CN103540307B - For compositions improving recovery efficiency of high-temperature oil reservoir and preparation method thereof - Google Patents

For compositions improving recovery efficiency of high-temperature oil reservoir and preparation method thereof Download PDF

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CN103540307B
CN103540307B CN201210240162.3A CN201210240162A CN103540307B CN 103540307 B CN103540307 B CN 103540307B CN 201210240162 A CN201210240162 A CN 201210240162A CN 103540307 B CN103540307 B CN 103540307B
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oil
polyacrylamide
solution
compositions
displacement
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CN103540307A (en
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夏燕敏
许汇
宋晓芳
蔡红
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/58Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
    • C09K8/588Compositions 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
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/58Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
    • C09K8/584Compositions 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

Abstract

The present invention relates to a kind of for compositions improving recovery efficiency of high-temperature oil reservoir and preparation method thereof, mainly solve in prior art the problem that the oil displacement agent containing polymer exists temperature-resistant anti-salt performance and poor heat stability, oil displacement efficiency is low.The present invention, by high-temperature oil reservoir displacement composition used for tertiary oil recovery, includes following component by weight percentage: (1) 0.01~the high temperature resistance polyacrylamide for oil displacement of 3.0%;(2) 0.01~the aliphatic alcohol polyethenoxy ether carboxylate surfactant of 5.0%;(3) 92.0~the injection water of 99.98%;Wherein (1) component is preferably to solve this problem by the technical scheme that with the addition of the prepared high temperature resistance polyacrylamide for oil displacement of inorganic or organically-modified montmorillonite and preparation method thereof, can be used in the tertiary oil recovery production of high-temperature oil reservoir.

Description

For compositions improving recovery efficiency of high-temperature oil reservoir and preparation method thereof
Technical field
The present invention relates to a kind of for compositions improving recovery efficiency of high-temperature oil reservoir and preparation method thereof.
Background technology
Domestic each elephant through once, secondary oil recovery, crude oil water content is continuously increased, and part elephant successively enters three The secondary oil recovery stage.Polymer flooding is the main technique methods of tertiary oil recovery, and mechanism of oil displacement understands, technique is relatively easy, technology day Become ripe, be an effective raising recovery efficiency technique measure.The mechanism of oil displacement of polymer is mainly by water-soluble polypropylene The viscosity of amide molecule chain, improves the mobility ratio of displacing fluid, improves displacement efficiency and swept volume, thus reaches to improve recovery ratio Purpose.
Owing to the tertiary oil recovery cycle is long, deep layer oil temperature is high, and therefore, polymer used for tertiary oil recovery must have good increasing Viscous, heatproof, salt-resistance, stable performance.
In recent years, the research about temperature-resistant and anti-salt type polyacrylamide is mainly passed through to introduce big side base on main polymer chain Or rigidity side base improves the heat stability of polymer, introduces the monomer of suppression hydrolysis or the monomer that salt is insensitive carries out copolymerization Improve the hydrolysis of polymer and anti-salt property, or improve the heatproof of polymer by the heat resistance and salt tolerance of hydrophobic group and resist Salt performance.But due to comonomer quality or price makes polymer be difficult to reach high molecular or product has higher one-tenth This, in commercial production or can be somewhat limited in the actual application of tertiary oil recovery.In tertiary oil recovery at present, heatproof can be met and resist The polymer that salt requires is little, be not price too higher position be unstable properties, particularly can not meet salinity 10000mg/L left The right side, is resistant to the polymer of 90 DEG C of high temperature above.
Montmorillonite (Montmorillonite is called for short MMT) mining deposits is the abundantest, cheap, and function admirable can For multiple industries such as light industry, oil, metallurgy, control of desert, sewage disposal, medicines, it is described as " universal material " by people.Natural Montmorillonite is the earthy mineral of the hydrous alumino silicates of a kind of layer structure, flaky crystal, is mainly composed of silicon oxide and oxidation Aluminum, structure cell parallel stacked, belong to 2: 1 type three-layer sandwich structures, there is the highest rigidity, interlayer not easy glide, this special Crystal structure gives the character that montmorillonite is unique, such as bigger surface activity, higher cation exchange capacity (CEC), abnormal aqueous spy The interlayer surface levied, the strong ability etc. changing fluid flow characteristics.It is carried out inorganic, organic or Organic-inorganic composite change Property process after significantly widened application, be particularly widely used in terms of flocculant material, polymer composites.But It is to introduce modified montmorillonite in acrylamide polymerization to be but rarely reported, through patent retrieval with the heat stability of raising polymer Not finding, only minority document has similar research at the aspect such as water-absorbing resins or thickening agent.Such as Shu little Wei, Shen Shangyue Deng (China's powder technology, 2005,2:9-11) with N,N methylene bis acrylamide as cross-linking agent, sodium peroxydisulfate is for causing Agent, uses aqua-solution method to prepare Kaolin composite polypropylene acid-acrylamide super water absorbent resin, kaolinic addition For acrylic monomers 50%;An Jingyun, Liu Hongyu etc. (Henan chemical industry, 2008,31 (3): 19-20,30) use AM, AA, AMPS and sodium-based montmorillonite have synthesized a kind of thickening agent with higher anti-electrolyte capability, and montmorillonite content is 1%~5% In the range of.Particularly imvite modified polyacrylamide be there is not yet report as oil displacement agent used for tertiary oil recovery.
The present invention utilizes montmorillonite-based nano layer and poly-third after inorganic or organic modification montmonrillonite and acrylamide in-situ polymerization Acrylamide strand interacts, and improves the heat-resisting of polymer and stability, of the present invention is suitable for the high temperature resistant displacement of reservoir oil And application in tertiary oil recovery compound by the preparation method of polymer, binary.
Summary of the invention
One of the technical problem to be solved is that the oil displacement agent containing polymer in prior art exists temperature-resistant anti-salt And the problem that heat stability can meet tertiary oil recovery requirement, oil displacement efficiency is low, it is provided that a kind of new being used for improves high temperature oil Hide the compositions of recovery ratio.Said composition, in oil displacement process, has concentration low, displacement of reservoir oil effect under the conditions of high temperature and high salt The feature that rate is high.The two of the technical problem to be solved are to provide a kind of use corresponding with solving one of technical problem Preparation method in the compositions improving recovery efficiency of high-temperature oil reservoir.
In order to solve above-mentioned technical problem, the technical solution used in the present invention is as follows: one is used for improving high-temperature oil reservoir and adopts The compositions of yield, includes following component by weight percentage:
(1) 0.01~the high temperature resistance polyacrylamide for oil displacement of 3.0%;
(2) 0.01~the aliphatic alcohol polyethenoxy ether carboxylate surfactant of 5.0%;
(3) 92.0~the injection water of 99.98%;
Wherein (1) component high temperature resistance polyacrylamide for oil displacement presses the survey of GBT12005.10-92 Molecular Weight for Polyacrylamide Mw Fixed (viscosimetry) measures intrinsic viscosity, and by [η]=3.73 × 10-4Mw0.66Calculating molecular weight is 2504~32,180,000, always Salinity is that in the aqueous solution that total amount is 48mg/L of 8730mg/L, wherein calcium ion and magnesium ion, 1500mg/L polymer is dense Degree solution is at 95 DEG C, 7.34s-1Under apparent viscosity be 38.4~41.7mps.
In technique scheme, the described preferred scope of total salinity injecting water: 5000~15000mg/L, Ca2++Mg2 +It is 30~600mg/L.Described surfactant preferred version is selected from aliphatic alcohol polyethenoxy ether carboxylate type the moon-non-surface Activating agent, general molecular formula is RO (CH2CH2O)nCH2COOM;Wherein the carbon number of R is 12~18, and n is adding of ethoxy group EO Closing number, any one integer in 2~8, metal ions M is selected from potassium, sodium or lithium.
In order to solve the two of above-mentioned technical problem, the technical solution used in the present invention is as follows: one is used for improving high temperature oil Hide the preparation method of the compositions of recovery ratio, comprise the following steps:
A) acrylamide monomer is made into the aqueous solution I that mass concentration is 10~40%;
B) adding acrylamide monomer weight 0.05~the inorganic or organic modification montmonrillonite of 5% in solution I, mixing is all Solution II is obtained after even;
C) in solution II letting nitrogen in and deoxidizing 10~add after 40 minutes relative to monomer mass concentration 0.02~5% compound Initiator system compositions, obtains solution III;
D) letting nitrogen in and deoxidizing 10~after 40 minutes in solution III, causes at 5~25 DEG C, obtains glue after be polymerized 2~10 hours Shape product I;
E) add after gum-like product I being shredded mass concentration 5~50% alkali liquor be hydrolyzed reaction 1~5 hour, wherein Temperature is 80~95 DEG C, obtains gum-like product II;
F) by gum-like product II drying, pulverize, sieve after fine particulate high temperature resistant type polyacrylamide;
G) by the desired amount of high temperature resistant type polyacrylamide, above-mentioned aliphatic alcohol polyethenoxy ether carboxylate and injection water Uniformly mixing, 5~35 DEG C are stirred 1~3 hour, obtain required compositions, by weight percentage, anionic polyacrylamide Amine, aliphatic alcohol polyethenoxy ether carboxylate and the proportioning injecting water are 0.01~3.0%: 0.01~5.0%: 92.0~99.98;
Wherein composite initiation system: compositions, includes following components by weight percentage: (a) 0.5~the persulfuric acid of 20% Salt;(b) 0.1~the sulphite of 40% or acid sulphite;(c) 0.5~20% by NR1R2R3The tertiary amines chemical combination represented Thing or by N+R4R5R6R7Represent quaternary ammonium compounds or by NH2R8The fat amine compound represented, R in formula1~R7It is selected from C1~C14Straight or branched alkyl or alkyl derivative, R8Selected from C1~C18Straight or branched alkyl or alkyl derivative;(d)10 ~the carbamide of 80%, thiourea or ammonia;(e) 5~the disodiumedetate of 60%.
The compositions for improving recovery efficiency of high-temperature oil reservoir prepared by the present invention, owing to have employed composite initiation system group Compound, and matched with preferred technique, therefore reacting balance, beneficially chain increase, product not only molecular weight is high, in certain ore deposit The saline of change degree also shows higher apparent viscosity;It is more special that the function monomer wherein added may make polymer be formed Structure so that it has preferable temperature-resistant anti-salt performance simultaneously;Have employed rear hydrolysis process, polymerization and hydrolysis the most accurately may be used Control, can obtain higher molecular weight and the product of certain degree of hydrolysis;Modified montmorillonoid is owing to tying containing polyvalent metal ion or stratiform Structure, can provide hapto during the in-situ polymerization of acrylamide, produce intermolecular physical crosslinking or slight chemistry Crosslinking, forms certain two dimension or three dimensional structure, even if still having stable structure at higher temperature or salinity, significantly Improve the heat-resisting of polymer and stability.The displacement of reservoir oil using preparation technology provided by the present invention to prepare is used with the high temperature resistant displacement of reservoir oil Polyacrylamide, molecular weight 25,000,000, apparent viscosity 38mPa s (saline total salinity 10000 mg in saline L-1Left and right, Ca2++Mg2+100 mg·L-1Left and right).
Use high temperature resistant type polyacrylamide prepared by the present invention, be 0.1~0.3wt% and 0.1~0.4wt% with consumption Aliphatic alcohol polyethenoxy ether carboxylate surfactant forms displacement of reservoir oil compositions, under the conditions of alkali-free, can be used for higher temperature With in-place oil and the water of the oil field block of salinity, determine molten at Henan Oil Field rivers 95 DEG C of water of simulation of this oil displacement agent Liquid apparent viscosity, more than the dynamical interfacial tension value between 38mPa.s, and VII time block crude oil of Henan Oil Field, up to 10-3~ 10-4The ultralow interfacial tension of mN/m, through physical modeling's displacement experiment Lab-evaluation, on high temperature, high salinity reservoir, this oil displacement agent can be On the basis of water drive, (water drive improves oil recovery factor and reaches 41.1%) raising oil recovery factor, up to 16.6%, achieves preferable technology Effect.
Below by embodiment, the present invention is further elaborated.
Detailed description of the invention
[embodiment 1]
First 125g acrylamide (AM) and 0.125g sodium-based montmorillonite (Na-MMT) are added in 352g deionized water, stirring It is uniformly dissolved, with the NaOH solution regulation pH value of 5% mass concentration to 8.5, and starts to be passed through high pure nitrogen, by water-bath after 30min Being cooled to 15 DEG C, be then sequentially added into 1.25% aqueous solution of urea 8g, 0.9% disodiumedetate (EDTA-disodium) is water-soluble Liquid 10g, 1.25% methacrylic acid N, N-dimethylaminoethyl (DMAEMA) aqueous solution 1g, the persulfate aqueous solution of 1.25% 1g, the aqueous solution of sodium bisulfite 1g of 1%, be gradually increased to 40 DEG C after 1 hour by reaction temperature, obtains gel after reacting 3 hours Polymerizate, cuts and adds 10%NaOH aqueous solution 120g after glue, and 90 C hydrolysis 2 hours, then at 75 DEG C, vacuum was done Dry 6h, smashes sample analysis after screening with pulverizer.
It is 88.5% by GB/T12005.2-89 polyacrylamide determination of solid content method test solid content, by GB/ T12005.8-89 powdered polypropylene amide measuring of dissolution velocity method test dissolution time 90min, by GB/T12005.6-89 Partially hydrolyzed polyacrylamide (PHPA) degree of hydrolysis assay method test degree of hydrolysis is 17.6%, by GB/T12005.10-92 polyacrylamide Molecular weight determination (viscosimetry) measures intrinsic viscosity, and by [η]=3.73 × 10-4Mw0.66Calculating molecular weight is 25,190,000, 1500mg/L polymer concentration solution is at 95 DEG C, 7.34s-1Under apparent viscosity be 41.1 mPa s (saline total salinities 8730 mg·L-1, Ca2++Mg2+: 48mg L-1), 95 DEG C of viscosity retention ratios after aging 30 days are 98%.
By synthesized high temperature resistance polyacrylamide for oil displacement 0.15wt%, above-mentioned aliphatic alcohol polyethenoxy ether carboxylate (n=4) 0.25wt% and 99.6wt% Henan Oil Field rivers injection water uniformly mixes, and 20 DEG C are stirred 2 hours, obtain the required displacement of reservoir oil Use compositions.At temperature 95 DEG C, salinity 8730mg/L, Ca2++Mg2+In the water of 48mg/L, record the apparent viscous of this compositions Degree is 41.3mPa.s.;The ultralow interface forming 0.0072mN/m between said composition and Henan Oil Field block dewatered oil is opened Power.Apparent viscosity is measured by the BROOKFIELD III type viscometer of Brookfield company of the U.S., and interfacial tension is by U.S.'s moral gram The TX500 type that Sa Si university produces rotates and drips interfacial tensimeter mensuration.
[embodiment 2]
First 125g acrylamide (AM) and 0.188g sodium-based montmorillonite (Na-MMT) are added in 370g deionized water, stirring After being uniformly dissolved, with the NaOH solution regulation pH value of 5% mass concentration to 9.0, and start to be passed through high pure nitrogen, by water after 30min Bath is cooled to 15 DEG C, is then sequentially added into 1.25% thiourea solution 1g, 0.81% disodiumedetate (EDTA-disodium) water Solution 1g, 1.25% β-dimethylaminopropionitrile aqueous solution 1g, the sodium persulfate aqueous solution 1g of 1.25%, the potassium sulfite water of 1.69% Solution 1g, was gradually increased to 35 DEG C after 0.5 hour by reaction temperature, obtains gel polymerizate, add after cutting glue after reacting 4 hours Enter 10%NaOH aqueous solution 120g, 90 C hydrolysis 2 hours, at 75 DEG C, be then vacuum dried 6h, smash with pulverizer Sample analysis after screening.
It is 87.9% by GB/T12005.2-89 polyacrylamide determination of solid content method test solid content, by GB/ T12005.8-89 powdered polypropylene amide measuring of dissolution velocity method test dissolution time 120min, by GB/T12005.6- 89 partially hydrolyzed polyacrylamide (PHPA) degree of hydrolysis assay method test degree of hydrolysis are 16.5%, by GB/T12005.10-92 polyacrylamide Amine molecule measures fixed (viscosimetry) and measures intrinsic viscosity, and by [η]=3.73 × 10-4Mw0.66Calculating molecular weight is 25,040,000, 1500mg/L polymer concentration solution is at 95 DEG C, 7.34s-1Under apparent viscosity be 38.8mPa s (saline total salinity 8730 mg·L-1, Ca2++Mg2+: 48 mg L-1), 95 DEG C of viscosity retention ratios after aging 30 days are 96%.
By synthesized high temperature resistance polyacrylamide for oil displacement 0.15wt%, above-mentioned aliphatic alcohol polyethenoxy ether carboxylate (n=4) 0.35wt% and 99.5wt% Henan Oil Field rivers injection water uniformly mixes, and 20 DEG C are stirred 2 hours, obtain the required displacement of reservoir oil Use compositions.At temperature 95 DEG C, salinity 8730mg/L, Ca2++Mg2+In the water of 48mg/L, record the apparent viscous of this compositions Degree is 39.1mPa.s.;The ultralow interface forming 0.0063mN/m between said composition and Henan Oil Field block dewatered oil is opened Power.Apparent viscosity is measured by the BROOKFIELD III type viscometer of Brookfield company of the U.S., and interfacial tension is by U.S.'s moral gram The TX500 type that Sa Si university produces rotates and drips interfacial tensimeter mensuration.
[embodiment 3]
First 125g acrylamide (AM) and 0.215g sodium-based montmorillonite (Na-MMT) are added in 370g deionized water, stirring After being uniformly dissolved, with the NaOH solution regulation pH value of 5% mass concentration to 8.6, and start to be passed through high pure nitrogen, by water after 30min Bath is cooled to 15 DEG C, is then sequentially added into 1.38% aqueous solution of urea 1g, 0.33% disodiumedetate (EDTA-disodium) water Solution 1g, 0.99%N, N-dimethyl diallyl ammonium chloride aqueous solution 1g, the ammonium persulfate aqueous solution 1g of 1.25%, 2.63% Potassium sulfite aqueous solution 1g, was gradually increased to 40 DEG C after 1 hour by reaction temperature, obtains gel polymerization and produce after reacting 3.5 hours Thing, cuts and adds 10%NaOH aqueous solution 120g after glue, 90 C hydrolysis 2 hours, is then vacuum dried 6h at 75 DEG C, uses Sample analysis after screening smashed by pulverizer.
It is 89.8% by GB/T12005.2-89 polyacrylamide determination of solid content method test solid content, by GB/ T12005.8-89 powdered polypropylene amide measuring of dissolution velocity method test dissolution time 90min, by GB/T12005.6-89 Partially hydrolyzed polyacrylamide (PHPA) degree of hydrolysis assay method test degree of hydrolysis is 15.6%, by GB/T12005.10-92 polyacrylamide Molecular weight determination (viscosimetry) measures intrinsic viscosity, and by [η]=3.73 × 10-4Mw0.66Calculating molecular weight is 32,180,000, 1500mg/L polymer concentration solution is at 95 DEG C, 7.34s-1Under apparent viscosity be 38.8mPa s (saline total salinity 8730mg·L-1, Ca2++Mg2+: 48 mg L-1), 95 DEG C of viscosity retention ratios after aging 30 days are 102%.
By synthesized high temperature resistance polyacrylamide for oil displacement 0.15wt%, above-mentioned aliphatic alcohol polyethenoxy ether carboxylate (n=4) 0.25wt% and 99.6wt% Henan Oil Field rivers injection water uniformly mixes, and 20 DEG C are stirred 2 hours, obtain the required displacement of reservoir oil Use compositions.At temperature 95 DEG C, salinity 8730mg/L, Ca2++Mg2+In the water of 48mg/L, record the apparent viscous of this compositions Degree is 39.8mPa.s.;The ultralow interface forming 0.0062mN/m between said composition and Henan Oil Field block dewatered oil is opened Power.Apparent viscosity is measured by the BROOKFIELD III type viscometer of Brookfield company of the U.S., and interfacial tension is by U.S.'s moral gram The TX500 type that Sa Si university produces rotates and drips interfacial tensimeter mensuration.
[embodiment 4]
First 125g acrylamide (AM) and 0.125g organic modification montmonrillonite (O-MMT) are added in 369g deionized water, After stirring and dissolving is uniform, with the NaOH solution regulation pH value of 5% mass concentration to 9.8, and start to be passed through high pure nitrogen, after 30min Water-bath is cooled to 15 DEG C, is then sequentially added into 3.13% thiourea solution 1g, 1.04% ammonia spirit 1g, 2.5% ethylenediamine tetraacetic Acetic acid disodium (EDTA-disodium) aqueous solution 1g, 1.56% methacrylic acid N, N-dimethylaminoethyl (DMAEMA) aqueous solution 1g, The ammonium persulfate aqueous solution 1g of 1.25%, the sodium sulfite aqueous solution 1g of 0.94%, be gradually increased to 40 by reaction temperature after 1.5 hours DEG C, obtain gel polymerizate after reacting 3 hours, after cutting glue, add 10%NaOH aqueous solution 115g, at 90 C hydrolysis 2 Hour, at 75 DEG C, then it is vacuum dried 6h, smashes sample analysis after screening with pulverizer.
It is 87.9% by GB/T12005.2-89 polyacrylamide determination of solid content method test solid content, by GB/ T12005.8-89 powdered polypropylene amide measuring of dissolution velocity method test dissolution time 90min, by GB/T12005.6-89 Partially hydrolyzed polyacrylamide (PHPA) degree of hydrolysis assay method test degree of hydrolysis is 16.4%, by GB/T12005.10-92 polyacrylamide Molecular weight determination (viscosimetry) measures intrinsic viscosity, and by [η]=3.73 × 10-4Mw0.66Calculating molecular weight is 26,160,000, 1500mg/L polymer concentration solution is at 95 DEG C, 7.34s-1Under apparent viscosity be 39.8 mPa s (saline total salinities 8730 mg·L-1, Ca2++Mg2+: 48mg L-1), 95 DEG C of viscosity retention ratios after aging 30 days are 105%.
By synthesized high temperature resistance polyacrylamide for oil displacement 0.15wt%, above-mentioned aliphatic alcohol polyethenoxy ether carboxylate (n=4) 0.40wt% and 99.45wt% Henan Oil Field rivers injection water uniformly mixes, and 15 DEG C are stirred 3 hours, obtain the required displacement of reservoir oil Use compositions.At temperature 95 DEG C, salinity 8730mg/L, Ca2++Mg2+In the water of 48mg/L, record the apparent viscous of this compositions Degree is 42.3mPa.s.;The ultralow interface forming 0.0069mN/m between said composition and Henan Oil Field block dewatered oil is opened Power.Apparent viscosity is measured by the BROOKFIELD III type viscometer of Brookfield company of the U.S., and interfacial tension is by U.S.'s moral gram The TX500 type that Sa Si university produces rotates and drips interfacial tensimeter mensuration.
[embodiment 5~8]
The high temperature resistant type polyacrylamide that [embodiment 1~4] is synthesized, with consumption be 0.1~0.3wt% and 0.1~ The aliphatic alcohol polyethenoxy ether carboxylate surfactant of 0.4wt% forms displacement of reservoir oil compositions, under the conditions of alkali-free, determines This oil displacement agent solution apparent viscosity at Henan Oil Field rivers 95 DEG C of water of simulation is more than 38mPa.s, with Henan Oil Field block Dynamical interfacial tension value between crude oil, up to 10-3~10-4The ultralow interfacial tension of mN/m;At a length of 30 centimetres, diameter Being 2.5 centimetres, permeability is 1.5 microns2Rock core on carry out physical modeling's displacement experiment, Lab-evaluation high temperature, high salt oil On Tibetan this oil displacement agent can on the basis of water drive (water drive can improve oil recovery factor 41.1~42.8%) improve oil recovery factor up to 15.2~16.6%, the results are shown in Table shown in 1.The TX500 type that interfacial tension is produced by Texas ,Usa university rotates an interface and opens Power instrument measures.
[comparative example 1]
Being added in 355g deionized water by 125g acrylamide monomer, stir after dissolving completely, the NaOH with 5% is molten Liquid regulation pH value, to 8, then leads to nitrogen 30min, and bath temperature is adjusted to 15 DEG C, be separately added into the potassium peroxydisulfate of 0.125wt% The aqueous solution of sodium bisulfite 10g of aqueous solution 10g, 0.0963wt%, is gradually increased to 45 DEG C after 30min by reaction temperature, reacts 4h Rear taking-up blob of viscose, after being ground into graininess, adds the NaOH aqueous solution 120 grams of 10%, and at 90 DEG C, hydrolysis 2h, then exists It is dried 6h under 75 DEG C of vacuum, smashes sample analysis after screening with pulverizer.
It is 88.65% by GBT12005.2-89 polyacrylamide determination of solid content method test solid content, presses GBT12005.6-89 partially hydrolyzed polyacrylamide (PHPA) degree of hydrolysis assay method test degree of hydrolysis is 17.3%, by GBT12005.10- 92 Molecular Weight for Polyacrylamide measure (viscosimetry) and measure intrinsic viscosity, and by [η]=3.73 × 10-4Mw0.66Calculating molecular weight is 19630000, in the aqueous solution that the total amount that total salinity is 8730mg/L, wherein calcium ion and magnesium ion is 48mg/L, 1500mg/L polymer concentration solution is at 95 DEG C, 7.34s-1Under apparent viscosity be 26.2mps, 95 DEG C of viscosity after aging 30 days are protected Staying rate is 55%.
[comparative example 2]
Being added in 345g deionized water by 125g acrylamide monomer, stir after dissolving completely, the NaOH with 5% is molten Liquid regulation pH value, to 8, then leads to nitrogen 30min, and bath temperature is adjusted to 15 DEG C, be separately added into the potassium peroxydisulfate of 0.125wt% The AIBI aqueous solution 10g of the aqueous solution of sodium bisulfite 10g, 0.125wt% of aqueous solution 10g, 0.0963wt%, will be anti-after 30min Answer temperature to be gradually increased to 45 DEG C, after reaction 4h, take out blob of viscose, after being ground into graininess, add the NaOH aqueous solution 120 grams of 10%, Hydrolysis 2h at 90 DEG C, is then dried 6h under 75 DEG C of vacuum, smashes sample analysis after screening with pulverizer.
It is 87.54% by GBT12005.2-89 polyacrylamide determination of solid content method test solid content, presses GBT12005.6-89 partially hydrolyzed polyacrylamide (PHPA) degree of hydrolysis assay method test degree of hydrolysis is 16.3%, by GBT12005.10- 92 Molecular Weight for Polyacrylamide measure (viscosimetry) and measure intrinsic viscosity, and by [η]=3.73 × 10-4Mw0.66Calculating molecular weight is 21320000, in the aqueous solution that the total amount that total salinity is 8730mg/L, wherein calcium ion and magnesium ion is 48mg/L, 1500mg/L polymer concentration solution is at 95 DEG C, 7.34s-1Under apparent viscosity be 31.9mps, 95 DEG C of viscosity after aging 30 days are protected Staying rate is 69%.
Table 1 different components is to VII time block oil displacement test result of Henan Oil Field

Claims (4)

1., for improving the compositions of recovery efficiency of high-temperature oil reservoir, include following component by weight percentage:
(1) 0.01~the high temperature resistance polyacrylamide for oil displacement of 3.0%;
(2) 0.01~the aliphatic alcohol polyethenoxy ether carboxylate surfactant of 5.0%;
(3) 92.0~the injection water of 99.98%;
Wherein (1) component high temperature resistance polyacrylamide for oil displacement is pressed GBT12005.10-92 " Molecular Weight for Polyacrylamide is measured viscous Degree method " measure intrinsic viscosity, and by [η]=3.73 × 10-4Mw0.66Calculating molecular weight is 2504~32,180,000, in total mineralising In the degree aqueous solution that total amount is 48mg/L for 8730mg/L, wherein calcium ion and magnesium ion, 1500mg/L polymer concentration is molten Liquid is at 95 DEG C, 7.34s-1Under apparent viscosity be 38.4~41.7mPa s;The system of described high temperature resistance polyacrylamide for oil displacement Preparation Method, comprises the following steps:
A) acrylamide monomer is made into the aqueous solution I that mass concentration is 10~40%;
B) in solution I, acrylamide monomer weight 0.05~the inorganic or organic modification montmonrillonite of 5% are added, after mix homogeneously Obtain solution II;
C) letting nitrogen in and deoxidizing 10~add after 40 minutes relative to monomer mass concentration 0.02~the compound initiation of 5% in solution II System combination, obtains solution III;
D) letting nitrogen in and deoxidizing 10~after 40 minutes in solution III, causes at 5~25 DEG C, obtains gluey product after be polymerized 2~10 hours Thing I;
E) add after gum-like product I being shredded mass concentration 5~50% alkali liquor be hydrolyzed reaction 1~5 hour, wherein temperature It is 80~95 DEG C, obtains gum-like product II;
F) by gum-like product II drying, pulverize, sieve after fine particulate high temperature resistance polyacrylamide for oil displacement;
Wherein composite initiation system: compositions, includes following components by weight percentage: (a) 0.5~the persulfate of 20%; (b) 0.1~the sulphite of 40% or acid sulphite;(c) 0.5~20% by NR1R2R3The tertiary amine compounds represented Or by N+R4R5R6R7Represent quaternary ammonium compounds or by NH2R8The fat amine compound represented, R in formula1~R7It is selected from C1 ~C14Straight or branched alkyl or alkyl derivative, R8Selected from C1~C18Straight or branched alkyl or alkyl derivative;(d) 10~ Carbamide, thiourea or the ammonia of 80%;(e) 5~the disodiumedetate of 60%.
Compositions for improving recovery efficiency of high-temperature oil reservoir the most according to claim 1, it is characterised in that described injection The total salinity of water is 5000~15000mg/L, Ca2++Mg2+It is 30~600mg/L.
Compositions for improving recovery efficiency of high-temperature oil reservoir the most according to claim 1, it is characterised in that described surface Activating agent is selected from aliphatic alcohol polyethenoxy ether carboxylate type the moon-non-surface-active agent, and general molecular formula is RO (CH2CH2O)nCH2COOM;Wherein the carbon number of R is 12~18, and n is the adduction number of ethoxy group EO, and any one in 2~8 is whole Number, metal ions M is selected from potassium, sodium or lithium.
4. the preparation method of the compositions for improving recovery efficiency of high-temperature oil reservoir described in claim 1, comprises the following steps:
A) acrylamide monomer is made into the aqueous solution I that mass concentration is 10~40%;
B) in solution I, acrylamide monomer weight 0.05~the inorganic or organic modification montmonrillonite of 5% are added, after mix homogeneously Obtain solution II;
C) letting nitrogen in and deoxidizing 10~add after 40 minutes relative to monomer mass concentration 0.02~the compound initiation of 5% in solution II System combination, obtains solution III;
D) letting nitrogen in and deoxidizing 10~after 40 minutes in solution III, causes at 5~25 DEG C, obtains gluey product after be polymerized 2~10 hours Thing I;
E) add after gum-like product I being shredded mass concentration 5~50% alkali liquor be hydrolyzed reaction 1~5 hour, wherein temperature It is 80~95 DEG C, obtains gum-like product II;
F) by gum-like product II drying, pulverize, sieve after fine particulate high temperature resistance polyacrylamide for oil displacement;
G) the desired amount of high temperature resistant type polyacrylamide, above-mentioned aliphatic alcohol polyethenoxy ether carboxylate and injection water are uniformly mixed Closing, 5~35 DEG C are stirred 1~3 hour, obtain required compositions, by weight percentage, high temperature resistant displacement of reservoir oil polyacrylamide Amine, aliphatic alcohol polyethenoxy ether carboxylate and inject water proportioning be 0.01~3.0%: 0.01~5.0%: 92.0~ 99.98%;
Wherein composite initiation system: compositions, includes following components by weight percentage: (a) 0.5~the persulfate of 20%; (b) 0.1~the sulphite of 40% or acid sulphite;(c) 0.5~20% by NR1R2R3The tertiary amine compounds represented Or by N+R4R5R6R7Represent quaternary ammonium compounds or by NH2R8The fat amine compound represented, R in formula1~R7It is selected from C1 ~C14Straight or branched alkyl or alkyl derivative, R8Selected from C1~C18Straight or branched alkyl or alkyl derivative;(d) 10~ Carbamide, thiourea or the ammonia of 80%;(e) 5~the disodiumedetate of 60%.
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CN101824103A (en) * 2009-03-03 2010-09-08 中国石油大学(北京) Polyacrylamide inorganic nano composite drilling fluid aid and preparation method thereof
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