ratio=1/0.35/0.0015, viscosity-average molecular weight 2055, are as a result shown in
Shown in table 8.
[embodiment 9]
Oil displacement experiment is carried out with [embodiment 7], the difference is that surfactant is S03, polymer is modified poly- third
Acrylamide P3 (AM/AMPS molar ratio=1.5:1, M=600 ten thousand) aqueous solution, oil field dewatered oil are east crude oil (83
DEG C when apparent viscosity be 2.1mPa.s), displacement of reservoir oil temperature be 83 DEG C, the results are shown in Table shown in 9.
[embodiment 10]
Oil displacement experiment is carried out with [embodiment 7], the difference is that surfactant is S06, the results are shown in Table shown in 10.
Table 1
Table 2
Table 3
Table 4
Table 5
Table 6
Table 7
Table 8
Table 9
Table 10
Claims (10)
1. a kind of displacement of reservoir oil fluid containing adsorption inhibitor, in terms of mass fraction, including following components:
1) 1 part of oil displacement agent；
2) 0.001~10 part of adsorption inhibitor；
Wherein, contain surfactant in the oil displacement agent；The adsorption inhibitor is the small molecule compound containing carboxyl, divides
At least one of polymer and alkali compounds of son amount 1000~500000 or two or more mixtures.
2. the displacement of reservoir oil fluid according to claim 1 containing adsorption inhibitor, it is characterised in that the displacement of reservoir oil fluid is table
Face surfactant flooding flow of oil, polymer-surfactant binary displacement oil fluid, polymer-surfactant-alkali ternary oil displacement stream
At least one of body.
3. the displacement of reservoir oil fluid according to claim 2 containing adsorption inhibitor, it is characterised in that the surfactant is
Nonionic surfactant, anionic surfactant, cationic surfactant, in amphoteric ionic surfactant extremely
Few one kind；In the polymer-surfactant binary displacement oil fluid, polymer-surfactant-alkali ternary oil displacement fluid
Polymer be independently selected from partially hydrolyzed polyacrylamide (PHPA), modified polyacrylamide, polymer microballoon, in biomass polymers extremely
Few one kind；Alkali in the polymer-surfactant-alkali ternary oil displacement fluid is selected from alkali metal hydroxide, alkaline-earth metal
In hydroxide, alkali carbonate, alkali silicate, alkali metal phosphate, alkali borate or short carbon chain organic amine
At least one.
4. the displacement of reservoir oil fluid according to claim 1 containing adsorption inhibitor, it is characterised in that described to contain the small of carboxyl
It is low lower than 8 carboxylic acid containing hydroxyl and/or salt, carbochain lower than 8 carboxylic acid and/or salt, carbochain that molecular compound is selected from carbochain
In 8 the carboxylic acid containing amino and/or salt or carbochain lower than 8 saccharide compound at least one of.
5. the displacement of reservoir oil fluid according to claim 4 containing adsorption inhibitor, it is characterised in that described to contain the small of carboxyl
Molecular compound is formic acid/salt, acetic acid and/or salt, propionic acid and/or salt, malonic acid and/or salt, butyric acid and/or salt, succinic acid
And/or salt, valeric acid and/or salt, glutaric acid and/or salt, caproic acid and/or salt, adipic acid and/or salt, citric acid and/or salt, wine
Stone acid and/or salt, alanine and/or salt, glutamic acid and/or at least one of salt or monosaccharide.
6. the displacement of reservoir oil fluid according to claim 1 containing adsorption inhibitor, it is characterised in that the adsorption inhibitor is
The polyacrylic acid and/or at least one of salt and/or ester of molecular weight 3000~200000.
7. the displacement of reservoir oil fluid according to claim 1 containing adsorption inhibitor, it is characterised in that the alkali compounds is
Alkali metal hydroxide, alkaline earth metal hydroxide, alkali carbonate, alkali silicate, alkali metal phosphate, alkali metal
At least one of borate or short carbon chain organic amine.
8. the displacement of reservoir oil fluid according to claim 1 containing adsorption inhibitor, it is characterised in that the displacement of reservoir oil fluid and suction
The mass ratio of attached inhibitor is 1:(0.1~4).
9. the preparation method of any displacement of reservoir oil fluid containing adsorption inhibitor of claim 1~8, comprising the following steps:
The desired amount of oil displacement agent and adsorption inhibitor are uniformly mixed, or the desired amount of oil displacement agent, adsorption inhibitor and water are mixed
It closes and uniformly obtains the displacement of reservoir oil fluid containing adsorption inhibitor.
10. any application of the displacement of reservoir oil fluid in tertiary oil recovery containing adsorption inhibitor of claim 1~8.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4217958A (en) * | 1978-11-24 | 1980-08-19 | Texaco Inc. | Sacrificial agents for petroleum recovery processes |
| US4574885A (en) * | 1984-06-27 | 1986-03-11 | Phillips Petroleum Company | Agents for petroleum recovery processes |
| US4610302A (en) * | 1985-07-03 | 1986-09-09 | Phillips Petroleum Company | Oil recovery processes |
| CN106590566A (en) * | 2015-10-20 | 2017-04-26 | 中国石油化工股份有限公司 | Method for reducing oil displacement surfactant adsorbed on clay-containing quartz sand |
-
2017
- 2017-08-16 CN CN201710699515.9A patent/CN109401744B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4217958A (en) * | 1978-11-24 | 1980-08-19 | Texaco Inc. | Sacrificial agents for petroleum recovery processes |
| US4574885A (en) * | 1984-06-27 | 1986-03-11 | Phillips Petroleum Company | Agents for petroleum recovery processes |
| US4610302A (en) * | 1985-07-03 | 1986-09-09 | Phillips Petroleum Company | Oil recovery processes |
| CN106590566A (en) * | 2015-10-20 | 2017-04-26 | 中国石油化工股份有限公司 | Method for reducing oil displacement surfactant adsorbed on clay-containing quartz sand |
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